Biomimetic nanoparticles with polynucleotide and PEG mixed-monolayers enhance calcium phosphate mineralization

NASA Astrophysics Data System (ADS)

Vasconcellos, Kayla B.; McHugh, Sean M.; Dapsis, Katherine J.; Petty, Alexander R.; Gerdon, Aren E.

2013-09-01

Biomineralization of hydroxyapatite (Ca10(PO4)6(OH)2) is of significant importance in biomedical applications such as bone and dental repair, and biomimetic control of mineral formation may lead to more effective restorative procedures. Gold nanoparticles are functional scaffolds on which to assemble multi-component monolayers capable of mimicking protein activity in the templated synthesis of calcium phosphate. The goal of this research was to explore nanoparticle templates with mixed-monolayers of uncharged polar polyethylene glycol (PEG) molecules and highly charged polynucleotide and amino acid molecules in their ability to influence mineralization rates and mineral particle size and morphology. This research demonstrates through time-resolved optical density and dynamic light scattering measurements that the combination of tiopronin, PEG, and DNA presented on a nanoparticle surface decreases nanoparticle aggregation from 59 to 21 nm solvated radius, increases mineralization kinetics from 1.5 × 10-3 to 3.1 × 10-3 OD/min, and decreases mineral particle size from 685 to 442 nm average radius. FT-IR and TEM data demonstrate that mineralized material, while initially amorphous, transforms to a semi-crystalline material when guided by template interactions. This demonstrates that surface-tailored monolayer protected cluster scaffolds are successful and controllable mineralization templates with further potential for biomedical applications involving calcium phosphate and other biomaterials.

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

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

Predictions for partial and monolayer coverages of O2 on graphite

NASA Technical Reports Server (NTRS)

Pan, R. P.; Etters, R. D.; Kobashi, K.; Chandrasekharan, V.

1982-01-01

Monolayer properties of O2 on graphite are calculated using a pattern recognition, optimization scheme. Equilibrium monolayers are predicted at two different densities with properties in agreement with recent X-ray diffraction, specific heat, and neutron scattering data. Properties of the extremely low density regime are calculated using a model based upon a distribution of two-dimensional O2 clusters. The results are consistent with experimental evidence.

Room-temperature isolation of V(benzene)2 sandwich clusters via soft-landing into n-alkanethiol self-assembled monolayers.

PubMed

Nagaoka, Shuhei; Matsumoto, Takeshi; Okada, Eiji; Mitsui, Masaaki; Nakajima, Atsushi

2006-08-17

The adsorption state and thermal stability of V(benzene)2 sandwich clusters soft-landed onto a self-assembled monolayer of different chain-length n-alkanethiols (Cn-SAM, n = 8, 12, 16, 18, and 22) were studied by means of infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD). The IRAS measurement confirmed that V(benzene)2 clusters are molecularly adsorbed and maintain a sandwich structure on all of the SAM substrates. In addition, the clusters supported on the SAM substrates are oriented with their molecular axes tilted 70-80 degrees off the surface normal. An Arrhenius analysis of the TPD spectra reveals that the activation energy for the desorption of the supported clusters increases linearly with the chain length of the SAMs. For the longest chain C22-SAM, the activation energy reaches approximately 150 kJ/mol, and the thermal desorption of the supported clusters can be considerably suppressed near room temperature. The clear chain-length-dependent thermal stability of the supported clusters observed here can be explained well in terms of the cluster penetration into the SAM matrixes.

Domain and network aggregation of CdTe quantum rods within Langmuir Blodgett monolayers

NASA Astrophysics Data System (ADS)

Zimnitsky, Dmitry; Xu, Jun; Lin, Zhiqun; Tsukruk, Vladimir V.

2008-05-01

Control over the organization of quantum rods was demonstrated by changing the surface area at the air-liquid interface by means of the Langmuir-Blodgett (LB) technique. The LB isotherm of CdTe quantum rods capped with a mixture of alkylphosphines shows a transition point in the liquid-solid state, which is caused by the inter-rod reorganization. As we observed, at low surface pressure the quantum rods are assembled into round-shaped aggregates composed of a monolayer of nanorods packed in limited-size clusters with random orientation. The increase of the surface pressure leads to the rearrangement of these aggregates into elongated bundles composed of uniformly oriented nanorod clusters. Further compression results in denser packing of nanorods aggregates and in the transformation of monolayered domains into a continuous network of locally ordered quantum rods.

Electric bistability induced by incorporating self-assembled monolayers/aggregated clusters of azobenzene derivatives in pentacene-based thin-film transistors.

PubMed

Tseng, Chiao-Wei; Huang, Ding-Chi; Tao, Yu-Tai

2012-10-24

Composite films of pentacene and a series of azobenzene derivatives are prepared and used as the active channel material in top-contact, bottom-gate field-effect transistors. The transistors exhibit high field-effect mobility as well as large I-V hysteresis as a function of the gate bias history. The azobenzene moieties, incorporated either in the form of self-assembled monolayer or discrete multilayer clusters at the dielectric surface, result in electric bistability of the pentacene-based transistor either by photoexcitation or gate biasing. The direction of threshold voltage shifts, size of hysteresis, response time, and retention characteristics all strongly depend on the substituent on the benzene ring. The results show that introducing a monolayer of azobenzene moieties results in formation of charge carrier traps responsible for slower switching between the bistable states and longer retention time. With clusters of azobenzene moieties as the trap sites, the switching is faster but the retention is shorter. Detailed film structure analyses and correlation with the transistor/memory properties of these devices are provided.

A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

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

Lu, Jinlian; Guo, Yanhua; Zhang, Yun

A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%,more » 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.« less

The Intrinsic Ferromagnetism in a MnO2 Monolayer.

PubMed

Kan, M; Zhou, J; Sun, Q; Kawazoe, Y; Jena, P

2013-10-17

The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

On atomic structure of Ge huts growing on the Ge/Si(001) wetting layer

NASA Astrophysics Data System (ADS)

Arapkina, Larisa V.; Yuryev, Vladimir A.

2013-09-01

Structural models of growing Ge hut clusters—pyramids and wedges—are proposed on the basis of data of recent STM investigations of nucleation and growth of Ge huts on the Si(001) surface in the process of molecular beam epitaxy. It is shown that extension of a hut base along ⟨110⟩ directions goes non-uniformly during the cluster growth regardless of its shape. Growing pyramids, starting from the second monolayer, pass through cyclic formation of slightly asymmetrical and symmetrical clusters, with symmetrical ones appearing after addition of every fourth monolayer. We suppose that pyramids of symmetrical configurations composed by 2, 6, 10, etc., monolayers over the wetting layer are more stable than asymmetrical ones. This might explain less stability of pyramids in comparison with wedges in dense arrays forming at low temperatures of Ge deposition. Possible nucleation processes of pyramids and wedges on wetting layer patches from identical embryos composed by 8 dimers through formation of 1 monolayer high 16-dimer nuclei different only in their symmetry is discussed. Schematics of these processes are presented. It is concluded from precise STM measurements that top layers of wetting layer patches are relaxed when huts nucleate on them.

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

DTIC Science & Technology

2012-03-16

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

Protecting the properties of monolayer MoS 2 on silicon based substrates with an atomically thin buffer

DOE PAGES

Man, Michael K. L.; Deckoff-Jones, Skylar; Winchester, Andrew; ...

2016-02-12

Semiconducting 2D materials, like transition metal dichalcogenides (TMDs), have gained much attention for their potential in opto-electronic devices, valleytronic schemes, and semi-conducting to metallic phase engineering. However, like graphene and other atomically thin materials, they lose key properties when placed on a substrate like silicon, including quenching of photoluminescence, distorted crystalline structure, and rough surface morphology. The ability to protect these properties of monolayer TMDs, such as molybdenum disulfide (MoS 2), on standard Si-based substrates, will enable their use in opto-electronic devices and scientific investigations. Here we show that an atomically thin buffer layer of hexagonal-boron nitride (hBN) protects themore » range of key opto-electronic, structural, and morphological properties of monolayer MoS 2 on Si-based substrates. The hBN buffer restores sharp diffraction patterns, improves monolayer flatness by nearly two-orders of magnitude, and causes over an order of magnitude enhancement in photoluminescence, compared to bare Si and SiO 2 substrates. Lastly, our demonstration provides a way of integrating MoS 2 and other 2D monolayers onto standard Si-substrates, thus furthering their technological applications and scientific investigations.« less

Ab initio metadynamics simulations of oxygen/ligand interactions in organoaluminum clusters

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

Alnemrat, Sufian; Hooper, Joseph P., E-mail: jphooper@nps.edu

2014-10-14

Car-Parrinello molecular dynamics combined with a metadynamics algorithm is used to study the initial interaction of O{sub 2} with the low-valence organoaluminum clusters Al{sub 4}Cp{sub 4} (Cp=C{sub 5}H{sub 5}) and Al{sub 4}Cp{sub 4}{sup *} (Cp{sup *}=C{sub 5}[CH{sub 3}]{sub 5}). Prior to reaction with the aluminum core, simulations suggest that the oxygen undergoes a hindered crossing of the steric barrier presented by the outer ligand monolayer. A combination of two collective variables based on aluminum/oxygen distance and lateral oxygen displacement was found to produce distinct reactant, product, and transition states for this process. In the methylated cluster with Cp{sup *} ligands,more » a broad transition state of 45 kJ/mol was observed due to direct steric interactions with the ligand groups and considerable oxygen reorientation. In the non-methylated cluster the ligands distort away from the oxidizer, resulting in a barrier of roughly 34 kJ/mol with minimal O{sub 2} reorientation. A study of the oxygen/cluster system fixed in a triplet multiplicity suggests that the spin state does not affect the initial steric interaction with the ligands. The metadynamics approach appears to be a promising means of analyzing the initial steps of such oxidation reactions for ligand-protected clusters.« less

Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored-Monolayer-Protected Gold Nanorods

DTIC Science & Technology

2013-03-20

FULL PAPER DOI:10.1002/ejic.201300010 Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored- Monolayer-Protected Gold Nanorods Xiang Ma,[a] Yuhua Xue... Cao , Q. Wang, H. Tian, Chem. Commun. 2011, 47, 3559–3561. [8] a) I. Hwang, K. Baek, M. Jung, Y. Kim, K. M. Park, D. W. Lee, N. Selvapalam, K. Kim, J. Am

In vivo testing for gold nanoparticle toxicity.

PubMed

Simpson, Carrie A; Huffman, Brian J; Cliffel, David E

2013-01-01

A technique for measuring the toxicity of nanomaterials using a murine model is described. Blood samples are collected via submandibular bleeding while urine samples are collected on cellophane sheets. Both biosamples are then analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) for nanotoxicity. Blood samples are further tested for immunological response using a standard Coulter counter. The major organs of interest for filtration are also digested and analyzed via ICP-OES, producing useful information regarding target specificity of the nanomaterial of interest. Collection of the biosamples and analysis afterward is detailed, and the operation of the technique is described and illustrated by analysis of the nanotoxicity of an injection of a modified tiopronin monolayer-protected cluster.

Formation and stability of dense arrays of Au nanoclusters on hexagonal boron nitride/Rh(111)

NASA Astrophysics Data System (ADS)

Patterson, Matthew C.; Habenicht, Bradley F.; Kurtz, Richard L.; Liu, Li; Xu, Ye; Sprunger, Phillip T.

2014-05-01

We have studied the nucleation and growth of Au clusters at submonolayer and greater coverages on the h-BN nanomesh grown on Rh(111) by means of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). STM reveals that submonolayer Au deposited at 115 K nucleates within the nanomesh pores and remains confined to the pores even after warming to room temperature. Whereas there is a propensity of monoatomic high islands at low temperature, upon annealing, bi- and multilayer Au clusters emerge. Deposition of higher coverages of Au similarly results in Au clusters primarily confined to the nanomesh pores at room temperature. XPS analysis of core-level electronic states in the deposited Au shows strong final-state effects induced by restricted particle size dominating for low Au coverage, with indications that larger Au clusters are negatively charged by interaction through the h-BN monolayer. DFT calculations suggest that the structure of the Au clusters transitions from monolayer to bilayer at a size between 30 and 37 atoms per cluster, in line with our experiment. Bader charge analysis supports the negative charge state of deposited Au.

Crystalline embryos at ice-vapor interfaces

NASA Technical Reports Server (NTRS)

Bartley, D. L.

1976-01-01

The nucleation of small monolayer ice-like clusters at the basal and prism ice-vapor interfaces is considered. It is found that the basal surfaces prefer triangular embryos with an orientation that reverses from layer to layer, whereas the most stable clusters on the prism surfaces are rectangular in configuration. At any given saturation ratio, the preferred prism clusters are found to have a critical energy of formation significantly lower than that of the basal clusters, basically because of differences in cluster corner free energies.

Slider thickness promotes lubricity: from 2D islands to 3D clusters

NASA Astrophysics Data System (ADS)

Guerra, Roberto; Tosatti, Erio; Vanossi, Andrea

2016-05-01

The sliding of three-dimensional clusters and two-dimensional islands adsorbed on crystal surfaces represents an important test case to understand friction. Even for the same material, monoatomic islands and thick clusters will not as a rule exhibit the same friction, but specific differences have not been explored. Through realistic molecular dynamics simulations of the static friction of gold on graphite, an experimentally relevant system, we uncover as a function of gold thickness a progressive drop of static friction from monolayer islands, that are easily pinned, towards clusters, that slide more readily. The main ingredient contributing to this thickness-induced lubricity appears to be the increased effective rigidity of the atomic contact, acting to reduce the cluster interdigitation with the substrate. A second element which plays a role is the lateral contact size, which can accommodate the solitons typical of the incommensurate interface only above a critical contact diameter, which is larger for monolayer islands than for thick clusters. The two effects concur to make clusters more lubric than islands, and large sizes more lubric than smaller ones. These conclusions are expected to be of broader applicability in diverse nanotribological systems, where the role played by static, and dynamic, friction is generally quite important.

Slider thickness promotes lubricity: from 2D islands to 3D clusters.

PubMed

Guerra, Roberto; Tosatti, Erio; Vanossi, Andrea

2016-06-07

The sliding of three-dimensional clusters and two-dimensional islands adsorbed on crystal surfaces represents an important test case to understand friction. Even for the same material, monoatomic islands and thick clusters will not as a rule exhibit the same friction, but specific differences have not been explored. Through realistic molecular dynamics simulations of the static friction of gold on graphite, an experimentally relevant system, we uncover as a function of gold thickness a progressive drop of static friction from monolayer islands, that are easily pinned, towards clusters, that slide more readily. The main ingredient contributing to this thickness-induced lubricity appears to be the increased effective rigidity of the atomic contact, acting to reduce the cluster interdigitation with the substrate. A second element which plays a role is the lateral contact size, which can accommodate the solitons typical of the incommensurate interface only above a critical contact diameter, which is larger for monolayer islands than for thick clusters. The two effects concur to make clusters more lubric than islands, and large sizes more lubric than smaller ones. These conclusions are expected to be of broader applicability in diverse nanotribological systems, where the role played by static, and dynamic, friction is generally quite important.

Electron transfer catalysis with monolayer protected Au25 clusters

NASA Astrophysics Data System (ADS)

Antonello, Sabrina; Hesari, Mahdi; Polo, Federico; Maran, Flavio

2012-08-01

Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors. This article was submitted as part of a Themed Issue on metallic clusters. Other papers on this topic can be found in issue 14 of vol. 4 (2012). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.

PubMed

Su, Bin; Zhang, Meiqin; Shao, Yuanhua; Girault, Hubert H

2006-11-02

The capacitance of monolayer-protected gold nanoclusters (MPCs), C(MPC), in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to C(MPC) and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparing the redox properties of MPCs in four organic solvents: 1,2-dichloroethane (DCE), dichloromethane (DCM), chlorobenzene (CB), and toluene (TOL), in all of which MPCs have excellent solubility. Furthermore, this set of organic solvents features a dielectric constant in a range from 10.37 (DCE) to 2.38 (TOL), which is wide enough to probe the solvent effect. In these organic solvents, tetrahexylammonium bis(trifluoromethylsulfonyl)imide (THATf2N) is used as the supporting electrolyte. Cyclic and differential pulse voltammetric results provide concrete evidence that, despite the monolayer protection, the solvent plays a significant effect on the properties of MPCs in solution.

Preservation of far-UV aluminum reflectance by means of overcoating with C60 films.

PubMed

Méndez, J A; Larruquert, J I; Aznárez, J A

2000-01-01

Thin films of C(60) were investigated as protective coatings of Al films to preserve their far-UV (FUV) reflectance by inhibition or retardation of their oxidation. Two methods were used for the overcoating of Al films with approximately one monolayer of C(60): (1) deposition of a multilayer film followed by temperature desorption of all but one monolayer and (2) direct deposition of approximately one-monolayer film. We exposed both types of sample to controlled doses of molecular oxygen and water vapor and measured their FUV reflectance before and after exposure to evaluate the achieved protection on the Al films. The whole process of sample preparation, reflectance measurement, sample heating, and oxidation was made without breaking vacuum. Results show that a C(60) monolayer protected Al from oxidation to some extent, although FUV reflectance of unprotected Al films was never exceeded. FUV optical constants of C(60) films and the FUV reflectance of the C(60) film as deposited and as a function of exposure to O(2) were also measured.

Electrochemical Properties of Organosilane Self Assembled Monolayers on Aluminum 2024

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Calle, Luz Marina

2004-01-01

Self assembled monolayers are commonly used to modify surfaces. Within the last 15 years, self assembled monolayers have been investigated as a way to protect from corrosion[1,2] or biofouling.[3] In this study, self assembled monolayers of decitriethoxysilane (C10H21Si(OC2H5)3) and octadecyltriethoxysilane (C18H37Si(OC2H5)3) were formed on aluminum 2024-T3. The modified surfaces and bare Al 2024 were characterized by dynamic water contact angle measurements, x-ray photoelectron spectroscopy (XIPS) and infrared spectroscopy. Electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl was used to characterize the monolayers and evaluate their corrosion protection properties. The advancing water contact angle and infrared measurements show that the mono layers form a surface where the hydrocarbon chains are packed and oriented away from the surface, consistent with what is found in similar systems. The contact angle hysteresis measured in these systems is relatively large, perhaps indicating that the hydrocarbon chains are not as well packed as monolayers formed on other substrates. The results of the EIS measurements were modeled using a Randle's circuit modified by changing the capacitor to a constant phase element. The constant phase element values were found to characterize the monolayer. The capacitance of the monolayer modified surface starts lower than the bare Al 2024, but approaches values similar to the bare Al 2024 within 24 hours as the monolayer is degraded. The n values found for bare Al 2024 quickly approach the value of a true capacitor and are greater than 0.9 within hours after the start of exposure. For the monolayer modified structure, n can stay lower than 0.9 for a longer period of time. In fact, n for the monolayer modified surfaces is different from the bare surface even after the capacitance values have converged. This indicates that the deviation from ideal capacitance is the most sensitive indicator of the presence of the monolayer.

Organization of Amphiphilic Molecular Disks with Branched Hydrophilic Tails and Hexa-peri-hexabenzocoronene Core

NASA Astrophysics Data System (ADS)

Lee, Myongsoo; Kim, Jung-Woo; Yoo, Yong-Sik; Peleshanko, Sergey; Larson, Kirsten; Vaknin, David; Markutsya, Sergei; Tsukruk, Vladimir V.

2002-03-01

Amphiphilic branched discotics consisting of the aromatic core and oligoethers as the branched peripheral chains have been characterized in bulk and monolayer states. The discotics based on di-branched oligoether side chains have been observed to self-organize into an ordered hexagonal columnar structure within liquid crystalline (LC) phases. The tetrabranched molecule showed only an isotropic liquid. The LC molecules with di-branched tails have been observed to form stable monolayers on the water surface in contrast to the tetra-branched tails. We suggest a crab-like molecular conformation and cluster-segregated monolayers with six-fold symmetry of face-on packing on a solid surface.

Cluster Formation of Anchored Proteins Induced by Membrane-Mediated Interaction

PubMed Central

Li, Shuangyang; Zhang, Xianren; Wang, Wenchuan

2010-01-01

Abstract Computer simulations were used to study the cluster formation of anchored proteins in a membrane. The rate and extent of clustering was found to be dependent upon the hydrophobic length of the anchored proteins embedded in the membrane. The cluster formation mechanism of anchored proteins in our work was ascribed to the different local perturbations on the upper and lower monolayers of the membrane and the intermonolayer coupling. Simulation results demonstrated that only when the penetration depth of anchored proteins was larger than half the membrane thickness, could the structure of the lower monolayer be significantly deformed. Additionally, studies on the local structures of membranes indicated weak perturbation of bilayer thickness for a shallowly inserted protein, while there was significant perturbation for a more deeply inserted protein. The origin of membrane-mediated protein-protein interaction is therefore due to the local perturbation of the membrane thickness, and the entropy loss—both of which are caused by the conformation restriction on the lipid chains and the enhanced intermonolayer coupling for a deeply inserted protein. Finally, in this study we addressed the difference of cluster formation mechanisms between anchored proteins and transmembrane proteins. PMID:20513399

Molecular adsorption properties of CO and H2O on Au-, Cu-, and AuxCuy-doped MoS2 monolayer

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Gökoğlu, Gökhan; Üzengi Aktürk, Olcay

2017-12-01

In this study, we investigate the adsorption properties of Au, Cu, and AuxCuy nanoclusters on MoS2 sheet and the interactions of the adsorbed systems with CO and H2O molecules by using first principles calculations. Results indicate that Au, Cu, or AuxCuy strongly binds to MoS2 monolayer resulting in enhanced chemical activity and sensitivity toward CO and H2O molecules compared to bare MoS2 monolayer. Although both CO and H2O molecules bind weakly to pristine MoS2 monolayer, CO strongly binds to MoS2 sheet in the presence of Au, Cu atoms or AuxCuy clusters. Semiconductor MoS2 monolayer turns into metal upon Au or Cu adsorption. AuxCuy nanocluster adsorption decreases the band gap of MoS2 monolayer acting as a n-type dopant. AuxCuy-doped MoS2 systems have improved adsorption properties for CO and H2O molecules, so the conclusions provided in this study can be useful as a guide for next generation device modeling.

Nanoparticle-Based Receptors Mimic Protein-Ligand Recognition.

PubMed

Riccardi, Laura; Gabrielli, Luca; Sun, Xiaohuan; De Biasi, Federico; Rastrelli, Federico; Mancin, Fabrizio; De Vivo, Marco

2017-07-13

The self-assembly of a monolayer of ligands on the surface of noble-metal nanoparticles dictates the fundamental nanoparticle's behavior and its functionality. In this combined computational-experimental study, we analyze the structure, organization, and dynamics of functionalized coating thiols in monolayer-protected gold nanoparticles (AuNPs). We explain how functionalized coating thiols self-organize through a delicate and somehow counterintuitive balance of interactions within the monolayer itself and with the solvent. We further describe how the nature and plasticity of these interactions modulate nanoparticle-based chemosensing. Importantly, we found that self-organization of coating thiols can induce the formation of binding pockets in AuNPs. These transient cavities can accommodate small molecules, mimicking protein-ligand recognition, which could explain the selectivity and sensitivity observed for different organic analytes in NMR chemosensing experiments. Thus, our findings advocate for the rational design of tailored coating groups to form specific recognition binding sites on monolayer-protected AuNPs.

Spatially selective formation of hydrocarbon, fluorocarbon, and hydroxyl-terminated monolayers on a microelectrode array.

PubMed

Cook, Kevin M; Nissley, Daniel A; Ferguson, Gregory S

2013-06-11

A protection-deprotection strategy, using gold oxide as a passivating layer, was used to direct the self-assembly of monolayers (SAMs) selectively at individual gold microelectrodes in an array. This approach allowed the formation of hydroxyl-terminated monolayers, without side reactions, in addition to hydrocarbon and fluorocarbon SAMs. Fluorescence microscopy was used to visualize selective dewetting of hydrophobic monolayers by an aqueous dye solution, and spatially resolved X-ray photoelectron spectroscopy was used to demonstrate a lack of cross-contamination on neighboring microelectrodes in the array.

Water penetration/accommodation and phase behaviour of the neutral Langmuir monolayer at the air/water interface probed with sum frequency generation vibrational spectroscopy (SFG-VS).

PubMed

Zhang, Zhen; Zheng, De-Sheng; Guo, Yuan; Wang, Hong-Fei

2009-02-14

A strong and broad hydrogen bonded O-H band around 3520 cm(-1) is observed in the insoluble monolayer of the neutral liquid crystal molecules of 4''-n-pentyl-4-p-cyanobiphenyl (5CB) and 4''-n-octyl-4-p-cyanobiphenyl (8CB) throughout the whole surface density range, but not in the 4-pentyl-4'-cyanoterphenyl (5CT) monolayer, at the air/water interface. This novel spectral feature suggests the existence of an oriented water cluster species which has penetrated or accommodated into the Langmuir monolayer of the 8CB and 5CB molecules. This finding provided a molecular level mechanism for the stark difference in the phase behaviour between the CB and CT insoluble Langmuir monolayers at the air/water interface. It also calls for attention to the details of the specific water-surface interaction in mediating the structure and the phase behaviour of the molecular assemblies at the heterogeneous aqueous interfaces.

Deposition of Bacillus subtilis spores using an airbrush-spray or spots to study surface decontamination by pulsed light.

PubMed

Levy, Caroline; Bornard, Isabelle; Carlin, Frédéric

2011-02-01

Microbial contamination on surfaces of food processing equipment is a major concern in industries. A new method to inoculate a single-cell layer (monolayer) of microorganisms onto polystyrene was developed, using a deposition with an airbrush. A homogeneous dispersion of Bacillus subtilis DSM 402 spores sprayed on the surface was observed using both plate count and scanning electron microscopy. No clusters were found, even with high spore concentrations (10(7) spores/inoculated surface). A monolayer of microorganisms was also obtained after deposition of 10 μL droplets containing 3×10(4) spores/spot on polystyrene disks, but not with a higher spore concentration. Pulsed light (PL) applied to monolayers of B. subtilis spores allowed log reductions higher than 6. As a consequence of clusters formation in spots of 10 μL containing more than 3×10(5) spores, log reductions obtained by PL were significantly lower. The comparative advantages of spot and spray depositions were discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

Scanning tunneling microscope observation of the phosphatidylserine domains in the phosphatidylcholine monolayer.

PubMed

Matsunaga, Soichiro; Yamada, Taro; Kobayashi, Toshihide; Kawai, Maki

2015-05-19

A mixed monolayer of 1,2-dihexanoyl-sn-glycero-3-phospho-l-serine (DHPS) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) on an 1-octanethiol-modified gold substrate was visualized on the nanometer scale using in situ scanning tunneling microscopy (STM) in aqueous solution. DHPS clusters were evident as spotty domains. STM enabled us to distinguish DHPS molecules from DHPC molecules depending on their electronic structures. The signal of the DHPS domains was abolished by neutralization with Ca(2+). The addition of the PS + Ca(2+)-binding protein of annexin V to the Ca(2+)-treated monolayer gave a number of spots corresponding to a single annexin V molecule.

Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

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

Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil

2012-12-01

Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP containsmore » carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.« less

Effect of Microcystin-LR on Cultured Rat Endothelial Cells

DTIC Science & Technology

1990-02-26

protection, silymarin , and dithioerythritol 19. ABSTRACT (Continue on reverse if necessary and identify by block number) Primary cultureLs of adult rat...8217 22.g-Ldenine nucleotides, and a small reduction of cell density in endothelial cell monolayers._ Silymarin at 0.2 mM but not(dithioerythritol;at 2.5...monolayers. Silymarin at 0.2 mM but not dithioerythritol at 2.5 mM, partially protected changes in endothelial cells produced by supernatants derived

Lanthanide-based NMR: a tool to investigate component distribution in mixed-monolayer-protected nanoparticles.

PubMed

Guarino, Gaetano; Rastrelli, Federico; Scrimin, Paolo; Mancin, Fabrizio

2012-05-02

Gd(3+) ions, once bound to the monolayer of organic molecules coating the surface of gold nanoparticles, produce a paramagnetic relaxation enhancement (PRE) that broadens and eventually cancels the signals of the nuclear spins located nearby (within 1.6 nm distance). In the case of nanoparticles coated with mixed monolayers, the signals arising from the different coating molecules experience different PRE, depending on their distance from the binding site. As a consequence, observation of the signal broadening patterns provides direct information on the monolayer organization. © 2012 American Chemical Society

Cellular dosimetry of (111)In using monte carlo N-particle computer code: comparison with analytic methods and correlation with in vitro cytotoxicity.

PubMed

Cai, Zhongli; Pignol, Jean-Philippe; Chan, Conrad; Reilly, Raymond M

2010-03-01

Our objective was to compare Monte Carlo N-particle (MCNP) self- and cross-doses from (111)In to the nucleus of breast cancer cells with doses calculated by reported analytic methods (Goddu et al. and Farragi et al.). A further objective was to determine whether the MCNP-predicted surviving fraction (SF) of breast cancer cells exposed in vitro to (111)In-labeled diethylenetriaminepentaacetic acid human epidermal growth factor ((111)In-DTPA-hEGF) could accurately predict the experimentally determined values. MCNP was used to simulate the transport of electrons emitted by (111)In from the cell surface, cytoplasm, or nucleus. The doses to the nucleus per decay (S values) were calculated for single cells, closely packed monolayer cells, or cell clusters. The cell and nucleus dimensions of 6 breast cancer cell lines were measured, and cell line-specific S values were calculated. For self-doses, MCNP S values of nucleus to nucleus agreed very well with those of Goddu et al. (ratio of S values using analytic methods vs. MCNP = 0.962-0.995) and Faraggi et al. (ratio = 1.011-1.024). MCNP S values of cytoplasm and cell surface to nucleus compared fairly well with the reported values (ratio = 0.662-1.534 for Goddu et al.; 0.944-1.129 for Faraggi et al.). For cross doses, the S values to the nucleus were independent of (111)In subcellular distribution but increased with cluster size. S values for monolayer cells were significantly different from those of single cells and cell clusters. The MCNP-predicted SF for monolayer MDA-MB-468, MDA-MB-231, and MCF-7 cells agreed with the experimental data (relative error of 3.1%, -1.0%, and 1.7%). The single-cell and cell cluster models were less accurate in predicting the SF. For MDA-MB-468 cells, relative error was 8.1% using the single-cell model and -54% to -67% using the cell cluster model. Individual cell-line dimensions had large effects on S values and were needed to estimate doses and SF accurately. MCNP simulation compared well with the reported analytic methods in the calculation of subcellular S values for single cells and cell clusters. Application of a monolayer model was most accurate in predicting the SF of breast cancer cells exposed in vitro to (111)In-DTPA-hEGF.

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

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

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2012-11-29

The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2.more » Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state was found to be Au11L52+ at lower coverage and Au11L5+ at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces.« less

Structural investigation on the adsorption of the MARCKS peptide on anionic lipid monolayers - effects beyond electrostatic.

PubMed

Dietrich, Undine; Krüger, Peter; Käs, Josef A

2011-05-01

The presence of charged lipids in the cell membrane constitutes the background for the interaction with numerous membrane proteins. As a result, the valence of the lipids plays an important role concerning their lateral organization in the membrane and therefore the very manner of this interaction. This present study examines this aspect, particularly regarding to the interaction of the anionic lipid DPPS with the highly basic charged effector domain of the MARCKS protein, examined in monolayer model systems. Film balance, fluorescence microscopy and X-ray reflection/diffraction measurements were used to study the behavior of DPPS in a mixture with DPPC for its dependance on the presence of MARCKS (151-175). In the mixed monolayer, both lipids are completely miscible therefore DPPS is incorporated in the ordered crystalline DPPC domains as well. The interaction of MARCKS peptide with the mixed monolayer leads to the formation of lipid/peptide clusters causing an elongation of the serine group of the DPPS up to 7Å in direction to surface normal into the subphase. The large cationic charge of the peptide pulls out the serine group of the interface which simultaneously causes an elongation of the phosphodiester group of the lipid fraction too. The obtained results were used to compare the interaction of MARCKS peptide with the polyvalent PIP(2) in mixed monolayers. On this way we surprisingly find out, that the relative small charge difference of the anionic lipids causes a significant different interaction with MARCKS (151-175). The lateral arrangement of the anionic lipids depends on their charge values and determines the diffusion of the electrostatic binding clusters within the membrane. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Enhanced Emission from Single Isolated Gold Quantum Dots Investigated Using Two-Photon-Excited Fluorescence Near-Field Scanning Optical Microscopy.

PubMed

Abeyasinghe, Neranga; Kumar, Santosh; Sun, Kai; Mansfield, John F; Jin, Rongchao; Goodson, Theodore

2016-12-21

New approaches in molecular nanoscopy are greatly desired for interrogation of biological, organic, and inorganic objects with sizes below the diffraction limit. Our current work investigates emergent monolayer-protected gold quantum dots (nanoclusters, NCs) composed of 25 Au atoms by utilizing two-photon-excited fluorescence (TPEF) near-field scanning optical microscopy (NSOM) at single NC concentrations. Here, we demonstrate an approach to synthesize and isolate single NCs on solid glass substrates. Subsequent investigation of the NCs using TPEF NSOM reveals that, even when they are separated by distances of several tens of nanometers, we can excite and interrogate single NCs individually. Interestingly, we observe an enhanced two-photon absorption (TPA) cross section for single Au 25 NCs that can be attributed to few-atom local field effects and to local field-induced microscopic cascading, indicating their potential for use in ultrasensitive sensing, disease diagnostics, cancer cell therapy, and molecular computers. Finally, we report room-temperature aperture-based TPEF NSOM imaging of these NCs for the first time at 30 nm point resolution, which is a ∼5-fold improvement compared to the previous best result for the same technique. This report unveils the unique combination of an unusually large TPA cross section and the high photostability of Au NCs to (non-destructively) investigate stable isolated single NCs using TPEF NSOM. This is the first reported optical study of monolayer-protected single quantum clusters, opening some very promising opportunities in spectroscopy of nanosized objects, bioimaging, ultrasensitive sensing, molecular computers, and high-density data storage.

Defect charge states in Si doped hexagonal boron-nitride monolayer

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Andrew, R. C.; Chetty, N.

2016-02-01

We perform ab initio density functional theory calculations to investigate the energetics, electronic and magnetic properties of isolated stoichiometric and non-stoichiometric substitutional Si complexes in a hexagonal boron-nitride monolayer. The Si impurity atoms substituting the boron atom sites SiB giving non-stoichiometric complexes are found to be the most energetically favourable, and are half-metallic and order ferromagnetically in the neutral charge state. We find that the magnetic moments and magnetization energies increase monotonically when Si defects form a cluster. Partial density of states and standard Mulliken population analysis indicate that the half-metallic character and magnetic moments mainly arise from the Si 3p impurity states. The stoichiometric Si complexes are energetically unfavorable and non-magnetic. When charging the energetically favourable non-stoichiometric Si complexes, we find that the formation energies strongly depend on the impurity charge states and Fermi level position. We also find that the magnetic moments and orderings are tunable by charge state modulation q  =  -2, -1, 0, +1, +2. The induced half-metallic character is lost (retained) when charging isolated (clustered) Si defect(s). This underlines the potential of a Si doped hexagonal boron-nitride monolayer for novel spin-based applications.

On atomic structure of Ge huts growing on the Ge/Si(001) wetting layer

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

Arapkina, Larisa V.; Yuryev, Vladimir A.

Structural models of growing Ge hut clusters—pyramids and wedges—are proposed on the basis of data of recent STM investigations of nucleation and growth of Ge huts on the Si(001) surface in the process of molecular beam epitaxy. It is shown that extension of a hut base along <110> directions goes non-uniformly during the cluster growth regardless of its shape. Growing pyramids, starting from the second monolayer, pass through cyclic formation of slightly asymmetrical and symmetrical clusters, with symmetrical ones appearing after addition of every fourth monolayer. We suppose that pyramids of symmetrical configurations composed by 2, 6, 10, etc., monolayersmore » over the wetting layer are more stable than asymmetrical ones. This might explain less stability of pyramids in comparison with wedges in dense arrays forming at low temperatures of Ge deposition. Possible nucleation processes of pyramids and wedges on wetting layer patches from identical embryos composed by 8 dimers through formation of 1 monolayer high 16-dimer nuclei different only in their symmetry is discussed. Schematics of these processes are presented. It is concluded from precise STM measurements that top layers of wetting layer patches are relaxed when huts nucleate on them.« less

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold.

PubMed

Colorado, Ramon; Crouse, Christopher A; Zeigler, Christopher N; Barron, Andrew R

2008-08-19

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

Failure mechanism of monolayer graphene under hypervelocity impact of spherical projectile

PubMed Central

Xia, Kang; Zhan, Haifei; Hu, De’an; Gu, Yuantong

2016-01-01

The excellent mechanical properties of graphene have enabled it as appealing candidate in the field of impact protection or protective shield. By considering a monolayer graphene membrane, in this work, we assessed its deformation mechanisms under hypervelocity impact (from 2 to 6 km/s), based on a serial of in silico studies. It is found that the cracks are formed preferentially in the zigzag directions which are consistent with that observed from tensile deformation. Specifically, the boundary condition is found to exert an obvious influence on the stress distribution and transmission during the impact process, which eventually influences the penetration energy and crack growth. For similar sample size, the circular shape graphene possesses the best impact resistance, followed by hexagonal graphene membrane. Moreover, it is found the failure shape of graphene membrane has a strong relationship with the initial kinetic energy of the projectile. The higher kinetic energy, the more number the cracks. This study provides a fundamental understanding of the deformation mechanisms of monolayer graphene under impact, which is crucial in order to facilitate their emerging future applications for impact protection, such as protective shield from orbital debris for spacecraft. PMID:27618989

Failure mechanism of monolayer graphene under hypervelocity impact of spherical projectile

NASA Astrophysics Data System (ADS)

Xia, Kang; Zhan, Haifei; Hu, De'An; Gu, Yuantong

2016-09-01

The excellent mechanical properties of graphene have enabled it as appealing candidate in the field of impact protection or protective shield. By considering a monolayer graphene membrane, in this work, we assessed its deformation mechanisms under hypervelocity impact (from 2 to 6 km/s), based on a serial of in silico studies. It is found that the cracks are formed preferentially in the zigzag directions which are consistent with that observed from tensile deformation. Specifically, the boundary condition is found to exert an obvious influence on the stress distribution and transmission during the impact process, which eventually influences the penetration energy and crack growth. For similar sample size, the circular shape graphene possesses the best impact resistance, followed by hexagonal graphene membrane. Moreover, it is found the failure shape of graphene membrane has a strong relationship with the initial kinetic energy of the projectile. The higher kinetic energy, the more number the cracks. This study provides a fundamental understanding of the deformation mechanisms of monolayer graphene under impact, which is crucial in order to facilitate their emerging future applications for impact protection, such as protective shield from orbital debris for spacecraft.

Electrochemistry of redox-active self-assembled monolayers

PubMed Central

Eckermann, Amanda L.; Feld, Daniel J.; Shaw, Justine A.; Meade, Thomas J.

2010-01-01

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C60). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs. PMID:20563297

First-principles studies of Te line-ordered alloys in a MoS2 monolayer

NASA Astrophysics Data System (ADS)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2018-04-01

The thermodynamic stability, structural and electronic properties of Te line-ordered alloys are investigated using density functional theory (DFT) methods. Thirty four possible Te line-ordered alloy configurations are found in a 5×5 supercell of a MoS2 monolayer. The calculated formation energies show that the Te line-ordered alloy configurations are thermodynamically stable at 0 K and agree very well with the random alloys. The lowest energy configurations at each concentration correspond to the configuration where the Te atom rows are far apart from each other (avoiding clustering) within the supercell. The variation of the lattice constant at different concentrations obey Vegard's law. The Te line-ordered alloys fine tune the band gap of a MoS2 monolayer although deviating from linearity behavior. Our results suggest that the Te line-ordered alloys can be an effective way to modulate the band gap of a MoS2 monolayer for nanoelectronic, optoelectronic and nanophotonic applications.

Potential of transition metal atoms embedded in buckled monolayer g-C3N4 as single-atom catalysts.

PubMed

Li, Shu-Long; Yin, Hui; Kan, Xiang; Gan, Li-Yong; Schwingenschlögl, Udo; Zhao, Yong

2017-11-15

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C 3 N 4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C 3 N 4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C 3 N 4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C 3 N 4 gives rise to promising single-atom catalysts at low temperature.

Lipopolysaccharide-Specific but Not Anti-Flagellar Immunoglobulin A Monoclonal Antibodies Prevent Salmonella enterica Serotype Enteritidis Invasion and Replication within HEp-2 Cell Monolayers

PubMed Central

Iankov, Ianko D.; Petrov, Dragomir P.; Mladenov, Ivan V.; Haralambieva, Iana H.; Mitov, Ivan G.

2002-01-01

The protective potential of immunoglobulin A (IgA) monoclonal antibodies (MAbs) directed against O and H antigens of Salmonella enterica serotype Enteritidis to prevent bacterial adhesion to and invasion of HEp-2 cells was evaluated. Although anti-flagellar IgA MAbs showed strong agglutinating capacities, they did not protect cell monolayers. In contrast, IgA MAbs specific for the O:9 epitope of Salmonella lipopolysaccharide antigen alone prevented S. enterica serotype Enteritidis entry and replication within HEp-2 cells, and the protection was not mediated by direct binding of antibodies to bacterial adhesins or by agglutination of microorganisms. PMID:11854252

Protecting nickel with graphene spin-filtering membranes: A single layer is enough

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

Martin, M.-B.; Dlubak, B.; Piquemal-Banci, M.

2015-07-06

We report on the demonstration of ferromagnetic spin injectors for spintronics which are protected against oxidation through passivation by a single layer of graphene. The graphene monolayer is directly grown by catalytic chemical vapor deposition on pre-patterned nickel electrodes. X-ray photoelectron spectroscopy reveals that even with its monoatomic thickness, monolayer graphene still efficiently protects spin sources against oxidation in ambient air. The resulting single layer passivated electrodes are integrated into spin valves and demonstrated to act as spin polarizers. Strikingly, the atom-thick graphene layer is shown to be sufficient to induce a characteristic spin filtering effect evidenced through the signmore » reversal of the measured magnetoresistance.« less

Nucleation and island growth of alkanethiolate ligand domains on gold nanoparticles.

PubMed

Wang, Yifeng; Zeiri, Offer; Neyman, Alevtina; Stellacci, Francesco; Weinstock, Ira A

2012-01-24

The metal oxide cluster α-AlW(11)O(39)(9-) (1), readily imaged by cryogenic transmission electron microscopy (cryo-TEM), is used as a diagnostic protecting anion to investigate the self-assembly of alkanethiolate monolayers on electrostatically stabilized gold nanoparticles in water. Monolayers of 1 on 13.8 ± 0.9 nm diameter gold nanoparticles are displaced from the gold surface by mercaptoundecacarboxylate, HS(CH(2))(10)CO(2)(-) (11-MU). During this process, no aggregation is observed by UV-vis spectroscopy, and the intermediate ligand-shell organizations of 1 in cryo-TEM images indicate the presence of growing hydrophobic domains, or "islands", of alkanethiolates. UV-vis spectroscopic "titrations", based on changes in the surface plasmon resonance upon exchange of 1 by thiol, reveal that the 330 ± 30 molecules of 1 initially present on each gold nanoparticle are eventually replaced by 2800 ± 30 molecules of 11-MU. UV-vis kinetic data for 11-MU-monolayer formation reveal a slow phase, followed by rapid self-assembly. The Johnson, Mehl, Avrami, and Kolmogorov model gives an Avrami parameter of 2.9, indicating continuous nucleation and two-dimensional island growth. During nucleation, incoming 11-MU ligands irreversibly displace 1 from the Au-NP surface via an associative mechanism, with k(nucleation) = (6.1 ± 0.4) × 10(2) M(-1) s(-1), and 19 ± 8 nuclei, each comprised of ca. 8 alkanethiolates, appear on the gold-nanoparticle surface before rapid growth becomes kinetically dominant. Island growth is also first-order in [11-MU], and its larger rate constant, k(growth), (2.3 ± 0.2) × 10(4) M(-1) s(-1), is consistent with destabilization of molecules of 1 at the boundaries between the hydrophobic (alkanethiolate) and the electrostatically stabilized (inorganic) domains. © 2011 American Chemical Society

Scaffold Architecture Controls Insulinoma Clustering, Viability, and Insulin Production

PubMed Central

Blackstone, Britani N.; Palmer, Andre F.; Rilo, Horacio R.

2014-01-01

Recently, in vitro diagnostic tools have shifted focus toward personalized medicine by incorporating patient cells into traditional test beds. These cell-based platforms commonly utilize two-dimensional substrates that lack the ability to support three-dimensional cell structures seen in vivo. As monolayer cell cultures have previously been shown to function differently than cells in vivo, the results of such in vitro tests may not accurately reflect cell response in vivo. It is therefore of interest to determine the relationships between substrate architecture, cell structure, and cell function in 3D cell-based platforms. To investigate the effect of substrate architecture on insulinoma organization and function, insulinomas were seeded onto 2D gelatin substrates and 3D fibrous gelatin scaffolds with three distinct fiber diameters and fiber densities. Cell viability and clustering was assessed at culture days 3, 5, and 7 with baseline insulin secretion and glucose-stimulated insulin production measured at day 7. Small, closely spaced gelatin fibers promoted the formation of large, rounded insulinoma clusters, whereas monolayer organization and large fibers prevented cell clustering and reduced glucose-stimulated insulin production. Taken together, these data show that scaffold properties can be used to control the organization and function of insulin-producing cells and may be useful as a 3D test bed for diabetes drug development. PMID:24410263

Interfacial binding of divalent cations to calixarene-based Langmuir monolayers

DOE PAGES

Tulli, Ludovico G.; Wang, Wenjie; Lindemann, William R.; ...

2015-02-20

The interactions of Langmuir monolayers produced through the self-assembly of an amphiphilic p-carboxycalix[4]arene with a series of divalent, fourth-period transition metals, at the air-water interface, were investigated. Changes in the interfacial behavior of 1 in response to the presence of CuCl 2, CoCl 2, MnCl 2, and NiCl 2 were studied by means of Langmuir compression isotherms and Brewster angle microscopy (BAM). The measurements revealed that the self-assembly properties of 1 are significantly affected by Cu 2+ ions. The interactions of 1-based monolayers with Co 2+ and Cu 2+ ions were further investigated by means of synchrotron radiation-based X-ray reflectivitymore » (XRR), X-ray near-total-reflection fluorescence (XNTRF), and grazing incidence X-ray diffraction (GIXD). XNTRF and XRR analyses revealed that the monolayer of 1 binds more strongly to Cu 2+ than Co 2+ ions. In the presence of relatively high concentrations of Cu 2+ ions in the subphase (1.4 × 10 -3 M), XNTRF exhibited anomalous depth profile behavior and GIXD measurements showed considerably strong diffuse scattering. Furthermore, both measurements suggest the formation of Cu 2+ clusters contiguous to the monolayer of 1.« less

Synthesis and characterization of mixed monolayer protected gold nanorods and their Raman activities

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

Mlambo, Mbuso; Nanotechnology Innovation Centre, Advanced Materials Division, Mintek, Private Bag X3015, Randburg 2125; Mdluli, Phumlani S.

2013-10-15

Graphical abstract: Gold nanorods surface functionalization. - Highlights: • Mixed monolayer protected gold nanorods. • Surface enhanced Raman spectroscopy. • HS-(CH{sub 2}){sub 11}-NHCO-coumarin as a Raman active compound. - Abstract: The cetyltrimethylammonium bromide (CTAB) gold nanorods (AuNRs) were prepared by seed-mediated route followed by the addition of a Raman active compound (HS-(CH{sub 2}){sub 11}-NHCO-coumarin) on the gold nanorods surfaces. Different stoichiometric mixtures of HS-(CH{sub 2}){sub 11}-NHCO-coumarin and HS-PEG-(CH{sub 2}){sub 11}COOH were evaluated for their Raman activities. The lowest stoichiometric ratio HS-(CH{sub 2}){sub 11}-NHCO-coumarin adsorbed on gold nanorods surface was detected and enhanced by Raman spectroscopy. The produced mixed monolayer protectedmore » gold nanorods were characterized by UV-vis spectrometer for optical properties, transmission electron microscope (TEM) for structural properties (shape and aspect ratio) and their zeta potentials (charges) were obtained from ZetaSizer to determine the stability of the produced mixed monolayer protected gold nanorods. The Raman results showed a surface enhanced Raman scattering (SERS) enhancement at the lowest stoichiometric ratio of 1% HS-(CH{sub 2}){sub 11}-NHCO-coumarin compared to high ratio of 50% HS-(CH{sub 2}){sub 11}-NHCO-coumarin on the surface of gold nanorods.« less

Demonstration of increased anti-mycobacterial activity in peripheral blood monocytes after BCG vaccination in British school children.

PubMed Central

Cheng, S H; Walker, L; Poole, J; Aber, V R; Walker, K B; Mitchison, D A; Lowrie, D B

1988-01-01

A blood sample was taken from children aged 13-15 years immediately before BCG vaccination and 8 weeks after. The children were tuberculin skin-test negative to PPD-S before vaccination and positive after. Mononuclear cells were separated from the blood, infected with Mycobacterium microti at a low bacterium/monocyte ratio and allowed to form monolayers in microtitre wells. The infected monolayers were rinsed daily and the change in number of live bacteria in monolayers and supernatants was monitored by colony counts on agar. The cells were bacteriostatic during the first day, thereafter growth accelerated in pre-vaccination monolayers. When monolayers received pulsed exposures to autologous lymphocytes that had been incubated with whole dead tubercle bacilli the growth rates of M. microti were increased. However, growth rates in lymphocyte-pulsed monolayers were significantly lower after vaccination than before. It is proposed that this difference reflects the protective effect of vaccination. PMID:3219800

Polycyclic aromatic hydrocarbons in model bacterial membranes - Langmuir monolayer studies.

PubMed

Broniatowski, Marcin; Binczycka, Martyna; Wójcik, Aneta; Flasiński, Michał; Wydro, Paweł

2017-12-01

High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. Copyright © 2017. Published by Elsevier B.V.

“Click” Immobilization on Alkylated Silicon Substrates: Model for the Study of Surface Bound Antimicrobial Peptides

PubMed Central

Li, Yan; Santos, Catherine M.; Kumar, Amit; Zhao, Meirong; Lopez, Analette I.; Qin, Guoting; McDermott, Alison M.

2011-01-01

We describe an effective approach for the covalent immobilization of antimicrobial peptides (AMPs) to bioinert substrates via CuI-catalyzed azide–alkyne cycloaddition (CuAAC). The bioinert substrates were prepared by surface hydrosilylation of oligo-(ethylene glycol) (OEG) terminated alkenes on hydrogen-terminated silicon surfaces. To render the OEG monolayers “clickable”, mixed monolayers were prepared using OEG-alkenes with and without a terminal alkyne protected by a trimethylgermanyl (TMG) group. The mixed monolayers were characterized by X-ray photoelectron spectroscopy (XPS), elliposometry and contact angle measurement. The TMG protecting group can be readily removed to yield a free terminal alkyne by catalytic amounts of CuI in an aqueous media. This step can then be combined with the subsequent CuAAC reaction. Thus, the immobilization of an azide modified AMP (N3-IG-25) was achieved in a one-pot de-protection/coupling reaction. Varying the ratio of the two alkenes in the deposition mixture allowed for control over the density of the alkynyl groups in the mixed monolayer, and subsequently the coverage of the AMPs on the monolayer. These samples allowed for study of the dependence of antimicrobial activities on the AMP density. The results show that a relative low coverage of AMPs (~1.6×1013 molecule per cm2) is sufficient to significantly suppress the viability of Pseudomonas aeruginosa, while the surface presenting the highest density of AMPs (~2.8×1013 molecule per cm2) is still cyto-compatible. The remarkable antibacterial activity is attributed to the long and flexible linker and the site-specific “click” immobilization, which may facilitate the covalently attached peptides to interact with and disrupt the bacterial membranes. PMID:21264959

Topology-Scaling Identification of Layered Solids and Stable Exfoliated 2D Materials.

PubMed

Ashton, Michael; Paul, Joshua; Sinnott, Susan B; Hennig, Richard G

2017-03-10

The Materials Project crystal structure database has been searched for materials possessing layered motifs in their crystal structures using a topology-scaling algorithm. The algorithm identifies and measures the sizes of bonded atomic clusters in a structure's unit cell, and determines their scaling with cell size. The search yielded 826 stable layered materials that are considered as candidates for the formation of two-dimensional monolayers via exfoliation. Density-functional theory was used to calculate the exfoliation energy of each material and 680 monolayers emerge with exfoliation energies below those of already-existent two-dimensional materials. The crystal structures of these two-dimensional materials provide templates for future theoretical searches of stable two-dimensional materials. The optimized structures and other calculated data for all 826 monolayers are provided at our database (https://materialsweb.org).

Biological and Computational Modeling of Mammographic Density and Stromal Patterning

DTIC Science & Technology

2010-07-01

clumping Score Monolayer Absent Many Absent Absent Absent 1 Nucl. overlap Mild Moderate Mild Micro- nucleoli Rare 2 Clustering Moderate...Few Moderate Micro- nucleoli Occasional 3 Loss cohesion Conspicuous Absent Frequent Macro- nucleoli Frequent 4 We performed serial RPFNA

Superior Valley Polarization and Coherence of 2s Excitons in Monolayer WSe_{2}.

PubMed

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-26

We report the experimental observation of 2s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2s exciton displays superior valley polarization and coherence than 1s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

Superior Valley Polarization and Coherence of 2 s Excitons in Monolayer WSe2

NASA Astrophysics Data System (ADS)

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-01

We report the experimental observation of 2 s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2 s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2 s exciton displays superior valley polarization and coherence than 1 s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

Quantum chemical analysis of thermodynamics of 2D cluster formation of alkanes at the water/vapor interface in the presence of aliphatic alcohols.

PubMed

Vysotsky, Yu B; Kartashynska, E S; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Miller, R

2015-11-21

Using the quantum chemical semi-empirical PM3 method it is shown that aliphatic alcohols favor the spontaneous clusterization of vaporous alkanes at the water surface due to the change of adsorption from the barrier to non-barrier mechanism. A theoretical model of the non-barrier mechanism for monolayer formation is developed. In the framework of this model alcohols (or any other surfactants) act as 'floats', which interact with alkane molecules of the vapor phase using their hydrophobic part, whereas the hydrophilic part is immersed into the water phase. This results in a significant increase of contact effectiveness of alkanes with the interface during the adsorption and film formation. The obtained results are in good agreement with the existing experimental data. To test the model the thermodynamic and structural parameters of formation and clusterization are calculated for vaporous alkanes C(n)H(2n+2) (n(CH3) = 6-16) at the water surface in the presence of aliphatic alcohols C(n)H(2n+1)OH (n(OH) = 8-16) at 298 K. It is shown that the values of clusterization enthalpy, entropy and Gibbs' energy per one monomer of the cluster depend on the chain lengths of corresponding alcohols and alkanes, the alcohol molar fraction in the monolayers formed, and the shift of the alkane molecules with respect to the alcohol molecules Δn. Two possible competitive structures of mixed 2D film alkane-alcohol are considered: 2D films 1 with single alcohol molecules enclosed by alkane molecules (the alcohols do not form domains) and 2D films 2 that contain alcohol domains enclosed by alkane molecules. The formation of the alkane films of the first type is nearly independent of the surfactant type present at the interface, but depends on their molar fraction in the monolayer formed and the chain length of the compounds participating in the clusterization, whereas for the formation of the films of the second type the interaction between the hydrophilic parts of the surfactant is essential and different for various types of amphiphilic compounds. The energetic preference of the film formation of both types depends significantly on the chain length of compounds. The surfactant concentration (in the range of X = 0-10%) exerts a slight influence on the process of film formation.

Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

NASA Astrophysics Data System (ADS)

Grabow, Lars C.; Yuan, Qiuyi; Doan, Hieu A.; Brankovic, Stanko R.

2015-10-01

A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

Colloidal layers in magnetic fields and under shear flow

NASA Astrophysics Data System (ADS)

Löwen, H.; Messina, R.; Hoffmann, N.; Likos, C. N.; Eisenmann, C.; Keim, P.; Gasser, U.; Maret, G.; Goldberg, R.; Palberg, T.

2005-11-01

The behaviour of colloidal mono- and bilayers in external magnetic fields and under shear is discussed and recent progress is summarized. Superparamagnetic colloidal particles form monolayers when they are confined to a air-water interface in a hanging water droplet. An external magnetic field allows us to tune the strength of the mutual dipole-dipole interaction between the colloids and the anisotropy of the interaction can be controlled by the tilt angle of the magnetic field relative to the surface normal of the air-water interface. For sufficiently large magnetic field strength crystalline monolayers are found. The role of fluctuations in these two-dimensional crystals is discussed. Furthermore, clustering phenomena in binary mixtures of superparamagnetic particles forming fluid monolayers are predicted. Finally, we address sheared colloidal bilayers and find that the orientation of confined colloidal crystals can be tailored by a previously applied shear direction.

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template.

PubMed

Lee, Kihong; Choi, Bonnie; Plante, Ilan Jen-La; Paley, Maria V; Zhong, Xinjue; Crowther, Andrew C; Owen, Jonathan S; Zhu, Xiaoyang; Roy, Xavier

2018-05-22

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C 60 as a polymerizable monomer. The C 60 building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C 60 monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C 60 . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

PubMed

Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio

2016-04-21

We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

Protective effects of Lactobacillus plantarum against epithelial barrier dysfunction of human colon cell line NCM460

PubMed Central

Liu, Zhi-Hua; Shen, Tong-Yi; Zhang, Peng; Ma, Yan-Lei; Moyer, Mary Pat; Qin, Huan-Long

2010-01-01

AIM: To investigate the effects of Lactobacillus plantarum (L. plantarum) in the intestinal permeability and expression of tight junction (TJ) using the normal human colon cell line NCM460. METHODS: Paracellular permeability of NCM460 monolayers was determined by transepithelial electrical resistance and dextran permeability. Expression of TJ proteins in NCM460 cell monolayers was detected by Western blotting and quantitative real-time polymerase chain reaction. RESULTS: L. plantarum played an important role in increasing transepithelial electrical resistance and decreasing the permeability to macromolecules of NCM460 monolayers against the disruption caused by enteropathogenic Escherichia coli (E. coli) or enteroinvasive E. coli. L. plantarum also prevented the decrease in the expression of TJ proteins and F-actin in NCM460 cells. CONCLUSION: L. plantarum can protect against dysfunction of NCM460 intestinal epithelial barrier caused by enteropathogenic E. coli or enteroinvasive E. coli, and thus can be a potential candidate of therapeutic agents for the treatment of intestinal diseases. PMID:21128328

Full superconducting dome of strong Ising protection in gated monolayer WS2.

PubMed

Lu, Jianming; Zheliuk, Oleksandr; Chen, Qihong; Leermakers, Inge; Hussey, Nigel E; Zeitler, Uli; Ye, Jianting

2018-04-03

Many recent studies show that superconductivity not only exists in atomically thin monolayers but can exhibit enhanced properties such as a higher transition temperature and a stronger critical field. Nevertheless, besides being unstable in air, the weak tunability in these intrinsically metallic monolayers has limited the exploration of monolayer superconductivity, hindering their potential in electronic applications (e.g., superconductor-semiconductor hybrid devices). Here we show that using field effect gating, we can induce superconductivity in monolayer WS 2 grown by chemical vapor deposition, a typical ambient-stable semiconducting transition metal dichalcogenide (TMD), and we are able to access a complete set of competing electronic phases over an unprecedented doping range from band insulator, superconductor, to a reentrant insulator at high doping. Throughout the superconducting dome, the Cooper pair spin is pinned by a strong internal spin-orbit interaction, making this material arguably the most resilient superconductor in the external magnetic field. The reentrant insulating state at positive high gating voltages is attributed to localization induced by the characteristically weak screening of the monolayer, providing insight into many dome-like superconducting phases observed in field-induced quasi-2D superconductors.

Monolayer and/or few-layer graphene on metal or metal-coated substrates

DOEpatents

Sutter, Peter Werner; Sutter, Eli Anguelova

2015-04-14

Disclosed is monolayer and/or few-layer graphene on metal or metal-coated substrates. Embodiments include graphene mirrors. In an example, a mirror includes a substrate that has a surface exhibiting a curvature operable to focus an incident beam onto a focal plane. A graphene layer conformally adheres to the substrate, and is operable to protect the substrate surface from degradation due to the incident beam and an ambient environment.

Protection against free radicals (UVB irradiation) of a water-soluble enzymatic extract from rice bran. Study using human keratinocyte monolayer and reconstructed human epidermis.

PubMed

Santa-María, C; Revilla, E; Miramontes, E; Bautista, J; García-Martínez, A; Romero, E; Carballo, M; Parrado, J

2010-01-01

The antioxidant capacity of a water-soluble enzymatic extract from rice bran (EERB) has been tested in two cell models: keratinocyte monolayers and human reconstructed epidermis. Cells were incubated in culture medium in presence of different amounts of EERB and were UVB irradiated. Cell population assessment (MTT assay) and MDA (malonaldehyde) production were evaluated. The EERB did not induce cytotoxic effect for concentrations inferior or equal to 100 microg/mL. Human keratinocyte monolayers were protected of irradiation preventing 33% the lipid peroxidation process at concentration of 10 microg/ml of EEBR. In reconstructed human epidermis, 100 microg/mL decreased lipid peroxidation process by 44% (p<0.01) with regards to irradiated negative control. This effect was comparable to that of vitamin E at 600 microg/mL. Our data indicate that EERB is potentially able to efficiently counteract UVB-induced response. The EERB, diluted at 10% with water has very good skin compatibility. This product showed a sun protection factor of 4.8+/-0.3. Thus we can propose EERB as a useful natural standardized extract in skin photoprotection with promising applications in the field of dermatology. Copyright 2009 Elsevier Ltd. All rights reserved.

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

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

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

DOE PAGES

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping; ...

2016-07-28

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

Diverse roles of guanine nucleotide exchange factors in regulating collective cell migration

PubMed Central

Tseng, Yun-Yu; Rabadán, M. Angeles; Krishna, Shefali; Hall, Alan

2017-01-01

Efficient collective migration depends on a balance between contractility and cytoskeletal rearrangements, adhesion, and mechanical cell–cell communication, all controlled by GTPases of the RHO family. By comprehensive screening of guanine nucleotide exchange factors (GEFs) in human bronchial epithelial cell monolayers, we identified GEFs that are required for collective migration at large, such as SOS1 and β-PIX, and RHOA GEFs that are implicated in intercellular communication. Down-regulation of the latter GEFs differentially enhanced front-to-back propagation of guidance cues through the monolayer and was mirrored by down-regulation of RHOA expression and myosin II activity. Phenotype-based clustering of knockdown behaviors identified RHOA-ARHGEF18 and ARHGEF3-ARHGEF28-ARHGEF11 clusters, indicating that the latter may signal through other RHO-family GTPases. Indeed, knockdown of RHOC produced an intermediate between the two phenotypes. We conclude that for effective collective migration, the RHOA-GEFs → RHOA/C → actomyosin pathways must be optimally tuned to compromise between generation of motility forces and restriction of intercellular communication. PMID:28512143

Ascorbate protects endothelial barrier function during septic insult: Role of protein phosphatase type 2A.

PubMed

Han, Min; Pendem, Suresh; Teh, Suet Ling; Sukumaran, Dinesh K; Wu, Feng; Wilson, John X

2010-01-01

Endothelial barrier dysfunction contributes to morbidity in sepsis. We tested the hypothesis that raising the intracellular ascorbate concentration protects the endothelial barrier from septic insult by inhibiting protein phosphatase type 2A. Monolayer cultures of microvascular endothelial cells were incubated with ascorbate, dehydroascorbic acid (DHAA), the NADPH oxidase inhibitors apocynin and diphenyliodonium, or the PP2A inhibitor okadaic acid and then were exposed to septic insult (lipopolysaccharide and interferon-gamma). Under standard culture conditions that depleted intracellular ascorbate, septic insult stimulated oxidant production and PP2A activity, dephosphorylated phosphoserine and phosphothreonine residues in the tight junction-associated protein occludin, decreased the abundance of occludin at cell borders, and increased monolayer permeability to albumin. NADPH oxidase inhibitors prevented PP2A activation and monolayer leak, showing that these changes required reactive oxygen species. Okadaic acid, at a concentration that inhibited PP2A activity and monolayer leak, prevented occludin dephosphorylation and redistribution, implicating PP2A in the response of occludin to septic insult. Incubation with ascorbate or DHAA raised intracellular ascorbate concentrations and mitigated the effects of septic insult. In conclusion, ascorbate acts within microvascular endothelial cells to inhibit septic stimulation of oxidant production by NADPH oxidase and thereby prevents PP2A activation, PP2A-dependent dephosphorylation and redistribution of occludin, and disruption of the endothelial barrier. Copyright 2009 Elsevier Inc. All rights reserved.

Characterization of iron surface modified by 2-mercaptobenzothiazole self-assembled monolayers

NASA Astrophysics Data System (ADS)

Feng, Yuanyuan; Chen, Shenhao; Zhang, Honglin; Li, Ping; Wu, Ling; Guo, Wenjuan

2006-12-01

A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) adsorbed on the iron surface was prepared. The films were characterized by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection spectroscopy (FT-IR) and scanning electron microscopy (SEM). Besides, the microcalorimetry method was utilized to study the self-assembled process on iron surface and the adsorption mechanism was discussed from the power-time curve. The results indicated that MBT was able to form a film spontaneously on iron surface and the presence of it could protect iron from corrosion effectively. However, the assembling time and the concentration influence the protection efficiency. Quantum chemical calculations, according to which adsorption mechanism was discussed, could explain the experimental results to some extent.

Gold nanoparticles protected by mixed hydrogenated/fluorinated monolayers: controlling and exploring the surface features

NASA Astrophysics Data System (ADS)

Şologan, Maria; Gentilini, Cristina; Bidoggia, Silvia; Boccalon, Mariangela; Pace, Alice; Pengo, Paolo; Pasquato, Lucia

2018-06-01

Harnessing the reciprocal phobicity of hydrogenated and fluorinated thiolates proved to be a valuable strategy in preparing gold nanoparticles displaying mixed monolayers with a well-defined and pre-determined morphology. Our studies display that the organisation of the fluorinated ligands in phase-separated domains takes place even when these represent a small fraction of the ligands grafted on the gold surface. Using simple model ligands and by combining 19F NMR or ESR spectroscopies, and multiscale molecular simulations, we could demonstrate how the monolayer morphology responds in a predictable manner to structural differences between the thiolates. This enables a straightforward preparation of gold nanoparticles with monolayers displaying stripe-like, Janus, patchy, and random morphologies. Additionally, solubility properties may be tuned as function of the nature of the ligands and of the monolayer morphology obtaining gold nanoparticles soluble in organic solvents or in aqueous solutions. Most importantly, this rich diversity can be achieved not by resorting to ad hoc developed fabrication techniques, but rather relying on the spontaneous self-sorting of the ligands upon assembly on the nanoparticle surface. Besides enabling control over the monolayer morphology, fluorinated ligands endow the nanoparticles with several properties that can be exploited in the development of novel materials with applications, for instance in drug delivery and diagnostic imaging.

Effects of dexamethasone on angiotensin II-induced changes of monolayer permeability and F-actin distribution in glomerular endothelial cells.

PubMed

Fang, Junyan; Wang, Miao; Zhang, Wei; Wang, Yingdeng

2013-11-01

The aim of this study was to investigate the changes in monolayer permeability and F-actin distribution caused by angiotensin II (Ang II)-induced injury in glomerular endothelial cells (GENCs) and the effects of dexamethasone on these changes. GENCs isolated and cultured from Wistar rats were used to examine the changes in monolayer permeability and F-actin distribution induced by Ang II. GENC permeability was evaluated by measuring the diffusion of biotin-conjugated bovine serum albumin (biotin-BSA) across a cell monolayer. The expression levels and distribution of F-actin were assessed by flow cytometry. The biotin-BSA concentrations were measured by capture enzyme-linked immunosorbent assay. Ang II at a concentration of 10 mg/l increased the permeability of the GENC monolayer at 6 h and 12 h (P<0.05 and P<0.01, respectively) and caused F-actin depolymerisation at 6 h and 12 h (P<0.01). The two effects attributed to Ang II were significantly inhibited by dexamethasone treatment (P<0.01). The increased permeability of the GENC monolayer induced by Ang II was significantly correlated with the depolymerisation of F-actin. Dexamethasone abrogated the Ang II-mediated damage to GENCs indicating that it may play an important role in protecting GENCs from injury.

Monolayer Cu2Si as a potential gas sensor for NOx and COx (x = 1, 2): A first-principles study

NASA Astrophysics Data System (ADS)

Zhu, Hao-Hao; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

2018-02-01

Although the metal-decoration can enhance the sensing properties of two-dimensional (2D) materials, the cyclic utilization of materials is hindered by the clustering tendency of metal atoms. Furthermore, there exists a risk of explosion of combustible gases with the electrical measure. Based on first-principles calculations, we investigate the adsorption of various gas molecules (O2, NO, NO2, NH3, N2, CO, CH4 and CO2) on the 2D Cu-Si extended system (Cu2Si). The NOx molecules are chemisorbed on the Cu2Si monolayer, while other gas molecules (except CH4 and N2) are held by an interaction intermediating between the physisorbed and chemisorbed states. The strong hybridizations between N 2p and Si 3p (Cu 4p) orbitals lead to the large adsorption energies. Interestingly, the adsorption of NOx (1 μB) and CO2 (2 μB) can induce magnetic moments on the intrinsically nonmagnetic Cu2Si monolayer. The magnetic moment of NO-Cu2Si mainly arises from the molecule, while the magnetic moments for the NO2 and CO2 adsorption almost origin from the monolayer. In addition, an antiferromagnetic coupling is found in CO-Cu2Si. The changes in magnetization upon the gas adsorption may be detected sensitively and safely, suggesting the Cu2Si monolayer is potential for gas sensing.

Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

PubMed

Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

2012-10-16

In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices.

Proton and hydrogen transport through two-dimensional monolayers

NASA Astrophysics Data System (ADS)

Seel, Max; Pandey, Ravindra

2016-06-01

Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS2) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene.

Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

PubMed

Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

2017-02-01

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

OPC-compounds prevent oxidant-induced carbonylation and depolymerization of the F-actin cytoskeleton and intestinal barrier hyperpermeability.

PubMed

Banan, A; Fitzpatrick, L; Zhang, Y; Keshavarzian, A

2001-02-01

Rebamipide (OPC-12759), a quinolone derivative, and OPC-6535, a thiazol-carboxylic acid derivative, are compounds with ability to protect gastrointestinal (GI) mucosal integrity against reactive oxygen metabolites (ROM). The underlying mechanism of OPC-mediated protection remains poorly understood. It is now established that ROM can injure the mucosa by disruption of the cytoskeletal network, a key component of mucosal barrier integrity. We, therefore, investigated whether OPC compounds prevent the oxidation, disassembly, and instability of the cytoskeletal protein actin and, in turn, protect intestinal barrier function against ROM. Human intestinal (Caco-2) cell monolayers were pretreated with OPC (-12759 or -6535) prior to incubation with ROM (H2O2) or HOCl). Effects on cell integrity (ethidium homodimer-1), epithelial barrier function (fluorescein sulfonic acid clearance), and actin cytoskeletal integrity (high-resolution laser confocal) were then determined. Cells were also processed for quantitative immunoblotting of G- and F-actin to measure oxidation (carbonylation) and disassembly of actin. In monolayers exposed to ROM, preincubation with OPC compounds prevented actin oxidation, decreased depolymerized G-actin, and enhanced the stable F-actin. Concomitantly, OPC agents abolished both actin cytoskeletal disruption and monolayer barrier dysfunction. Data suggest for the first time that OPC drugs prevent oxidation of actin and lead to the protection of actin cytoskeleton and intestinal barrier integrity against oxidant insult. Accordingly, these compounds may be used as novel therapeutic agents for the treatment of a variety of oxidative inflammatory intestinal disorders with an abnormal mucosal barrier such as inflammatory bowel disease.

Structure formation of lipid membranes: Membrane self-assembly and vesicle opening-up to octopus-like micelles

NASA Astrophysics Data System (ADS)

Noguchi, Hiroshi

2013-02-01

We briefly review our recent studies on self-assembly and vesicle rupture of lipid membranes using coarse-grained molecular simulations. For single component membranes, lipid molecules self-assemble from random gas states to vesicles via disk-shaped clusters. Clusters aggregate into larger clusters, and subsequently the large disks close into vesicles. The size of vesicles are determined by kinetics than by thermodynamics. When a vesicle composed of lipid and detergent types of molecules is ruptured, a disk-shaped micelle called bicelle can be formed. When both surfactants have negligibly low critical micelle concentration, it is found that bicelles connected with worm-like micelles are also formed depending on the surfactant ratio and spontaneous curvature of the membrane monolayer.

Magnetic Ordering in Gold Nanoclusters

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

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Magnetic Ordering in Gold Nanoclusters

DOE PAGES

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano; ...

2017-06-12

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Proximity-induced mixed odd- and even-frequency pairing in monolayer NbSe2

NASA Astrophysics Data System (ADS)

Aliabad, Mojtaba Rahimi; Zare, Mohammad-Hossein

2018-06-01

Monolayer superconducting transition-metal dichalcogenide NbSe2 is a candidate for a nodal topological superconductor by magnetic field. Because of the so-called Ising spin-orbit coupling that strongly pins the electron spins to the out-of-plane direction, Cooper pairs in monolayer superconductor NbSe2 are protected against an applied in-plane magnetic field much larger than the Pauli limit. In monolayer NbSe2, in addition to the Fermi pockets at the corners of Brillouin zone with opposite crystal momentum similar to other semiconducting transition-metal dichalcogenids, there is an extra Fermi pocket around the Γ point with much smaller spin splitting, which could lead to an alternative strategy for pairing possibilities that are manipulable by a smaller magnetic field. By considering a monolayer NbSe2-ferromagnet substrate junction, we explore the modified pairing correlations on the pocket at Γ point in hole-doped monolayer NbSe2. The underlying physics is fascinating as there is a delicate interplay of the induced exchange field and the Ising spin-orbit coupling. We realize a mixed singlet-triplet superconductivity, s +f , due to the Ising spin-orbit coupling. Moreover, our results reveal the admixture state including both odd- and even-frequency components, associated with the ferromagnetic proximity effect. Different frequency symmetries of the induced pairing correlations can be realized by manipulating the magnitude and direction of the induced magnetization.

Effects of Graphene Monolayer Coating on the Optical Performance of Remote Phosphors

NASA Astrophysics Data System (ADS)

Yazdan Mehr, M.; Volgbert, S.; van Driel, W. D.; Zhang, G. Q.

2017-10-01

A graphene monolayer has been successfully coated on one side of a bisphenol-A-polycarbonate (BPA-PC) plate, used as a substrate for remote phosphor applications in light-emitting diode (LED)-based products. Using a photoresist transferring method, graphene sheet has been coated on BPA-PC plates. The results show that this graphene monolayer significantly improves the lifetime and performance of LEDs mainly by protecting them against external degradation factors such as moisture and oxygen. Also, LED-based products composed of graphene-coated BPA-PC plates exhibit longer stability with comparatively less loss of luminous efficiency. This method has great potential to significantly improve the reliability of not only LED-based products but also many other microelectronics packaging and components, in which moisture and oxygen are the key causes of failures.

Plasma combined self-assembled monolayer pretreatment on electroplated-Cu surface for low temperature Cu-Sn bonding in 3D integration

NASA Astrophysics Data System (ADS)

Wang, Junqiang; Wang, Qian; Wu, Zijian; Tan, Lin; Cai, Jian; Wang, Dejun

2017-05-01

A novel pretreatment of plasma combined self-assembled monolayer (PcSAM) was proposed to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D integration. Measurement results revealed that self-assemble monolayer (SAM) would be easier absorbed on plasma-activated Cu surface and protect the clean surface from re-oxidation when storage. The absorbed SAM layer could be removed by thermal desorption during bonding process. With optimal PcSAM pretreatment, oxygen content of the Cu surface was reduced to as low as 1.39%. The followed Cu-Sn bonding was realized at low temperature of 200 °C. Finally, bonding interface exhibited a defect-free interconnection, and bonding strength has reached as high as 68.7 MPa.

Barrier mechanism of multilayers graphene coated copper against atomic oxygen irradiation

NASA Astrophysics Data System (ADS)

Zhang, Haijing; Ren, Siming; Pu, Jibin; Xue, Qunji

2018-06-01

Graphene has been demonstrated as a protective coating for Cu under ambient condition because of its high impermeability and light-weight oxidation barrier. However, it lacks the research of graphene as a protective coating in space environment. Here, we experimentally and theoretically study the oxidation behavior of graphene-coated Cu in vacuum atomic oxygen (AO) condition. After AO irradiation, the experimental results show multilayer graphene has better anti-oxidation than monolayer graphene. Meanwhile, the calculation results show the oxidation appeared on the graphene's grain boundaries or the film's vacancy defects for the monolayer graphene coated Cu foil. Moreover, the calculation results show the oxidation process proceeds slowly in multilayers because of the matched defects overlaps each other to form a steric hindrance to suppress the O atom diffusion in the vertical direction, and the mismatched defects generates potential energy barriers for interlayer to suppress the O atom diffusion in the horizontal direction. Hence, multilayer graphene films could serve as protection coatings to prevent diffusion of O atom.

Template growth of Au, Ni and Ni–Au nanoclusters on hexagonal boron nitride/Rh(111): a combined STM, TPD and AES study

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

Wu, Fanglue; Huang, Dali; Yue, Yuan

In this study, the template growth of Au, Ni, and Ni–Au bimetallic nanoclusters on hexagonal boron nitride/Rh(111), i.e. h-BN/Rh(111), was investigated via scanning tunneling microscopy (STM), temperature programmed-desorption (TPD), and Auger electron spectroscopy (AES). STM study shows that template growth of Au clusters on h-BN/Rh(111) forms mainly well-dispersed monolayer clusters. In contrast, Ni forms large multilayer clusters showing a relatively high diffusivity on h-BN/Rh(111) substrate. Ni–Au bimetallic clusters are effectively formed first by Au deposition followed by Ni deposition, with the Au clusters functioning as nucleation sites for the subsequently deposited Ni. Further structural analysis was carried out via TPDmore » and AES. The resulting TPD and AES data show the surface composition and charge transfer between Au and Ni of the bimetallic clusters. These results suggest that the h-BN/Rh(111) substrate represents a unique candidate for supporting Ni–Au bimetallic clusters in further catalytic reactions.« less

Template growth of Au, Ni and Ni–Au nanoclusters on hexagonal boron nitride/Rh(111): a combined STM, TPD and AES study

DOE PAGES

Wu, Fanglue; Huang, Dali; Yue, Yuan; ...

2017-09-12

In this study, the template growth of Au, Ni, and Ni–Au bimetallic nanoclusters on hexagonal boron nitride/Rh(111), i.e. h-BN/Rh(111), was investigated via scanning tunneling microscopy (STM), temperature programmed-desorption (TPD), and Auger electron spectroscopy (AES). STM study shows that template growth of Au clusters on h-BN/Rh(111) forms mainly well-dispersed monolayer clusters. In contrast, Ni forms large multilayer clusters showing a relatively high diffusivity on h-BN/Rh(111) substrate. Ni–Au bimetallic clusters are effectively formed first by Au deposition followed by Ni deposition, with the Au clusters functioning as nucleation sites for the subsequently deposited Ni. Further structural analysis was carried out via TPDmore » and AES. The resulting TPD and AES data show the surface composition and charge transfer between Au and Ni of the bimetallic clusters. These results suggest that the h-BN/Rh(111) substrate represents a unique candidate for supporting Ni–Au bimetallic clusters in further catalytic reactions.« less

Heterogeneous Nucleation of Colloidal Crystals on a Glass Substrate with Depletion Attraction.

PubMed

Guo, Suxia; Nozawa, Jun; Hu, Sumeng; Koizumi, Haruhiko; Okada, Junpei; Uda, Satoshi

2017-10-10

The heterogeneous nucleation of colloidal crystals with attractive interactions has been investigated via in situ observations. We have found two types of nucleation processes: a cluster that overcomes the critical size for nucleation with a monolayer, and a method that occurs with two layers. The Gibbs free energy changes (ΔG) for these two types of nucleation processes are evaluated by taking into account the effect of various interfacial energies. In contrast to homogeneous nucleation, the change in interfacial free energy, Δσ, is generated for colloidal nucleation on a foreign substrate such as a cover glass in the present study. The Δσ and step free energy of the first layer, γ 1 , are obtained experimentally based on the equation deduced from classical nucleation theory (CNT). It is concluded that the ΔG of q-2D nuclei is smaller than of monolayer nuclei, provided that the same number of particles are used, which explains the experimental result that the critical size in q-2D nuclei is smaller than that in monolayer nuclei.

Ab Initio Cluster Calculations for the Adsorption of Small Molecules on Oxide Surfaces - from Single Molecules to Monolayers

NASA Astrophysics Data System (ADS)

Pykavy, M.; Staemmler, V.; Rittner, F.

2000-04-01

Quantum chemical ab initio cluster calculations were performed for the adsorption of small molecules on metal oxide surfaces. Two systems were studied in detail: The adsorption of N2 on the (110) surface plane of TiO2 (rutile) and the adsorption of CO on the polar (0001) surface of Cr2O3. In both cases a full five-dimensional potential for the interaction of a single molecule with the respective surface was calculated. For N2/TiO2 (110) the minimum was found for the end-on adsorption of N2 atop a coordinately unsaturated surface Ti atom, with an adsorption energy of (35 ± 5) kJ/mol. In the case of CO/Cr2O3 (0001) the CO molecule is adsorbed strongly tilted (almost side-on) along a line connecting two Cr3+ ions at the surface; the calculated adsorption energy is 22 kJ/mol. In conjunction with empirical pair potentials for the N2/N2 and CO/CO interaction in the gas phase, Monte Carlo simulations were carried out to determine adsorption isotherms and the geometric structure of adsorbed monolayers.

Ultrafast photocurrents in monolayer MoS2

NASA Astrophysics Data System (ADS)

Parzinger, Eric; Wurstbauer, Ursula; Holleitner, Alexander W.

Two-dimensional transition metal dichalcogenides such as MoS2 have emerged as interesting materials for optoelectronic devices. In particular, the ultrafast dynamics and lifetimes of photoexcited charge carriers have attracted great interest during the last years. We investigate the photocurrent response of monolayer MoS2 on a picosecond time scale utilizing a recently developed pump-probe spectroscopy technique based on coplanar striplines. We discuss the ultrafast dynamics within MoS2 including photo-thermoelectric currents and the impact of built-in fields due to Schottky barriers as well as the Fermi level pinning at the contact region. We acknowledge support by the ERC via Project 'NanoREAL', the DFG via excellence cluster 'Nanosystems Initiative Munich' (NIM), and through the TUM International Graduate School of Science and Engineering (IGSSE) and BaCaTeC.

Density control of dodecamanganese clusters anchored on silicon(100).

PubMed

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Nativo, Paola; Fragalà, Ignazio L; Gatteschi, Dante

2006-04-24

A synthetic strategy to control the density of Mn12 clusters anchored on silicon(100) was investigated. Diluted monolayers suitable for Mn12 anchoring were prepared by Si-grafting mixtures of the methyl 10-undecylenoate precursor ligand with 1-decene spectator spacers. Different ratios of these mixtures were tested. The grafted surfaces were hydrolyzed to reveal the carboxylic groups available for the subsequent exchange with the [Mn12O12(OAc)16(H2O)4]4 H2O2 AcOH cluster. Modified surfaces were analyzed by attenuated total reflection (ATR)-FTIR spectroscopy, X-ray photoemission spectroscopy (XPS), and AFM imaging. Results of XPS and ATR-FTIR spectroscopy show that the surface mole ratio between grafted ester and decene is higher than in the source solution. The surface density of the Mn12 cluster is, in turn, strictly proportional to the ester mole fraction. Well-resolved and isolated clusters were observed by AFM, using a diluted ester/decene 1:1 solution.

Sun Protection Belief Clusters: Analysis of Amazon Mechanical Turk Data.

PubMed

Santiago-Rivas, Marimer; Schnur, Julie B; Jandorf, Lina

2016-12-01

This study aimed (i) to determine whether people could be differentiated on the basis of their sun protection belief profiles and individual characteristics and (ii) explore the use of a crowdsourcing web service for the assessment of sun protection beliefs. A sample of 500 adults completed an online survey of sun protection belief items using Amazon Mechanical Turk. A two-phased cluster analysis (i.e., hierarchical and non-hierarchical K-means) was utilized to determine clusters of sun protection barriers and facilitators. Results yielded three distinct clusters of sun protection barriers and three distinct clusters of sun protection facilitators. Significant associations between gender, age, sun sensitivity, and cluster membership were identified. Results also showed an association between barrier and facilitator cluster membership. The results of this study provided a potential alternative approach to developing future sun protection promotion initiatives in the population. Findings add to our knowledge regarding individuals who support, oppose, or are ambivalent toward sun protection and inform intervention research by identifying distinct subtypes that may best benefit from (or have a higher need for) skin cancer prevention efforts.

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

PubMed

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study for fabrication, evaluation, and testing of monolayer woven type materials for space suit insulation

NASA Technical Reports Server (NTRS)

Merrick, E. B.

1979-01-01

An alternative space suit insulation concept using a monolayer woven pile material is discussed. The material reduces cost and improves the durability of the overgarment, while providing protection similar to that provided by multilayer insulation (MLI). Twelve samples of different configurations were fabricated and tested for compressibility and thermal conductivity as a function of compression loading. Two samples which showed good results in the initial tests were further tested for thermal conductivity with respect to ambient pressure and temperature. Results of these tests were similar to results of the MLI tests, indicating the potential of the monolayer fabric to replace the present MLI. A seaming study illustrated that the fabric can be sewn in a structurally sound seam with minimal heat loss. It is recommended that a prototype thermal meteroid garment be fabricated.

Unusual behavior in magnesium-copper cluster matter produced by helium droplet mediated deposition.

PubMed

Emery, S B; Xin, Y; Ridge, C J; Buszek, R J; Boatz, J A; Boyle, J M; Little, B K; Lindsay, C M

2015-02-28

We demonstrate the ability to produce core-shell nanoclusters of materials that typically undergo intermetallic reactions using helium droplet mediated deposition. Composite structures of magnesium and copper were produced by sequential condensation of metal vapors inside the 0.4 K helium droplet baths and then gently deposited onto a substrate for analysis. Upon deposition, the individual clusters, with diameters ∼5 nm, form a cluster material which was subsequently characterized using scanning and transmission electron microscopies. Results of this analysis reveal the following about the deposited cluster material: it is in the un-alloyed chemical state, it maintains a stable core-shell 5 nm structure at sub-monolayer quantities, and it aggregates into unreacted structures of ∼75 nm during further deposition. Surprisingly, high angle annular dark field scanning transmission electron microscopy images revealed that the copper appears to displace the magnesium at the core of the composite cluster despite magnesium being the initially condensed species within the droplet. This phenomenon was studied further using preliminary density functional theory which revealed that copper atoms, when added sequentially to magnesium clusters, penetrate into the magnesium cores.

Modeling the self-assembly of functionalized fullerenes on solid surfaces using Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bubnis, Gregory J.

Since their discovery 25 years ago, carbon fullerenes have been widely studied for their unique physicochemical properties and for applications including organic electronics and photovoltaics. For these applications it is highly desirable for crystalline fullerene thin films to spontaneously self-assemble on surfaces. Accordingly, many studies have functionalized fullerenes with the aim of tailoring their intermolecular interactions and controlling interactions with the solid substrate. The success of these rational design approaches hinges on the subtle interplay of intermolecular forces and molecule-substrate interactions. Molecular modeling is well-suited to studying these interactions by directly simulating self-assembly. In this work, we consider three different fullerene functionalization approaches and for each approach we carry out Monte Carlo simulations of the self-assembly process. In all cases, we use a "coarse-grained" molecular representation that preserves the dominant physical interactions between molecules and maximizes computational efficiency. The first approach we consider is the traditional gold-thiolate SAM (self-assembled monolayer) strategy which tethers molecules to a gold substrate via covalent sulfur-gold bonds. For this we study an asymmetric fullerene thiolate bridged by a phenyl group. Clusters of 40 molecules are simulated on the Au(111) substrate at different temperatures and surface coverage densities. Fullerenes and S atoms are found to compete for Au(111) surface sites, and this competition prevents self-assembly of highly ordered monolayers. Next, we investigate self-assembled monolayers formed by fullerenes with hydrogen-bonding carboxylic acid substituents. We consider five molecules with different dimensions and symmetries. Monte Carlo cooling simulations are used to find the most stable solid structures of clusters adsorbed to Au(111). The results show cases where fullerene-Au(111) attraction, fullerene close-packing, and hydrogen-bonding interactions can cooperate to guide self-assembly or compete to hinder it. Finally, we consider three bis-fullerene molecules, each with a different "bridging group" covalently joining two fullerenes. To effectively study the competing "standing-up" and "lying-down" morphologies, we use Monte Carlo simulations in conjunction with replica exchange and force field biasing methods. For clusters adsorbed to smooth model surfaces, we determine free energy landscapes and demonstrate their utility for rationalizing and predicting self-assembly.

Protective effect of Growth Hormone-Releasing Hormone agonist in bacterial toxin-induced pulmonary barrier dysfunction.

PubMed

Czikora, Istvan; Sridhar, Supriya; Gorshkov, Boris; Alieva, Irina B; Kasa, Anita; Gonzales, Joyce; Potapenko, Olena; Umapathy, Nagavedi S; Pillich, Helena; Rick, Ferenc G; Block, Norman L; Verin, Alexander D; Chakraborty, Trinad; Matthay, Michael A; Schally, Andrew V; Lucas, Rudolf

2014-01-01

Antibiotic treatment of patients infected with G(-) or G(+) bacteria promotes release of the toxins lipopolysaccharide (LPS) and pneumolysin (PLY) in their lungs. Growth Hormone-releasing Hormone (GHRH) agonist JI-34 protects human lung microvascular endothelial cells (HL-MVEC), expressing splice variant 1 (SV-1) of the receptor, from PLY-induced barrier dysfunction. We investigated whether JI-34 also blunts LPS-induced hyperpermeability. Since GHRH receptor (GHRH-R) signaling can potentially stimulate both cAMP-dependent barrier-protective pathways as well as barrier-disruptive protein kinase C pathways, we studied their interaction in GHRH agonist-treated HL-MVEC, in the presence of PLY, by means of siRNA-mediated protein kinase A (PKA) depletion. Barrier function measurements were done in HL-MVEC monolayers using Electrical Cell substrate Impedance Sensing (ECIS) and VE-cadherin expression by Western blotting. Capillary leak was assessed by Evans Blue dye (EBD) incorporation. Cytokine generation in broncho-alveolar lavage fluid (BALF) was measured by multiplex analysis. PKA and PKC-α activity were assessed by Western blotting. GHRH agonist JI-34 significantly blunts LPS-induced barrier dysfunction, at least in part by preserving VE-cadherin expression, while not affecting inflammation. In addition to activating PKA, GHRH agonist also increases PKC-α activity in PLY-treated HL-MVEC. Treatment with PLY significantly decreases resistance in control siRNA-treated HL-MVEC, but does so even more in PKA-depleted monolayers. Pretreatment with GHRH agonist blunts PLY-induced permeability in control siRNA-treated HL-MVEC, but fails to improve barrier function in PKA-depleted PLY-treated monolayers. GHRH signaling in HL-MVEC protects from both LPS and PLY-mediated endothelial barrier dysfunction and concurrently induces a barrier-protective PKA-mediated and a barrier-disruptive PKC-α-induced pathway in the presence of PLY, the former of which dominates the latter.

Pseudoislet formation enhances gene expression, insulin secretion and cytoprotective mechanisms of clonal human insulin-secreting 1.1B4 cells.

PubMed

Green, Alastair D; Vasu, Srividya; McClenaghan, Neville H; Flatt, Peter R

2015-10-01

We have studied the effects of cell communication on human beta cell function and resistance to cytotoxicity using the novel human insulin-secreting cell line 1.1B4 configured as monolayers and pseudoislets. Incubation with the incretin gut hormones GLP-1 and GIP caused dose-dependent stimulation of insulin secretion from 1.1B4 cell monolayers and pseudoislets. The secretory responses were 1.5-2.7-fold greater than monolayers. Cell viability (MTT), DNA damage (comet assay) and apoptosis (acridine orange/ethidium bromide staining) were investigated following 2-h exposure of 1.1B4 monolayers and pseudoislets to ninhydrin, H2O2, streptozotocin, glucose, palmitate or cocktails of proinflammatory cytokines. All agents tested decreased viability and increased DNA damage and apoptosis in both 1.1B4 monolayers and pseudoislets. However, pseudoislets exhibited significantly greater resistance to cytotoxicity (1.5-2.7-fold increases in LD50) and lower levels of DNA damage (1.3-3.4-fold differences in percentage tail DNA and olive tail moment) and apoptosis (1.3-1.5-fold difference) compared to monolayers. Measurement of gene expression by reverse-transcription, real-time PCR showed that genes involved with insulin secretion (INS, PDX1, PCSK1, PCSK2, GLP1R and GIPR), cell-cell communication (GJD2, GJA1 and CDH1) and antioxidant defence (SOD1, SOD2, GPX1 and CAT) were significantly upregulated in pseudoislets compared to monolayers, whilst the expression of proapoptotic genes (NOS2, MAPK8, MAPK10 and NFKB1) showed no significant differences. In summary, these data indicate cell-communication associated with three-dimensional islet architecture is important both for effective insulin secretion and for protection of human beta cells against cytotoxicity.

Establishing linear solvation energy relationships between VOCs and monolayer-protected gold nanoclusters using quartz crystal microbalance.

PubMed

Li, Chi-Lin; Lu, Chia-Jung

2009-08-15

Linear solvation energy relationships (LSERs) have been recognized as a useful model for investigating the chemical forces behind the partition coefficients between vapor molecules and absorbents. This study is the first to determine the solvation properties of monolayer-protected gold nanoclusters (MPCs) with different surface ligands. The ratio of partition coefficients/MPC density (K/rho) of 18 volatile organic compounds (VOCs) for four different MPCs obtained through quartz crystal microbalance (QCM) experiments were used for the LSER model calculations. LSER modeling results indicate that all MPC surfaces showed a statistically significant (p<0.05) preference to hydrogen-bond acidic molecules. Through dipole-dipole attraction, 4-methoxythiophenol-capped MPCs can also interact with polar organics (s=1.04). Showing a unique preference for the hydrogen bond basicity of vapors (b=1.11), 2-benzothiazolethiol-capped MPCs provide evidence of an intra-molecular, proton-shift mechanism on surface of nano-gold.

Electrical-field-induced magnetic Skyrmion ground state in a two-dimensional chromium tri-iodide ferromagnetic monolayer

NASA Astrophysics Data System (ADS)

Liu, Jie; Shi, Mengchao; Mo, Pinghui; Lu, Jiwu

2018-05-01

Using fully first-principles non-collinear self-consistent field density functional theory (DFT) calculations with relativistic spin-orbital coupling effects, we show that, by applying an out-of-plane electrical field on a free-standing two-dimensional chromium tri-iodide (CrI3) ferromagnetic monolayer, the Néel-type magnetic Skyrmion spin configurations become more energetically-favorable than the ferromagnetic spin configurations. It is revealed that the topologically-protected Skyrmion ground state is caused by the breaking of inversion symmetry, which induces the non-trivial Dzyaloshinskii-Moriya interaction (DMI) and the energetically-favorable spin-canting configuration. Combining the ferromagnetic and the magnetic Skyrmion ground states, it is shown that 4-level data can be stored in a single monolayer-based spintronic device, which is of practical interests to realize the next-generation energy-efficient quaternary logic devices and multilevel memory devices.

Stable surface passivation process for compound semiconductors

DOEpatents

Ashby, Carol I. H.

2001-01-01

A passivation process for a previously sulfided, selenided or tellurated III-V compound semiconductor surface. The concentration of undesired mid-gap surface states on a compound semiconductor surface is reduced by the formation of a near-monolayer of metal-(sulfur and/or selenium and/or tellurium)-semiconductor that is effective for long term passivation of the underlying semiconductor surface. Starting with the III-V compound semiconductor surface, any oxidation present thereon is substantially removed and the surface is then treated with sulfur, selenium or tellurium to form a near-monolayer of chalcogen-semiconductor of the surface in an oxygen-free atmosphere. This chalcogenated surface is then contacted with a solution of a metal that will form a low solubility chalcogenide to form a near-monolayer of metal-chalcogen-semiconductor. The resulting passivating layer provides long term protection for the underlying surface at or above the level achieved by a freshly chalcogenated compound semiconductor surface in an oxygen free atmosphere.

Inhibition of c-Src protects paraquat induced microvascular endothelial injury by modulating caveolin-1 phosphorylation and caveolae mediated transcellular permeability.

PubMed

Huang, Yu; He, Qing

2017-06-01

The mechanisms underlying paraquat induced acute lung injury (ALI) is still not clear. C-Src plays an important role in the regulation of microvascular endothelial barrier function and the pathogenesis of ALI. In the present study, we found that paraquat induced cell toxicity and an increase of reactive oxygen species (ROS) in endothelium. Paraquat exposure also induced significant increase of caveolin-1 phosphorylation, caveolae trafficking and albumin permeability in endothelial monolayers. C-Src depletion by siRNA significantly attenuate paraquat induced cell toxicity, caveolin-1 phosphorylation, caveolae formation and endothelial hyperpermeability. N-acetylcysteine (NAC) failed to protect endothelial monolayers against paraquat induced toxicity. Thus, our findings suggest that paraquat exposure increases paracellular endothelial permeability by increasing caveolin-1 phosphorylation in a c-Src dependant manner. The depletion of c-Src might protect microvascular endothelial function by regulating caveolin-1 phosphorylation and caveolae trafficking during paraquat exposure, and might have potential therapeutic effects on paraquat induced ALI. Copyright © 2017 Elsevier B.V. All rights reserved.

Single molecule magnets with protective ligand shells on gold and titanium dioxide surfaces: In situ electrospray deposition and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Handrup, Karsten; Richards, Victoria J.; Weston, Matthew; Champness, Neil R.; O'Shea, James N.

2013-10-01

Two single molecule magnets based on the dodecamanganese (III, IV) cluster with either benzoate or terphenyl-4-carboxylate ligands, have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the benzoate-functionalised complex reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4-carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn3+ and Mn4+ oxidation states necessary for magnetic behaviour are preserved.

Carbohydrate Cluster Microarrays Fabricated on 3-Dimensional Dendrimeric Platforms for Functional Glycomics Exploration

PubMed Central

Zhou, Xichun; Turchi, Craig; Wang, Denong

2009-01-01

We reported here a novel, ready-to-use bioarray platform and methodology for construction of sensitive carbohydrate cluster microarrays. This technology utilizes a 3-dimensional (3-D) poly(amidoamine) starburst dendrimer monolayer assembled on glass surface, which is functionalized with terminal aminooxy and hydrazide groups for site-specific coupling of carbohydrates. A wide range of saccharides, including monosaccharides, oligosaccharides and polysaccharides of diverse structures, are applicable for the 3-D bioarray platform without prior chemical derivatization. The process of carbohydrate coupling is effectively accelerated by microwave radiation energy. The carbohydrate concentration required for microarray fabrication is substantially reduced using this technology. Importantly, this bioarray platform presents sugar chains in defined orientation and cluster configurations. It is, thus, uniquely useful for exploration of the structural and conformational diversities of glyco-epitope and their functional properties. PMID:19791771

Controlled deposition of size-selected MnO nanoparticle thin films for water splitting applications: reduction of onset potential with particle size

NASA Astrophysics Data System (ADS)

Khojasteh, Malak; Haghighat, Shima; Dawlaty, Jahan M.; Kresin, Vitaly V.

2018-05-01

Emulating water oxidation catalyzed by the oxomanganese clusters in the photosynthetic apparatus of plants has been a long-standing scientific challenge. The use of manganese oxide films has been explored, but while they may be catalytically active on the surface, their poor conductivity hinders their overall performance. We have approached this problem by using manganese oxide nanoparticles with sizes of 4, 6 and 8 nm, produced in a sputter-gas-aggregation source and soft-landed onto conducting electrodes. The mass loading of these catalytic particles was kept constant and corresponded to 45%–80% of a monolayer coverage. Measurements of the water oxidation threshold revealed that the onset potential decreases significantly with decreasing particle size. The final stoichiometry of the catalytically active nanoparticles, after exposure to air, was identified as predominantly MnO. The ability of such a sub-monolayer film to lower the reaction threshold implies that the key role is played by intrinsic size effects, i.e., by changes in the electronic properties and surface fields of the nanoparticles with decreasing size. We anticipate that this work will serve to bridge the knowledge gap between bulk thick film electrocatalysts and natural photosynthetic molecular-cluster complexes.

In Situ Observations of UV-Induced Restructuring of Self-Assembled Porphyrin Monolayer on Liquid/Au(111) Interface at Molecular Level.

PubMed

Kim, Yongman; Doh, Won Hui; Kim, Jeongjin; Park, Jeong Young

2018-05-29

Porphyrin-derived molecules have received much attention for use in solar energy conversion devices, such as artificial leaves and dye-sensitized solar cells. Because of their technological importance, a molecular-level understanding of the mechanism for supramolecular structure formation in a liquid, as well as their stability under ultraviolet (UV) irradiation, is important. Here, we observed the self-assembled structure of free-base, copper(II), and nickel(II) octaethylporphyrin formed on Au(111) in a dodecane solution using scanning tunneling microscopy (STM). As evident in the STM images, the self-assembled monolayers (SAMs) of these three porphyrins on the Au(111) surface showed hexagonal close-packed structures when in dodecane solution. Under UV irradiation (λ = 365 nm), the porphyrin molecules in the SAM or the dodecane solution move extensively and form new porphyrin clusters on the Au sites that have a high degree of freedom. Consequently, the Au(111) surface was covered with disordered porphyrin clusters. However, we found that the porphyrin molecules decomposed under UV irradiation at 254 nm. Molecular-scale observation of the morphological evolution of the porphyrin SAM under UV irradiation can provide a fundamental understanding of the degradation processes of porphyrin-based energy conversion devices.

Two- and three-dimensional growth of Bi on i -Al-Pd-Mn studied using medium-energy ion scattering

NASA Astrophysics Data System (ADS)

Noakes, T. C. Q.; Bailey, P.; McConville, C. F.; Draxler, M.; Walker, M.; Brown, M. G.; Hentz, A.; Woodruff, D. P.; Lograsso, T. A.; Ross, A. R.; Smerdon, J. A.; Leung, L.; McGrath, R.

2010-11-01

Recent work on the growth of thin metal films on quasicrystalline substrates has indicated the formation of so-called “magic height” islands with multiples of 4 atomic layers (AL) arising as a result of quantum size effects, which lead to enhanced stability. Here the results of a study are reported of Bi deposition on i -Al-Pd-Mn using medium-energy ion scattering to characterize the island thickness and the structural arrangement of Bi atoms within the islands. In addition, data were taken from annealed surfaces after Bi cluster desorption to leave a single aperiodic monolayer of Bi at the surface. Scattered-ion energy spectra from the Bi islands are consistent with a single Bi monolayer covered with mainly 4 AL islands for both 1.8 and 3.2 monolayer equivalent coverages but with some occupation of 2 and 8 Al islands as well. The angular dependence of the scattered-ion intensity (“blocking curve”) from Bi has been compared with simulations for various models of both rhombohedral Bi and a distorted “black-phosphorus”-like structure. The data demonstrate bilayer formation within the Bi islands. In the case of the aperiodic Bi monolayer, the blocking curves from substrate scattering are found to be inconsistent with two high-symmetry sites on the quasicrystalline surface that theory indicates are energetically favorable but do not exclude the formation of pentagonal arrangements of Bi atoms as seen in other recent experimental work.

Ethylene glycol monolayer protected nanoparticles: synthesis, characterization, and interactions with biological molecules.

PubMed

Zheng, Ming; Li, Zhigang; Huang, Xueying

2004-05-11

The usefulness of the hybrid materials of nanoparticles and biological molecules on many occasions depends on how well one can achieve a rational design based on specific binding and programmable assembly. Nonspecific binding between nanoparticles and biomolecules is one of the major barriers for achieving their utilities in a biological system. In this paper, we demonstrate a new approach to eliminate nonspecific interactions between nanoparticles and biological molecules by shielding the nanoparticle with a monolayer of ethylene glycol. A direct synthesis of di-, tri-, and tetra(ethylene glycol)-protected gold nanoparticles (Au-S-EGn, n = 2, 3, and 4) was achieved under the condition that the water content was optimized in the range of 9-18% in the reaction mixture. With controlled ratio of [HAuCl4]/[EGn-SH] at 2, the synthesized particles have an average diameter of 3.5 nm and a surface plasma resonance band around 510 nm. Their surface structures were confirmed by 1H NMR spectra. These gold nanoparticles are bonded with a uniform monolayer with defined lengths of 0.8, 1.2, and 1.6 nm for Au-S-EG2, Au-S-EG3, and Au-S-EG4, respectively. They have great stabilities in aqueous solutions with a high concentration of electrolytes as well as in organic solvents. Thermogravimetric analysis revealed that the ethylene glycol monolayer coating is ca. 14% of the total nanoparticle weight. Biological binding tests by using ion-exchange chromatography and gel electrophoresis demonstrated that these Au-S-EGn (n = 2, 3, or 4) nanoparticles are free of any nonspecific bindings with various proteins, DNA, and RNA. These types of nanoparticles provide a fundamental starting material for designing hybrid materials composed of metallic nanoparticles and biomolecules.

Self-assembly of organic monolayers as protective and conductive bridges for nanometric surface-mount applications.

PubMed

Platzman, Ilia; Haick, Hossam; Tannenbaum, Rina

2010-09-01

In this work, we present a novel surface-mount placement process that could potentially overcome the inadequacies of the currently used stencil-printing technology, when applied to devices in which either their lateral and/or their horizontal dimensions approach the nanometric scale. Our novel process is based on the "bottom-up" design of an adhesive layer, operative in the molecular/nanoscale level, through the use of self-assembled monolayers (SAMs) that could form protective and conductive bridges between pads and components. On the basis of previous results, 1,4-phenylene diisocyanide (PDI) and terephthalic acid (TPA) were chosen to serve as the best candidates for the achievement of this goal. The quality and stability of these SAMs on annealed Cu surfaces (Rrms=0.15-1.1 nm) were examined in detail. Measurements showed that the SAMs of TPA and PDI molecules formed on top of Cu substrates created thermally stable organic monolayers with high surface coverage (∼90%), in which the molecules were closely packed and well-ordered. Moreover, the molecules assumed a standing-up phase conformation, in which the molecules bonded to the Cu substrate through one terminal functional group, with the other terminal group residing away from the substrate. To examine the ability of these monolayers to serve as "molecular wires," i.e., the capability to provide electrical conductivity, we developed a novel fabrication method of a parallel plate junction (PPJ) in order to create symmetric Cu-SAM-Cu electrical junctions. The current-bias measurements of these junctions indicated high tunneling efficiency. These achievements imply that the SAMs used in this study can serve as conductive molecular bridges that can potentially bind circuital pads/components.

Unconventional Current Scaling and Edge Effects for Charge Transport through Molecular Clusters

PubMed Central

2017-01-01

Metal–molecule–metal junctions are the key components of molecular electronics circuits. Gaining a microscopic understanding of their conducting properties is central to advancing the field. In the present contribution, we highlight the fundamental differences between single-molecule and ensemble junctions focusing on the fundamentals of transport through molecular clusters. In this way, we elucidate the collective behavior of parallel molecular wires, bridging the gap between single molecule and large-area monolayer electronics, where even in the latter case transport is usually dominated by finite-size islands. On the basis of first-principles charge-transport simulations, we explain why the scaling of the conductivity of a junction has to be distinctly nonlinear in the number of molecules it contains. Moreover, transport through molecular clusters is found to be highly inhomogeneous with pronounced edge effects determined by molecules in locally different electrostatic environments. These effects are most pronounced for comparably small clusters, but electrostatic considerations show that they prevail also for more extended systems. PMID:29043825

Effects of lateral diffusion on morphology and dynamics of a microscopic lattice-gas model of pulsed electrodeposition.

PubMed

Frank, Stefan; Roberts, Daniel E; Rikvold, Per Arne

2005-02-08

The influence of nearest-neighbor diffusion on the decay of a metastable low-coverage phase (monolayer adsorption) in a square lattice-gas model of electrochemical metal deposition is investigated by kinetic Monte Carlo simulations. The phase-transformation dynamics are compared to the well-established Kolmogorov-Johnson-Mehl-Avrami theory. The phase transformation is accelerated by diffusion, but remains in accord with the theory for continuous nucleation up to moderate diffusion rates. At very high diffusion rates the phase-transformation kinetic shows a crossover to instantaneous nucleation. Then, the probability of medium-sized clusters is reduced in favor of large clusters. Upon reversal of the supersaturation, the adsorbate desorbs, but large clusters still tend to grow during the initial stages of desorption. Calculation of the free energy of subcritical clusters by enumeration of lattice animals yields a quasiequilibrium distribution which is in reasonable agreement with the simulation results. This is an improvement relative to classical droplet theory, which fails to describe the distributions, since the macroscopic surface tension is a bad approximation for small clusters.

Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters.

PubMed

Valkenier, Hennie; Huisman, Everardus H; van Hal, Paul A; de Leeuw, Dago M; Chiechi, Ryan C; Hummelen, Jan C

2011-04-06

This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of β=0.15 Å(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained. © 2011 American Chemical Society

Gold nanoparticles with patterned surface monolayers for nanomedicine: current perspectives.

PubMed

Pengo, Paolo; Şologan, Maria; Pasquato, Lucia; Guida, Filomena; Pacor, Sabrina; Tossi, Alessandro; Stellacci, Francesco; Marson, Domenico; Boccardo, Silvia; Pricl, Sabrina; Posocco, Paola

2017-12-01

Molecular self-assembly is a topic attracting intense scientific interest. Various strategies have been developed for construction of molecular aggregates with rationally designed properties, geometries, and dimensions that promise to provide solutions to both theoretical and practical problems in areas such as drug delivery, medical diagnostics, and biosensors, to name but a few. In this respect, gold nanoparticles covered with self-assembled monolayers presenting nanoscale surface patterns-typically patched, striped or Janus-like domains-represent an emerging field. These systems are particularly intriguing for use in bio-nanotechnology applications, as presence of such monolayers with three-dimensional (3D) morphology provides nanoparticles with surface-dependent properties that, in turn, affect their biological behavior. Comprehensive understanding of the physicochemical interactions occurring at the interface between these versatile nanomaterials and biological systems is therefore crucial to fully exploit their potential. This review aims to explore the current state of development of such patterned, self-assembled monolayer-protected gold nanoparticles, through step-by-step analysis of their conceptual design, synthetic procedures, predicted and determined surface characteristics, interactions with and performance in biological environments, and experimental and computational methods currently employed for their investigation.

Confirmation of heavy metal ions in used lubricating oil from a passenger car using chelating self-assembled monolayer.

PubMed

Ko, Young Gun; Kim, Choong Hyun

2006-09-01

In order to prevent engine failure, the oil must be changed before it loses its protective properties. It is necessary to monitor the actual physical and chemical condition of the oil to reliably determine the optimum oil-change interval. Our study focuses on the condition of the lubricating oil in an operated car engine. Shear stress curves and viscosity curves as a function of the shear rate for fresh and used lubricating oil were examined. Metal nitrate was detected in the lubricating oil from the operated car engine through the use of a chelating self-assembled monolayer.

Unusual behavior in magnesium-copper cluster matter produced by helium droplet mediated deposition

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

Emery, S. B., E-mail: samuel.emery@navy.mil; Little, B. K.; Air Force Research Laboratory, Munitions Directorate, 2306 Perimeter Rd., Eglin AFB, Florida 32542

2015-02-28

We demonstrate the ability to produce core-shell nanoclusters of materials that typically undergo intermetallic reactions using helium droplet mediated deposition. Composite structures of magnesium and copper were produced by sequential condensation of metal vapors inside the 0.4 K helium droplet baths and then gently deposited onto a substrate for analysis. Upon deposition, the individual clusters, with diameters ∼5 nm, form a cluster material which was subsequently characterized using scanning and transmission electron microscopies. Results of this analysis reveal the following about the deposited cluster material: it is in the un-alloyed chemical state, it maintains a stable core-shell 5 nm structuremore » at sub-monolayer quantities, and it aggregates into unreacted structures of ∼75 nm during further deposition. Surprisingly, high angle annular dark field scanning transmission electron microscopy images revealed that the copper appears to displace the magnesium at the core of the composite cluster despite magnesium being the initially condensed species within the droplet. This phenomenon was studied further using preliminary density functional theory which revealed that copper atoms, when added sequentially to magnesium clusters, penetrate into the magnesium cores.« less

Solvent effects on the adsorption and self-organization of Mn12 on Au(111).

PubMed

Pineider, Francesco; Mannini, Matteo; Sessoli, Roberta; Caneschi, Andrea; Barreca, Davide; Armelao, Lidia; Cornia, Andrea; Tondello, Eugenio; Gatteschi, Dante

2007-11-06

A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces.

Two-dimensional freezing criteria for crystallizing colloidal monolayers

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

Wang Ziren; Han Yilong; Alsayed, Ahmed M.

Video microscopy was employed to explore crystallization of colloidal monolayers composed of diameter-tunable microgel spheres. Two-dimensional (2D) colloidal liquids were frozen homogenously into polycrystalline solids, and four 2D criteria for freezing were experimentally tested in thermal systems for the first time: the Hansen-Verlet freezing rule, the Loewen-Palberg-Simon dynamical freezing criterion, and two other rules based, respectively, on the split shoulder of the radial distribution function and on the distribution of the shape factor of Voronoi polygons. Importantly, these freezing criteria, usually applied in the context of single crystals, were demonstrated to apply to the formation of polycrystalline solids. At themore » freezing point, we also observed a peak in the fluctuations of the orientational order parameter and a percolation transition associated with caged particles. Speculation about these percolated clusters of caged particles casts light on solidification mechanisms and dynamic heterogeneity in freezing.« less

A neural-network potential through charge equilibration for WS2: From clusters to sheets

NASA Astrophysics Data System (ADS)

Hafizi, Roohollah; Ghasemi, S. Alireza; Hashemifar, S. Javad; Akbarzadeh, Hadi

2017-12-01

In the present work, we use a machine learning method to construct a high-dimensional potential for tungsten disulfide using a charge equilibration neural-network technique. A training set of stoichiometric WS2 clusters is prepared in the framework of density functional theory. After training the neural-network potential, the reliability and transferability of the potential are verified by performing a crystal structure search on bulk phases of WS2 and by plotting energy-area curves of two different monolayers. Then, we use the potential to investigate various triangular nano-clusters and nanotubes of WS2. In the case of nano-structures, we argue that 2H atomic configurations with sulfur rich edges are thermodynamically more stable than the other investigated configurations. We also studied a number of WS2 nanotubes which revealed that 1T tubes with armchair chirality exhibit lower bending stiffness.

Characterization of Surface-Active Biofilm Protein BslA in Self-Assembling Langmuir Monolayer at the Air-Water Interface.

PubMed

Liu, Wei; Li, Shanghao; Wang, Zhuguang; Yan, Elsa C Y; Leblanc, Roger M

2017-08-01

Biofilm is an extracellular matrix of bacteria and serves as a protective shield of bacterial communities. It is crucial for microbial growth and one of the leading causes of human chronic infections as well. However, the structures and molecular mechanism of biofilm formation remain largely unknown. Here, we examined a protein, BslA, expressed in the biofilms of Bacillus subtilis. We characterized the Langmuir monolayers of BslA at the air/water interface. Using techniques in surface chemistry and spectroscopy, we found that BslA forms a stable and robust Langmuir monolayer at the air/water interface. Our results show that the BslA Langmuir monolayer underwent two-stage elasticity in the solid state phase upon mechanical compression: one is possibly due to the intermolecular interaction and the other is likely due to both the intermolecular compulsion and the intramolecular distortion. The Langmuir monolayer of BslA shows abrupt changes in rigidities and elasticities at ∼25 mN/m. This surface pressure is close to the one at which BlsA saturates the air/water interface as a self-assembled film without mechanical compression, corresponding to a mean molecular area of ∼700 Å 2 per molecule. Based on the results of surface UV-visible spectroscopy and infrared reflective-absorption spectroscopy, we propose that the BslA Langmuir monolayer carries intermolecular elasticity before ∼25 mN/m and both intermolecular and intramolecular elasticity after ∼25 mN/m. These results provide valuable insights into the understanding of biofilm-associated protein under high mechanical force, shedding light on further investigation of biofilm structure and functionalities.

Inhibiting the corrosion of MNZh 5-1 alloy in neutral solutions of 5-chloro-1,2,3-benzotrialzol

NASA Astrophysics Data System (ADS)

Kuznetsov, Yu. I.; Agafonkina, M. O.; Andreeva, N. P.; Arkhipushkin, I. A.; Kazansky, L. P.

2017-11-01

The adsorption and protective properties of 5-chloro-1,2,3-benzotriazol (5-chloro-BTA) are studied in relation to MNZh 5-1 alloy in a chloride borate buffer solution with pH 7.4. It is shown that this inhibitor can stabilize the passive state of the alloy at a concentration of 0.12 mmol/g. The adsorption of 5-chloro-BTA on a surface of MNZh 5-1 alloy is polymolecular; the free energy of adsorption is about 80 kJ/mol. The advantages of adsorption and protective properties of 5-chloro-BTA compared to BTA on both MNZh 5-1 alloy and the metals contained in the alloy (Ni, Cu) are shown. XPS data indicate a 5-chloro-BTA monolayer formed on the surface of the alloy. This monolayer was composed of inhibitor molecules, which are normally oriented toward a surface and are not removed during ultrasonic washing of the electrode.

Quantum spin Hall state in monolayer 1T '-WTe 2

DOE PAGES

Tang, Shujie; Zhang, Chaofan; Wong, Dillon; ...

2017-06-26

A quantum spin Hall (QSH) insulator is a novel two-dimensional quantum state of matter that features quantized Hall conductance in the absence of a magnetic field, resulting from topologically protected dissipationless edge states that bridge the energy gap opened by band inversion and strong spin–orbit coupling. By investigating the electronic structure of epitaxially grown monolayer 1T '-WTe 2 using angle-resolved photoemission (ARPES) and first-principles calculations, we observe clear signatures of topological band inversion and bandgap opening, which are the hallmarks of a QSH state. Scanning tunnelling microscopy measurements further confirm the correct crystal structure and the existence of a bulkmore » bandgap, and provide evidence for a modified electronic structure near the edge that is consistent with the expectations for a QSH insulator. Our results establish monolayer 1T '-WTe 2 as a new class of QSH insulator with large band gap in a robust two-dimensional materials family of transition metal dichalcogenides (TMDCs).« less

Quantum spin Hall state in monolayer 1T '-WTe 2

DOE PAGES

Tang, Shujie; Zhang, Chaofan; Wong, Dillon; ...

2017-06-26

A quantum spin Hall (QSH) insulator is a novel two-dimensional quantum state of matter that features quantized Hall conductance in the absence of a magnetic field, resulting from topologically protected dissipationless edge states that bridge the energy gap opened by band inversion and strong spin–orbit coupling. By investigating the electronic structure of epitaxially grown monolayer 1T '-WTe 2 using angle-resolved photoemission (ARPES) and first-principles calculations, we observe clear signatures of topological band inversion and bandgap opening, which are the hallmarks of a QSH state. Scanning tunnelling microscopy measurements further confirm the correct crystal structure and the existence of a bulkmore » bandgap, and provide evidence for a modified electronic structure near the edge that is consistent with the expectations for a QSH insulator. Finally, our results establish monolayer 1T '-WTe 2 as a new class of QSH insulator with large band gap in a robust two-dimensional materials family of transition metal dichalcogenides (TMDCs).« less

Proteolytic Enzymes Clustered in Specialized Plasma-Membrane Domains Drive Endothelial Cells’ Migration

PubMed Central

Salamone, Monica; Carfì Pavia, Francesco

2016-01-01

In vitro cultured endothelial cells forming a continuous monolayer establish stable cell-cell contacts and acquire a “resting” phenotype; on the other hand, when growing in sparse conditions these cells acquire a migratory phenotype and invade the empty area of the culture. Culturing cells in different conditions, we compared expression and clustering of proteolytic enzymes in cells having migratory versus stationary behavior. In order to observe resting and migrating cells in the same microscopic field, a continuous cell monolayer was wounded. Increased expression of proteolytic enzymes was evident in cell membranes of migrating cells especially at sprouting sites and in shed membrane vesicles. Gelatin zymography and western blotting analyses confirmed that in migrating cells, expression of membrane-bound and of vesicle-associated proteolytic enzymes are increased. The enzymes concerned include MMP-2, MMP-9, MT1-MMP, seprase, DPP4 (DiPeptidyl Peptidase 4) and uPA. Shed membrane vesicles were shown to exert degradative activity on ECM components and produce substrates facilitating cell migration. Vesicles shed by migrating cells degraded ECM components at an increased rate; as a result their effect on cell migration was amplified. Inhibiting either Matrix Metallo Proteases (MMPs) or Serine Integral Membrane Peptidases (SIMPs) caused a decrease in the stimulatory effect of vesicles, inhibiting the spontaneous migratory activity of cells; a similar result was also obtained when a monoclonal antibody acting on DPP4 was tested. We conclude that proteolytic enzymes have a synergistic stimulatory effect on cell migration and that their clustering probably facilitates the proteolytic activation cascades needed to produce maximal degradative activity on cell substrates during the angiogenic process. PMID:27152413

Growth kinetics of indium metal atoms on Si(1 1 2) surface

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

Raj, Vidur; Chauhan, Amit Kumar Singh; Gupta, Govind, E-mail: govind@nplindia.org

Graphical abstract: Controlled growth of indium atoms on Si(1 1 2) surface has been carried out systematically and the influence of substrate temperature on the kinetics is analysed under various growth conditions. Temperature induced anomalous layer-to-clusters transformation during thermal desorption has also been reported. - Highlights: • Controlled growth of indium atoms on Si(1 1 2) surface & their thermal stability. • Influence of substrate temperature on the kinetics under various growth conditions. • Temperature induced layer-to-clusters transformation during thermal desorption. - Abstract: The growth kinetics and desorption behavior of indium (In) atoms grown on high index Si(1 1 2)more » surface at different substrate temperatures has been studied. Auger electron spectroscopy analysis revealed that In growth at room temperature (RT) and high substrate temperature (HT) ∼250 °C follows Frank–van der Merve growth mode whereas at temperatures ≥450 °C, In growth evolves through Volmer–Weber growth mode. Thermal desorption studies of RT and 250 °C grown In/Si(1 1 2) systems show temperature induced rearrangement of In atoms over Si(1 1 2) surface leading to clusters to layer transformation. The monolayer and bilayer desorption energies for RT grown In/Si(1 1 2) system are calculated to be 2.5 eV and 1.52 eV, while for HT-250 °C the values are found to be 1.6 eV and 1.3 eV, respectively. This study demonstrates the effect of temperature on growth kinetics as well as on the multilayer/monolayer desorption pathway of In on Si(1 1 2) surface.« less

Magnetic anisotropy and chirality of frustrated Cr nanostructures on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Balogh, L.; Udvardi, L.; Szunyogh, L.

2014-10-01

By using a fully relativistic embedded cluster Green's function technique we investigated the magnetic anisotropy properties of four different compact Cr trimers (equilateral triangles) and Cr mono-layers deposited on the Au(1 1 1) surface in both fcc and hcp stackings. For all trimers the magnetic ground state was found to be a frustrated 120° Néel configuration. Applying global spin rotations to the magnetic ground state, predictions of an appropriate second order spin Hamiltonian were reproduced with high accuracy by first principles calculations. For the Cr trimers with adjacent Au atoms in similar geometry, we obtained similar values for the in-plane and out-of-plane anisotropy parameters, however, the Dzyaloshinskii-Moriya (DM) interactions appeared to differ remarkably. For two kinds of trimers we found an unconventional magnetic ground state showing 90° in-the-plane rotation with respect to the high symmetry directions. Due to higher symmetry, the in-plane anisotropy term was missing for the mono-layers and distinctly different DM interactions were obtained for the different stackings. The chiral degeneracy of the Néel configurations was lifted by an energy less than 2 meV for the trimers, while this value increased up to about 15 meV per 3 Cr atoms for the hcp packed mono-layer.

Probing membrane permeabilization by the antimicrobial peptide distinctin in mercury-supported biomimetic membranes.

PubMed

Becucci, Lucia; Papini, Martina; Mullen, Daniel; Scaloni, Andrea; Veglia, Gianluigi; Guidelli, Rolando

2011-11-01

The mechanism of membrane permeabilization by the antimicrobial peptide distinctin was investigated by using two different mercury-supported biomimetic membranes, namely a lipid self-assembled monolayer and a lipid bilayer tethered to the mercury surface through a hydrophilic spacer (tethered bilayer lipid membrane: tBLM). Incorporation of distinctin into a lipid monolayer from its aqueous solution yields rapidly ion channels selective toward inorganic cations, such as Tl(+) and Cd(2+). Conversely, its incorporation in a tBLM allows the formation of ion channels permeable to potassium ions only at non-physiological transmembrane potentials, more negative than -340mV. These channels, once formed, are unstable at less negative transmembrane potentials. The kinetics of their formation is consistent with the disruption of distinctin clusters adsorbed on top of the lipid bilayer, incorporation of the resulting monomers and their aggregation into hydrophilic pores by a mechanism of nucleation and growth. Comparing the behavior of distinctin in tBLMs with that in conventional black lipid membranes strongly suggests that distinctin channel formation in lipid bilayer requires the partitioning of distinctin molecules between the two sides of the lipid bilayer. We can tentatively hypothesize that an ion channel is formed when one distinctin cluster on one side of the lipid bilayer matches another one on the opposite side. Copyright © 2011 Elsevier B.V. All rights reserved.

Synthesis and Catalytic Activity of Pt Monolayer on Pd Tetrahedral Nanocrystals with CO-adsorption-induced Removal of Surfactants

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

Gong K.; Vukmirovic M.B.; Ma C.

2011-11-01

We synthesized the Pt monolayer shell-Pd tetrahedral core electrocatalysts that are notable for their high activity and stable performance. A small number of low-coordination sites and defects, and high content of the (1 1 1)-oriented facets on Pd tetrahedron makes them a suitable support for a Pt monolayer to obtain an active O{sub 2} reduction reaction (ORR) electrocatalyst. The surfactants, used to control size and shape of Pd tetrahedral nanoparticles, are difficult to remove and cause adverse effects on the ORR. We describe a simple and noninvasive method to synthesize high-purity tetrahedral Pd nanocrystals (TH Pd) by combining a hydrothermalmore » route and CO adsorption-induced removal of surfactants. Poly(vinylpyrrolidone) (PVP), used as a protecting and reducing agent in hydrothermal reactions, is strongly bonded to the surface of the resulting nanocrystals. We demonstrate that PVP was displaced efficiently by adsorbed CO. A clean surface was achieved upon CO stripping at a high potential (1.0 V vs RHE). It played a decisive role in improving the activity of the Pt monolayer/TH Pd electrocatalyst for the ORR. Furthermore, the results demonstrate a versatile method for removal of surfactants from various nanoparticles that severely limited their applications.« less

Linking Strengths: Identifying and Exploring Protective Factor Clusters in Academically Resilient Low-Socioeconomic Urban Students of Color

ERIC Educational Resources Information Center

Morales, Erik E.

2010-01-01

Based on data from qualitative interviews with 50 high-achieving low-socioeconomic students of color, two "clusters" of important and symbiotic protective factors are identified and explored. Each cluster consists of a series of interrelated protective factors identified by the participants as crucial to their statistically exceptional academic…

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

NASA Astrophysics Data System (ADS)

Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

2013-05-01

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources. Electronic supplementary information (ESI) available: The full GISAXS image sequence of the experiment, the model-based IsGISAXS-simulation sequence as movie files for comparison and detailed information about sample cleaning, XRR, FESEM, IsGISAXS, comparison μGIWAXS/μGISAXS, and sampling statistics. See DOI: 10.1039/c3nr34216f

In vitro motility evaluation of aggregated cancer cells by means of automatic image processing.

PubMed

De Hauwer, C; Darro, F; Camby, I; Kiss, R; Van Ham, P; Decaesteker, C

1999-05-01

Set up of an automatic image processing based method that enables the motility of in vitro aggregated cells to be evaluated for a number of hours. Our biological model included the PC-3 human prostate cancer cell line growing as a monolayer on the bottom of Falcon plastic dishes containing conventional culture media. Our equipment consisted of an incubator, an inverted phase contrast microscope, a Charge Coupled Device (CCD) video camera, and a computer equipped with an image processing software developed in our laboratory. This computer-assisted microscope analysis of aggregated cells enables global cluster motility to be evaluated. This analysis also enables the trajectory of each cell to be isolated and parametrized within a given cluster or, indeed, the trajectories of individual cells outside a cluster. The results show that motility inside a PC-3 cluster is not restricted to slight motion due to cluster expansion, but rather consists of a marked cell movement within the cluster. The proposed equipment enables in vitro aggregated cell motility to be studied. This method can, therefore, be used in pharmacological studies in order to select anti-motility related compounds. The compounds selected by the equipment described could then be tested in vivo as potential anti-metastatic.

Gd-functionalised Au nanoparticles as targeted contrast agents in MRI: relaxivity enhancement by polyelectrolyte coating.

PubMed

Warsi, Muhammad Farooq; Adams, Ralph W; Duckett, Simon B; Chechik, Victor

2010-01-21

Monolayer-protected, Gd(3+)-functionalised gold nanoparticles with enhanced spin-lattice relaxivity (r(1)) were prepared; adsorption of polyelectrolytes on these materials further increased r(1) and ligand exchange with a biotin-derivatised disulfide led to a prototype avidin-targeted contrast agent.

Biophysical characterization of monofilm model systems composed of selected tear film phospholipids.

PubMed

Patterson, Matthew; Vogel, Hans J; Prenner, Elmar J

2016-02-01

The tear film protects the eye from foreign particles and pathogens, prevents excess evaporation, provides lubrication, and maintains a high quality optical surface necessary for vision. The anterior layer of tear film consists of polar and non-polar lipid layers. The polar lipids form a monolayer on the aqueous subphase, acting as surfactants for the non-polar lipid multilayer. A tear film polar lipid biomimetic consisting of dipalmitoyl phosphatidylcholine (DPPC), dipalmitoyl phosphatidylethanolamine (DPPE), palmitoyl glucosylceramide (PGC), and palmitoyl sphingomyelin (PSM) was characterized using Langmuir monolayers and Brewster angle microscopy (BAM). Lipid combinations formed very stable monolayers, especially those containing DPPC or PSM. Surface experiments and elasticity analyses revealed that PGC resulted in more condensed and rigid mixed monolayers. DPPE provided resistance to large changes in lipid ordering over a wide surface pressure range. Ternary mixtures containing DPPE and PGC with either DPPC or PSM experienced the greatest lipid ordering within the natural tear film surface pressure range suggesting that these lipids are important to maintain tear film integrity during the inter-blink period. Finally, BAM images revealed unique structures within monolayers of DPPC, DPPE, and PGC at the natural tear film surface pressure. 3D analysis of these domains suggested either the formation of multilayers or outward protrusions at surface pressures far below the point of irreversible collapse as seen on the isotherm. This entails that the polar lipids of tear film may be capable of multilayer formation or outward folding as a mechanism to prevent rupture of the tear film during a blink. Copyright © 2015 Elsevier B.V. All rights reserved.

Use of micro-optical coherence tomography to analyze barrier integrity of intestinal epithelial cells (Conference Presentation)

NASA Astrophysics Data System (ADS)

Som, Avira; Leung, Hui Min; Chu, Kengyeh; Eaton, Alex D.; Hurley, Bryan P.; Tearney, Guillermo J.

2017-02-01

The intestinal epithelial barrier provides protection from external threats that enter the digestive system and persist beyond passage through the stomach. The effects of toxic agents on the intestinal epithelial cell monolayer have not been fully characterized at a cellular level as live imaging of this dynamic interplay at sufficient resolution to interpret cellular responses presents technological challenges. Using a high-resolution native contrast modality called Micro-Optical Coherence Tomography (μOCT), we generated real-time 3D images depicting the impact of the chemical agent EDTA on polarized intestinal epithelial monolayers. Within minutes following application of EDTA, we observed a change in the uniformity of epithelial surface thickness and loss of the edge brightness associated with the apical surface. These observations were measured by generating computer algorithms which quantify imaged-based events changing over time, thus providing parallel graphed data to pair with video. The imaging platform was designed to monitor epithelial monolayers prior to and following application of chemical agents in order to provide a comprehensive account of monolayer behavior at baseline conditions and immediately following exposure. Furthermore, the platform was designed to simultaneously measure continuous trans-epithelial electric resistance (TEER) in order to define the progressive loss of barrier integrity of the cell monolayer following exposure to toxic agents and correlate these findings to image-based metrics. This technological image-based experimental platform provides a novel means to characterize mechanisms that impact the intestinal barrier and, in future efforts, can be applied to study the impact of disease relevant agents such as enteric pathogens and enterotoxins.

Neutrophil-mediated protection of cultured human vascular endothelial cells from damage by growing Candida albicans hyphae

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

Edwards, J.E. Jr.; Rotrosen, D.; Fontaine, J.W.

1987-05-01

Interactions were studied between human neutrophils and cultured human umbilical vein endothelial cells invaded by Candida albicans. In the absence of neutrophils, progressive Candida germination and hyphal growth extensively damaged endothelial cell monolayers over a period of 4 to 6 hours, as determined both by morphological changes and release of /sup 51/Cr from radiolabeled endothelial cells. Monolayers were completely destroyed and replaced by hyphae after 18 hours of incubation. In contrast, when added 2 hours after the monolayers had been infected with Candida, neutrophils selectively migrated toward and attached to hyphae at points of hyphal penetration into individual endothelial cellsmore » (observed by time-lapse video-microscopy). Attached neutrophils spread over hyphal surfaces both within and beneath the endothelial cells; neutrophil recruitment to initial sites of leukocyte-Candida-endothelial cell interactions continued throughout the first 60 minutes of observation. Neutrophil spreading and stasis were observed only along Candida hyphae and at sites of Candida-endothelial cell interactions. These events resulted in 58.0% killing of Candida at 2 hours and subsequent clearance of Candida from endothelial cell monolayers, as determined by microcolony counts and morphological observation. On introduction of additional neutrophils to yield higher ratios of neutrophils to endothelial cells (10 neutrophils:1 endothelial cell), neutrophil migration toward hyphal elements continued. Despite retraction or displacement of occasional endothelial cells by invading Candida and neutrophils, most endothelial cells remained intact, viable, and motile as verified both by morphological observations and measurement of /sup 51/Cr release from radiolabeled monolayers.« less

Biofunctionalization on alkylated silicon substrate surfaces via "click" chemistry.

PubMed

Qin, Guoting; Santos, Catherine; Zhang, Wen; Li, Yan; Kumar, Amit; Erasquin, Uriel J; Liu, Kai; Muradov, Pavel; Trautner, Barbara Wells; Cai, Chengzhi

2010-11-24

Biofunctionalization of silicon substrates is important to the development of silicon-based biosensors and devices. Compared to conventional organosiloxane films on silicon oxide intermediate layers, organic monolayers directly bound to the nonoxidized silicon substrates via Si-C bonds enhance the sensitivity of detection and the stability against hydrolytic cleavage. Such monolayers presenting a high density of terminal alkynyl groups for bioconjugation via copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC, a "click" reaction) were reported. However, yields of the CuAAC reactions on these monolayer platforms were low. Also, the nonspecific adsorption of proteins on the resultant surfaces remained a major obstacle for many potential biological applications. Herein, we report a new type of "clickable" monolayers grown by selective, photoactivated surface hydrosilylation of α,ω-alkenynes, where the alkynyl terminal is protected with a trimethylgermanyl (TMG) group, on hydrogen-terminated silicon substrates. The TMG groups on the film are readily removed in aqueous solutions in the presence of Cu(I). Significantly, the degermanylation and the subsequent CuAAC reaction with various azides could be combined into a single step in good yields. Thus, oligo(ethylene glycol) (OEG) with an azido tag was attached to the TMG-alkyne surfaces, leading to OEG-terminated surfaces that reduced the nonspecific adsorption of protein (fibrinogen) by >98%. The CuAAC reaction could be performed in microarray format to generate arrays of mannose and biotin with varied densities on the protein-resistant OEG background. We also demonstrated that the monolayer platform could be functionalized with mannose for highly specific capturing of living targets (Escherichia coli expressing fimbriae) onto the silicon substrates.

Bragg Curve, Biological Bragg Curve and Biological Issues in Space Radiation Protection with Shielding

NASA Technical Reports Server (NTRS)

Honglu, Wu; Cucinotta, F.A.; Durante, M.; Lin, Z.; Rusek, A.

2006-01-01

The space environment consists of a varying field of radiation particles including high-energy ions, with spacecraft shielding material providing the major protection to astronauts from harmful exposure. Unlike low-LET gamma or X-rays, the presence of shielding does not always reduce the radiation risks for energetic charged particle exposure. Since the dose delivered by the charged particle increases sharply as the particle approaches the end of its range, a position known as the Bragg peak, the Bragg curve does not necessarily represent the biological damage along the particle traversal since biological effects are influenced by the track structure of both primary and secondary particles. Therefore, the biological Bragg curve is dependent on the energy and the type of the primary particle, and may vary for different biological endpoints. To achieve a Bragg curve distribution, we exposed cells to energetic heavy ions with the beam geometry parallel to a monolayer of fibroblasts. Qualitative analyses of gamma-H2AX fluorescence, a known marker of DSBs, indicated increased clustering of DNA damage before the Bragg peak, enhanced homogenous distribution at the peak, and provided visual evidence of high linear energy transfer (LET) particle traversal of cells beyond the Bragg peak. A quantitative biological response curve generated for micronuclei (MN) induction across the Bragg curve did not reveal an increased yield of MN at the location of the Bragg peak. However, the ratio of mono-to bi-nucleated cells, which indicates inhibition in cell progression, increased at the Bragg peak location. These results, along with other biological concerns, show that space radiation protection with shielding can be a complicated issue.

Fluorescence lifetime imaging of induced pluripotent stem cells

NASA Astrophysics Data System (ADS)

Uchugonova, Aisada; Batista, Ana; König, Karsten

2014-02-01

The multiphoton FLIM tomograph MPTflex with its flexible scan head, articulated arm, and the tunable femtosecond laser source was employed to study cell monolayers and 3D cell clusters. FLIM was performed with 250 ps temporal resolution and submicron special resolution using time-correlated single photon counting. The autofluorescence based on NAD(P)H and flavins/flavoproteins has been measured in mouse embryonic fibroblasts, induced pluripotent stem cells (iPS cells) originated from mouse embryonic fibroblasts and non-proliferative mouse embryonic fibroblasts.

Magnetic assembly of 3D cell clusters: visualizing the formation of an engineered tissue.

PubMed

Ghosh, S; Kumar, S R P; Puri, I K; Elankumaran, S

2016-02-01

Contactless magnetic assembly of cells into 3D clusters has been proposed as a novel means for 3D tissue culture that eliminates the need for artificial scaffolds. However, thus far its efficacy has only been studied by comparing expression levels of generic proteins. Here, it has been evaluated by visualizing the evolution of cell clusters assembled by magnetic forces, to examine their resemblance to in vivo tissues. Cells were labeled with magnetic nanoparticles, then assembled into 3D clusters using magnetic force. Scanning electron microscopy was used to image intercellular interactions and morphological features of the clusters. When cells were held together by magnetic forces for a single day, they formed intercellular contacts through extracellular fibers. These kept the clusters intact once the magnetic forces were removed, thus serving the primary function of scaffolds. The cells self-organized into constructs consistent with the corresponding tissues in vivo. Epithelial cells formed sheets while fibroblasts formed spheroids and exhibited position-dependent morphological heterogeneity. Cells on the periphery of a cluster were flattened while those within were spheroidal, a well-known characteristic of connective tissues in vivo. Cells assembled by magnetic forces presented visual features representative of their in vivo states but largely absent in monolayers. This established the efficacy of contactless assembly as a means to fabricate in vitro tissue models. © 2016 John Wiley & Sons Ltd.

Electrochemical Protection of Thin Film Electrodes in Solid State Nanopores

PubMed Central

Harrer, Stefan; Waggoner, Philip S.; Luan, Binquan; Afzali-Ardakani, Ali; Goldfarb, Dario L.; Peng, Hongbo; Martyna, Glenn; Rossnagel, Stephen M.; Stolovitzky, Gustavo A.

2011-01-01

We have eliminated electrochemical surface oxidation and reduction as well as water decomposition inside sub-5-nm wide nanopores in conducting TiN membranes using a surface passivation technique. Nanopore ionic conductances, and therefore pore diameters, were unchanged in passivated pores after applying potentials of ±4.5 V for as long as 24 h. Water decomposition was eliminated by using aqueous 90% glycerol solvent. The use of a protective self-assembled monolayer of hexadecylphosphonic acid was also investigated. PMID:21597142

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

NASA Astrophysics Data System (ADS)

Liu, Siqi; Xu, Yi-Jun

2016-03-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

NASA Astrophysics Data System (ADS)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

A dynamic cellular vertex model of growing epithelial tissues

NASA Astrophysics Data System (ADS)

Lin, Shao-Zhen; Li, Bo; Feng, Xi-Qiao

2017-04-01

Intercellular interactions play a significant role in a wide range of biological functions and processes at both the cellular and tissue scales, for example, embryogenesis, organogenesis, and cancer invasion. In this paper, a dynamic cellular vertex model is presented to study the morphomechanics of a growing epithelial monolayer. The regulating role of stresses in soft tissue growth is revealed. It is found that the cells originating from the same parent cell in the monolayer can orchestrate into clustering patterns as the tissue grows. Collective cell migration exhibits a feature of spatial correlation across multiple cells. Dynamic intercellular interactions can engender a variety of distinct tissue behaviors in a social context. Uniform cell proliferation may render high and heterogeneous residual compressive stresses, while stress-regulated proliferation can effectively release the stresses, reducing the stress heterogeneity in the tissue. The results highlight the critical role of mechanical factors in the growth and morphogenesis of epithelial tissues and help understand the development and invasion of epithelial tumors.

Mesoscale Graphene-like Honeycomb Mono- and Multilayers Constructed via Self-Assembly of Coclusters.

PubMed

Hou, Xue-Sen; Zhu, Guo-Long; Ren, Li-Jun; Huang, Zi-Han; Zhang, Rui-Bin; Ungar, Goran; Yan, Li-Tang; Wang, Wei

2018-02-07

Honeycomb structure endows graphene with extraordinary properties. But could a honeycomb monolayer superlattice also be generated via self-assembly of colloids or nanoparticles? Here we report the construction of mono- and multilayer molecular films with honeycomb structure that can be regarded as self-assembled artificial graphene (SAAG). We construct fan-shaped molecular building blocks by covalently connecting two kinds of clusters, one polyoxometalate and four polyhedral oligomeric silsesquioxanes. The precise shape control enables these complex molecules to self-assemble into a monolayer 2D honeycomb superlattice that mirrors that of graphene but on the mesoscale. The self-assembly of the SAAG was also reproduced via coarse-grained molecular simulations of a fan-shaped building block. It revealed a hierarchical process and the key role of intermediate states in determining the honeycomb structure. Experimental images also show a diversity of bi- and trilayer stacking modes. The successful creation of SAAG and its stacks opens up prospects for the preparation of novel self-assembled nanomaterials with unique properties.

Work Functions for Models of Scandate Surfaces

NASA Technical Reports Server (NTRS)

Mueller, Wolfgang

1997-01-01

The electronic structure, surface dipole properties, and work functions of scandate surfaces have been investigated using the fully relativistic scattered-wave cluster approach. Three different types of model surfaces are considered: (1) a monolayer of Ba-Sc-O on W(100), (2) Ba or BaO adsorbed on Sc2O3 + W, and (3) BaO on SC2O3 + WO3. Changes in the work function due to Ba or BaO adsorption on the different surfaces are calculated by employing the depolarization model of interacting surface dipoles. The largest work function change and the lowest work function of 1.54 eV are obtained for Ba adsorbed on the Sc-O monolayer on W(100). The adsorption of Ba on Sc2O3 + W does not lead to a low work function, but the adsorption of BaO results in a work function of about 1.6-1.9 eV. BaO adsorbed on Sc2O3 + WO3, or scandium tungstates, may also lead to low work functions.

Immobilization of alkaline phosphatase on solid surface through self-assembled monolayer and by active-site protection.

PubMed

Gao, En-Feng; Kang, Kyung Lhi; Kim, Jeong Hee

2014-06-01

Retaining biological activity of a protein after immobilization is an important issue and many studies reported to enhance the activity of proteins after immobilization. We recently developed a new immobilization method of enzyme using active-site protection and minimization of the cross-links between enzyme and surface with a DNA polymerase as a model system. In this study, we extended the new method to an enzyme with a small mono-substrate using alkaline phosphatase (AP) as another model system. A condition to apply the new method is that masking agents, in this case its own substrate needs to stay at the active-site of the enzyme to be immobilized in order to protect the active-site during the harsh immobilization process. This could be achieved by removal of essential divalent ion, Zn2+ that is required for full enzyme activity of AP from the masking solution while active-site of AP was protected with p-nitrophenyl phosphate (pNPP). Approximately 40% of the solution-phase activity was acquired with active-site protected immobilized AP. In addition to protection active-site of AP, the number of immobilization links was kinetically controlled. When the mole fraction of the activated carboxyl group of the linker molecule in self-assembled monolayer (SAM) of 12-mercaptododecanoic acid and 6-mercapto-1-ethanol was varied, 10% of 12-mercaptododecanoic acid gave the maximum enzyme activity. Approximately 51% increase in enzyme activity of the active-site protected AP was observed compared to that of the unprotected group. It was shown that the concept of active-site protection and kinetic control of the number of covalent immobilization bonds can be extended to enzymes with small mono-substrates. It opens the possibility of further extension of the new methods of active-site protection and kinetic control of immobilization bond to important enzymes used in research and industrial fields.

Dietary fibre-based SCFA mixtures promote both protection and repair of intestinal epithelial barrier function in a Caco-2 cell model.

PubMed

Chen, Tingting; Kim, Choon Young; Kaur, Amandeep; Lamothe, Lisa; Shaikh, Maliha; Keshavarzian, Ali; Hamaker, Bruce R

2017-03-22

Impaired gut barrier function plays an important role in the development of many diseases such as obesity, inflammatory bowel disease, and in HIV infection. Dietary fibres have been shown to improve intestinal barrier function through their fermentation products, short chain fatty acids (SCFAs), and the effects of individual SCFAs have been studied. Here, different SCFA mixtures representing possible compositions from fibre fermentation products were studied for protective and reparative effects on intestinal barrier function. The effect of fermentation products from four dietary fibres, i.e. resistant starch, fructooligosaccharides, and sorghum and corn arabinoxylan (varying in their branched structure) on barrier function was positively correlated with their SCFA concentration. Pure SCFA mixtures of various concentrations and compositions were tested using a Caco-2 cell model. SCFAs at a moderate concentration (40-80 mM) improved barrier function without causing damage to the monolayer. In a 40 mM SCFA mixture, the butyrate proportion at 20% and 50% showed both a protective and a reparative effect on the monolayer to disrupting agents (LPS/TNF-α) applied simultaneously or prior to the SCFA mixtures. Relating this result to dietary fibre selection, slow fermenting fibres that deliver appropriate concentrations of SCFAs to the epithelium with a high proportion of butyrate may improve barrier function.

Hydraulic fracture and resilience of epithelial monolayers under stretch

NASA Astrophysics Data System (ADS)

Arroyo, Marino; Lucantonio, Alessandro; Noselli, Giovanni; Casares, Laura; Desimone, Antonio; Trepat, Xavier

Epithelial monolayers are very simple and prevalent tissues. Their functions include delimiting distinct physicochemical containers and protecting us from pathogens. Epithelial fracture disrupts the mechanical integrity of this barrier, and hence compromises these functions. Here, we show that in addition to the conventional fracture resulting from excessive tissue tension, epithelia can hydraulically fracture under stretch as a result of the poroelastic nature of the matrix. We will provide experimental evidence of this counterintuitive mechanism of fracture, in which cracks appear under compression. Intriguingly, unlike tensional fracture, which is localized and catastrophic, hydraulic epithelial fracture is distributed and reversible. We will also describe the active mechanisms responsible for crack healing, and the physical principles by which the poroelastic matrix contributes to this resilient behavior.

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

NASA Astrophysics Data System (ADS)

Łuczak, Teresa; Pankiewicz, Radosław; Łęska, Bogusława; Schroeder, Grzegorz; Bełtowska-Brzezinska, Maria; Brzezinski, Bogumil

2006-12-01

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li + cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.

Kinetics of copper growth on graphene revealed by time-resolved small-angle x-ray scattering

NASA Astrophysics Data System (ADS)

Hodas, M.; Siffalovic, P.; Jergel, M.; Pelletta, M.; Halahovets, Y.; Vegso, K.; Kotlar, M.; Majkova, E.

2017-01-01

Metal growth on graphene has many applications. Transition metals are known to favor three-dimensional (3D) cluster growth on graphene. Copper is of particular interest for cost-effective surface-supported catalysis applications and as a contact material in electronics. This paper presents an in situ real-time study of Cu growth kinetics on graphene covering all stages preceding formation of a continuous film performed by laboratory-based grazing-incidence small-angle x-ray scattering (GISAXS) technique. In particular, nucleation and 3D cluster growth, coalescence, and percolation stages were identified. The cluster nucleation saturates after reaching a density of 1012c m-2 at ≈1 monolayer thickness. A Kratky plot and a paracrystal model with cumulative structural disorder were necessary to evaluate properly cluster growth and coalescence, respectively. The power law scaling constants 0.27 ±0.05 and 0.81 ±0.02 of the temporal evolution of Cu cluster size suggest the growth of isolated clusters and dynamic cluster coalescence keeping the cluster shape, respectively. Coalescence and percolation thresholds occur at Cu thicknesses of 2 ±0.4 and 8.8 ±0.7 nm , respectively. This paper demonstrates the potential of laboratory-based in situ GISAXS as a vital diagnostic tool for tailoring a large variety of Cu nanostructures on graphene based on an in situ Cu growth monitoring which is applicable in a broad range of deposition times.

Organosilane self-assembled layers (SAMs) and hybrid silicate magnesium-rich primers for the corrosion protection of aluminum alloy 2024 T3

NASA Astrophysics Data System (ADS)

Wang, Duhua

Although current chromate coatings function very well in corrosion protection for aircraft alloys, such as aluminum alloy 2024 T3, the U.S. Environmental Protection Agency is planning to totally ban the use of chromates as coating materials in the next decade or so because of their extremely toxic effect. For this purpose, both self-assembled layers and silicate magnesium-rich primers were tested to provide the corrosion protection for aluminum alloy. The long-term goal of this research is to develop a coating system to replace the current chromate coating for aircraft corrosion protection. Aluminum alloy 2024 T3 substrates were modified with self-assembled monolayer or multilayer thin films from different alkylsilane compounds. Mono-functional silanes, such as octadecyltrichlorosilane (C18SiCl3), can form a mixed hydrophobic monolayer or multilayer thin film on the aluminum oxide surface to provide a barrier to water and other electrolytes, so the corrosion resistance of the SAMs modified surface was increased significantly. On the other hand, the bi-functional silane self-assembly could attach the aluminum surface through the silicon headgroup while using its functional tailgroup to chemically bond the polymer coating, thus improving the adhesion between the aluminum substrate and coating substantially, and seems to contribute more to corrosion protection of aluminum substrate. Organosilanes were also combined with tetraethyl orthosilicate (TEOS) in propel ratios to form a sol-gel binder to make silicate magnesium-rich primers. Analogue to the inorganic zinc-rich coatings, the silicate magnesium-rich primers also showed excellent adhesion and solvent resistance. The sacrificial magnesium pigments and the chemically inert silicate binder both contribute to the anti-corrosion properties. Future studies will be focused on the formula optimization for better toughness, chemical resistance and anticorrosion performance.

Rapid Grafting of Azido-labeled Oligo(ethylene glycol)s onto an Alkynyl-terminated Monolayer on Non-oxidized Silicon via Microwave-assisted “Click” Reaction

PubMed Central

Li, Yan; Wang, Jun; Cai, Chengzhi

2011-01-01

Microwave (MW) irradiation was used for the grafting of azido-labeled oligo(ethylene oxide) (OEG) on alkynyl-terminated non-oxidized silicon substrates via copper-catalyzed “click” reaction. The “clickable” monolayers were prepared by photografting of an α,ω-alkynene, where the alkynyl terminus was protected by a trimethylgermanyl (TMG) group, onto hydrogen-terminated Si(111) surfaces. X-ray photoelectron spectroscopy (XPS) was primarily employed to characterize the monolayers, and the data obtained were utilized to calculate the surface density of the TMG-alkynyl-functionalized substrate. MW-assisted one-pot deprotection/click reaction was optimized on the surfaces using azido-tagged OEG derivatives. Using MW instead of conventional heating led to a substantial improvement on the rate of the reaction while suppressing the oxidation of the silicon interface and OEG degradation. The antifouling property of the resulting substrates was evaluated using fibrinogen as a model protein. Results show that the OEG-modification reduced the protein adsorption by >90%. PMID:21306165

Protective role of arzanol against lipid peroxidation in biological systems.

PubMed

Rosa, Antonella; Pollastro, Federica; Atzeri, Angela; Appendino, Giovanni; Melis, M Paola; Deiana, Monica; Incani, Alessandra; Loru, Debora; Dessì, M Assunta

2011-01-01

This study examines the protective effect of arzanol, a pyrone-phloroglucinol etherodimer from Helichrysum italicum subsp. microphyllum, against the oxidative modification of lipid components induced by Cu(2+) ions in human low density lipoprotein (LDL) and by tert-butyl hydroperoxide (TBH) in cell membranes. LDL pre-treatment with arzanol significantly preserved lipoproteins from oxidative damage at 2h of oxidation, and showed a remarkable protective effect on the reduction of polyunsaturated fatty acids and cholesterol levels, inhibiting the increase of oxidative products (conjugated dienes fatty acids hydroperoxides, 7β-hydroxycholesterol, and 7-ketocholesterol). Arzanol, at non-cytotoxic concentrations, exerted a noteworthy protection on TBH-induced oxidative damage in a line of fibroblasts derived from monkey kidney (Vero cells) and in human intestinal epithelial cells (Caco-2), decreasing, in both cell lines, the formation of oxidative products (hydroperoxides and 7-ketocholesterol) from the degradation of unsaturated fatty acids and cholesterol. The cellular uptake and transepithelial transport of the compound were also investigated in Caco-2 cell monolayers. Arzanol appeared to accumulate in Caco-2 epithelial cells. This phenol was able to pass through the intestinal Caco-2 monolayers, the apparent permeability coefficients (P(app)) in the apical-to-basolateral and basolateral-to-apical direction at 2h were 1.93±0.36×10(-5) and 2.20±0.004×10(-5)cm/s, respectively, suggesting a passive diffusion pathway. The results of the work qualify arzanol as a potent natural antioxidant with a protective effect against lipid oxidation in biological systems. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Layer specific optical band gap measurement at nanoscale in MoS{sub 2} and ReS{sub 2} van der Waals compounds by high resolution electron energy loss spectroscopy

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

Dileep, K., E-mail: dileep@jncasr.ac.in, E-mail: ranjan@jncasr.ac.in; Sahu, R.; Datta, R., E-mail: dileep@jncasr.ac.in, E-mail: ranjan@jncasr.ac.in

2016-03-21

Layer specific direct measurement of optical band gaps of two important van der Waals compounds, MoS{sub 2} and ReS{sub 2}, is performed at nanoscale by high resolution electron energy loss spectroscopy. For monolayer MoS{sub 2}, the twin excitons (1.8 and 1.95 eV) originating at the K point of the Brillouin zone are observed. An indirect band gap of 1.27 eV is obtained from the multilayer regions. Indirect to direct band gap crossover is observed which is consistent with the previously reported strong photoluminescence from the monolayer MoS{sub 2}. For ReS{sub 2}, the band gap is direct, and a value of 1.52 andmore » 1.42 eV is obtained for the monolayer and multilayer, respectively. The energy loss function is dominated by features due to high density of states at both the valence and conduction band edges, and the difference in analyzing band gap with respect to ZnO is highlighted. Crystalline 1T ReS{sub 2} forms two dimensional chains like superstructure due to the clustering between four Re atoms. The results demonstrate the power of HREELS technique as a nanoscale optical absorption spectroscopy tool.« less

The glass-liquid transition of water on hydrophobic surfaces

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2008-09-01

Interactions of thin water films with surfaces of graphite and vitrified room-temperature ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])] were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature and annealing time to elucidate the glass-liquid transition of water at the molecular level. Surface diffusion of water occurs at temperatures higher than 120K, thereby forming three-dimensional clusters (a two-dimensional layer) on the [bmim][PF6] (graphite) surface. The hydrophobic effect of the surface decreases with increasing coverage of water; the bulklike properties evolve up to 40 ML, as evidenced by the occurrence of film dewetting at around the conventional glass transition temperature (140K). Results also showed that aging is necessary for the water monolayer (a 40 ML water film) to dewet the graphite ([bmim][PF6]) surface. The occurrence of aging is explainable by the successive evolution of two distinct liquids during the glass-liquid transition: low density liquid is followed by supercooled liquid water. The water monolayer on graphite is characterized by the preferred orientation of unpaired OH groups toward the surface; this structure is arrested during the aging time despite the occurrence of surface diffusion. However, the water monolayer formed on the [bmim][PF6] surface agglomerates immediately after the commencement of surface diffusion. The structure of low density liquid tends to be arrested by the attractive interaction with the neighbors.

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Structural and theoretical basis for ligand exchange on thiolate monolayer protected gold nanoclusters.

PubMed

Heinecke, Christine L; Ni, Thomas W; Malola, Sami; Mäkinen, Ville; Wong, O Andrea; Häkkinen, Hannu; Ackerson, Christopher J

2012-08-15

Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering.

Morphological Behavior of Printed Silver Electrodes with Protective Self-Assembled Monolayers for Electrochemical Migration.

PubMed

Sekine, Tomohito; Sato, Jun; Takeda, Yasunori; Kumaki, Daisuke; Tokito, Shizuo

2018-05-09

We evaluated the electrochemical behaviors and reliability of printed silver (Ag) electrodes prepared from nanoparticle inks with the use of protective self-assembled monolayers (SAMs) under electronic bias conditions. The printed Ag electrodes were fabricated by inkjet printing on a hydrophobic substrate. The SAMs, which acted as barriers to moisture, were prepared by immersing the substrate in a pentafluorobenzenethiol solution at ambient temperature (25 °C). We investigated the electrochemical migration phenomenon using the water drop method, and the results showed that the formation of dendrites connecting the cathode and the anode, which can affect the electrochemical reliability of an electric device, was suppressed in the presence of the SAMs. The time before short circuit occurred was found to depend on the spacing between the electrodes, i.e., 130 s, when the distance between the electrodes was 200 μm in the presence of an SAM. We demonstrated that Ag electrodes treated using the procedure described in this work suppress the occurrence of electrical short circuits caused by Ag dendrite formation and thus their electrochemical properties are substantially improved.

The Saccharomyces boulardii CNCM I-745 strain shows protective effects against the B. anthracis LT toxin.

PubMed

Pontier-Bres, Rodolphe; Rampal, Patrick; Peyron, Jean-François; Munro, Patrick; Lemichez, Emmanuel; Czerucka, Dorota

2015-10-30

The probiotic yeast Saccharomyces boulardii (S. boulardii) has been prescribed for the prophylaxis and treatment of several infectious diarrheal diseases. Gastrointestinal anthrax causes fatal systemic disease. In the present study, we investigated the protective effects conferred by Saccharomyces boulardii CNCM I-745 strain on polarized T84 columnar epithelial cells intoxicated by the lethal toxin (LT) of Bacillus anthracis. Exposure of polarized T84 cells to LT affected cell monolayer integrity, modified the morphology of tight junctions and induced the formation of actin stress fibers. Overnight treatment of cells with S. boulardii before incubation with LT maintained the integrity of the monolayers, prevented morphological modification of tight junctions, restricted the effects of LT on actin remodeling and delayed LT-induced MEK-2 cleavage. Mechanistically, we demonstrated that in the presence of S. boulardii, the medium is depleted of both LF and PA sub-units of LT and the appearance of a cleaved form of PA. Our study highlights the potential of the S. boulardii CNCM I-745 strain as a prophylactic agent against the gastrointestinal form of anthrax.

The Saccharomyces boulardii CNCM I-745 Strain Shows Protective Effects against the B. anthracis LT Toxin

PubMed Central

Pontier-Bres, Rodolphe; Rampal, Patrick; Peyron, Jean-François; Munro, Patrick; Lemichez, Emmanuel; Czerucka, Dorota

2015-01-01

The probiotic yeast Saccharomyces boulardii (S. boulardii) has been prescribed for the prophylaxis and treatment of several infectious diarrheal diseases. Gastrointestinal anthrax causes fatal systemic disease. In the present study, we investigated the protective effects conferred by Saccharomyces boulardii CNCM I-745 strain on polarized T84 columnar epithelial cells intoxicated by the lethal toxin (LT) of Bacillus anthracis. Exposure of polarized T84 cells to LT affected cell monolayer integrity, modified the morphology of tight junctions and induced the formation of actin stress fibers. Overnight treatment of cells with S. boulardii before incubation with LT maintained the integrity of the monolayers, prevented morphological modification of tight junctions, restricted the effects of LT on actin remodeling and delayed LT-induced MEK-2 cleavage. Mechanistically, we demonstrated that in the presence of S. boulardii, the medium is depleted of both LF and PA sub-units of LT and the appearance of a cleaved form of PA. Our study highlights the potential of the S. boulardii CNCM I-745 strain as a prophylactic agent against the gastrointestinal form of anthrax. PMID:26529015

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

PubMed Central

Liu, Siqi; Xu, Yi-Jun

2016-01-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

Protective effects of lactoferrin against intestinal mucosal damage induced by lipopolysaccharide in human intestinal Caco-2 cells.

PubMed

Hirotani, Yoshihiko; Ikeda, Kenji; Kato, Ryuji; Myotoku, Michiaki; Umeda, Takashi; Ijiri, Yoshio; Tanaka, Kazuhiko

2008-09-01

Indirect evidence suggests that lactoferrin (Lf), a major iron-binding protein in human milk, induces enterocyte growth and proliferation, depending on its concentration and affects the function and permeability of the intestinal mucosa. The bacterial endotoxin (lipopolysaccharide, LPS) is known to cause mucosal hyperpermeability in vivo. However, protective effects of Lf against LPS-mediated intestinal mucosal damage and barrier function in epithelial cells are not yet fully clarified. The aim of this study was to investigate whether Lf can reduce the cellular injury and alter epithelial hyperpermeability caused by LPS in human intestinal Caco-2 cells. When cell viability was measured by a WST-1 assay (tetrazolium salt-based assay), the protective effects against LPS-induced damage to Caco-2 cells were observed at doses of 800 and 1000 microg/ml Lf. The barrier function of Caco-2 monolayer tight junctions was assessed by measuring transepithelial electrical resistance (TEER) and permeability of FITC-labeled dextran 4000 (FD-4). The treatment of Caco-2 cells with Lf at doses of 400 and 1000 microg/ml significantly increased TEER as compared to treatment with LPS alone for 2 h (p<0.05). Further, at doses of 400 and 1000 microg/ml, Lf inhibited the enhancement of LPS-mediated permeability in Caco-2 cell monolayer. The results of this study suggest that Lf may have protective effects against LPS-mediated intestinal mucosal damage and impairment of barrier function in intestinal epithelial cells.

Development of a high-density nonwoven structure to improve the stab resistance of protective clothing material.

PubMed

Bao, Limin; Wang, Yanling; Baba, Takeichiro; Fukuda, Yasuhiro; Wakatsuki, Kaoru; Morikawa, Hideaki

2017-12-07

The purpose of this research was to enhance the stab resistance of protective clothing material by developing a new high-density nonwoven structure. Ice picks often injure Japanese police officers due to the strict regulation of swords in the country. Consequently, this study was designed to improve stab resistance against ice picks. Most existing anti-stab protective clothing research has focused on various fabrics impregnated with resin, an approach that brings with it problems of high cost and complicated processing. Seldom has research addressed the potential for improving stab resistance by using nonwoven structures, which exhibit better stab resistance than fabric. In this research, we prepared a series of nonwoven structures with densities ranging from about 0.14 g/cm 3 to 0.46 g/cm 3 by varying the number of stacked layers of Kevlar/polyester nonwoven under a hot press. We then proposed two methods for producing such hot-press nonwovens: the multilayer hot-press method and the monolayer hot-press method. Stab resistance was evaluated according to NIJ Standard-0115.00. We also investigated the relationship among nonwoven density, stab resistance, and flexural rigidity, and here we discuss the respective properties of the two proposed methods. Our results show that stab resistance and flexural rigidity increase with nonwoven density, but flexural rigidity of nonwovens prepared using the monolayer hot-press method only shows a slight change as nonwoven density increases. Though the two methods exhibit little difference in maximum load, the flexural rigidity of nonwovens prepared using the monolayer hot-press method is much lower, which contributes to superior wear comfort. Finally, we investigated the mechanism behind the stabbing process. Stabbing with an ice pick is a complicated process that involves many factors. Our findings indicate that nonwovens stop penetration primarily in two ways: nonwoven deformation and fiber fractures.

Development of a high-density nonwoven structure to improve the stab resistance of protective clothing material

PubMed Central

BAO, Limin; WANG, Yanling; BABA, Takeichiro; FUKUDA, Yasuhiro; WAKATSUKI, Kaoru; MORIKAWA, Hideaki

2017-01-01

The purpose of this research was to enhance the stab resistance of protective clothing material by developing a new high-density nonwoven structure. Ice picks often injure Japanese police officers due to the strict regulation of swords in the country. Consequently, this study was designed to improve stab resistance against ice picks. Most existing anti-stab protective clothing research has focused on various fabrics impregnated with resin, an approach that brings with it problems of high cost and complicated processing. Seldom has research addressed the potential for improving stab resistance by using nonwoven structures, which exhibit better stab resistance than fabric. In this research, we prepared a series of nonwoven structures with densities ranging from about 0.14 g/cm3 to 0.46 g/cm3 by varying the number of stacked layers of Kevlar/polyester nonwoven under a hot press. We then proposed two methods for producing such hot-press nonwovens: the multilayer hot-press method and the monolayer hot-press method. Stab resistance was evaluated according to NIJ Standard-0115.00. We also investigated the relationship among nonwoven density, stab resistance, and flexural rigidity, and here we discuss the respective properties of the two proposed methods. Our results show that stab resistance and flexural rigidity increase with nonwoven density, but flexural rigidity of nonwovens prepared using the monolayer hot-press method only shows a slight change as nonwoven density increases. Though the two methods exhibit little difference in maximum load, the flexural rigidity of nonwovens prepared using the monolayer hot-press method is much lower, which contributes to superior wear comfort. Finally, we investigated the mechanism behind the stabbing process. Stabbing with an ice pick is a complicated process that involves many factors. Our findings indicate that nonwovens stop penetration primarily in two ways: nonwoven deformation and fiber fractures. PMID:28978816

Organic vapor discrimination with chemiresistor arrays of temperature modulated tin-oxide nanowires and thiolate-monolayer-protected gold nanoparticles.

PubMed

Scholten, K; Bohrer, F I; Dattoli, E; Lu, W; Zellers, E T

2011-03-25

This paper explores the discrimination of organic vapors with arrays of chemiresistors (CRs) employing interface layers of tin-oxide nanowires (NWs) and thiolate-monolayer-protected gold nanoparticles (MPNs). The former devices use contact-printed mats of NWs on micro-hotplate membranes to bridge a pair of metal electrodes. Oxidation at the NW surface causes changes in charge transport, the temperature dependence of which differs among different vapors, permitting vapor discrimination. The latter devices use solvent cast films of MPNs on interdigital electrodes operated at room temperature. Sorption into the organic monolayers causes changes in film tunneling resistance that differ among different vapors and MPN structures, permitting vapor discrimination. Here, we compare the performance and assess the 'complementarity' of these two types of sensors. Calibrated responses from an NW CR operated at two different temperatures and from a set of four different MPN CRs were generated for three test vapors: n-hexane, toluene, and nitromethane. This pooled data set was then analyzed using principal components regression classification models with varying degrees of random error superimposed on the responses via Monte Carlo simulation in order to estimate the rates of recognition/discrimination for arrays comprising different combinations of sensors. Results indicate that the diversity of most of the dual MPN-CR arrays exceeds that of the dual NW-CR array. Additionally, in assessing all possible arrays of 4-6 CR sensors, the recognition rates of the hybrid arrays (i.e. MPN + NW) were no better than that of the 4-sensor array containing only MPN CRs.

Magnetic MoS2 pizzas and sandwiches with Mnn (n = 1-4) cluster toppings and fillings: A first-principles investigation

NASA Astrophysics Data System (ADS)

Zhang, Meng; Huang, Zhongjia; Wang, Xiao; Zhang, Hongyu; Li, Taohai; Wu, Zhaolong; Luo, Youhua; Cao, Wei

2016-01-01

The inorganic layered crystal (ILC) MoS2 in low dimensions is considered as one of the most promising and efficient semiconductors. To enable the magnetism and keep intrinsic crystal structures, we carried out a first-principles study of the magnetic and semiconductive monolayer MoS2 adsorbed with the Mnn (n = 1-4) clusters, and bilayer MoS2 intercalated with the same clusters. Geometric optimizations of the Mnn@MoS2 systems show the complexes prefer to have Mnn@MoS2(M) pizza and Mnn@MoS2(B) sandwich forms in the mono- and bi-layered cases, respectively. Introductions of the clusters will enhance complex stabilities, while bonds and charge transfers are found between external Mn clusters and the S atoms in the hosts. The pizzas have medium magnetic moments of 3, 6, 9, 4 μB and sandwiches of 3, 2, 3, 2 μB following the manganese numbers. The pizzas and sandwiches are semiconductors, but with narrower bandgaps compared to their corresponding pristine hosts. Direct bandgaps were found in the Mnn@MoS2(M) (n = 1,4) pizzas, and excitingly in the Mn1@MoS2(B) sandwich. Combining functional clusters to the layered hosts, the present work shows a novel material manipulation strategy to boost semiconductive ILCs applications in magnetics.

Ligand-protected gold clusters: the structure, synthesis and applications

NASA Astrophysics Data System (ADS)

Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

2015-11-01

Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

Half-metallic ferromagnetism in substitutionally doped boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-11-01

We perform first-principles molecular dynamics simulations to investigate the magnetoelectronic response of substitutionally doped boronitrene to thermal excitation. We show that the local geometry, size, and edge termination of the substitutional complexes of boron, carbon, or nitrogen determine the thermodynamic stability of the monolayer. We find that hexagonal boron or triangular carbon clusters induce finite magnetic moments with 100% spin-polarized Fermi-level electrons in boronitrene. In such carbon substitutions, the spontaneous magnetic moment increases with the size of the embedded carbon cluster, and results in half-metallic ferrimagnetism above 750 K with a corresponding Curie point of 1250 K, above which the magnetization density vanishes. We predict an ultrahigh temperature half-metallic ferromagnetic phase in impurity-free boronitrene, when any three nearest-neighbor nitrogen atoms are substituted with boron, with unquenched magnetic moment up to its melting point.

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

NASA Astrophysics Data System (ADS)

Zheng, Zhikun; Yang, Menglong; Liu, Yaqing; Zhang, Bailin

2006-11-01

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Functionalization of biodegradable magnesium alloy implants with alkylphosphonate self-assembled films.

PubMed

Grubač, Z; Metikoš-Huković, M; Babić, R; Rončević, I Škugor; Petravić, M; Peter, R

2013-05-01

Mg and Mg-alloys are promising materials for biodegradable implants. In order to slowdown the Mg-alloy (AZ91D) degradation and enhance its biocompatibility, the alloy surface was modified with alkylphosphonate self-assembling films. The binding configuration and the structural organization of alkylphosphonate monolayers on the Mg-alloy surface were investigated using contact angle measurements, FTIR, and XPS. Combination of FTIR and XPS data indicated the presence of several different bonding modes (mono-, di-, and tri dentate) of phosphonate head groups with the alloy surface. The existence of well organized and ordered self-assembled alkylphosphonate monolayers with good barrier protecting properties in a physiological solution is a key step in the development of biocompatible Mg-alloy implants. Copyright © 2013 Elsevier B.V. All rights reserved.

Sun Protection Motivational Stages and Behavior: Skin Cancer Risk Profiles

ERIC Educational Resources Information Center

Pagoto, Sherry L.; McChargue, Dennis E.; Schneider, Kristin; Cook, Jessica Werth

2004-01-01

Objective: To create skin cancer risk profiles that could be used to predict sun protection among Midwest beachgoers. Method: Cluster analysis was used with study participants (N=239), who provided information about sun protection motivation and behavior, perceived risk, burn potential, and tan importance. Participants were clustered according to…

Characterization of supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

PubMed

Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

2003-06-11

Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

In situ nanoplasmonic probing of enzymatic activity of monolayer-confined glucose oxidase on colloidal nanoparticles.

PubMed

He, Haili; Xu, Xiaolong; Wu, Haoxi; Zhai, Yujuan; Jin, Yongdong

2013-05-07

In situ probing protein-particle interactions and activities of proteins on colloidal nanoparticle (NP) surfaces is a long-standing key challenge in understanding the nanobio interfaces and virtually important for a variety of biological and biomedical applications. The interactions of NPs with proteins, for instance, are known to form NP bioconjugates or protein coronas; protein surface immobilization and molecular layer-by-layer deposition techniques are widely used, but a clear understanding of the confinement effect on protein activity by molecular coating, at the monolayer level, remains poorly understood. We explore here a novel approach, using colloidal plasmonic nanocomplexes coated with glucose oxidase (GOx) as self-sensing nanoprobes for in situ optical probing of surface-confined enzymatic activity, which is at least 1-2 orders of magnitude more sensitive than standard colorimetric assays for detecting GOx activity. We found that enzymatic activity of monolayer-confined GOx on colloidal NPs was significantly enhanced as compared with free GOx (also proved by conformational changes from circular dichroism studies), with a low apparent Michaelis-Menten constant Km of ~0.115 mM and high turnover kcat/Km of ~8394 M(-1)·s(-1); compared with the "anchored-type" suspending GOx, the outmost polyelectrolyte monolayer-protected "sandwiched-type" GOx exhibits significantly improved enzymatic activities toward higher temperatures and wider pH range. This finding is of fundamental important and instructive for safe use of such nanomaterials for bioapplications.

Atomic layer-by-layer thermoelectric conversion in topological insulator bismuth/antimony tellurides.

PubMed

Sung, Ji Ho; Heo, Hoseok; Hwang, Inchan; Lim, Myungsoo; Lee, Donghun; Kang, Kibum; Choi, Hee Cheul; Park, Jae-Hoon; Jhi, Seung-Hoon; Jo, Moon-Ho

2014-07-09

Material design for direct heat-to-electricity conversion with substantial efficiency essentially requires cooperative control of electrical and thermal transport. Bismuth telluride (Bi2Te3) and antimony telluride (Sb2Te3), displaying the highest thermoelectric power at room temperature, are also known as topological insulators (TIs) whose electronic structures are modified by electronic confinements and strong spin-orbit interaction in a-few-monolayers thickness regime, thus possibly providing another degree of freedom for electron and phonon transport at surfaces. Here, we explore novel thermoelectric conversion in the atomic monolayer steps of a-few-layer topological insulating Bi2Te3 (n-type) and Sb2Te3 (p-type). Specifically, by scanning photoinduced thermoelectric current imaging at the monolayer steps, we show that efficient thermoelectric conversion is accomplished by optothermal motion of hot electrons (Bi2Te3) and holes (Sb2Te3) through 2D subbands and topologically protected surface states in a geometrically deterministic manner. Our discovery suggests that the thermoelectric conversion can be interiorly achieved at the atomic steps of a homogeneous medium by direct exploiting of quantum nature of TIs, thus providing a new design rule for the compact thermoelectric circuitry at the ultimate size limit.

Specialized activities and expression differences for Clostridium thermocellum biofilm and planktonic cells.

PubMed

Dumitrache, Alexandru; Klingeman, Dawn M; Natzke, Jace; Rodriguez, Miguel; Giannone, Richard J; Hettich, Robert L; Davison, Brian H; Brown, Steven D

2017-02-27

Clostridium (Ruminiclostridium) thermocellum is a model organism for its ability to deconstruct plant biomass and convert the cellulose into ethanol. The bacterium forms biofilms adherent to lignocellulosic feedstocks in a continuous cell-monolayer in order to efficiently break down and uptake cellulose hydrolysates. We developed a novel bioreactor design to generate separate sessile and planktonic cell populations for omics studies. Sessile cells had significantly greater expression of genes involved in catabolism of carbohydrates by glycolysis and pyruvate fermentation, ATP generation by proton gradient, the anabolism of proteins and lipids and cellular functions critical for cell division consistent with substrate replete conditions. Planktonic cells had notably higher gene expression for flagellar motility and chemotaxis, cellulosomal cellulases and anchoring scaffoldins, and a range of stress induced homeostasis mechanisms such as oxidative stress protection by antioxidants and flavoprotein co-factors, methionine repair, Fe-S cluster assembly and repair in redox proteins, cell growth control through tRNA thiolation, recovery of damaged DNA by nucleotide excision repair and removal of terminal proteins by proteases. This study demonstrates that microbial attachment to cellulose substrate produces widespread gene expression changes for critical functions of this organism and provides physiological insights for two cells populations relevant for engineering of industrially-ready phenotypes.

Nanosized insulin-complexes based on biodegradable amine-modified graft polyesters poly[vinyl-3-(diethylamino)-propylcarbamate-co-(vinyl acetate)-co-(vinyl alcohol)]-graft-poly(L-lactic acid): protection against enzymatic degradation, interaction with Caco-2 cell monolayers, peptide transport and cytotoxicity.

PubMed

Simon, Michael; Behrens, Isabel; Dailey, Lea Anne; Wittmar, Matthias; Kissel, Thomas

2007-05-01

Non-parenteral insulin delivery by the oral route is limited by epithelial barriers and enzymatic degradation. Nanosized insulin-complexes based on amine modified comb-like polyesters were designed to overcome these barriers. Protection of insulin in nanocomplexes (NC) from enzymatic degradation was investigated. The interaction with enterocyte-like Caco-2 cells in terms of cytotoxicity, transport through and uptake in the cell layers was evaluated by measuring transepithelial electrical resistance (TEER), release of lactate dehydrogenase (LDH) and insulin transport. The protection capacity of NC and their interaction with Caco-2 cells varied strongly as a function of lactide-grafting (hydrophobicity). With increasing lactide-grafting (P(26) < or = P(26)-1(LL) < or = P(26)-2(LL)) NC protected up to 95% of the insulin against degradation by trypsin. Transport and uptake into cell monolayers increased with higher l-lactid grafting. About 25% of a 1.25mg/ml TRITC-insulin NC dispersion with P(26)-2(LL) was recovered in Caco-2 cells after 90 min. A concentration dependent cytotoxicity profile was observed showing elevated LDH release and decreased TEER values. The cytotoxicity correlates with the surfactant like character of the polymers, decreasing the surface tension to 46 mN/m for the amphiphilic P(26)-2(LL). The observed TEER decrease was reversible after 20 h, suggesting that the biodegradable comb-polyesters offer a promising approach to overcome mucosal barriers.

Intercellular spread of Shigella flexneri through a monolayer mediated by membranous protrusions and associated with reorganization of the cytoskeletal protein vinculin.

PubMed Central

Kadurugamuwa, J L; Rohde, M; Wehland, J; Timmis, K N

1991-01-01

The spread of Shigella flexneri in a monolayer of infected Henle and HeLa cells was studied by using immunofluorescence and electron microscopy. Infected cells produced numerous bacterium-containing membranous protrusions up to 18 microns in length that penetrated adjacent cells and were subsequently phagocytosed. Fluorescence staining of actin and vinculin in infected cells with phalloidin and monoclonal antibody to vinculin, respectively, demonstrated that the protrusions containing the bacteria consisted of these cytoskeletal proteins. Actin accumulated predominantly at the poles of bacteria distal to the tip of protrusions and appeared as trails extending back towards the host cell cytoplasm. Vinculin, however, was distributed uniformly around the bacteria and throughout the protrusion. A profound rearrangement of vinculin occurred in Henle and HeLa cells following infection with shigellae: whereas in uninfected cells it was distributed mainly around the cell periphery, in infected cells it concentrated mainly around clusters of bacteria in the cytoplasm. This suggests a possible involvement of the vinculin cytoskeletal protein in the intercellular spread of shigellae during an infection. Images PMID:1910001

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide.

DOE PAGES

Chou, Stanley Shihyao; Sai, Na; Lu, Ping; ...

2015-10-07

Establishing processing–structure–property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T' (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T'more » transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Furthermore, we show basal plane activation of 1T' molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T', comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.« less

Listeria monocytogenes InlP interacts with afadin and facilitates basement membrane crossing.

PubMed

Faralla, Cristina; Bastounis, Effie E; Ortega, Fabian E; Light, Samuel H; Rizzuto, Gabrielle; Nocadello, Salvatorre; Anderson, Wayne F; Robbins, Jennifer R; Theriot, Julie A; Bakardjiev, Anna I

2018-05-30

During pregnancy, the placenta protects the fetus against the maternal immune response, as well as bacterial and viral pathogens. Bacterial pathogens that have evolved specific mechanisms of breaching this barrier, such as Listeria monocytogenes, present a unique opportunity for learning how the placenta carries out its protective function. We previously identified the L. monocytogenes protein Internalin P (InlP) as a secreted virulence factor critical for placental infection. Here, we show that InlP, but not the highly similar L. monocytogenes internalin Lmo2027, binds to human afadin (encoded by AF-6), a protein associated with cell-cell junctions. A crystal structure of InlP reveals several unique features, including an extended leucine-rich repeat (LRR) domain with a distinctive Ca2+-binding site. Despite afadin's involvement in the formation of cell-cell junctions, MDCK epithelial cells expressing InlP displayed a decrease in the magnitude of the traction stresses they could exert on deformable substrates, similar to the decrease in traction exhibited by AF-6 knock-out MDCK cells. L. monocytogenes ΔinlP mutants were deficient in their ability to form actin-rich protrusions from the basal face of polarized epithelial monolayers, a necessary step in the crossing of such monolayers (transcytosis). A similar phenotype was observed for bacteria expressing an internal in-frame deletion in inlP (inlP ΔLRR5) that specifically disrupts its interaction with afadin. However, afadin deletion in the host cells did not rescue the transcytosis defect. We conclude that secreted InlP targets cytosolic afadin to specifically promote L. monocytogenes transcytosis across the basal face of epithelial monolayers, which may contribute to the crossing of the basement membrane during placental infection.

Lactobacillus plantarum L9 but not Lactobacillus acidophilus LA reduces tumour necrosis factor induced bacterial translocation in Caco-2 cells.

PubMed

Wang, B; Chen, J; Wang, S; Zhao, X; Lu, G; Tang, X

2017-05-30

Translocation of bacteria across the intestinal barrier is important in the pathogenesis of systemic sepsis and multiple organ dysfunction syndromes. Inflammatory cytokines increase paracellular permeability that allows increased luminal bacteria to translocate across mucosal epithelium and further deteriorate the gut barrier. In order to reduce this risk, the prophylactic use of probiotics has been recently addressed. In this paper, we investigate the protective role toward tumour necrosis factor (TNF)-α induced non-pathogenic Escherichia coli translocation across Caco-2 monolayers of Lactobacillus strains. According to our experimental data, Lactobacillus plantarum L9 and Lactobacillus acidophilus LA have good capacities to adhere to Caco-2 cells. Addition of L. plantarum L9 and L. acidophilus LA to the enterocyte monolayer surface result in significant inhibition of E. coli adhesion and cell internalisation. However, L. plantarum L9 and L. acidophilus LA did not inhibit the growth of the non-pathogenic E. coli B5 after 24 h incubation. Exposure to TNF-α for 6 h caused a dramatic increase in E. coli B5 translocation across Caco-2 cells, which was uncoupled from increases in paracellular permeability. Pretreatment with L. plantarum L9 prevent TNF-α induced transcellular bacterial translocation and IL-8 production in Caco-2 cells. L. plantarum L9 also did not affect the integrity of the monolayers, as indicated by lactate dehydrogenase release, horseradish peroxidase permeability, and transepithelial electrical resistance. L. plantarum L9 showed the potential to protect enterocytes from an acute inflammatory response and therefore could be good potential prophylactic agents in counteracting bacterial translocation.

Electronic and geometric structures of Au30 clusters: a network of 2e-superatom Au cores protected by tridentate protecting motifs with u3-S

NASA Astrophysics Data System (ADS)

Tian, Zhimei; Cheng, Longjiu

2015-12-01

Density functional theory calculations have been performed to study the experimentally synthesized Au30S(SR)18 and two related Au30(SR)18 and Au30S2(SR)18 clusters. The patterns of thiolate ligands on the gold cores for the three thiolate-protected Au30 nanoclusters are on the basis of the ``divide and protect'' concept. A novel extended protecting motif with u3-S, S(Au2(SR)2)2AuSR, is discovered, which is termed the tridentate protecting motif. The Au cores of Au30S(SR)18, Au30(SR)18 and Au30S2(SR)18 clusters are Au17, Au20 and Au14, respectively. The superatom-network (SAN) model and the superatom complex (SAC) model are used to explain the chemical bonding patterns, which are verified by chemical bonding analysis based on the adaptive natural density partitioning (AdNDP) method and aromatic analysis on the basis of the nucleus-independent chemical shift (NICS) method. The Au17 core of the Au30S(SR)18 cluster can be viewed as a SAN of one Au6 superatom and four Au4 superatoms. The shape of the Au6 core is identical to that revealed in the recently synthesized Au18(SR)14 cluster. The Au20 core of the Au30(SR)18 cluster can be viewed as a SAN of two Au6 superatoms and four Au4 superatoms. The Au14 core of Au30S2(SR)18 can be regarded as a SAN of two pairs of two vertex-sharing Au4 superatoms. Meanwhile, the Au14 core is an 8e-superatom with 1S21P6 configuration. Our work may aid understanding and give new insights into the chemical synthesis of thiolate-protected Au clusters.Density functional theory calculations have been performed to study the experimentally synthesized Au30S(SR)18 and two related Au30(SR)18 and Au30S2(SR)18 clusters. The patterns of thiolate ligands on the gold cores for the three thiolate-protected Au30 nanoclusters are on the basis of the ``divide and protect'' concept. A novel extended protecting motif with u3-S, S(Au2(SR)2)2AuSR, is discovered, which is termed the tridentate protecting motif. The Au cores of Au30S(SR)18, Au30(SR)18 and Au30S2(SR)18 clusters are Au17, Au20 and Au14, respectively. The superatom-network (SAN) model and the superatom complex (SAC) model are used to explain the chemical bonding patterns, which are verified by chemical bonding analysis based on the adaptive natural density partitioning (AdNDP) method and aromatic analysis on the basis of the nucleus-independent chemical shift (NICS) method. The Au17 core of the Au30S(SR)18 cluster can be viewed as a SAN of one Au6 superatom and four Au4 superatoms. The shape of the Au6 core is identical to that revealed in the recently synthesized Au18(SR)14 cluster. The Au20 core of the Au30(SR)18 cluster can be viewed as a SAN of two Au6 superatoms and four Au4 superatoms. The Au14 core of Au30S2(SR)18 can be regarded as a SAN of two pairs of two vertex-sharing Au4 superatoms. Meanwhile, the Au14 core is an 8e-superatom with 1S21P6 configuration. Our work may aid understanding and give new insights into the chemical synthesis of thiolate-protected Au clusters. Electronic supplementary information (ESI) available: The AdNDP localized natural bonding orbitals of the valence shells of the Au30S(SH)18 cluster. IR spectra, absorption spectra and coordinates of Au30S(SCH3)18, Au30(SCH3)18 and Au30S2(SCH3)18 clusters. See DOI: 10.1039/c5nr05020k

Self-Assembly of Trimer Colloids: Effect of Shape and Interaction Range†

PubMed Central

Hatch, Harold W.; Yang, Seung-Yeob; Mittal, Jeetain; Shen, Vincent K.

2016-01-01

Trimers with one attractive bead and two repulsive beads, similar to recently synthesized trimer patchy colloids, were simulated with flat-histogram Monte Carlo methods to obtain the stable self-assembled structures for different shapes and interaction potentials. Extended corresponding states principle was successfully applied to self-assembling systems in order to approximately collapse the results for models with the same shape, but different interaction range. This helps us directly compare simulation results with previous experiment, and good agreement was found between the two. In addition, a variety of self-assembled structures were observed by varying the trimer geometry, including spherical clusters, elongated clusters, monolayers, and spherical shells. In conclusion, our results help to compare simulations and experiments, via extended corresponding states, and we predict the formation of self-assembled structures for trimer shapes that have not been experimentally synthesized. PMID:27087490

Theoretical study of structure, bonding, and electronic behavior of novel sandwich compounds M₃(C6R6)₂ (M = Ni, Pd, Pt; R = H, F).

PubMed

Zhou, Ke

2012-10-01

The correlations between the structural and electronic properties of the monolayer clusters M₃ (where M = Ni, Pd, Pt) and the sandwich complexes M₃(C₆R₆)₂ (where M = Ni, Pd, Pt; R = H, F) were studied by performing quantum-chemical calculations. All of the sandwich complexes are strongly donating and backdonating metal-ligand bonding structures. The influence of the ligand as well as significant variations in the M-C, M-M, and C-C bond lengths and binding energies were examined to obtain a qualitative and quantitative picture of the intramolecular interactions in C₆R₆-M₃. Our theoretical investigations show that the binding energies of these sandwich complexes gradually decrease from Ni to Pt as well as from H to F, which can be explained via the frontier orbitals of the clusters M₃ and C₆R₆.

Low rank factorization of the Coulomb integrals for periodic coupled cluster theory.

PubMed

Hummel, Felix; Tsatsoulis, Theodoros; Grüneis, Andreas

2017-03-28

We study a tensor hypercontraction decomposition of the Coulomb integrals of periodic systems where the integrals are factorized into a contraction of six matrices of which only two are distinct. We find that the Coulomb integrals can be well approximated in this form already with small matrices compared to the number of real space grid points. The cost of computing the matrices scales as O(N 4 ) using a regularized form of the alternating least squares algorithm. The studied factorization of the Coulomb integrals can be exploited to reduce the scaling of the computational cost of expensive tensor contractions appearing in the amplitude equations of coupled cluster methods with respect to system size. We apply the developed methodologies to calculate the adsorption energy of a single water molecule on a hexagonal boron nitride monolayer in a plane wave basis set and periodic boundary conditions.

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Methanethiol chemistry on TiO 2-supported Ni clusters

NASA Astrophysics Data System (ADS)

Ozturk, O.; Park, J. B.; Black, T. J.; Rodriguez, J. A.; Hrbek, J.; Chen, D. A.

2008-10-01

The thermal decomposition of methanethiol on Ni clusters grown on TiO 2(1 1 0) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). On all of the Ni surfaces investigated, methane and hydrogen were observed as gaseous products in the TPD experiments, and the only sulfur-containing species that desorbed from the surface was methanethiol itself at low temperatures. The two pathways for methanethiol reaction were hydrodesulfurization to produce methane and nonselective decomposition, which leaves atomic carbon and sulfur on the surface. From high resolution XPS studies, methyl thiolate was identified as the surface intermediate for reaction on TiO 2 and on all of the Ni surfaces investigated, similar to what is observed on single-crystal Ni surfaces. However, the binding sites for methyl thiolate on the 1 ML (monolayer) Ni clusters were different from those on the Ni clusters at coverages of 2.5 ML and higher, based on the S(2p) binding energies for methyl thiolate. No distinct changes in activity or selectivity were observed for the smaller Ni clusters grown at low coverage compared to the more film-like Ni surfaces other than what could be accounted for by changes in total surface area. Interactions between the Ni clusters and the TiO 2 support had two main effects on chemical activity. First, carbon was oxidized by oxygen from the TiO 2 lattice to produce CO at temperatures above 800 K. Second, annealing induced encapsulation of the Ni clusters by reduced TiO x and chemisorbed oxygen. At 800 K, the Ni clusters were totally encapsulated, resulting in a complete loss of methanethiol activity; partial encapsulation at 700 K caused a smaller decrease in activity accompanied by increased oxidation of carbon by lattice oxygen.

Clustering and phase behaviour of attractive active particles with hydrodynamics.

PubMed

Navarro, Ricard Matas; Fielding, Suzanne M

2015-10-14

We simulate clustering, phase separation and hexatic ordering in a monolayered suspension of active squirming disks subject to an attractive Lennard-Jones-like pairwise interaction potential, taking hydrodynamic interactions between the particles fully into account. By comparing the hydrodynamic case with counterpart simulations for passive and active Brownian particles, we elucidate the relative roles of self-propulsion, interparticle attraction, and hydrodynamic interactions in determining clustering and phase behaviour. Even in the presence of an attractive potential, we find that hydrodynamic interactions strongly suppress the motility induced phase separation that might a priori have been expected in a highly active suspension. Instead, we find only a weak tendency for the particles to form stringlike clusters in this regime. At lower activities we demonstrate phase behaviour that is broadly equivalent to that of the counterpart passive system at low temperatures, characterized by regimes of gas-liquid, gas-solid and liquid-solid phase coexistence. In this way, we suggest that a dimensionless quantity representing the level of activity relative to the strength of attraction plays the role of something like an effective non-equilibrium temperature, counterpart to the (dimensionless) true thermodynamic temperature in the passive system. However there are also some important differences from the equilibrium case, most notably with regards the degree of hexatic ordering, which we discuss carefully.

Protected Designation of Origin (PDO), Protected Geographical Indication (PGI) and Traditional Speciality Guaranteed (TSG): A bibiliometric analysis.

PubMed

Dias, Claudia; Mendes, Luís

2018-01-01

Despite the importance of the literature on food quality labels in the European Union (PDO, PGI and TSG), our search did not find any review joining the various research topics on this subject. This study aims therefore to consolidate the state of academic research in this field, and so the methodological option was to elaborate a bibliometric analysis resorting to the term co-occurrence technique. Analysis was made of 501 articles on the ISI Web of Science database, covering publications up to 2016. The results of the bibliometric analysis allowed identification of four clusters: "Protected Geographical Indication", "Certification of Olive Oil and Cultivars", "Certification of Cheese and Milk" and "Certification and Chemical Composition". Unlike the other clusters, where the PDO label predominates, the "Protected Geographical Indication" cluster covers the study of PGI products, highlighting analysis of consumer behaviour in relation to this type of product. The focus of studies in the "Certification of Olive Oil and Cultivars" cluster and the "Certification of Cheese and Milk" cluster is the development of authentication methods for certified traditional products. In the "Certification and Chemical Composition" cluster, standing out is analysis of the profiles of fatty acids present in this type of product. Copyright © 2017 Elsevier Ltd. All rights reserved.

Protection of microelectronic devices during packaging

DOEpatents

Peterson, Kenneth A.; Conley, William R.

2002-01-01

The present invention relates to a method of protecting a microelectronic device during device packaging, including the steps of applying a water-insoluble, protective coating to a sensitive area on the device; performing at least one packaging step; and then substantially removing the protective coating, preferably by dry plasma etching. The sensitive area can include a released MEMS element. The microelectronic device can be disposed on a wafer. The protective coating can be a vacuum vapor-deposited parylene polymer, silicon nitride, metal (e.g. aluminum or tungsten), a vapor deposited organic material, cynoacrylate, a carbon film, a self-assembled monolayered material, perfluoropolyether, hexamethyldisilazane, or perfluorodecanoic carboxylic acid, silicon dioxide, silicate glass, or combinations thereof. The present invention also relates to a method of packaging a microelectronic device, including: providing a microelectronic device having a sensitive area; applying a water-insoluble, protective coating to the sensitive area; providing a package; attaching the device to the package; electrically interconnecting the device to the package; and substantially removing the protective coating from the sensitive area.

Temporary coatings for protection of microelectronic devices during packaging

DOEpatents

Peterson, Kenneth A.; Conley, William R.

2005-01-18

The present invention relates to a method of protecting a microelectronic device during device packaging, including the steps of applying a water-insoluble, temporary protective coating to a sensitive area on the device; performing at least one packaging step; and then substantially removing the protective coating, preferably by dry plasma etching. The sensitive area can include a released MEMS element. The microelectronic device can be disposed on a wafer. The protective coating can be a vacuum vapor-deposited parylene polymer, silicon nitride, metal (e.g. aluminum or tungsten), a vapor deposited organic material, cynoacrylate, a carbon film, a self-assembled monolayered material, perfluoropolyether, hexamethyldisilazane, or perfluorodecanoic carboxylic acid, silicon dioxide, silicate glass, or combinations thereof. The present invention also relates to a method of packaging a microelectronic device, including: providing a microelectronic device having a sensitive area; applying a water-insoluble, protective coating to the sensitive area; providing a package; attaching the device to the package; electrically interconnecting the device to the package; and substantially removing the protective coating from the sensitive area.

Interface-Induced Zeeman-Protected Superconductivity in Ultrathin Crystalline Lead Films

NASA Astrophysics Data System (ADS)

Liu, Yi; Wang, Ziqiao; Zhang, Xuefeng; Liu, Chaofei; Liu, Yongjie; Zhou, Zhimou; Wang, Junfeng; Wang, Qingyan; Liu, Yanzhao; Xi, Chuanying; Tian, Mingliang; Liu, Haiwen; Feng, Ji; Xie, X. C.; Wang, Jian

2018-04-01

Two-dimensional (2D) superconducting systems are of great importance for exploring exotic quantum physics. The recent development of fabrication techniques has stimulated studies of high-quality single-crystalline 2D superconductors, where intrinsic properties give rise to unprecedented physical phenomena. Here, we report the observation of Zeeman-type spin-orbit interaction protected superconductivity (Zeeman-protected superconductivity) in 4-monolayer (ML) to 6-ML crystalline Pb films grown on striped incommensurate Pb layers on Si(111) substrates by molecular beam epitaxy. An anomalously large in-plane critical field far beyond the Pauli limit is detected, which can be attributed to the Zeeman-protected superconductivity due to the in-plane inversion symmetry breaking at the interface. Our work demonstrates that, in superconducting heterostructures, the interface can induce Zeeman-type spin-orbit interactions and modulate the superconductivity.

Interface Engineering to Create a Strong Spin Filter Contact to Silicon

NASA Astrophysics Data System (ADS)

Caspers, C.; Gloskovskii, A.; Gorgoi, M.; Besson, C.; Luysberg, M.; Rushchanskii, K. Z.; Ležaić, M.; Fadley, C. S.; Drube, W.; Müller, M.

2016-03-01

Integrating epitaxial and ferromagnetic Europium Oxide (EuO) directly on silicon is a perfect route to enrich silicon nanotechnology with spin filter functionality. To date, the inherent chemical reactivity between EuO and Si has prevented a heteroepitaxial integration without significant contaminations of the interface with Eu silicides and Si oxides. We present a solution to this long-standing problem by applying two complementary passivation techniques for the reactive EuO/Si interface: (i) an in situ hydrogen-Si (001) passivation and (ii) the application of oxygen-protective Eu monolayers-without using any additional buffer layers. By careful chemical depth profiling of the oxide-semiconductor interface via hard x-ray photoemission spectroscopy, we show how to systematically minimize both Eu silicide and Si oxide formation to the sub-monolayer regime-and how to ultimately interface-engineer chemically clean, heteroepitaxial and ferromagnetic EuO/Si (001) in order to create a strong spin filter contact to silicon.

Preservation of York Minster historic limestone by hydrophobic surface coatings.

PubMed

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

2012-01-01

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

Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

PubMed

Devi, J Meena

2017-06-01

The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

Self-assemblies of luminescent rare earth compounds in capsules and multilayers.

PubMed

Zhang, Renjie; Shang, Juanjuan; Xin, Jing; Xie, Beibei; Li, Ya; Möhwald, Helmuth

2014-05-01

This review addresses luminescent rare earth compounds assembled in microcapsules as well as in planar films fabricated by the layer-by-layer (LbL) technique, the Langmuir-Blodgett (LB) method and in self-assembled monolayers. Chemical precipitation, electrostatic, van der Waals interactions and covalent bonds are involved in the assembly of these compounds. Self-organized ring patterns of rare earth complexes in Langmuir monolayers and on planar surfaces with stripe patterns, as well as fluorescence enhancement due to donor-acceptor pairs, microcavities, enrichment of rare earth compounds, and shell protection against water are described. Recent information on the tuning of luminescence intensity and multicolors by the excitation wavelength and the ratio of rare earth ions, respectively, are also reviewed. Potential applications of luminescent rare earth complex assemblies serving as biological probes, temperature and gas sensors are pointed out. Copyright © 2014 Elsevier B.V. All rights reserved.

Shallow Heavily Doped n++ Germanium by Organo-Antimony Monolayer Doping.

PubMed

Alphazan, Thibault; Díaz Álvarez, Adrian; Martin, François; Grampeix, Helen; Enyedi, Virginie; Martinez, Eugénie; Rochat, Névine; Veillerot, Marc; Dewitte, Marc; Nys, Jean-Philippe; Berthe, Maxime; Stiévenard, Didier; Thieuleux, Chloé; Grandidier, Bruno

2017-06-14

Functionalization of Ge surfaces with the aim of incorporating specific dopant atoms to form high-quality junctions is of particular importance for the development of solid-state devices. In this study, we report the shallow doping of Ge wafers with a monolayer doping strategy that is based on the controlled grafting of Sb precursors and the subsequent diffusion of Sb into the wafer upon annealing. We also highlight the key role of citric acid in passivating the surface before its reaction with the Sb precursors and the benefit of a protective SiO 2 overlayer that enables an efficient incorporation of Sb dopants with a concentration higher than 10 20 cm -3 . Microscopic four-point probe measurements and photoconductivity experiments show the full electrical activation of the Sb dopants, giving rise to the formation of an n++ Sb-doped layer and an enhanced local field-effect passivation at the surface of the Ge wafer.

Preservation of York Minster historic limestone by hydrophobic surface coatings

NASA Astrophysics Data System (ADS)

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

2012-11-01

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

Synergistic effects of Candida and Escherichia coli on gut barrier function.

PubMed

Diebel, L N; Liberati, D M; Diglio, C A; Dulchavsky, S A; Brown, W J

1999-12-01

Disruption of the indigenous gut microflora with overgrowth of gram-negative bacteria and Candida species is common in the critically ill patient. These organisms readily translocate in vitro, which may cause septic complications and organ failure. A synergistic effect between Escherichia coli and C. albicans in polymicrobial infections has been demonstrated. An interaction between these organisms at the mucosal barrier is unknown. Ca(CO2) monolayers were grown to confluence in a two compartment culture system. E. coli and C. albicans or E. coli alone were added to the apical chambers. Secretory immunoglobulin A was added to half of the apical chambers as well. Cell cultures were incubated for a total of 240 minutes. Basal media were sampled at timed intervals for quantitative culture. Monolayer integrity was confirmed by serial measurement of transepithelial electrical resistance. Secretory immunoglobulin A decreased bacterial translocation across Ca(CO2) monolayers challenged with E. coli alone. Transepithelial passage of E. coli was significantly increased by coculture of bacteria with C. albicans. Augmentation of bacterial translocation by Candida occurred even in the presence of secretory immunoglobulin A. Candida colonization of the GI tract may impair mucosal barrier defense against gram-negative bacteria. The clinical role of gut antifungal prophylaxis in protecting against gut derived gram-negative sepsis is speculative.

Electronic structure and optical properties of the thiolate-protected Au28(SMe)20 cluster.

PubMed

Knoppe, Stefan; Malola, Sami; Lehtovaara, Lauri; Bürgi, Thomas; Häkkinen, Hannu

2013-10-10

The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: p-tert-butylbenzenethiolate) is analyzed with (time-dependent) density functional theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au14(6+) core and the ligand-protected cluster were analyzed, and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and circular dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.

Adsorption and dynamics of Si atoms at the monolayer Pb/Si(111) surface

NASA Astrophysics Data System (ADS)

Kumar, Rakesh; Fang, Chuang-Kai; Lee, Chih-Hao; Hwang, Ing-Shouh

2017-06-01

In this work, we studied the adsorption behavior of deposited Si atoms along with their diffusion and other dynamic processes on a Pb monolayer-covered Si(111) surface from 125 to 230 K using a variable-temperature scanning tunneling microscope. The Pb-covered Si(111) surface forms a low-symmetry rowlike (√{7 }×√{3 } ) structure in this temperature range and the Si atoms bind favorably to two specific on-top sites (T1 A and T1 B) on the trimer row after deposition at the sample temperature of ˜125 K . The Si atoms were immobile at low temperatures and started to switch between the two neighboring T1 A and T1 B sites within the same trimer when the temperature was raised to ˜150 K . When the temperature was raised above ˜160 K , the adsorbed Si atoms could hop to other trimers along the same trimer row. Below ˜170 K , short hops to adjacent trimers dominated, but long hops dominated at temperatures above ˜170 K . The activation energy and prefactor for the Si atoms diffusion were derived through analysis of continuous-time imaging at temperatures from 160 to 174 K. In addition, irreversible aggregation of single Si atoms into Si clusters started to occur at the phase boundaries or defective sites at temperatures above ˜170 K . At temperature above ˜180 K , nearly all Si atoms aggregated into clusters, which may have important implications for the atomic mechanism of epitaxial growth of Si on the Pb-covered Si(111) surface. In addition, our study provides strong evidence for breaking in the mirror symmetry in the (√{7 }×√{3 } )-Pb structure, which has implications for the atomic model of this controversial structure.

Charge retention of soft-landed phosphotungstate Keggin anions on self-assembled monolayers

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

Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Andersen, Amity

Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, PW12O403- (WPOM3-) and PW12O402- (WPOM2-), were soft-landed onto different self-assembled monolayer (SAM) surfaces and examined using in situ infrared reflection absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. Partial retention of the 3- charge was observed when WPOM3- was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM3- and WPOM2- were deposited ontomore » a hydrophilic alkylthiol SAM terminated with cationic NH3+ functional groups (NH3+SAM). We found that during the course of the soft landing of WPOM3-, the relative abundance of WPOM3- on FSAM decreased while that of WPOM2- increased. We propose that the higher stability of immobilized WPOM2- in comparison with WPOM3- makes it the preferred charge state of WPOM on both the FSAM and NH3+SAM. We also observe weaker binding of WPOM anions to SAMs in comparison with phosphomolybdate ions (MoPOM) reported previously (J. Phys. Chem. C 2014, 118, 27611–27622). The weaker binding of WPOM to SAMs is attributed to the lower reactivity of WPOM reported in the literature. This study demonstrates that both the charge retention and the reactivity of deposited anionic POM clusters on surfaces are determined by the type of addenda metal atoms in the cluster.« less

Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

PubMed Central

Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

2012-01-01

Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

NASA Astrophysics Data System (ADS)

Rhinow, Daniel; Hampp, Norbert A.

2012-06-01

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).

Toward high value sensing: monolayer-protected metal nanoparticles in multivariable gas and vapor sensors.

PubMed

Potyrailo, Radislav A

2017-08-29

For detection of gases and vapors in complex backgrounds, "classic" analytical instruments are an unavoidable alternative to existing sensors. Recently a new generation of sensors, known as multivariable sensors, emerged with a fundamentally different perspective for sensing to eliminate limitations of existing sensors. In multivariable sensors, a sensing material is designed to have diverse responses to different gases and vapors and is coupled to a multivariable transducer that provides independent outputs to recognize these diverse responses. Data analytics tools provide rejection of interferences and multi-analyte quantitation. This review critically analyses advances of multivariable sensors based on ligand-functionalized metal nanoparticles also known as monolayer-protected nanoparticles (MPNs). These MPN sensing materials distinctively stand out from other sensing materials for multivariable sensors due to their diversity of gas- and vapor-response mechanisms as provided by organic and biological ligands, applicability of these sensing materials for broad classes of gas-phase compounds such as condensable vapors and non-condensable gases, and for several principles of signal transduction in multivariable sensors that result in non-resonant and resonant electrical sensors as well as material- and structure-based photonic sensors. Such features should allow MPN multivariable sensors to be an attractive high value addition to existing analytical instrumentation.

Unexpected Giant-Gap Quantum Spin Hall Insulator in Chemically Decorated Plumbene Monolayer

PubMed Central

Zhao, Hui; Zhang, Chang-wen; Ji, Wei-xiao; Zhang, Run-wu; Li, Sheng-shi; Yan, Shi-shen; Zhang, Bao-min; Li, Ping; Wang, Pei-ji

2016-01-01

Quantum spin Hall (QSH) effect of two-dimensional (2D) materials features edge states that are topologically protected from backscattering by time-reversal symmetry. However, the major obstacles to the application for QSH effect are the lack of suitable QSH insulators with a large bulk gap. Here, we predict a novel class of 2D QSH insulators in X-decorated plumbene monolayers (PbX; X = H, F, Cl, Br, I) with extraordinarily giant bulk gaps from 1.03 eV to a record value of 1.34 eV. The topological characteristic of PbX mainly originates from s-px,y band inversion related to the lattice symmetry, while the effect of spin-orbital coupling (SOC) is only to open up a giant gap. Their QSH states are identified by nontrivial topological invariant Z2 = 1, as well as a single pair of topologically protected helical edge states locating inside the bulk gap. Noticeably, the QSH gaps of PbX are tunable and robust via external strain. We also propose high-dielectric-constant BN as an ideal substrate for the experimental realization of PbX, maintaining its nontrivial topology. These novel QSH insulators with giant gaps are a promising platform to enrich topological phenomena and expand potential applications at high temperature. PMID:26833133

Optimization of flexible substrate by gradient elastic modulus design for performance improvement of flexible electronic devices

NASA Astrophysics Data System (ADS)

Xia, Minggang; Liang, Chunping; Hu, Ruixue; Cheng, Zhaofang; Liu, Shiru; Zhang, Shengli

2018-05-01

It is imperative and highly desirable to buffer the stress in flexible electronic devices. In this study, we designed and fabricated lamellate poly(dimethylsiloxane) (PDMS) samples with gradient elastic moduli, motivated by the protection of the pomelo pulp by its skin, followed by the measurements of their elastic moduli. We demonstrated that the electrical and fatigue performances of a Ag-nanowire thin film device on the PDMS substrate with a gradient elastic modulus are significantly better than those of a device on a substrate with a monolayer PDMS. This study provides a robust scheme to effectively protect flexible electronic devices.

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

Löytynoja, T., E-mail: tuomas.loytynoja@oulu.fi; Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, SE-106 91 Stockholm; Li, X.

We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process canmore » be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM–CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.« less

Hydrogel scaffolds promote neural gene expression and structural reorganization in human astrocyte cultures.

PubMed

Knight, V Bleu; Serrano, Elba E

2017-01-01

Biomaterial scaffolds have the potential to enhance neuronal development and regeneration. Understanding the genetic responses of astrocytes and neurons to biomaterials could facilitate the development of synthetic environments that enable the specification of neural tissue organization with engineered scaffolds. In this study, we used high throughput transcriptomic and imaging methods to determine the impact of a hydrogel, PuraMatrix™, on human glial cells in vitro . Parallel studies were undertaken with cells grown in a monolayer environment on tissue culture polystyrene. When the Normal Human Astrocyte (NHA) cell line is grown in a hydrogel matrix environment, the glial cells adopt a structural organization that resembles that of neuronal-glial cocultures, where neurons form clusters that are distinct from the surrounding glia. Statistical analysis of next generation RNA sequencing data uncovered a set of genes that are differentially expressed in the monolayer and matrix hydrogel environments. Functional analysis demonstrated that hydrogel-upregulated genes can be grouped into three broad categories: neuronal differentiation and/or neural plasticity, response to neural insult, and sensory perception. Our results demonstrate that hydrogel biomaterials have the potential to transform human glial cell identity, and may have applications in the repair of damaged brain tissue.

Beyond the Young-Laplace model for cluster growth during dewetting of thin films: effective coarsening exponents and the role of long range dewetting interactions.

PubMed

Constantinescu, Adi; Golubović, Leonardo; Levandovsky, Artem

2013-09-01

Long range dewetting forces acting across thin films, such as the fundamental van der Waals interactions, may drive the formation of large clusters (tall multilayer islands) and pits, observed in thin films of diverse materials such as polymers, liquid crystals, and metals. In this study we further develop the methodology of the nonequilibrium statistical mechanics of thin films coarsening within continuum interface dynamics model incorporating long range dewetting interactions. The theoretical test bench model considered here is a generalization of the classical Mullins model for the dynamics of solid film surfaces. By analytic arguments and simulations of the model, we study the coarsening growth laws of clusters formed in thin films due to the dewetting interactions. The ultimate cluster growth scaling laws at long times are strongly universal: Short and long range dewetting interactions yield the same coarsening exponents. However, long range dewetting interactions, such as the van der Waals forces, introduce a distinct long lasting early time scaling behavior characterized by a slow growth of the cluster height/lateral size aspect ratio (i.e., a time-dependent Young angle) and by effective coarsening exponents that depend on cluster size. In this study, we develop a theory capable of analytically calculating these effective size-dependent coarsening exponents characterizing the cluster growth in the early time regime. Such a pronounced early time scaling behavior has been indeed seen in experiments; however, its physical origin has remained elusive to this date. Our theory attributes these observed phenomena to ubiquitous long range dewetting interactions acting across thin solid and liquid films. Our results are also applicable to cluster growth in initially very thin fluid films, formed by depositing a few monolayers or by a submonolayer deposition. Under this condition, the dominant coarsening mechanism is diffusive intercluster mass transport while the cluster coalescence plays a minor role, both in solid and in fluid films.

Stabilizing ultrasmall Au clusters for enhanced photoredox catalysis.

PubMed

Weng, Bo; Lu, Kang-Qiang; Tang, Zichao; Chen, Hao Ming; Xu, Yi-Jun

2018-04-18

Recently, loading ligand-protected gold (Au) clusters as visible light photosensitizers onto various supports for photoredox catalysis has attracted considerable attention. However, the efficient control of long-term photostability of Au clusters on the metal-support interface remains challenging. Herein, we report a simple and efficient method for enhancing the photostability of glutathione-protected Au clusters (Au GSH clusters) loaded on the surface of SiO 2 sphere by utilizing multifunctional branched poly-ethylenimine (BPEI) as a surface charge modifying, reducing and stabilizing agent. The sequential coating of thickness controlled TiO 2 shells can further significantly improve the photocatalytic efficiency, while such structurally designed core-shell SiO 2 -Au GSH clusters-BPEI@TiO 2 composites maintain high photostability during longtime light illumination conditions. This joint strategy via interfacial modification and composition engineering provides a facile guideline for stabilizing ultrasmall Au clusters and rational design of Au clusters-based composites with improved activity toward targeting applications in photoredox catalysis.

Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

PubMed

Yao, Hiroshi; Iwatsu, Mana

2016-04-05

Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au 30 (SR) 18

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

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar

Here we investigate via first-principles simulations the optical absorption spectra of three different Au30(SR)18 monolayer-protected clusters (MPC): Au30(StBu)18, which is known in the literature and whose crystal structure is available, and two species – Au30(SPh)18 and Au30(SPh-pNO2)18 – which have been designed by replacing the tert-butyl organic residues with aromatic ones so as to investigate the effects of ligand replacement on the optical response of Au nanomolecules. In analogy with previously studied but rather different Au23(SR)16- anionic species, a substantial ligand-enhancement of the absorption intensity in the optical region is obtained for the Au30(SPhpNO2)18 neutral MPC. This demonstrates that usingmore » conjugated aromatic ligands with properly chosen electron withdrawal substituents and exhibiting steric hindrance so as to also achieve charge decompression at the surface is a general approach to enhance MPC photo-absorption intensity in the optical region. Moreover, the ligand-enhancement phenomenon is subjected to a detailed analysis based on fragment projection of electronic excited states and on induced transition densities, leading to a better understanding of its physical origin, thus opening avenues to its more precise control and exploitation.« less

Sulfur-vacancy-dependent geometric and electronic structure of bismuth adsorbed on Mo S2

NASA Astrophysics Data System (ADS)

Park, Youngsin; Li, Nannan; Lee, Geunsik; Kim, Kwang S.; Kim, Ki-Jeong; Hong, Soon Cheol; Han, Sang Wook

2018-03-01

Through Bi deposition on the single-crystalline Mo S2 surface, we find that the density of the sulfur vacancy is a critical parameter for the growth of the crystalline Bi overlayer or cluster at room temperature. Also, the Mo S2 band structure is significantly modified near Γ due to the orbital hybridization with an adsorbed Bi monolayer. Our experimental observations and analysis in combination with density functional theory calculation suggest the importance of controlling the sulfur vacancy concentration in realizing an exotic quantum phase based on the van der Waals interface of Bi and Mo S2 .

Characterizing the mechanics of cultured cell monolayers

PubMed Central

Peter, Loic; Bellis, Julien; Baum, Buzz; Kabla, Alexandre J.; Charras, Guillaume T.

2012-01-01

One-cell-thick monolayers are the simplest tissues in multicellular organisms, yet they fulfill critical roles in development and normal physiology. In early development, embryonic morphogenesis results largely from monolayer rearrangement and deformation due to internally generated forces. Later, monolayers act as physical barriers separating the internal environment from the exterior and must withstand externally applied forces. Though resisting and generating mechanical forces is an essential part of monolayer function, simple experimental methods to characterize monolayer mechanical properties are lacking. Here, we describe a system for tensile testing of freely suspended cultured monolayers that enables the examination of their mechanical behavior at multi-, uni-, and subcellular scales. Using this system, we provide measurements of monolayer elasticity and show that this is two orders of magnitude larger than the elasticity of their isolated cellular components. Monolayers could withstand more than a doubling in length before failing through rupture of intercellular junctions. Measurement of stress at fracture enabled a first estimation of the average force needed to separate cells within truly mature monolayers, approximately ninefold larger than measured in pairs of isolated cells. As in single cells, monolayer mechanical properties were strongly dependent on the integrity of the actin cytoskeleton, myosin, and intercellular adhesions interfacing adjacent cells. High magnification imaging revealed that keratin filaments became progressively stretched during extension, suggesting they participate in monolayer mechanics. This multiscale study of monolayer response to deformation enabled by our device provides the first quantitative investigation of the link between monolayer biology and mechanics. PMID:22991459

Mapping Health Data: Improved Privacy Protection With Donut Method Geomasking

PubMed Central

Hampton, Kristen H.; Fitch, Molly K.; Allshouse, William B.; Doherty, Irene A.; Gesink, Dionne C.; Leone, Peter A.; Serre, Marc L.; Miller, William C.

2010-01-01

A major challenge in mapping health data is protecting patient privacy while maintaining the spatial resolution necessary for spatial surveillance and outbreak identification. A new adaptive geomasking technique, referred to as the donut method, extends current methods of random displacement by ensuring a user-defined minimum level of geoprivacy. In donut method geomasking, each geocoded address is relocated in a random direction by at least a minimum distance, but less than a maximum distance. The authors compared the donut method with current methods of random perturbation and aggregation regarding measures of privacy protection and cluster detection performance by masking multiple disease field simulations under a range of parameters. Both the donut method and random perturbation performed better than aggregation in cluster detection measures. The performance of the donut method in geoprivacy measures was at least 42.7% higher and in cluster detection measures was less than 4.8% lower than that of random perturbation. Results show that the donut method provides a consistently higher level of privacy protection with a minimal decrease in cluster detection performance, especially in areas where the risk to individual geoprivacy is greatest. PMID:20817785

Mapping health data: improved privacy protection with donut method geomasking.

PubMed

Hampton, Kristen H; Fitch, Molly K; Allshouse, William B; Doherty, Irene A; Gesink, Dionne C; Leone, Peter A; Serre, Marc L; Miller, William C

2010-11-01

A major challenge in mapping health data is protecting patient privacy while maintaining the spatial resolution necessary for spatial surveillance and outbreak identification. A new adaptive geomasking technique, referred to as the donut method, extends current methods of random displacement by ensuring a user-defined minimum level of geoprivacy. In donut method geomasking, each geocoded address is relocated in a random direction by at least a minimum distance, but less than a maximum distance. The authors compared the donut method with current methods of random perturbation and aggregation regarding measures of privacy protection and cluster detection performance by masking multiple disease field simulations under a range of parameters. Both the donut method and random perturbation performed better than aggregation in cluster detection measures. The performance of the donut method in geoprivacy measures was at least 42.7% higher and in cluster detection measures was less than 4.8% lower than that of random perturbation. Results show that the donut method provides a consistently higher level of privacy protection with a minimal decrease in cluster detection performance, especially in areas where the risk to individual geoprivacy is greatest.

Optical imaging beyond the diffraction limit by SNEM: effects of AFM tip modifications with thiol monolayers on imaging quality.

PubMed

Cumurcu, Aysegul; Diaz, Jordi; Lindsay, Ian D; de Beer, Sissi; Duvigneau, Joost; Schön, Peter; Julius Vancso, G

2015-03-01

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast. Copyright © 2014 Elsevier B.V. All rights reserved.

Protection of scaffold protein Isu from degradation by the Lon protease Pim1 as a component of Fe-S cluster biogenesis regulation.

PubMed

Ciesielski, Szymon J; Schilke, Brenda; Marszalek, Jaroslaw; Craig, Elizabeth A

2016-04-01

Iron-sulfur (Fe-S) clusters, essential protein cofactors, are assembled on the mitochondrial scaffold protein Isu and then transferred to recipient proteins via a multistep process in which Isu interacts sequentially with multiple protein factors. This pathway is in part regulated posttranslationally by modulation of the degradation of Isu, whose abundance increases >10-fold upon perturbation of the biogenesis process. We tested a model in which direct interaction with protein partners protects Isu from degradation by the mitochondrial Lon-type protease. Using purified components, we demonstrated that Isu is indeed a substrate of the Lon-type protease and that it is protected from degradation by Nfs1, the sulfur donor for Fe-S cluster assembly, as well as by Jac1, the J-protein Hsp70 cochaperone that functions in cluster transfer from Isu. Nfs1 and Jac1 variants known to be defective in interaction with Isu were also defective in protecting Isu from degradation. Furthermore, overproduction of Jac1 protected Isu from degradation in vivo, as did Nfs1. Taken together, our results lead to a model of dynamic interplay between a protease and protein factors throughout the Fe-S cluster assembly and transfer process, leading to up-regulation of Isu levels under conditions when Fe-S cluster biogenesis does not meet cellular demands. © 2016 Ciesielski et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

Lower lattice thermal conductivity in SbAs than As or Sb monolayers: a first-principles study.

PubMed

Guo, San-Dong; Liu, Jiang-Tao

2017-12-06

Phonon transport in group-VA element (As, Sb and Bi) monolayer semiconductors has been widely investigated in theory, and, of them, monolayer Sb (antimonene) has recently been synthesized. In this work, phonon transport in monolayer SbAs is investigated with a combination of first-principles calculations and the linearized phonon Boltzmann equation. It is found that the lattice thermal conductivity of monolayer SbAs is lower than those of both monolayer As and Sb, and the corresponding sheet thermal conductance is 28.8 W K -1 at room temperature. To understand the lower lattice thermal conductivity in monolayer SbAs than those in monolayer As and Sb, the group velocities and phonon lifetimes of monolayer As, SbAs and Sb are calculated. The calculated results show that the group velocities of monolayer SbAs are between those of monolayer As and Sb, but that the phonon lifetimes of SbAs are smaller than those of both monolayer As and Sb. Hence, the low lattice thermal conductivity in monolayer SbAs is attributed to very small phonon lifetimes. Unexpectedly, the ZA branch has very little contribution to the total thermal conductivity, only 2.4%, which is obviously different from those of monolayer As and Sb with very large contributions. This can be explained by very small phonon lifetimes for the ZA branch of monolayer SbAs. The lower lattice thermal conductivity of monolayer SbAs compared to that of monolayer As or Sb can be understood by the alloying of As (Sb) with Sb (As), which should introduce phonon point defect scattering. We also consider the isotope and size effects on the lattice thermal conductivity. It is found that isotope scattering produces a neglectful effect, and the lattice thermal conductivity with a characteristic length smaller than 30 nm can reach a decrease of about 47%. These results may offer perspectives on tuning the lattice thermal conductivity by the mixture of multiple elements for applications of thermal management and thermoelectricity, and motivate further experimental efforts to synthesize monolayer SbAs.

Adhesion and growth inhibitory effect of chicken egg yolk antibody (IgY) on Salmonella enterica serovars Enteritidis and Typhimurium in vitro.

PubMed

Chalghoumi, Raja; Théwis, André; Beckers, Yves; Marcq, Christopher; Portetelle, Daniel; Schneider, Yves-Jacques

2009-06-01

The protective effects of powder preparation of egg yolk immunoglobulin Y (IgY), specific to Salmonella Enteritidis and Salmonella Typhimurium outer membrane proteins (OMP), against these two Salmonella sp. serovars were investigated in vitro in two different assays: adhesion-prevention and growth-inhibition. The adhesion-prevention assay was conducted using polarized monolayers of the human intestinal epithelial Caco-2 cell line. First, the conditions of Salmonella adherence to Caco-2 cells were optimized, and interferences of bacteria with the transepithelial electrical resistance (TER) of fully differentiated Caco-2 cell monolayers and the lactate dehydrogenase release upon exposure of the cells to Salmonella were evaluated. Both Salmonella sp. serovars were able to adhere to Caco-2 cells and decreased TER. Results from the adhesion-prevention assay demonstrated that specific IgY reduced the decrease in TER of the infected Caco-2 cell monolayers and blocked the Salmonella sp. adhesion in a concentration-dependent manner (p < 0.05). Nonspecific IgY also exhibited an inhibitory effect on these two parameters, but to a lesser extent than that of the specific IgY (p < 0.05). The protective effect of nonspecific IgY could be attributed to the low-density lipoprotein component of the water-soluble fraction of egg yolks that may not have been eliminated during ultrafiltration. The growth-inhibition assay revealed that specific IgY had an inhibitory effect on the bacterial growth, markedly during the late exponential phase, whereas nonspecific IgY failed to do so. Taken together, these results suggest that the in vitro growth inhibitory effect of specific IgY on Salmonella spp. resulted from the specific binding activity of these IgY to Salmonella sp. OMP. Passive immunization with Salmonella sp. OMP-specific IgY could thus be useful to prevent Salmonella colonization in broiler chickens and the subsequent carcass contamination during processing.

Efficient red luminescence from organic-soluble Au25 clusters by ligand structure modification

NASA Astrophysics Data System (ADS)

Mathew, Ammu; Varghese, Elizabeth; Choudhury, Susobhan; Pal, Samir Kumar; Pradeep, T.

2015-08-01

An efficient method to enhance visible luminescence in a visibly non-luminescent organic-soluble 4-(tert butyl)benzyl mercaptan (SBB)-stabilized Au25 cluster has been developed. This method relies mainly on enhancing the surface charge density on the cluster by creating an additional shell of thiolate on the cluster surface, which enhances visible luminescence. The viability of this method has been demonstrated by imparting red luminescence to various ligand-protected quantum clusters (QCs), observable to the naked eye. The bright red luminescent material derived from Au25SBB18 clusters was characterized using UV-vis and luminescence spectroscopy, TEM, SEM/EDS, XPS, TG, ESI and MALDI mass spectrometry, which collectively proposed an uncommon molecular formula of Au29SBB24S, suggested to be due to different stapler motifs protecting the Au25 core. The critical role of temperature on the emergence of luminescence in QCs has been studied. The restoration of the surface ligand shell on the Au25 cluster and subsequent physicochemical modification to the cluster were probed by various mass spectral and spectroscopic techniques. Our results provide fundamental insights into the ligand characteristics determining luminescence in QCs.An efficient method to enhance visible luminescence in a visibly non-luminescent organic-soluble 4-(tert butyl)benzyl mercaptan (SBB)-stabilized Au25 cluster has been developed. This method relies mainly on enhancing the surface charge density on the cluster by creating an additional shell of thiolate on the cluster surface, which enhances visible luminescence. The viability of this method has been demonstrated by imparting red luminescence to various ligand-protected quantum clusters (QCs), observable to the naked eye. The bright red luminescent material derived from Au25SBB18 clusters was characterized using UV-vis and luminescence spectroscopy, TEM, SEM/EDS, XPS, TG, ESI and MALDI mass spectrometry, which collectively proposed an uncommon molecular formula of Au29SBB24S, suggested to be due to different stapler motifs protecting the Au25 core. The critical role of temperature on the emergence of luminescence in QCs has been studied. The restoration of the surface ligand shell on the Au25 cluster and subsequent physicochemical modification to the cluster were probed by various mass spectral and spectroscopic techniques. Our results provide fundamental insights into the ligand characteristics determining luminescence in QCs. Electronic supplementary information (ESI) available: Additional data on characterization of red luminescent Au29 QC and comparison with parent Au25SBB18 are given. See DOI: 10.1039/c5nr03457d

Differential effects of human SP-A1 and SP-A2 variants on phospholipid monolayers containing surfactant protein B

PubMed Central

Wang, Guirong; Taneva, Svetla; Keough, Kevin M.W.; Floros, Joanna

2010-01-01

Summary Surfactant protein A (SP-A), the most abundant protein in the lung alveolar surface, has multiple activities, including surfactant-related functions. SP-A is required for the formation of tubular myelin and the lung surface film. The human SP-A locus consists of two functional SP-A genes, SP-A1 and SP-A2, with a number of alleles characterized for each gene. We have found that the human in vitro expressed variants, SP-A1 (6A2) and SP-A2 (1A0), and the coexpressed SP-A1/SP-A2 (6A2/1A0) protein have a differential influence on the organization of phospholipid monolayers containing surfactant protein B (SP-B). Lipid films containing SP-B and SP-A2 (1A0) showed surface features similar to those observed in lipid films with SP-B and native human SP-A. Fluorescence images revealed the presence of characteristic fluorescent probe-excluding clusters coexisting with the traditional lipid liquid-expanded and liquid-condensed phase. Images of the films containing SP-B and SP-A1 (6A2) showed different distribution of the proteins. The morphology of lipid films containing SP-B and the coexpressed SP-A1/SP-A2 (6A2/1A0) combined features of the individual films containing the SP-A1 or SP-A2 variant. The results indicate that human SP-A1 and SP-A2 variants exhibit differential effects on characteristics of phospholipid monolayers containing SP-B. This may differentially impact surface film activity. PMID:17678872

Diamondoid monolayers as electron emitters

DOEpatents

Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

2012-04-10

Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

Diamondoid monolayers as electron emitters

DOEpatents

Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

2013-10-29

Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

Monolayer coated aerogels and method of making

DOEpatents

Zemanian, Thomas Samuel [Richland, WA; Fryxell, Glen [Kennwick, WA; Ustyugov, Oleksiy A [Spokane, WA

2006-03-28

Aerogels having a monolayer coating are described. The aerogel and a monolayer forming precursor are provided in a supercritical fluid, whereupon the aerogel and the monolayer forming precursor are reacted in said supercritical fluid to form a covalent bond between the aerogel and the monolayer forming precursor. Suitable aerogels are ceramic oxides such as silica, alumina, aluminosilicate, and combinations thereof. Suitable monolayer forming precursors include alkyl silanes, chlorosilanes, boranes, chloroboranes, germanes, and combinations thereof. The method may also include providing a surface preparation agent such as water, or hydroetching an aerogel to enhance the coating of the monolayer.

Asymmetric or symmetric bilayer formation during oblique drop impact depends on rheological properties of saturated and unsaturated lipid monolayers.

PubMed

Vranceanu, Marcel; Terinte, Nicoleta; Nirschl, Hermann; Leneweit, Gero

2011-02-01

Bilayer structures are formed by approaching two liquid surfaces with phospholipid monolayers, which are brought into contact by oblique drop impact on a liquid surface. Asymmetric bilayers can be produced by the coupling of drop and target monolayers. In contrast, symmetric bilayers or multilayers are formed by collapse of the compressed target monolayer. We show that under all studied conditions bilayer/multilayer synthesis takes place. The experimental conditions for the synthesis of asymmetric or symmetric bilayers are described quantitatively in terms of the surface rheological (surface elasticity and dilational viscosity) and the hydrodynamical parameters (Weber number and impact angle). The composition and mechanical properties of the phospholipid monolayers strongly influences the patterns of drop impact and the bilayer/multilayer formation. Cholesterol stiffens unsaturated phospholipid monolayers and fluidifies saturated monolayers. All monolayers form asymmetric vesicle-like structures, which are stable in the aqueous medium. Additionally, unsaturated phospholipid monolayers without cholesterol form symmetric vesicles by folding parts of the target monolayer. Sufficient presence of cholesterol in unsaturated phospholipid monolayers inhibits the folding of the target monolayer and the subsequent formation of symmetric bilayers. The rheological properties of saturated and unsaturated phospholipid monolayers and their mixtures with cholesterol are discussed. Based on drop impact results it is shown that the state of a so far undefined region in the DPPC/cholesterol phase diagram is a fluid phase. Copyright © 2010 Elsevier Inc. All rights reserved.

Selectivity and Sensitivity of Ultrathin Monolayer Electrodes

NASA Astrophysics Data System (ADS)

Cheng, Quan

The objective of this work is to build a molecular architecture on the electrode surface with a well-defined morphology and desirable electrochemical characteristics. The goal is accomplished by means of self-assembly of thioctic acid, a sulfur-terminated organic molecule with a short alkyl chain and a hydrophilic carboxylic headgroup, on a gold electrode. Characterization of the monolayer structure and the electrochemical response of the monolayer electrodes is performed by means of capacitance measurements and voltammetry. Investigation of the capacitance of the self-assembled monolayers provides insight into the macroscopic permeability of the films and reveals that penetration of solvent/ions into the thioctic acid monolayer film occurs extensively. Voltammetric results demonstrate that permselectivity of the monolayer electrode can be obtained as a result of the induced electrostatic interactions between the monolayer interface and the electroactive species. Measurement of the voltammetric response of the redox probes at the monolayers as a function of the electrolyte concentration and composition is used to qualitatively analyze the effect of electrolyte on response. A model describing the role of the interfacial charge in the electrochemical response of the monolayers as a function of the solution composition and surface smoothness is proposed. A strategy is developed to further explore the applications of the monolayer electrodes to control the electrochemical response of the biological molecules such as catecholamines. The ability to control the surface hydrophobicity of the monolayer electrodes through coadsorption of thioctic acid and hexanethiol, to display different electrochemical properties towards biological molecules is tested. The optimum conditions for detection of the biological molecules on the monolayer electrodes are discussed. In order to pursue selective analysis in microenvironments, the thioctic acid monolayer formed on the ultramicroelectrodes (UME) is investigated, demonstrating high permselectivity and high sensitivity of the monolayer modified UMEs. Because of the more effective mass transport to the UMEs, effects of electrolyte on the monolayer response can be characterized facilely. Amperometric pH sensing on the thioctic acid UMEs using a redox mediator is discussed. Finally, the thioctic acid monolayer microelectrode is applied to investigate direct electrochemistry of a redox protein, cytochrome c. A sketch for developing a biosensor via mediation effects using the monolayer assembly is proposed.

Miscibility of binary monolayers at the air-water interface and interaction of protein with immobilized monolayers by surface plasmon resonance technique.

PubMed

Wang, Yuchun; Du, Xuezhong

2006-07-04

The miscibility and stability of the binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA) at the air-water interface and the interaction of ferritin with the immobilized monolayers have been studied in detail using surface pressure-area isotherms and surface plasmon resonance technique, respectively. The surface pressure-area isotherms indicated that the binary monolayers of DPPC and DOMA at the air-water interface were miscible and more stable than the monolayers of the two individual components. The surface plasmon resonance studies indicated that ferritin binding to the immobilized monolayers was primarily driven by the electrostatic interaction and that the amount of adsorbed protein at saturation was closely related not only to the number of positive charges in the monolayers but also to the pattern of positive charges at a given mole fraction of DOMA. The protein adsorption kinetics was determined by the properties of the monolayers (i.e., the protein-monolayer interaction) and the structure of preadsorbed protein molecules (i.e., the protein-protein interaction).

Soft Landing of Mass-Selected Gold Clusters: Influence of Ion and Ligand on Charge Retention and Reactivity

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

Johnson, Grant E.; Laskin, Julia

Herein, we employ a combination of reduction synthesis in solution, soft landing of mass-selected precursor and product ions, and in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the influence of ion and the length of diphosphine ligands on the charge retention and reactivity of ligated gold clusters deposited onto self-assembled monolayer surfaces (SAMs). Product ions (Au10L42+, (10,4)2+, L = 1,3-bis(diphenyl-phosphino)propane, DPPP) were prepared through in-source collision induced dissociation (CID) and precursor ions [(8,4)2+, L = 1,6-bis(diphenylphosphino)hexane, DPPH] were synthesized in solution for comparison to (11,5)3+ precursor ions ligated with DPPP investigated previously (ACS Nano 2012, 6, 573 andmore » J. Phys. Chem. C. 2012, 116, 24977). Similar to (11,5)3+ precursor ions, the (10,4)2+ product ions are shown to retain charge on 1H,1H,2H,2H-perfluorodecanethiol monolayers (FSAMs). Additional abundant peaks at higher m/z indicative of reactivity are observed in the TOF-SIMS spectrum of (10,4)2+ product ions that are not seen for (11,5)3+ precursor ions. The abundance of (10,4)2+ on 16-mercaptohexadecanoic acid (COOH-SAMs) is demonstrated to be lower than on FSAMs, consistent with partial reduction of charge. The (10,4)2+ product ion on 1-dodecanethiol (HSAMs) exhibits peaks similar to those seen on the COOH-SAM. On the HSAM, higher m/z peaks indicative of reactivity are observed similar to those on the FSAM. The (8,4)2+ DPPH precursor ions are shown to retain charge on FSAMs similar to (11,5)3+ precursor ions prepared with DPPP. An additional peak corresponding to attachment of one gold atom to (8,4)2+ is observed at higher m/z for DPPH-ligated clusters. On the COOH-SAM, (8,4)2+ is less abundant than on the FSAM consistent with partial neutralization. The results indicate that although retention of charge by product ions generated by CID is similar to precursor ions their reactivity during analysis with SIMS is different resulting in the formation of peaks corresponding to reaction products. The length of the ligand exerts only a minor influence on the charge retention and reactivity of gold clusters. Based on the observed reactivity of (10,4)2+ it is anticipated that in-source CID will be increasingly applied for the preparation of a distribution of product ions, including undercoordinated and reactive species, for soft landing onto surfaces.« less

Protective effects of ψ taraxasterol 3-O-myristate and arnidiol 3-O-myristate isolated from Calendula officinalis on epithelial intestinal barrier.

PubMed

Dall'Acqua, Stefano; Catanzaro, Daniela; Cocetta, Veronica; Igl, Nadine; Ragazzi, Eugenio; Giron, Maria Cecilia; Cecconello, Laura; Montopoli, Monica

2016-03-01

The triterpene esters ᴪ taraxasterol-3-O-myristate (1) and arnidiol-3-O-myristate (2) were tested for their ability to protect epithelial intestinal barrier in an in vitro model. Their effects on ROS production and on trans-epithelial resistance were investigated on CaCo-2 cell monolayers both in basal and stress-induced conditions. Both compounds were able to modulate the stress damage induced by H2O2 and INFγ+TNFα, showing a potential use as model compounds for the study of new therapeutic agents for intestinal inflammations. Copyright © 2016 Elsevier B.V. All rights reserved.

Parallel fabrication of sub-50-nm uniformly sized nanoparticles by deposition through a patterned silicon nitride nanostencil.

PubMed

Yan, X-M; Contreras, A M; Koebel, M M; Liddle, J A; Somorjai, G A

2005-06-01

Using low-pressure chemical vapor deposition of silicon dioxide, we have reduced the size of 56-nm features in a silicon nitride membrane, called a stencil, down to 36 nm. Sub-50-nm uniformly sized nanoparticles are fabricated by electron-beam deposition of Pt through the stencil mask. A self-assembled monolayer (SAM) of tridecafluoro-1,1,2,2-tetrahydrooctyl-1-trichlorosilane was used to reduce Pt clogging of the nanosize holes during deposition as well as to protect the stencil during the postdeposition Pt removal. X-ray photoelectron spectroscopy shows that the SAM protects the stencil efficiently during this postdeposition removal of Pt.

Structure and dynamics of H2O vis-á-vis phenylalanine recognition at a DPPC lipid membrane via interfacial H-bond types: insights from polarized FT-IRRAS and ADMP simulations.

PubMed

Sarangi, Nirod Kumar; Ramesh, Nivarthi; Patnaik, Archita

2015-01-14

Preferential and enantioselective interactions of L-/D-Phenylalanine (L-Phe and D-Phe) and butoxycarbonyl-protected L-/D-Phenylalanine (LPA and DPA) as guest with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (L-DPPC) as host were tapped by using real time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Polarization-modulated FT-IRRAS of DPPC monolayers above the phenylalanine modified subphases depicted fine structure/conformation differences under considerations of controlled 2D surface pressure. Selective molecular recognition of D-enantiomer over L-enantiomer driven by the DPPC head group via H-bonding and electrostatic interactions was evident spectroscopically. Accordingly, binding constants (K) of 145, 346, 28, and 56 M(-1) for LPA, DPA, L-Phe, and D-Phe, respectively, were estimated. The real time FT-IRRAS water bands were strictly conformation sensitive. The effect of micro-solvation on the structure and stability of the 1:1 diastereomeric L-lipid⋯, LPA/DPA and L-lipid⋯, (L/D)-Phe adducts was investigated with the aid of Atom-centered Density Matrix Propagation (ADMP), a first principle quantum mechanical molecular dynamics approach. The phosphodiester fragment was the primary site of hydration where specific solvent interactions were simulated through single- and triple- "water-phosphate" interactions, as water cluster's "tetrahedral dice" to a "trimeric motif" transformation as a partial de-clusterization was evident. Under all the hydration patterns considered in both static and dynamic descriptions of density functional theory, L-lipid/D-amino acid enantiomer adducts continued to be stable structures while in dynamic systems, water rearranged without getting "squeezed-out" in the process of recognition. In spite of the challenging computational realm of this multiscale problem, the ADMP simulated molecular interactions complying with polarized vibrational spectroscopy unraveled a novel route to chiral recognition and interfacial water structure.

Structure and dynamics of H2O vis-á-vis phenylalanine recognition at a DPPC lipid membrane via interfacial H-bond types: Insights from polarized FT-IRRAS and ADMP simulations

NASA Astrophysics Data System (ADS)

Sarangi, Nirod Kumar; Ramesh, Nivarthi; Patnaik, Archita

2015-01-01

Preferential and enantioselective interactions of l-/d-Phenylalanine (l-Phe and d-Phe) and butoxycarbonyl-protected l-/d-Phenylalanine (LPA and DPA) as guest with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (l-DPPC) as host were tapped by using real time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Polarization-modulated FT-IRRAS of DPPC monolayers above the phenylalanine modified subphases depicted fine structure/conformation differences under considerations of controlled 2D surface pressure. Selective molecular recognition of d-enantiomer over l-enantiomer driven by the DPPC head group via H-bonding and electrostatic interactions was evident spectroscopically. Accordingly, binding constants (K) of 145, 346, 28, and 56 M-1 for LPA, DPA, l-Phe, and d-Phe, respectively, were estimated. The real time FT-IRRAS water bands were strictly conformation sensitive. The effect of micro-solvation on the structure and stability of the 1:1 diastereomeric l-lipid⋯, LPA/DPA and l-lipid⋯, (l/d)-Phe adducts was investigated with the aid of Atom-centered Density Matrix Propagation (ADMP), a first principle quantum mechanical molecular dynamics approach. The phosphodiester fragment was the primary site of hydration where specific solvent interactions were simulated through single- and triple- "water-phosphate" interactions, as water cluster's "tetrahedral dice" to a "trimeric motif" transformation as a partial de-clusterization was evident. Under all the hydration patterns considered in both static and dynamic descriptions of density functional theory, l-lipid/d-amino acid enantiomer adducts continued to be stable structures while in dynamic systems, water rearranged without getting "squeezed-out" in the process of recognition. In spite of the challenging computational realm of this multiscale problem, the ADMP simulated molecular interactions complying with polarized vibrational spectroscopy unraveled a novel route to chiral recognition and interfacial water structure.

Clustered Integrin Ligands as a Novel Approach for the Targeting of Non-Viral Vectors

NASA Astrophysics Data System (ADS)

Ng, Quinn Kwan Tai

Gene transfer or gene delivery is described as the process in which foreign DNA is introduced into cells. Over the years, gene delivery has gained the attention of many researchers and has been developed as powerful tools for use in biotechnology and medicine. With the completion of the Human Genome Project, such advances in technology allowed for the identification of diseases ranging from hereditary disorders to acquired ones (cancer) which were thought to be incurable. Gene therapy provides the means necessary to treat or eliminate genetic diseases from its origin, unlike traditional medicine which only treat symptoms. With ongoing clinical trials for gene therapy increasing, the greatest difficulty still lies in developing safe systems which can target cells of interest to provide efficient delivery. Nature, over millions of years of evolution, has provided an example of one of the most efficient delivery systems: viruses. Although the use of viruses for gene delivery has been well studied, the safety issues involving immunogenicity, insertional mutagenesis, high cost, and poor reproducibility has provided problems for their clinical application. From understanding viruses, we gain insight to designing new systems for non-viral gene delivery. One of these techniques utilized by adenoviruses is the clustering of ligands on its surface through the use of a protein called a penton base. Through the use of nanotechnology we can mimic this basic concept in non-viral gene delivery systems. This dissertation research is focused on developing and applying a novel system for displaying the integrin binding ligand (RGD) in a constrained manner to form a clustered integrin ligand binding platform to be used to enhance the targeting and efficiency of non-viral gene delivery vectors. Peptide mixed monolayer protected gold nanoparticles provides a suitable surface for ligand clustering. A relationship between the peptide ratios in the reaction solution used to form these ligand clusters compared to the reacted amounts on the surface of the particle was studied. This provided us the ability to control the size of the clusters formed and the spacing between the integrins for gold nanoparticles of various sizes. We then applied the clustered ligand binding system for targeting of DNA/PEI polyplexes and demonstrated that the use of RGD nanoclusters enhances gene transfer up to 35-fold which was dependent on the density of alphavbeta3 integrins on the cell surface. Cell integrin sensitivity was shown in which cells with higher alpha vbeta3 densities resulting in higher luciferase transgene expression. The targeting of RGD nanoclusters for DNA/PEI polyplexes was further shown in vivo using PET/CT technology which displayed improved targeting towards high level alphavbeta3 integrin expression (U87MG) tumors over medium level alphavbeta 3 integrin expression (HeLa). In addition to studying the clustered integrin binding system, the current non-viral vectors used suffer from stability and toxicity issues in vitro and in vivo. We have applied a new chemistry for synthesizing nanogels utilizing a Traut's reagent initiated Michael addition reaction for modification of diamine containing crosslikers which will allow for the development of stable and cell demanded release of oligonucleotides. We have shown bulk gels made were capable of encapsulating and holding DNA within the gel and were able to synthesize them into nanogels. The combined research shown here using clustered integrin ligands and a new type of nanogel synthesis provides an ideal system for gene delivery in the future.

Molecular-dynamics simulations of energetic C{sub 60} impacts on (2x1)-(100) silicon

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

Hu, Xiaoyuan; Albe, Karsten; Averback, Robert S.

2000-07-01

Single impacts of energetic C{sub 60} clusters on (2x1)-(100) silicon substrates are studied by molecular-dynamics simulations. The role of impact energies and internal cluster energy are investigated in detail. Six different energy regimes can be identified at the end of the ballistic phase: At thermal energies below 20 eV the fullerene cages undergo elastic deformation, while impinging on the surface, and are mostly chemisorpted on top of the (2x1)-dimer rows. Between 20 and 100 eV the cage structure is preserved after the collision, but the cluster comes to rest within a few monolayers of the silicon surface. At energies ofmore » 100-500 eV the cluster partially decomposes and small coherent carbon caps are embedded in the surface. At higher energies up to 1.5 keV complete decomposition of the fullerene cluster occurs and an amorphous zone is formed in the subsurface area. At energies greater than approximately 1.5 keV craters form and above 6 keV sputtering becomes significant. In all cases the substrate temperature is of minor influence on the final result, but the projectile temperature is important for impacts at lower energies (<1.5 keV). For high energy impacts the ballistics resemble that of single atom impacts. Nearly 1:1 stoichiometry is obtained for impact energies around 1 keV. These results reveal an interesting possibility for controlled implantation of C in Si at high local concentrations, which might allow the formation of silicon carbide. (c) 2000 American Institute of Physics.« less

Molecular dynamics investigations of liquid-vapor interaction and adsorption of formaldehyde, oxocarbons, and water in graphitic slit pores.

PubMed

Huang, Pei-Hsing; Hung, Shang-Chao; Huang, Ming-Yueh

2014-08-07

Formaldehyde exposure has been associated with several human cancers, including leukemia and nasopharyngeal carcinoma, motivating the present investigation on the microscopic adsorption behaviors of formaldehyde in multi-component-mixture-filled micropores. Molecular dynamics (MD) simulation was used to investigate the liquid-vapor interaction and adsorption of formaldehyde, oxocarbons, and water in graphitic slit pores. The effects of the slit width, system temperature, concentration, and the constituent ratio of the mixture on the diffusion and adsorption properties are studied. As a result of interactions between the components, the z-directional self-diffusivity (D(z)) in the mixture substantially decreased by about one order of magnitude as compared with that of pure (single-constituent) adsorbates. When the concentration exceeds a certain threshold, the D(z) values dramatically decrease due to over-saturation inducing barriers to diffusion. The binding energy between the adsorbate and graphite at the first adsorption monolayer is calculated to be 3.99, 2.01, 3.49, and 2.67 kcal mol(-1) for CO2, CO, CH2O, and H2O, respectively. These values agree well with those calculated using the density functional theory coupled cluster method and experimental results. A low solubility of CO2 in water and water preferring to react with CH2O, forming hydrated methanediol clusters, are observed. Because the cohesion in a hydrated methanediol cluster is much higher than the adhesion between clusters and the graphitic surface, the hydrated methanediol clusters were hydrophobic, exhibiting a large contact angle on graphite.

The nucleation and growth of uranium on the basal plane of graphite studied by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tench, R. J.

1992-11-01

For the first time, nanometer scale uranium clusters were created on the basal plane of highly oriented pyrolytic graphite by laser ablation under ultra-high vacuum conditions. The physical and chemical properties of these clusters were investigated by scanning tunneling microscopy (STM) as well as standard surface science techniques. Auger electron and X-ray photoelectron spectroscopies found the uranium deposit to be free of contamination and showed that no carbide had formed with the underlying graphite. Clusters with sizes ranging from 42 to 630 sq A were observed upon initial room temperature deposition. Surface diffusion of uranium was observed after annealing the substrate above 800 K, as evidenced by the decreased number density and the increased size of the clusters. Preferential depletion of clusters on terraces near step edges as a result of annealing was observed. The activation energy for diffusion deduced from these measurements was found to be 15 Kcal/mole. Novel formation of ordered uranium thin films was observed for coverages greater than two monolayers after annealing above 900 K. These ordered films displayed islands with hexagonally faceted edges rising in uniform step heights characteristic of the unit cell of the P-phase of uranium. In addition, atomic resolution STM images of these ordered films indicated the formation of the (beta)-phase of uranium. The chemical properties of these surfaces were investigated and it was shown that these uranium films had a reduced oxidation rate in air as compared to bulk metal and that STM imaging in air induced a polarity-dependent enhancement of the oxidation rate.

Preservation of York Minster historic limestone by hydrophobic surface coatings

PubMed Central

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

2012-01-01

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

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

PubMed Central

Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

2016-01-01

We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

Morphological Effects and Antioxidant Capacity of Solanum crispum (Natre) In Vitro Assayed on Human Erythrocytes.

PubMed

Suwalsky, Mario; Ramírez, Patricia; Avello, Marcia; Villena, Fernando; Gallardo, María José; Barriga, Andrés; Manrique-Moreno, Marcela

2016-06-01

In order to gain insight into the molecular mechanism of the antioxidant properties of Solanum crispum, aqueous extracts of its leaves were assayed on human erythrocytes and molecular models of its membrane. Phenolics and alkaloids were detected by HPLC-MS. Scanning electron and defocusing microscopy showed that S. crispum changed erythrocytes from the normal shape to echinocytes. These results imply that molecules present in the aqueous extracts were located in the outer monolayer of the erythrocyte membrane. Dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE) were chosen as representative of phospholipid classes located in the outer and inner monolayers of the erythrocyte membrane, respectively. X-ray diffraction showed that S. crispum preferentially interacted with DMPC bilayers. Experiments regarding its antioxidant properties showed that S. crispum neutralized the oxidative capacity of HClO on DMPE bilayers; defocusing microscopy and hemolysis assays demonstrated the protective effect of S. crispum against the oxidant effects of HClO on human erythrocytes.

Rapid vapor deposition of highly conformal silica nanolaminates.

PubMed

Hausmann, Dennis; Becker, Jill; Wang, Shenglong; Gordon, Roy G

2002-10-11

Highly uniform and conformal coatings can be made by the alternating exposures of a surface to vapors of two reactants, in a process commonly called atomic layer deposition (ALD). The application of ALD has, however, been limited because of slow deposition rates, with a theoretical maximum of one monolayer per cycle. We show that alternating exposure of a surface to vapors of trimethylaluminum and tris(tert-butoxy)silanol deposits highly conformal layers of amorphous silicon dioxide and aluminum oxide nanolaminates at rates of 12 nanometers (more than 32 monolayers) per cycle. This process allows for the uniform lining or filling of long, narrow holes. We propose that these ALD layers grow by a previously unknown catalytic mechanism that also operates during the rapid ALD of many other metal silicates. This process should allow improved production of many devices, such as trench insulation between transistors in microelectronics, planar waveguides, microelectromechanical structures, multilayer optical filters, and protective layers against diffusion, oxidation, or corrosion.

All-optical materials design of chiral edge modes in transition-metal dichalcogenides

DOE PAGES

Claassen, Martin; Jia, Chunjing; Moritz, Brian; ...

2016-10-10

Monolayer transition-metal dichalcogenides are novel materials which at low energies constitute a condensed-matter realization of massive relativistic fermions in two dimensions. Here, we show that this picture breaks for optical pumping—instead, the added complexity of a realistic materials description leads to a new mechanism to optically induce topologically protected chiral edge modes, facilitating optically switchable conduction channels that are insensitive to disorder. In contrast to graphene and previously discussed toy models, the underlying mechanism relies on the intrinsic three-band nature of transition-metal dichalcogenide monolayers near the band edges. Photo-induced band inversions scale linearly in applied pump field and exhibit transitionsmore » from one to two chiral edge modes on sweeping from red to blue detuning. As a result, we develop an ab initio strategy to understand non-equilibrium Floquet–Bloch bands and topological transitions, and illustrate for WS 2 that control of chiral edge modes can be dictated solely from symmetry principles and is not qualitatively sensitive to microscopic materials details.« less

All-optical materials design of chiral edge modes in transition-metal dichalcogenides

PubMed Central

Claassen, Martin; Jia, Chunjing; Moritz, Brian; Devereaux, Thomas P.

2016-01-01

Monolayer transition-metal dichalcogenides are novel materials which at low energies constitute a condensed-matter realization of massive relativistic fermions in two dimensions. Here, we show that this picture breaks for optical pumping—instead, the added complexity of a realistic materials description leads to a new mechanism to optically induce topologically protected chiral edge modes, facilitating optically switchable conduction channels that are insensitive to disorder. In contrast to graphene and previously discussed toy models, the underlying mechanism relies on the intrinsic three-band nature of transition-metal dichalcogenide monolayers near the band edges. Photo-induced band inversions scale linearly in applied pump field and exhibit transitions from one to two chiral edge modes on sweeping from red to blue detuning. We develop an ab initio strategy to understand non-equilibrium Floquet–Bloch bands and topological transitions, and illustrate for WS2 that control of chiral edge modes can be dictated solely from symmetry principles and is not qualitatively sensitive to microscopic materials details. PMID:27721504

The interaction of insulin, glucose, and insulin-glucose mixtures with a phospholipid monolayer.

PubMed

Shigenobu, Hayato; McNamee, Cathy E

2012-12-15

We determined how glucose or insulin interacts with a phospholipid monolayer at the air/water interface and explained these mechanisms from a physico-chemical point of view. The 1,2-dipalmitoyl-2-sn-glycero-3-phosphatidylcholine (DPPC) monolayer at an air/water interface acted as a model membrane, which allowed the effect of the molecular packing density in the monolayer on the interactions to be determined. The interaction of glucose, insulin, and a mixture of glucose and insulin to the DPPC monolayer were investigated via surface pressure-area per molecule Langmuir isotherms and fluorescence microscopy. Glucose adsorbed to the underside of the DPPC monolayer, while insulin was able to penetrate through the monolayer when the phospholipid molecules were not densely packed. The presence of a mixture of insulin and glucose affected the molecular packing in the DPPC monolayer differently than the pure insulin or glucose solutions, and the glucose-insulin mixture was seen to be able to penetrate through the monolayer. These results indicated that glucose and insulin interact with one another, giving a material that may then transported through a pore in the monolayer or through the spaces between the molecules of the monolayer. Copyright © 2012 Elsevier Inc. All rights reserved.

Phorbol ester phorbol-12-myristate-13-acetate promotes anchorage-independent growth and survival of melanomas through MEK-independent activation of ERK1/2

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

Jorgensen, Kjersti; Skrede, Martina; Cruciani, Veronique

2005-04-01

The phorbol ester, phorbol-12-myristate-13-acetate (PMA), an activator of PKCs, is known to stimulate the in vitro growth of monolayer cultures of normal human melanocytes whereas it inhibits the growth of most malignant melanoma cell lines. We examined the effect of PMA on proliferation and survival of melanoma cells grown as multicellular aggregates in suspension (spheroids), and aimed to elucidate downstream targets of PKC signaling. In contrast to monolayer cultures, PMA increased cell proliferation as well as protected melanoma cells from suspension-mediated apoptosis (anoikis). Supporting the importance of PKC in anchorage-independent growth, treatment of anoikis-resistant melanoma cell lines with antisense oligonucleotidesmore » against PKC-{alpha}, or the PKC inhibitor Goe6976, strongly induced anoikis. PMA induced activation of ERK1/2, but this effect was not prevented by the MEK inhibitors PD98059 or by U0126. Whereas PD98059 treatment alone led to marked activation of the pro-apoptotic Bim and Bad proteins and significantly increased anoikis, these effects were clearly reversed by PMA. In conclusion, our results indicate that the protective effect of PMA on anchorage-independent survival of melanoma cells at least partly is mediated by MEK-independent activation of ERK1/2 and inactivation of downstream pro-apoptotic effector proteins.« less

Self-protection against gliotoxin--a component of the gliotoxin biosynthetic cluster, GliT, completely protects Aspergillus fumigatus against exogenous gliotoxin.

PubMed

Schrettl, Markus; Carberry, Stephen; Kavanagh, Kevin; Haas, Hubertus; Jones, Gary W; O'Brien, Jennifer; Nolan, Aine; Stephens, John; Fenelon, Orla; Doyle, Sean

2010-06-10

Gliotoxin, and other related molecules, are encoded by multi-gene clusters and biosynthesized by fungi using non-ribosomal biosynthetic mechanisms. Almost universally described in terms of its toxicity towards mammalian cells, gliotoxin has come to be considered as a component of the virulence arsenal of Aspergillus fumigatus. Here we show that deletion of a single gene, gliT, in the gliotoxin biosynthetic cluster of two A. fumigatus strains, rendered the organism highly sensitive to exogenous gliotoxin and completely disrupted gliotoxin secretion. Addition of glutathione to both A. fumigatus Delta gliT strains relieved gliotoxin inhibition. Moreover, expression of gliT appears to be independently regulated compared to all other cluster components and is up-regulated by exogenous gliotoxin presence, at both the transcript and protein level. Upon gliotoxin exposure, gliT is also expressed in A. fumigatus Delta gliZ, which cannot express any other genes in the gliotoxin biosynthetic cluster, indicating that gliT is primarily responsible for protecting this strain against exogenous gliotoxin. GliT exhibits a gliotoxin reductase activity up to 9 microM gliotoxin and appears to prevent irreversible depletion of intracellular glutathione stores by reduction of the oxidized form of gliotoxin. Cross-species resistance to exogenous gliotoxin is acquired by A. nidulans and Saccharomyces cerevisiae, respectively, when transformed with gliT. We hypothesise that the primary role of gliotoxin may be as an antioxidant and that in addition to GliT functionality, gliotoxin secretion may be a component of an auto-protective mechanism, deployed by A. fumigatus to protect itself against this potent biomolecule.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks

PubMed Central

Heo, Hoseok; Sung, Ji Ho; Cha, Soonyoung; Jang, Bo-Gyu; Kim, Joo-Youn; Jin, Gangtae; Lee, Donghun; Ahn, Ji-Hoon; Lee, Myoung-Jae; Shim, Ji Hoon; Choi, Hyunyong; Jo, Moon-Ho

2015-01-01

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system. PMID:26099952

What is the role and authority of gatekeepers in cluster randomized trials in health research?

PubMed Central

2012-01-01

This article is part of a series of papers examining ethical issues in cluster randomized trials (CRTs) in health research. In the introductory paper in this series, we set out six areas of inquiry that must be addressed if the CRT is to be set on a firm ethical foundation. This paper addresses the sixth of the questions posed, namely, what is the role and authority of gatekeepers in CRTs in health research? ‘Gatekeepers’ are individuals or bodies that represent the interests of cluster members, clusters, or organizations. The need for gatekeepers arose in response to the difficulties in obtaining informed consent because of cluster randomization, cluster-level interventions, and cluster size. In this paper, we call for a more restrictive understanding of the role and authority of gatekeepers. Previous papers in this series have provided solutions to the challenges posed by informed consent in CRTs without the need to invoke gatekeepers. We considered that consent to randomization is not required when cluster members are approached for consent at the earliest opportunity and before any study interventions or data-collection procedures have started. Further, when cluster-level interventions or cluster size means that obtaining informed consent is not possible, a waiver of consent may be appropriate. In this paper, we suggest that the role of gatekeepers in protecting individual interests in CRTs should be limited. Generally, gatekeepers do not have the authority to provide proxy consent for cluster members. When a municipality or other community has a legitimate political authority that is empowered to make such decisions, cluster permission may be appropriate; however, gatekeepers may usefully protect cluster interests in other ways. Cluster consultation may ensure that the CRT addresses local health needs, and is conducted in accord with local values and customs. Gatekeepers may also play an important role in protecting the interests of organizations, such as hospitals, nursing homes, general practices, and schools. In these settings, permission to access the organization relies on resource implications and adherence to institutional policies. PMID:22834691

Non-Saccharomyces yeasts protect against epithelial cell barrier disruption induced by Salmonella enterica subsp. enterica serovar Typhimurium.

PubMed

Smith, I M; Baker, A; Arneborg, N; Jespersen, L

2015-11-01

The human gastrointestinal epithelium makes up the largest barrier separating the body from the external environment. Whereas invasive pathogens cause epithelial barrier disruption, probiotic micro-organisms modulate tight junction regulation and improve epithelial barrier function. In addition, probiotic strains may be able to reduce epithelial barrier disruption caused by pathogenic species. The aim of this study was to explore non-Saccharomyces yeast modulation of epithelial cell barrier function in vitro. Benchmarking against established probiotic strains, we evaluated the ability of four nonpathogenic yeast species to modulate transepithelial electrical resistance (TER) across a monolayer of differentiated human colonocytes (Caco-2 cells). Further, we assessed yeast modulation of a Salmonella Typhimurium-induced epithelial cell barrier function insult. Our findings demonstrate distinct patterns of non-Saccharomyces yeast modulation of epithelial cell barrier function. While the established probiotic yeast Saccharomyces boulardii increased TER across a Caco-2 monolayer by 30%, Kluyveromyces marxianus exhibited significantly stronger properties of TER enhancement (50% TER increase). In addition, our data demonstrate significant yeast-mediated modulation of Salmonella-induced epithelial cell barrier disruption and identify K. marxianus and Metschnikowia gruessii as two non-Saccharomyces yeasts capable of protecting human epithelial cells from pathogen invasion. This study demonstrates distinct patterns of non-Saccharomyces yeast modulation of epithelial cell barrier function in vitro. Further, our data demonstrate significant yeast-mediated modulation of Salmonella Typhimurium-induced epithelial cell barrier disruption and identify Kluyveromyces marxianus and Metschnikowia gruessii as two non-Saccharomyces yeasts capable of protecting human epithelial cells from pathogen invasion. This study is the first to demonstrate significant non-Saccharomyces yeast-mediated epithelial cell barrier protection from Salmonella invasion, thus encouraging future efforts aimed at confirming the observed effects in vivo and driving further strain development towards novel yeast probiotics. © 2015 The Society for Applied Microbiology.

Structural, electronic and magnetic properties of Au-based monolayer derivatives in honeycomb structure

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

Kapoor, Pooja, E-mail: pupooja16@gmail.com; Sharma, Munish; Ahluwalia, P. K.

2016-05-23

We present electronic properties of atomic layer of Au, Au{sub 2}-N, Au{sub 2}-O and Au{sub 2}-F in graphene-like structure within the framework of density functional theory (DFT). The lattice constant of derived monolayers are found to be higher than the pristine Au monolayer. Au monolayer is metallic in nature with quantum ballistic conductance calculated as 4G{sub 0}. Similarly, Au{sub 2}-N and Au{sub 2}-F monolayers show 4G{sub 0} and 2G{sub 0} quantum conductance respectively while semiconducting nature with calculated band gap of 0.28 eV has been observed for Au{sub 2}-O monolayer. Most interestingly, half metalicity has been predicted for Au{sub 2}-Nmore » and Au{sub 2}-F monolayers. Our findings may have importance for the application of these monolayers in nanoelectronic and spintronics.« less

Effects of metformin treatment on glioma-induced brain edema

PubMed Central

Zhao, Bin; Wang, Xiaoke; Zheng, Jun; Wang, Hailiang; Liu, Jun

2016-01-01

Considerable evidence has demonstrated that metformin can activate 5’-AMP-activated protein kinase (AMPK) signaling pathway, which plays a critical role in protection of endothelial cell permeability. Hence, the present study evaluated the effects of metformin on blood brain barrier permeability and AQP4 expression in vitro, and assessed the effects of metformin treatment on tumor-induced brain edema in vivo. Hypoxia or VEGF exposure enhanced bEnd3 endothelial cell monolayer permeability and attenuated the expression of tight junction proteins including Occludin, Claudin-5, ZO-1, and ZO-2. However, 0.5 mM metformin treatment protected bEnd3 endothelial cell monolayer from hypoxia or VEGF-induced permeability, which was correlated with increased expression of tight junction proteins. Furthermore, metformin treatment attenuated AQP4 protein expression in cultured astrocytes. Such an effect involved the activation of AMPK and inhibition of NF-κB. Finally, metformin treatment dose-dependently reduced glioma induced vascular permeability and cerebral edema in vivo in rats. Thus, our results suggested that metformin may protect endothelial cell tight junction, prevent damage to the blood brain barrier induced by brain tumor growth, and alleviate the formation of cerebral edema. Furthermore, since the formation of cytotoxic edema and AQP4 expression was positively correlated, our results indicated that metformin may reduce the formation of cytotoxic edema. However, given that AQP4 plays a key role in the elimination of cerebral edema, attenuation of AQP4 expression by metformin may reduce the elimination of cerebral edema. Hence, future studies will be necessary to dissect the specific mechanisms of metformin underlying the dynamics of tumor-induced brain edema in vivo. PMID:27648126

Effects of metformin treatment on glioma-induced brain edema.

PubMed

Zhao, Bin; Wang, Xiaoke; Zheng, Jun; Wang, Hailiang; Liu, Jun

2016-01-01

Considerable evidence has demonstrated that metformin can activate 5'-AMP-activated protein kinase (AMPK) signaling pathway, which plays a critical role in protection of endothelial cell permeability. Hence, the present study evaluated the effects of metformin on blood brain barrier permeability and AQP4 expression in vitro, and assessed the effects of metformin treatment on tumor-induced brain edema in vivo. Hypoxia or VEGF exposure enhanced bEnd3 endothelial cell monolayer permeability and attenuated the expression of tight junction proteins including Occludin, Claudin-5, ZO-1, and ZO-2. However, 0.5 mM metformin treatment protected bEnd3 endothelial cell monolayer from hypoxia or VEGF-induced permeability, which was correlated with increased expression of tight junction proteins. Furthermore, metformin treatment attenuated AQP4 protein expression in cultured astrocytes. Such an effect involved the activation of AMPK and inhibition of NF-κB. Finally, metformin treatment dose-dependently reduced glioma induced vascular permeability and cerebral edema in vivo in rats. Thus, our results suggested that metformin may protect endothelial cell tight junction, prevent damage to the blood brain barrier induced by brain tumor growth, and alleviate the formation of cerebral edema. Furthermore, since the formation of cytotoxic edema and AQP4 expression was positively correlated, our results indicated that metformin may reduce the formation of cytotoxic edema. However, given that AQP4 plays a key role in the elimination of cerebral edema, attenuation of AQP4 expression by metformin may reduce the elimination of cerebral edema. Hence, future studies will be necessary to dissect the specific mechanisms of metformin underlying the dynamics of tumor-induced brain edema in vivo.

Quantum mechanics capacitance molecular mechanics modeling of core-electron binding energies of methanol and methyl nitrite on Ag(111) surface.

PubMed

Löytynoja, T; Li, X; Jänkälä, K; Rinkevicius, Z; Ågren, H

2016-07-14

We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process can be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM-CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.

Quantum mechanics capacitance molecular mechanics modeling of core-electron binding energies of methanol and methyl nitrite on Ag(111) surface

NASA Astrophysics Data System (ADS)

Löytynoja, T.; Li, X.; Jänkälä, K.; Rinkevicius, Z.; Ågren, H.

2016-07-01

We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process can be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM-CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.

Edge functionalised & Li-intercalated 555-777 defective bilayer graphene for the adsorption of CO2 and H2O

NASA Astrophysics Data System (ADS)

Lalitha, Murugan; Lakshmipathi, Senthilkumar; Bhatia, Suresh K.

2017-04-01

The adsorption of CO2 and H2O on divacanacy (DV) defected graphene cluster, and its bilayer counterpart is investigated using first-principles calculations. Both single and bilayer DV graphene cluster, are functionalised with H and F atoms. On these sheets the gas molecules are physisorbed, and the divacancy defect effectively improves the adsorption of CO2, while fluorination enhances the hydrophobicity of the graphene cluster. Among the convex and concave curvature regions induced due to the DV defect, the adsorption of the gas molecules on the concave meniscus is more favourable. Fluorine termination induces 73% reduction in Henry law constants for H2O, while for the CO2 molecule it increases by 8%, which indicates the DV defective sheet is a better candidate for CO2 capture compared to the STW defective sheet. Besides, both AA and AB divacant defect bilayer sheets are equally stable, wherein AA stacking results in a cavity between the sheets, while in AB stacking, the layers slide one over the other. Nevertheless, both these bilayer sheets are comparatively stabler than the monolayer. However, intercalation of lithium decreases the interlayer separation, particularly in AA stacking, which enhances the CO2 adsorption, but in the Bernal stacking enhances it hydrophobicity.

Theory-Guided Innovation of Noncarbon Two-Dimensional Nanomaterials

DTIC Science & Technology

2016-05-24

unique structures and exceptional properties, such as Be5C2 monolayers with quasi -planaer pentacoordinate carbon, FeB6 monolayers hypercoordinate...properties, such as Be5C2 monolayers with quasi -planaer pentacoordinate carbon, FeB6 monolayers hypercoordinate transition metal, semiconducting Group 15...theoretical and experimental studies, we have developed a convenient chemical approach to etch hexagonal boron nitride monolayers to achieve holes

Lipid monolayer structure and interactions in the presence of peptides and proteins

NASA Astrophysics Data System (ADS)

Freites, Juan Alfredo

Structural aspects of two simple model systems, protein-lipid monolayer and peptide-lipid monolayer, were studied by experimental and computer simulation techniques. In both cases, both the choice of system and the approach employed to studying it, were motivated by specific biological problems. The interaction of annexin A1 with monolayers of dipalmitoylphosphatidylcholine (DPPC) was studied by fluorescence microscopy as a function of lipid monolayer phase and pH. It was shown that the annexin A1-DPPC interaction depends strongly on both the domain structure and phase behavior of the DPPC monolayer, and only weakly on the subphase pH. Annexin A1 was found to be line-active, adsorbing preferentially at phase boundaries. Also, annexin A1 was found to form networks in the presence of a domain structure in the lipid monolayer. Molecular dynamics simulations were carried out on a model system composed of a surfactant protein B peptide, SP-B1--25, and a monolayer of hexadecanoic acid. A detailed structural characterization was performed as a function of the lipid monolayer specic area. It was found that the peptide remains inserted in the monolayer up to values of specific area corresponding to an untilted condensed phase of the pure hexadecanoic acid monolayer. The system remains stable by altering the conformational order of both the anionic lipid monolayer and the peptide secondary structure, and effectively constitutes a unique disordered lipid-peptide monolayer phase. Two elements appear to be key for the constitution of this phase: an electrostatic interaction between the cationic residues of the peptide with the anionic headgroups of the lipids, and an exclusion of the aromatic residues on the hydrophobic end of the peptide from the hydrophilic and aqueous regions of the system. A direct comparison between molecular dynamics simulations and laboratory experiments was performed for hexadecanoic acid monolayer systems. In order to simulate specific points on the surface pressure vs. area isotherm, an algorithm for the control of surface pressure was developed based on previous work by Martyna, Tobias and Klein. The algorithm was implemented and tested with the hexadecanoic acid monolayer system.

Antiphase boundaries on low-energy-ion bombarded Ge(001)

NASA Astrophysics Data System (ADS)

Zandvliet, H. J. W.; de Groot, E.

1997-01-01

Surface vacancy and adatom clusters have been created on Ge(001) by bombarding the surface with 800 eV argon ions at various substrate temperatures ranging from room temperature to 600 K. The vacancies preferentially annihilate at the ends rather than at the sides of the dimer rows, resulting in monolayer deep vacancy islands which are elongated in a direction of the dimer rows of the upper terrace. As vacancy islands nucleate and expand, the dimer rows in neighbouring vacancy islands need not, in general, align with each other. An antiphase boundary will develop if two growing vacancy islands meet, but their internal dimer rows are not in the same registry. In contrast to Si(001), where only one type of antiphase boundary is found, we have found three different types of antiphase boundaries on Ge(001). Higher dose (> several monolayers) room temperature ion bombardment followed by annealing at temperatures in the range 400-500 K results in a surface which contains a high density of valleys. In addition to the preference for the annihilation of dimer vacancies at descending versus ascending steps we also suggest that the development of antiphase boundaries drives the roughening of this surface. Finally, several atomic rearrangement events, which might be induced by the tunneling process, are observed after low-dose ion bombardment at room temperature.

Enhancing photothermal cancer therapy by clustering gold nanoparticles into spherical polymeric nanoconstructs

NASA Astrophysics Data System (ADS)

Iodice, Carmen; Cervadoro, Antonio; Palange, AnnaLisa; Key, Jaehong; Aryal, Santosh; Ramirez, Maricela R.; Mattu, Clara; Ciardelli, Gianluca; O'Neill, Brian E.; Decuzzi, Paolo

2016-01-01

Gold nanoparticles (AuNPs) have been proposed as agents for enhancing photothermal therapy in cancer and cardiovascular diseases. Different geometrical configurations have been used, ranging from spheres to rods and more complex star shapes, to modulate optical and ablating properties. In this work, multiple, ultra-small 6 nm AuNPs are encapsulated into larger spherical polymeric nanoconstructs (SPNs), made out of a poly(lactic acid-co-glycol acid) (PLGA) core stabilized by a superficial lipid-PEG monolayer. The optical and photothermal properties of the resulting nanoconstructs (Au-SPNs) are modulated by varying the initial loading input of AuNPs, ranging between 25 and 150 μgAu. Au-SPNs exhibit a hydrodynamic diameter varying from ~100 to 180 nm, growing with the gold content, and manifest up to 2-fold increase in thermal energy production per unit mass of gold for an initial input of 100 μgAu. Au-SPNs are stable under physiological conditions up to 7 days and have direct cytotoxic effect on tumor cells. The superior photothermal performance of Au-SPNs is assessed in vitro on monolayers of breast cancer cells (SUM-159) and tumor spheroids of glioblastoma multiforme cells (U87-MG). The encapsulation of small AuNPs into larger spherical nanoconstructs enhances photothermal ablation and could favor tumor accumulation.

Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye

NASA Astrophysics Data System (ADS)

Iwamoto, Mitsumasa; Majima, Yutaka; Hirayama, Fuminori; Furuki, Makoto; Pu, Lyong Sun

1992-07-01

Maxwell displacement currents generated from monolayers of squarylium dye with propyl groups (SQ) and from mixed monolayers with arachidic acid were investigated during the course of monolayer compression in connection with the formation of J-aggregates in the monolayers. Abrupt changes in the generation of displacement current were observed for monolayers of SQ due to the transformation between two types of J-aggregates with different absorption spectra. In contrast, for mixed monolayers with arachidic acid which show no transition of J-aggregates, abrupt changes in the displacement current were not observed. It was concluded that displacement current measurement is effective in the detection of the transformation of the molecular arrangement in aggregates.

Chain Stretching and Order-Disorder Transitions in Block Copolymer Monolayers and Multilayers

NASA Astrophysics Data System (ADS)

Kramer, Edward J.; Mishra, Vindhya; Stein, Gila E.; Sohn, Karen E.; Hur, Sumi; Fredrickson, Glenn H.; Cochran, Eric W.

2009-03-01

Both monolayers of block copolymer cylinders and spheres undergo order to disorder transitions (ODT) at temperatures well below those of the bulk. Monolayers of PS-b-P2VP cylinders undergo a ``nematic'' to ``isotropic'' transition at temperatures about 20 K below the bulk ODT while monolayers of PS-b-P2VP with P2VP spheres undergo a 2D crystal to hexatic transition at least 10 K below the bulk ODT. Bilayers of each structure disorder at temperatures well above that of the monolayers. While one is tempted to attribute all of the difference to the fact that ordered monolayers are quasi 2 dimensional while bilayers are not, an alternative explanation exists. In the cylinder monolayer the corona PS chains must stretch to fill a nearly square cross-section domain rather than a hexagonal one in the bulk, while the corona PS chains in a sphere monolayer must stretch to fill a hexagonal prism rather than an octahedron in the bulk. The more non-uniform stretching of the chains in the monolayer should increase its free energy and decrease its order-disorder temperature.

Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

NASA Astrophysics Data System (ADS)

Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

Structure-based design of broadly protective group a streptococcal M protein-based vaccines.

PubMed

Dale, James B; Smeesters, Pierre R; Courtney, Harry S; Penfound, Thomas A; Hohn, Claudia M; Smith, Jeremy C; Baudry, Jerome Y

2017-01-03

A major obstacle to the development of broadly protective M protein-based group A streptococcal (GAS) vaccines is the variability within the N-terminal epitopes that evoke potent bactericidal antibodies. The concept of M type-specific protective immune responses has recently been challenged based on the observation that multivalent M protein vaccines elicited cross-reactive bactericidal antibodies against a number of non-vaccine M types of GAS. Additionally, a new "cluster-based" typing system of 175M proteins identified a limited number of clusters containing closely related M proteins. In the current study, we used the emm cluster typing system, in combination with computational structure-based peptide modeling, as a novel approach to the design of potentially broadly protective M protein-based vaccines. M protein sequences (AA 16-50) from the E4 cluster containing 17 emm types of GAS were analyzed using de novo 3-D structure prediction tools and the resulting structures subjected to chemical diversity analysis to identify sequences that were the most representative of the 3-D physicochemical properties of the M peptides in the cluster. Five peptides that spanned the range of physicochemical attributes of all 17 peptides were used to formulate synthetic and recombinant vaccines. Rabbit antisera were assayed for antibodies that cross-reacted with E4 peptides and whole bacteria by ELISA and for bactericidal activity against all E4GAS. The synthetic vaccine rabbit antisera reacted with all 17 E4M peptides and demonstrated bactericidal activity against 15/17 E4GAS. A recombinant hybrid vaccine containing the same E4 peptides also elicited antibodies that cross-reacted with all E4M peptides. Comprehensive studies using structure-based design may result in a broadly protective M peptide vaccine that will elicit cluster-specific and emm type-specific antibody responses against the majority of clinically relevant emm types of GAS. Copyright © 2016 Elsevier Ltd. All rights reserved.

Robust nanofabrication of monolayer MoS2 islands with strong photoluminescence enhancement via local anodic oxidation

NASA Astrophysics Data System (ADS)

Fernandes, Thales F. D.; Gadelha, Andreij de C.; Barboza, Ana P. M.; Paniago, Roberto M.; Campos, Leonardo C.; Soares Guimarães, Paulo S.; de Assis, Pierre-Louis; Neves, Bernardo R. A.

2018-04-01

In this work, we demonstrate the nanofabrication of monolayer MoS2 islands using local anodic oxidation of few-layer and bulk MoS2 flakes. The nanofabricated islands present true monolayer Raman signal and photoluminescence intensity up to two orders of magnitude larger than that of a pristine monolayer. This technique is robust enough to result in monolayer islands without the need of meticulously fine-tuning the oxidation process, thus providing a fast and reliable way of creating monolayer regions with enhanced optical properties and with controllable size, shape, and position.

DNA-modified electrodes fabricated using copper-free click chemistry for enhanced protein detection.

PubMed

Furst, Ariel L; Hill, Michael G; Barton, Jacqueline K

2013-12-31

A method of DNA monolayer formation has been developed using copper-free click chemistry that yields enhanced surface homogeneity and enables variation in the amount of DNA assembled; extremely low-density DNA monolayers, with as little as 5% of the monolayer being DNA, have been formed. These DNA-modified electrodes (DMEs) were characterized visually, with AFM, and electrochemically, and were found to facilitate DNA-mediated reduction of a distally bound redox probe. These low-density monolayers were found to be more homogeneous than traditional thiol-modified DNA monolayers, with greater helix accessibility through an increased surface area-to-volume ratio. Protein binding efficiency of the transcriptional activator TATA-binding protein (TBP) was also investigated on these surfaces and compared to that on DNA monolayers formed with standard thiol-modified DNA. Our low-density monolayers were found to be extremely sensitive to TBP binding, with a signal decrease in excess of 75% for 150 nM protein. This protein was detectable at 4 nM, on the order of its dissociation constant, with our low-density monolayers. The improved DNA helix accessibility and sensitivity of our low-density DNA monolayers to TBP binding reflects the general utility of this method of DNA monolayer formation for DNA-based electrochemical sensor development.

Testing the effectiveness of monolayers under wind and wave conditions.

PubMed

Palada, C; Schouten, P; Lemckert, C

2012-01-01

Monolayers are highly desirable for their evaporation reducing capabilities due to their relatively minimal cost and ease of application. Despite these positive attributes, monolayers have consistently failed to perform effectively due to the harsh wind and wave conditions prevalent across real-world water reserves. An exhaustive and consistent study testing the influence of wind and wave combinations on monolayer performance has yet to be presented in the literature. To remedy this, the effect of simultaneous wind and wave conditions on a benchmark high-performance monolayer (octadecanol suspension, CH(3)(CH(2))(16)CH(2)OH) has been analysed. Subjected only to waves, the monolayer remained intact due to its innate ability to compress and expand. However, the constant simultaneous application of wind and waves caused the monolayer to break up and gather down-wind where it volatilised over time. At wind speeds above 1.3 m s(-1) the monolayer was completely ineffective. For wind speeds below this threshold, the monolayer had an influence on the evaporation rate dependent on wind speed. From these results a series of application protocols can now be developed for the optimised deployment of monolayers in real-world water reserves. This will be of interest to private, commercial and government organisations involved in the storage and management of water resources.

Understanding and Practical Use of Ligand and Metal Exchange Reactions in Thiolate-Protected Metal Clusters to Synthesize Controlled Metal Clusters.

PubMed

Niihori, Yoshiki; Hossain, Sakiat; Sharma, Sachil; Kumar, Bharat; Kurashige, Wataru; Negishi, Yuichi

2017-05-01

It is now possible to accurately synthesize thiolate (SR)-protected gold clusters (Au n (SR) m ) with various chemical compositions with atomic precision. The geometric structure, electronic structure, physical properties, and functions of these clusters are well known. In contrast, the ligand or metal atom exchange reactions between these clusters and other substances have not been studied extensively until recently, even though these phenomena were observed during early studies. Understanding the mechanisms of these reactions could allow desired functional metal clusters to be produced via exchange reactions. Therefore, we have studied the exchange reactions between Au n (SR) m and analogous clusters and other substances for the past four years. The results have enabled us to gain deep understanding of ligand exchange with respect to preferential exchange sites, acceleration means, effect on electronic structure, and intercluster exchange. We have also synthesized several new metal clusters using ligand and metal exchange reactions. In this account, we summarize our research on ligand and metal exchange reactions. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unanticipated C=C bonds in covalent monolayers on silicon revealed by NEXAFS.

PubMed

Lee, Michael V; Lee, Jonathan R I; Brehmer, Daniel E; Linford, Matthew R; Willey, Trevor M

2010-02-02

Interfaces are crucial to material properties. In the case of covalent organic monolayers on silicon, molecular structure at the interface controls the self-assembly of the monolayers, which in turn influences the optical properties and electrical transport. These properties intrinsically affect their application in biology, tribology, optics, and electronics. We use near-edge X-ray absorption fine structure spectroscopy to show that the most basic covalent monolayers formed from 1-alkenes on silicon retain a double bond in one-fifth to two-fifths of the resultant molecules. Unsaturation in the predominantly saturated monolayers will perturb the regular order and affect the dependent properties. The presence of unsaturation in monolayers produced by two different methods also prompts the re-evaluation of other radical-based mechanisms for forming covalent monolayers on silicon.

Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids.

PubMed

Liu, Jianxi; Li, Jinlong; Yu, Bo; Ma, Baodong; Zhu, Yangwen; Song, Xinwang; Cao, Xulong; Yang, Wu; Zhou, Feng

2011-09-20

A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates. © 2011 American Chemical Society

Ni-P/Zn-Ni compositionally modulated multilayer coatings - Part 2: Corrosion and protection mechanisms

NASA Astrophysics Data System (ADS)

Bahadormanesh, Behrouz; Ghorbani, Mohammad

2018-06-01

The Ni-P/Zn-Ni compositionally modulated multilayer coatings CMMCs were electrodeposited from a single bath by switching the deposition current density. The corrosion resistance of the deposits was studied and compared with that of monolayers of Ni-P and Zn-Ni alloys via Tafel polarization, EIS and salt spray tests. Characterization of corrosion products by means of EDS and XRD revealed more details from the corrosion mechanism of the monolayers and multilayers. The corrosion current density of Ni-P/Zn-Ni CMMCs were around one tenth of Zn-Ni monolayer. The CMMC with incomplete layers performed lower polarization resistance and higher corrosion current density compared to the CMMC with complete layers. The electrical circuit that was proposed for modeling the corrosion process based on the EIS spectrum, proved that layering reduces the porosity and consequently improves the barrier properties. Although, layering of Zn-Ni layers with Ni-P deposits increased the time to red rust in salt spray test, the time for white rust formation decreased. The corrosion mechanism of both Zn-Ni and Ni-P (containing small amount of Zn) was preferential dissolution of Zn and the corrosion products were comprised of mainly Zn hydroxychloride and Zn hydroxycarbonate. Also, Ni and P did not take part in the corrosion products. Based on the electrochemical character of the layers and the morphology of the corroded surface, the corrosion mechanism of multilayers was discussed.

Are additive effects of dietary surfactants on intestinal tight junction integrity an overlooked human health risk? - A mixture study on Caco-2 monolayers.

PubMed

Glynn, Anders; Igra, Annachiara Malin; Sand, Salomon; Ilbäck, Nils Gunnar; Hellenäs, Karl Erik; Rosén, Johan; Aspenström-Fagerlund, Bitte

2017-08-01

Surfactants may cause dysfunction of intestinal tight junctions (TJs), which is a common feature of intestinal autoimmune diseases. Effects of dietary surfactants on TJ integrity, measured as trans-epithelial resistance (TEER), were studied in Caco-2 cell monolayers. Cytotoxicity was assessed as apical LDH leakage. Monolayers were apically exposed for 60 min to the dietary surfactants solanine and chaconine (SC, potato glycoalkaloids, 0-0.25 mM), perfluorooctane sulfonic acid (PFOS, industrial contaminant, 0-0.8 mM), and sucrose monolaurate (SML, food emulsifier E 473, 0-2.0 mM) separately and as a mixture. Dose-response modelling of TEER EC 50 showed that SC were 2.7- and 12-fold more potent than PFOS and SML, respectively. The mixture was composed of 1 molar unit SC, 2.7 units PFOS and 12 units SML ("SC TEER equivalent" proportions 1:1:1). Mixture exposure (0-0.05 mM SC equivalents) dose-response modelling suggested additive action on TJ integrity. Increasing SC and SML concentrations caused increased LDH leakage, but PFOS decreased LDH leakage at intermediate exposure concentrations. In the mixture PFOS appeared to protect from extensive SC- and SML-induced LDH leakage. Complex mixtures of surfactants in food may act additively on intestinal TJ integrity, which should be considered in risk assessment of emulsifier authorisation for use in food production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fullerene-derivative PC61BM forms three types of phase-pure monolayer on the surface of Au(111)

NASA Astrophysics Data System (ADS)

Li, Wen-Jie; Du, Ying-Ying; Zhang, Han-Jie; Chen, Guang-Hua; Sheng, Chun-Qi; Wu, Rui; Wang, Jia-Ou; Qian, Hai-Jie; Ibrahim, Kurash; He, Pi-Mo; Li, Hong-Nian

2016-12-01

We have studied the packing structures of C60-derivative PC61BM on the surface of Au(111) in ultrahigh vacuum using scanning tunneling microscopy. The Au(111) has a triangle-like reconstructed surface, which results in some packing structures different from those reported for low coverages. PC61BM can form three types of phase-pure monolayer, namely, the compact straight molecular double-row monolayer, the hexagonal-packing monolayer and the glassy monolayer. The different types of monolayer form for different molecular densities and different annealing temperatures. In addition to the already known inter-molecular interactions (Van de Waals interaction and hydrogen bond), the steric effect of the phenyl-butyric-acid-methyl-ester side tail plays conspicuous role in the molecular self-assembly at high coverages. The steric effect makes it difficult to prepare a hexagonal-packing monolayer at room temperature and decides the instability of the hexagonal-packing monolayer prepared by thermal annealing.

Strain and electric field induced metallization in the GaX (X = N, P, As & Sb) monolayer

NASA Astrophysics Data System (ADS)

Bahuguna, Bhagwati Prasad; Saini, L. K.; Sharma, Rajesh O.; Tiwari, Brajesh

2018-05-01

We investigate the strain and electric field dependent electronic properties of two dimensional Ga-based group III-V monolayer from the first-principles approach within density functional theory. The energy bandgap of GaX monolayer increases upto the certain value of compressive strain and then decreases. On the other hand, the energy bandgap of GaX monolayer is monotonically decreased with increasing tensile strain and become metallic at the higher value. Furthermore, the perpendicular electric field decreases the energy band gap of unstrained GaX monolayer and shows semiconductor to metal transition. These results suggest that the nature of energy bands and value of energy bandgap in GaX monolayer can be tuned by the biaxial mechanical strain or perpendicular electrical field. Additionally, we have also studied the optical response of unstrained GaX monolayer in term of optical conductivity. These findings may provide valuable information to develop the Ga-based optoelectronic devices and further the understanding of the GaX monolayer.

GaAs monolayer: Excellent SHG responses and semi metallic to metallic transition modulated by vacancy effect

NASA Astrophysics Data System (ADS)

Rozahun, Ilmira; Bahti, Tohtiaji; He, Guijie; Ghupur, Yasenjan; Ablat, Abduleziz; Mamat, Mamatrishat

2018-05-01

Monolayer materials are considered as a promising candidate for novel applications due to their attractive magnetic, electronic and optical properties. Investigation on nonlinear optical (NLO) properties and effect of vacancy on monolayer materials are vital to property modulations of monolayers and extending their applications. In this work, with the aid of first-principles calculations, the crystal structure, electronic, magnetic, and optical properties of GaAs monolayers with the vacancy were investigated. The result shows gallium arsenic (GaAs) monolayer produces a strong second harmonic generation (SHG) response. Meanwhile, the vacancy strongly affects structural, electronic, magnetic and optical properties of GaAs monolayers. Furthermore, arsenic vacancy (VAs) brings semi metallic to metallic transition, while gallium vacancy (VGa) causes nonmagnetic to magnetic conversion. Our result reveals that GaAs monolayer possesses application potentials in Nano-amplifying modulator and Nano-optoelectronic devices, and may provide useful guidance in designing new generation of Nano-electronic devices.

Specialized activities and expression differences for Clostridium thermocellum biofilm and planktonic cells

DOE PAGES

Dumitrache, Alexandru; Klingeman, Dawn M.; Natzke, Jace; ...

2017-02-27

Clostridium thermocellum forms biofilms adherent to lignocellulosic feedstock in a typical continuous cell-monolayer to efficiently break down and uptake cellulose hydrolysates. The sessile cells of biofilms may revert to non-adherent planktonic cells through generation of offspring cells or microenvironment constraints such as limited surface area. These interdependent cell populations co-exist and have different contributions to culture activity and growth. Here, we developed a novel bioreactor design to rapidly harvest sessile and planktonic cell populations for omics studies. In RNA-seq analyses, within 3299 protein coding genes, 59% (or 1958 genes) were differentially expressed with a minimum two-fold change between the twomore » cell populations isolated simultaneously at high culture activity. Furthermore, sessile cells had definitive greater expression of genes involved in catabolism of carbohydrates by glycolysis and pyruvate fermentation, ATP generation by proton gradient, the anabolism of proteins and lipids and cellular functions critical for cell division; planktonic cells had notably higher gene expression for flagellar motility and chemotaxis, cellulosomal cellulases and anchoring scaffoldins, and a range of stress induced homeostasis mechanisms such as oxidative stress protection by antioxidants and flavoprotein co-factors, methionine repair, Fe-S cluster assembly and repair in redox proteins, cell growth control through tRNA thiolation, recovery of damaged DNA by nucleotide excision repair and removal of terminal proteins by proteases. Our knowledge of these cellular adaptations will aid the engineering of industrially relevant strains for consolidated bioprocessing of solid lignocellulosic biomass« less

Specialized activities and expression differences for Clostridium thermocellum biofilm and planktonic cells

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

Dumitrache, Alexandru; Klingeman, Dawn M.; Natzke, Jace

Clostridium thermocellum forms biofilms adherent to lignocellulosic feedstock in a typical continuous cell-monolayer to efficiently break down and uptake cellulose hydrolysates. The sessile cells of biofilms may revert to non-adherent planktonic cells through generation of offspring cells or microenvironment constraints such as limited surface area. These interdependent cell populations co-exist and have different contributions to culture activity and growth. Here, we developed a novel bioreactor design to rapidly harvest sessile and planktonic cell populations for omics studies. In RNA-seq analyses, within 3299 protein coding genes, 59% (or 1958 genes) were differentially expressed with a minimum two-fold change between the twomore » cell populations isolated simultaneously at high culture activity. Furthermore, sessile cells had definitive greater expression of genes involved in catabolism of carbohydrates by glycolysis and pyruvate fermentation, ATP generation by proton gradient, the anabolism of proteins and lipids and cellular functions critical for cell division; planktonic cells had notably higher gene expression for flagellar motility and chemotaxis, cellulosomal cellulases and anchoring scaffoldins, and a range of stress induced homeostasis mechanisms such as oxidative stress protection by antioxidants and flavoprotein co-factors, methionine repair, Fe-S cluster assembly and repair in redox proteins, cell growth control through tRNA thiolation, recovery of damaged DNA by nucleotide excision repair and removal of terminal proteins by proteases. Our knowledge of these cellular adaptations will aid the engineering of industrially relevant strains for consolidated bioprocessing of solid lignocellulosic biomass« less

Atomically resolved structure of ligand-protected Au{sub 9} clusters on TiO{sub 2} nanosheets using aberration-corrected STEM

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

Al Qahtani, Hassan S.; Andersson, Gunther G., E-mail: gunther.andersson@flinders.edu.au, E-mail: nakayama.tomonobu@nims.go.jp; Kimoto, Koji

2016-03-21

Triphenylphosphine ligand-protected Au{sub 9} clusters deposited onto titania nanosheets show three different atomic configurations as observed by scanning transmission electron microscopy. The configurations observed are a 3-dimensional structure, corresponding to the previously proposed Au{sub 9} core of the clusters, and two pseudo-2-dimensional (pseudo-2D) structures, newly found by this work. With the help of density functional theory (DFT) calculations, the observed pseudo-2D structures are attributed to the low energy, de-ligated structures formed through interaction with the substrate. The combination of scanning transmission electron microscopy with DFT calculations thus allows identifying whether or not the deposited Au{sub 9} clusters have been de-ligatedmore » in the deposition process.« less

Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

PubMed

Summers, Andrew Z; Iacovella, Christopher R; Cummings, Peter T; McCabe, Clare

2017-10-24

Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

Sodium adsorption and diffusion on monolayer black phosphorus with intrinsic defects

NASA Astrophysics Data System (ADS)

Sun, Xiaoli; Wang, Zhiguo

2018-01-01

Monolayer black phosphorus is a potential anode material for rechargeable ion batteries. In this work, the effects of intrinsic defects including mono-vacancy (MV), di-vacancy, and Stone-Wales (SW) defects on the adsorption and diffusion of sodium on monolayer black phosphorus were investigated using first-principles calculations. The adsorption energies for sodium on monolayer black phosphorus are in the range of -1.80 to -0.56 eV, which is lower than the value of -0.48 eV for sodium adsorbed on pristine monolayer phosphorus. This indicates that these defects can enhance the adsorption of sodium on monolayer black phosphorus. The diffusivity of sodium on monolayer phosphorus with SW and MV defects is 2.35 × 10-4-3.36 × 10-6 cm2/s, and 7.38 × 10-5-1.48 × 10-9 cm2/s, respectively. Although these values are smaller than that of the pristine monolayer phosphorus at 7.38 × 10-5 cm2/s, defects are inevitably introduced during these fabrication processes. These diffusivity values are reasonable for defective monolayer phosphorus used as an effective anode for sodium ion batteries.

Mitochondrial nucleoid clusters protect newly synthesized mtDNA during Doxorubicin- and Ethidium Bromide-induced mitochondrial stress

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

Alán, Lukáš, E-mail: lukas.alan@fgu.cas.cz; Špaček

Mitochondrial DNA (mtDNA) is compacted in ribonucleoprotein complexes called nucleoids, which can divide or move within the mitochondrial network. Mitochondrial nucleoids are able to aggregate into clusters upon reaction with intercalators such as the mtDNA depletion agent Ethidium Bromide (EB) or anticancer drug Doxorobicin (DXR). However, the exact mechanism of nucleoid clusters formation remains unknown. Resolving these processes may help to elucidate the mechanisms of DXR-induced cardiotoxicity. Therefore, we addressed the role of two key nucleoid proteins; mitochondrial transcription factor A (TFAM) and mitochondrial single-stranded binding protein (mtSSB); in the formation of mitochondrial nucleoid clusters during the action of intercalators.more » We found that both intercalators cause numerous aberrations due to perturbing their native status. By blocking mtDNA replication, both agents also prevented mtDNA association with TFAM, consequently causing nucleoid aggregation into large nucleoid clusters enriched with TFAM, co-existing with the normal nucleoid population. In the later stages of intercalation (> 48 h), TFAM levels were reduced to 25%. In contrast, mtSSB was released from mtDNA and freely distributed within the mitochondrial network. Nucleoid clusters mostly contained nucleoids with newly replicated mtDNA, however the nucleoid population which was not in replication mode remained outside the clusters. Moreover, the nucleoid clusters were enriched with p53, an anti-oncogenic gatekeeper. We suggest that mitochondrial nucleoid clustering is a mechanism for protecting nucleoids with newly replicated DNA against intercalators mediating genotoxic stress. These results provide new insight into the common mitochondrial response to mtDNA stress and can be implied also on DXR-induced mitochondrial cytotoxicity. - Highlights: • The mechanism for mitochondrial nucleoid clustering is proposed. • DNA intercalators (Doxorubicin or Ethidium Bromide) prevent TFAM binding to mtDNA. • Replicating nucleoids are less prone to DNA intercalator and preserve more TFAM. • Nucleoid clusters mostly contain nucleoids with newly replicated mtDNA. • Recently replicated nucleoids are protected in clusters by increased TFAM and p53.« less

Molecular organization of phospholipid monolayers on the water surface by Maxwell displacement current measurement

NASA Astrophysics Data System (ADS)

Sulaiman, Khaulah; Majid, Wan Haliza Abdul; Muhamad, Muhamad Rasat

2006-02-01

The monolayer of organic molecules at the air-water interface has been studied using the Maxwell displacement current (MDC) technique. The materials used in this study were the biological materials of phosphatidyl ethanolamine (PE) and phosphatidic acids (PA). The configuration of the experimental set-up consists of the metal/air-gap/monolayer/metal coupled with the Langmuir method. This measurement enables the detection of current without destroying the monolayer. The phase transition and molecular orientation of the phospholipid monolayers were investigated using MDC measurement without mechanical contact between electrodes and the materials. Direct evidence of phase transition from gaseous to the polar ordering phase can be obtained across phospholipid monolayers even though at very low surface pressure. Relaxation process of the phospholipid monolayers was investigated by using the step compression on the MDC signals.

Peptide protected gold clusters: chemical synthesis and biomedical applications

NASA Astrophysics Data System (ADS)

Yuan, Qing; Wang, Yaling; Zhao, Lina; Liu, Ru; Gao, Fuping; Gao, Liang; Gao, Xueyun

2016-06-01

Bridging the gap between atoms and nanoparticles, noble metal clusters with atomic precision continue to attract considerable attention due to their important applications in catalysis, energy transformation, biosensing and biomedicine. Greatly different to common chemical synthesis, a one-step biomimetic synthesis of peptide-conjugated metal clusters has been developed to meet the demand of emerging bioapplications. Under mild conditions, multifunctional peptides containing metal capturing, reactive and targeting groups are rationally designed and elaborately synthesized to fabricate atomically precise peptide protected metal clusters. Among them, peptide-protected Au Cs (peptide-Au Cs) possess a great deal of exceptional advantages such as nanometer dimensions, high photostability, good biocompatibility, accurate chemical formula and specific protein targeting capacity. In this review article, we focus on the recent advances in potential theranostic fields by introducing the rising progress of peptide-Au Cs for biological imaging, biological analysis and therapeutic applications. The interactions between Au Cs and biological systems as well as potential mechanisms are also our concerned theme. We expect that the rapidly growing interest in Au Cs-based theranostic applications will attract broader concerns across various disciplines.

Qudit quantum computation on matrix product states with global symmetry

NASA Astrophysics Data System (ADS)

Wang, Dongsheng; Stephen, David; Raussendorf, Robert

Resource states that contain nontrivial symmetry-protected topological order are identified for universal measurement-based quantum computation. Our resource states fall into two classes: one as the qudit generalizations of the qubit cluster state, and the other as the higher-symmetry generalizations of the spin-1 Affleck-Kennedy-Lieb-Tasaki (AKLT) state, namely, with unitary, orthogonal, or symplectic symmetry. The symmetry in cluster states protects information propagation (identity gate), while the higher symmetry in AKLT-type states enables nontrivial gate computation. This work demonstrates a close connection between measurement-based quantum computation and symmetry-protected topological order.

Qudit quantum computation on matrix product states with global symmetry

NASA Astrophysics Data System (ADS)

Wang, Dong-Sheng; Stephen, David T.; Raussendorf, Robert

2017-03-01

Resource states that contain nontrivial symmetry-protected topological order are identified for universal single-qudit measurement-based quantum computation. Our resource states fall into two classes: one as the qudit generalizations of the one-dimensional qubit cluster state, and the other as the higher-symmetry generalizations of the spin-1 Affleck-Kennedy-Lieb-Tasaki (AKLT) state, namely, with unitary, orthogonal, or symplectic symmetry. The symmetry in cluster states protects information propagation (identity gate), while the higher symmetry in AKLT-type states enables nontrivial gate computation. This work demonstrates a close connection between measurement-based quantum computation and symmetry-protected topological order.

Optical properties of two-dimensional GaS and GaSe monolayers

NASA Astrophysics Data System (ADS)

Jappor, Hamad Rahman; Habeeb, Majeed Ali

2018-07-01

Optical properties of GaS and GaSe monolayers are investigated using first-principles calculations. The optical properties are studied up to 35 eV. Precisely, our results demonstrated that the optical properties appearance of GaS monolayer is comparative with GaSe monolayer with few informations contrasts. Moreover, the absorption begins in the visible region, although the peaks in the ultraviolet (UV) region. The refractive index values are 1.644 (GaS monolayer) and 2.01 (GaSe monolayer) at zero photon energy limit and increase to 2.092 and 2.698 respectively and both located in the visible region. Furthermore, we notice that the optical properties of both monolayers are obtained in the ultraviolet range and the results are significant. Accordingly, it can be used as a highly promising material in the solar cell, ultraviolet optical nanodevices, nanoelectronics, optoelectronic, and photocatalytic applications.

The ferromagnetic monolayer Fe(110) on W(110)

NASA Astrophysics Data System (ADS)

Gradmann, U.; Liu, G.; Elmers, H. J.; Przybylski, M.

1990-07-01

Ferromagnetic order in the pseudomorphic monolayer Fe(110) on W(110) was analyzed experimentally using Conversion Electron Mössbauer Spectroscopy (CEMS) and Torsion Oscillation Magnetometry (TOM). The monolayer is thermodynamically stable, crystallizes to large monolayer patches at elevated temperatures and therefore forms an excellent approximation to the ideal monolayer structure. It is ferromagnetic below a Curie-temperature T c,mono, which is given by (282±3) K for the Ag-coated layer, (290±10) K for coating by Cu, Ag or Au and ≈210 K for the free monolayer. For the Ag-coated monolayer, ground state hyperfine field B hf (0)=(11.9±0.3) T and magnetic moment per atom μ=2.53 μB could be determined, in fair agreement with theoretical predictions. Unusual properties of the phase transition are detected by the combination of both experimental techniques. Strong magnetic anisotropies, which are essential for ferromagnetic order, are determined by CEMS.

First-principles study on the electronic, optical, and transport properties of monolayer α- and β-GeSe

DOE PAGES

Xu, Yuanfeng; Zhang, Hao; Shao, Hezhu; ...

2017-12-15

The extraordinary properties and the novel applications of black phosphorene induce the research interest in the monolayer group-IV monochalcogenides. Here using first-principles calculations, we systematically investigate the electronic, transport, and optical properties of monolayer α- and β-GeSe, revealing a direct band gap of 1.61 eV for monolayer α-GeSe and an indirect band gap of 2.47 eV for monolayer β-GeSe. For monolayer β-GeSe, the electronic/hole transport is anisotropic, with an extremely high electron mobility of 2.93×104cm2/Vs along the armchair direction, comparable to that of black phosphorene. However, for β-GeSe, robust band gaps nearly independent of the applied tensile strain along themore » armchair direction are observed. Both monolayer α- and β-GeSe exhibit anisotropic optical absorption in the visible spectrum.« less

Wet formation and structural characterization of quasi-hexagonal monolayers.

PubMed

Batys, Piotr; Weroński, Paweł; Nosek, Magdalena

2016-01-01

We have presented a simple and efficient method for producing dense particle monolayers with controlled surface coverage. The method is based on particle sedimentation, manipulation of the particle-substrate electrostatic interaction, and gentle mechanical vibration of the system. It allows for obtaining quasi-hexagonal structures under wet conditions. Using this method, we have produced a monolayer of 3 μm silica particles on a glassy carbon substrate. By optical microscopy, we have determined the coordinates of the particles and surface coverage of the obtained structure to be 0.82. We have characterized the monolayer structure by means of the pair-correlation function and power spectrum. We have also compared the results with those for a 2D hexagonal monolayer and monolayer generated by random sequential adsorption at the coverage 0.50. We have found the surface fractal dimension to be 2.5, independently of the monolayer surface coverage. Copyright © 2015 Elsevier Inc. All rights reserved.

Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

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

Cui, Chaonan; Han, Jinyu; Zhu, Xinli

Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, formingmore » a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing Center of Tianjin University is acknowledged for providing services to the computing cluster. CC acknowledges the support of 24 China Scholarship Council (CSC). QG acknowledges the support of NSF-CBET program (Award no. CBET-1438440). DM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington.« less

Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction

PubMed Central

Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)

2015-01-01

A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247

Insights into hydrogen bond dynamics at the interface of the charged monolayer-protected Au nanoparticle from molecular dynamics simulation.

PubMed

Li, Yunzhi; Yang, Zhen; Hu, Na; Zhou, Rongfei; Chen, Xiangshu

2013-05-14

The structure and dynamics properties of water molecules at the interface of the charged monolayer-protected Au nanoparticle (MPAN) have been investigated in detail by using classical molecular dynamics simulation. The simulation results demonstrated clearly that a well-defined hydration layer is formed at the interface of MPAN and a stable "ion wall" consisting of terminal NH3 (+) groups and Cl(-) counterions exists at the outmost region of self-assembled monolayer (SAM) where the translational and rotational motions of water molecules slow considerably down compared to those in the bulk owing to the presence of SAM and ion wall. Furthermore, we found that the translational motions of interfacial water molecules display a subdiffusive behavior while their rotational motions exhibit a nonexponential feature. The unique behavior of interfacial water molecules around the MPAN can be attributed to the interfacial hydrogen bond (HB) dynamics. By comparison, the lifetime of NH3 (+)-Cl(-) HBs was found to be the longest, favoring the stability of ion wall. Meanwhile, the lifetime of H2O-H2O HBs shows an obvious increase when the water molecules approach the Au core, suggesting the enhanced H2O-H2O HBs around the charged MPAN, which is contrary to the weaken H2O-H2O HBs around the neutral MPAN. Moreover, the HB lifetimes between water molecules and the ion wall (i.e., the Cl(-)-H2O and NH3 (+)-H2O HBs) are much longer than that of interfacial H2O-H2O HBs, which leads to the increasing rotational relaxation time and residence time of water molecules surrounding the ion wall. In addition, the corresponding binding energies for different HB types obtained from the precise density functional theory are in excellent accordance with above simulation results. The detailed HB dynamics studied in this work provides insights into the unique behavior of water molecules at the interface of charged self-assemblies of nanoparticles as well as proteins.

Morphological variation of stimuli-responsive polypeptide at air-water interface

NASA Astrophysics Data System (ADS)

Shin, Sungchul; Ahn, Sungmin; Cheng, Jie; Chang, Hyejin; Jung, Dae-Hong; Hyun, Jinho

2016-12-01

The morphological variation of stimuli-responsive polypeptide molecules at the air-water interface as a function of temperature and compression was described. The surface pressure-area (π-A) isotherms of an elastin-like polypeptide (ELP) monolayer were obtained under variable external conditions, and Langmuir-Blodgett (LB) monolayers were deposited onto a mica substrate for characterization. As the compression of the ELP monolayer increased, the surface pressure increased gradually, indicating that the ELP monolayer could be prepared with high stability at the air-water interface. The temperature in the subphase of the ELP monolayer was critical in the preparation of LB monolayers. The change in temperature induced a shift in the π-A isotherms as well as a change in ELP secondary structures. Surprisingly, the compression of the ELP monolayer influenced the ELP secondary structure due to the reduction in the phase transition temperature with decreasing temperature. The change in the ELP secondary structure formed at the air-water interface was investigated by surface-enhanced Raman scattering. Moreover, the morphology of the ELP monolayer was subsequently imaged using atomic force microscopy. The temperature responsive behavior resulted in changes in surface morphology from relatively flat structures to rugged labyrinth structures, which suggested conformational changes in the ELP monolayers.

Biodegradation of artificial monolayers applied to water storages to reduce evaporative loss.

PubMed

Pittaway, P; Herzig, M; Stuckey, N; Larsen, K

2015-01-01

Repeat applications of an artificial monolayer to the interfacial boundary layer of large agricultural water storages during periods of high evaporative demand remains the most commercially feasible water conservation strategy. However, the interfacial boundary layer (or microlayer) is ecologically distinct from subsurface water, and repeat monolayer applications may adversely affect microlayer processes. In this study, the natural cleansing mechanisms operating within the microlayer were investigated to compare the biodegradability of two fatty alcohol (C16OH and C18OH) and one glycol ether (C18E1) monolayer compound. The C16OH and C18OH compounds were more susceptible to microbial degradation, but the C18E1 compound was most susceptible to indirect photodegradation. On clean water the surface pressure and evaporation reduction achieved with a compressed C18E1 monolayer was superior to the C18OH monolayer, but on brown water the surface pressure dropped rapidly. These results suggest artificial monolayers are readily degraded by the synergy between photo and microbial degradation. The residence time of C18OH and C18E1 monolayers on clear water is sufficient for cost-effective water conservation. However, the susceptibility of C18E1 to photodegradation indicates the application of this monolayer to brown water may not be cost-effective.

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

Das, Kaushik, E-mail: kaushikdas2089@gmail.com; Kundu, Sarathi

Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba{sup 2+} ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (π{sub c} > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structuremore » at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.« less

First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

NASA Astrophysics Data System (ADS)

Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

2018-06-01

Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Shi, Wenwu; Wang, Zhiguo

2018-05-01

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

Structural and dynamic characteristics in monolayer square ice.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-07-28

When water is constrained between two sheets of graphene, it becomes an intriguing monolayer solid with a square pattern due to the ultrahigh van der Waals pressure. However, the square ice phase has become a matter of debate due to the insufficient experimental interpretation and the slightly rhomboidal feature in simulated monolayer square-like structures. Here, we performed classical molecular dynamics simulations to reveal monolayer square ice in graphene nanocapillaries from the perspective of structure and dynamic characteristics. Monolayer square-like ice (instantaneous snapshot), assembled square-rhombic units with stacking faults, is a long-range ordered structure, in which the square and rhombic units are assembled in an order of alternative distribution, and the other rhombic unit forms stacking faults (polarized water chains). Spontaneous flipping of water molecules in monolayer square-like ice is intrinsic and induces transformations among different elementary units, resulting in the structural evolution of monolayer square ice in dynamics. The existence of stacking faults should be attributed to the spontaneous flipping behavior of water molecules under ambient temperature. Statistical averaging results (thermal average positions) demonstrate the inherent square characteristic of monolayer square ice. The simulated data and insight obtained here might be significant for understanding the topological structure and dynamic behavior of monolayer square ice.

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Austin W. H.; Kim, Dongho; Gates, Byron D.

2018-04-01

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

Growth Mechanism of Transition Metal Dichalcogenide Monolayers: The Role of Self-Seeding Fullerene Nuclei.

PubMed

Cain, Jeffrey D; Shi, Fengyuan; Wu, Jinsong; Dravid, Vinayak P

2016-05-24

Due to their unique optoelectronic properties and potential for next generation devices, monolayer transition metal dichalcogenides (TMDs) have attracted a great deal of interest since the first observation of monolayer MoS2 a few years ago. While initially isolated in monolayer form by mechanical exfoliation, the field has evolved to more sophisticated methods capable of direct growth of large-area monolayer TMDs. Chemical vapor deposition (CVD) is the technique used most prominently throughout the literature and is based on the sulfurization of transition metal oxide precursors. CVD-grown monolayers exhibit excellent quality, and this process is widely used in studies ranging from the fundamental to the applied. However, little is known about the specifics of the nucleation and growth mechanisms occurring during the CVD process. In this study, we have investigated the nucleation centers or "seeds" from which monolayer TMDs typically grow. This was accomplished using aberration-corrected scanning transmission electron microscopy to analyze the structure and composition of the nuclei present in CVD-grown MoS2-MoSe2 alloys. We find that monolayer growth proceeds from nominally oxi-chalcogenide nanoparticles which act as heterogeneous nucleation sites for monolayer growth. The oxi-chalcogenide nanoparticles are typically encased in a fullerene-like shell made of the TMD. Using this information, we propose a step-by-step nucleation and growth mechanism for monolayer TMDs. Understanding this mechanism may pave the way for precise control over the synthesis of 2D materials, heterostructures, and related complexes.

Respiratory syncytial virus infection disrupts monolayer integrity and function in cystic fibrosis airway cells.

PubMed

Kong, Michele; Maeng, Patrick; Hong, Jeong; Szczesniak, Rhonda; Sorscher, Eric; Sullender, Wayne; Clancy, John Paul

2013-09-19

Respiratory Syncytial Virus (RSV) infection is a common contributor to pulmonary symptoms in children with cystic fibrosis (CF). Here we examined RSV infection in immortalized bronchial epithelial cells (CFBE41o-) expressing wild-type (wt) or F508del cystic fibrosis transmembrane conductance regulator (CFTR), for monolayer integrity and RSV replication. CFBE41o- monolayers expressing wt or F508del CFTR were grown on permeable supports and inoculated with RSV A2 strain. Control experiments utilized UV-inactivated RSV and heat-killed RSV. Monolayer resistance and RSV production was monitored for up to six days post-infection. Within 24 h, a progressive decrease in monolayer resistance was observed in RSV infected F508del CFBE41o- cells, while the monolayer integrity of RSV infected wt CFTR CFBE41o- cells remained stable. RSV replication was necessary to disrupt F508del CFBE41o- monolayers as UV-irradiated and heat killed RSV had no effect on monolayer integrity, with an earlier and much more pronounced peak in RSV titer noted in F508del relative to wt CFTR-expressing cells. RSV infection of wt CFBE41o- monolayers also resulted in blunting of CFTR response. These findings identify an enhanced sensitivity of CFBE41o- cells expressing F508del CFTR to RSV infection, replication and monolayer disruption independent of the cellular immune response, and provide a novel mechanism by which cystic fibrosis airway epithelia are susceptible to RSV-dependent injury.

Symmetrical metallic and magnetic edge states of nanoribbon from semiconductive monolayer PtS2

NASA Astrophysics Data System (ADS)

Liu, Shan; Zhu, Heyu; Liu, Ziran; Zhou, Guanghui

2018-03-01

Transition metal dichalcogenides (TMD) MoS2 or graphene could be designed to metallic nanoribbons, which always have only one edge show metallic properties due to symmetric protection. In present work, a nanoribbon with two parallel metallic and magnetic edges was designed from a noble TMD PtS2 by employing first-principles calculations based on density functional theory (DFT). Edge energy, bonding charge density, band structure, density of states (DOS) and simulated scanning tunneling microscopy (STM) of four possible edge states of monolayer semiconductive PtS2 were systematically studied. Detailed calculations show that only Pt-terminated edge state among four edge states was relatively stable, metallic and magnetic. Those metallic and magnetic properties mainly contributed from 5d orbits of Pt atoms located at edges. What's more, two of those central symmetric edges coexist in one zigzag nanoribbon, which providing two atomic metallic wires thus may have promising application for the realization of quantum effects, such as Aharanov-Bohm effect and atomic power transmission lines in single nanoribbon.

Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

DOE PAGES

Hu, J.; Wu, L.; Kuttiyiel, K.; ...

2016-06-30

We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

Self-assembly and nanosphere lithography for large-area plasmonic patterns on graphene.

PubMed

Lotito, Valeria; Zambelli, Tomaso

2015-06-01

Plasmonic structures on graphene can tailor its optical properties, which is essential for sensing and optoelectronic applications, e.g. for the enhancement of photoresponsivity of graphene photodetectors. Control over their structural and, hence, spectral properties can be attained by using electron beam lithography, which is not a viable solution for the definition of patterns over large areas. For the fabrication of large-area plasmonic nanostructures, we propose to use self-assembled monolayers of nanospheres as a mask for metal evaporation and etching processes. An optimized approach based on self-assembly at air/water interface with a properly designed apparatus allows the attainment of monolayers of hexagonally closely packed patterns with high long-range order and large area coverage; special strategies are devised in order to protect graphene against damage resulting from surface treatment and further processing steps such as reactive ion etching, which could potentially impair graphene properties. Therefore we demonstrate that nanosphere lithography is a cost-effective solution to create plasmonic patterns on graphene. Copyright © 2014 Elsevier Inc. All rights reserved.

Lipophilization of ascorbic acid: a monolayer study and biological and antileishmanial activities.

PubMed

Kharrat, Nadia; Aissa, Imen; Sghaier, Manel; Bouaziz, Mohamed; Sellami, Mohamed; Laouini, Dhafer; Gargouri, Youssef

2014-09-17

Ascorbyl lipophilic derivatives (Asc-C2 to Asc-C(18:1)) were synthesized in a good yield using lipase from Staphylococcus xylosus produced in our laboratory and immobilized onto silica aerogel. Results showed that esterification had little effect on radical-scavenging capacity of purified ascorbyl esters using DPPH assay in ethanol. However, long chain fatty acid esters displayed higher protection of target lipids from oxidation. Moreover, compared to ascorbic acid, synthesized derivatives exhibited an antibacterial effect. Furthermore, ascorbyl derivatives were evaluated, for the first time, for their antileishmanial effects against visceral (Leishmania infantum) and cutaneous parasites (Leishmania major). Among all the tested compounds, only Asc-C10, Asc-C12, and Asc-C(18:1) exhibited antileishmanial activities. The interaction of ascorbyl esters with a phospholipid monolayer showed that only medium and unsaturated long chain (Asc-C10 to Asc-C(18:1)) derivative esters were found to interact efficiently with mimetic membrane of leishmania. These properties would make ascorbyl derivatives good candidates to be used in cosmetic and pharmaceutical lipophilic formulations.

Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

PubMed

Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

2015-11-04

Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation.

Interactions of doxorubicin with self-assembled monolayer-modified electrodes: electrochemical, surface plasmon resonance (SPR), and gravimetric studies.

PubMed

Nieciecka, Dorota; Krysinski, Pawel

2011-02-01

We present the results on the partitioning of doxorubicin (DOX), a potent anticancer drug, through the model membrane system, self-assembled monolayers (SAMs) on gold electrodes. The monolayers were formed from alkanethiols of comparable length with different ω-terminal groups facing the aqueous electrolyte: the hydrophobic -CH(3) groups for the case of dodecanethiol SAMs or hydrophilic -OH groups of mercaptoundecanol SAMs. The electrochemical experiments combined with the surface plasmon resonance (SPR) and gravimetric studies show that doxorubicin is likely adsorbed onto the surface of hydrophilic monolayer, while for the case of the hydrophobic one the drug mostly penetrates the monolayer moiety. The adsorption of the drug hinders further penetration of doxorubicin into the monolayer moiety.

Novel Soluble Dietary Fiber-Tannin Self-Assembled Film: A Promising Protein Protective Material.

PubMed

Song, Guo-Bin; Xu, Juan; Zheng, Hua; Feng, Ying; Zhang, Wen-Wen; Li, Kun; Ge, Shuang-shuang; Li, Kai; Zhang, Hong

2015-06-24

In this experiment, a natural promising protein protective film was fabricated through soluble dietary fiber (SDF)-tannin nanocluster self-assembly. FT-IR, XRD, and DSC tests were employed to investigate the interaction between the SDF and tannins before and after cross-linking induced by calcium ion. On the other hand, referring to the SEM and TEM results, the self-assembly process of the protein protective film could be indicated as follows: first, calcium ion, with its cross-ability, served as the "nucleus"; SDF and tannins were combined to prepare the nanoscale SDF-tannin clusters; then, the clusters were homogeneously deposited on the surface of protein to form a protective film by self-assembling hydrogen bond between tannin component of clusters as "adhesive" and protein in aqueous solutions under very mild conditions. Film thickness could also be controlled by tannin of different concentrations ranging from 114 to 1384 μm. Antibacterial test and in vitro cytotoxicity test proved that the film had a broad spectrum of antimicrobial properties and excellent cell biocompatibility, respectively, which might open up new applications in the food preservation and biomedical fields.

Clusters of isoleucine, leucine, and valine side chains define cores of stability in high-energy states of globular proteins: Sequence determinants of structure and stability.

PubMed

Kathuria, Sagar V; Chan, Yvonne H; Nobrega, R Paul; Özen, Ayşegül; Matthews, C Robert

2016-03-01

Measurements of protection against exchange of main chain amide hydrogens (NH) with solvent hydrogens in globular proteins have provided remarkable insights into the structures of rare high-energy states that populate their folding free-energy surfaces. Lacking, however, has been a unifying theory that rationalizes these high-energy states in terms of the structures and sequences of their resident proteins. The Branched Aliphatic Side Chain (BASiC) hypothesis has been developed to explain the observed patterns of protection in a pair of TIM barrel proteins. This hypothesis supposes that the side chains of isoleucine, leucine, and valine (ILV) residues often form large hydrophobic clusters that very effectively impede the penetration of water to their underlying hydrogen bond networks and, thereby, enhance the protection against solvent exchange. The linkage between the secondary and tertiary structures enables these ILV clusters to serve as cores of stability in high-energy partially folded states. Statistically significant correlations between the locations of large ILV clusters in native conformations and strong protection against exchange for a variety of motifs reported in the literature support the generality of the BASiC hypothesis. The results also illustrate the necessity to elaborate this simple hypothesis to account for the roles of adjacent hydrocarbon moieties in defining stability cores of partially folded states along folding reaction coordinates. © 2015 The Protein Society.

The behavior of the adsorption of cytochrome C on lipid monolayers: A study by the Langmuir-Blodgett technique and theoretical analysis.

PubMed

Li, Junhua; Sun, Runguang; Hao, Changchun; He, Guangxiao; Zhang, Lei; Wang, Juan

2015-10-01

Cytochrome c (Cyt c) is an essential component of the inner mitochondrial respiratory chain because of its function of transferring electrons. The feature is closely related to the interaction between Cyt c and membrane lipids. We used Langmuir-Blodgett monolayer technique combined with AFM to study the interaction of Cyt c with lipid monolayers at air-buffer interface. In our work, by comparing the mixed Cyt c-anionic (DPPS) and Cyt c-zwitterionic (DPPC/DPPE) monolayers, the adsorption capacity of Cyt c on lipid monolayers is DPPS>DPPE>DPPC, which is attributed to their different headgroup structures. π-A isothermal data show that Cyt c (v=2.5 μL) molecules are at maximum adsorption quantity on lipid monolayer. Moreover, Cyt c molecules would form aggregations and drag some lipids with them into subphase if the protein exceeds the maximum adsorption quantity. π-T curve indicates that it takes more time for Cyt c molecular conformation to rearrange on DPPE monolayer than on DPPC. The compressibility study reveals that the adsorption or intermolecular aggregation of Cyt c molecules on lipid monolayer will change the membrane fluidization. In order to quantitatively estimate Cyt c molecular adsorption properties on lipid monolayers, we fit the experimental isotherm with a simple surface state equation. A theoretical model is also introduced to analyze the liquid expanded (LE) to liquid condensed (LC) phase transition of DPPC monolayer. The results of theoretical analysis are in good agreement with the experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

PubMed

Onclin, Steffen; Mulder, Alart; Huskens, Jurriaan; Ravoo, Bart Jan; Reinhoudt, David N

2004-06-22

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Refractive index and thickness determination in Langmuir monolayers of myelin lipids.

PubMed

Pusterla, Julio M; Malfatti-Gasperini, Antonio A; Puentes-Martinez, Ximena E; Cavalcanti, Leide P; Oliveira, Rafael G

2017-05-01

Langmuir monolayers at the air/water interface are widely used as biomembrane models and for amphiphilic molecules studies in general. Under controlled intermolecular organization (lateral molecular area), surface pressure, surface potential, reflectivity (R) and other magnitudes can be precisely determined on these planar monomolecular films. However, some physical parameters such as the refractive index of the monolayer (n) still remain elusive. The refractive index is very relevant because (in combination with R) it allows for the determination of the thickness of the film. The uncertainties of n determine important errors that propagate non-linearly into the calculation of monolayers thickness. Here we present an analytical method for the determination of n in monolayers based on refractive index matching. By using a Brewster angle microscopy (BAM) setup and monolayers spread over subphases with variable refractive index (n 2 ), a minimum in R is search as a function of n 2 . In these conditions, n equals n 2 . The results shown correspond to monolayers of myelin lipids. The n values remain constant at 1.46 upon compression and equals the obtained value for myelin lipid bilayers in suspension. The values for n and R allow for the determination of thickness. We establish comparisons between these thicknesses for the monolayer and those obtained from two X-ray scattering techniques: 1) GIXOS for monolayers at the air/water interface and 2) SAXS for bilayers in bulk suspension. This allows us to conclude that the thickness that we measure by BAM includes the apolar and polar headgroup regions of the monolayer. Copyright © 2017 Elsevier B.V. All rights reserved.

Particle characteristics of different materials after ultra-short pulsed laser (USPL) irradiation

NASA Astrophysics Data System (ADS)

Meister, Joerg; Schelle, Florian; Kowalczyk, Philip; Frentzen, Matthias

2012-01-01

The exposition of nanoparticles caused by laser application in dental health care is an open discussion. Based on the fact that nanoparticles can penetrate through the mucosa, the knowledge about particle characteristics after irradiation with an USPL is of high importance. Therefore, the aim of this study was to investigate the particle characteristics, especially the size of the ablated debris after USPL irradiation. The irradiation was carried out with an USP Nd:YVO4 laser with a center wavelength of 1064 nm. Based on the pulse duration of 8 ps and a pulse repetition rate of 500 kHz the laser emits an average power of 9 W. The materials investigated were dental tissues and dental restorative materials (composite and amalgam), ceramic and different metals (gold and aluminium). The samples were irradiated with a power density in the order of 300 GW/cm2 at distances of 5, 10, 15, and 20 mm. The debris was collected on an object plate. SEM pictures were used for analysis of the ablation debris. Depending on the irradiated material, we observed different kinds of structures: vitreous, flocculent, and pellet-like. The mean particle sizes were 10 x 10 up to 30 x 30 μm2. In addition, a cluster of ablated matter (nanometer range) distributed over the whole irradiated area was found. With increasing distances the cluster structure reduced from multi-layer to mono-layer clusters. Particle sizes in the micrometer and nanometer range were found after irradiation with an USPL. The nanoparticles create a cluster structure which is influenced by increasing distances.

Next generation of the self-consistent and environment-dependent Hamiltonian: Applications to various boron allotropes from zero- to three-dimensional structures

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

Tandy, P.; Yu, Ming; Leahy, C.

2015-03-28

An upgrade of the previous self-consistent and environment-dependent linear combination of atomic orbitals Hamiltonian (referred as SCED-LCAO) has been developed. This improved version of the semi-empirical SCED-LCAO Hamiltonian, in addition to the inclusion of self-consistent determination of charge redistribution, multi-center interactions, and modeling of electron-electron correlation, has taken into account the effect excited on the orbitals due to the atomic aggregation. This important upgrade has been subjected to a stringent test, the construction of the SCED-LCAO Hamiltonian for boron. It was shown that the Hamiltonian for boron has successfully characterized the electron deficiency of boron and captured the complex chemicalmore » bonding in various boron allotropes, including the planar and quasi-planar, the convex, the ring, the icosahedral, and the fullerene-like clusters, the two-dimensional monolayer sheets, and the bulk alpha boron, demonstrating its transferability, robustness, reliability, and predictive power. The molecular dynamics simulation scheme based on the Hamiltonian has been applied to explore the existence and the energetics of ∼230 compact boron clusters B{sub N} with N in the range from ∼100 to 768, including the random, the rhombohedral, and the spherical icosahedral structures. It was found that, energetically, clusters containing whole icosahedral B{sub 12} units are more stable for boron clusters of larger size (N > 200). The ease with which the simulations both at 0 K and finite temperatures were completed is a demonstration of the efficiency of the SCED-LCAO Hamiltonian.« less

Next generation of the self-consistent and environment-dependent Hamiltonian: Applications to various boron allotropes from zero- to three-dimensional structures

NASA Astrophysics Data System (ADS)

Tandy, P.; Yu, Ming; Leahy, C.; Jayanthi, C. S.; Wu, S. Y.

2015-03-01

An upgrade of the previous self-consistent and environment-dependent linear combination of atomic orbitals Hamiltonian (referred as SCED-LCAO) has been developed. This improved version of the semi-empirical SCED-LCAO Hamiltonian, in addition to the inclusion of self-consistent determination of charge redistribution, multi-center interactions, and modeling of electron-electron correlation, has taken into account the effect excited on the orbitals due to the atomic aggregation. This important upgrade has been subjected to a stringent test, the construction of the SCED-LCAO Hamiltonian for boron. It was shown that the Hamiltonian for boron has successfully characterized the electron deficiency of boron and captured the complex chemical bonding in various boron allotropes, including the planar and quasi-planar, the convex, the ring, the icosahedral, and the fullerene-like clusters, the two-dimensional monolayer sheets, and the bulk alpha boron, demonstrating its transferability, robustness, reliability, and predictive power. The molecular dynamics simulation scheme based on the Hamiltonian has been applied to explore the existence and the energetics of ˜230 compact boron clusters BN with N in the range from ˜100 to 768, including the random, the rhombohedral, and the spherical icosahedral structures. It was found that, energetically, clusters containing whole icosahedral B12 units are more stable for boron clusters of larger size (N > 200). The ease with which the simulations both at 0 K and finite temperatures were completed is a demonstration of the efficiency of the SCED-LCAO Hamiltonian.

Induced formation and maturation of acetylcholine receptor clusters in a defined 3D bio-artificial muscle.

PubMed

Wang, Lin; Shansky, Janet; Vandenburgh, Herman

2013-12-01

Dysfunction of the neuromuscular junction is involved in a wide range of muscular diseases. The development of neuromuscular junction through which skeletal muscle is innervated requires the functional modulation of acetylcholine receptor (AchR) clustering on myofibers. However, studies on AchR clustering in vitro are mostly done on monolayer muscle cell culture, which lacks a three-dimensional (3D) structure, a prominent limitation of the two-dimensional (2D) system. To enable a better understanding on the structure-function correlation underlying skeletal muscle innervation, a muscle system with a well-defined geometry mimicking the in vivo muscular setting is needed. Here, we report a 3D bio-artificial muscle (BAM) bioengineered from green fluorescent protein-transduced C3H murine myoblasts as a novel in vitro tissue-based model for muscle innervation studies. Our cell biological and molecular analysis showed that this BAM is structurally similar to in vivo muscle tissue and can reach the perinatal differentiation stage, higher than does 2D culture. Effective clustering and morphological maturation of AchRs on BAMs induced by agrin and laminin indicate the functional activity and plasticity of this BAM system toward innervation. Taken together, our results show that the BAM provides a favorable 3D environment that at least partially recapitulates real physiological skeletal muscle with regard to innervation. With a convenience of fabrication and manipulation, this 3D in vitro system offers a novel model for studying mechanisms underlying skeletal muscle innervation and testing therapeutic strategies for relevant nervous and muscular diseases.

FRET study of G-quadruplex forming fluorescent oligonucleotide probes at the lipid monolayer interface.

PubMed

Swiatkowska, Angelika; Kosman, Joanna; Juskowiak, Bernard

2016-01-05

Spectral properties and G-quadruplex folding ability of fluorescent oligonucleotide probes at the cationic dioctadecyldimethylammonium bromide (DODAB) monolayer interface are reported. Two oligonucleotides, a 19-mer bearing thrombin binding aptamer sequence and a 21-mer with human telomeric sequence, were end-labeled with fluorescent groups (FAM and TAMRA) to give FRET probes F19T and F21T, respectively. The probes exhibited abilities to fold into a quadruplex structure and to bind metal cations (Na(+) and K(+)). Fluorescence spectra of G-quadruplex FRET probes at the monolayer interface are reported for the first time. Investigations included film balance measurements (π-A isotherms) and fluorescence spectra recording using a fiber optic accessory interfaced with a spectrofluorimeter. The effect of the presence of DODAB monolayer, metal cations and the surface pressure of monolayer on spectral behavior of FRET probes were examined. Adsorption of probe at the cationic monolayer interface resulted in the FRET signal enhancement even in the absence of metal cations. Variation in the monolayer surface pressure exerted rather modest effect on the spectral properties of probes. The fluorescence energy transfer efficiency of monolayer adsorbed probes increased significantly in the presence of sodium or potassium ion in subphase, which indicated that the probes retained their cation binding properties when adsorbed at the monolayer interface. Copyright © 2015 Elsevier B.V. All rights reserved.

A Model for Spheroid versus Monolayer Response of SK-N-SH Neuroblastoma Cells to Treatment with 15-Deoxy-PGJ 2

PubMed Central

Dunham, Ann; Chen, Paula X.; Chen, Michelle; Huynh, Milan; Rheingold, Evan; Prosper, Olivia

2016-01-01

Researchers have observed that response of tumor cells to treatment varies depending on whether the cells are grown in monolayer, as in vitro spheroids or in vivo. This study uses data from the literature on monolayer treatment of SK-N-SH neuroblastoma cells with 15-deoxy-PGJ 2 and couples it with data on growth rates for untreated SK-N-SH neuroblastoma cells grown as multicellular spheroids. A linear model is constructed for untreated and treated monolayer data sets, which is tuned to growth, death, and cell cycle data for the monolayer case for both control and treatment with 15-deoxy-PGJ 2. The monolayer model is extended to a five-dimensional nonlinear model of in vitro tumor spheroid growth and treatment that includes compartments of the cell cycle (G 1, S, G 2/M) as well as quiescent (Q) and necrotic (N) cells. Monolayer treatment data for 15-deoxy-PGJ 2 is used to derive a prediction of spheroid response under similar treatments. For short periods of treatment, spheroid response is less pronounced than monolayer response. The simulations suggest that the difference in response to treatment of monolayer versus spheroid cultures observed in laboratory studies is a natural consequence of tumor spheroid physiology rather than any special resistance to treatment. PMID:28044089

Ionic channels and nerve membrane constituents. Tetrodotoxin-like interaction of saxitoxin with cholesterol monolayers.

PubMed

Villegas, R; Barnola, F V

1972-01-01

Saxitoxin (STX) and tetrodotoxin (TTX) have the same striking property of blocking the Na(+) channels in the axolemma. Experiments with nerve plasma membrane components of the squid Dosidicus gigas have shown that TTX interacts with cholesterol monolayers. Similar experiments were carried out with STX. The effect of STX on the surface pressure-area diagrams of lipid monolayers and on the fluorescence emission spectra of sonicated nerve membranes was studied. The results indicate a TTX-like interaction of STX with cholesterol monolayers. The expansion of the monolayers caused by 10(-6)M STX was 2.2 A(2)/cholesterol molecule at 25 degrees C. From surface pressure measurements at constant cholesterol area (39 A(2)/molecule) in media with various STX concentrations, it was calculated that the STX/cholesterol surface concentration ratio is 0.54. The apparent dissociation constant of the STX-cholesterol monolayer complex is 4.0 x 10(-7)M. The STX/cholesterol ratio and the apparent dissociation constant are similar to those determined for TTX. The presence of other lipids in the monolayers affects the STX-cholesterol association. The interactions of STX and TTX with cholesterol monolayers suggest (a) that cholesterol molecules may be part of the nerve membrane Na(+) channels, or (b) that the toxin receptor at the nerve membrane shares similar chemical features with the cholesterol monolayers.

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

PubMed

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Multiscale Simulation and Modeling of Multilayer Heteroepitactic Growth of C60 on Pentacene.

PubMed

Acevedo, Yaset M; Cantrell, Rebecca A; Berard, Philip G; Koch, Donald L; Clancy, Paulette

2016-03-29

We apply multiscale methods to describe the strained growth of multiple layers of C60 on a thin film of pentacene. We study this growth in the presence of a monolayer pentacene step to compare our simulations to recent experimental studies by Breuer and Witte of submonolayer growth in the presence of monolayer steps. The molecular-level details of this organic semiconductor interface have ramifications on the macroscale structural and electronic behavior of this system and allow us to describe several unexplained experimental observations for this system. The growth of a C60 thin film on a pentacene surface is complicated by the differing crystal habits of the two component species, leading to heteroepitactical growth. In order to probe this growth, we use three computational methods that offer different approaches to coarse-graining the system and differing degrees of computational efficiency. We present a new, efficient reaction-diffusion continuum model for 2D systems whose results compare well with mesoscale kinetic Monte Carlo (KMC) results for submonolayer growth. KMC extends our ability to simulate multiple layers but requires a library of predefined rates for event transitions. Coarse-grained molecular dynamics (CGMD) circumvents KMC's need for predefined lattices, allowing defects and grain boundaries to provide a more realistic thin film morphology. For multilayer growth, in this particularly suitable candidate for coarse-graining, CGMD is a preferable approach to KMC. Combining the results from these three methods, we show that the lattice strain induced by heteroepitactical growth promotes 3D growth and the creation of defects in the first monolayer. The CGMD results are consistent with experimental results on the same system by Conrad et al. and by Breuer and Witte in which C60 aggregates change from a 2D structure at low temperature to 3D clusters along the pentacene step edges at higher temperatures.

Monolayer collapse regulating process of adsorption-desorption of palladium nanoparticles at fatty acid monolayers at the air-water interface.

PubMed

Goto, Thiago E; Lopez, Ricardo F; Iost, Rodrigo M; Crespilho, Frank N; Caseli, Luciano

2011-03-15

In this paper, we investigate the affinity of palladium nanoparticles, stabilized with glucose oxidase, for fatty acid monolayers at the air-water interface, exploiting the interaction between a planar system and spheroids coming from the aqueous subphase. A decrease of the monolayer collapse pressure in the second cycle of interface compression proved that the presence of the nanoparticles causes destabilization of the monolayer in a mechanism driven by the interpenetration of the enzyme into the bilayer/multilayer structure formed during collapse, which is not immediately reversible after monolayer expansion. Surface pressure and surface potential-area isotherms, as well as infrared spectroscopy [polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS)] and deposition onto solid plates as Langmuir-Blodgett (LB) films, were employed to construct a model in which the nanoparticle has a high affinity for the hydrophobic core of the structure formed after collapse, which provides a slow desorption rate from the interface after monolayer decompression. This may have important consequences on the interaction between the metallic particles and fatty acid monolayers, which implies the regulation of the multifunctional properties of the hybrid material.

Electronic structure in 1T-ZrS2 monolayer by strain

NASA Astrophysics Data System (ADS)

Xin, Qianqian; Zhao, Xu; Ma, Xu; Wu, Ninghua; Liu, Xiaomeng; Wei, Shuyi

2017-09-01

We report electronic structure of 1T-ZrS2 monolayer with biaxial strain from -10% to 15%, basing the first principles calculations. Our calculation results indicate that the band structure of ZrS2 monolayer was changed clearly. The location of conduction band minimum (CBM) and valence band maximum (VBM) changed with the variation of isotropic strain. At compressive strain, the location of CBM and VBM retains at M and Γ point, respectively. The band gap of ZrS2 monolayer decreases from 1.111 eV to 0 eV when compressive strain increases from 0% to -8%, which means that the ZrS2 monolayer turns to metal at -8% compressive strain. Under the tensile strain, the ZrS2 monolayer also retains be an indirect band gap semiconductor. The location of CBM moves from M to Γ point and the location of VBM moves along Γ-A-K-Γ direction. The band gap of ZrS2 monolayer firstly increases and then decreases and the biggest band gap is 1.577 eV at tensile strain 6%. We can see the compression strain is more effective than tensile strain in modulating band gap of 1T-ZrS2 monolayer.

Grain wall boundaries in centimeter-scale continuous monolayer WS2 film grown by chemical vapor deposition.

PubMed

Jia, Zhiyan; Hu, Wentao; Xiang, Jianyong; Wen, Fusheng; Nie, Anmin; Mu, Congpu; Zhao, Zhisheng; Xu, Bo; Tian, Yongjun; Liu, Zhongyuan

2018-06-22

Centimeter-scale continuous monolayer WS 2 film with large tensile strain has been successfully grown on oxidized silicon substrate by chemical vapor deposition, in which monolayer grains can be more than 200 μm in size. Monolayer WS 2 grains are observed to merge together via not only traditional grain boundaries but also non-traditional ones, which are named as grain walls (GWs) due to their nanometer-scale widths. The GWs are revealed to consist of two or three layers. Though not a monolayer, the GWs exhibit significantly enhanced fluorescence and photoluminescence. This enhancement may be attributed to abundant structural defects such as stacking faults and partial dislocations in the GWs, which are clearly observable in atomically resolved high resolution transmission electron microscopy and scanning transmission electron microscopy images. Moreover, GW-based phototransistor is found to deliver higher photocurrent than that based on monolayer film. These features of GWs provide a clue to microstructure engineering of monolayer WS 2 for specific applications in (opto)electronics.

First principles study of the electronic properties and band gap modulation of two-dimensional phosphorene monolayer: Effect of strain engineering

NASA Astrophysics Data System (ADS)

Phuc, Huynh V.; Hieu, Nguyen N.; Ilyasov, Victor V.; Phuong, Le T. T.; Nguyen, Chuong V.

2018-06-01

The effect of strain on the structural and electronic properties of monolayer phosphorene is studied by using first-principle calculations based on the density functional theory. The intra- and inter-bond length and bond angle for monolayer phosphorene is also evaluated. The intra- and inter-bond length and the bond angle for phosphorene show an opposite tendency under different directions of the applied strain. At the equilibrium state, monolayer phosphorene is a semiconductor with a direct band gap at the Γ-point of 0.91 eV. A direct-indirect band gap transition is found in monolayer phosphorene when both the compression and tensile strain are simultaneously applied along both zigzag and armchair directions. Under the applied compression strain, a semiconductor-metal transition for monolayer phosphorene is observed at -13% and -10% along armchair and zigzag direction, respectively. The direct-indirect and phase transition will largely constrain application of monolayer phosphorene to electronic and optical devices.

Controllable Growth of Monolayer MoS2 and MoSe2 Crystals Using Three-temperature-zone Furnace

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu

2017-12-01

Monolayer molybdenum disulfide (MoS2) and molybdenum diselenide (MoSe2) have attracted a great attention for their exceptional electronic and optoelectronic properties among the two dimensional family. However, controllable synthesis of monolayer crystals with high quality needs to be improved urgently. Here we demonstrate a chemical vapor deposition (CVD) growth of monolayer MoS2 and MoSe2 crystals using three-temperature-zone furnace. Systematical study of the effects of growth pressure, temperature and time on the thickness, morphology and grain size of crystals shows the good controllability. The photoluminescence (PL) characterizations indicate that the as-grown monolayer MoS2 and MoSe2 crystals possess excellent optical qualities with very small full-width-half-maximum (FWHM) of 96 me V and 57 me V, respectively. It is comparable to that of exfoliated monolayers and reveals their high crystal quality. It is promising that our strategy should be applicable for the growth of other transition metal dichalcogenides (TMDs) monolayer crystals.

Apparatus and method for intra-layer modulation of the material deposition and assist beam and the multilayer structure produced therefrom

NASA Technical Reports Server (NTRS)

Wadley, Hadyn N. G. (Inventor); Zhou, Xiaowang (Inventor); Quan, Junjie (Inventor)

2002-01-01

A method of producing a multilayer structure that has reduced interfacial roughness and interlayer mixing by using a physical-vapor deposition apparatus. In general the method includes forming a bottom layer having a first material wherein a first plurality of monolayers of the first material is deposited on an underlayer using a low incident adatom energy. Next, a second plurality of monolayers of the first material is deposited on top of the first plurality of monolayers of the first material using a high incident adatom energy. Thereafter, the method further includes forming a second layer having a second material wherein a first plurality of monolayers of the second material is deposited on the second plurality of monolayers of the first material using a low incident adatom energy. Next, a second plurality of monolayers of the second material is deposited on the first plurality of monolayers of the second material using a high incident adatom energy.

Grain wall boundaries in centimeter-scale continuous monolayer WS2 film grown by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Jia, Zhiyan; Hu, Wentao; Xiang, Jianyong; Wen, Fusheng; Nie, Anmin; Mu, Congpu; Zhao, Zhisheng; Xu, Bo; Tian, Yongjun; Liu, Zhongyuan

2018-06-01

Centimeter-scale continuous monolayer WS2 film with large tensile strain has been successfully grown on oxidized silicon substrate by chemical vapor deposition, in which monolayer grains can be more than 200 μm in size. Monolayer WS2 grains are observed to merge together via not only traditional grain boundaries but also non-traditional ones, which are named as grain walls (GWs) due to their nanometer-scale widths. The GWs are revealed to consist of two or three layers. Though not a monolayer, the GWs exhibit significantly enhanced fluorescence and photoluminescence. This enhancement may be attributed to abundant structural defects such as stacking faults and partial dislocations in the GWs, which are clearly observable in atomically resolved high resolution transmission electron microscopy and scanning transmission electron microscopy images. Moreover, GW-based phototransistor is found to deliver higher photocurrent than that based on monolayer film. These features of GWs provide a clue to microstructure engineering of monolayer WS2 for specific applications in (opto)electronics.

The stability of aluminium oxide monolayer and its interface with two-dimensional materials

NASA Astrophysics Data System (ADS)

Song, Ting Ting; Yang, Ming; Chai, Jian Wei; Callsen, Martin; Zhou, Jun; Yang, Tong; Zhang, Zheng; Pan, Ji Sheng; Chi, Dong Zhi; Feng, Yuan Ping; Wang, Shi Jie

2016-07-01

The miniaturization of future electronic devices requires the knowledge of interfacial properties between two-dimensional channel materials and high-κ dielectrics in the limit of one atomic layer thickness. In this report, by combining particle-swarm optimization method with first-principles calculations, we present a detailed study of structural, electronic, mechanical, and dielectric properties of Al2O3 monolayer. We predict that planar Al2O3 monolayer is globally stable with a direct band gap of 5.99 eV and thermal stability up to 1100 K. The stability of this high-κ oxide monolayer can be enhanced by substrates such as graphene, for which the interfacial interaction is found to be weak. The band offsets between the Al2O3 monolayer and graphene are large enough for electronic applications. Our results not only predict a stable high-κ oxide monolayer, but also improve the understanding of interfacial properties between a high-κ dielectric monolayer and two-dimensional material.

Effect of Doping on Hydrogen Evolution Reaction of Vanadium Disulfide Monolayer.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat; Wang, Zisheng

2015-12-01

As cheap and abundant materials, transitional metal dichalcogenide monolayers have attracted increasing interests for their application as catalysts in hydrogen production. In this work, the hydrogen evolution reduction of doped vanadium disulfide monolayers is investigated based on first-principles calculations. We find that the doping elements and concentration affect strongly the catalytic ability of the monolayer. We show that Ti-doping can efficiently reduce the Gibbs free energy of hydrogen adsorption in a wide range of hydrogen coverage. The catalytic ability of the monolayer at high hydrogen coverage can be improved by low Ti-density doping, while that at low hydrogen coverage is enhanced by moderate Ti-density doping. We further show that it is much easier to substitute the Ti atom to the V atom in the vanadium disulfide (VS2) monolayer than other transitional metal atoms considered here due to its lowest and negative formation energy. It is expected that the Ti-doped VS2 monolayer may be applicable in water electrolysis with improved efficiency.

Does optimism act as a buffer against posttraumatic stress over time? A longitudinal study of the protective role of optimism after the 2011 Oslo bombing.

PubMed

Birkeland, Marianne Skogbrott; Blix, Ines; Solberg, Øivind; Heir, Trond

2017-03-01

Cross-sectional studies have revealed that high levels of optimism can protect against high levels of posttraumatic stress after exposure to trauma. However, this is the first study to explore (a) the protective role of optimism in a longitudinal perspective and (b) optimism's protective effects on specific symptom clusters within the posttraumatic stress symptomatology. This study used prospective survey data from ministerial employees (n = 256) collected approximately 1, 2, and 3 years after the 2011 Oslo bombing. To examine relationships between optimism and development of posttraumatic stress, we applied a series of latent growth curve analyses of both overall posttraumatic stress and the 5 clusters within the posttraumatic stress symptomatology (intrusions, avoidance, numbing, dysphoric arousal, and anxious arousal) with predictors and interaction terms. The results showed that levels of exposure and optimism had main effects on starting levels of all clusters of posttraumatic stress. In addition, optimism had a protective-stabilizing effect on starting levels of avoidance, numbing, and dysphoric arousal. No associations between optimism and rate of change in symptoms clusters were found. These results suggest that optimism may help to neutralize the effects of high exposure on levels of symptoms of avoidance, numbing, and dysphoric arousal but not on the symptoms of intrusions and anxious arousal. Thus, individuals high in optimism still experience intrusions and anxious arousal after trauma, but may be better equipped to cope with these so they do not develop into avoidance, numbing and dyshorical arousal. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

SiP monolayers: New 2D structures of group IV-V compounds for visible-light photohydrolytic catalysts

NASA Astrophysics Data System (ADS)

Ma, Zhinan; Zhuang, Jibin; Zhang, Xu; Zhou, Zhen

2018-06-01

Because of graphene and phosphorene, two-dimensional (2D) layered materials of group IV and group V elements arouse great interest. However, group IV-V monolayers have not received due attention. In this work, three types of SiP monolayers were computationally designed to explore their electronic structure and optical properties. Computations confirm the stability of these monolayers, which are all indirect-bandgap semiconductors with bandgaps in the range 1.38-2.21 eV. The bandgaps straddle the redox potentials of water at pH = 0, indicating the potential of the monolayers for use as watersplitting photocatalysts. The computed optical properties demonstrate that certain monolayers of SiP 2D materials are absorbers of visible light and would serve as good candidates for optoelectronic devices.

Experimental validation of the Helmoltz equation for the surface potential of Langmuir monolayers

NASA Astrophysics Data System (ADS)

El Abed, Abdel I.

2009-10-01

We show in this paper that monolayers of the nonhydrophilic F8H18 semifluorinated n -alkane constitute when spread on the hydrophobic top of an alamethicin Langmuir monolayer, a very good experimental system in order to check the validity of Helmoltz equation. This system allows for a good agreement between measured and calculated surface potentials of unionized Langmuir monolayers. We show also that the relative dielectric constant of the F8H18 monolayer does not vary upon compression of the monolayer, the measured 2.9 value is in a very good agreement with literature data. We attribute this behavior to the self-aggregation of F8H18 molecules in nanosized circular domains whose size remains constant upon compression as shown by atomic force microscopy.

Graphene shield enhanced photocathodes and methods for making the same

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

Moody, Nathan Andrew

Disclosed are graphene shield enhanced photocathodes, such as high QE photocathodes. In certain embodiments, a monolayer graphene shield membrane ruggedizes a high quantum efficiency photoemission electron source by protecting a photosensitive film of the photocathode, extending operational lifetime and simplifying its integration in practical electron sources. In certain embodiments of the disclosed graphene shield enhanced photocathodes, the graphene serves as a transparent shield that does not inhibit photon or electron transmission but isolates the photosensitive film of the photocathode from reactive gas species, preventing contamination and yielding longer lifetime.

Culture on 3D Chitosan-Hyaluronic Acid Scaffolds Enhances Stem Cell Marker Expression and Drug Resistance in Human Glioblastoma Cancer Stem Cells.

PubMed

Wang, Kui; Kievit, Forrest M; Erickson, Ariane E; Silber, John R; Ellenbogen, Richard G; Zhang, Miqin

2016-12-01

The lack of in vitro models that support the growth of glioblastoma (GBM) stem cells (GSCs) that underlie clinical aggressiveness hinders developing new, effective therapies for GBM. While orthotopic patient-derived xenograft models of GBM best reflect in vivo tumor behavior, establishing xenografts is a time consuming, costly, and frequently unsuccessful endeavor. To address these limitations, a 3D porous scaffold composed of chitosan and hyaluronic acid (CHA) is synthesized. Growth and expression of the cancer stem cell (CSC) phenotype of the GSC GBM6 taken directly from fresh xenogratfs grown on scaffolds or as adherent monolayers is compared. While 2D adherent cultures grow as monolayers of flat epitheliod cells, GBM6 cells proliferate within pores of CHA scaffolds as clusters of self-adherent ovoid cells. Growth on scaffolds is accompanied by greater expression of genes that mediate epithelial-mesenchymal transition and maintain a primitive, undifferentiated phenotype, hallmarks of CSCs. Scaffold-grown cells also display higher expression of genes that promote resistance to hypoxia-induced oxidative stress. In accord, scaffold-grown cells show markedly greater resistance to clinically utilized alkylating agents compared to adherent cells. These findings suggest that our CHA scaffolds better mimic in vivo biological and clinical behavior and provide insights for developing novel individualized treatments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

NASA Astrophysics Data System (ADS)

Miranda, Paulo Barbeitas

Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayers are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayers at liquid/vapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the conformational order of surfactant monolayers. The first part of the Thesis is concerned with surfactant monolayers at the air/water interface (Langmuir films). Surface crystallization of an alcohol Langmuir film and of liquid alkanes are studied and their phase transition behaviors are found to be of different nature, although driven by similar intermolecular interactions. The effect of crystalline order of Langmuir monolayers on the interfacial water structure is also investigated. It is shown that water forms a well-ordered hydrogen-bonded network underneath an alcohol monolayer, in contrast to a fatty acid monolayer which induces a more disordered structure. In the latter case, ionization of the monolayer becomes more significant with increase of the water pH value, leading to an electric-field-induced ordering of interfacial water molecules. We also show that the orientation and conformation of fairly complicated molecules in a Langmuir monolayer can be completely mapped out using a combination of SFG and second harmonic generation (SHG). For a quantitative analysis of molecular orientation at an interface, local-field corrections must be included. The second part is a study of self-assembled surfactant monolayers at the solid/liquid interface. It is shown that the conformation of a monolayer adsorbed onto a solid substrate and immersed in a liquid is highly dependent on the monolayer surface density and on the nature of intermolecular interactions in the liquid. Fully packed monolayers are well ordered in any environment due to strong surfactant-surfactant interactions and limited liquid penetration into the monolayer. In contrast, loosely packed monolayers are very sensitive to the liquid environment. Non-polar liquids cause a mild increase in the surfactant conformational disorder. Polar liquids induce more disorder and hydrogen-bonding liquids produce highly disordered conformations due to the hydrophobic effect. When immersed in alkanes, under certain conditions the surfactant chains may become highly ordered due to their interaction with the liquid molecules (chain-chain interaction). In the case of long-chain alcohols, competition between the hydrophobic effect and chain-chain interaction is observed.

Children's loneliness, sense of coherence, family climate, and hope: developmental risk and protective factors.

PubMed

Sharabi, Adi; Levi, Uzi; Margalit, Malka

2012-01-01

The study examined the contributions of individual and familial variables for the prediction of loneliness as a developmental risk and the sense of coherence as a protective factor. The sample consisted of 287 children from grades 5-6. Their loneliness, sense of coherence, hope, effort, and family climate were assessed. Separate hierarchical multiple regression analyses revealed that family cohesion and children's hope contributed to the explanation of the risk and protective outcomes. Yet, the contribution of the family adaptability was not significant. Cluster analysis of the family climate dimensions (i.e., cohesion and adaptability) was performed to clarify the interactive roles of family adaptability together with family cohesion. The authors identified 4 separate family profiles: Children in the 2 cohesive families' clusters (Cohesive Structured Families and Cohesive Adaptable Families) reported the lowest levels of loneliness and the highest levels of personal strengths. Children within rigid and noncohesive family cluster reported the highest levels of loneliness and the lowest levels of children's sense of coherence. The unique role of the family flexibility within nonsupportive family systems was demonstrated. The results further clarified the unique profiles' characteristics of the different family clusters and their adjustment indexes in terms of loneliness and personal strengths.

Electronic structure, stability and magnetic properties of small M1-4(M = Fe, Co, Ni) clusters encapsulated inside a (BN)48 cage

NASA Astrophysics Data System (ADS)

Liang, Wenjuan; Jia, Jianfeng; Lv, Jin; Wu, Haishun

2015-02-01

The geometrical structure and magnetic properties of M1-4(M = Fe, Co and Ni) clusters within a (BN)48 cage were calculated at the BPW91/LanL2DZ level. The small M1-4 clusters generally prefer an off-centered position near the hexagonal rings in the (BN)48 cages. The (BN)48 cages can increase the stability of these small magnetic clusters while protecting the magnetic nature of M and M2 clusters.

The Personal Protective Behaviors of College Student Drinkers: Evidence of Indigenous Protective Norms

ERIC Educational Resources Information Center

Haines, Michael P.; Barker, Gregory; Rice, Richard M.

2006-01-01

Given the prevalence of alcohol consumption and the relative infrequency of harm among college students, the authors sought to determine how most college students protect themselves from alcohol-related harm. An analysis of the aggregate National College Health Assessment data identified a cluster of personal protective behaviors that correlated…

Interfacial and thermal energy driven growth and evolution of Langmuir-Schaefer monolayers of Au-nanoparticles.

PubMed

Mukhopadhyay, Mala; Hazra, S

2018-01-03

Structures of Langmuir-Schaefer (LS) monolayers of thiol-coated Au-nanoparticles (DT-AuNPs) deposited on H-terminated and OTS self-assembled Si substrates (of different hydrophobic strength and stability) and their evolution with time under ambient conditions, which plays an important role for their practical use as 2D-nanostructures over large areas, were investigated using the X-ray reflectivity technique. The strong effect of substrate surface energy (γ) on the initial structures and the competitive role of room temperature thermal energy (kT) and the change in interfacial energy (Δγ) at ambient conditions on the evolution and final structures of the DT-AuNP LS monolayers are evident. The strong-hydrophobic OTS-Si substrate, during transfer, seems to induce strong attraction towards hydrophobic DT-AuNPs on hydrophilic (repulsive) water to form vertically compact partially covered (with voids) monolayer structures (of perfect monolayer thickness) at low pressure and nearly covered buckled monolayer structures (of enhanced monolayer thickness) at high pressure. After transfer, the small kT-energy (in absence of repulsive water) probably fluctuates the DT-AuNPs to form vertically expanded monolayer structures, through systematic exponential growth with time. The effect is prominent for the film deposited at low pressure, where the initial film-coverage and film-thickness are low. On the other hand, the weak-hydrophobic H-Si substrate, during transfer, appears to induce optimum attraction towards DT-AuNPs to better mimic the Langmuir monolayer structures on it. After transfer, the change in the substrate surface nature, from weak-hydrophobic to weak-hydrophilic with time (i.e. Δγ-energy, apart from the kT-energy), enhances the size of the voids and weakens the monolayer/bilayer structure to form a similar expanded monolayer structure, the thickness of which is probably optimized by the available thermal energy.

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

Y Itoh; B Kim; R Gearba

C{sub 60} and C{sub 60}-ferrocene conjugated molecule bearing five carboxylic acids successfully anchor onto a silicon oxide surface as a monolayer through a simple method of simply dipping an amino-terminated surface into the solution of the C{sub 60} derivatives. The monolayer structure was characterized by UV-vis spectroscopy, X-ray reflectivity, X-ray photoelectron spectroscopy, and IR spectroscopy to reveal that the molecules are standing presenting its C{sub 60} spherical face at the surface. The electronic effect of the C{sub 60} monolayer and the ferrocene-functionalized C{sub 60} monolayer in OFET devices was investigated. When an n-type OFET was fabricated on the ferrocene functionalizedmore » monolayer, we see an enhancement in the mobility. When a p-type OFET was made the ferrocene-functionalized C{sub 60} monolayer showed a lowering of the carrier mobility.« less

Broadband nonlinear optical response of monolayer MoSe2 under ultrafast excitation

NASA Astrophysics Data System (ADS)

Nie, Zhonghui; Trovatello, Chiara; Pogna, Eva A. A.; Dal Conte, Stefano; Miranda, Paulo B.; Kelleher, Edmund; Zhu, Chunhui; Turcu, Ion Crisitan Edmond; Xu, Yongbing; Liu, Kaihui; Cerullo, Giulio; Wang, Fengqiu

2018-01-01

Due to their strong light-matter interaction, monolayer transition metal dichalcogenides (TMDs) have proven to be promising candidates for nonlinear optics and optoelectronics. Here, we characterize the nonlinear absorption of chemical vapour deposition (CVD)-grown monolayer MoSe2 in the 720-810 nm wavelength range. Surprisingly, despite the presence of strong exciton resonances, monolayer MoSe2 exhibits a uniform modulation depth of ˜80 ± 3% and a saturation intensity of ˜2.5 ± 0.4 MW/cm2. In addition, pump-probe spectroscopy is performed to confirm the saturable absorption and reveal the photocarrier relaxation dynamics over hundreds of picoseconds. Our results unravel the unique broadband nonlinear absorptive behavior of monolayer MoSe2 under ultrafast excitation and highlight the potential of using monolayer TMDs as broadband ultrafast optical switches with customizable saturable absorption characteristics.

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

Xu, Yuanfeng; Zhang, Hao; Shao, Hezhu

The extraordinary properties and the novel applications of black phosphorene induce the research interest in the monolayer group-IV monochalcogenides. Here using first-principles calculations, we systematically investigate the electronic, transport, and optical properties of monolayer α- and β-GeSe, revealing a direct band gap of 1.61 eV for monolayer α-GeSe and an indirect band gap of 2.47 eV for monolayer β-GeSe. For monolayer β-GeSe, the electronic/hole transport is anisotropic, with an extremely high electron mobility of 2.93×104cm2/Vs along the armchair direction, comparable to that of black phosphorene. However, for β-GeSe, robust band gaps nearly independent of the applied tensile strain along themore » armchair direction are observed. Both monolayer α- and β-GeSe exhibit anisotropic optical absorption in the visible spectrum.« less

Superheating of monolayer ice in graphene nanocapillaries

NASA Astrophysics Data System (ADS)

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-04-01

The freezing and melting of low-dimensional materials, either via a first-order phase transition or without any discontinuity in thermodynamic, still remain a matter of debate. Melting (superheating) in two-dimensional (2D) ice is fundamentally different from that in bulk counterpart. Here, we perform comprehensive molecular dynamics simulations of the superheating of monolayer ice in graphene nanocapillaries to understand the nature of melting transition in 2D water/ice. We find four different superheating (melting) scenarios can happen in the superheating of monolayer square-like ice, which are closely related to the lateral pressure and the channel width. The anomalous two-stage melting transition with arisen coexistence phase is found, which reveals the unknown extraordinary characteristics of melting in 2D water/ice. Under ultrahigh lateral pressure, the intermediate monolayer triangular amorphous ice will be formed during the superheating of monolayer square-like ice with both continuous-like and first-order phase transitions. Whereas, under low lateral pressure, the melting in monolayer square-like ice manifests typical discontinuity with notable hysteresis-loop in potential energy during the heating/cooling process. Moreover, we also find that highly puckered monolayer square-like ice can transform into bilayer AB-stacked amorphous ice with square pattern in the superheating process. The superheating behavior under high lateral pressure can be partly regarded as the compression limit of superheated monolayer water. The intrinsic phenomena in our simulated superheating of monolayer ice may be significant for understanding the melting behavior in 2D water/ice.

Superheating of monolayer ice in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-04-07

The freezing and melting of low-dimensional materials, either via a first-order phase transition or without any discontinuity in thermodynamic, still remain a matter of debate. Melting (superheating) in two-dimensional (2D) ice is fundamentally different from that in bulk counterpart. Here, we perform comprehensive molecular dynamics simulations of the superheating of monolayer ice in graphene nanocapillaries to understand the nature of melting transition in 2D water/ice. We find four different superheating (melting) scenarios can happen in the superheating of monolayer square-like ice, which are closely related to the lateral pressure and the channel width. The anomalous two-stage melting transition with arisen coexistence phase is found, which reveals the unknown extraordinary characteristics of melting in 2D water/ice. Under ultrahigh lateral pressure, the intermediate monolayer triangular amorphous ice will be formed during the superheating of monolayer square-like ice with both continuous-like and first-order phase transitions. Whereas, under low lateral pressure, the melting in monolayer square-like ice manifests typical discontinuity with notable hysteresis-loop in potential energy during the heating/cooling process. Moreover, we also find that highly puckered monolayer square-like ice can transform into bilayer AB-stacked amorphous ice with square pattern in the superheating process. The superheating behavior under high lateral pressure can be partly regarded as the compression limit of superheated monolayer water. The intrinsic phenomena in our simulated superheating of monolayer ice may be significant for understanding the melting behavior in 2D water/ice.

Simultaneous measurement of displacement current and absorption spectra of Langmuir film

NASA Astrophysics Data System (ADS)

Xu, Xiaobin; Kubota, Tohru; Iwamoto, Mitsumasa

1995-07-01

A Maxwell-displacement-current measuring system coupled with the system used for the measurement of absorption spectra of monolayers on a water surface has been developed. Using this system, the displacement current and the absorbance across monolayers of squarylium dye at the air/water surface were detected. It was found that the change in J aggregate in the monolayers with monolayer compression was detectable using the system.

Large-area synthesis of high-quality monolayer 1T’-WTe2 flakes

NASA Astrophysics Data System (ADS)

Naylor, Carl H.; Parkin, William M.; Gao, Zhaoli; Kang, Hojin; Noyan, Mehmet; Wexler, Robert B.; Tan, Liang Z.; Kim, Youngkuk; Kehayias, Christopher E.; Streller, Frank; Zhou, Yu Ren; Carpick, Robert; Luo, Zhengtang; Park, Yung Woo; Rappe, Andrew M.; Drndić, Marija; Kikkawa, James M.; Johnson, A. T. Charlie

2017-06-01

Large-area growth of monolayer films of the transition metal dichalcogenides is of the utmost importance in this rapidly advancing research area. The mechanical exfoliation method offers high quality monolayer material but it is a problematic approach when applied to materials that are not air stable. One important example is 1T’-WTe2, which in multilayer form is reported to possess a large non saturating magnetoresistance, pressure induced superconductivity, and a weak antilocalization effect, but electrical data for the monolayer is yet to be reported due to its rapid degradation in air. Here we report a reliable and reproducible large-area growth process for obtaining many monolayer 1T’-WTe2 flakes. We confirmed the composition and structure of monolayer 1T’-WTe2 flakes using x-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, atomic force microscopy, Raman spectroscopy and aberration corrected transmission electron microscopy. We studied the time dependent degradation of monolayer 1T’-WTe2 under ambient conditions, and we used first-principles calculations to identify reaction with oxygen as the degradation mechanism. Finally we investigated the electrical properties of monolayer 1T’-WTe2 and found metallic conduction at low temperature along with a weak antilocalization effect that is evidence for strong spin-orbit coupling.

Pressure-induced enhancement in the thermoelectric properties of monolayer and bilayer SnSe2

NASA Astrophysics Data System (ADS)

Zou, Daifeng; Yu, Chuanbin; Li, Yuhao; Ou, Yun; Gao, Yongyi

2018-03-01

The electronic structures of monolayer and bilayer SnSe2 under pressure were investigated by using first-principles calculations including van der Waals interactions. For monolayer SnSe2, the variation of electronic structure under pressure is controlled by pressure-dependent lattice parameters. For bilayer SnSe2, the changes in electronic structure under pressure are dominated by intralayer and interlayer atomic interactions. The n-type thermoelectric properties of monolayer and bilayer SnSe2 under pressure were calculated on the basis of the semi-classical Boltzmann transport theory. It was found that the electrical conductivity of monolayer and bilayer SnSe2 can be enhanced under pressure, and such dependence can be attributed to the pressure-induced changes of the Se-Sn antibonding states in conduction band. Finally, the doping dependence of power factors of n-type monolayer and bilayer SnSe2 at three different pressures were estimated, and the results unveiled that thermoelectric performance of n-type monolayer and bilayer SnSe2 can be improved by applying external pressure. This study benefits to understand the nature of the transport properties for monolayer and bilayer SnSe2 under pressure, and it offers valuable insight for designing high-performance thermoelectric few-layered SnSe2 through strain engineering induced by external pressure.

Impact of Lipid Oxidization on Vertical Structures and Electrostatics of Phospholipid Monolayers Revealed by Combination of Specular X-ray Reflectivity and Grazing-Incidence X-ray Fluorescence.

PubMed

Korytowski, Agatha; Abuillan, Wasim; Makky, Ali; Konovalov, Oleg; Tanaka, Motomu

2015-07-30

The influence of phospholipid oxidization of floating monolayers on the structure perpendicular to the global plane and on the density profiles of ions near the lipid monolayer has been investigated by a combination of grazing incidence X-ray fluorescence (GIXF) and specular X-ray reflectivity (XRR). Systematic variation of the composition of the floating monolayers unravels changes in the thickness, roughness and electron density of the lipid monolayers as a function of molar fraction of oxidized phospholipids. Simultaneous GIXF measurements enable one to qualitatively determine the element-specific density profiles of monovalent (K(+) or Cs(+)) and divalent ions (Ca(2+)) in the vicinity of the interface in the presence and absence of two types of oxidized phospholipids (PazePC and PoxnoPC) with high spatial accuracy (±5 Å). We found the condensation of Ca(2+) near carboxylated PazePC was more pronounced compared to PoxnoPC with an aldehyde group. In contrast, the condensation of monovalent ions could hardly be detected even for pure oxidized phospholipid monolayers. Moreover, pure phospholipid monolayers exhibited almost no ion specific condensation near the interface. The quantitative studies with well-defined floating monolayers revealed how the elevation of lipid oxidization level alters the structures and functions of cell membranes.

Pressure-induced enhancement in the thermoelectric properties of monolayer and bilayer SnSe2.

PubMed

Zou, Daifeng; Yu, Chuanbin; Li, Yuhao; Ou, Yun; Gao, Yongyi

2018-03-01

The electronic structures of monolayer and bilayer SnSe 2 under pressure were investigated by using first-principles calculations including van der Waals interactions. For monolayer SnSe 2 , the variation of electronic structure under pressure is controlled by pressure-dependent lattice parameters. For bilayer SnSe 2 , the changes in electronic structure under pressure are dominated by intralayer and interlayer atomic interactions. The n -type thermoelectric properties of monolayer and bilayer SnSe 2 under pressure were calculated on the basis of the semi-classical Boltzmann transport theory. It was found that the electrical conductivity of monolayer and bilayer SnSe 2 can be enhanced under pressure, and such dependence can be attributed to the pressure-induced changes of the Se-Sn antibonding states in conduction band. Finally, the doping dependence of power factors of n -type monolayer and bilayer SnSe 2 at three different pressures were estimated, and the results unveiled that thermoelectric performance of n -type monolayer and bilayer SnSe 2 can be improved by applying external pressure. This study benefits to understand the nature of the transport properties for monolayer and bilayer SnSe 2 under pressure, and it offers valuable insight for designing high-performance thermoelectric few-layered SnSe 2 through strain engineering induced by external pressure.

Impact of artificial monolayer application on stored water quality at the air-water interface.

PubMed

Pittaway, P; Martínez-Alvarez, V; Hancock, N; Gallego-Elvira, B

2015-01-01

Evaporation mitigation has the potential to significantly improve water use efficiency, with repeat applications of artificial monolayer formulations the most cost-effective strategy for large water storages. Field investigations of the impact of artificial monolayers on water quality have been limited by wind and wave turbulence, and beaching. Two suspended covers differing in permeability to wind and light were used to attenuate wind turbulence, to favour the maintenance of a condensed monolayer at the air/water interface of a 10 m diameter tank. An octadecanol formulation was applied twice-weekly to one of two covered tanks, while a third clean water tank remained uncovered for the 14-week duration of the trial. Microlayer and subsurface water samples were extracted once a week to distinguish impacts associated with the installation of covers, from the impact of prolonged monolayer application. The monolayer was selectively toxic to some phytoplankton, but the toxicity of hydrocarbons leaching from a replacement liner had a greater impact. Monolayer application did not increase water temperature, humified dissolved organic matter, or the biochemical oxygen demand, and did not reduce dissolved oxygen. The impact of an octadecanol monolayer on water quality and the microlayer may not be as detrimental as previously considered.

Liquid-Phase Exfoliation into Monolayered BiOBr Nanosheets for Photocatalytic Oxidation and Reduction

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

Yu, Hongjian; Huang, Hongwei; Xu, Kang

2017-09-26

Monolayered photocatalytic materials have attracted huge research interests in terms of their large specific surface area and ample active sites. Sillén-structured layered BiOX (X = Cl, Br, I) casts great prospects owing to their strong photo-oxidation ability and high stability. Fabrication of monolayered BiOX by a facile, low-cost, and scalable approach is highly challenging and anticipated. Herein, we describe the large-scale preparation of monolayered BiOBr nanosheets with a thickness of ~0.85 nm via a readily achievable liquid-phase exfoliation strategy with assistance of formamide at ambient conditions. The as-obtained monolayered BiOBr nanosheets are allowed diverse superiorities, such as enhanced specific surfacemore » area, promoted band structure, and strengthened charge separation. Profiting from these benefits, the advanced BiOBr monolayers not only show excellent adsorption and photodegradation performance for treating contaminants, but also demonstrate a greatly promoted photocatalytic activity for CO2 reduction into CO and CH4. Additionally, monolayered BiOI nanosheets have also been obtained by the same synthetic approach. Our work offers a mild and general approach for preparation of monolayered BiOX, and may have huge potential to be extended to the synthesis of other single-layer two-dimensional materials.« less

Chemisorbed monolayers of corannulene penta-thioethers on gold.

PubMed

Angelova, Polina; Solel, Ephrath; Parvari, Galit; Turchanin, Andrey; Botoshansky, Mark; Gölzhäuser, Armin; Keinan, Ehud

2013-02-19

Penta(tert-butylthio)corannulene and penta(4-dimethylaminophenylthio)corannulene form highly stable monolayers on gold surfaces, as indicated by X-ray photoelectron spectroscopy (XPS). Formation of these homogeneous monolayers involves multivalent coordination of the five sulfur atoms to gold with the peripheral alkyl or aryl substituents pointing away from the surface. No dissociation of C-S bonds upon binding could be observed at room temperature. Yet, the XPS experiments reveal strong chemical bonding between the thioether groups and gold. Temperature-dependent XPS study shows that the thermal stability of the monolayers is higher than the typical stability of self-assembled monolayers (SAMs) of thiolates on gold.

Femtosecond transient absorption dynamics of close-packed gold nanocrystal monolayer arrays*1

NASA Astrophysics Data System (ADS)

Eah, Sang-Kee; Jaeger, Heinrich M.; Scherer, Norbert F.; Lin, Xiao-Min; Wiederrecht, Gary P.

2004-03-01

Femtosecond transient absorption spectroscopy is used to investigate hot electron dynamics of close-packed 6 nm gold nanocrystal monolayers. Morphology changes of the monolayer caused by the laser pump pulse are monitored by transmission electron microscopy. At low pump power, the monolayer maintains its structural integrity. Hot electrons induced by the pump pulse decay through electron-phonon (e-ph) coupling inside the nanocrystals with a decay constant that is similar to the value for bulk films. At high pump power, irreversible particle aggregation and sintering occur in the nanocrystal monolayer, which cause damping and peak shifting of the transient bleach signal.

First-principles study of the heavy metal atoms X (X=Au, Hg, Tl or Pb) doped monolayer WS2

NASA Astrophysics Data System (ADS)

Xie, Ling-Yun; Zhang, Jian-Min

2017-12-01

The heavy metal atoms X (X = Au, Hg, Tl or Pb) doped monolayer WS2 systems have been studied by using the spin-polarized first-principles calculations. Although pure monolayer WS2 system is a nonmagnetic semiconductor with a direct band gap of 1.820 eV, the Au and Hg atoms doped monolayer WS2 systems change to half-metal (HM) ferromagnets with the total magnetic moments 0.697 and 1.776 μB as well as the smaller spin-down gaps 0.605 and 0.527 eV, respectively, while the Tl and Pb atoms doped monolayer WS2 systems change to magnetic metal with the total magnetic moment 0.584 μB and a nonmagnetic metal. From the minimization of the formation energy, we find that it is easy to incorporate these heavy metal atoms into monolayer WS2 system under S-rich condition, especially for the Au doped monolayer WS2 system not only easily to be formed but also a HM ferromagnet, and thus the best candidate used in the spintronic devices.

Strain-mediated electronic properties of pristine and Mn-doped GaN monolayers

NASA Astrophysics Data System (ADS)

Sharma, Venus; Srivastava, Sunita

2018-04-01

Graphene-like two-dimensional (2D) monolayer structures GaN has gained enormous amount of interest due to high thermal stability and inherent energy band gap for practical applications. First principles calculations are performed to investigate the electronic structure and strain-mediated electronic properties of pristine and Mn-doped GaN monolayer. Binding energy of Mn dopant at various adsorption site is found to be nearly same indicating these sites to be equally favorable for adsorption of foreign atom. Depending on the adsorption site, GaN monolayer can act as p-type or n-type magnetic semiconductor. The tensile strength of both pristine and doped GaN monolayer (∼24 GPa) at ultimate tensile strain of 34% is comparable with the tensile strength of graphene. The in-plane biaxial strain modulate the energy band gap of both pristine and doped-monolayer from direct to indirect gap semiconductor and finally retendered theme into metal at critical value of applied strain. These characteristics make GaN monolayer to be potential candidate for the future applications in tunable optoelectronics.

Charge injection and transport in a single organic monolayer island

NASA Astrophysics Data System (ADS)

Vuillaume, Dominique

2005-03-01

We report how electrons and holes, that are locally injected in a single organic monolayer island (where organic monolayers are made from sublimated oligomers (pentacene and other oligoacenes), or made from chemisorption in solution (self-assembled monolayers) of pi-conjugated moieties), stay localized or are able to delocalize over the island as a function of the molecular conformation (order vs. disorder) of this island. Charge carriers were locally injected by the apex of an atomic force microscope tip, and the resulting two-dimensional distribution and concentration of injected charges were measured by electrical force microscopy (EFM) experiments. We show that in crystalline monolayer islands, both electrons and holes can be equally injected, at a similar charge concentration for symmetric injection bias conditions, and that both charge carriers are delocalized over the whole island. On the contrary, charges injected into a more disordered monolayer stay localized at their injection point. These different results are discussed in relation with the electrical performances of molecular devices made from these monolayers (OFET, SAMFET). These results provide insight into the electronic properties, at the nanometer scale, of these molecular devices.

Mixed Monolayers of Spiropyrans Maximize Tunneling Conductance Switching by Photoisomerization at the Molecule–Electrode Interface in EGaIn Junctions

PubMed Central

2016-01-01

This paper describes the photoinduced switching of conductance in tunneling junctions comprising self-assembled monolayers of a spiropyran moiety using eutectic Ga–In top contacts. Despite separation of the spiropyran unit from the electrode by a long alkyl ester chain, we observe an increase in the current density J of a factor of 35 at 1 V when the closed form is irradiated with UV light to induce the ring-opening reaction, one of the highest switching ratios reported for junctions incorporating self-assembled monolayers. The magnitude of switching of hexanethiol mixed monolayers was higher than that of pure spiropyran monolayers. The first switching event recovers 100% of the initial value of J and in the mixed-monolayers subsequent dampening is not the result of degradation of the monolayer. The observation of increased conductivity is supported by zero-bias DFT calculations showing a change in the localization of the density of states near the Fermi level as well as by simulated transmission spectra revealing positive resonances that broaden and shift toward the Fermi level in the open form. PMID:27602432

Large-area snow-like MoSe2 monolayers: synthesis, growth mechanism, and efficient electrocatalyst application.

PubMed

Huang, Jingwen; Liu, Huiqiang; Jin, Bo; Liu, Min; Zhang, Qingchun; Luo, Liqiong; Chu, Shijin; Chu, Sheng; Peng, Rufang

2017-07-07

This study explores the large-area synthesis of controllable morphology, uniform, and high-quality monolayer. MoSe 2 is essential for its potential application in optoelectronics, photocatalysis, and renewable energy sources. In this study, we successfully synthesized snow-like MoSe 2 monolayers using a simple chemical vapor deposition method. Results reveal that snow-like MoSe 2 is a single crystal with a hexagonal structure, a thickness of ∼0.9 nm, and a lateral dimension of up to 20 μm. The peak position of the photoluminescence spectra is ∼1.52 eV corresponding to MoSe 2 monolayer. The growth mechanism of the snow-like MoSe 2 monolayer was investigated and comprised a four-step process during growth. Finally, we demonstrate that the snow-like MoSe 2 monolayers are ideal electrocatalysts for hydrogen evolution reactions (HERs), reflected by a low Tafel slope of ∼68 mV/decade. Compared with the triangular-shaped MoSe 2 monolayer, the hexangular snow-like shape with plentiful edges is superior for perfect electrocatalysts for HERs or transmission devices of optoelectronic signals.

Ultra-thin ZnSe: Anisotropic and flexible crystal structure

NASA Astrophysics Data System (ADS)

Bacaksiz, C.; Senger, R. T.; Sahin, H.

2017-07-01

By performing density functional theory-based calculations, we investigate the structural, electronic, and mechanical properties of the thinnest ever ZnSe crystal [11]. The vibrational spectrum analysis reveals that the monolayer ZnSe is dynamically stable and has flexible nature with its soft phonon modes. In addition, a direct electronic band gap is found at the gamma point for the monolayer structure of ZnSe. We also elucidate that the monolayer ZnSe has angle dependent in-plane elastic parameters. In particular, the in-plane stiffness values are found to be 2.07 and 6.89 N/m for the arm-chair and zig-zag directions, respectively. The angle dependency is also valid for the Poisson ratio of the monolayer ZnSe. More significantly, the in-plane stiffness of the monolayer ZnSe is the one-tenth of Young modulus of bulk zb-ZnSe which indicates that the monolayer ZnSe is a quite flexible single layer crystal. With its flexible nature and in-plane anisotropic mechanical properties, the monolayer ZnSe is a good candidate for nanoscale mechanical applications.

Size-tunable Lateral Confinement in Monolayer Semiconductors

DOE PAGES

Wei, Guohua; Czaplewski, David A.; Lenferink, Erik J.; ...

2017-06-12

Three-dimensional confinement allows semiconductor quantum dots to exhibit size-tunable electronic and optical properties that enable a wide range of opto-electronic applications from displays, solar cells and bio-medical imaging to single-electron devices. Additional modalities such as spin and valley properties in monolayer transition metal dichalcogenides provide further degrees of freedom requisite for information processing and spintronics. In nanostructures, however, spatial confinement can cause hybridization that inhibits the robustness of these emergent properties. Here in this paper, we show that laterally-confined excitons in monolayer MoS 2 nanodots can be created through top-down nanopatterning with controlled size tunability. Unlike chemically-exfoliated monolayer nanoparticles, themore » lithographically patterned monolayer semiconductor nanodots down to a radius of 15 nm exhibit the same valley polarization as in a continuous monolayer sheet. The inherited bulk spin and valley properties, the size dependence of excitonic energies, and the ability to fabricate MoS 2 nanostructures using semiconductor-compatible processing suggest that monolayer semiconductor nanodots have potential to be multimodal building blocks of integrated optoelectronics and spintronics systems« less

From the Superatom Model to a Diverse Array of Super-Elements: A Systematic Study of Dopant Influence on the Electronic Structure of Thiolate-Protected Gold Clusters.

PubMed

Schacht, Julia; Gaston, Nicola

2016-10-18

The electronic properties of doped thiolate-protected gold clusters are often referred to as tunable, but their study to date, conducted at different levels of theory, does not allow a systematic evaluation of this claim. Here, using density functional theory, the applicability of the superatomic model to these clusters is critically evaluated, and related to the degree of structural distortion and electronic inhomogeneity in the differently doped clusters, with dopant atoms Pd, Pt, Cu, and Ag. The effect of electron number is systematically evaluated by varying the charge on the overall cluster, and the nominal number of delocalized electrons, employed in the superatomic model, is compared to the numbers obtained from Bader analysis of individual atomic charges. We find that the superatomic model is highly applicable to all of these clusters, and is able to predict and explain the changing electronic structure as a function of charge. However, significant perturbations of the model arise due to doping, due to distortions of the core structure of the Au 13 [RS(AuSR) 2 ] 6 - cluster. In addition, analysis of the electronic structure indicates that the superatomic character is distributed further across the ligand shell in the case of the doped clusters, which may have implications for the self-assembly of these clusters into materials. The prediction of appropriate clusters for such superatomic solids relies critically on such quantitative analysis of the tunability of the electronic structure. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Planar CoB18- Cluster: a New Motif for - and Metallo-Borophenes

NASA Astrophysics Data System (ADS)

Chen, Teng-Teng; Jian, Tian; Lopez, Gary; Li, Wan-Lu; Chen, Xin; Li, Jun; Wang, Lai-Sheng

2016-06-01

Combined Photoelectron Spectroscopy (PES) and theoretical calculations have found that anion boron clusters (Bn-) are planar and quasi-planar up to B25-. Recent works show that anion pure boron clusters continued to be planar at B27-,B30-,B35- and B36-. B35- and B36- provide the first experimental evidence for the viability of the two-dimensional (2D) boron sheets (Borophene). The 2D to three-dimensional (3D) transitions are shown to happen at B40-,B39- and B28-, which possess cage-like structures. These fullerene-like boron cage clusters are named as Borospherene. Recently, borophenes or similar structures are claimed to be synthesized by several groups. Following an electronic design principle, a series of transition-metal-doped boron clusters (M©Bn-, n=8-10) are found to possess the monocyclic wheel structures. Meanwhile, CoB12- and RhB12- are revealed to adopt half-sandwich-type structures with the quasi-planar B12 moiety similar to the B12- cluster. Very lately, we show that the CoB16- cluster possesses a highly symmetric Cobalt-centered drum-like structure, with a new record of coordination number at 16. Here we report the CoB18- cluster to possess a unique planar structure, in which the Co atom is doped into the network of a planar boron cluster. PES reveals that the CoB18- cluster is a highly stable electronic system with the first adiabatic detachment energy (ADE) at 4.0 eV. Global minimum searches along with high-level quantum calculations show the global minimum for CoB18- is perfectly planar and closed shell (1A1) with C2v symmetry. The Co atom is bonded with 7 boron atoms in the closest coordination shell and the other 11 boron atoms in the outer coordination shell. The calculated vertical detachment energy (VDE) values match quite well with our experimental results. Chemical bonding analysis by the Adaptive Natural Density Partitioning (AdNDP) method shows the CoB18- cluster is π-aromatic with four 4-centered-2-electron (4c-2e) π bonds and one 19-centered-2-electron (19c-2e) π bond, 10 π electrons in total. This perfectly planar structure reveals the viability of creating a new class of hetero-borophenes and metallo-borophenes by doping metal atoms into the plane of monolayer boron atoms. This gives a new approach to design perspective hetero-borophenes and metallo-borophenes materials with tunable chemical, magnetic and optical properties.

Ellipsometric study of Al2O3/Ag/Si and SiO2/Ag/quartz ashed in an oxygen plasma. [protective coatings to prevent degradation of materials in low earth orbits

NASA Technical Reports Server (NTRS)

De, Bhola N.; Woollam, John A.

1989-01-01

The growth of silver oxide (proposed as a potentially useful protective coating for space environment) on a silver mirror coated with an Al2O3 or a SiO2 protective layer was investigated using the monolayer-sensitive variable angle of incidence spectroscopic ellipsometry technique. The samples were exposed to a pure oxygen plasma in a plasma asher, and the silver oxide growth was monitored as a function of the exposure time. It was found that atomic oxygen in the asher penetrated through the SiO2 or Al2O3 coatings to convert the silver underneath to silver oxide, and that the quantity of the silver oxide formed was proportional to the ashing time. The band gap of silver oxide was determined to be 1.3 eV. A schematic diagram of the variable angle of incidence spectroscopic ellipsometer is included.

Penta-SiC5 monolayer: A novel quasi-planar indirect semiconductor with a tunable wide band gap

NASA Astrophysics Data System (ADS)

Naseri, Mosayeb

2018-03-01

In this paper, by using of the first principles calculations in the framework of the density functional theory, we systematically investigated the structure, stability, electronic and optical properties of a novel two-dimensional pentagonal monolayer semiconductors namely penta-SiC5 monolayer. Comparing elemental silicon, diamond, and previously reported 2D carbon allotropes, our calculation shows that the predicted penta-SiC5 monolayer has a metastable nature. The calculated results indicate that the predicted monolayer is an indirect semiconductor with a wide band gap of about 2.82 eV by using Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional level of theory which can be effectively tuned by external biaxial strains. The obtained exceptional electronic properties suggest penta-SiC5 monolayer as promising candidates for application in new electronic devices in nano scale.

Methylene blue adsorption on a DMPA lipid langmuir monolayer.

PubMed

Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

2010-07-12

Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed.

Assembling and compressing a semifluorinated alkane monolayer on a hydrophobic surface: Structural and dielectric properties

NASA Astrophysics Data System (ADS)

El Abed, Abdel I.; Ionov, Radoslav; Daoud, Mohamed; Abillon, Olivier

2004-11-01

We investigate the dynamic behavior upon lateral compression of a semifluorinated alkane F(CF2)8(CH2)18H (denoted F8H18 ), spread on the hydrophobic top of a suitable amphiphilic monolayer: namely, a natural α -helix alamethicin peptide (alam). We show, in particular, the formation of an asymmetric flat bilayer by compressing at the air-water interface a mixed Langmuir film made of F8H18 and alam. The particular chemical structure of F8H18 , the suitable structure of the underlying alam monolayer and its collapse properties, allow for a continuous compression of the upper F8H18 monolayer while the density of the lower alam monolayer remains constant. Combining grazing incidence x-ray reflectivity, surface potential, and atomic force microscopy data allow for the determination of the orientation and dielectric constant of the upper F8H18 monolayer.

X-ray photoelectron spectroscopy study of para-substituted benzoic acids chemisorbed to aluminum oxide thin films

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

Kreil, Justin; Ellingsworth, Edward; Szulczewski, Greg

A series of para-substituted, halogenated (F, Cl, Br, and I) benzoic acid monolayers were prepared on the native oxide of aluminum surfaces by solution self-assembly and spin-coating techniques. The monolayers were characterized by x-ray photoelectron spectroscopy (XPS) and water contact angles. Several general trends are apparent. First, the polarity of the solvent is critical to monolayer formation. Protic polar solvents produced low coverage monolayers; in contrast, nonpolar solvents produced higher coverage monolayers. Second, solution deposition yields a higher surface coverage than spin coating. Third, the thickness of the monolayers determined from XPS suggests the plane of the aromatic ring ismore » perpendicular to the surface with the carboxylate functional group most likely binding in a bidentate chelating geometry. Fourth, the saturation coverage (∼2.7 × 10{sup 14} molecules cm{sup −2}) is independent of the para-substituent.« less

A pentacene monolayer trapped between graphene and a substrate.

PubMed

Zhang, Qicheng; Peng, Boyu; Chan, Paddy Kwok Leung; Luo, Zhengtang

2015-09-21

A self-assembled pentacene monolayer can be fabricated between the solid-solid interface of few-layered graphene (FLG) and the mica substrate, through a diffusion-spreading method. By utilizing a transfer method that allows us to sandwich pentacene between graphene and mica, followed by controlled annealing, we enabled the diffused pentacene to be trapped in the interfaces and led to the formation of a stable monolayer. We found that the formation of a monolayer is kinetically favored by using a 2D Ising lattice gas model for pentacene trapped between the graphene-substrate interfaces. This kinetic Monte Carlo simulation results indicate that, due to the graphene substrate enclosure, the spreading of the first layer proceeds faster than the second layer, as the kinetics favors the filling of voids by molecules from the second layer. This graphene assisted monolayer assembly method provides a new avenue for the fabrication of two-dimensional monolayer structures.

Topological insulator behavior of WS{sub 2} monolayer with square-octagon ring structure

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

Kumar, Ashok, E-mail: ashok@cup.ac.in; Pandey, Ravindra; Ahluwalia, P. K.

We report electronic behavior of an allotrope of monolayer WS{sub 2} with a square octagon ring structure, refereed to as (so-WS{sub 2}) within state-of-the-art density functional theory (DFT) calculations. The WS{sub 2} monolayer shows semi-metallic characteristics with Dirac-cone like features around Γ. Unlike p-orbital’s Dirac-cone in graphene, the Dirac-cone in the so-WS{sub 2} monolayer originates from the d-electrons of the W atom in the lattice. Most interestingly, the spin-orbit interaction associated with d-electrons induce a finite band-gap that results into the metal-semiconductor transition and topological insulator-like behavior in the so-WS{sub 2} monolayer. These characteristics suggest the so-WS{sub 2} monolayer tomore » be a promising candidate for the next-generation electronic and spintronics devices.« less

A micro GC detector array based on chemiresistors employing various surface functionalized monolayer-protected gold nanoparticles.

PubMed

Jian, Rih-Sheng; Huang, Rui-Xuan; Lu, Chia-Jung

2012-01-15

Aspects of the design, fabrication, and characterization of a chemiresistor type of microdetector for use in conjunction with gas chromatograph are described. The detector was manufactured on silicon chips using microelectromechanical systems (MEMS) technology. Detection was based on measuring changes in resistance across a film comprised of monolayer-protected gold nanoclusters (MPCs). When chromatographic separated molecules entered the detector cell, the MPC film absorbed vapor and undergoes swelling, then the resistance changes accordingly. Thiolates were used as ligand shells to encapsulate the nano-gold core and to manipulate the selectivity of the detector array. The dimensions of the μ-detector array were 14(L)×3.9(W)×1.2(H)mm. Mixtures of eight volatile organic compounds with different functional groups and volatility were tested to characterize the selectivity of the μ-detector array. The detector responses were rapid, reversible, and linear for all of the tested compounds. The detection limits ranged from 2 to 111ng, and were related to both the compound volatility and the selectivity of the surface ligands on the gold nanoparticles. Design and operation parameters such as flow rate, detector temperature, and width of the micro-fluidic channel were investigated. Reduction of the detector temperature resulted in improved sensitivity due to increased absorption. When a wider flow channel was used, the signal-to-noise ratio was improved due to the larger sensing area. The extremely low power consumption and small size makes this μ-detector array potentially useful for the development of integrated μ-GC. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrophilic bile acids protect human blood-brain barrier endothelial cells from disruption by unconjugated bilirubin: an in vitro study

PubMed Central

Palmela, Inês; Correia, Leonor; Silva, Rui F. M.; Sasaki, Hiroyuki; Kim, Kwang S.; Brites, Dora; Brito, Maria A.

2015-01-01

Ursodeoxycholic acid and its main conjugate glycoursodeoxycholic acid are bile acids with neuroprotective properties. Our previous studies demonstrated their anti-apoptotic, anti-inflammatory, and antioxidant properties in neural cells exposed to elevated levels of unconjugated bilirubin (UCB) as in severe jaundice. In a simplified model of the blood-brain barrier, formed by confluent monolayers of a cell line of human brain microvascular endothelial cells, UCB has shown to induce caspase-3 activation and cell death, as well as interleukin-6 release and a loss of blood-brain barrier integrity. Here, we tested the preventive and restorative effects of these bile acids regarding the disruption of blood-brain barrier properties by UCB in in vitro conditions mimicking severe neonatal hyperbilirubinemia and using the same experimental blood-brain barrier model. Both bile acids reduced the apoptotic cell death induced by UCB, but only glycoursodeoxycholic acid significantly counteracted caspase-3 activation. Bile acids also prevented the upregulation of interleukin-6 mRNA, whereas only ursodeoxycholic acid abrogated cytokine release. Regarding barrier integrity, only ursodeoxycholic acid abrogated UCB-induced barrier permeability. Better protective effects were obtained by bile acid pre-treatment, but a strong efficacy was still observed by their addition after UCB treatment. Finally, both bile acids showed ability to cross confluent monolayers of human brain microvascular endothelial cells in a time-dependent manner. Collectively, data disclose a therapeutic time-window for preventive and restorative effects of ursodeoxycholic acid and glycoursodeoxycholic acid against UCB-induced blood-brain barrier disruption and damage to human brain microvascular endothelial cells. PMID:25821432

April 27 2015 Water Cluster Leaders Meeting Report

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) partnered with the Water Economy Network (WEN) to host a Water Technology Innovation Cluster Leaders Meeting on April 27, 2015, in Pittsburgh, Pennsylvania. Approximately 75 individuals attended. The meeting was organized to bring to...

Nonequilibrium 2-Hydroxyoctadecanoic Acid Monolayers: Effect of Electrolytes

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

Lendrum, Conrad D.; Ingham, Bridget; Lin, Binhua

2012-02-06

2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position {alpha} to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of {approx}6. Themore » role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.« less

Strain Control of Exciton-Phonon Coupling in Atomically Thin Semiconductors.

PubMed

Niehues, Iris; Schmidt, Robert; Drüppel, Matthias; Marauhn, Philipp; Christiansen, Dominik; Selig, Malte; Berghäuser, Gunnar; Wigger, Daniel; Schneider, Robert; Braasch, Lisa; Koch, Rouven; Castellanos-Gomez, Andres; Kuhn, Tilmann; Knorr, Andreas; Malic, Ermin; Rohlfing, Michael; Michaelis de Vasconcellos, Steffen; Bratschitsch, Rudolf

2018-03-14

Semiconducting transition metal dichalcogenide (TMDC) monolayers have exceptional physical properties. They show bright photoluminescence due to their unique band structure and absorb more than 10% of the light at their excitonic resonances despite their atomic thickness. At room temperature, the width of the exciton transitions is governed by the exciton-phonon interaction leading to strongly asymmetric line shapes. TMDC monolayers are also extremely flexible, sustaining mechanical strain of about 10% without breaking. The excitonic properties strongly depend on strain. For example, exciton energies of TMDC monolayers significantly redshift under uniaxial tensile strain. Here, we demonstrate that the width and the asymmetric line shape of excitonic resonances in TMDC monolayers can be controlled with applied strain. We measure photoluminescence and absorption spectra of the A exciton in monolayer MoSe 2 , WSe 2 , WS 2 , and MoS 2 under uniaxial tensile strain. We find that the A exciton substantially narrows and becomes more symmetric for the selenium-based monolayer materials, while no change is observed for atomically thin WS 2 . For MoS 2 monolayers, the line width increases. These effects are due to a modified exciton-phonon coupling at increasing strain levels because of changes in the electronic band structure of the respective monolayer materials. This interpretation based on steady-state experiments is corroborated by time-resolved photoluminescence measurements. Our results demonstrate that moderate strain values on the order of only 1% are already sufficient to globally tune the exciton-phonon interaction in TMDC monolayers and hold the promise for controlling the coupling on the nanoscale.

Tiopronin Gold Nanoparticle Precursor Forms Aurophilic Ring Tetramer

PubMed Central

Simpson, Carrie A.; Farrow, Christopher L.; Tian, Peng; Billinge, Simon J.L.; Huffman, Brian J.; Harkness, Kellen M.; Cliffel, David E.

2010-01-01

In the two step synthesis of thiolate-monolayer protected clusters (MPCs), the first step of the reaction is a mild reduction of gold(III) by thiols that generates gold(I) thiolate complexes as intermediates. Using tiopronin (Tio) as the thiol reductant, the characterization of the intermediate Au4Tio4 complex was accomplished with various analytical and structural techniques. Nuclear magnetic resonance (NMR), elemental analysis, thermogravimetric analysis (TGA), and matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) were all consistent with a cyclic gold(I)-thiol tetramer structure, and final structural analysis was gathered through the use of powder diffraction and pair distribution functions (PDF). Crystallographic data has proved challenging for almost all previous gold(I)-thiolate complexes. Herein, a novel characterization technique when combined with standard analytical assessment to elucidate structure without crystallographic data proved invaluable to the study of these complexes. This in conjunction with other analytical techniques, in particular mass spectrometry, can elucidate a structure when crystallographic data is unavailable. In addition, luminescent properties provided evidence of aurophilicity within the molecule. The concept of aurophilicity has been introduced to describe a select group of gold-thiolate structures, which possess unique characteristics, mainly red photoluminescence and a distinct Au-Au intramolecular distance indicating a weak metal-metal bond as also evidenced by the structural model of the tetramer. Significant features of both the tetrameric and aurophilic properties of the intermediate gold(I) tiopronin complex are retained after borohydride reduction to form the MPC, including gold(I) tiopronin partial rings as capping motifs, or “staples”, and weak red photoluminescence that extends into the Near Infrared region. PMID:21067183

Invertebrate hematopoiesis: an anterior proliferation center as a link between the hematopoietic tissue and the brain.

PubMed

Noonin, Chadanat; Lin, Xionghui; Jiravanichpaisal, Pikul; Söderhäll, Kenneth; Söderhäll, Irene

2012-11-20

During evolution, the innate and adaptive immune systems were developed to protect organisms from non-self substances. The innate immune system is phylogenetically more ancient and is present in most multicellular organisms, whereas adaptive responses are restricted to vertebrates. Arthropods lack the blood cells of the lymphoid lineage and oxygen-carrying erythrocytes, making them suitable model animals for studying the regulation of the blood cells of the innate immune system. Many crustaceans have a long life span and need to continuously synthesize blood cells, in contrast to many insects. The hematopoietic tissue (HPT) of Pacifastacus leniusculus provides a simple model for studying hematopoiesis, because the tissue can be isolated, and the proliferation of stem cells and their differentiation can be studied both in vivo and in vitro. Here, we demonstrate new findings of a physical link between the HPT and the brain. Actively proliferating cells were localized to an anterior proliferation center (APC) in the anterior part of the tissue near the area linking the HPT to the brain, whereas more differentiated cells were detected in the posterior part. The central areas of HPT expand in response to lipopolysaccharide-induced blood loss. Cells isolated from the APC divide rapidly and form cell clusters in vitro; conversely, the cells from the remaining HPT form monolayers, and they can be induced to differentiate in vitro. Our findings offer an opportunity to learn more about invertebrate hematopoiesis and its connection to the central nervous system, thereby obtaining new information about the evolution of different blood and nerve cell lineages.

Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au 30 (SR) 18

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

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar

We investigate via first-principles simulations the optical absorption spectra of three different Au 30(SR) 18 monolayer-protected clusters (MPC): Au 30(StBu) 18, Au 30(SPh) 18, and Au 30(SPh-pNO 2) 18. Au 30(StBu) 18 is known in the literature, and its crystal structure is available. In contrast, Au 30(SPh) 18 and Au 30(SPh-pNO 2) 18 are two species that have been designed by replacing the tert-butyl organic residues of Au 30(StBu) 18 with aromatic ones so as to investigate the effects of ligand replacement on the optical response of Au nanomolecules. By analogy to a previously studied Au 23(SR)16– anionic species, despitemore » distinct differences in charge and chemical composition, a substantial ligand enhancement of the absorption intensity in the optical region is also obtained for the Au 30(SPh-pNO 2) 18 MPC. Furthermore, the use of conjugated aromatic ligands with properly chosen electron-withdrawing substituents and exhibiting steric hindrance so as to also achieve charge decompression at the surface is therefore demonstrated as a general approach to enhancing the MPC photoabsorption intensity in the optical region. In addition, we here subject the ligand-enhancement phenomenon to a detailed analysis based on the fragment projection of electronic excited states and on induced transition densities, leading to a better understanding of the physical origin of this phenomenon, thus opening avenues to its more precise control and exploitation.« less

Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au 30 (SR) 18

DOE PAGES

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar; ...

2017-01-24

We investigate via first-principles simulations the optical absorption spectra of three different Au 30(SR) 18 monolayer-protected clusters (MPC): Au 30(StBu) 18, Au 30(SPh) 18, and Au 30(SPh-pNO 2) 18. Au 30(StBu) 18 is known in the literature, and its crystal structure is available. In contrast, Au 30(SPh) 18 and Au 30(SPh-pNO 2) 18 are two species that have been designed by replacing the tert-butyl organic residues of Au 30(StBu) 18 with aromatic ones so as to investigate the effects of ligand replacement on the optical response of Au nanomolecules. By analogy to a previously studied Au 23(SR)16– anionic species, despitemore » distinct differences in charge and chemical composition, a substantial ligand enhancement of the absorption intensity in the optical region is also obtained for the Au 30(SPh-pNO 2) 18 MPC. Furthermore, the use of conjugated aromatic ligands with properly chosen electron-withdrawing substituents and exhibiting steric hindrance so as to also achieve charge decompression at the surface is therefore demonstrated as a general approach to enhancing the MPC photoabsorption intensity in the optical region. In addition, we here subject the ligand-enhancement phenomenon to a detailed analysis based on the fragment projection of electronic excited states and on induced transition densities, leading to a better understanding of the physical origin of this phenomenon, thus opening avenues to its more precise control and exploitation.« less

DNA adsorption characteristics of hollow spherule allophane nano-particles.

PubMed

Matsuura, Yoko; Iyoda, Fumitoshi; Arakawa, Shuichi; John, Baiju; Okamoto, Masami; Hayashi, Hidetomo

2013-12-01

To understand the propensity of natural allophane to adsorb the DNA molecules, the adsorption characteristics were assessed against natural allophane (AK70), using single-stranded DNA (ss-DNA) and adenosine 5'-monophosphate (5'-AMP) as a reference molecule. The adsorption capacity of ss-DNA on AK70 exhibited one order of magnitude lower value as compared with that of 5'-AMP. The adsorption capacity of ss-DNA decreased with increasing pH due to the interaction generated between phosphate groups of ss-DNA and functional Al-OH groups on the wall perforations through deprotonating, associated with higher energy barrier for the adsorption of ss-DNA. The adsorption morphologies consisting of the individual ss-DNA with mono-layer coverage of the clustered allophane particle were observed successfully through transmission electron microscopy analysis. © 2013.

Vaccines for preventing anthrax.

PubMed

Donegan, Sarah; Bellamy, Richard; Gamble, Carrol L

2009-04-15

Anthrax is a bacterial zoonosis that occasionally causes human disease and is potentially fatal. Anthrax vaccines include a live-attenuated vaccine, an alum-precipitated cell-free filtrate vaccine, and a recombinant protein vaccine. To evaluate the effectiveness, immunogenicity, and safety of vaccines for preventing anthrax. We searched the following databases (November 2008): Cochrane Infectious Diseases Group Specialized Register; CENTRAL (The Cochrane Library 2008, Issue 4); MEDLINE; EMBASE; LILACS; and mRCT. We also searched reference lists. We included randomized controlled trials (RCTs) of individuals and cluster-RCTs comparing anthrax vaccine with placebo, other (non-anthrax) vaccines, or no intervention; or comparing administration routes or treatment regimens of anthrax vaccine. Two authors independently considered trial eligibility, assessed risk of bias, and extracted data. We presented cases of anthrax and seroconversion rates using risk ratios (RR) and 95% confidence intervals (CI). We summarized immunoglobulin G (IgG) concentrations using geometric means. We carried out a sensitivity analysis to investigate the effect of clustering on the results from one cluster-RCT. No meta-analysis was undertaken. One cluster-RCT (with 157,259 participants) and four RCTs of individuals (1917 participants) met the inclusion criteria. The cluster-RCT from the former USSR showed that, compared with no vaccine, a live-attenuated vaccine (called STI) protected against clinical anthrax whether given by a needleless device (RR 0.16; 102,737 participants, 154 clusters) or the scarification method (RR 0.25; 104,496 participants, 151 clusters). Confidence intervals were statistically significant in unadjusted calculations, but when a small amount of association within clusters was assumed, the differences were not statistically significant. The four RCTs (of individuals) of inactivated vaccines (anthrax vaccine absorbed and recombinant protective antigen) showed a dose response relationship for the anti-protective antigen IgG antibody titre. Intramuscular administration was associated with fewer injection site reactions than subcutaneous injection, and injection site reaction rates were lower when the dosage interval was longer. One cluster-RCT provides limited evidence that a live-attenuated vaccine is effective in preventing cutaneous anthrax. Vaccines based on anthrax antigens are immunogenic in most vaccinees with few adverse events or reactions. Ongoing randomized controlled trials are investigating the immunogenicity and safety of anthrax vaccines.

Active cell-matrix coupling regulates cellular force landscapes of cohesive epithelial monolayers

NASA Astrophysics Data System (ADS)

Zhao, Tiankai; Zhang, Yao; Wei, Qiong; Shi, Xuechen; Zhao, Peng; Chen, Long-Qing; Zhang, Sulin

2018-03-01

Epithelial cells can assemble into cohesive monolayers with rich morphologies on substrates due to competition between elastic, edge, and interfacial effects. Here we present a molecularly based thermodynamic model, integrating monolayer and substrate elasticity, and force-mediated focal adhesion formation, to elucidate the active biochemical regulation over the cellular force landscapes in cohesive epithelial monolayers, corroborated by microscopy and immunofluorescence studies. The predicted extracellular traction and intercellular tension are both monolayer size and substrate stiffness dependent, suggestive of cross-talks between intercellular and extracellular activities. Our model sets a firm ground toward a versatile computational framework to uncover the molecular origins of morphogenesis and disease in multicellular epithelia.

Adsorption of radionuclides on the monolayer MoS2

NASA Astrophysics Data System (ADS)

Zhao, Qiang; Zhang, Zheng; Ouyang, Xiaoping

2018-04-01

How to remove radionuclides from radioactive wastewater has long been a difficult problem, especially in nuclear accidents. In this paper, the adsorption of radionuclides Cs, Sr, and Ba on the monolayer MoS2 was investigated by using the first principles calculation method. Through the calculation of adsorption energy and Hirshfeld charge of the radionuclides on the monolayer MoS2 at six adsorption sites, the results show that all of the radionuclides chemisorbed on the monolayer MoS2, and the adsorption strength of these three kinds of radionuclides on the monolayer MoS2 is Ba > Sr > Cs. This work might shed some light on the treatment of the radioactive wastewater.

Strain induced chemical potential difference between monolayer graphene sheets.

PubMed

Zhang, Yupeng; Luo, Chengzhi; Li, Weiping; Pan, Chunxu

2013-04-07

Monolayer graphene sheets were deposited on a transparent and flexible polydimethylsiloxane (PDMS) substrate, and a tensile strain was loaded by stretching the substrate in one direction. It was found that an electric potential difference between stretched and static monolayer graphene sheets reached 8 mV when the strain was 5%. Theoretical calculations for the band structure and total energy revealed an alternative way to experimentally tune the band gap of monolayer graphene, and induce the generation of electricity.

Neutrophil-endothelial cell interactions on endothelial monolayers grown on micropore filters.

PubMed Central

Taylor, R F; Price, T H; Schwartz, S M; Dale, D C

1981-01-01

We have developed a technique for growing endothelial monolayers on micropore filters. These monolayers demonstrate confluence by phase and electron microscopy and provide a functional barrier to passage of radiolabeled albumin. Neutrophils readily penetrate the monolayer in response to chemotaxin, whereas there is little movement in the absence of chemotaxin. This system offers unique advantages over available chemotaxis assays and may have wider applications in the study of endothelial function. Images PMID:7007441

Radiationless Electronic Excitation Energy Transfer Between Monolayers of J-Aggregates

NASA Astrophysics Data System (ADS)

Chmereva, T. M.; Kucherenko, M. G.

2018-06-01

Radiationless electronic excitation energy transfer between monolayers of cyanine dye molecules forming J-aggregates by means of surface plasmons of the metal film of nanometer thickness inserted between the monolayers is theoretically investigated. A dependence of the rate of energy transfer on the geometrical and electrodynamic parameters of the system is established. It is demonstrated that the energy transfer between the monolayers is more effective in the presence of the metal film than in a nonconductive medium.

Effect of surface charge of immortalized mouse cerebral endothelial cell monolayer on transport of charged solutes.

PubMed

Yuan, Wei; Li, Guanglei; Gil, Eun Seok; Lowe, Tao Lu; Fu, Bingmei M

2010-04-01

Charge carried by the surface glycocalyx layer (SGL) of the cerebral endothelium has been shown to significantly modulate the permeability of the blood-brain barrier (BBB) to charged solutes in vivo. The cultured monolayer of bEnd3, an immortalized mouse cerebral endothelial cell line, is becoming a popular in vitro BBB model due to its easy growth and maintenance of many BBB characteristics over repeated passages. To test whether the SGL of bEnd3 monolayer carries similar charge as that in the intact BBB and quantify this charge, which can be characterized by the SGL thickness (L(f)) and charge density (C(mf)), we measured the solute permeability of bEnd3 monolayer to neutral solutes and to solutes with similar size but opposite charges: negatively charged alpha-lactalbumin (-11) and positively charged ribonuclease (+3). Combining the measured permeability data with a transport model across the cell monolayer, we predicted the L(f) and the C(mf) of bEnd3 monolayer, which is approximately 160 nm and approximately 25 mEq/L, respectively. We also investigated whether orosomucoid, a plasma glycoprotein modulating the charge of the intact BBB, alters the charge of bEnd3 monolayer. We found that 1 mg/mL orosomucoid would increase SGL charge density of bEnd3 monolayer to approximately 2-fold of its control value.

Exploring Ag(111) Substrate for Epitaxially Growing Monolayer Stanene: A First-Principles Study

PubMed Central

Gao, Junfeng; Zhang, Gang; Zhang, Yong-Wei

2016-01-01

Stanene, a two-dimensional topological insulator composed of Sn atoms in a hexagonal lattice, is a promising contender to Si in nanoelectronics. Currently it is still a significant challenge to achieve large-area, high-quality monolayer stanene. We explore the potential of Ag(111) surface as an ideal substrate for the epitaxial growth of monolayer stanene. Using first-principles calculations, we study the stability of the structure of stanene in different epitaxial relations with respect to Ag(111) surface, and also the diffusion behavior of Sn adatom on Ag(111) surface. Our study reveals that: (1) the hexagonal structure of stanene monolayer is well reserved on Ag(111) surface; (2) the height of epitaxial stanene monolayer is comparable to the step height of the substrate, enabling the growth to cross the surface step and achieve a large-area stanene; (3) the perfect lattice structure of free-standing stanene can be achieved once the epitaxial stanene monolayer is detached from Ag(111) surface; and finally (4) the diffusion barrier of Sn adatom on Ag(111) surface is found to be only 0.041 eV, allowing the epitaxial growth of stanene monolayer even at low temperatures. Our above revelations strongly suggest that Ag(111) surface is an ideal candidate for growing large-area, high-quality monolayer stanene. PMID:27373464

Tribology of monolayer films: comparison between n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon.

PubMed

Booth, Brandon D; Vilt, Steven G; McCabe, Clare; Jennings, G Kane

2009-09-01

This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n

Surface chemistry of lipid raft and amyloid Aβ (1-40) Langmuir monolayer.

PubMed

Thakur, Garima; Pao, Christine; Micic, Miodrag; Johnson, Sheba; Leblanc, Roger M

2011-10-15

Lipid rafts being rich in cholesterol and sphingolipids are considered to provide ordered lipid environment in the neuronal membranes, where it is hypothesized that the cleavage of amyloid precursor protein (APP) to Aβ (1-40) and Aβ (1-42) takes place. It is highly likely that the interaction of lipid raft components like cholesterol, sphingomylein or GM1 leads to nucleation of Aβ and results in aggregation or accumulation of amyloid plaques. One has investigated surface pressure-area isotherms of the lipid raft and Aβ (1-40) Langmuir monolayer. The compression-decompression cycles and the stability of the lipid raft Langmuir monolayer are crucial parameters for the investigation of interaction of Aβ (1-40) with the lipid raft Langmuir monolayer. It was revealed that GM1 provides instability to the lipid raft Langmuir monolayer. Adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing neutral (POPC) or negatively charged phospholipid (DPPG) was examined. The adsorption isotherms revealed that the concentration of cholesterol was important for adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing POPC whereas for the lipid raft Langmuir monolayer containing DPPG:cholesterol or GM1 did not play any role. In situ UV-vis absorption spectroscopy supported the interpretation of results for the adsorption isotherms. Copyright © 2011 Elsevier B.V. All rights reserved.

Orientation and Interaction of Oblique Cylindrical Inclusions Embedded in a Lipid Monolayer: A Theoretical Model for Viral Fusion Peptides

PubMed Central

Kozlovsky, Yonathan; Zimmerberg, Joshua; Kozlov, Michael M.

2004-01-01

We consider the elastic behavior of flat lipid monolayer embedding cylindrical inclusions oriented obliquely with respect to the monolayer plane. An oblique inclusion models a fusion peptide, a part of a specialized protein capable of inducing merger of biological membranes in the course of fundamental cellular processes. Although the crucial importance of the fusion peptides for membrane merger is well established, the molecular mechanism of their action remains unknown. This analysis is aimed at revealing mechanical deformations and stresses of lipid monolayers induced by the fusion peptides, which, potentially, can destabilize the monolayer structure and enhance membrane fusion. We calculate the deformation of a monolayer embedding a single oblique inclusion and subject to a lateral tension. We analyze the membrane-mediated interactions between two inclusions, taking into account bending of the monolayer and tilt of the hydrocarbon chains with respect to the surface normal. In contrast to a straightforward prediction that the oblique inclusions should induce tilt of the lipid chains, our analysis shows that the monolayer accommodates the oblique inclusion solely by bending. We find that the interaction between two inclusions varies nonmonotonically with the interinclusion distance and decays at large separations as square of the distance, similar to the electrostatic interaction between two electric dipoles in two dimensions. This long-range interaction is predicted to dominate the other interactions previously considered in the literature. PMID:15298906

Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

PubMed Central

Lee, Chi-Ying; Gong, Ping; Harbers, Gregory M.; Grainger, David W.; Castner, David G.; Gamble, Lara J.

2006-01-01

Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s → π* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in complex milieu (i.e., serum) were characterized by surface plasmon resonance (SPR) and 32P-radiometric assays and reported in a related study PMID:16689533

Dimensionality effects on magnetic properties of FexCo1-x nanoclusters on Pt(1 1 1)

NASA Astrophysics Data System (ADS)

Miranda, I. P.; Igarashi, R. N.; Klautau, A. B.; Petrilli, H. M.

2017-11-01

The behavior of local magnetic moments and exchange coupling parameters of FexCo1-x nanostructures (nanowires and compact clusters) on the fcc Pt(1 1 1) surface is here investigated using the first-principles real-space RS-LMTO-ASA method, in the framework of the DFT. Different configurations of FexCo1-x trimers and heptamers on Pt(1 1 1) are considered, varying the positions and the concentration of Fe or Co atoms. We discuss the influence of dimensionality and stoichiometry changes on the magnetic properties, specially on the orbital moments, which are very important in establishing a nanoscopic understanding of delocalized electron systems. We demonstrate the existence of a strictly decreasing nonlinear trend of the average orbital moments with the Fe concentration for the compact clusters, different from what was found for FexCo1-x nanowires on Pt(1 1 1) and also for corresponding higher-dimensional systems (FexCo1-x monolayer on Pt(1 1 1) and FexCo1-x bulk). The average spin moments, however, are invariably described by a linear function with respect to stoichiometry. In all studied cases, the nearest neighbors exchange couplings have shown to be strongly ferromagnetic.

On the mechanism of the ring zone effect obtained with the mixed haemadsorption technique

PubMed Central

Jonsson, J.; Fagraeus, Astrid

1969-01-01

A ring zone effect noted with the radial diffusion disc test modification of the mixed haemadsorption technique has been studied using human anti-thyroid sera reacting with thyroid monolayer cultures. Results are presented which suggest that the `empty' centre of the ring zones is due to an excess of attached antibody. Sera giving the ring zone effect contain a larger number of antibody specificities than those producing filled zones. The appearance of ring zones is favoured by a low density of antigens on the culture. These findings and a number of synergistic effects produced by mixing ring and filled zone reactions are compatible with the hypothesis that the ring zone is produced when several antibodies of different specificities react with restricted antigenic areas carrying densely located clusters of antigenic determinants representing the different specificities contained in the ring zone sera. The crowding of antibodies on the clusters in the centre of the ring zones creates a steric hindrance for the indicator cells so that they are not firmly attached in this area. The antibody zone is therefore indicated as a peripheral haemadsorption ring. ImagesFIG. 1FIG. 2FIG. 4FIG. 6FIG. 7FIG. 9 PMID:5307718

Effects of different wetting layers on the growth of smooth ultra-thin silver thin films

NASA Astrophysics Data System (ADS)

Ni, Chuan; Shah, Piyush; Sarangan, Andrew M.

2014-09-01

Ultrathin silver films (thickness below 10 nm) are of great interest as optical coatings on windows and plasmonic devices. However, producing these films has been a continuing challenge because of their tendency to form clusters or islands rather than smooth contiguous thin films. In this work we have studied the effect of Cu, Ge and ZnS as wetting layers (1.0 nm) to achieve ultrasmooth thin silver films. The silver films (5 nm) were grown by RF sputter deposition on silicon and glass substrates using a few monolayers of the different wetting materials. SEM imaging was used to characterize the surface properties such as island formation and roughness. Also the optical properties were measured to identify the optical impact of the different wetting layers. Finally, a multi-layer silver based structure is designed and fabricated, and its performance is evaluated. The comparison between the samples with different wetting layers show that the designs with wetting layers which have similar optical properties to silver produce the best overall performance. In the absence of a wetting layer, the measured optical spectra show a significant departure from the model predictions, which we attribute primarily to the formation of clusters.

Snapshots of crystal growth: Nanoclusters of organic conductors on Au(111) surfaces

NASA Astrophysics Data System (ADS)

Schott, J. H.; Ward, M. D.

1994-06-01

Mono- and multilayer crystalline nanoclusters of tetra-hiafulvalene-tetracyanoquinodimethane ((TTF) (TCNO)), a low-dimensional organic conductor in the bulk form, can be formed readily on Au(111) surfaces by vapor phase sublimation under ambient conditions. Scanning tunneling microscopy of monolayer (TTF)(TCNQ) films reveals a two-dimensional density of states (DOS) that is consistent with the arrangement of TTF and TCNO molecules in the ac face of bulk (TTF)(TCNO), in which the molecular planes are nearly parallel to the Au(111) substrate. In contrast, clusters with thicknesses corresponding to two or three molecular layers exhibit a transformation to a highly anisotropic DOS that can be attributed to interlayer molecular overlap in segregated TTF and TCNQ molecular chains along the c-axis, which can be described as 'molecular wires'. The orientation of the crystalline (TTF)(TCNO) clusters is preserved throughout the crystal growth sequence, leading to meso- and macroscopic (TTF)(TCNO) needles that are oriented perpendicular to the Au(111) substrate. These studies provide visualization of crystal growth from the initial stages of nucleation to macroscopic crystals, and a revealing example of the changes in electronic structure that occur during the evolution of molecular (TTF)(TCNQ) nuclei into a bulk crystalline phase.

Contact inhibition of locomotion determines cell-cell and cell-substrate forces in tissues.

PubMed

Zimmermann, Juliane; Camley, Brian A; Rappel, Wouter-Jan; Levine, Herbert

2016-03-08

Cells organized in tissues exert forces on their neighbors and their environment. Those cellular forces determine tissue homeostasis as well as reorganization during embryonic development and wound healing. To understand how cellular forces are generated and how they can influence the tissue state, we develop a particle-based simulation model for adhesive cell clusters and monolayers. Cells are contractile, exert forces on their substrate and on each other, and interact through contact inhibition of locomotion (CIL), meaning that cell-cell contacts suppress force transduction to the substrate and propulsion forces align away from neighbors. Our model captures the traction force patterns of small clusters of nonmotile cells and larger sheets of motile Madin-Darby canine kidney (MDCK) cells. In agreement with observations in a spreading MDCK colony, the cell density in the center increases as cells divide and the tissue grows. A feedback between cell density, CIL, and cell-cell adhesion gives rise to a linear relationship between cell density and intercellular tensile stress and forces the tissue into a nonmotile state characterized by a broad distribution of traction forces. Our model also captures the experimentally observed tissue flow around circular obstacles, and CIL accounts for traction forces at the edge.

Biaxial tensile strain tuned up-and-down behavior on lattice thermal conductivity in β-AsP monolayer

NASA Astrophysics Data System (ADS)

Guo, San-Dong; Dong, Jun

2018-07-01

Various two-dimensional (2D) materials with a graphene-like buckled structure have emerged, and the β-phase AsP monolayer has been recently proposed to be thermodynamically stable from first-principles calculations. The studies of thermal transport are very useful for these 2D materials-based nano-electronics devices. Motivated by this, a comparative study of strain-dependent phonon transport of AsP monolayers is performed by solving the linearized phonon Boltzmann equation within the single-mode relaxation time approximation (RTA). It is found that the lattice thermal conductivity () of the AsP monolayer is very close to the one of As monolayer with a similar buckled structure, which is due to neutralization between the reduction of phonon lifetimes and group velocity enhancement from As to AsP monolayer. The corresponding room-temperature sheet thermal conductance of AsP monolayer is 152.5 . It is noted that the increasing tensile strain can harden a long wavelength out-of-plane (ZA) acoustic mode, and soften the in-plane longitudinal acoustic (LA) and transversal acoustic (TA) modes. Calculated results show that of AsP monolayer presents a nonmonotonic up-and-down behavior with increased strain. The unusual strain dependence is due to the competition among the reduction of phonon group velocities, improved phonon lifetimes of ZA mode and nonmonotonic up-and-down phonon lifetimes of TA/LA mode. It is found that acoustic branches dominate the in the considered strain range, and the contribution from ZA branch increases with increased strain, while it is opposite for TA/LA branch. By analyzing cumulative with respect to phonon mean free path, tensile strain can modulate effectively the size effects on in the AsP monolayer. Our work enriches the studies of thermal transports of 2D materials with graphene-like buckled structures, and strengthens the idea to engineer thermal transport properties by simple mechanical strain, and stimulates further experimental works to synthesize AsP monolayers.

Interaction of cholesterol with sphingomyelins and acyl-chain-matched phosphatidylcholines: a comparative study of the effect of the chain length.

PubMed Central

Ramstedt, B; Slotte, J P

1999-01-01

In this study we have synthesized sphingomyelins (SM) and phosphatidylcholines (PC) with amide-linked or sn-2 linked acyl chains with lengths from 14 to 24 carbons. The purpose was to examine how the chain length and degree of unsaturation affected the interaction of cholesterol with these phospholipids in model membrane systems. Monolayers of saturated SMs and PCs with acyl chain lengths above 14 carbons were condensed and displayed a high collapse pressure ( approximately 70 mN/m). Monolayers of N-14:0-SM and 1(16:0)-2(14:0)-PC had a much lower collapse pressure (58-60 mN/m) and monounsaturated SMs collapsed at approximately 50 mN/m. The relative interaction of cholesterol with these phospholipids was determined at 22 degreesC by measuring the rate of cholesterol desorption from mixed monolayers (50 mol % cholesterol; 20 mN/m) to beta-cyclodextrin in the subphase (1.7 mM). The rate of cholesterol desorption was lower from saturated SM monolayers than from chain-matched PC monolayers. In SM monolayers, the rate of cholesterol desorption was very slow for all N-linked chains, whereas for PC monolayers we could observe higher desorption rates from monolayers of longer PCs. These results show that cholesterol interacts favorably with SMs (low rate of desorption), whereas its interaction (or miscibility) with long chain PCs is weaker. Introduction of a single cis-unsaturation in the N-linked acyl chain of SMs led to faster rates of cholesterol desorption as compared with saturated SMs. The exception was monolayers of N-22:1-SM and N-24:1-SM from which cholesterol desorbed almost as slowly as from the corresponding saturated SM monolayers. The results of this study suggest that cholesterol is most likely capable of interacting with all physiologically relevant (including long-chain) SMs present in the plasma membrane of cells. PMID:9929492

Molecular dynamics simulation of the evolution of hydrophobic defects in one monolayer of a phosphatidylcholine bilayer: relevance for membrane fusion mechanisms.

PubMed Central

Tieleman, D Peter; Bentz, Joe

2002-01-01

The spontaneous formation of the phospholipid bilayer underlies the permeability barrier function of the biological membrane. Tears or defects that expose water to the acyl chains are spontaneously healed by lipid lateral diffusion. However, mechanical barriers, e.g., protein aggregates held in place, could sustain hydrophobic defects. Such defects have been postulated to occur in processes such as membrane fusion. This gives rise to a new question in bilayer structure: What do the lipids do in the absence of lipid lateral diffusion to minimize the free energy of a hydrophobic defect? As a first step to understand this rather fundamental question about bilayer structure, we performed molecular dynamic simulations of up to 10 ns of a planar bilayer from which lipids have been deleted randomly from one monolayer. In one set of simulations, approximately one-half of the lipids in the defect monolayer were restrained to form a mechanical barrier. In the second set, lipids were free to diffuse around. The question was simply whether the defects caused by removing a lipid would aggregate together, forming a large hydrophobic cavity, or whether the membrane would adjust in another way. When there are no mechanical barriers, the lipids in the defect monolayer simply spread out and thin with little effect on the other intact monolayer. In the presence of a mechanical barrier, the behavior of the lipids depends on the size of the defect. When 3 of 64 lipids are removed, the remaining lipids adjust the lower one-half of their chains, but the headgroup structure changes little and the intact monolayer is unaffected. When 6 to 12 lipids are removed, the defect monolayer thins, lipid disorder increases, and lipids from the intact monolayer move toward the defect monolayer. Whereas this is a highly simplified model of a fusion site, this engagement of the intact monolayer into the fusion defect is strikingly consistent with recent results for influenza hemagglutinin mediated fusion. PMID:12202375

High Selective Gas Detection for small molecules based on Germanium selenide monolayer

NASA Astrophysics Data System (ADS)

Liu, Lian; Yang, Qun; Wang, Zeping; Ye, Huaiyu; Chen, Xianping; Fan, Xuejun; Zhang, Guoqi

2018-03-01

Predictive calculations based on density functional theory (DFT) are used here to study the electronic and optical properties of GeSe monolayer after adsorbing gas molecules (O2, NH3, SO2, H2, CO2, H2S, NO2, CH4, H2O, NO, CO). Our results reveal that for all the gas molecules considered, only NH3 is adsorbed on GeSe monolayer by physisorption. Whereas SO2 and NO2 are chemisorbed on GeSe monolayer with strong adsorption energies. In addition, the adsorption of O2, NO and NO2 distinctly enhances the optical absorbance and broaden the absorbance range of GeSe monolayer in visible light region. Also, it is found that the adsorption of H2S, NO and NH3 can reduce the work function of the GeSe monolayer. The results indicate that GeSe monolayer is not only a promising candidate for the sensing, capture, and storage of NH3, but also an anticipated disposable gas sensor or metal-free catalyst for detecting and catalyzing SO2 and NO2. Furthermore, it has excellent potential to be applied to optical sensors, solar cells, nanoelectronics or optoelectronics devices.

Treponema pallidum Invades Intercellular Junctions of Endothelial Cell Monolayers

NASA Astrophysics Data System (ADS)

Thomas, D. Denee; Navab, Mahamad; Haake, David A.; Fogelman, Alan M.; Miller, James N.; Lovett, Michael A.

1988-05-01

The pathogenesis of syphilis reflects invasive properties of Treponema pallidum, but the actual mode of tissue invasion is unknown. We have found two in vitro parallels of treponemal invasiveness. We tested whether motile T. pallidum could invade host cells by determining the fate of radiolabeled motile organisms added to a HeLa cell monolayer; 26% of treponemes associated with the monolayer in a trypsin-resistant niche, presumably between the monolayer and the surface to which it adhered, but did not attain intracellularity. Attachment of T. pallidum to cultured human and rabbit aortic and human umbilical vein endothelial cells was 2-fold greater than to HeLa cells. We added T. pallidum to aortic endothelial cells grown on membrane filters under conditions in which tight intercellular junctions had formed. T. pallidum was able to pass through the endothelial cell monolayers without altering tight junctions, as measured by electrical resistance. In contrast, heat-killed T. pallidum and the nonpathogen Treponema phagedenis biotype Reiter failed to penetrate the monolayer. Transmission electron micrographs of sections of the monolayer showed T. pallidum in intercellular junctions. Our in vitro observations suggest that these highly motile spirochetes may leave the circulation by invading the junctions between endothelial cells.

Rectification of current responds to incorporation of fullerenes into mixed-monolayers of alkanethiolates in tunneling junctions.

PubMed

Qiu, Li; Zhang, Yanxi; Krijger, Theodorus L; Qiu, Xinkai; Hof, Patrick Van't; Hummelen, Jan C; Chiechi, Ryan C

2017-03-01

This paper describes the rectification of current through molecular junctions comprising self-assembled monolayers of decanethiolate through the incorporation of C 60 fullerene moieties bearing undecanethiol groups in junctions using eutectic Ga-In (EGaIn) and Au conducting probe AFM (CP-AFM) top-contacts. The degree of rectification increases with increasing exposure of the decanethiolate monolayers to the fullerene moieties, going through a maximum after 24 h. We ascribe this observation to the resulting mixed-monolayer achieving an optimal packing density of fullerene cages sitting above the alkane monolayer. Thus, the degree of rectification is controlled by the amount of fullerene present in the mixed-monolayer. The voltage dependence of R varies with the composition of the top-contact and the force applied to the junction and the energy of the lowest unoccupied π-state determined from photoelectron spectroscopy is consistent with the direction of rectification. The maximum value of rectification R = | J (+)/ J (-)| = 940 at ±1 V or 617 at ±0.95 V is in agreement with previous studies on pure monolayers relating the degree of rectification to the volume of the head-group on which the frontier orbitals are localized.

Melting of the Dipalmitoylphosphatidylcholine Monolayer.

PubMed

Xu, Lu; Bosiljevac, Gordon; Yu, Kyle; Zuo, Yi Y

2018-04-17

Langmuir monolayer self-assembled at the air-water interface represents an excellent model for studying phase transition and lipid polymorphism in two dimensions. Compared with numerous studies of phospholipid phase transitions induced by isothermal compression, there are very scarce reports on two-dimensional phase transitions induced by isobaric heating. This is mainly due to technical difficulties of continuously regulating temperature variations while maintaining a constant surface pressure in a classical Langmuir-type film balance. Here, with technological advances in constrained drop surfactometry and closed-loop axisymmetric drop shape analysis, we studied the isobaric heating process of the dipalmitoylphosphatidylcholine (DPPC) monolayer. It is found that temperature and surface pressure are two equally important intensive properties that jointly determine the phase behavior of the phospholipid monolayer. We have determined a critical point of the DPPC monolayer at a temperature of 44 °C and a surface pressure of 57 mN/m. Beyond this critical point, no phase transition can exist in the DPPC monolayer, either by isothermal compression or by isobaric heating. The melting process of the DPPC monolayer studied here provides novel insights into the understanding of a wide range of physicochemical and biophysical phenomena, such as surface thermodynamics, critical phenomena, and biophysical study of pulmonary surfactants.

Integration of Ganglioside GT1b Receptor into DPPE and DPPC Phospholipid Monolayers: An X-Ray Reflectivity and Grazing-Incidence Diffraction Study

PubMed Central

Miller, C. E.; Busath, D. D.; Strongin, B.; Majewski, J.

2008-01-01

Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structures of mixed-ganglioside GT1b-phospholipid monolayers were investigated at the air-liquid interface and compared with monolayers of the pure components. The receptor GT1b is involved in the binding of lectins and toxins, including botulinum neurotoxin, to cell membranes. Monolayers composed of 20 mol % ganglioside GT1b, the phospholipid dipalmitoyl phosphatidylethanolamine (DPPE), and the phospholipid dipalmitoyl phosphatidylcholine (DPPC) were studied in the gel phase at 23°C and at surface pressures of 20 and 40 mN/m, and at pH 7.4 and 5. Under these conditions, the two components did not phase-separate, and no evidence of domain formation was observed. The x-ray scattering measurements revealed that GT1b was intercalated within the host DPPE/DPPC monolayers, and slightly expanded DPPE but condensed the DPPC matrix. The oligosaccharide headgroups extended normally from the monolayer surfaces into the subphase. This study demonstrated that these monolayers can serve as platforms for investigating toxin membrane binding and penetration. PMID:18599631

Large surface-enhanced Raman scattering from self-assembled gold nanosphere monolayers

NASA Astrophysics Data System (ADS)

Fontana, Jake; Livenere, John; Bezares, Francisco J.; Caldwell, Joshua D.; Rendell, Ronald; Ratna, Banahalli R.

2013-05-01

We demonstrate an average surface-enhanced Raman scattering enhancement on the order of 108 from benzenethiol molecules using self-assembled, macroscopic, and tunable gold nanosphere monolayers on non-templated substrates. The self-assembly of the nanosphere monolayers uses a simple and efficient technique that allows for the creation of a high-density, chemically functionalized gold nanosphere monolayers with enhancement factors comparable to those produced using top-down fabrication techniques. These films may provide an approach for the future development of portable chemical/biological sensors.

Influence of coexisting phases on the surface dilatational viscosity of Langmuir monolayers.

PubMed

Lopez, Juan M; Vogel, Michael J; Hirsa, Amir H

2004-11-01

Monolayer hydrodynamics are usually described in terms of a Newtonian constitutive relationship. However, this macroscopic view fails to account for small-scale coexisting phase domains, which are generally present in the monolayer and appear to have profound macroscopic effects. Here, we provide direct evidence of these effects, consisting of Brewster angle microscopy images of the monolayer, space- and time-resolved interfacial velocity measurements, and comparisons with predictions based on the Navier-Stokes equations together with the classic model for a Newtonian interface.

Methods of making monolayers

DOEpatents

Alford, Kentin L [Pasco, WA; Simmons, Kevin L [Kennewick, WA; Samuels, William D [Richland, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [Albuquerque, NM; Shin, Yongsoon [Richland, WA; Fryxell, Glen E [Kennewick, WA

2009-12-08

The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

Methods of making monolayers

DOEpatents

Alford, Kentin L [Pasco, WA; Simmons, Kevin L [Kennewick, WA; Samuels, William D [Richland, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [Albuquerque, NM; Shin, Yongsoon [Richland, WA; Fryxell, Glen E [Kennewick, WA

2009-09-15

The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

Insights about α-tocopherol and Trolox interaction with phosphatidylcholine monolayers under peroxidation conditions through Brewster angle microscopy.

PubMed

Castro, Carla M; Pinheiro, Marina; Lúcio, Marlene; Giner-Casares, Juan J; Camacho, Luis; Lima, José L F C; Reis, Salette; Segundo, Marcela A

2013-11-01

Membranes are major targets to oxidative damage, particularly due to lipid oxidation, which has been associated to aging. The role, efficacy and membrane interaction of antioxidants is still unclear, requiring further understanding of molecular interaction. Hence, the objective of this work was to evaluate the interaction between antioxidants (α-tocopherol and its aqueous soluble analog Trolox) and the monolayer formed by phosphatidylcholine molecules at air/liquid interface upon peroxidation conditions, promoted by peroxyl radicals from thermal decomposition of 2,2'-azobis(2-methylpropionamidine) (AAPH). The interaction with three different monolayers, containing (i) 1,2-dihexadecanoyl-sn-glycero-3-phosphocholine (DPPC), (ii) DDPC+α-linolenic acid, or (iii) egg yolk l-α-phosphatidylcholine (EPC), was ascertain by surface pressure (π)-molecular area (A) isotherms and by monitoring monolayer features through Brewster angle microscopy (BAM). The interaction of antioxidants with DPPC monolayers was confirmed by modifications on DPPC domain shape for α-tocopherol and through the maintenance of typical multilobed domain shape during an extended surface pressure interval for Trolox. Under peroxidation conditions, BAM images showed a clear interaction between components of AAPH subphase with the monolayer through changes on DPPC domain shape and appearance of white dots, located mainly at the frontier between the condensed and expanded liquid phases. White branched structures were also observed whenever both α-linolenic acid and α-tocopherol were present, indicating the segregation of these components within the monolayer, which is highly significant in biological systems. For EPC monolayers, no information from BAM was obtained but π-A isotherms confirmed the existence of the same interactions observed within the other two monolayers. Copyright © 2013 Elsevier B.V. All rights reserved.

Phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles: Specific characteristics of the condensed phases.

PubMed

Vollhardt, D

2015-08-01

For understanding the role of amide containing amphiphiles in inherently complex biological processes, monolayers at the air-water interface are used as simple biomimetic model systems. The specific characteristics of the condensed phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles are surveyed to highlight the effect of the chemical structure of the amide amphiphiles on the interfacial interactions in model monolayers. The mesoscopic topography and/or two-dimensional lattice structures of selected amino acid amphiphiles, amphiphilic N-alkylaldonamide, amide amphiphiles with specific tailored headgroups, such as amide amphiphiles based on derivatized ethanolamine, e.g. acylethanolamines (NAEs) and N-,O-diacylethanolamines (DAEs) are presented. Special attention is devoted the dominance of N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers. The evidence that a first order phase transition can occur in adsorption layers and that condensed phase domains of mesoscopic scale can be formed in adsorption layers was first obtained on the basis of the experimental characteristics of a tailored amide amphiphile. New thermodynamic and kinetic concepts for the theoretical description of the characteristics of amide amphiphile's monolayers were developed. In particular, the equation of state for Langmuir monolayers generalized for the case that one, two or more phase transitions occur, and the new theory for phase transition in adsorbed monolayers are experimentally confirmed at first by amide amphiphile monolayers. Despite the significant progress made towards the understanding the model systems, these model studies are still limited to transfer the gained knowledge to biological systems where the fundamental physical principles are operative in the same way. The study of biomimetic systems, as described in this review, is only a first step in this direction. Copyright © 2014 Elsevier B.V. All rights reserved.

Transport of decursin and decursinol angelate across Caco-2 and MDR-MDCK cell monolayers: in vitro models for intestinal and blood-brain barrier permeability.

PubMed

Madgula, Vamsi L; Avula, Bharathi; Reddy V L, Niranjan; Khan, Ikhlas A; Khan, Shabana I

2007-04-01

Decursin (DE) and decursinol angelate (DA) were isolated from the roots of Angelica gigas (Apiaceae) and purified by HPLC. DE and DA have been reported to exhibit significant neuropharmacological activities, but their intestinal transport and permeability in terms of CNS penetration across the blood-brain barrier (BBB) are unknown. This study was undertaken to evaluate the IN VITRO intestinal and BBB transport of DE and DA using Caco-2 and MDR-MDCK cell monolayer models, respectively. The bidirectional transport of DE and DA across Caco-2 and MDR-MDCK monolayers was examined for 2 hours. Integrity of the monolayer was determined by TEER value and by monitoring the transport of Lucifer yellow (Ly) across the monolayers. Quantitation of DE and DA was performed by HPLC. DE and DA exhibited bidirectional transport with a Papp value in the range of 9.0-12.0x10(-6) cm/sec and 7.2-11.7x10(-6) cm/sec in Caco-2 and MDR-MDCK monolayers, respectively. The TEER values were in the range of 410-440 and 1170-1230 ohm cm2 for Caco-2 and MDR-MDCK monolayers, respectively. Ly measurement, the fluorescent marker of passive paracellular diffusion, resulted in Papp values of 2.5-5.0x10(-6) in Caco-2 and 6.0-8.0x10(-6) cm/sec in MDR-MDCK monolayers, confirming that the monolayer integrity was intact at the end of the experiment. Caco-2:human colonic adenocarcinoma DA:decursinol angelate DE:decursin Ly:Lucifer yellow MDCK:Madin-Darby canine kidney MDR:multidrug resistant Papp:apparent permeability TEER:transepithelial electrical resistance.

The Electronic Properties of O-Doped Pure and Sulfur Vacancy-Defect Monolayer WS₂: A First-Principles Study.

PubMed

Wang, Weidong; Bai, Liwen; Yang, Chenguang; Fan, Kangqi; Xie, Yong; Li, Minglin

2018-01-31

Based on the density functional theory (DFT), the electronic properties of O-doped pure and sulfur vacancy-defect monolayer WS₂ are investigated by using the first-principles method. For the O-doped pure monolayer WS₂, four sizes (2 × 2 × 1, 3 × 3 × 1, 4 × 4 × 1 and 5 × 5 × 1) of supercell are discussed to probe the effects of O doping concentration on the electronic structure. For the 2 × 2 × 1 supercell with 12.5% O doping concentration, the band gap of O-doped pure WS₂ is reduced by 8.9% displaying an indirect band gap. The band gaps in 3 × 3 × 1 and 4 × 4 × 1 supercells are both opened to some extent, respectively, for 5.55% and 3.13% O doping concentrations, while the band gap in 5 × 5 × 1 supercell with 2.0% O doping concentration is quite close to that of the pure monolayer WS₂. Then, two typical point defects, including sulfur single-vacancy (V S ) and sulfur divacancy (V 2S ), are introduced to probe the influences of O doping on the electronic properties of WS₂ monolayers. The observations from DFT calculations show that O doping can broaden the band gap of monolayer WS₂ with V S defect to a certain degree, but weaken the band gap of monolayer WS₂ with V 2S defect. Doping O element into either pure or sulfur vacancy-defect monolayer WS₂ cannot change their band gaps significantly, however, it still can be regarded as a potential method to slightly tune the electronic properties of monolayer WS₂.

Pulmonary surfactant protein C containing lipid films at the air-water interface as a model for the surface of lung alveoli.

PubMed

Post, A; Nahmen, A V; Schmitt, M; Ruths, J; Riegler, H; Sieber, M; Galla, H J

1995-01-01

The pulmonary surfactant lines as a complex monolayer of lipids and proteins the alveolar epithelial surface. The monolayer dynamically adapts the surface tension of this interface to the varying surface areas during inhalation and exhalation. Its presence in the alveoli is thus a prerequisite for a proper lung function. The lipid moiety represents about 90% of the surfactant and contains mainly dipalmitoylphosphatidylcholine (DPPC) and phosphatidylglycerol (PG). The surfactant proteins involved in the surface tension adaption are called SP-A, SP-B and SP-C. The aim of the present investigation is to analyse the properties of monolayer films made from pure SP-C and from mixtures of DPPC, DPPG and SP-C in order to mimic the surfactant monolayer with minimal compositional requirement. Pressure-area diagrams were taken. Ellipsometric measurements at the air-water interface of a Langmuir film balance allowed measurement of the changes in monolayer thickness upon compression. Isotherms of pure SP-C monolayers exhibit a plateau between 22 and 25 mN/m. A further plateau is reached at higher compression. Structures of the monolayer formed during compression are reversible during expansion. Together with ellipsometric data which show a stepwise increase in film thickness (coverage) during compression, we conclude that pure SP-C films rearrange reversibly into multilayers of homogenous thickness. Lipid monolayers collapse locally and irreversibly if films are compressed to approximately 0.4 nm2/molecule. In contrast, mixed DPPG/SP-C monolayers with less than 5 mol% protein collapse in a controlled and reversible way. The pressure-area diagrams exhibit a plateau at 20 mN/m, indicating partial demixing of SP-C and DPPG.(ABSTRACT TRUNCATED AT 250 WORDS)

Characterization of Self-Assembled Monolayers on a Ruthenium Surface

PubMed Central

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours. PMID:28585831

Lattice distortion of square iron nitride monolayers induced by changing symmetry of substrate

NASA Astrophysics Data System (ADS)

Hattori, Takuma; Iimori, Takushi; Miyamachi, Toshio; Komori, Fumio

2018-04-01

Rectangular iron nitride monatomic layers are fabricated on the threefold symmetric Cu(111) substrate by taking advantage of the stability of the square nitride film. Two different ordered structures are observed on the Cu(111) substrate by scanning tunneling microscopy after annealing at 510 K and 580 K. Their chemical composition and lattice symmetry are investigated by x-ray photoelectron spectroscopy and low energy electron diffraction. The monolayer film prepared at 580 K is a distorted Fe2N monolayer analogous to a ferromagnetic square Fe2N monolayer with a clock reconstruction on the Cu(001) substrate. The lattice deformation of the square Fe2N monolayer is induced by using Cu(111) with threefold symmetry.

Direct measurement of adhesion energy of monolayer graphene as-grown on copper and its application to renewable transfer process.

PubMed

Yoon, Taeshik; Shin, Woo Cheol; Kim, Taek Yong; Mun, Jeong Hun; Kim, Taek-Soo; Cho, Byung Jin

2012-03-14

Direct measurement of the adhesion energy of monolayer graphene as-grown on metal substrates is important to better understand its bonding mechanism and control the mechanical release of the graphene from the substrates, but it has not been reported yet. We report the adhesion energy of large-area monolayer graphene synthesized on copper measured by double cantilever beam fracture mechanics testing. The adhesion energy of 0.72 ± 0.07 J m(-2) was found. Knowing the directly measured value, we further demonstrate the etching-free renewable transfer process of monolayer graphene that utilizes the repetition of the mechanical delamination followed by the regrowth of monolayer graphene on a copper substrate. © 2012 American Chemical Society

The Rise of Radicals in Bioinorganic Chemistry.

PubMed

Gray, Harry B; Winkler, Jay R

2016-10-01

Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O 2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O 2 -reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O 2 is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O 2 reduction.

Applying Concept Mapping Methodology to Identify the Perceptions of Risk and Protective Factors for Childhood Obesity among Southeast Asian Refugees.

PubMed

Keita, Akilah Dulin; Whittaker, Shannon; Wynter, Jamila; Kidanu, Tamnnet Woldemichael; Chhay, Channavy; Cardel, Michelle; Gans, Kim M

2016-01-01

This study identifies Southeast Asian refugee parents' and grandparents' perceptions of the risk and protective factors for childhood obesity. We used a mixed methods approach (concept mapping) for data collection and analyses. Fifty-nine participants engaged in modified nominal group meetings where they generated statements about children's weight status and structuring meetings where they sorted statements into piles based on similarity and rated statements on relative importance. Concept Systems® software generated clusters of ideas, cluster ratings, and pattern matches. Eleven clusters emerged. Participants rated "Healthy Food Changes Made within the School" and "Parent-related Physical Activity Factors" as most important, whereas "Neighborhood Built Features" was rated as the least important. Cambodian and Hmong participants agreed the most on cluster ratings of relative importance (r = 0.62). The study findings may be used to inform the development of culturally appropriate obesity prevention interventions for Southeast Asian refugee communities.

High-density lipoprotein promotes endothelial cell migration and reendothelialization via scavenger receptor-B type I.

PubMed

Seetharam, Divya; Mineo, Chieko; Gormley, Andrew K; Gibson, Linda L; Vongpatanasin, Wanpen; Chambliss, Ken L; Hahner, Lisa D; Cummings, Melissa L; Kitchens, Richard L; Marcel, Yves L; Rader, Daniel J; Shaul, Philip W

2006-01-06

Vascular disease risk is inversely related to circulating levels of high-density lipoprotein (HDL) cholesterol. However, the mechanisms by which HDL provides vascular protection are unclear. The disruption of endothelial monolayer integrity is an important contributing factor in multiple vascular disorders, and vascular lesion severity is tempered by enhanced endothelial repair. Here, we show that HDL stimulates endothelial cell migration in vitro in a nitric oxide-independent manner via scavenger receptor B type I (SR-BI)-mediated activation of Rac GTPase. This process does not require HDL cargo molecules, and it is dependent on the activation of Src kinases, phosphatidylinositol 3-kinase, and p44/42 mitogen-activated protein kinases. Rapid initial stimulation of lamellipodia formation by HDL via SR-BI, Src kinases, and Rac is also demonstrable. Paralleling the in vitro findings, carotid artery reendothelialization after perivascular electric injury is blunted in apolipoprotein A-I(-/-) mice, and reconstitution of apolipoprotein A-I expression rescues normal reendothelialization. Furthermore, reendothelialization is impaired in SR-BI(-/-) mice. Thus, HDL stimulates endothelial cell migration via SR-BI-initiated signaling, and these mechanisms promote endothelial monolayer integrity in vivo.

Valley-symmetric quasi-1D transport in ballistic graphene

NASA Astrophysics Data System (ADS)

Lee, Hu-Jong

We present our recent studies on gate-defined valley-symmetric one-dimensional (1D) carrier guiding in ballistic monolayer graphene and valley-symmetry-protected topological 1D transport in ballistic bilayer graphene. Successful carrier guiding was realized in ballistic monolayer graphene even in the absence of a band gap by inducing a high distinction ( more than two orders of magnitude) in the carrier density between the region of a quasi-1D channel and the rest of the top-gated regions. Conductance of a channel shows quantized values in units of 4e2/ h, suggesting that the valley symmetry is preserved. For the latter, the topological 1D conduction was realized between two closely arranged insulating regions with inverted band gaps, induced under a pair of split dual gating with polarities opposite to each other. The maximum conductance along the boundary channel showed 4e2/ h, again with the preserved valley symmetry. The 1D topological carrier guiding demonstrated in this study affords a promising route to robust valleytronic applications and sophisticated valley-associated functionalities based on 2D materials. This work was funded by the National Research Foundation of Korea.

Impact of in Vitro Gastrointestinal Digestion and Transepithelial Transport on Antioxidant and ACE-Inhibitory Activities of Brewer's Spent Yeast Autolysate.

PubMed

Vieira, Elsa F; das Neves, José; Vitorino, Rui; Dias da Silva, Diana; Carmo, Helena; Ferreira, Isabel M P L V O

2016-10-05

Brewer's spent yeast (BSY) autolysates may have potential applications as food ingredients or nutraceuticals due to their antioxidant and ACE-inhibitory activities. The impact of simulated gastrointestinal (GI) digestion, the interaction with intracellular sources of oxidative stress, the intestinal cell permeability of BSY peptides, and the antioxidant and ACE-inhibitory activities of BSY permeates were assayed. Gastrointestinal digestion of BSY autolysates enhanced antioxidant and ACE-inhibitory activities as measured in vitro. No cytotoxic effects were observed on Caco-2 cells after exposure to the digested BSY autolysates within a concentration range of 0.5 to 3.0 mg of peptides/mL. A protective role to induced oxidative stress was observed. The transepithelial transport assays indicate high apparent permeability coefficient (P app ) values for BSY peptides across Caco-2/HT29-MTX cell monolayer (14.5-26.1 × 10 -6 cm/s) and for Caco-2 cell monolayer model (12.4-20.8 × 10 -6 cm/s), while the antioxidant and ACE-inhibitory activities found in flux material from the basolateral side suggest transepithelial absorption of bioactive compounds.

Gender and Health Behavior Clustering among U.S. Young Adults

PubMed Central

Olson, Julie Skalamera; Hummer, Robert A.; Harris, Kathleen Mullan

2016-01-01

U.S. trends in population health suggest alarming disparities among young adults who are less healthy across most measureable domains than their counterparts in other high-income countries; these international comparisons are particularly troubling for women. To deepen our understanding of gender disparities in health and underlying behavioral contributions, we document gender-specific clusters of health behavior among U.S. young adults using nationally representative data from the National Longitudinal Study of Adolescent to Adult Health. We find high levels of poor health behavior, but especially among men; 40 percent of men clustered into a group characterized by unhealthy behavior (e.g., poor diet, no exercise, substance use), compared to only 22 percent of women. Additionally, women tend to age out of unhealthy behaviors in young adulthood more than men. Further, we uncover gender differences in the extent to which sociodemographic position and adolescent contexts inform health behavior clustering. For example, college education was more protective for men, whereas marital status was equally protective across gender. Parental drinking mattered for health behavior clustering among men, whereas peer drinking mattered for clustering among women. We discuss these results in the context of declining female advantage in U.S. health and changing young adult social and health contexts. PMID:28287308

Gender and Health Behavior Clustering among U.S. Young Adults.

PubMed

Olson, Julie Skalamera; Hummer, Robert A; Harris, Kathleen Mullan

2017-01-01

U.S. trends in population health suggest alarming disparities among young adults, who are less healthy across most measureable domains than their counterparts in other high-income countries; these international comparisons are particularly troubling for women. To deepen our understanding of gender disparities in health and underlying behavioral contributions, we document gender-specific clusters of health behavior among U.S. young adults using nationally representative data from the National Longitudinal Study of Adolescent to Adult Health. We find high levels of poor health behavior, but especially among men; 40 percent of men clustered into a group characterized by unhealthy behavior (e.g., poor diet, no exercise, substance use), compared to only 22 percent of women. Additionally, women tend to age out of unhealthy behaviors in young adulthood more than men. Further, we uncover gender differences in the extent to which sociodemographic position and adolescent contexts inform health behavior clustering. For example, college education was more protective for men, whereas marital status was equally protective across gender. Parental drinking mattered for health behavior clustering among men, whereas peer drinking mattered for clustering among women. We discuss these results in the context of declining female advantage in U.S. health and changing young adult social and health contexts.

The triply troubled teenager--chronic conditions associated with fewer protective factors and clustered risk behaviours.

PubMed

Nylander, Charlotte; Seidel, Carina; Tindberg, Ylva

2014-02-01

This study aimed to measure protective factors and risk behaviour among adolescents with chronic conditions (CCs) and to evaluate the impact of protective factors on risk-taking. A population-based study of 7262 students aged 15 and 17 years old was performed in Sörmland, Sweden 2008 (response rate 82%). The questionnaire explored background factors, CCs, risk behaviours and protective factors. CCs were reported by 8%, while 58% had no health problems. Girls with CCs encompassed less individual protective factors, while boys with CCs tended to over-report all individual risk behaviours compared with healthy peers. Both boys and girls with CCs were more likely to report few protective factors and co-occurrence of risk behaviours. The adjOR for clustered health risk behaviours was 1.6 (1.0-2.5) in youths with CCs and ≥4 protective factors and 6.3 (3.6-10.9) in youths with CCs and 0-3 protective factors, as compared to healthy peers with ≥4 protective factors. Adolescents with CCs reported fewer protective factors and more risk behaviours than their healthy peers. The vulnerability of adolescents with CCs and few protective factors is important to acknowledge. Professionals should provide stronger protection for these adolescents, to prevent risky behaviour. ©2013 Foundation Acta Paediatrica. Published by John Wiley & Sons Ltd.

Characterizing microbiota-independent effects of oligosaccharides on intestinal epithelial cells: insight into the role of structure and size : Structure-activity relationships of non-digestible oligosaccharides.

PubMed

Akbari, Peyman; Fink-Gremmels, Johanna; Willems, Rianne H A M; Difilippo, Elisabetta; Schols, Henk A; Schoterman, Margriet H C; Garssen, Johan; Braber, Saskia

2017-08-01

The direct effects of galacto-oligosaccharides (GOS), including Vivinal ® GOS syrup (VGOS) and purified Vivinal ® GOS (PGOS), on the epithelial integrity and corresponding interleukin-8 (IL-8/CXCL8) release were examined in a Caco-2 cell model for intestinal barrier dysfunction. To investigate structure-activity relationships, the effects of individual DP fractions of VGOS were evaluated. Moreover, the obtained results with GOS were compared with Caco-2 monolayers incubated with fructo-oligosaccharides (FOS) and inulin. Caco-2 monolayers were pretreated (24 h) with or without specific oligosaccharides or DP fractions of VGOS (DP2 to DP6) before being exposed for 12 or 24 h to the fungal toxin deoxynivalenol (DON). Transepithelial electrical resistance and lucifer yellow permeability were measured to investigate barrier integrity. A calcium switch assay was used to study the reassembly of tight junction proteins. Release of CXCL8, a typical marker for inflammation, was quantified by ELISA. In comparison with PGOS, FOS and inulin, VGOS showed the most pronounced protective effect on the DON-induced impairment of the monolayer integrity, acceleration of the tight junction reassembly and the subsequent CXCL8 release. DP2 and DP3 in concentrations occurring in VGOS prevented the DON-induced epithelial barrier disruption, which could be related to their high prevalence in VGOS. However, no effects of the separate DP GOS fractions were observed on CXCL8 release. This comparative study demonstrates the direct, microbiota-independent effects of oligosaccharides on the intestinal barrier function and shows the differences between individual galacto- and fructo-oligosaccharides. This microbiota-independent effect of oligosaccharides depends on the oligosaccharide structure, DP length and concentration.

Proteolytic Inhibition of Salmonella enterica Serovar Typhimurium-Induced Activation of the Mitogen-Activated Protein Kinases ERK and JNK in Cultured Human Intestinal Cells

PubMed Central

Mynott, Tracey L.; Crossett, Ben; Prathalingam, S. Radhika

2002-01-01

Bromelain, a mixture of cysteine proteases from pineapple stems, blocks signaling by the mitogen-activated protein (MAP) kinases extracellular regulated kinase 1 (ERK-1) and ERK-2, inhibits inflammation, and protects against enterotoxigenic Escherichia coli infection. In this study, we examined the effect of bromelain on Salmonella enterica serovar Typhimurium infection, since an important feature of its pathogenesis is its ability to induce activation of ERK-1 and ERK-2, which leads to internalization of bacteria and induction of inflammatory responses. Our results show that bromelain dose dependently blocks serovar Typhimurium-induced ERK-1, ERK-2, and c-Jun NH2-terminal kinase (JNK) activation in Caco-2 cells. Bromelain also blocked signaling induced by carbachol and anisomycin, pharmacological MAP kinase agonists. Despite bromelain inhibition of serovar Typhimurium-induced MAP kinase signaling, it did not prevent subsequent invasion of the Caco-2 cells by serovar Typhimurium or alter serovar Typhimurium -induced decreases in resistance across Caco-2 monolayers. Surprisingly, bromelain also did not block serovar Typhimurium-induced interleukin-8 (IL-8) secretion but synergized with serovar Typhimurium to enhance IL-8 production. We also found that serovar Typhimurium does not induce ERK phosphorylation in Caco-2 cells in the absence of serum but that serovar Typhimurium-induced invasion and decreases in monolayer resistance are unaffected. Collectively, these data indicate that serovar Typhimurium-induced invasion of Caco-2 cells, changes in the resistance of epithelial cell monolayers, and IL-8 production can occur independently of the ERK and JNK signaling pathways. Data also confirm that bromelain is a novel inhibitor of MAP kinase signaling pathways and suggest a novel role for proteases as inhibitors of signal transduction pathways in intestinal epithelial cells. PMID:11748167

A DMPA Langmuir monolayer study: from gas to solid phase. An atomistic description by molecular dynamics Simulation.

PubMed

Giner-Casares, J J; Camacho, L; Martín-Romero, M T; Cascales, J J López

2008-03-04

In this work, a DMPA Langmuir monolayer at the air/water interface was studied by molecular dynamics simulations. Thus, an atomistic picture of a Langmuir monolayer was drawn from its expanded gas phase to its final solid condensed one. In this sense, some properties of monolayers that were traditionally poorly or even not reproduced in computer simulations, such as lipid domain formation or pressure-area per lipid isotherm, were properly reproduced in this work. Thus, the physical laws that control the lipid domain formation in the gas phase and the structure of lipid monolayers from the gas to solid condensed phase were studied. Thanks to the atomistic information provided by the molecular dynamics simulations, we were able to add valuable information to the experimental description of these processes and to access experimental data related to the lipid monolayers in their expanded phase, which is difficult or inaccessible to study by experimental techniques. In this sense, properties such as lipids head hydration and lipid structure were studied.

Semi-metallic Be5C2 monolayer global minimum with quasi-planar pentacoordinate carbons and negative Poisson's ratio.

PubMed

Wang, Yu; Li, Feng; Li, Yafei; Chen, Zhongfang

2016-05-03

Designing new materials with novel topological properties and reduced dimensionality is always desirable for material innovation. Here we report the design of a two-dimensional material, namely Be5C2 monolayer on the basis of density functional theory computations. In Be5C2 monolayer, each carbon atom binds with five beryllium atoms in almost the same plane, forming a quasi-planar pentacoordinate carbon moiety. Be5C2 monolayer appears to have good stability as revealed by its moderate cohesive energy, positive phonon modes and high melting point. It is the lowest-energy structure with the Be5C2 stoichiometry in two-dimensional space and therefore holds some promise to be realized experimentally. Be5C2 monolayer is a gapless semiconductor with a Dirac-like point in the band structure and also has an unusual negative Poisson's ratio. If synthesized, Be5C2 monolayer may find applications in electronics and mechanics.

Piezoelectric effect on the thermal conductivity of monolayer gallium nitride

NASA Astrophysics Data System (ADS)

Zhang, Jin

2018-01-01

Using molecular dynamics and density functional theory simulations, in this work, we find that the heat transport property of the monolayer gallium nitride (GaN) can be efficiently tailored by external electric field due to its unique piezoelectric characteristic. As the monolayer GaN possesses different piezoelectric properties in armchair and zigzag directions, different effects of the external electric field on thermal conductivity are observed when it is applied in the armchair and zigzag directions. Our further study reveals that due to the elastoelectric effect in the monolayer GaN, the external electric field changes the Young's modulus and therefore changes the phonon group velocity. Also, due to the inverse piezoelectric effect, the applied electric field induces in-plane stress in the monolayer GaN subject to a length constraint, which results in the change in the lattice anharmonicity and therefore affects the phonon mean free path. Furthermore, for relatively long GaN monolayers, the in-plane stress may trigger the buckling instability, which can significantly reduce the phonon mean free path.

Liquid-Crystalline Collapse of Pulmonary Surfactant Monolayers

PubMed Central

Schief, William R.; Antia, Meher; Discher, Bohdana M.; Hall, Stephen B.; Vogel, Viola

2003-01-01

During exhalation, the surfactant film of lipids and proteins that coats the alveoli in the lung is compressed to high surface pressures, and can remain metastable for prolonged periods at pressures approaching 70 mN/m. Monolayers of calf lung surfactant extract (CLSE), however, collapse in vitro, during an initial compression at ∼45 mN/m. To gain information on the source of this discrepancy, we investigated how monolayers of CLSE collapse from the interface. Observations with fluorescence, Brewster angle, and light scattering microscopies show that monolayers containing CLSE, CLSE-cholesterol (20%), or binary mixtures of dipalmitoyl phosphatidylcholine(DPPC)-dihydrocholesterol all form bilayer disks that reside above the monolayer. Upon compression and expansion, lipids flow continuously from the monolayer into the disks, and vice versa. In several respects, the mode of collapse resembles the behavior of other amphiphiles that form smectic liquid-crystal phases. These findings suggest that components of surfactent films must collapse collectively rather than being squeezed out individually. PMID:12770885

Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis

NASA Astrophysics Data System (ADS)

Zhou, Yangen; Zhang, Yongfan; Lin, Mousheng; Long, Jinlin; Zhang, Zizhong; Lin, Huaxiang; Wu, Jeffrey C.-S.; Wang, Xuxu

2015-09-01

Two-dimensional-layered heterojunctions have attracted extensive interest recently due to their exciting behaviours in electronic/optoelectronic devices as well as solar energy conversion systems. However, layered heterojunction materials, especially those made by stacking different monolayers together by strong chemical bonds rather than by weak van der Waal interactions, are still challenging to fabricate. Here the monolayer Bi2WO6 with a sandwich substructure of [BiO]+-[WO4]2--[BiO]+ is reported. This material may be characterized as a layered heterojunction with different monolayer oxides held together by chemical bonds. Coordinatively unsaturated Bi atoms are present as active sites on the surface. On irradiation, holes are generated directly on the active surface layer and electrons in the middle layer, which leads to the outstanding performances of the monolayer material in solar energy conversion. Our work provides a general bottom-up route for designing and preparing novel monolayer materials with ultrafast charge separation and active surface.

Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis

PubMed Central

Zhou, Yangen; Zhang, Yongfan; Lin, Mousheng; Long, Jinlin; Zhang, Zizhong; Lin, Huaxiang; Wu, Jeffrey C.-S.; Wang, Xuxu

2015-01-01

Two-dimensional-layered heterojunctions have attracted extensive interest recently due to their exciting behaviours in electronic/optoelectronic devices as well as solar energy conversion systems. However, layered heterojunction materials, especially those made by stacking different monolayers together by strong chemical bonds rather than by weak van der Waal interactions, are still challenging to fabricate. Here the monolayer Bi2WO6 with a sandwich substructure of [BiO]+–[WO4]2−–[BiO]+ is reported. This material may be characterized as a layered heterojunction with different monolayer oxides held together by chemical bonds. Coordinatively unsaturated Bi atoms are present as active sites on the surface. On irradiation, holes are generated directly on the active surface layer and electrons in the middle layer, which leads to the outstanding performances of the monolayer material in solar energy conversion. Our work provides a general bottom-up route for designing and preparing novel monolayer materials with ultrafast charge separation and active surface. PMID:26359212

Doping effect on monolayer MoS2 for visible light dye degradation - A DFT study

NASA Astrophysics Data System (ADS)

Cheriyan, Silpa; Balamurgan, D.; Sriram, S.

2018-04-01

The electronic and optical properties of, Nitrogen (N), Cobalt (Co), and Co-N co-doped monolayers of MoS2 has been studied by using density functional theory (DFT) for visible light photocatalytic activity. From the calculations, it has been observed that the band gap of monolayer MoS2 has been reduced while doping. However, the band gaps of pristine and N doped MoS2 monolayers only falls in the visible region while for Co and Co-N co-doped systems, the band gap shifted to IR region. The optical calculation also confirms the results. The formation energy values of the doped system reaveal that MoS2 monolayer drops its stability while doping. To evaluate the photocatalytic response, band edge potentials of pristine and N-MoS2 are calculated, and the observed results show that compared to N-doped MoS2 monolayer, pure MoS2 is highly suitable for visible light photocatalytic dye degradation.

Monolayer PtSe₂, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt.

PubMed

Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J T; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; Wang, Eryin; Shao, Yan; Zhang, Y Y; Yang, Hai-tao; Schwier, Eike F; Iwasawa, Hideaki; Shimada, Kenya; Taniguchi, Masaki; Cheng, Zhaohua; Zhou, Shuyun; Du, Shixuan; Pennycook, Stephen J; Pantelides, Sokrates T; Gao, Hong-Jun

2015-06-10

Single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe2), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. A combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe2/Pt(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe2 (in contrast to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe2 film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe2 has also potential applications in valleytronics.

Monolayer optical memory cells based on artificial trap-mediated charge storage and release

NASA Astrophysics Data System (ADS)

Lee, Juwon; Pak, Sangyeon; Lee, Young-Woo; Cho, Yuljae; Hong, John; Giraud, Paul; Shin, Hyeon Suk; Morris, Stephen M.; Sohn, Jung Inn; Cha, Seungnam; Kim, Jong Min

2017-03-01

Monolayer transition metal dichalcogenides are considered to be promising candidates for flexible and transparent optoelectronics applications due to their direct bandgap and strong light-matter interactions. Although several monolayer-based photodetectors have been demonstrated, single-layered optical memory devices suitable for high-quality image sensing have received little attention. Here we report a concept for monolayer MoS2 optoelectronic memory devices using artificially-structured charge trap layers through the functionalization of the monolayer/dielectric interfaces, leading to localized electronic states that serve as a basis for electrically-induced charge trapping and optically-mediated charge release. Our devices exhibit excellent photo-responsive memory characteristics with a large linear dynamic range of ~4,700 (73.4 dB) coupled with a low OFF-state current (<4 pA), and a long storage lifetime of over 104 s. In addition, the multi-level detection of up to 8 optical states is successfully demonstrated. These results represent a significant step toward the development of future monolayer optoelectronic memory devices.

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

Smith, R. Scott; Kay, Bruce D.

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer TPD spectra have the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An inversion analysis of the monolayer benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 1017 ±more » 1 s-1. The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 1016 ± 1 ML s-1.« less

Ultraviolet photodetector using pn junction formed by transferrable hollow n-TiO2 nano-spheres monolayer.

PubMed

Yang, Taeyoung; Park, Seong-Jin; Kim, Taek Gon; Shin, Dong Su; Suh, Kyung-do; Park, Jinsub

2017-12-11

We report an ultraviolet (UV) photodetector with a universally transferable monolayer film with ordered hollow TiO 2 spheres on p-GaN. After forming a TiO 2 monolayer film by unidirectional rubbing of hollow TiO 2 spheres on a polydimethylsiloxane (PDMS) supporting plate, we used a 5% polyvinyl alcohol (PVA) aqueous solution to transfer the film onto the target substrate. The PVA/TiO 2 monolayer film was detached from the PDMS film and transferred to the p-GaN/Al 2 O 3 substrate. To investigate the effects of crystallized phases of the TiO 2 hollow spheres, anatase and rutile TiO 2 sphere monolayers prepared by combining template synthesis and thermal treatment. The responsiveness of the UV photodetectors using anatase and rutile hollow n-TiO 2 monolayer/p-GaN was 0.203 A/W at 312 nm and 0.093 A/W at 327 nm, respectively.

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

Wei, Guohua; Czaplewski, David A.; Lenferink, Erik J.

Three-dimensional confinement allows semiconductor quantum dots to exhibit size-tunable electronic and optical properties that enable a wide range of opto-electronic applications from displays, solar cells and bio-medical imaging to single-electron devices. Additional modalities such as spin and valley properties in monolayer transition metal dichalcogenides provide further degrees of freedom requisite for information processing and spintronics. In nanostructures, however, spatial confinement can cause hybridization that inhibits the robustness of these emergent properties. Here in this paper, we show that laterally-confined excitons in monolayer MoS 2 nanodots can be created through top-down nanopatterning with controlled size tunability. Unlike chemically-exfoliated monolayer nanoparticles, themore » lithographically patterned monolayer semiconductor nanodots down to a radius of 15 nm exhibit the same valley polarization as in a continuous monolayer sheet. The inherited bulk spin and valley properties, the size dependence of excitonic energies, and the ability to fabricate MoS 2 nanostructures using semiconductor-compatible processing suggest that monolayer semiconductor nanodots have potential to be multimodal building blocks of integrated optoelectronics and spintronics systems« less

Surface studies of barium and barium oxide on tungsten and its application to understanding the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

Surface studies have been made of multilayer and monolayer films of barium and barium oxide on a tungsten substrate. The purpose of the investigation was to synthesize the surface conditions that exist on an activated impregnated tungsten cathode and obtain a better understanding of the mechanism of operation of such cathodes. The techniques employed in these measurements were Auger spectroscopy and work-function measurements. The results of this study show that the surface of an impregnated cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on oxidized tungsten by evaluating Auger spectra and work-function measurements. Data obtained from desorption studies of barium monolayers on a tungsten substrate in conjunction with Auger and work-function results have been interpreted to show that throughout most of its life an impreganated cathode has a partial monolayer, rather than a monolayer, of barium on its surface.

A Novel 3D Label-Free Monitoring System of hES-Derived Cardiomyocyte Clusters: A Step Forward to In Vitro Cardiotoxicity Testing

PubMed Central

Jahnke, Heinz-Georg; Steel, Daniella; Fleischer, Stephan; Seidel, Diana; Kurz, Randy; Vinz, Silvia; Dahlenborg, Kerstin; Sartipy, Peter; Robitzki, Andrea A.

2013-01-01

Unexpected adverse effects on the cardiovascular system remain a major challenge in the development of novel active pharmaceutical ingredients (API). To overcome the current limitations of animal-based in vitro and in vivo test systems, stem cell derived human cardiomyocyte clusters (hCMC) offer the opportunity for highly predictable pre-clinical testing. The three-dimensional structure of hCMC appears more representative of tissue milieu than traditional monolayer cell culture. However, there is a lack of long-term, real time monitoring systems for tissue-like cardiac material. To address this issue, we have developed a microcavity array (MCA)-based label-free monitoring system that eliminates the need for critical hCMC adhesion and outgrowth steps. In contrast, feasible field potential derived action potential recording is possible immediately after positioning within the microcavity. Moreover, this approach allows extended observation of adverse effects on hCMC. For the first time, we describe herein the monitoring of hCMC over 35 days while preserving the hCMC structure and electrophysiological characteristics. Furthermore, we demonstrated the sensitive detection and quantification of adverse API effects using E4031, doxorubicin, and noradrenaline directly on unaltered 3D cultures. The MCA system provides multi-parameter analysis capabilities incorporating field potential recording, impedance spectroscopy, and optical read-outs on individual clusters giving a comprehensive insight into induced cellular alterations within a complex cardiac culture over days or even weeks. PMID:23861955

Dynamics of mono- and dual-species biofilm formation and interactions between Staphylococcus aureus and Gram-negative bacteria.

PubMed

Makovcova, Jitka; Babak, Vladimir; Kulich, Pavel; Masek, Josef; Slany, Michal; Cincarova, Lenka

2017-07-01

Microorganisms are not commonly found in the planktonic state but predominantly form dual- and multispecies biofilms in almost all natural environments. Bacteria in multispecies biofilms cooperate, compete or have neutral interactions according to the involved species. Here, the development of mono- and dual-species biofilms formed by Staphylococcus aureus and other foodborne pathogens such as Salmonella enterica subsp. enterica serovar Enteritidis, potentially pathogenic Raoultella planticola and non-pathogenic Escherichia coli over the course of 24, 48 and 72 h was studied. Biofilm formation was evaluated by the crystal violet assay (CV), enumeration of colony-forming units (CFU cm -2 ) and visualization using confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). In general, Gram-negative bacterial species and S. aureus interacted in a competitive manner. The tested Gram-negative bacteria grew better in mixed dual-species biofilms than in their mono-species biofilms as determined using the CV assay, CFU ml -2 enumeration, and CLSM and SEM visualization. In contrast, the growth of S. aureus biofilms was reduced when cultured in dual-species biofilms. CLSM images revealed grape-like clusters of S. aureus and monolayers of Gram-negative bacteria in both mono- and dual-species biofilms. S. aureus clusters in dual-species biofilms were significantly smaller than clusters in S. aureus mono-species biofilms. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

LANTCET: laser nanotechnology for screening and treating tumors ex vivo and in vivo

NASA Astrophysics Data System (ADS)

Lapotko, Dmitri O.; Lukianova-Hleb, Ekaterina Y.; Zhdanok, Sergei A.; Hafner, Jason H.; Rostro, Betty C.; Scully, Peter; Konopleva, Marina; Andreeff, Michael; Li, Chun; Hanna, Ehab Y.; Myers, Jeffrey N.; Oraevsky, Alexander A.

2007-06-01

LANTCET (laser-activated nano-thermolysis as cell elimination technology) was developed for selective detection and destruction of individual tumor cells through generation of photothermal bubbles around clusters of light absorbing gold nanoparticles (nanorods and nanoshells) that are selectively formed in target tumor cells. We have applied bare nanoparticles and their conjugates with cell-specific vectors such as monoclonal antibodies CD33 (specific for Acute Myeloid Leukemia) and C225 (specific for carcinoma cells that express epidermal growth factor -EGF). Clusters were formed by using vector-receptor interactions with further clusterization of nanoparticles due to endocytosis. Formation of clusters was verified directly with optical resonance scattering microscopy and microspectroscopy. LANTCET method was tested in vitro for living cell samples with: (1) model myeloid K562 cells (CD33 positive), (2) primary human bone marrow CD33-positive blast cells from patients with the diagnosis of acute myeloid leukemia, (3) monolayers of living EGF-positive carcinoma cells (Hep-2C), (4) human lymphocytes and red blood cells as normal cells. The LANTCET method was also tested in vivo using rats with experimental polymorphic sarcoma. Photothermal bubbles were generated and detected in vitro with a photothermal microscope equipped with a tunable Ti-Sa pulsed laser. We have found that cluster formation caused an almost 100-fold decrease in the bubble generation threshold of laser pulse fluence in tumor cells compared to the bubble generation threshold for normal cells. The animal tumor that was treated with a single laser pulse showed a necrotic area of diameter close to the pump laser beam diameter and a depth of 1-2 mm. Cell level selectivity of tumor damage with single laser pulse was demonstrated. Combining lightscattering imaging with bubble imaging, we introduced a new image-guided mode of the LANTCET operation for screening and treatment of tumors ex vivo and in vivo.

Dermaseptin 01 as antimicrobial peptide with rich biotechnological potential: study of peptide interaction with membranes containing Leishmania amazonensis lipid-rich extract and membrane models.

PubMed

Salay, Luiz C; Nobre, Thatyane M; Colhone, Marcelle C; Zaniquelli, Maria E D; Ciancaglini, Pietro; Stabeli, Rodrigo G; Leite, José Roberto S A; Zucolotto, Valtencir

2011-10-01

This article addresses the interactions of the synthetic antimicrobial peptide dermaseptin 01 (GLWSTIKQKGKEAAIAAA- KAAGQAALGAL-NH(2) , DS 01) with phospholipid (PL) monolayers comprising (i) a lipid-rich extract of Leishmania amazonensis (LRE-La), (ii) zwitterionic PL (dipalmitoylphosphatidylcholine, DPPC), and (iii) negatively charged PL (dipalmitoylphosphatidylglycerol, DPPG). The degree of interaction of DS 01 with the different biomembrane models was quantified from equilibrium and dynamic liquid-air interface parameters. At low peptide concentrations, interactions between DS 01 and zwitterionic PL, as well as with the LRE-La monolayers were very weak, whereas with negatively charged PLs the interactions were stronger. For peptide concentrations above 1 µg/ml, a considerable expansion of negatively charged monolayers occurred. In the case of DPPC, it was possible to return to the original lipid area in the condensed phase, suggesting that the peptide was expelled from the monolayer. However, in the case of DPPG, the average area per lipid molecule in the presence of DS 01 was higher than pure PLs even at high surface pressures, suggesting that at least part of DS 01 remained incorporated in the monolayer. For the LRE-La monolayers, DS 01 also remained in the monolayer. This is the first report on the antiparasitic activity of AMPs using Langmuir monolayers of a natural lipid extract from L. amazonensis. Copyright © 2011 European Peptide Society and John Wiley & Sons, Ltd.

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

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

Vukmirovic,M.B.; Sasaki, K.; Zhou, W.-P.

2008-09-15

For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supportedmore » nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution.« less

A class of monolayer metal halogenides MX{sub 2}: Electronic structures and band alignments

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

Lu, Feng; Wang, Weichao; Luo, Xiaoguang

2016-03-28

With systematic first principles calculations, a class of monolayer metal halogenides MX{sub 2} (M = Mg, Ca, Zn, Cd, Ge, Pb; M = Cl, Br, I) has been proposed. Our study indicates that these monolayer materials are semiconductors with the band gaps ranging from 2.03 eV of ZnI{sub 2} to 6.08 eV of MgCl{sub 2}. Overall, the band gap increases with the increase of the electronegativity of the X atom or the atomic number of the metal M. Meanwhile, the band gaps of monolayer MgX{sub 2} (X = Cl, Br) are direct while those of other monolayers are indirect. Based on the band edge curvatures, the derived electronmore » (m{sub e}) and hole (m{sub h}) effective masses of MX{sub 2} monolayers are close to their corresponding bulk values except that the m{sub e} of CdI{sub 2} is three times larger and the m{sub h} for PbI{sub 2} is twice larger. Finally, the band alignments of all the studied MX{sub 2} monolayers are provided using the vacuum level as energy reference. These theoretical results may not only introduce the monolayer metal halogenides family MX{sub 2} into the emerging two-dimensional materials, but also provide insights into the applications of MX{sub 2} in future electronic, visible and ultraviolet optoelectronic devices.« less

Structural evolution and properties of small-size thiol-protected gold nanoclusters

NASA Astrophysics Data System (ADS)

Ma, Miaomiao; Liu, Liren; Zhu, Hengjiang; Lu, Junzhe; Tan, Guiping

2018-07-01

Ligand-protected gold clusters are widely used in biosensors and catalysis. Understanding the structural evolution of these kinds of nanoclusters is important for experimental synthesis. Herein, based on the particle swarm optimisation algorithm and density functional theory method, we use [Au1(SH)2]n, [Au2(SH)3]n, [Au3(SH)4]n (n = 1-3) as basic units to research the structural evolution relationships from building blocks to the final whole structures. Results show that there is a 'line-ring-core' structural evolution pattern in the growth process of the nanoclusters. The core structures of the ligand-protected gold clusters consist of Au3, Au4, Au6 and Au7 atoms. The electronics and optics analysis reflects that stability and optical properties gradually enhance with increase in size. These results can be used to understand the initial growth stage and design new ligand-protected nanoclusters.

Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

PubMed

Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

2016-07-07

The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements.

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

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

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

DOE PAGES

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie; ...

2017-10-06

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Marmoset induced pluripotent stem cells: Robust neural differentiation following pretreatment with dimethyl sulfoxide.

PubMed

Qiu, Zhifang; Mishra, Anuja; Li, Miao; Farnsworth, Steven L; Guerra, Bernadette; Lanford, Robert E; Hornsby, Peter J

2015-07-01

The marmoset is an important nonhuman primate model for regenerative medicine. For experimental autologous cell therapy based on induced pluripotent (iPS) cells in the marmoset, cells must be able to undergo robust and reliable directed differentiation that will not require customization for each specific iPS cell clone. When marmoset iPS cells were aggregated in a hanging drop format for 3 days, followed by exposure to dual SMAD inhibitors and retinoic acid in monolayer culture for 3 days, we found substantial variability in the response of different iPS cell clones. However, when clones were pretreated with 0.05-2% dimethyl sulfoxide (DMSO) for 24 hours, all clones showed a very similar maximal response to the directed differentiation scheme. Peak responses were observed at 0.5% DMSO in two clones and at 1% DMSO in a third clone. When patterns of gene expression were examined by microarray analysis, hierarchical clustering showed very similar responses in all 3 clones when they were pretreated with optimal DMSO concentrations. The change in phenotype following exposure to DMSO and the 6 day hanging drop/monolayer treatment was confirmed by immunocytochemistry. Analysis of DNA content in DMSO-exposed cells indicated that it is unlikely that DMSO acts by causing cells to exit from the cell cycle. This approach should be generally valuable in the directed neural differentiation of pluripotent cells for experimental cell therapy. Copyright © 2015. Published by Elsevier B.V.

Dielectric anomaly and relaxation natures in a Zn-Cr pillar-layered metal-organic framework with cages and channels

NASA Astrophysics Data System (ADS)

Xue, Chen; Yao, Zhi-Yuan; Liu, Shao-Xian; Luo, Hong-Bin; Zou, Yang; Li, Li; Ren, Xiao-Ming

2017-06-01

A bimetallic metal-organic framework (MOF) with the formula [Zn3btc2{Cr3O(isonic)6(H2O)2(OH)}]·(DMF)15.5(H2O)8 (H3btc=1,3,5-benzenetricarboxylic acid; isonic=isonicotinicate) shows a pillar-layered structure. The monolayer consists of hexagon-like rings formed by the [Zn(isonic)2(btc)2] tetrahedral and the consecutive monolayers are pillared by trigonal-prismatic clusters of [Cr3O(isonic)6(H2O)2(OH)]through the remaining binding sites of the Zn2+ ions. DMF and water molecules are confined in the cages and channels. TGA indicates that the lattice DMF and water molecules begin to be released at temperatures above 363 K. Dielectric measurements were carried out in the range of 173-363 K and 1-107 Hz for three successive thermal cycles. The dielectric spectroscopy obtained in the first thermal cycle was different from that observed in the next two thermal cycles, while the dielectric spectra in the last two thermal cycles were almost identical. The dielectric nature of this MOF is discussed in detail for each thermal cycle. Since MOFs are unique host-guest systems in which the structure of the host framework is designable and the guests are exchangeable, it is no doubt those MOFs are materials with a variety of dielectric natures. This study gives a fresh impetus to achieve MOFs-based dielectric materials.

Observation of High-Harmonic Generation from an Atomically Thin Semiconductor [Observation of High Harmonics from and Atomically Thin Semiconductor

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

Liu, Hanzhe; Li, Yilei; You, Yongsing

We report the observation of nonperturbative high-harmonic generation from monolayer MoS 2. Here, the yield is higher in monolayer compared to a single layer of the bulk, an effect attributed to strong electron-hole interactions in the monolayer.

Observation of High-Harmonic Generation from an Atomically Thin Semiconductor [Observation of High Harmonics from and Atomically Thin Semiconductor

DOE PAGES

Liu, Hanzhe; Li, Yilei; You, Yongsing; ...

2016-01-01

We report the observation of nonperturbative high-harmonic generation from monolayer MoS 2. Here, the yield is higher in monolayer compared to a single layer of the bulk, an effect attributed to strong electron-hole interactions in the monolayer.

Semi-Metallic Be5C2 Monolayer Global Minimum with Quasi-Planar Pentacoordinate Carbons and Negative Poissons Ratio (Open Access Publisher’s Version)

DTIC Science & Technology

2016-05-03

ARTICLE Received 25 Nov 2015 | Accepted 1 Apr 2016 | Published 3 May 2016 Semi-metallic Be5C2 monolayer global minimum with quasi -planar...forming a quasi -planar pentacoordinate carbon moiety. Be5C2 monolayer appears to have good stability as revealed by its moderate cohesive energy...some promise to be realized experimentally . Be5C2 monolayer is a gapless semiconductor with a Dirac-like point in the band structure and also has an

Monolayer coated gold nanoparticles for delivery applications

PubMed Central

Rana, Subinoy; Bajaj, Avinash; Mout, Rubul; Rotello, Vincent M.

2011-01-01

Gold nanoparticles (AuNPs) provide attractive vehicles for delivery of drugs, genetic materials, proteins, and small molecules. AuNPs feature low core toxicity coupled with the ability to parametrically control particle size and surface properties. In this review, we focus on engineering of the AuNP surface monolayer, highlighting recent advances in tuning monolayer structures for efficient delivery of drugs and biomolecules. This review covers two broad categories of particle functionalization, organic monolayers and biomolecule coatings, and discusses their applications in drug, DNA/RNA, protein and small molecule delivery. PMID:21925556

Methods of making functionalized nanorods

DOEpatents

Gur, Ilan [San Francisco, CA; Milliron, Delia [Berkeley, CA; Alivisatos, A Paul [Oakland, CA; Liu, Haitao [Berkeley, CA

2012-01-10

A process for forming functionalized nanorods. The process includes providing a substrate, modifying the substrate by depositing a self-assembled monolayer of a bi-functional molecule on the substrate, wherein the monolayer is chosen such that one side of the bi-functional molecule binds to the substrate surface and the other side shows an independent affinity for binding to a nanocrystal surface, so as to form a modified substrate. The process further includes contacting the modified substrate with a solution containing nanocrystal colloids, forming a bound monolayer of nanocrystals on the substrate surface, depositing a polymer layer over the monolayer of nanocrystals to partially cover the monolayer of nanocrystals, so as to leave a layer of exposed nanocrystals, functionalizing the exposed nanocrystals, to form functionalized nanocrystals, and then releasing the functionalized nanocrystals from the substrate.

Experimental study of thermal rectification in suspended monolayer graphene

PubMed Central

Wang, Haidong; Hu, Shiqian; Takahashi, Koji; Zhang, Xing; Takamatsu, Hiroshi; Chen, Jie

2017-01-01

Thermal rectification is a fundamental phenomenon for active heat flow control. Significant thermal rectification is expected to exist in the asymmetric nanostructures, such as nanowires and thin films. As a one-atom-thick membrane, graphene has attracted much attention for realizing thermal rectification as shown by many molecular dynamics simulations. Here, we experimentally demonstrate thermal rectification in various asymmetric monolayer graphene nanostructures. A large thermal rectification factor of 26% is achieved in a defect-engineered monolayer graphene with nanopores on one side. A thermal rectification factor of 10% is achieved in a pristine monolayer graphene with nanoparticles deposited on one side or with a tapered width. The results indicate that the monolayer graphene has great potential to be used for designing high-performance thermal rectifiers for heat flow control and energy harvesting. PMID:28607493

Electric field induced self-assembly of monolayers of gold nanoparticles for surface enhanced Raman scattering applications

NASA Astrophysics Data System (ADS)

Das, Suchandra; Musunuri, Naga; Kucheryavy, Pavel; Lockard, Jenny; Fischer, Ian; Singh, Pushpendra; New Jersey Institute of Technology Collaboration; Rutgers University Newark Collaboration

2017-11-01

We present a technique that uses an electric field in the direction normal to the interface for self-assembling monolayers of gold nanoparticles on fluid-liquid interfaces and freezing these monolayers onto the surface of a flexible thin film. The electric field gives rise to dipole-dipole and capillary forces which cause the particles to arrange in a triangular pattern. The technique involves assembling the monolayer on the interface between a UV-curable resin and another fluid by applying an electric field, and then curing the resin by applying UV light. The monolayer becomes embedded on the surface of the solidified resin film. We are using these films for surface enhanced Raman scattering (SERS) applications. Initial measurements indicate improved performance over commercially available SERS substrates.

The structure and dynamics of Nano Particles encapsulated by the SDS monolayer collapse at the water/TCE interface

PubMed Central

Shi, Wenxiong

2016-01-01

The super-saturated surfactant monolayer collapses with the nanoparticles (NPs) at the water/trichloroethylene (TCE) interface are investigated using molecular dynamics (MD) simulations. The results show that sodium alkyl sulfate (SDS) monolayer collapse is initiated by buckling and followed primarily by budding and the bud encapsulating the NPs and oil molecules. The developed bud detaches from the monolayer into a water phase and forms the swollen micelle emulsion with NPs and oil molecules. We investigate the wavelength of the initial budding and the theoretical description of the budding process. The wavelength of the monolayer increases with bending modulus. The energy barrier of the budding can be easily overcome by thermal fluctuation energy, which indicates that budding process proceeds rapidly. PMID:27853312

The structure and dynamics of Nano Particles encapsulated by the SDS monolayer collapse at the water/TCE interface

NASA Astrophysics Data System (ADS)

Shi, Wenxiong

2016-11-01

The super-saturated surfactant monolayer collapses with the nanoparticles (NPs) at the water/trichloroethylene (TCE) interface are investigated using molecular dynamics (MD) simulations. The results show that sodium alkyl sulfate (SDS) monolayer collapse is initiated by buckling and followed primarily by budding and the bud encapsulating the NPs and oil molecules. The developed bud detaches from the monolayer into a water phase and forms the swollen micelle emulsion with NPs and oil molecules. We investigate the wavelength of the initial budding and the theoretical description of the budding process. The wavelength of the monolayer increases with bending modulus. The energy barrier of the budding can be easily overcome by thermal fluctuation energy, which indicates that budding process proceeds rapidly.

Unsupported single-atom-thick copper oxide monolayers

NASA Astrophysics Data System (ADS)

Yin, Kuibo; Zhang, Yu-Yang; Zhou, Yilong; Sun, Litao; Chisholm, Matthew F.; Pantelides, Sokrates T.; Zhou, Wu

2017-03-01

Oxide monolayers may present unique opportunities because of the great diversity of properties of these materials in bulk form. However, reports on oxide monolayers are still limited. Here we report the formation of single-atom-thick copper oxide layers with a square lattice both in graphene pores and on graphene substrates using aberration-corrected scanning transmission electron microscopy. First-principles calculations find that CuO is energetically stable and its calculated lattice spacing matches well with the measured value. Furthermore, free-standing copper oxide monolayers are predicted to be semiconductors with band gaps ˜3 eV. The new wide-bandgap single-atom-thick copper oxide monolayers usher a new frontier to study the highly diverse family of two-dimensional oxides and explore their properties and their potential for new applications.

Experimental study of thermal rectification in suspended monolayer graphene.

PubMed

Wang, Haidong; Hu, Shiqian; Takahashi, Koji; Zhang, Xing; Takamatsu, Hiroshi; Chen, Jie

2017-06-13

Thermal rectification is a fundamental phenomenon for active heat flow control. Significant thermal rectification is expected to exist in the asymmetric nanostructures, such as nanowires and thin films. As a one-atom-thick membrane, graphene has attracted much attention for realizing thermal rectification as shown by many molecular dynamics simulations. Here, we experimentally demonstrate thermal rectification in various asymmetric monolayer graphene nanostructures. A large thermal rectification factor of 26% is achieved in a defect-engineered monolayer graphene with nanopores on one side. A thermal rectification factor of 10% is achieved in a pristine monolayer graphene with nanoparticles deposited on one side or with a tapered width. The results indicate that the monolayer graphene has great potential to be used for designing high-performance thermal rectifiers for heat flow control and energy harvesting.

Enhanced photoresponse of monolayer molybdenum disulfide (MoS2) based on microcavity structure

NASA Astrophysics Data System (ADS)

Lu, Yanan; Yang, Guofeng; Wang, Fuxue; Lu, Naiyan

2018-05-01

There is an increasing interest in using monolayer molybdenum disulfide (MoS2) for optoelectronic devices because of its inherent direct band gap characteristics. However, the weak absorption of monolayer MoS2 restricts its applications, novel concepts need to be developed to address the weakness. In this work, monolayer MoS2 monolithically integrates with plane microcavity structure, which is formed by the top and bottom chirped distributed Bragg reflector (DBR), is demonstrated to improve the absorption of MoS2. The optical absorption is 17-fold enhanced, reaching values over 70% at work wavelength. Moreover, the monolayer MoS2-based photodetector device with microcavity presents a significantly increased photoresponse, demonstrating its promising prospects in MoS2-based optoelectronic devices.

Laser thinning for monolayer graphene formation: heat sink and interference effect.

PubMed

Han, Gang Hee; Chae, Seung Jin; Kim, Eun Sung; Güneş, Fethullah; Lee, Il Ha; Lee, Sang Won; Lee, Si Young; Lim, Seong Chu; Jeong, Hae Kyung; Jeong, Mun Seok; Lee, Young Hee

2011-01-25

Despite the availability of large-area graphene synthesized by chemical vapor deposition (CVD), the control of a uniform monolayer graphene remained challenging. Here, we report a method of acquiring monolayer graphene by laser irradiation. The accumulation of heat on graphene by absorbing light, followed by oxidative burning of upper graphene layers, which strongly relies on the wavelength of light and optical parameters of the substrate, was in situ measured by the G-band shift in Raman spectroscopy. The substrate plays a crucial role as a heat sink for the bottom monolayer graphene, resulting in no burning or etching. Oscillatory thinning behavior dependent on the substrate oxide thickness was evaluated by adopting a simple Fresnel's equation. This paves the way for future research in utilizing monolayer graphene for high-speed electronic devices.

Strain transfer across grain boundaries in MoS2 monolayers grown by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Niehues, Iris; Blob, Anna; Stiehm, Torsten; Schmidt, Robert; Jadriško, Valentino; Radatović, Borna; Čapeta, Davor; Kralj, Marko; Michaelis de Vasconcellos, Steffen; Bratschitsch, Rudolf

2018-07-01

Monolayers of transition metal dichalcogenides (TMDC) mechanically exfoliated from bulk crystals have exceptional mechanical and optical properties. They are extremely flexible, sustaining mechanical strain of about 10% without breaking. Their optical properties dramatically change with applied strain. However, the fabrication of a large number of mechanical devices is tedious due to the micromechanical exfoliation process. Alternatively, monolayers can be grown by chemical vapor deposition (CVD) on the wafer scale, with the drawback of cracks and grain boundaries in the material. Therefore, it is important to investigate the mechanical properties of CVD-grown material and its potential as a material for mass production of nanomechanical devices. Here, we measure the optical absorption of CVD-grown MoS2 monolayers with applied uniaxial tensile strain. We derive a strain-dependent shift for the A exciton of  ‑42 meV/%. This value is identical to MoS2 monolayers, which are mechanically exfoliated from natural molybdenite crystals. Using angle-resolved second-harmonic generation spectroscopy, we find that the applied uniaxial tensile strain is fully transferred across grain boundaries of the CVD-grown monolayer. Our work demonstrates that large-area artificially grown MoS2 monolayers are promising for mass-produced nanomechanical devices.

Growth of Monolayer Graphene on Nanoscale Copper-Nickel Alloy Thin Films

PubMed Central

Cho, Joon Hyong; Gorman, Jason J.; Na, Seung Ryul; Cullinan, Michael

2017-01-01

Growth of high quality and monolayer graphene on copper thin films on silicon wafers is a promising approach to massive and direct graphene device fabrication in spite of the presence of potential dewetting issues in the copper film during graphene growth. Current work demonstrates roles of a nickel adhesion coupled with the copper film resulting in mitigation of dewetting problem as well as uniform monolayer graphene growth over 97 % coverage on films. The feasibility of monolayer graphene growth on Cu-Ni alloy films as thin as 150 nm in total is also demonstrated. During the graphene growth on Cu-Ni films, the nickel adhesion layer uniformly diffuses into the copper thin film resulting in a Cu-Ni alloy, helping to promote graphene nucleation and large area surface coverage. Furthermore, it was found that the use of extremely thin metal catalyst films also constraint the total amount of carbon that can be absorbed into the film during growth, which helps to eliminate adlayer formation and promote monolayer growth regardless of alloying content, thus improving the monolayer fraction of graphene coverage on the thinner films. These results suggest a path forward for the large scale integration of high quality, monolayer graphene into nanoelectronic and nanomechanical devices. PMID:28669999

Vacancy-Induced Formation and Growth of Inversion Domains in Transition-Metal Dichalcogenide Monolayer

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

Lin, Junhao; Pantelides, Sokrates T.; Zhou, Wu

2015-04-23

Sixty degree grain boundaries in semiconducting transition-metal dichalcogenide (TMDC) monolayers have been shown to act as conductive channels that have profound influence on both the transport properties and exciton behavior of the monolayers. We show that annealing TMDC monolayers at high temperature induces the formation of large-scale inversion domains surrounded by such 60° grain boundaries. To study the formation mechanism of such inversion domains, we use the electron beam in a scanning transmission electron microscope to activate the dynamic process within pristine TMDC monolayers. Moreover, the electron beam acts to generate chalcogen vacancies in TMDC monolayers and provide energy formore » them to undergo structural evolution. We directly visualize the nucleation and growth of such inversion domains and their 60° grain boundaries atom-by-atom within a MoSe 2 monolayer and explore their formation mechanism. Combined with density functional theory, we conclude that the nucleation of the inversion domains and migration of their 60° grain boundaries are driven by the collective evolution of Se vacancies and subsequent displacement of Mo atoms, where such a dynamical process reduces the vacancy-induced lattice shrinkage and stabilizes the system. Our results can help to understand the performance of such materials under severe conditions (e.g., high temperature).« less

Measuring mechanodynamics in an unsupported epithelial monolayer grown at an air–water interface

PubMed Central

Gullekson, Corinne; Walker, Matthew; Harden, James L.; Pelling, Andrew E.

2017-01-01

Actomyosin contraction and relaxation in a monolayer is a fundamental biophysical process in development and homeostasis. Current methods used to characterize the mechanodynamics of monolayers often involve cells grown on solid supports such as glass or gels. The results of these studies are fundamentally influenced by these supporting structures. Here we describe a new method for measuring the mechanodynamics of epithelial monolayers by culturing cells at an air–liquid interface. These model monolayers are grown in the absence of any supporting structures, removing cell–substrate effects. This method’s potential was evaluated by observing and quantifying the generation and release of internal stresses upon actomyosin contraction (800 ± 100 Pa) and relaxation (600 ± 100 Pa) in response to chemical treatments. Although unsupported monolayers exhibited clear major and minor strain axes, they were not correlated with nuclear alignment as observed when the monolayers were grown on soft deformable gels. It was also observed that both gels and glass substrates led to the promotion of long-range cell nuclei alignment not seen in the hanging-drop model. This new approach provides us with a picture of basal actomyosin mechanodynamics in a simplified system, allowing us to infer how the presence of a substrate affects contractility and long-range multicellular organization and dynamics. PMID:28035043

Origin of the instability of octadecylamine Langmuir monolayer at low pH

DOE PAGES

Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan; ...

2015-11-30

In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less

Thermoelectric properties of SnSe2 monolayer.

PubMed

Li, Guanpeng; Ding, Guangqian; Gao, Guoying

2017-01-11

The 2H (MoS 2 -type) phase of 2D transition metal dichalcogenides (TMDCs) has been extensively studied and exhibits excellent electronic and optoelectronic properties, but the high phonon thermal conductivity is detrimental to the thermoelectric performances. Here, we use first-principles methods combined with Boltzmann transport theory to calculate the electronic and phononic transport properties of 1T (CdI 2 -type) SnSe 2 monolayer, a recently realized 2D metal dichalcogenide semiconductor. The calculated band gap is 0.85 eV, which is a little larger than the bulk value. Lower phonon thermal conductivity and higher power factor are obtained in 1T-SnSe 2 monolayer compared to 2H-TMDCs monolayers. The low phonon thermal conductivity (3.27 W mK -1 at room temperature) is mainly due to the low phonon frequency of acoustic modes and the coupling of acoustic modes with optical modes. We also find that the p-type has better thermoelectric performance than the n-type, and the figure of merit within p-type can reach 0.94 at 600 K for 1T-SnSe 2 monolayer, which is higher than those of most 2H-TMDCs monolayers, making 1T-SnSe 2 monolayer a promising candidate for thermoelectric applications.

Directed assembly of binary monolayers with a high protein affinity: infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR).

PubMed

Du, Xuezhong; Wang, Yuchun

2007-03-08

Infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR) techniques have been employed to investigate human serum albumin (HSA) binding to binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA). At the air-water interface, the favorable electrostatic interaction between DPPC and DOMA leads to a dense chain packing. The tilt angle of the hydrocarbon chains decreases with increasing mole fraction of DOMA (X(DOMA)) in the monolayers at the surface pressure 30 mN/m: DPPC ( approximately 30 degrees ), X(DOMA) = 0.1 ( approximately 15 degrees ), and X(DOMA) = 0.3 ( approximately 0 degrees ). Negligible protein binding to the DPPC monolayer is observed in contrast to a significant binding to the binary monolayers. After HSA binding, the hydrocarbon chains at X(DOMA) = 0.1 undergo an increase in tilt angle from 15 degrees to 25 approximately 30 degrees , and the chains at X(DOMA) = 0.3 remain almost unchanged. The two components in the monolayers deliver through lateral reorganization, induced by the protein in the subphase, to form multiple interaction sites favorable for protein binding. The surfaces with a high protein affinity are created through the directed assembly of binary monolayers for use in biosensing.

Defects and oxidation of group-III monochalcogenide monolayers

NASA Astrophysics Data System (ADS)

Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

2017-09-01

Among various two-dimensional (2D) materials, monolayer group-III monochalcogenides (GaS, GaSe, InS, and InSe) stand out owing to their potential applications in microelectronics and optoelectronics. Devices made of these novel 2D materials are sensitive to environmental gases, especially O2 molecules. To address this critical issue, here we systematically investigate the oxidization behaviors of perfect and defective group-III monochalcogenide monolayers by first-principles calculations. The perfect monolayers show superior oxidation resistance with large barriers of 3.02-3.20 eV for the dissociation and chemisorption of O2 molecules. In contrast, the defective monolayers with single chalcogen vacancy are vulnerable to O2, showing small barriers of only 0.26-0.36 eV for the chemisorption of an O2 molecule. Interestingly, filling an O2 molecule to the chalcogen vacancy of group-III monochalcogenide monolayers could preserve the electronic band structure of the perfect system—the bandgaps are almost intact and the carrier effective masses are only moderately disturbed. On the other hand, the defective monolayers with single vacancies of group-III atoms carry local magnetic moments of 1-2 μB. These results help experimental design and synthesis of group-III monochalcogenides based 2D devices with high performance and stability.

Ion specific 2D to 3D structural modification of Langmuir monolayer at lower surface pressure

NASA Astrophysics Data System (ADS)

Das, Kaushik; Kundu, Sarathi

2017-05-01

2D to 3D structural transformation of stearic acid Langmuir monolayer in presence of Ca2+ and Zn2+ ions at lower surface pressure (≈25 mN/m) has been studied at lower (pH ≈ 6.8) and higher (pH ≈ 9.5) subphase pH. Generally, 2D to 3D structural transformation of monolayer occurs at higher surface pressure (>50 mN/m) after collapse point which can be identified from surface pressure (π) vs. specific molecular area (A) isotherms. In presence of Ca2+ ions and for both lower and higher subphase pH, stearic acid monolayer remains as 2D monolayer at that lower surface pressure as confirmed from the Atomic Force Microscopy (AFM) studies on the films deposited at π ≈ 25mN/m. However, in presence of Zn2+ at higher subphase pH, stearic acid monolayer shows 2D to 3D structural transformation where less covered bilayer-like structure forms on top of the monolayer as obtained from the AFM studies. Fourier transform infrared (FTIR) spectroscopy results reveal that formation of relatively more amount of bidentate bridging coordination of metal carboxylate headgroup may be the key reason of such 2D to 3D structural transformation for Zn2+.

Conservation priorities for endangered Indian tigers through a genomic lens.

PubMed

Natesh, Meghana; Atla, Goutham; Nigam, Parag; Jhala, Yadvendradev V; Zachariah, Arun; Borthakur, Udayan; Ramakrishnan, Uma

2017-08-29

Tigers have lost 93% of their historical range worldwide. India plays a vital role in the conservation of tigers since nearly 60% of all wild tigers are currently found here. However, as protected areas are small (<300 km 2 on average), with only a few individuals in each, many of them may not be independently viable. It is thus important to identify and conserve genetically connected populations, as well as to maintain connectivity within them. We collected samples from wild tigers (Panthera tigris tigris) across India and used genome-wide SNPs to infer genetic connectivity. We genotyped 10,184 SNPs from 38 individuals across 17 protected areas and identified three genetically distinct clusters (corresponding to northwest, southern and central India). The northwest cluster was isolated with low variation and high relatedness. The geographically large central cluster included tigers from central, northeastern and northern India, and had the highest variation. Most genetic diversity (62%) was shared among clusters, while unique variation was highest in the central cluster (8.5%) and lowest in the northwestern one (2%). We did not detect signatures of differential selection or local adaptation. We highlight that the northwest population requires conservation attention to ensure persistence of these tigers.

To assess whether indoor residual spraying can provide additional protection against clinical malaria over current best practice of long-lasting insecticidal mosquito nets in The Gambia: study protocol for a two-armed cluster-randomised trial

PubMed Central

2011-01-01

Background Recently, there has been mounting interest in scaling-up vector control against malaria in Africa. It needs to be determined if indoor residual spraying (IRS with DDT) will provide significant marginal protection against malaria over current best practice of long-lasting insecticidal nets (LLINs) and prompt treatment in a controlled trial, given that DDT is currently the most persistent insecticide for IRS. Methods A 2 armed cluster-randomised controlled trial will be conducted to assess whether DDT IRS and LLINs combined provide better protection against clinical malaria in children than LLINs alone in rural Gambia. Each cluster will be a village, or a group of small adjacent villages; all clusters will receive LLINs and half will receive IRS in addition. Study children, aged 6 months to 13 years, will be enrolled from all clusters and followed for clinical malaria using passive case detection to estimate malaria incidence for 2 malaria transmission seasons in 2010 and 2011. This will be the primary endpoint. Exposure to malaria parasites will be assessed using light and exit traps followed by detection of Anopheles gambiae species and sporozoite infection. Study children will be surveyed at the end of each transmission season to estimate the prevalence of Plasmodium falciparum infection and the prevalence of anaemia. Discussion Practical issues concerning intervention implementation, as well as the potential benefits and risks of the study, are discussed. Trial Registration ISRCTN01738840 - Spraying And Nets Towards malaria Elimination (SANTE) PMID:21663656

Diphosphine-protected ultrasmall gold nanoclusters: opened icosahedral Au 13 and heart-shaped Au 8 clusters

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

Zhang, Shan-Shan; Feng, Lei; Senanayake, Ravithree D.

Two ultrasmall gold clusters, Au 13 and Au 8 , were identified as a distorted I h icosahedral Au 13 and edge-shared “core + 4 exo ” structure Au 8 S 2 cores, respectively. They showed interesting luminescence and electrochemical properties.

Diphosphine-protected ultrasmall gold nanoclusters: opened icosahedral Au 13 and heart-shaped Au 8 clusters

DOE PAGES

Zhang, Shan-Shan; Feng, Lei; Senanayake, Ravithree D.; ...

2018-01-01

Two ultrasmall gold clusters, Au 13 and Au 8 , were identified as a distorted I h icosahedral Au 13 and edge-shared “core + 4 exo ” structure Au 8 S 2 cores, respectively. They showed interesting luminescence and electrochemical properties.

Methionine sulphoxide reductases protect iron-sulphur clusters from oxidative inactivation in yeast

PubMed Central

Sideri, Theodora C.; Willetts, Sylvia A.; Avery, Simon V.

2008-01-01

Methionine residues and iron-sulphur (FeS) clusters are primary targets of reactive oxygen species in the proteins of microorganisms. Here we show that methionine redox-modifications help to preserve essential FeS cluster activities in yeast. Mutants defective for the highly conserved methionine sulphoxide reductases (MSRs; which re-reduce oxidized methionines) are sensitive to many pro-oxidants, but here exhibited an unexpected copper resistance. This phenotype was mimicked by methionine sulphoxide supplementation. Microarray analyses highlighted several Cu and Fe homeostasis genes that were upregulated in the mxrΔ double mutant, which lacks both of the yeast MSRs. Of the upregulated genes, the Cu-binding Fe-transporter Fet3p proved to be required for the Cu-resistance phenotype. FET3 is known to be regulated by the Aft1 transcription factor, which responds to low mitochondrial FeS-cluster status. Here, constitutive Aft1p expression in the wild type reproduced the Cu-resistance phenotype, and FeS cluster functions were found to be defective in the mxrΔ mutant. Genetic perturbation of FeS activity also mimicked FET3-dependent Cu resistance. 55Fe-labeling studies showed that FeS clusters are turned over more rapidly in the mxrΔ mutant than the wild type, consistent with elevated oxidative targeting of the clusters in MSR-deficient cells. The potential underlying molecular mechanisms of this targeting are discussed. Moreover, the results indicate an important new role for cellular MSR enzymes, in helping to protect the essential function of FeS clusters in aerobic settings. PMID:19202110

Room Temperature Intrinsic Ferromagnetism in Epitaxial Manganese Selenide Films in the Monolayer Limit

NASA Astrophysics Data System (ADS)

O'Hara, Dante J.; Zhu, Tiancong; Trout, Amanda H.; Ahmed, Adam S.; Luo, Yunqiu Kelly; Lee, Choong Hee; Brenner, Mark R.; Rajan, Siddharth; Gupta, Jay A.; McComb, David W.; Kawakami, Roland K.

2018-05-01

Monolayer van der Waals (vdW) magnets provide an exciting opportunity for exploring two-dimensional (2D) magnetism for scientific and technological advances, but the intrinsic ferromagnetism has only been observed at low temperatures. Here, we report the observation of room temperature ferromagnetism in manganese selenide (MnSe$_x$) films grown by molecular beam epitaxy (MBE). Magnetic and structural characterization provides strong evidence that in the monolayer limit, the ferromagnetism originates from a vdW manganese diselenide (MnSe$_2$) monolayer, while for thicker films it could originate from a combination of vdW MnSe$_2$ and/or interfacial magnetism of $\\alpha$-MnSe(111). Magnetization measurements of monolayer MnSe$_x$ films on GaSe and SnSe$_2$ epilayers show ferromagnetic ordering with large saturation magnetization of ~ 4 Bohr magnetons per Mn, which is consistent with density functional theory calculations predicting ferromagnetism in monolayer 1T-MnSe$_2$. Growing MnSe$_x$ films on GaSe up to high thickness (~ 40 nm) produces $\\alpha$-MnSe(111), and an enhanced magnetic moment (~ 2x) compared to the monolayer MnSe$_x$ samples. Detailed structural characterization by scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), and reflection high energy electron diffraction (RHEED) reveal an abrupt and clean interface between GaSe(0001) and $\\alpha$-MnSe(111). In particular, the structure measured by STEM is consistent with the presence of a MnSe$_2$ monolayer at the interface. These results hold promise for potential applications in energy efficient information storage and processing.