The Properties and Applications of Nanodiamonds.

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

Mochalin, Vadym N.; Shenderova, Olga; Ho, Dean

Nanodiamonds have excellent mechanical and optical properties, high surface areas and tunable surface structures. They are also non-toxic, which makes them well suited to biomedical applications. Here we review the synthesis, structure, properties, surface chemistry and phase transformations of individual nanodiamonds and clusters of nanodiamonds. In particular we discuss the rational control of the mechanical, chemical, electronic and optical properties of nanodiamonds through surface doping, interior doping and the introduction of functional groups. These little gems have a wide range of potential applications in tribology, drug delivery, bioimaging and tissue engineering, and also as protein mimics and a filler materialmore » for nanocomposites.« less

The properties and applications of nanodiamonds.

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

Mochalin, Vadym; Shenderova, Olga; Ho, Dean

Nanodiamonds have excellent mechanical and optical properties, high surface areas and tunable surface structures. They are also non-toxic, which makes them well suited to biomedical applications. Here we review the synthesis, structure, properties, surface chemistry and phase transformations of individual nanodiamonds and clusters of nanodiamonds. In particular we discuss the rational control of the mechanical, chemical, electronic and optical properties of nanodiamonds through surface doping, interior doping and the introduction of functional groups. These little gems have a wide range of potential applications in tribology, drug delivery, bioimaging and tissue engineering, and also as protein mimics and a filler materialmore » for nanocomposites.« less

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-05-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01006c

Tuning Wettability and Adhesion of Structured Surfaces

NASA Astrophysics Data System (ADS)

Badge, Ila

Structured surfaces with feature size ranging from a few micrometers down to nanometers are of great interest in the applications such as design of anti-wetting surfaces, tissue engineering, microfluidics, filtration, microelectronic devices, anti-reflective coatings and reversible adhesives. A specific surface property demands particular roughness geometry along with suitable surface chemistry. Plasma Enhanced Chemical Vapor Deposition (PECVD) is a technique that offers control over surface chemistry without significantly affecting the roughness and thus, provides a flexibility to alter surface chemistry selectively for a given structured surface. In this study, we have used PECVD to fine tune wetting and adhesion properties. The research presented focuses on material design aspects as well as the fundamental understanding of wetting and adhesion phenomena of structured surfaces. In order to study the effect of surface roughness and surface chemistry on the surface wettability independently, we developed a model surface by combination of colloidal lithography and PECVD. A systematically controlled hierarchical roughness using spherical colloidal particles and surface chemistry allowed for quantitative prediction of contact angles corresponding to metastable and stable wetting states. A well-defined roughness and chemical composition of the surface enabled establishing a correlation between theory predictions and experimental measurements. We developed an extremely robust superhydrophobic surface based on Carbon-Nanotubes (CNT) mats. The surface of CNTs forming a nano-porous mesh was modified using PECVD to deposit a layer of hydrophobic coating (PCNT). The PCNT surface thus formed is superhydrophobic with almost zero contact angle hysteresis. We demonstrated that the PCNT surface is not wetted under steam condensation even after prolonged exposure and also continues to retain its superhydrophobicity after multiple frosting-defrosting cycles. The anti-wetting behavior of PCNT surface is consistent with our model predictions, derived based on thermodynamic theory of wetting. The surface of gecko feet is a very unique natural structured surface. The hierarchical surface structure of a Gecko toe pad is responsible for its reversible adhesive properties and superhydrophobicity. van der Waals interactions is known to be the key mechanism behind Gecko adhesion. However, we found that the wettability, thus the surface chemistry plays a significant role in Gecko adhesion mechanism, especially in the case of underwater adhesion. We used PECVD process to deposit a layer of coating with known chemistry on the surface of sheds of gecko toes to study the effect that wettability of the toe surface has on its adhesion. In summary, we demonstrated that PECVD can be effectively used as means of surface chemistry control for tunable structure-property relationship of three types of structured surfaces; each having unique surface features.

From tunable core-shell nanoparticles to plasmonic drawbridges: Active control of nanoparticle optical properties

PubMed Central

Byers, Chad P.; Zhang, Hui; Swearer, Dayne F.; Yorulmaz, Mustafa; Hoener, Benjamin S.; Huang, Da; Hoggard, Anneli; Chang, Wei-Shun; Mulvaney, Paul; Ringe, Emilie; Halas, Naomi J.; Nordlander, Peter; Link, Stephan; Landes, Christy F.

2015-01-01

The optical properties of metallic nanoparticles are highly sensitive to interparticle distance, giving rise to dramatic but frequently irreversible color changes. By electrochemical modification of individual nanoparticles and nanoparticle pairs, we induced equally dramatic, yet reversible, changes in their optical properties. We achieved plasmon tuning by oxidation-reduction chemistry of Ag-AgCl shells on the surfaces of both individual and strongly coupled Au nanoparticle pairs, resulting in extreme but reversible changes in scattering line shape. We demonstrated reversible formation of the charge transfer plasmon mode by switching between capacitive and conductive electronic coupling mechanisms. Dynamic single-particle spectroelectrochemistry also gave an insight into the reaction kinetics and evolution of the charge transfer plasmon mode in an electrochemically tunable structure. Our study represents a highly useful approach to the precise tuning of the morphology of narrow interparticle gaps and will be of value for controlling and activating a range of properties such as extreme plasmon modulation, nanoscopic plasmon switching, and subnanometer tunable gap applications. PMID:26665175

Functionalization of alkyne-terminated thermally hydrocarbonized porous silicon nanoparticles with targeting peptides and antifouling polymers: effect on the human plasma protein adsorption.

PubMed

Wang, Chang-Fang; Mäkilä, Ermei M; Bonduelle, Colin; Rytkönen, Jussi; Raula, Janne; Almeida, Sérgio; Närvänen, Ale; Salonen, Jarno J; Lecommandoux, Sebastien; Hirvonen, Jouni T; Santos, Hélder A

2015-01-28

Porous silicon (PSi) nanomaterials combine a high drug loading capacity and tunable surface chemistry with various surface modifications to meet the requirements for biomedical applications. In this work, alkyne-terminated thermally hydrocarbonized porous silicon (THCPSi) nanoparticles were fabricated and postmodified using five bioactive molecules (targeting peptides and antifouling polymers) via a single-step click chemistry to modulate the bioactivity of the THCPSi nanoparticles, such as enhancing the cellular uptake and reducing the plasma protein association. The size of the nanoparticles after modification was increased from 176 to 180-220 nm. Dextran 40 kDa modified THCPSi nanoparticles showed the highest stability in aqueous buffer. Both peptide- and polymer-functionalized THCPSi nanoparticles showed an extensive cellular uptake which was dependent on the functionalized moieties presented on the surface of the nanoparticles. The plasma protein adsorption study showed that the surface modification with different peptides or polymers induced different protein association profiles. Dextran 40 kDa functionalized THCPSi nanoparticles presented the least protein association. Overall, these results demonstrate that the "click" conjugation of the biomolecules onto the alkyne-terminated THCPSi nanoparticles is a versatile and simple approach to modulate the surface chemistry, which has high potential for biomedical applications.

Surface functionalization of thin-film diamond for highly stable and selective biological interfaces

PubMed Central

Stavis, Courtney; Clare, Tami Lasseter; Butler, James E.; Radadia, Adarsh D.; Carr, Rogan; Zeng, Hongjun; King, William P.; Carlisle, John A.; Aksimentiev, Aleksei; Bashir, Rashid; Hamers, Robert J.

2011-01-01

Carbon is an extremely versatile family of materials with a wide range of mechanical, optical, and mechanical properties, but many similarities in surface chemistry. As one of the most chemically stable materials known, carbon provides an outstanding platform for the development of highly tunable molecular and biomolecular interfaces. Photochemical grafting of alkenes has emerged as an attractive method for functionalizing surfaces of diamond, but many aspects of the surface chemistry and impact on biological recognition processes remain unexplored. Here we report investigations of the interaction of functionalized diamond surfaces with proteins and biological cells using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and fluorescence methods. XPS data show that functionalization of diamond with short ethylene glycol oligomers reduces the nonspecific binding of fibrinogen below the detection limit of XPS, estimated as > 97% reduction over H-terminated diamond. Measurements of different forms of diamond with different roughness are used to explore the influence of roughness on nonspecific binding onto H-terminated and ethylene glycol (EG)-terminated surfaces. Finally, we use XPS to characterize the chemical stability of Escherichia coli K12 antibodies on the surfaces of diamond and amine-functionalized glass. Our results show that antibody-modified diamond surfaces exhibit increased stability in XPS and that this is accompanied by retention of biological activity in cell-capture measurements. Our results demonstrate that surface chemistry on diamond and other carbon-based materials provides an excellent platform for biomolecular interfaces with high stability and high selectivity. PMID:20884854

Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

PubMed

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

Bio-inspired reversible underwater adhesive.

PubMed

Zhao, Yanhua; Wu, Yang; Wang, Liang; Zhang, Manman; Chen, Xuan; Liu, Minjie; Fan, Jun; Liu, Junqiu; Zhou, Feng; Wang, Zuankai

2017-12-20

The design of smart surfaces with switchable adhesive properties in a wet environment has remained a challenge in adhesion science and materials engineering. Despite intense demands in various industrial applications and exciting progress in mimicking the remarkable wet adhesion through the delicate control of catechol chemistry, polyelectrolyte complex, and supramolecular architectures, the full recapitulation of nature's dynamic function is limited. Here, we show a facile approach to synthesize bioinspired adhesive, which entails the reversible, tunable, and fast regulation of the wet adhesion on diverse surfaces. The smart wet adhesive takes advantage of the host-guest molecular interaction and the adhesive nature of catechol chemistry, as well as the responsive polymer, allowing for screening and activation of the interfacial interaction simply by a local temperature trigger in an on-demand manner. Our work opens up an avenue for the rational design of bioinspired adhesives with performances even beyond nature.

Particle self-assembly at ionic liquid-based interfaces.

PubMed

Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

2014-04-01

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. © 2013.

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

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

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia

2017-07-24

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. We resolved the atomic structure of Ni-oxo species deposited in the MOF NU-1000 through atomic layer deposition using local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imaging and computational modeling.

Approach to Rapid Synthesis and Functionalization of Iron Oxide Nanoparticles for High Gene Transfection.

PubMed

Stephen, Zachary R; Dayringer, Christopher J; Lim, Josh J; Revia, Richard A; Halbert, Mackenzie V; Jeon, Mike; Bakthavatsalam, Arvind; Ellenbogen, Richard G; Zhang, Miqin

2016-03-01

Surface functionalization of theranostic nanoparticles (NPs) typically relies on lengthy, aqueous postsynthesis labeling chemistries that have limited ability to fine-tune surface properties and can lead to NP heterogeneity. The need for a rapid, simple synthesis approach that can provide great control over the display of functional moieties on NP surfaces has led to increased use of highly selective bioorthoganol chemistries including metal-affinity coordination. Here we report a simple approach for rapid production of a superparamagnetic iron oxide NPs (SPIONs) with tunable functionality and high reproducibility under aqueous conditions. We utilize the high affinity complex formed between catechol and Fe((III)) as a means to dock well-defined catechol modified polymer modules on the surface of SPIONs during sonochemical coprecipitation synthesis. Polymer modules consisted of chitosan and poly(ethylene glycol) (PEG) copolymer (CP) modified with catechol (CCP), and CCP functionalized with cationic polyethylenimine (CCP-PEI) to facilitate binding and delivery of DNA for gene therapy. This rapid synthesis/functionalization approach provided excellent control over the extent of PEI labeling, improved SPION magnetic resonance imaging (MRI) contrast enhancement and produced an efficient transfection agent.

Surface Chemistry and Nano-/Microstructure Engineering on Photocatalytic In2S3 Nanocrystals.

PubMed

Berestok, Taisiia; Guardia, Pablo; Portals, Javier Blanco; Estradé, Sònia; Llorca, Jordi; Peiró, Francesca; Cabot, Andreu; Brock, Stephanie L

2018-06-05

Colloidal nanocrystals (NCs) compete with molecular catalysts in the field of homogenous catalysis, offering easier recyclability and a number of potentially advantageous functionalities, such as tunable band gaps, plasmonic properties, or a magnetic moment. Using high-throughput printing technologies, colloidal NCs can also be supported onto substrates to produce cost-effective electronic, optoelectronic, electrocatalytic, and sensing devices. For both catalytic and technological application, NC surface chemistry and supracrystal organization are key parameters determining final performance. Here, we study the influence of the surface ligands and the NC organization on the catalytic properties of In 2 S 3 , both as a colloid and as a supported layer. As a colloid, NCs stabilized by inorganic ligands show the highest photocatalytic activities, which we associate with their large and more accessible surfaces. On the other hand, when NCs are supported on a substrate, their organization becomes an essential parameter determining performance. For instance, NC-based films produced through a gelation process provided five-fold higher photocurrent densities than those obtained from dense films produced by the direct printing of NCs.

Sol-Gel Chemistry for Carbon Dots.

PubMed

Malfatti, Luca; Innocenzi, Plinio

2018-03-14

Carbon dots are an emerging class of carbon-based nanostructures produced by low-cost raw materials which exhibit a widely-tunable photoluminescence and a high quantum yield. The potential of these nanomaterials as a substitute of semiconductor quantum dots in optoelectronics and biomedicine is very high, however they need a customized chemistry to be integrated in host-guest systems or functionalized in core-shell structures. This review is focused on recent advances of the sol-gel chemistry applied to the C-dots technology. The surface modification, the fine tailoring of the chemical composition and the embedding into a complex nanostructured material are the main targets of combining sol-gel processing with C-dots chemistry. In addition, the synergistic effect of the sol-gel precursor combined with the C-dots contribute to modify the intrinsic chemo-physical properties of the dots, empowering the emission efficiency or enabling the tuning of the photoluminescence over a wide range of the visible spectrum. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Role of Water in Mediating Interfacial Adhesion and Shear Strength in Graphene Oxide.

PubMed

Soler-Crespo, Rafael A; Gao, Wei; Mao, Lily; Nguyen, Hoang T; Roenbeck, Michael R; Paci, Jeffrey T; Huang, Jiaxing; Nguyen, SonBinh T; Espinosa, Horacio D

2018-06-12

Graphene oxide (GO), whose highly tunable surface chemistry enables the formation of strong interfacial hydrogen-bond networks, has garnered increasing interest in the design of devices that operate in the presence of water. For instance, previous studies have suggested that controlling GO's surface chemistry leads to enhancements in interfacial shear strength, allowing engineers to manage deformation pathways and control failure mechanisms. However, these previous reports have not explored the role of ambient humidity and only offer extensive chemical modifications to GO's surface as the main pathway to control GO's interfacial properties. Herein, through atomic force microscopy experiments on GO-GO interfaces, the adhesion energy and interfacial shear strength of GO were measured as a function of ambient humidity. Experimental evidence shows that adhesion energy and interfacial shear strength can be improved by a factor of 2-3 when GO is exposed to moderate (∼30% water weight) water content. Furthermore, complementary molecular dynamics simulations uncovered the mechanisms by which these nanomaterial interfaces achieve their properties. They reveal that the strengthening mechanism arises from the formation of strongly interacting hydrogen-bond networks, driven by the chemistry of the GO basal plane and intercalated water molecules between two GO surfaces. In summary, the methodology and findings here reported provide pathways to simultaneously optimize GO's interfacial and in-plane mechanical properties, by tailoring the chemistry of GO and accounting for water content, in engineering applications such as sensors, filtration membranes, wearable electronics, and structural materials.

Photothermal Superheating of Water with Ion-Implanted Silicon Nanowires

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

Roder, Paden B.; Manandhar, Sandeep; Smith, Bennett E.

2015-07-21

Nanoparticle-mediated photothermal (PT) cancer therapy has been a major focus in nanomedicine due to its potential as an effective, non-invasive, and targeted alternative to traditional cancer therapy based on small-molecule pharmaceuticals[1,2]. Gold nanocrystals have been a primary focus of PT research[3], which can be attributed to their size tunability[4], well understood conjugation chemistry[5], and efficient absorption of NIR radiation in the tissue transparency window (800 nm – 1 μm) due to their size-dependent localized surface plasmon resonances[6].

Water at surfaces with tunable surface chemistries

NASA Astrophysics Data System (ADS)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Tuning cell adhesive properties via layer-by-layer assembly of chitosan and alginate

PubMed Central

Silva, Joana M.; García, José R.; Reis, Rui L.; García, Andrés J.; Mano, João F.

2017-01-01

Understanding the mechanisms controlling cell-multilayer film interactions is crucial to the successful engineering of these coatings for biotechnological and biomedical applications. Herein, we present a strategy to tune the cell adhesive properties of multilayers based on marine polysaccharides with and without cross-linking and/or coating with extracellular matrix proteins. Chemical cross-linking of multilayers improved mechanical properties of the coatings but also elicited changes in surface chemistry that alter the adhesion of human umbilical vein endothelial cells. We evaluated a strategy to decouple the mechanical and chemical properties of these films, enabling the transition from cell-adhesive to cell-resistant multilayers. Addition of chitosan/alginate multilayers on top of cross-linked films decreased endothelial cell adhesion, spreading, and proliferation to similar levels as uncross-linked films. Our findings highlight the key role of surface chemistry in cell-multilayer film interactions, and these engineered nanocoatings represent a tunable model of cell adhesive and non-adhesive multilayered films. PMID:28126597

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy.

PubMed

DeVetter, Brent M; Mukherjee, Prabuddha; Murphy, Catherine J; Bhargava, Rohit

2015-05-21

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min(-1). This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

PubMed Central

DeVetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-01-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min 1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. PMID:25905515

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

NASA Technical Reports Server (NTRS)

Worsnop, Douglas R.; Nelson, David D.; Zahniser, Mark S.

1993-01-01

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

A tunable electronic beam splitter realized with crossed graphene nanoribbons

NASA Astrophysics Data System (ADS)

Brandimarte, Pedro; Engelund, Mads; Papior, Nick; Garcia-Lekue, Aran; Frederiksen, Thomas; Sánchez-Portal, Daniel

2017-03-01

Graphene nanoribbons (GNRs) are promising components in future nanoelectronics due to the large mobility of graphene electrons and their tunable electronic band gap in combination with recent experimental developments of on-surface chemistry strategies for their growth. Here, we explore a prototype 4-terminal semiconducting device formed by two crossed armchair GNRs (AGNRs) using state-of-the-art first-principles transport methods. We analyze in detail the roles of intersection angle, stacking order, inter-GNR separation, GNR width, and finite voltages on the transport characteristics. Interestingly, when the AGNRs intersect at θ =60° , electrons injected from one terminal can be split into two outgoing waves with a tunable ratio around 50% and with almost negligible back-reflection. The split electron wave is found to propagate partly straight across the intersection region in one ribbon and partly in one direction of the other ribbon, i.e., in analogy with an optical beam splitter. Our simulations further identify realistic conditions for which this semiconducting device can act as a mechanically controllable electronic beam splitter with possible applications in carbon-based quantum electronic circuits and electron optics. We rationalize our findings with a simple model suggesting that electronic beam splitters can generally be realized with crossed GNRs.

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

DOE PAGES

Walter, Andrew L.; Schiller, Frederik; Corso, Martina; ...

2015-11-12

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

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

Walter, Andrew L.; Schiller, Frederik; Corso, Martina

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

Pollenkitt wetting mechanism enables species-specific tunable pollen adhesion.

PubMed

Lin, Haisheng; Gomez, Ismael; Meredith, J Carson

2013-03-05

Plant pollens are microscopic particles exhibiting a remarkable breadth of complex solid surface features. In addition, many pollen grains are coated with a viscous liquid, "pollenkitt", thought to play important roles in pollen dispersion and adhesion. However, there exist no quantitative studies of the effects of solid surface features or pollenkitt on adhesion of pollen grains, and it remains unclear what role these features play in pollen adhesion and transport. We report AFM adhesion measurements of five pollen species with a series of test surfaces in which each pollen has a unique solid surface morphology and pollenkitt volume. The results indicate that the combination of surface morphology (size and shape of echinate or reticulate features) with the pollenkitt volume provides pollens with a remarkably tunable adhesion to surfaces. With pollenkitt removed, pollen grains had relatively low adhesion strengths that were independent of surface chemistry and scalable with the tip radius of the pollen's ornamentation features, according to the Hamaker model. With the pollenkitt intact, adhesion was up to 3-6 times higher than the dry grains and exhibited strong substrate dependence. The adhesion enhancing effect of pollenkitt was driven by the formation of pollenkitt capillary bridges and was surprisingly species-dependent, with echinate insect-pollinated species (dandelion and sunflower) showing significantly stronger adhesion and higher substrate dependence than wind-pollinated species (ragweed, poplar, and olive). The combination of high pollenkitt volume and large convex, spiny surface features in echinate entomophilous varieties appears to enhance the spreading area of the liquid pollenkitt relative to varieties of pollen with less pollenkitt volume and less pronounced surface features. Measurements of pollenkitt surface energy indicate that the adhesive strength of capillary bridges is primarily dependent on nonpolar van der Waals interactions, with some contribution from the Lewis basic component of surface energy.

Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit

PubMed Central

2011-01-01

Self-assembled monolayer (SAM) with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry. PMID:21812994

Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

PubMed

Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

2016-01-01

Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

Understanding improved osteoblast behavior on select nanoporous anodic alumina

PubMed Central

Ni, Siyu; Li, Changyan; Ni, Shirong; Chen, Ting; Webster, Thomas J

2014-01-01

The aim of this study was to prepare different sized porous anodic alumina (PAA) and examine preosteoblast (MC3T3-E1) attachment and proliferation on such nanoporous surfaces. In this study, PAA with tunable pore sizes (25 nm, 50 nm, and 75 nm) were fabricated by a two-step anodizing procedure in oxalic acid. The surface morphology and elemental composition of PAA were characterized by field emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis. The nanopore arrays on all of the PAA samples were highly regular. X-ray photoelectron spectroscopy analysis suggested that the chemistry of PAA and flat aluminum surfaces were similar. However, contact angles were significantly greater on all of the PAA compared to flat aluminum substrates, which consequently altered protein adsorption profiles. The attachment and proliferation of preosteoblasts were determined for up to 7 days in culture using field emission scanning electron microscopy and a Cell Counting Kit-8. Results showed that nanoporous surfaces did not enhance initial preosteoblast attachment, whereas preosteoblast proliferation dramatically increased when the PAA pore size was either 50 nm or 75 nm compared to all other samples (P<0.05). Thus, this study showed that one can alter surface energy of aluminum by modifying surface nano-roughness alone (and not changing chemistry) through an anodization process to improve osteoblast density, and, thus, should be further studied as a bioactive interface for orthopedic applications. PMID:25045263

Tunable particles alter macrophage uptake based on combinatorial effects of physical properties

PubMed Central

Garapaty, Anusha

2017-01-01

Abstract The ability to tune phagocytosis of particle‐based therapeutics by macrophages can enhance their delivery to macrophages or reduce their phagocytic susceptibility for delivery to non‐phagocytic cells. Since phagocytosis is affected by the physical and chemical properties of particles, it is crucial to identify any interplay between physical properties of particles in altering phagocytic interactions. The combinatorial effect of physical properties size, shape and stiffness was investigated on Fc receptor mediated macrophage interactions by fabrication of layer‐by‐layer tunable particles of constant surface chemistry. Our results highlight how changing particle stiffness affects phagocytic interaction intricately when combined with varying size or shape. Increase in size plays a dominant role over reduction in stiffness in reducing internalization by macrophages for spherical particles. Internalization of rod‐shaped, but not spherical particles, was highly dependent on stiffness. These particles demonstrate the interplay between size, shape and stiffness in interactions of Fc‐functionalized particles with macrophages during phagocytosis. PMID:29313025

Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.

PubMed

Greenwood, John; Phan, Thanh Hai; Fujita, Yasuhiko; Li, Zhi; Ivasenko, Oleksandr; Vanderlinden, Willem; Van Gorp, Hans; Frederickx, Wout; Lu, Gang; Tahara, Kazukuni; Tobe, Yoshito; Uji-I, Hiroshi; Mertens, Stijn F L; De Feyter, Steven

2015-05-26

We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.

Hierarchical micron-sized mesoporous/macroporous graphene with well-tuned surface oxygen chemistry for high capacity and cycling stability Li-O2 battery.

PubMed

Zhou, Wei; Zhang, Hongzhang; Nie, Hongjiao; Ma, Yiwen; Zhang, Yining; Zhang, Huamin

2015-02-11

Nonaqueous Li-O2 battery is recognized as one of the most promising energy storage devices for electric vehicles due to its super-high energy density. At present, carbon or catalyst-supporting carbon materials are widely used for cathode materials of Li-O2 battery. However, the unique electrode reaction and complex side reactions lead to numerous hurdles that have to be overcome. The pore blocking caused by the solid products and the byproducts generated from the side reactions severely limit the capacity performance and cycling stability. Thus, there is a great need to develop carbon materials with optimized pore structure and tunable surface chemistry to meet the special requirement of Li-O2 battery. Here, we propose a strategy of vacuum-promoted thermal expansion to fabricate one micron-sized graphene matrix with a hierarchical meso-/macroporous structure, combining with a following deoxygenation treatment to adjust the surface chemistry by reducing the amount of oxygen and selectively removing partial unstable groups. The as-made graphene demonstrates dramatically tailored pore characteristics and a well-tuned surface chemical environment. When applied in Li-O2 battery as cathode, it exhibits an outstanding capacity up to 19 800 mA h g(-1) and is capable of enduring over 50 cycles with a curtaining capacity of 1000 mA h g(-1) at a current density of 1000 mA g(-1). This will provide a novel pathway for the design of cathodes for Li-O2 battery.

Carbon Dots as Versatile Photosensitizers for Solar-Driven Catalysis with Redox Enzymes.

PubMed

Hutton, Georgina A M; Reuillard, Bertrand; Martindale, Benjamin C M; Caputo, Christine A; Lockwood, Colin W J; Butt, Julea N; Reisner, Erwin

2016-12-28

Light-driven enzymatic catalysis is enabled by the productive coupling of a protein to a photosensitizer. Photosensitizers used in such hybrid systems are typically costly, toxic, and/or fragile, with limited chemical versatility. Carbon dots (CDs) are low-cost, nanosized light-harvesters that are attractive photosensitizers for biological systems as they are water-soluble, photostable, nontoxic, and their surface chemistry can be easily modified. We demonstrate here that CDs act as excellent light-absorbers in two semibiological photosynthetic systems utilizing either a fumarate reductase (FccA) for the solar-driven hydrogenation of fumarate to succinate or a hydrogenase (H 2 ase) for reduction of protons to H 2 . The tunable surface chemistry of the CDs was exploited to synthesize positively charged ammonium-terminated CDs (CD-NHMe 2 + ), which were capable of transferring photoexcited electrons directly to the negatively charged enzymes with high efficiency and stability. Enzyme-based turnover numbers of 6000 mol succinate (mol FccA) -1 and 43,000 mol H 2 (mol H 2 ase) -1 were reached after 24 h. Negatively charged carboxylate-terminated CDs (CD-CO 2 - ) displayed little or no activity, and the electrostatic interactions at the CD-enzyme interface were determined to be essential to the high photocatalytic activity observed with CD-NHMe 2 + . The modular surface chemistry of CDs together with their photostability and aqueous solubility make CDs versatile photosensitizers for redox enzymes with great scope for their utilization in photobiocatalysis.

Inorganic Nanoparticle Induced Morphological Transition for Confined Self-Assembly of Block Copolymers within Emulsion Droplets.

PubMed

Zhang, Yan; He, Yun; Yan, Nan; Zhu, Yutian; Hu, Yuexin

2017-09-07

Recently, it has been reported that the incorporation of functional inorganic nanoparticles (NPs) into the three-dimensional (3D) confined self-assembly of block copolymers (BCPs) creates the unique nanostructured hybrid composites, which can not only introduce new functions to BCPs but also induce some interesting morphological transitions of BCPs. In the current study, we systematically investigate the cooperative self-assembly of a series of size-controlled and surface chemistry-tunable gold nanoparticles (AuNPs) and polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer within the emulsion droplets. The influences of the size, content, and surface chemistry of the AuNPs on the coassembled nanostructures as well as the spatial distribution of AuNPs in the hybrid particles are examined. It is found that the size and content of the AuNPs are related to the entropic interaction, while the surface chemistry of AuNPs is related to the enthalpic interaction, which can be utilized to tailor the self-assembled morphologies of block copolymer confined in the emulsion droplets. As the content of PS-coated AuNPs increases, the morphology of the resulting AuNPs/PS-b-P2VP hybrid particles changes from the pupa-like particles to the bud-like particles and then to the onion-like particles. However, a unique morphological transition from the pupa-like particles to the mushroom-like particles is observed as the content of P4VP-coated AuNPs increases. More interestingly, it is observed that the large AuNPs are expelled to the surface of the BCP particles to reduce the loss in the conformational entropy of the block segment, which can arrange into the strings of necklaces on the surfaces of the hybrid particles.

Tunable vertical cavity surface emitting lasers for use in the near infrared biological window

NASA Astrophysics Data System (ADS)

Kitsmiller, Vincent J.; Dummer, Matthew; Johnson, Klein; O'Sullivan, Thomas D.

2018-02-01

We present a near-infrared tunable vertical cavity surface emitting laser (VCSEL) based upon a unique electrothermally tunable microelectromechanical systems (MEMS) topside mirror designed for tissue imaging and sensing. At room temperature, the laser is tunable from 769-782nm with single mode CW output and a peak output power of 1.3mW. We show that the tunable VCSEL is suitable for use in frequency domain diffuse optical spectroscopy by measuring the optical properties of a tissue-simulating phantom over the tunable range. These results indicate that tunable VCSELs may be an attractive choice to enable high spectral resolution optical sensing in a wearable format.

Molecularly precise dendrimer-drug conjugates with tunable drug release for cancer therapy.

PubMed

Zhou, Zhuxian; Ma, Xinpeng; Murphy, Caitlin J; Jin, Erlei; Sun, Qihang; Shen, Youqing; Van Kirk, Edward A; Murdoch, William J

2014-10-06

The structural preciseness of dendrimers makes them perfect drug delivery carriers, particularly in the form of dendrimer-drug conjugates. Current dendrimer-drug conjugates are synthesized by anchoring drug and functional moieties onto the dendrimer peripheral surface. However, functional groups exhibiting the same reactivity make it impossible to precisely control the number and the position of the functional groups and drug molecules anchored to the dendrimer surface. This structural heterogeneity causes variable pharmacokinetics, preventing such conjugates to be translational. Furthermore, the highly hydrophobic drug molecules anchored on the dendrimer periphery can interact with blood components and alter the pharmacokinetic behavior. To address these problems, we herein report molecularly precise dendrimer-drug conjugates with drug moieties buried inside the dendrimers. Surprisingly, the drug release rates of these conjugates were tailorable by the dendrimer generation, surface chemistry, and acidity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable lasers and their application in analytical chemistry

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.

1975-01-01

The impact that laser techniques might have in chemical analysis is examined. Absorption, scattering, and heterodyne detection is considered. Particular emphasis is placed on the advantages of using frequency-tunable sources, and dye solution lasers are regarded as the outstanding example of this type of laser. Types of spectroscopy that can be carried out with lasers are discussed along with the ultimate sensitivity or minimum detectable concentration of molecules that can be achieved with each method. Analytical applications include laser microprobe analysis, remote sensing and instrumental methods such as laser-Raman spectroscopy, atomic absorption/fluorescence spectrometry, fluorescence assay techniques, optoacoustic spectroscopy, and polarization measurements. The application of lasers to spectroscopic methods of analysis would seem to be a rewarding field both for research in analytical chemistry and for investments in instrument manufacturing.

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

Bio-Orthogonally Crosslinked, Engineered Protein Hydrogels with Tunable Mechanics and Biochemistry for Cell Encapsulation.

PubMed

Madl, Christopher M; Katz, Lily M; Heilshorn, Sarah C

2016-06-07

Covalently-crosslinked hydrogels are commonly used as 3D matrices for cell culture and transplantation. However, the crosslinking chemistries used to prepare these gels generally cross-react with functional groups present on the cell surface, potentially leading to cytotoxicity and other undesired effects. Bio-orthogonal chemistries have been developed that do not react with biologically relevant functional groups, thereby preventing these undesirable side reactions. However, previously developed biomaterials using these chemistries still possess less than ideal properties for cell encapsulation, such as slow gelation kinetics and limited tuning of matrix mechanics and biochemistry. Here, engineered elastin-like proteins (ELPs) are developed that cross-link via strain-promoted azide-alkyne cycloaddition (SPAAC) or Staudinger ligation. The SPAAC-crosslinked materials form gels within seconds and complete gelation within minutes. These hydrogels support the encapsulation and phenotypic maintenance of human mesenchymal stem cells, human umbilical vein endothelial cells, and murine neural progenitor cells. SPAAC-ELP gels exhibit independent tuning of stiffness and cell adhesion, with significantly improved cell viability and spreading observed in materials containing a fibronectin-derived arginine-glycine-aspartic acid (RGD) domain. The crosslinking chemistry used permits further material functionalization, even in the presence of cells and serum. These hydrogels are anticipated to be useful in a wide range of applications, including therapeutic cell delivery and bioprinting.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

NASA Astrophysics Data System (ADS)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

Gold nanoparticles enlighten the future of cancer theranostics

PubMed Central

Guo, Jianfeng; Rahme, Kamil; He, Yan; Li, Lin-Lin; Holmes, Justin D; O’Driscoll, Caitriona M

2017-01-01

Development of multifunctional nanomaterials, one of the most interesting and advanced research areas in the field of nanotechnology, is anticipated to revolutionize cancer diagnosis and treatment. Gold nanoparticles (AuNPs) are now being widely utilized in bio-imaging and phototherapy due to their tunable and highly sensitive optical and electronic properties (the surface plasmon resonance). As a new concept, termed “theranostics,” multifunctional AuNPs may contain diagnostic and therapeutic functions that can be integrated into one system, thereby simultaneously facilitating diagnosis and therapy and monitoring therapeutic responses. In this review, the important properties of AuNPs relevant to diagnostic and phototherapeutic applications such as structure, shape, optics, and surface chemistry are described. Barriers for translational development of theranostic AuNPs and recent advances in the application of AuNPs for cancer diagnosis, photothermal, and photodynamic therapy are discussed. PMID:28883725

Compact Biocompatible Quantum Dots Functionalized for Cellular Imaging

PubMed Central

Liu, Wenhao; Howarth, Mark; Greytak, Andrew B.; Zheng, Yi; Nocera, Daniel G.; Ting, Alice Y.; Bawendi, Moungi G.

2009-01-01

We present a family of water-soluble quantum dots (QDs) that exhibit low nonspecific binding to cells, small hydrodynamic diameter, tunable surface charge, high quantum yield, and good solution stability across a wide pH range. These QDs are amenable to covalent modification via simple carbodiimide coupling chemistry, which is achieved by functionalizing the surface of QDs with a new class of heterobifunctional ligands incorporating dihydrolipoic acid, a short poly(ethylene glycol) (PEG) spacer, and an amine or carboxylate terminus. The covalent attachment of molecules is demonstrated by appending a rhodamine dye to form a QD-dye conjugate exhibiting fluorescence resonance energy transfer (FRET). High-affinity labeling is demonstrated by covalent attachment of streptavidin, thus enabling the tracking of biotinylated epidermal growth factor (EGF) bound to EGF receptor on live cells. In addition, QDs solubilized with the heterobifunctional ligands retain their metal-affinity driven conjugation chemistry with polyhistidine-tagged proteins. This dual functionality is demonstrated by simultaneous covalent attachment of a rhodamine FRET acceptor and binding of polyhistidine-tagged streptavidin on the same nanocrystal to create a targeted QD, which exhibits dual-wavelength emission. Such emission properties could serve as the basis for ratiometric sensing of the cellular receptor’s local chemical environment. PMID:18177042

Recent advancements in ion concentration polarization.

PubMed

Li, Min; Anand, Robbyn K

2016-06-21

In this minireview, we discuss advancements in ion concentration polarization (ICP)-based preconcentration, separation, desalination, and dielectrophoresis that have been made over the past three years. ICP as a means of controlling the distribution of the ions and electric field in a microfluidic device has rapidly expanded its areas of application. Recent advancements have focused on the development of ion-permselective materials with tunable dimensions and surface chemistry, adaptation to paper microfluidics, higher-throughput device geometries, and coupling ICP with other separation (isotachophoresis and dielectrophoresis) and fluidic (valve and droplet microfluidic) strategies. These studies have made great strides toward solving real-world problems such as low-cost and rapid analysis, accessible desalination technology, and single-cell research tools.

Power Play, Laser Style

NASA Technical Reports Server (NTRS)

1998-01-01

Under a NASA SBIR (Small Business Innovation Research) SDL, Inc., has developed the TC40 Single-Frequency Continuously Tunable 500 mw Laser Diode System. This is the first commercially available single frequency diode laser system that offers the broad tunability and the high powers needed for atomic cooling and trapping as well as a variety of atomic spectroscopy techniques. By greatly decreasing both the equipment and the costs of entry, the TC40 enables researchers to pursue some of the most interesting areas of physical chemistry, biochemistry, and atomic physics.

Tunable Bifunctional Activity of Mnx Co3-x O4 Nanocrystals Decorated on Carbon Nanotubes for Oxygen Electrocatalysis.

PubMed

Zhao, Tingting; Gadipelli, Srinivas; He, Guanjie; Ward, Matthew J; Do, David; Zhang, Peng; Guo, Zhengxiao

2018-04-25

Noble-metal-free electrocatalysts are attractive for cathodic oxygen catalysis in alkaline membrane fuel cells, metal-air batteries, and electrolyzers. However, much of the structure-activity relationship is poorly understood. Herein, the comprehensive development of manganese cobalt oxide/nitrogen-doped multiwalled carbon nanotube hybrids (Mn x Co 3-x O 4 @NCNTs) is reported for highly reversible oxygen reduction and evolution reactions (ORR and OER, respectively). The hybrid structures are rationally designed by fine control of surface chemistry and synthesis conditions, including tuning of functional groups at surfaces, congruent growth of nanocrystals with controllable phases and particle sizes, and ensuring strong coupling across catalyst-support interfaces. Electrochemical tests reveal distinctly different oxygen catalytic activities among the hybrids, Mn x Co 3-x O 4 @NCNTs. Nanocrystalline MnCo 2 O 4 @NCNTs (MCO@NCNTs) hybrids show superior ORR activity, with a favorable potential to reach 3 mA cm -2 and a high current density response, equivalent to that of the commercial Pt/C standard. Moreover, the hybrid structure exhibits tunable and durable catalytic activities for both ORR and OER, with a lowest overall potential of 0.93 V. It is clear that the long-term electrochemical activities can be ensured by rational design of hybrid structures from the nanoscale. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Towards an in vitro model mimicking the foreign body response: tailoring the surface properties of biomaterials to modulate extracellular matrix.

PubMed

Damanik, Febriyani F R; Rothuizen, Tonia C; van Blitterswijk, Clemens; Rotmans, Joris I; Moroni, Lorenzo

2014-09-19

Despite various studies to minimize host reaction following a biomaterial implantation, an appealing strategy in regenerative medicine is to actively use such an immune response to trigger and control tissue regeneration. We have developed an in vitro model to modulate the host response by tuning biomaterials' surface properties through surface modifications techniques as a new strategy for tissue regeneration applications. Results showed tunable surface topography, roughness, wettability, and chemistry by varying treatment type and exposure, allowing for the first time to correlate the effect of these surface properties on cell attachment, morphology, strength and proliferation, as well as proinflammatory (IL-1β, IL-6) and antiinflammatory cytokines (TGF-β1, IL-10) secreted in medium, and protein expression of collagen and elastin. Surface microstructuring, derived from chloroform partial etching, increased surface roughness and oxygen content. This resulted in enhanced cell adhesion, strength and proliferation as well as a balance of soluble factors for optimum collagen and elastin synthesis for tissue regeneration. By linking surface parameters to cell activity, we could determine the fate of the regenerated tissue to create successful soft tissue-engineered replacement.

Towards an in vitro model mimicking the foreign body response: tailoring the surface properties of biomaterials to modulate extracellular matrix

NASA Astrophysics Data System (ADS)

Damanik, Febriyani F. R.; Rothuizen, Tonia C.; van Blitterswijk, Clemens; Rotmans, Joris I.; Moroni, Lorenzo

2014-09-01

Despite various studies to minimize host reaction following a biomaterial implantation, an appealing strategy in regenerative medicine is to actively use such an immune response to trigger and control tissue regeneration. We have developed an in vitro model to modulate the host response by tuning biomaterials' surface properties through surface modifications techniques as a new strategy for tissue regeneration applications. Results showed tunable surface topography, roughness, wettability, and chemistry by varying treatment type and exposure, allowing for the first time to correlate the effect of these surface properties on cell attachment, morphology, strength and proliferation, as well as proinflammatory (IL-1β, IL-6) and antiflammatory cytokines (TGF-β1, IL-10) secreted in medium, and protein expression of collagen and elastin. Surface microstructuring, derived from chloroform partial etching, increased surface roughness and oxygen content. This resulted in enhanced cell adhesion, strength and proliferation as well as a balance of soluble factors for optimum collagen and elastin synthesis for tissue regeneration. By linking surface parameters to cell activity, we could determine the fate of the regenerated tissue to create successful soft tissue-engineered replacement.

Lithium storage in structurally tunable carbon anode derived from sustainable source

DOE PAGES

Lim, Daw Gen; Kim, Kyungho; Razdan, Mayuri; ...

2017-09-01

Here, a meticulous solid state chemistry approach has been developed for the synthesis of carbon anode from a sustainable source. The reaction mechanism of carbon formation during pyrolysis of sustainable feed-stock was studied in situ by employing Raman microspectroscopy. No Raman spectral changes observed below 160°C (thermally stable precursor) followed by color change, however above 280°C characteristic D and G bands of graphitic carbon are recorded. Derived carbon particles exhibited high specific surface area with low structural ordering (active carbons) to low specific surface area with high graphitic ordering as a function of increasing reaction temperature. Carbons synthesized at 600°Cmore » demonstrated enhanced reversible lithiation capacity (390 mAh g -1), high charge-discharge rate capability, and stable cycle life. On the contrary, carbons synthesized at higher temperatures (>1200°C) produced more graphite-like structure yielding longer specific capacity retention with lower reversible capacity.« less

Chemical modulation of M13 bacteriophage and its functional opportunities for nanomedicine

PubMed Central

Chung, Woo-Jae; Lee, Doe-Young; Yoo, So Young

2014-01-01

M13 bacteriophage (phage) has emerged as an attractive bionanomaterial owing to its genetically tunable surface chemistry and its potential to self-assemble into hierarchical structures. Furthermore, because of its unique nanoscopic structure, phage has been proposed as a model system in soft condensed physics and as a biomimetic building block for structured functional materials. Genetic engineering of phage provides great opportunities to develop novel nanomaterials with functional surface peptide motifs; however, this biological approach is generally limited to peptides containing the 20 natural amino acids. To extend the scope of phage applications, strategies involving chemical modification have been employed to incorporate a wider range of functional groups, including synthetic chemical compounds. In this review, we introduce the design of chemoselective phage functionalization and discuss how such a strategy is combined with genetic engineering for a variety of medical applications, as reported in recent literature. PMID:25540583

Chemical modulation of M13 bacteriophage and its functional opportunities for nanomedicine.

PubMed

Chung, Woo-Jae; Lee, Doe-Young; Yoo, So Young

2014-01-01

M13 bacteriophage (phage) has emerged as an attractive bionanomaterial owing to its genetically tunable surface chemistry and its potential to self-assemble into hierarchical structures. Furthermore, because of its unique nanoscopic structure, phage has been proposed as a model system in soft condensed physics and as a biomimetic building block for structured functional materials. Genetic engineering of phage provides great opportunities to develop novel nanomaterials with functional surface peptide motifs; however, this biological approach is generally limited to peptides containing the 20 natural amino acids. To extend the scope of phage applications, strategies involving chemical modification have been employed to incorporate a wider range of functional groups, including synthetic chemical compounds. In this review, we introduce the design of chemoselective phage functionalization and discuss how such a strategy is combined with genetic engineering for a variety of medical applications, as reported in recent literature.

Nanomaterials modulate stem cell differentiation: biological interaction and underlying mechanisms.

PubMed

Wei, Min; Li, Song; Le, Weidong

2017-10-25

Stem cells are unspecialized cells that have the potential for self-renewal and differentiation into more specialized cell types. The chemical and physical properties of surrounding microenvironment contribute to the growth and differentiation of stem cells and consequently play crucial roles in the regulation of stem cells' fate. Nanomaterials hold great promise in biological and biomedical fields owing to their unique properties, such as controllable particle size, facile synthesis, large surface-to-volume ratio, tunable surface chemistry, and biocompatibility. Over the recent years, accumulating evidence has shown that nanomaterials can facilitate stem cell proliferation and differentiation, and great effort is undertaken to explore their possible modulating manners and mechanisms on stem cell differentiation. In present review, we summarize recent progress in the regulating potential of various nanomaterials on stem cell differentiation and discuss the possible cell uptake, biological interaction and underlying mechanisms.

Direct monolithic integration of vertical single crystalline octahedral molecular sieve nanowires on silicon

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

Carretero-Genevrier, Adrian; Oro-Sole, Judith; Gazquez, Jaume

2013-12-13

We developed an original strategy to produce vertical epitaxial single crystalline manganese oxide octahedral molecular sieve (OMS) nanowires with tunable pore sizes and compositions on silicon substrates by using a chemical solution deposition approach. The nanowire growth mechanism involves the use of track-etched nanoporous polymer templates combined with the controlled growth of quartz thin films at the silicon surface, which allowed OMS nanowires to stabilize and crystallize. α-quartz thin films were obtained after thermal activated crystallization of the native amorphous silica surface layer assisted by Sr 2+- or Ba 2+-mediated heterogeneous catalysis in the air at 800 °C. These α-quartzmore » thin films work as a selective template for the epitaxial growth of randomly oriented vertical OMS nanowires. Furthermore, the combination of soft chemistry and epitaxial growth opens new opportunities for the effective integration of novel technological functional tunneled complex oxides nanomaterials on Si substrates.« less

Controlling Surface Chemistry of Gallium Liquid Metal Alloys to Enhance their Fluidic Properties

NASA Astrophysics Data System (ADS)

Ilyas, Nahid; Cumby, Brad; Cook, Alexander; Durstock, Michael; Tabor, Christopher; Materials; Manufacturing Directorate Team

Gallium liquid metal alloys (GaLMAs) are one of the key components of emerging technologies in reconfigurable electronics, such as tunable radio frequency antennas and electronic switches. Reversible flow of GaLMA in microchannels of these types of devices is hindered by the instantaneous formation of its oxide skin in ambient environment. The oxide film sticks to most surfaces leaving unwanted metallic residues that can cause undesired electronic properties. In this report, residue-free reversible flow of a binary alloy of gallium (eutectic gallium indium) is demonstrated via two types of surface modifications where the oxide film is either protected by an organic thin film or chemically removed. An interface modification layer (alkyl phosphonic acids) was introduced into the microfluidic system to modify the liquid metal surface and protect its oxide layer. Alternatively, an ion exchange membrane was utilized as a 'sponge-like' channel material to store and slowly release small amounts of HCl to react with the surface oxide of the liquid metal. Characterization of these interfaces at molecular level by surface spectroscopy and microscopy provided with mechanistic details for the interfacial interactions between the liquid metal surface and the channel materials.

Low-energy ion beamline scattering apparatus for surface science investigations

NASA Astrophysics Data System (ADS)

Gordon, M. J.; Giapis, K. P.

2005-08-01

We report on the design, construction, and performance of a high current (monolayers/s), mass-filtered ion beamline system for surface scattering studies using inert and reactive species at collision energies below 1500 eV. The system combines a high-density inductively coupled plasma ion source, high-voltage floating beam transport line with magnet mass-filter and neutral stripping, decelerator, and broad based detection capabilities (ions and neutrals in both mass and energy) for products leaving the target surface. The entire system was designed from the ground up to be a robust platform to study ion-surface interactions from a more global perspective, i.e., high fluxes (>100μA/cm2) of a single ion species at low, tunable energy (50-1400±5eV full width half maximum) can be delivered to a grounded target under ultrahigh vacuum conditions. The high current at low energy problem is solved using an accel-decel transport scheme where ions are created at the desired collision energy in the plasma source, extracted and accelerated to high transport energy (20 keV to fight space charge repulsion), and then decelerated back down to their original creation potential right before impacting the grounded target. Scattered species and those originating from the surface are directly analyzed in energy and mass using a triply pumped, hybrid detector composed of an electron impact ionizer, hemispherical electrostatic sector, and rf/dc quadrupole in series. With such a system, the collision kinematics, charge exchange, and chemistry occurring on the target surface can be separated by fully analyzing the scattered product flux. Key design aspects of the plasma source, beamline, and detection system are emphasized here to highlight how to work around physical limitations associated with high beam flux at low energy, pumping requirements, beam focusing, and scattered product analysis. Operational details of the beamline are discussed from the perspective of available beam current, mass resolution, projectile energy spread, and energy tunability. As well, performance of the overall system is demonstrated through three proof-of-concept examples: (1) elastic binary collisions at low energy, (2) core-level charge exchange reactions involving Ne+20 with Mg /Al/Si/P targets, and (3) reactive scattering of CF2+/CF3+ off Si. These studies clearly demonstrate why low, tunable incident energy, as well as mass and energy filtering of products leaving the target surface is advantageous and often essential for studies of inelastic energy losses, hard-collision charge exchange, and chemical reactions that occur during ion-surface scattering.

Tunable PhoXonic Band Gap Materials from Self-Assembly of Block Copoliymers and Colloidal Nanocrystals (NBIT Phase II)

DTIC Science & Technology

2011-05-06

electric fields. For that, we are going to use PS - b - P2VP block copolymers as a model system, utilizing the quite versatile chemistry of the P2VP ...displays. Our efforts at Hanyang have focused on tunable PBG materials self-assembled from polystyrene- b -poly(2-vinyl pyridine) ( PS - b - P2VP ) block...small angle x-ray scattering measurements during swelling of low molecular weight PS - P2VP polymers at the Cornell High Energy Synchrotron Source

Color-Tunable ZnO/GaN Heterojunction LEDs Achieved by Coupling with Ag Nanowire Surface Plasmons.

PubMed

Yang, Liu; Wang, Yue; Xu, Haiyang; Liu, Weizhen; Zhang, Cen; Wang, Chunliang; Wang, Zhongqiang; Ma, Jiangang; Liu, Yichun

2018-05-09

Color-tunable light-emitting devices (LEDs) have a great impact on our daily life. Herein, LEDs with tunable electroluminescence (EL) color were achieved via introducing Ag nanowires surface plasmons into p-GaN/n-ZnO film heterostructures. By optimizing the surface coverage density of coated Ag nanowires, the EL color was changed continuously from yellow-green to blue-violet. Transient-state and temperature-variable fluorescence emission characterizations uncovered that the spontaneous emission rate and the internal quantum efficiency of the near-UV emission were increased as a consequence of the resonance coupling interaction between Ag nanowires surface plasmons and ZnO excitons. This effect induces the selective enhancement of the blue-violet EL component but suppresses the defect-related yellow-green emission, leading to the observed tunable EL color. The proposed strategy of introducing surface plasmons can be further applied to many other kinds of LEDs for their selective enhancement of EL intensity and effective adjustment of the emission color.

Lasers '81

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

Collins, C.B.

1982-01-01

Progress in lasers is discussed. The subjects addressed include: excimer lasers, surface spectroscopy, modern laser spectroscopy, free electron lasers, cavities and propagation, lasers in medicine, X-ray and gamma ray lasers, laser spectroscopy of small molecules and clusters, optical bistability, excitons, nonlinear optics in the X-ray and gamma ray regions, collective atomic phenomena, tunable IR lasers, far IR/submillimeter lasers, and laser-assisted collisions. Also treated are: special applications, multiphoton processes in atoms and small molecules, nuclear pumped lasers, material processing and applications, polarization, high energy lasers, laser chemistry, IR molecular lasers, laser applications of collision and dissociation phenomena, solid state laser materials,more » phase conjugation, advances in laser technology for fusion, metal vapor lasers, picosecond phenomena, laser ranging and geodesy, and laser photochemistry of complex molecules.« less

Recent Progress on Stability and Passivation of Black Phosphorus.

PubMed

Abate, Yohannes; Akinwande, Deji; Gamage, Sampath; Wang, Han; Snure, Michael; Poudel, Nirakar; Cronin, Stephen B

2018-05-11

From a fundamental science perspective, black phosphorus (BP) is a canonical example of a material that possesses fascinating surface and electronic properties. It has extraordinary in-plane anisotropic electrical, optical, and vibrational states, as well as a tunable band gap. However, instability of the surface due to chemical degradation in ambient conditions remains a major impediment to its prospective applications. Early studies were limited by the degradation of black phosphorous surfaces in air. Recently, several robust strategies have been developed to mitigate these issues, and these novel developments can potentially allow researchers to exploit the extraordinary properties of this material and devices made out of it. Here, the fundamental chemistry of BP degradation and the tremendous progress made to address this issue are extensively reviewed. Device performances of encapsulated BP are also compared with nonencapsulated BP. In addition, BP possesses sensitive anisotropic photophysical surface properties such as excitons, surface plasmons/phonons, and topologically protected and Dirac semi-metallic surface states. Ambient degradation as well as any passivation method used to protect the surface could affect the intrinsic surface properties of BP. These properties and the extent of their modifications by both the degradation and passivation are reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible Immobilization of Proteins in Sensors and Solid-State Nanopores.

PubMed

Ananth, Adithya; Genua, María; Aissaoui, Nesrine; Díaz, Leire; Eisele, Nico B; Frey, Steffen; Dekker, Cees; Richter, Ralf P; Görlich, Dirk

2018-05-01

The controlled functionalization of surfaces with proteins is crucial for many analytical methods in life science research and biomedical applications. Here, a coating for silica-based surfaces is established which enables stable and selective immobilization of proteins with controlled orientation and tunable surface density. The coating is reusable, retains functionality upon long-term storage in air, and is applicable to surfaces of complex geometry. The protein anchoring method is validated on planar surfaces, and then a method is developed to measure the anchoring process in real time using silicon nitride solid-state nanopores. For surface attachment, polyhistidine tags that are site specifically introduced into recombinant proteins are exploited, and the yeast nucleoporin Nsp1 is used as model protein. Contrary to the commonly used covalent thiol chemistry, the anchoring of proteins via polyhistidine tag is reversible, permitting to take proteins off and replace them by other ones. Such switching in real time in experiments on individual nanopores is monitored using ion conductivity. Finally, it is demonstrated that silica and gold surfaces can be orthogonally functionalized to accommodate polyhistidine-tagged proteins on silica but prevent protein binding to gold, which extends the applicability of this surface functionalization method to even more complex sensor devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystals in compression: unexpected structural phase transition and amorphization due to surface impurities.

PubMed

Liu, Gang; Kong, Lingping; Yan, Jinyuan; Liu, Zhenxian; Zhang, Hengzhong; Lei, Pei; Xu, Tao; Mao, Ho-Kwang; Chen, Bin

2016-06-09

We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium-doped brookite amorphizes above 20 GPa. The abnormal structural evolution observed in yttrium-doped TiO2 does not agree with the reported phase stability of nano titania polymorphs, thus suggesting that the physical properties of the interior of nanocrystals can be controlled by the surface, providing an unconventional and new degree of freedom in search for nanocrystals with novel tunable properties that can trigger applications in multiple areas of industry and provoke more related basic science research.

Tunable optofluidic microring laser based on a tapered hollow core microstructured optical fiber.

PubMed

Li, Zhi-Li; Zhou, Wen-Yuan; Luo, Ming-Ming; Liu, Yan-Ge; Tian, Jian-Guo

2015-04-20

A tunable optofluidic microring dye laser within a tapered hollow core microstructured optical fiber was demonstrated. The fiber core was filled with a microfluidic gain medium plug and axially pumped by a nanosecond pulse laser at 532 nm. Strong radial emission and low-threshold lasing (16 nJ/pulse) were achieved. Lasing was achieved around the surface of the microfluidic plug. Laser emission was tuned by changing the liquid surface location along the tapered fiber. The possibility of developing a tunable laser within the tapered simplified hollow core microstructured optical fiber presents opportunities for developing liquid surface position sensors and biomedical analysis.

Tunable photonic multilayer sensors from photo-crosslinkable polymers

NASA Astrophysics Data System (ADS)

Chiappelli, Maria; Hayward, Ryan

2014-03-01

The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

Polarization-independent actively tunable colour generation on imprinted plasmonic surfaces

PubMed Central

Franklin, Daniel; Chen, Yuan; Vazquez-Guardado, Abraham; Modak, Sushrut; Boroumand, Javaneh; Xu, Daming; Wu, Shin-Tson; Chanda, Debashis

2015-01-01

Structural colour arising from nanostructured metallic surfaces offers many benefits compared to conventional pigmentation based display technologies, such as increased resolution and scalability of their optical response with structure dimensions. However, once these structures are fabricated their optical characteristics remain static, limiting their potential application. Here, by using a specially designed nanostructured plasmonic surface in conjunction with high birefringence liquid crystals, we demonstrate a tunable polarization-independent reflective surface where the colour of the surface is changed as a function of applied voltage. A large range of colour tunability is achieved over previous reports by utilizing an engineered surface which allows full liquid crystal reorientation while maximizing the overlap between plasmonic fields and liquid crystal. In combination with imprinted structures of varying periods, a full range of colours spanning the entire visible spectrum is achieved, paving the way towards dynamic pixels for reflective displays. PMID:26066375

Superhydrophobic surfaces fabricated by femtosecond laser with tunable water adhesion: from lotus leaf to rose petal.

PubMed

Long, Jiangyou; Fan, Peixun; Gong, Dingwei; Jiang, Dafa; Zhang, Hongjun; Li, Lin; Zhong, Minlin

2015-05-13

Superhydrophobic surfaces with tunable water adhesion have attracted much interest in fundamental research and practical applications. In this paper, we used a simple method to fabricate superhydrophobic surfaces with tunable water adhesion. Periodic microstructures with different topographies were fabricated on copper surface via femtosecond (fs) laser irradiation. The topography of these microstructures can be controlled by simply changing the scanning speed of the laser beam. After surface chemical modification, these as-prepared surfaces showed superhydrophobicity combined with different adhesion to water. Surfaces with deep microstructures showed self-cleaning properties with extremely low water adhesion, and the water adhesion increased when the surface microstructures became flat. The changes in surface water adhesion are attributed to the transition from Cassie state to Wenzel state. We also demonstrated that these superhydrophobic surfaces with different adhesion can be used for transferring small water droplets without any loss. We demonstrate that our approach provides a novel but simple way to tune the surface adhesion of superhydrophobic metallic surfaces for good potential applications in related areas.

A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems

PubMed Central

Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T.; Ware, Taylor; Voit, Walter E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

2014-01-01

The synthetic design and thermomechanical characterization of shape memory polymers (SMPs) built from a new polyurethane chemistry that enables facile, bulk and tunable cross-linking of low-molecular weight thermoplastics by electron beam irradiation is reported in this study. SMPs exhibit stimuli-induced geometry changes and are being proposed for applications in numerous fields. We have previously reported a polyurethane SMP system that exhibits the complex processing capabilities of thermoplastic polymers and the mechanical robustness and tunability of thermomechanical properties that are often characteristic of thermoset materials. These previously reported polyurethanes suffer practically because the thermoplastic molecular weights needed to achieve target cross-link densities severely limit high-throughput thermoplastic processing and because thermally unstable radiation-sensitizing additives must be used to achieve high enough cross-link densities to enable desired tunable shape memory behavior. In this study, we demonstrate the ability to manipulate cross-link density in low-molecular weight aliphatic thermoplastic polyurethane SMPs (Mw as low as ~1.5 kDa) without radiation-sensitizing additives by incorporating specific structural motifs into the thermoplastic polymer side chains that we hypothesized would significantly enhance susceptibility to e-beam cross-linking. A custom diol monomer was first synthesized and then implemented in the synthesis of neat thermoplastic polyurethane SMPs that were irradiated at doses ranging from 1 to 500 kGy. Dynamic mechanical analysis (DMA) demonstrated rubbery moduli to be tailorable between 0.1 and 55 MPa, and both DMA and sol/gel analysis results provided fundamental insight into our hypothesized mechanism of electron beam cross-linking, which enables controllable bulk cross-linking to be achieved in highly processable, low-molecular weight thermoplastic shape memory polymers without sensitizing additives. PMID:25411511

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

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

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques

PubMed Central

Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Stine, Keith J.

2018-01-01

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing. PMID:29547580

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques.

PubMed

Bhattarai, Jay K; Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Demchenko, Alexei V; Stine, Keith J

2018-03-16

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing.

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

DOE PAGES

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei; ...

2018-05-12

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

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

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generatemore » a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.« less

Out-of-Plane Designed Soft Metasurface for Tunable Surface Plasmon Polariton.

PubMed

Liu, Xin; Huang, Zhao; Zhu, Chengkai; Wang, Li; Zang, Jianfeng

2018-02-14

Reliable and repeatable tunability gives functional diversity for reconfigurable plasmonics devices, while reversible and large mechanical deformation enabled by soft materials provides a new way for the global or partial regulation of metadevices. Here, we demonstrate a soft metasurface with an out-of-plane design for tuning the energy of surface plasmon polaritons (SPPs) bloch wave using theory, simulation, and experiments. Our metasurface is composed of two-layered gold nanoribbon arrays (2GNRs) on a soft substrate. The out-of-plane coupling mechanism is systematically analyzed in terms of separation height effect. Moreover, by harnessing mechanical deformation, continuously tunable plasmonic resonance has been achieved in the visible and near-infrared ranges. We further studied the angle-dependent reflection spectra of our metastructure. Compared with its planar counterpart, our soft and two-layered metastructure exhibits diverse tunability and significant field enhancement by out-of-plane interactions. Our approach in designing soft metasurface with out-of-plane structures can be extended to more-complex photonic devices and finds prominent applications such as biosensing, high-density plasmonic circuits, surface-enhanced luminescence, and surface-enhanced Raman scattering.

A thermo-degradable hydrogel with light-tunable degradation and drug release.

PubMed

Hu, Jingjing; Chen, Yihua; Li, Yunqi; Zhou, Zhengjie; Cheng, Yiyun

2017-01-01

The development of thermo-degradable hydrogels is of great importance in drug delivery. However, it still remains a huge challenge to prepare thermo-degradable hydrogels with inherent degradation, reproducible, repeated and tunable dosing. Here, we reported a thermo-degradable hydrogel that is rapidly degraded above 44 °C by a facile chemistry. Besides thermo-degradability, the hydrogel also undergoes rapid photolysis with ultraviolet light. By embedding photothermal nanoparticles or upconversion nanoparticles into the gel, it can release the entrapped cargoes such as dyes, enzymes and anticancer drugs in an on-demand and dose-tunable fashion upon near-infrared light exposure. The smart hydrogel works well both in vitro and in vivo without involving sophisticated syntheses, and is well suited for clinical cancer therapy due to the high transparency and non-invasiveness features of near-infrared light. Copyright © 2016 Elsevier Ltd. All rights reserved.

Custom 3D Printable Silicones with Tunable Stiffness

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

Durban, Matthew M.; Lenhardt, Jeremy M.; Wu, Amanda S.

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. Furthermore, a series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures. Here, the capability to tune the stiffness of printable silicone materials via careful control over the chemistry, network formation, and crosslink density of the ink formulations in order to overcome the challenging interplay between ink development, post-processing, material properties, and performancemore » is demonstrated.« less

Custom 3D Printable Silicones with Tunable Stiffness

DOE PAGES

Durban, Matthew M.; Lenhardt, Jeremy M.; Wu, Amanda S.; ...

2017-12-06

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. Furthermore, a series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures. Here, the capability to tune the stiffness of printable silicone materials via careful control over the chemistry, network formation, and crosslink density of the ink formulations in order to overcome the challenging interplay between ink development, post-processing, material properties, and performancemore » is demonstrated.« less

Tunable Nanowire Patterning Using Standing Surface Acoustic Waves

PubMed Central

Chen, Yuchao; Ding, Xiaoyun; Lin, Sz-Chin Steven; Yang, Shikuan; Huang, Po-Hsun; Nama, Nitesh; Zhao, Yanhui; Nawaz, Ahmad Ahsan; Guo, Feng; Wang, Wei; Gu, Yeyi; Mallouk, Thomas E.; Huang, Tony Jun

2014-01-01

Patterning of nanowires in a controllable, tunable manner is important for the fabrication of functional nanodevices. Here we present a simple approach for tunable nanowire patterning using standing surface acoustic waves (SSAW). This technique allows for the construction of large-scale nanowire arrays with well-controlled patterning geometry and spacing within 5 seconds. In this approach, SSAWs were generated by interdigital transducers (IDTs), which induced a periodic alternating current (AC) electric field on the piezoelectric substrate and consequently patterned metallic nanowires in suspension. The patterns could be deposited onto the substrate after the liquid evaporated. By controlling the distribution of the SSAW field, metallic nanowires were assembled into different patterns including parallel and perpendicular arrays. The spacing of the nanowire arrays could be tuned by controlling the frequency of the surface acoustic waves. Additionally, we observed 3D spark-shape nanowire patterns in the SSAW field. The SSAW-based nanowire-patterning technique presented here possesses several advantages over alternative patterning approaches, including high versatility, tunability, and efficiency, making it promising for device applications. PMID:23540330

Active Plasmonics: Principles, Structures, and Applications.

PubMed

Jiang, Nina; Zhuo, Xiaolu; Wang, Jianfang

2018-03-28

Active plasmonics is a burgeoning and challenging subfield of plasmonics. It exploits the active control of surface plasmon resonance. In this review, a first-ever in-depth description of the theoretical relationship between surface plasmon resonance and its affecting factors, which forms the basis for active plasmon control, will be presented. Three categories of active plasmonic structures, consisting of plasmonic structures in tunable dielectric surroundings, plasmonic structures with tunable gap distances, and self-tunable plasmonic structures, will be proposed in terms of the modulation mechanism. The recent advances and current challenges for these three categories of active plasmonic structures will be discussed in detail. The flourishing development of active plasmonic structures opens access to new application fields. A significant part of this review will be devoted to the applications of active plasmonic structures in plasmonic sensing, tunable surface-enhanced Raman scattering, active plasmonic components, and electrochromic smart windows. This review will be concluded with a section on the future challenges and prospects for active plasmonics.

Tunable metasurface with two non-coplanar and inter-perpendicular graphene nanoribbon arrays for the coupling between localized and delocalized surface plasmon polaritons

NASA Astrophysics Data System (ADS)

Xie, Ze Tao; Ni, Feng Chao; Ma, Qi Chang; Tao, Jin; Li, Jian; Meng, Hongyun; Huang, Xu Guang

2018-07-01

Graphene metasurface has attracted a lot of attentions due to the unique tunability for exotic electromagnetic properties. In this work, we propose and numerically investigate a tunable metasurface with two non-coplanar and inter-perpendicular graphene nanoribbon arrays. The variation of transmission at different substrate thickness and the coupled mode are analyzed. It is shown that the Rabi-like splitting can be achieved by the coupling between localized and delocalized graphene surface plasmon polaritons. Tunable coupling strength and positions with different gate-voltages have been discussed. The effect of relaxation time and oblique incidences to resonant responses are also investigated. Additionally, we find an optical analogue of a spring, where the spectral dip vibrates around its equilibrium position at a certain wavelength. Our study suggests that the proposed structure is potentially attractive for realization of tunable double-channel filter, optical switch, and variable optical attenuator based on the graphene metasurface.

A new approach to explore the binding space of polysaccharide-based ligands: selectin antagonists.

PubMed

Calosso, Mickael; Charpentier, Daniel; Vaillancourt, Marc; Bencheqroun, Mohammed; St-Pierre, Gabrielle; Wilkes, Brian C; Guindon, Yvan

2012-12-13

The discovery of molecules that interfere with the binding of a ligand to a receptor remains a topic of great interest in medicinal chemistry. Herein, we report that a monosaccharide unit of a polysaccharide ligand can be replaced advantageously by a conformationally locked acyclic molecular entity. A cyclic component of the selectin ligand Sialyl Lewis(x), GlcNAc, is replaced by an acyclic tether, tartaric esters, which link two saccharide units. The conformational bias of this acyclic tether originates from the minimization of intramolecular dipole-dipole interaction and the gauche effect. The evaluation of the binding of these derivatives to P-selectin was measured by surface plasmon resonance spectroscopy. The results obtained in our pilot study suggest that the discovery of tunable tethers could facilitate the exploration of the carbohydrate recognition domain of various receptors.

Green Chemistry for Nanotechnology: Opportunities and Future Challenges

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

Preeti Nigam, Joshi, E-mail: ph.joshi@ncl.res.in

2016-01-26

Nanotechnology is a paradigm for emerging technologies and much talked about area of science. It is the technology of future and has revolutionized all fields of medicine, agriculture, environmental and electronics by providing abilities that would never have previously dreamt of. It is a unique platform of multidisciplinary approaches integrating diverse fields of engineering, biology, physics and chemistry. In recent years, nanotechnology has seen the fastest pace in its all aspects of synthesis methodologies and wide applications in all areas of medicine, agricultural, environmental, and electronics. It is the impact of nanotechnology approaches that new fields of nanomedicine, cancer nanotechnology,more » nanorobotics and nanoelectronics have been emerged and are flourishing with the advances in this expanding field. Nanotechnology holds the potential for pervasive and promising applications and getting significant attention and financial aids also. Although there are different definitions of nanotechnology, in broad prospective, nanotechnology can be described as designing or exploiting materials at nanometer dimensions (i.e., one dimension less than 100 nanometers). At nanoscale, substances have a larger surface area to volume ratio than conventional materials which is the prime reason behind their increased level of reactivity, improved and size tunable magnetic, optical and electrical properties and more toxicity also.« less

Synthesis and click chemistry of a new class of biodegradable polylactide towards tunable thermo-responsive biomaterials.

PubMed

Zhang, Quanxuan; Ren, Hong; Baker, Gregory L

2015-02-28

A new class of clickable and biodegradable polylactide was designed and prepared via bulk polymerization of 3,6-dipropargyloxymethyl-1,4-dioxane-2,5-dione ( 1 ) which was synthesized from easily accessible propargyloxylactic acid ( 5 ). A homopolymer of 1 and random copolymer of 1 with l-lactide were obtained as amorphous materials and exhibit low T g of 8.5 and 34 °C, respectively, indicating their promising potentials for biomedical applications. The statistical nature of random copolymers was investigated by DSC analysis and 13 C NMR spectroscopy, which implies the random distribution of terminal alkyne groups along the back bone of copolymers. The efficient click post-modification of this new class of polylactide with alkyl and mPEG azides affords novel hydrophilic biomaterials, which exhibit reversible thermo-responsive properties as evidenced by their tunable LCST ranging from 22 to 69 °C depending on the balance of the incorporated hydrophilic/hydrophobic side chains. These results indicate the generality of this new class of clickable polylactide in preparing novel smart biomaterials in a simple and efficient manner via click chemistry.

Development of thin-film tunable band-pass filters based hyper-spectral imaging system applied for both surface enhanced Raman scattering and plasmon resonance Rayleigh scattering

NASA Astrophysics Data System (ADS)

Iga, Mitsuhiro; Kakuryu, Nobuyuki; Tanaami, Takeo; Sajiki, Jiro; Isozaki, Katsumi; Itoh, Tamitake

2012-10-01

We describe the development of a hyper-spectral imaging (HSI) system composed of thin-film tunable band-pass filters (TF-TBPFs) and its application to inhomogeneous sample surfaces. Compared with existing HSI systems, the system has a simpler optical arrangement and has an optical transmittance of up to 80% owing to polarization independence. The HSI system exhibits a constant spectral resolution over a spectral window of 80 nm (530 to 610 nm) and tunable spectral resolution from 1.5 to 3.0 nm, and requires only 5.4 s per measurement. Plasmon resonance and surface enhanced Raman scattering (SERS) from inhomogeneous surfaces dispersed with Ag nanoparticles (NP) have been measured with the HSI system. The measurement of multiple Ag NPs is consistent with conventional isolated NP measurements as explained by the electromagnetic mechanism of SERS, demonstrating the validity of the HSI system.

Liquid-assisted tunable metasurface for simultaneous manipulation of surface elastic and acoustic waves

NASA Astrophysics Data System (ADS)

Yuan, Si-Min; Ma, Tian-Xue; Chen, A.-Li; Wang, Yue-Sheng

2018-03-01

A tunable and multi-functional one-dimensional metasurface, which is formed by engraving periodic semi-ellipse grooves on the surface of an aluminum half-space, is proposed in this paper. One characteristic of the metasurface is the manipulation of multi-physical fields, i.e. it could be utilized to manipulate surface elastic and acoustic waves simultaneously. The dispersion curves of the elastic and acoustic waves can be effectively tuned by adding liquids into the grooves. Based on the tunability different applications can be realized by adding different volumes of different liquids into the grooves. As an example, simultaneous rainbow trapping of the surface elastic and acoustic waves is demonstrated in the metasurface. Moreover, a resonant cavity where the elastic and acoustic waves are highly confined is reported. The proposed metasurface paves the way to the design of multi-functional devices for simultaneous control of elastic and acoustic waves.

Annealing temperature dependent reversible wettability switching of micro/nano structured ZnO superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Velayi, Elmira; Norouzbeigi, Reza

2018-05-01

Superhydrophobic ZnO surfaces with reversibly tunable wettability were fabricated on stainless steel meshes via a facile chemical bath deposition method just by regulating the micro/nano structured ZnO needles without using chemical post modifications. The obtained surfaces can be easily and reversibly switched between superhydrophobic and superhydrophilic/underwater superoleophobic characteristics by altering the annealing temperatures. As-prepared sample exhibited long-term superhydrophobic properties with a water contact angle (WCA) of 163.8° ± 1.8° and contact angle hysteresis (CAH) of 1.1° ± 0.8°. The SEM, XRD, XPS and Raman analyses were employed to characterize the morphological features and surface chemistry of the prepared samples. SEM images showed the formation of ZnO micro/nanoneedles with a diameter of ∼90 nm on the substrate. The superhydrophobic ZnO surface was switched to highly hydrophilic and underwater superoleophobic properties with an oil contact angle (OCA) of about 172.5° after being annealed at 400 °C in air for 30 min and restored to superhydrophobic state again by altering the annealing temperature to 150 °C. Mechanical durability of the ZnO superhydrophobic surface was tested by an abrasion test. Results confirmed that the prepared surface exhibited an excellent robustness after 20 abrasion cycles under the pressure of 4.7 kPa.

Custom 3D Printable Silicones with Tunable Stiffness.

PubMed

Durban, Matthew M; Lenhardt, Jeremy M; Wu, Amanda S; Small, Ward; Bryson, Taylor M; Perez-Perez, Lemuel; Nguyen, Du T; Gammon, Stuart; Smay, James E; Duoss, Eric B; Lewicki, James P; Wilson, Thomas S

2018-02-01

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. A series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures. Herein, the capability to tune the stiffness of printable silicone materials via careful control over the chemistry, network formation, and crosslink density of the ink formulations in order to overcome the challenging interplay between ink development, post-processing, material properties, and performance is demonstrated. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of pendular butterfly Rydberg molecules

PubMed Central

Niederprüm, Thomas; Thomas, Oliver; Eichert, Tanita; Lippe, Carsten; Pérez-Ríos, Jesús; Greene, Chris H.; Ott, Herwig

2016-01-01

Engineering molecules with a tunable bond length and defined quantum states lies at the heart of quantum chemistry. The unconventional binding mechanism of Rydberg molecules makes them a promising candidate to implement such tunable molecules. A very peculiar type of Rydberg molecules are the so-called butterfly molecules, which are bound by a shape resonance in the electron–perturber scattering. Here we report the observation of these exotic molecules and employ their exceptional properties to engineer their bond length, vibrational state, angular momentum and orientation in a small electric field. Combining the variable bond length with their giant dipole moment of several hundred Debye, we observe counter-intuitive molecules which locate the average electron position beyond the internuclear distance. PMID:27703143

Widely tunable telecom MEMS-VCSEL for terahertz photomixing.

PubMed

Haidar, Mohammad Tanvir; Preu, Sascha; Paul, Sujoy; Gierl, Christian; Cesar, Julijan; Emsia, Ali; Küppers, Franko

2015-10-01

We report frequency-tunable terahertz (THz) generation with a photomixer driven by an ultra-broadband tunable micro-electro-mechanical system vertical-cavity surface-emitting laser (MEMS-VCSEL) and a fixed-wavelength VCSEL, as well as a tunable MEMS-VCSEL mixed with a distributed feedback (DFB) diode. A total frequency span of 3.4 THz is covered in direct detection mode and 3.23 THz in the homodyne mode. The tuning range is solely limited by the dynamic range of the photomixers and the Schottky diode/photoconductor used in the experiment.

Bioinspired, dynamic, structured surfaces for biofilm prevention

NASA Astrophysics Data System (ADS)

Epstein, Alexander K.

Bacteria primarily exist in robust, surface-associated communities known as biofilms, ubiquitous in both natural and anthropogenic environments. Mature biofilms resist a wide range of biocidal treatments and pose persistent pathogenic threats. Treatment of adherent biofilm is difficult, costly, and, in medical systems such as catheters, frequently impossible. Adding to the challenge, we have discovered that biofilm can be both impenetrable to vapors and extremely nonwetting, repelling even low surface tension commercial antimicrobials. Our study shows multiple contributing factors, including biochemical components and multiscale reentrant topography. Reliant on surface chemistry, conventional strategies for preventing biofilm only transiently affect attachment and/or are environmentally toxic. In this work, we look to Nature's antifouling solutions, such as the dynamic spiny skin of the echinoderm, and we develop a versatile surface nanofabrication platform. Our benchtop approach unites soft lithography, electrodeposition, mold deformation, and material selection to enable many degrees of freedom—material, geometric, mechanical, dynamic—that can be programmed starting from a single master structure. The mechanical properties of the bio-inspired nanostructures, verified by AFM, are precisely and rationally tunable. We examine how synthetic dynamic nanostructured surfaces control the attachment of pathogenic biofilms. The parameters governing long-range patterning of bacteria on high-aspect-ratio (HAR) nanoarrays are combinatorially elucidated, and we discover that sufficiently low effective stiffness of these HAR arrays mechanoselectively inhibits ˜40% of Pseudomonas aeruginosa biofilm attachment. Inspired by the active echinoderm skin, we design and fabricate externally actuated dynamic elastomer surfaces with active surface microtopography. We extract from a large parameter space the critical topographic length scales and actuation time scales for achieving nearly ˜80% attachment reduction. We furthermore investigate an atomically mobile, slippery liquid infused porous surface (SLIPS) inspired by the pitcher plant. We show up to 99.6% reduction of multiple pathogenic biofilms over a 7-day period under both static and physiologically realistic flow conditions—a ˜35x improvement over state-of-the-art surface chemistry, and over a far longer timeframe. Moreover, SLIPS is shown to be nontoxic: bacteria simply cannot attach to the smooth liquid interface. These bio-inspired strategies significantly advance biofilm attachment prevention and promise a tremendous range of industrial, clinical, and consumer applications.

Atomic Mechanism of Hybridization-Dependent Surface Reconstruction with Tailored Functionality in Hexagonal Multiferroics.

PubMed

Deng, Shiqing; Cheng, Shaobo; Xu, Changsong; Ge, Binghui; Sun, Xuefeng; Yu, Rong; Duan, Wenhui; Zhu, Jing

2017-08-16

The broken symmetry along with anomalous defect structures and charging conditions at multiferroics surface can alter both crystal structures and electronic configurations, bringing in emergent physical properties. Extraordinary surface states are induced into original mutually coupled order parameters in such strongly correlated oxides, which flourish in diverse properties but remain less explored. Here, we report the peculiar surface ferroelectric states and reconfigurable functionalities driven by the relaxation of surface and consequent changes in O 2p and Y 4d orbital (p-d) hybridization within a representative hexagonal multiferroics, YMnO 3 . An unprecedented surface reconstruction is achieved by tailored p-d hybridization coupling with in-plane oxygen vacancies, which is atomically revealed on the basis of the advantages of state-of-the-art aberration-corrected (scanning) transmission electron microscopy. Further ab initio density functional theory calculations verify the key roles of in-plane oxygen vacancies in modulating polarization properties and electronic structure, which should be regarded as the atomic multiferroic element. This surface configuration is found to induce tunable functionalities, such as surface ferromagnetism and conductivity. Meanwhile, the controversial origin of improper ferroelectricity that is unexpectedly free from critical size has also been atomically unraveled. Our findings provide new insights into the design and implementation of surface chemistry devices by simply controlling the oxygen stoichiometry, greatly advance our understandings of surface science in strongly correlated oxides, and enable exciting innovations and new technological functionality paradigms.

Dynamically tunable interface states in 1D graphene-embedded photonic crystal heterostructure

NASA Astrophysics Data System (ADS)

Huang, Zhao; Li, Shuaifeng; Liu, Xin; Zhao, Degang; Ye, Lei; Zhu, Xuefeng; Zang, Jianfeng

2018-03-01

Optical interface states exhibit promising applications in nonlinear photonics, low-threshold lasing, and surface-wave assisted sensing. However, the further application of interface states in configurable optics is hindered by their limited tunability. Here, we demonstrate a new approach to generate dynamically tunable and angle-resolved interface states using graphene-embedded photonic crystal (GPC) heterostructure device. By combining the GPC structure design with in situ electric doping of graphene, a continuously tunable interface state can be obtained and its tuning range is as wide as the full bandgap. Moreover, the exhibited tunable interface states offer a possibility to study the correspondence between space and time characteristics of light, which is beyond normal incident conditions. Our strategy provides a new way to design configurable devices with tunable optical states for various advanced optical applications such as beam splitter and dynamically tunable laser.

High-speed wavelength switching of tunable MEMS vertical cavity surface emitting laser by ringing suppression

NASA Astrophysics Data System (ADS)

Inoue, Shunya; Nishimura, Shun; Nakahama, Masanori; Matsutani, Akihiro; Sakaguchi, Takahiro; Koyama, Fumio

2018-04-01

For use in wavelength division multiplexing (WDM) with high-speed wavelength routing functions, the fast wavelength switching of tunable lasers is a key function. A tunable MEMS vertical cavity surface emitting laser (VCSEL) is a good candidate as a light source for this purpose. The cantilever in MEMS VCSELs has a high mechanical resonance frequency thanks to its small size, but the switching time is limited by the ringing of the cantilever structure. In this paper, we analyzed the mechanical behavior of a cantilever MEMS mirror and demonstrated ringing-free operation with an engineered voltage signal. The applied voltage waveform was optimized in a two-step format and we experimentally obtained ringing free wavelength switching. We measured the transient response of the wavelength by inserting a tunable filter, exhibiting the settling time of less than 2.5 µs, which corresponds to a half period of the cantilever resonance frequency.

External cavity tunable quantum cascade lasers and their applications to trace gas monitoring.

PubMed

Rao, Gottipaty N; Karpf, Andreas

2011-02-01

Since the first quantum cascade laser (QCL) was demonstrated approximately 16 years ago, we have witnessed an explosion of interesting developments in QCL technology and QCL-based trace gas sensors. QCLs operate in the mid-IR region (3-24 μm) and can directly access the rotational vibrational bands of most molecular species and, therefore, are ideally suited for trace gas detection with high specificity and sensitivity. These sensors have applications in a wide range of fields, including environmental monitoring, atmospheric chemistry, medical diagnostics, homeland security, detection of explosive compounds, and industrial process control, to name a few. Tunable external cavity (EC)-QCLs in particular offer narrow linewidths, wide ranges of tunability, and stable power outputs, which open up new possibilities for sensor development. These features allow for the simultaneous detection of multiple species and the study of large molecules, free radicals, ions, and reaction kinetics. In this article, we review the current status of EC-QCLs and sensor developments based on them and speculate on possible future developments.

R&D 100, 2016: Stress-Induced Fabrication

ScienceCinema

Fan, Hongyou; Brennan, Tom; Wise, Jack; Liu, Sheng; Hickman, Randy

2018-06-13

Stress-induced fabrication (SIF) uses compressive mechanical stress to create new nanomaterials with lower production costs and enhanced materials performance compared to traditional fabrication routes. Simple, innovative, and with more degrees of freedom than current chemical synthesis methods, SIF uses physical force instead of chemistry applied to form new nanomaterials with precisely controlled structure and tunable properties.

R&D 100, 2016: Stress-Induced Fabrication

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

Fan, Hongyou; Brennan, Tom; Wise, Jack

Stress-induced fabrication (SIF) uses compressive mechanical stress to create new nanomaterials with lower production costs and enhanced materials performance compared to traditional fabrication routes. Simple, innovative, and with more degrees of freedom than current chemical synthesis methods, SIF uses physical force instead of chemistry applied to form new nanomaterials with precisely controlled structure and tunable properties.

Controllable superhydrophobic aluminum surfaces with tunable adhesion fabricated by femtosecond laser

NASA Astrophysics Data System (ADS)

Song, Yuxin; Wang, Cong; Dong, Xinran; Yin, Kai; Zhang, Fan; Xie, Zheng; Chu, Dongkai; Duan, Ji'an

2018-06-01

In this study, a facile and detailed strategy to fabricate superhydrophobic aluminum surfaces with controllable adhesion by femtosecond laser ablation is presented. The influences of key femtosecond laser processing parameters including the scanning speed, laser power and interval on the wetting properties of the laser-ablated surfaces are investigated. It is demonstrated that the adhesion between water and superhydrophobic surface can be effectively tuned from extremely low adhesion to high adhesion by adjusting laser processing parameters. At the same time, the mechanism is discussed for the changes of the wetting behaviors of the laser-ablated surfaces. These superhydrophobic surfaces with tunable adhesion have many potential applications, such as self-cleaning surface, oil-water separation, anti-icing surface and liquid transportation.

Design & synthesis of silicone elastomer networks with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Willoughby, Julie Ann-Crowe

2007-05-01

We have engineered functional surfaces via the manipulation of silicone elastomers (SEs). The most common silicone, poly(dimethylsiloxane) PDMS, can be both challenging and advantageous in the design of surfaces due to its inherent inertness and flexibility of the siloxane backbone. This unique polymer is approaching a $10 billion dollar market attributed to its formulation in a wide array of applications; from the personal care industry to the electronics industry. While it can be used for many applications, surface design with PDMS usually requires a chemical or physical modification of the polymeric network. In addition, surface characteristics are tailored for specific functions since there is not one surface that fits all end-uses. In studying the intrinsic behavior of engineered SEs, we asked questions regarding surface stability, environmental conformation and adaptability, and tuning physical features. We report on the formation of responsive surfaces with tailorable surface-reconstruction kinetics and switching hysteresis by thiol-ene radical addition of mercaptoalkanols with variable lengths to poly(vinylmethylsiloxane) networks. Exposing the modified surfaces to water led to a rearrangement of the hydrophilic alkanes at the surface. The rearrangement kinetics decreases with increasing number of the methylene spacers (n) in the mercaptoalkanol. The response kinetics is found to be very fast for n = 2 and 6. For instance, upon exposing to water, the water contact angle on 3-mercaptopropanol-based surfaces decreases by ≈35° at the rate of 2°/second. The high flexibility of the siloxane backbone endows these materials with switching longevity; the materials were able to switch their wettability over 10 cycles with minimum hysteresis. Increasing the number of methylene spacers to n = 11 decreases the surface reorganization dramatically. Formation of semi-crystalline regions in such materials (detected via IR) is responsible for initial "sluggish" kinetics and eventual surface "freezing". The effects of surface chemistry and topology on cellular adhesion and proliferation have been studied extensively in the past. However, little work exists that aims at probing the effects of surface morphology and elastic modulus on cell behavior. To achieve timely and comprehensive experimental design, there is need for the availability of novel substrata with tunable mechanical properties (or compliance) at the micro and meso-scale level ranging from individual cells to whole tissues. Despite expansive research that has targeted the understanding of cellular response to its host scaffold, the choice of material and extrapolation of findings from one cell/material system to another has proven difficult. Thus establishing general relationships between substrate compliance and cell behavior cannot be considered independent of the material and cell type. In our work, we have explored creating surfaces from SEs comprising gradients in stiffness (or elastic modulus), by controlling the degree of cross-linking. Network regions consisting of higher cross-linking demonstrate a greater elastic modulus. We present two methods to control the mechanical properties of silicone elastomers. The first technique utilizes interdiffusion of multiple SEs with varied molecular weights that are subsequently cross-linked into a network. The second method involves synthesizing a UV-curable SE. This method controls the degree of cross-linking by regulating the intensity of the UV light via a transparency with tunable transmittance placed on top of the SE film. Our results show that it is possible to generate compliance gradients through either route, enabling a large range of both gradient patterns and stiffness.

Nanoparticles for Biomedical Imaging

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

Nune, Satish K.; Gunda, Padmaja; Thallapally, Praveen K.

2009-11-01

Background: Synthetic nanoparticles are emerging as versatile tools in biomedical applications, particularly in the area of biomedical imaging. Nanoparticles 1 to 100 nm in diameter possess dimensions comparable to biological functional units. Diverse surface chemistries, unique magnetic properties, tunable absorption and emission properties, and recent advances in the synthesis and engineering of various nanoparticles suggest their potential as probes for early detection of diseases such as cancer. Surface functionalization has further expanded the potential of nanoparticles as probes for molecular imaging. Objective: To summarize emerging research of nanoparticles for biomedical imaging with increased selectivity and reduced non-specific uptake with increasedmore » spatial resolution containing stabilizers conjugated with targeting ligands. Methods: This review summarizes recent technological advances in the synthesis of various nanoparticle probes, and surveys methods to improve the targeting of nanoparticles for their applications in biomedical imaging. Conclusion: Structural design of nanomaterials for biomedical imaging continues to expand and diversify. Synthetic methods have aimed to control the size and surface characteristics of nanoparticles to control distribution, half-life and elimination. Although molecular imaging applications using nanoparticles are advancing into clinical applications, challenges such as storage stability and long-term toxicology should continue to be addressed. Keywords: nanoparticle synthesis, surface modification, targeting, molecular imaging, and biomedical imaging.« less

Monitoring gas concentrations in environmental and atmospheric applications using tunable diode lasers

NASA Astrophysics Data System (ADS)

Awtry, Andrew R.

Two atmospheric chemistry processes that contribute to environmental concerns have been explored using mid-infrared, lead-salt diode lasers. Tunable diode laser absorption spectroscopy was used to determine concentrations of both NF3 and NH3. The focus of the NF3 research was to determine the magnitude of the nu1 absorption band in order to determine the effects of this molecule on global warming. Deposition velocity is a proportionality constant between concentration and vertical flux to a surface. The magnitude of this constant for NH 3 depositing onto water is experimentally determined using both a small cell (425 mL) and a large chamber (335 L). The results from the chamber are then incorporated into a model in an attempt to better understand the atmospheric contribution to aqueous concentrations. Near-infrared diode lasers were used in both integrated cavity output spectroscopy and cavity ringdown spectroscopy in an attempt to develop an air monitoring sensor. The following experiments were then performed determine the sensitivity, durability and dynamic range of these two techniques: flame characterization of HCN and C2H2 in a flame from a Wolfhard-Parker burner, obtaining isolated absorption features of CO, CO2, H 2O, HCN, NH3, CH4, and C2H4 in order to create calibration curves and determine detection limits, CO 2 classroom measurements, and CO2 isotope ratio measurements.

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE PAGES

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.; ...

2015-07-02

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Understanding oxidative dehydrogenation of ethane on Co 3O 4 nanorods from density functional theory

DOE PAGES

Fung, Victor; Tao, Franklin; Jiang, De-en

2016-05-20

Co 3O 4 is a metal oxide catalyst with weak, tunable M–O bonds promising for catalysis. Here, density functional theory (DFT) is used to study the oxidative dehydrogenation (ODH) of ethane on Co 3O 4 nanorods based on the preferred surface orientation (111) from the experimental electron-microscopy image. The pathway and energetics of the full catalytic cycle including the first and second C–H bond cleavages, hydroxyl clustering, water formation, and oxygen-site regeneration are determined. We find that both lattice O and Co may participate as active sites in the dehydrogenation, with the lattice-O pathway being favored. Here, we identify themore » best ethane ODH pathway based on the overall energy profiles of several routes. We identify that water formation from the lattice oxygen has the highest energy barrier and is likely a rate-determining step. This work of the complete catalytic cycle of ethane ODH will allow further study into tuning the surface chemistry of Co 3O 4 nanorods for high selectivity of alkane ODH reactions.« less

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

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

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Polysaccharide based nanogels in the drug delivery system: Application as the carrier of pharmaceutical agents.

PubMed

Debele, Tilahun Ayane; Mekuria, Shewaye Lakew; Tsai, Hsieh-Chih

2016-11-01

Polysaccharide-based nanoparticles have fascinated attention as a vesicle of different pharmaceutical agents due to their unique multi-functional groups in addition to their physicochemical properties, including biocompatibility and biodegradability. The existence of multi-functional groups on the polysaccharide backbone permits facile chemical or biochemical modification to synthesize polysaccharide based nanoparticles with miscellaneous structures. Polysaccharide-based nanogels have high water content, large surface area for multivalent bioconjugation, tunable size, and interior network for the incorporation of different pharmaceutical agents. These unique properties offer great potential for the utilization of polysaccharide-based nanogels in the drug delivery systems. Hence, this review describes chemistry of certain common polysaccharides, several methodologies used to synthesize polysaccharide nanoparticles and primarily focused on the polysaccharide (or polysaccharide derivative) based nanogels as the carrier of pharmaceutical agents. Copyright © 2016 Elsevier B.V. All rights reserved.

The Role of Helium Metastable States in Radio-Frequency Helium-Oxygen Atmospheric Pressure Plasma Jets: Measurement and Numerical Simulation

NASA Astrophysics Data System (ADS)

Niemi, Kari; Waskoenig, Jochen; Sadeghi, Nader; Gans, Timo; O'Connell, Deborah

2011-10-01

Absolute densities of metastable He atoms were measured line-of sight integrated along the plasma channel of a capacitively-coupled radio-frequency driven atmospheric pressure plasma jet operated in helium oxygen mixtures by tunable diode-laser absorption spectroscopy. Dependencies of the He metastable density with oxygen admixtures up to 1 percent were investigated. Results are compared to a 1-d numerical simulation, which includes a semi-kinetical treatment of the electron dynamics and the complex plasma chemistry (20 species, 184 reactions), and very good agreement is found. The main formation mechanisms for the helium metastables are identified and analyzed, including their pronounced spatio-temporal dynamics. Penning ionization through helium metastables is found to be significant for plasma sustainment, while it is revealed that helium metastables are not an important energy carrying species into the jet effluent and therefore will not play a direct role in remote surface treatments.

Magnetic ionic liquids in analytical chemistry: A review.

PubMed

Clark, Kevin D; Nacham, Omprakash; Purslow, Jeffrey A; Pierson, Stephen A; Anderson, Jared L

2016-08-31

Magnetic ionic liquids (MILs) have recently generated a cascade of innovative applications in numerous areas of analytical chemistry. By incorporating a paramagnetic component within the cation or anion, MILs exhibit a strong response toward external magnetic fields. Careful design of the MIL structure has yielded magnetoactive compounds with unique physicochemical properties including high magnetic moments, enhanced hydrophobicity, and the ability to solvate a broad range of molecules. The structural tunability and paramagnetic properties of MILs have enabled magnet-based technologies that can easily be added to the analytical method workflow, complement needed extraction requirements, or target specific analytes. This review highlights the application of MILs in analytical chemistry and examines the important structural features of MILs that largely influence their physicochemical and magnetic properties. Copyright © 2016 Elsevier B.V. All rights reserved.

Generation of tunable narrow-band surface-emitted terahertz radiation in periodically poled lithium niobate.

PubMed

Weiss, C; Torosyan, G; Avetisyan, Y; Beigang, R

2001-04-15

Generation of tunable narrow-band terahertz (THz) radiation perpendicular to the surface of periodically poled lithium niobate by optical rectification of femtosecond pulses is reported. The generated THz radiation can be tuned by use of different poling periods and different observation angles, limited only by the available bandwidth of the pump pulse. Typical bandwidths were 50-100 GHz, depending on the collection angle and the number of periods involved.

Integrated MEMS-tunable VCSELs for reconfigurable optical interconnects

NASA Astrophysics Data System (ADS)

Kögel, Benjamin; Debernardi, Pierluigi; Westbergh, Petter; Gustavsson, Johan S.; Haglund, Åsa; Haglund, Erik; Bengtsson, Jörgen; Larsson, Anders

2012-03-01

A simple and low-cost technology for tunable vertical-cavity surface-emitting lasers (VCSELs) with curved movable micromirror is presented. The micro-electro-mechanical system (MEMS) is integrated with the active optical component (so-called half-VCSEL) by means of surface-micromachining using a reflown photoresist droplet as sacrificial layer. The technology is demonstrated for electrically pumped, short-wavelength (850 nm) tunable VCSELs. Fabricated devices with 10 μm oxide aperture are singlemode with sidemode suppression >35 dB, tunable over 24 nm with output power up to 0.5mW, and have a beam divergence angle <6 °. An improved high-speed design with reduced parasitic capacitance enables direct modulation with 3dB-bandwidths up to 6GHz and error-free data transmission at 5Gbit/s. The modulation response of the MEMS under electrothermal actuation has a bandwidth of 400 Hz corresponding to switching times of about 10ms. The thermal crosstalk between MEMS and half-VCSEL is negligible and not degrading the device performance. With these characteristics the integrated MEMS-tunable VCSELs are basically suitable for use in reconfigurable optical interconnects and ready for test in a prototype system. Schemes for improving output power, tuning speed, and modulation bandwidth are briefly discussed.

Color-tunable mixed photoluminescence emission from Alq3 organic layer in metal-Alq3-metal surface plasmon structure.

PubMed

Chen, Nai-Chuan; Liao, Chung-Chi; Chen, Cheng-Chang; Fan, Wan-Ting; Wu, Jin-Han; Li, Jung-Yu; Chen, Shih-Pu; Huang, Bohr-Ran; Lee, Li-Ling

2014-01-01

This work reports the color-tunable mixed photoluminescence (PL) emission from an Alq3 organic layer in an Au-Alq3-Au plasmonic structure through the combination of organic fluorescence emission and another form of emission that is enabled by the surface plasmons in the plasmonic structure. The emission wavelength of the latter depends on the Alq3 thickness and can be tuned within the Alq3 fluorescent spectra. Therefore, a two-color broadband, color-tunable mixed PL structure was obtained. Obvious changes in the Commission Internationale d'Eclairage (CIE) coordinates and the corresponding emission colors of Au-Alq3-Au samples clearly varied with the Alq3 thickness (90, 130, and 156 nm).

Color-tunable mixed photoluminescence emission from Alq3 organic layer in metal-Alq3-metal surface plasmon structure

PubMed Central

2014-01-01

This work reports the color-tunable mixed photoluminescence (PL) emission from an Alq3 organic layer in an Au-Alq3-Au plasmonic structure through the combination of organic fluorescence emission and another form of emission that is enabled by the surface plasmons in the plasmonic structure. The emission wavelength of the latter depends on the Alq3 thickness and can be tuned within the Alq3 fluorescent spectra. Therefore, a two-color broadband, color-tunable mixed PL structure was obtained. Obvious changes in the Commission Internationale d’Eclairage (CIE) coordinates and the corresponding emission colors of Au-Alq3-Au samples clearly varied with the Alq3 thickness (90, 130, and 156 nm). PMID:25328506

Tunable surface plasmon devices

DOEpatents

Shaner, Eric A [Rio Rancho, NM; Wasserman, Daniel [Lowell, MA

2011-08-30

A tunable extraordinary optical transmission (EOT) device wherein the tunability derives from controlled variation of the dielectric constant of a semiconducting material (semiconductor) in evanescent-field contact with a metallic array of sub-wavelength apertures. The surface plasmon resonance wavelength can be changed by changing the dielectric constant of the dielectric material. In embodiments of this invention, the dielectric material is a semiconducting material. The dielectric constant of the semiconducting material in the metal/semiconductor interfacial region is controllably adjusted by adjusting one or more of the semiconductor plasma frequency, the concentration and effective mass of free carriers, and the background high-frequency dielectric constant in the interfacial region. Thermal heating and/or voltage-gated carrier-concentration changes may be used to variably adjust the value of the semiconductor dielectric constant.

2004 Army Research Office in Review

DTIC Science & Technology

2004-01-01

23 Uncool Tunable LWIR Microbolometer...but also for speech in multimedia applications. ELECTRONICS Uncooled Tunable LWIR Microbolometer – Multi- or hyper- spectral images contain...Analysis of NURBS Curves and Surfaces Jian-Ao Lian, Prairie View A&M University The multiresolution structure of NURBS ( nonuniform rational B

Spoof surface plasmons resonance effect and tunable electric response of improved metamaterial in the terahertz regime

NASA Astrophysics Data System (ADS)

Wang, Yue; Zhang, Li-Ying; Mei, Jin-Shuo; Zhang, Wen-Chao; Tong, Yi-Jing

2015-12-01

We propose an improved design and numerical study of an optimized tunable plasmonics artificial material resonator in the terahertz regime. We demonstrate that tunability can be realized with a transmission intensity as much as ˜61% in the lower frequency resonance, which is implemented through the effect of photoconductive switching under photoexcitation. In the higher frequency resonance, we show that spoof surface plasmons along the interface of metal/dielectric provide new types of electromagnetic resonances. Our approach opens up possibilities for the interface of metamaterial and plasmonics to be applied to optically tunable THz switching. Project supported by the National Natural Science Foundation of China (Grant No. 61201075), the Natural Science Foundation of Heilongjiang Province, China (Grant No. F2015039), the Young Scholar Project of Heilongjiang Provincial Education Bureau, China (Grant No. 1254G021), the China Postdoctoral Science Foundation (Grant No. 2012M511507), and the Science Funds for the Young Innovative Talents of Harbin University of Science and Technology, China (Grant No. 201302).

Poly(amidoamine) dendrimer-enabled simultaneous stabilization and functionalization of electrospun poly(γ-glutamic acid) nanofibers.

PubMed

Wang, Shige; Zhu, Jingyi; Shen, Mingwu; Zhu, Meifang; Shi, Xiangyang

2014-02-12

We report a facile and general approach to using generation 2 (G2) poly(amidoamine) (PAMAM) dendrimers for simultaneous stabilization and functionalization of electrospun poly(γ-glutamic acid) nanofibers (γ-PGA NFs). In this study, uniform γ-PGA NFs with a smooth morphology were generated using electrospinning technology. In order to endow the NFs with good water stability, amine-terminated G2.NH2 PAMAM dendrimers were utilized to crosslink the γ-PGA NFs via 1-ethyl-3-(3-dimethylami-nopropyl) carbodiimide coupling chemistry. Under the optimized crosslinking conditions, G2.NH2 dendrimers partially modified with fluorescein isothiocyanate (FI) or folic acid (FA) were used to crosslink γ-PGA NFs. Our results reveal that G2.NH2-FI is able to simultaneously render the NFs with good water stability and fluorescence property, while G2.NH2-FA is able to simultaneously endow the NFs with water stability and the ability to capture FA receptor-overexpressing cancer cells in vitro via ligand-receptor interaction. With the tunable dendrimer surface chemistry, multifunctional water-stable γ-PGA-based NFs may be generated via a dendrimer crosslinking approach, thereby providing diverse applications in the areas of biosensing, tissue engineering, drug delivery, and environmental sciences.

Engineered liquid crystal anchoring energies with nanopatterned surfaces.

PubMed

Gear, Christopher; Diest, Kenneth; Liberman, Vladimir; Rothschild, Mordechai

2015-01-26

The anchoring energy of liquid crystals was shown to be tunable by surface nanopatterning of periodic lines and spaces. Both the pitch and height were varied using hydrogen silsesquioxane negative tone electron beam resist, providing for flexibility in magnitude and spatial distribution of the anchoring energy. Using twisted nematic liquid crystal cells, it was shown that this energy is tunable over an order of magnitude. These results agree with a literature model which predicts the anchoring energy of sinusoidal grooves.

Freely-tunable broadband polarization rotator for terahertz waves

NASA Astrophysics Data System (ADS)

Peng, Ru-Wen; Fan, Ren-Hao; Zhou, Yu; Jiang, Shang-Chi; Xiong, Xiang; Huang, Xian-Rong; Wang, Mu

It is known that commercially-available terahertz (THz) emitters usually generate linearly polarized waves only along certain directions, but in practice, a polarization rotator that is capable of rotating the polarization of THz waves to any direction is particularly desirable and it will have various important applications. In this work, we demonstrate a freely tunable polarization rotator for broadband THz waves using a three-rotating-layer metallic grating structure, which can conveniently rotate the polarization of a linearly polarized THz wave to any desired direction with nearly perfect conversion efficiency. The device performance has been experimentally demonstrated by both THz transmission spectra and direct imaging. The polarization rotation originates from multi wave interference in the three-layer grating structure based on the scattering-matrix analysis. We can expect that this active broadband polarization rotator has wide applications in analytical chemistry, biology, communication technology, imaging, etc.. Reference: R. H. Fan, Y. Zhou, X. P. Ren, R. W. Peng, S. C. Jiang, D. H. Xu, X. Xiong, X. R. Huang, and Mu Wang, Advanced Materials 27,1201(2015). Freely-tunable broadband polarization rotator for terahertz waves.

Multilength Scale Patterning of Functional Layers by Roll-to-Roll Ultraviolet-Light-Assisted Nanoimprint Lithography.

PubMed

Leitgeb, Markus; Nees, Dieter; Ruttloff, Stephan; Palfinger, Ursula; Götz, Johannes; Liska, Robert; Belegratis, Maria R; Stadlober, Barbara

2016-05-24

Top-down fabrication of nanostructures with high throughput is still a challenge. We demonstrate the fast (>10 m/min) and continuous fabrication of multilength scale structures by roll-to-roll UV-nanoimprint lithography on a 250 mm wide web. The large-area nanopatterning is enabled by a multicomponent UV-curable resist system (JRcure) with viscous, mechanical, and surface properties that are tunable over a wide range to either allow for usage as polymer stamp material or as imprint resist. The adjustable elasticity and surface chemistry of the resist system enable multistep self-replication of structured resist layers. Decisive for defect-free UV-nanoimprinting in roll-to-roll is the minimization of the surface energies of stamp and resist, and the stepwise reduction of the stiffness from one layer to the next is essential for optimizing the reproduction fidelity especially for nanoscale features. Accordingly, we demonstrate the continuous replication of 3D nanostructures and the high-throughput fabrication of multilength scale resist structures resulting in flexible polyethylenetherephtalate film rolls with superhydrophobic properties. Moreover, a water-soluble UV-imprint resist (JRlift) is introduced that enables residue-free nanoimprinting in roll-to-roll. Thereby we could demonstrate high-throughput fabrication of metallic patterns with only 200 nm line width.

Tunable dual-band nearly perfect absorption based on a compound metallic grating

NASA Astrophysics Data System (ADS)

Gao, Hua; Zheng, Zhi-Yuan; Feng, Juan

2017-02-01

Traditional metallic gratings and novel metamaterials are two basic kinds of candidates for perfect absorption. Comparatively speaking, metallic grating is the preferred choice for the same absorption effect because it is structurally simpler and more convenient to fabricate. However, to date, most of the perfect absorption effects achieved based on metamaterials are also available using an metallic grating except the tunable dual(multi)-band perfect absorption. To fill this gap, in this paper, by adding subgrooves on the rear surface as well as inside the grating slits to a free-standing metallic grating, tunable dual-band perfect absorption is also obtained for the first time. The grooves inside the slits is to tune the frequency of the Cavity Mode(CM) resonance which enhances the transmission and suppresses the reflectance simultaneously. The grooves on the rear surface give rise to the phase resonance which not only suppresses the transmission but also reinforces the reflectance depression effect. Thus, when the phase resonance and the frequency tunable CM resonance occur together, transmission and reflection can be suppressed simultaneously, dual-band nearly perfect absorption with tunable frequencies is obtained. To our knowledge, this perfect absorption phenomenon is achieved for the first time in a designed metallic grating structure.

From Flexible and Stretchable Meta-Atom to Metamaterial: A Wearable Microwave Meta-Skin with Tunable Frequency Selective and Cloaking Effects

PubMed Central

Yang, Siming; Liu, Peng; Yang, Mingda; Wang, Qiugu; Song, Jiming; Dong, Liang

2016-01-01

This paper reports a flexible and stretchable metamaterial-based “skin” or meta-skin with tunable frequency selective and cloaking effects in microwave frequency regime. The meta-skin is composed of an array of liquid metallic split ring resonators (SRRs) embedded in a stretchable elastomer. When stretched, the meta-skin performs as a tunable frequency selective surface with a wide resonance frequency tuning range. When wrapped around a curved dielectric material, the meta-skin functions as a flexible “cloaking” surface to significantly suppress scattering from the surface of the dielectric material along different directions. We studied frequency responses of multilayer meta-skins to stretching in a planar direction and to changing the spacing between neighboring layers in vertical direction. We also investigated scattering suppression effect of the meta-skin coated on a finite-length dielectric rod in free space. This meta-skin technology will benefit many electromagnetic applications, such as frequency tuning, shielding, and scattering suppression. PMID:26902969

Far-field emission characteristics and linewidth measurements of surface micro-machined MEMS tunable VCSELs

NASA Astrophysics Data System (ADS)

Paul, Sujoy; Gierl, Christian; Gründl, Tobias; Zogal, Karolina; Meissner, Peter; Amann, Markus-Christian; Küppers, Franko

2013-03-01

In this paper, we demonstrate for the first time the far-field experimental results and the linewidth characteris- tics for widely tunable surface-micromachined micro-electro-mechanical system (MEMS) vertical-cavity surface- emitting lasers (VCSELs) operating at 1550 nm. The fundamental Gaussian mode emission is confirmed by optimizing the radius of curvature of top distributed Bragg reflector (DBR) membrane and by choosing an ap- propriate diameter of circular buried tunnel junctions (BTJs) so that only the fundamental Gaussian mode can sustain. For these VCSELs, a mode-hop free continuous tuning over 100 nm has already been demonstrated, which is achieved by electro-thermal tuning of the MEMS mirror. The fiber-coupled optical power of 2mW over the entire tuning range has been reported. The singlemode laser emission has more than 40 dB of side-mode suppression ratio (SMSR). The smallest linewidth achieved with these of MEMS tunable VCSELs is 98MHz which is one order of magnitude higher than that of fixed-wavelength VCSELs.

Anodic Aluminum Oxide (AAO) Membranes for Cellular Devices

NASA Astrophysics Data System (ADS)

Ventura, Anthony P.

Anodic Aluminum Oxide (AAO) membranes can be fabricated with a highly tunable pore structure making them a suitable candidate for cellular hybrid devices with single-molecule selectivity. The objective of this study was to characterize the cellular response of AAO membranes with varying pore sizes to serve as a proof-of-concept for an artificial material/cell synapse system. AAO membranes with pore diameters ranging from 34-117 nm were achieved via anodization at a temperature of -1°C in a 2.7% oxalic acid electrolyte. An operating window was established for this setup to create membranes with through-pore and disordered pore morphologies. C17.2 neural stem cells were seeded onto the membranes and differentiated via serum withdrawal. The data suggests a highly tunable correlation between AAO pore diameter and differentiated cell populations. Analysis of membranes before and after cell culture indicated no breakdown of the through-pore structure. Immunocytochemistry (ICC) showed that AAO membranes had increased neurite outgrowth when compared to tissue culture treated (TCT) glass, and neurite outgrowth varied with pore diameter. Additionally, lower neuronal percentages were found on AAO as compared to TCT glass; however, neuronal population was also found to vary with pore diameter. Scanning electron microscopy (SEM) and ICC images suggested the presence of a tissue-like layer with a mixed-phenotype population. AAO membranes appear to be an excellent candidate for cellular devices, but more work must be completed to understand the surface chemistry of the AAO membranes as it relates to cellular response.

Development of solid tunable optics for ultra-miniature imaging systems

NASA Astrophysics Data System (ADS)

Yongchao, Zou

This thesis focuses on the optimal design, fabrication and testing of solid tunable optics and exploring their applications in miniature imaging systems. It starts with the numerical modelling of such lenses, followed by the optimum design method and alignment tolerance analysis. A miniature solid tunable lens driven by a piezo actuator is then developed. To solve the problem of limited maximum optical power and tuning range in conventional lens designs, a novel multi-element solid tunable lens is proposed and developed. Inspired by the Alvarez principle, a novel miniature solid tunable dual-focus lens, which is designed using freeform surfaces and driven by one micro-electro-mechanical-systems (MEMS) rotary actuator, is demonstrated. To explore the applications of these miniature solid tunable lenses, a miniature adjustable-focus endoscope and one compact adjustable-focus camera module are developed. The adjustable-focus capability of these two miniature imaging systems is fully proved by electrically focusing targets placed at different positions.

Tunable surface plasmon resonance frequency of Au-Ag bimetallic asymmetric structure thin films in the UV and IR region

NASA Astrophysics Data System (ADS)

Hong, Ruijin; Ji, Jialin; Tao, Chunxian; Zhang, Dawei

2016-10-01

Au/ZnO/Ag sandwich structure films were fabricated by DC magnetron sputter at room temperature. The tunability of the surface plasmon resonance wavelength was realized by varying the thickness of ZnO thin film. The effects of ZnO layer on the optical properties of Au/ZnO/Au thin films were investigated by optical absorption and Raman scattering measurements. It has been found that both the surface plasmon resonance frequency and SERS can be controlled by adjusting the thickness of ZnO layer due to the coupling of metal and semiconductor.

Synthesis of polybenzoxazine based nitrogen-rich porous carbons for carbon dioxide capture

NASA Astrophysics Data System (ADS)

Wan, Liu; Wang, Jianlong; Feng, Chong; Sun, Yahui; Li, Kaixi

2015-04-01

Nitrogen-rich porous carbons (NPCs) were synthesized from 1,5-dihydroxynaphthalene, urea, and formaldehyde based on benzoxazine chemistry by a soft-templating method with KOH chemical activation. They possess high surface areas of 856.8-1257.8 m2 g-1, a large pore volume of 0.15-0.65 cm3 g-1, tunable pore structure, high nitrogen content (5.21-5.32 wt%), and high char yields. The amount of the soft-templating agent F127 has multiple influences on the textural and chemical properties of the carbons, affecting the surface area and pore structure, impacting the compositions of nitrogen species and resulting in an improvement of the CO2 capture performance. At 1 bar, high CO2 uptake of 4.02 and 6.35 mmol g-1 at 25 and 0 °C was achieved for the sample NPC-2 with a molar ratio of F127 : urea = 0.010 : 1. This can be attributed to its well-developed micropore structure and abundant pyridinic nitrogen, pyrrolic nitrogen and pyridonic nitrogen functionalities. The sample NPC-2 also exhibits a remarkable selectivity for CO2/N2 separation and a fast adsorption/desorption rate and can be easily regenerated. This suggests that the polybenzoxazine-based NPCs are desirable for CO2 capture because of possessing a high micropore surface area, a large micropore volume, appropriate pore size distribution, and a large number of basic nitrogen functionalities.Nitrogen-rich porous carbons (NPCs) were synthesized from 1,5-dihydroxynaphthalene, urea, and formaldehyde based on benzoxazine chemistry by a soft-templating method with KOH chemical activation. They possess high surface areas of 856.8-1257.8 m2 g-1, a large pore volume of 0.15-0.65 cm3 g-1, tunable pore structure, high nitrogen content (5.21-5.32 wt%), and high char yields. The amount of the soft-templating agent F127 has multiple influences on the textural and chemical properties of the carbons, affecting the surface area and pore structure, impacting the compositions of nitrogen species and resulting in an improvement of the CO2 capture performance. At 1 bar, high CO2 uptake of 4.02 and 6.35 mmol g-1 at 25 and 0 °C was achieved for the sample NPC-2 with a molar ratio of F127 : urea = 0.010 : 1. This can be attributed to its well-developed micropore structure and abundant pyridinic nitrogen, pyrrolic nitrogen and pyridonic nitrogen functionalities. The sample NPC-2 also exhibits a remarkable selectivity for CO2/N2 separation and a fast adsorption/desorption rate and can be easily regenerated. This suggests that the polybenzoxazine-based NPCs are desirable for CO2 capture because of possessing a high micropore surface area, a large micropore volume, appropriate pore size distribution, and a large number of basic nitrogen functionalities. Electronic supplementary information (ESI) available: Elemental and XPS analyses and XPS peak positions and relative content of N species in the NPCs. See DOI: 10.1039/c4nr07409b

Film-Evaporation MEMS Tunable Array for Picosat Propulsion and Thermal Control

NASA Technical Reports Server (NTRS)

Alexeenko, Alina; Cardiff, Eric; Martinez, Andres; Petro, Andrew

2015-01-01

The Film-Evaporation MEMS Tunable Array (FEMTA) concept for propulsion and thermal control of picosats exploits microscale surface tension effect in conjunction with temperature- dependent vapor pressure to realize compact, tunable and low-power thermal valving system. The FEMTA is intended to be a self-contained propulsion unit requiring only a low-voltage DC power source to operate. The microfabricated thermal valving and very-high-integration level enables fast high-capacity cooling and high-resolution, low-power micropropulsion for picosats that is superior to existing smallsat micropropulsion and thermal management alternatives.

Controlling the Photophysical Properties of Semiconductor Quantum Dot Arrays by Strategically Altering Their Surface Chemistry

NASA Astrophysics Data System (ADS)

Marshall, Ashley R.

Semiconductor quantum dots (QDs) are interesting materials that, after less than 40 years of research, are used in commercial products. QDs are now found in displays, such as Samsung televisions and the Kindle Fire, and have applications in lighting, bio-imaging, quantum computing, and photovoltaics. They offer a large range of desirable properties: a controllable band gap, solution processability, controlled energy levels, and are currently the best materials for multiple exciton generation. The tunable optoelectronic properties of QDs can be controlled using size, shape, composition, and surface treatments--as shown here. Due to the quasi-spherical shape of QDs the surface to volume ratio is high, i.e. many of the constituent atoms are found on the QD surface. This makes QDs highly sensitive to surface chemistry modifications. This thesis encompasses the effects of surface treatments for QDs of two semiconducting materials: lead chalcogenides and CsPbI3. Our group developed a new synthetic technique for lead chalcogenide QDs via the cation exchange of cadmium chalcogenides. An in-depth chemical analysis is paired with optical and electrical studies and we find that metal halide residue contributes to the oxidative stability and decreased trap state density in cation-exchanged PbS QDs. We exploit these properties to make air-stable QD photovoltaic devices from both PbS and PbSe QD materials. Beyond the effects of residual atoms left from the synthetic technique, I investigated how to controllably add atoms onto the surface of QDs. I found that by introducing metal halides as a post-treatment in an electronically coupled array I am able to control the performance parameters in QD photovoltaic devices. These treatments fully infiltrate the assembled film, even under short exposure times and allow me to add controlled quantities of surface atoms to study their effects on film properties and photovoltaic device performance. Finally, I sought to apply the knowledge of the lead chalcogenide QD surfaces to produce QD photovoltaics from a new material: CsPbI3. I fabricated the first perovskite QD photovoltaic devices and using similar treatment methods as the lead chalcogenide QD arrays, I am able to influence the photophysical properties of CsPbI3 QD arrays.

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

NASA Astrophysics Data System (ADS)

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

PubMed Central

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-01-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g−1) and large pore volumes (up to 0.90 cm3 g−1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4′-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405−; the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane. PMID:26062725

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers.

PubMed

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-11

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m(2) g(-1)) and large pore volumes (up to 0.90 cm(3) g(-1)). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4'-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O40(5-); the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

FEL for the polymer processing industries

NASA Astrophysics Data System (ADS)

Kelley, Michael J.

1997-05-01

Polymers are everywhere in modern life because of their unique combination of end-use functionalities, ease of processing, recycling potential and modest cost. The physical and economic scope of the infrastructure committed to present polymers makes the introduction of entirely new chemistry unlikely. Rather, the breadth of commercial offerings more likely to shrink in the face of the widening mandate for recycling, especially of packaging. Improved performance and new functionality must therefore come by routes such as surface modification. However they must come with little environmental impact and at painfully low cost. Processing with strongly absorbed light offers unique advantages. The journal and patent literatures disclose a number of examples of benefits that can be achieved, principally by use of excimer lasers or special UV lamps. Examples of commercialization are few, however, because of the unit cost and maximum scale of existing light sources. A FEL, however, offers unique advantages: tunability to the optimum wavelength, potential for scale up to high average power, and a path to attractively low unit cost of light. A business analysis of prospective applications defines the technical and economic requirements a FEL for polymer surface processing must meet. These are compared to FEL technology as it now stands and as it is envisioned.

Solvent-induced synthesis of nitrogen-doped hollow carbon spheres with tunable surface morphology for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Feng; Yuan, Ren-Lu; Zhang, Ning; Ke, Chang-Ce; Ma, Shao-Xia; Zhang, Ru-Liang; Liu, Lei

2018-04-01

Nitrogen doped hollow carbon spheres (NHCSs) with tunable surface morphology have been prepared through one-pot carbonization method by using melamine-formaldehyde spheres as template and resorcinol-based resin as carbon precursor in ethanol-water solution. Well-dispersed NHCSs with particle size of 800 nm were obtained and the surface of NHCSs turn from smooth to tough, wrinkled, and finally concave by increasing the ethanol concentration. The fabricated NHCSs possessed high nitrogen content (3.99-4.83%) and hierarchical micro-dual mesoporous structure with surface area range of 265-405 m2 g-1 and total pore volume of 0.18-0.29 cm3 g-1, which contributed to high specific capacitance, excellent rate capability and long cycle life.

Seed-mediated growth of Au nanorings with size control on Pd ultrathin nanosheets and their tunable surface plasmonic properties

NASA Astrophysics Data System (ADS)

Wang, Wenxing; Yan, Yucong; Zhou, Ning; Zhang, Hui; Li, Dongsheng; Yang, Deren

2016-02-01

Nanorings made of noble metals such as Au and Ag have attracted particular interest in plasmonic properties since they allow remarkable tunability of plasmon resonance wavelengths associated with their unique structural features. Unfortunately, most of the syntheses for Au nanorings involve complex procedures and/or require highly specialized and expensive facilities. Here, we report a seed-mediated approach for selective deposition of Au nanorings on the periphery of Pd seeds with the structure of an ultrathin nanosheet through the island growth mode. In combination with selective etching of Pd nanosheets, Au nanorings are eventually produced. We can control the outer diameter and wall thickness of the nanorings by simply varying the size of the Pd nanosheets and reaction time. By taking the advantage of this size controllability, the nanorings show tunable surface plasmonic properties in the near infrared (NIR) region arising from both the in-plane dipole and face resonance modes. Owing to their good surface plasmonic properties, the nanorings show substantially enhanced surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G, and are therefore confirmed as good SERS substrates to detect trace amounts of molecules.Nanorings made of noble metals such as Au and Ag have attracted particular interest in plasmonic properties since they allow remarkable tunability of plasmon resonance wavelengths associated with their unique structural features. Unfortunately, most of the syntheses for Au nanorings involve complex procedures and/or require highly specialized and expensive facilities. Here, we report a seed-mediated approach for selective deposition of Au nanorings on the periphery of Pd seeds with the structure of an ultrathin nanosheet through the island growth mode. In combination with selective etching of Pd nanosheets, Au nanorings are eventually produced. We can control the outer diameter and wall thickness of the nanorings by simply varying the size of the Pd nanosheets and reaction time. By taking the advantage of this size controllability, the nanorings show tunable surface plasmonic properties in the near infrared (NIR) region arising from both the in-plane dipole and face resonance modes. Owing to their good surface plasmonic properties, the nanorings show substantially enhanced surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G, and are therefore confirmed as good SERS substrates to detect trace amounts of molecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08613b

Dimensional and compositional change of 1D chalcogen nanostructures leading to tunable localized surface plasmon resonances.

PubMed

Min, Yuho; Seo, Ho Jun; Choi, Jong-Jin; Hahn, Byung-Dong; Moon, Geon Dae

2018-08-24

As part of the oxygen family, chalcogen (Se, Te) nanostructures have been considered important elements for various practical fields and further exploited to constitute metal chalcogenides for each targeted application. Here, we report a controlled synthesis of well-defined one-dimensional chalcogen nanostructures such as nanowries, nanorods, and nanotubes by controlling reduction reaction rate to fine-tune the dimension and composition of the products. Tunable optical properties (localized surface plasmon resonances) of these chalcogen nanostructures are observed depending on their morphological, dimensional, and compositional variation.

Enhanced tunability of magnetron sputtered Ba0.5Sr0.5TiO3 thin films on c-plane sapphire substrates

NASA Astrophysics Data System (ADS)

Fardin, E. A.; Holland, A. S.; Ghorbani, K.; Reichart, P.

2006-07-01

Thin films of Ba0.5Sr0.5TiO3 (BST) were deposited on c-plane (0001) sapphire by rf magnetron sputtering and investigated by complementary materials analysis methods. Microwave properties of the films, including tunability and Q factor were measured from 1to20GHz by patterning interdigital capacitors (IDCs) on the film surface. The tunability is correlated with texture, strain, and grain size in the deposited films. An enhanced capacitance tunability of 56% at a bias field of 200kV/cm and total device Q of more than 15 (up to 20GHz) were achieved following postdeposition annealing at 900°C.

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry.

PubMed

Ryder, Christopher R; Wood, Joshua D; Wells, Spencer A; Yang, Yang; Jariwala, Deep; Marks, Tobin J; Schatz, George C; Hersam, Mark C

2016-06-01

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)-a layered two-dimensional semiconductor-exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

NASA Astrophysics Data System (ADS)

Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

2016-06-01

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

Polymeric Janus Nanoparticles: Recent Advances in Synthetic Strategies, Materials Properties, and Applications.

PubMed

Fan, Xiaoshan; Yang, Jing; Loh, Xian Jun; Li, Zibiao

2018-06-13

Polymeric Janus nanoparticles with two sides of incompatible chemistry have received increasing attention due to their tunable asymmetric structure and unique material characteristics. Recently, with the rapid progress in controlled polymerization combined with novel fabrication techniques, a large array of functional polymeric Janus particles are diversified with sophisticated architecture and applications. In this review, the most recently developed strategies for controlled synthesis of polymeric Janus nanoparticles with well-defined size and complex superstructures are summarized. In addition, the pros and cons of each approach in mediating the anisotropic shapes of polymeric Janus particles as well as their asymmetric spatial distribution of chemical compositions and functionalities are discussed and compared. Finally, these newly developed structural nanoparticles with specific shapes and surface functions orientated applications in different domains are also discussed, followed by the perspectives and challenges faced in the further advancement of polymeric Janus nanoparticles as high performance materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced mobility CsPbI3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells

PubMed Central

Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.; Harvey, Steven P.; Ciesielski, Peter N.; Wheeler, Lance M.; Schulz, Philip; Lin, Lih Y.; Beard, Matthew C.; Luther, Joseph M.

2017-01-01

We developed lead halide perovskite quantum dot (QD) films with tuned surface chemistry based on A-site cation halide salt (AX) treatments. QD perovskites offer colloidal synthesis and processing using industrially friendly solvents, which decouples grain growth from film deposition, and at present produce larger open-circuit voltages (VOC’s) than thin-film perovskites. CsPbI3 QDs, with a tunable bandgap between 1.75 and 2.13 eV, are an ideal top cell candidate for all-perovskite multijunction solar cells because of their demonstrated small VOC deficit. We show that charge carrier mobility within perovskite QD films is dictated by the chemical conditions at the QD-QD junctions. The AX treatments provide a method for tuning the coupling between perovskite QDs, which is exploited for improved charge transport for fabricating high-quality QD films and devices. The AX treatments presented here double the film mobility, enabling increased photocurrent, and lead to a record certified QD solar cell efficiency of 13.43%. PMID:29098184

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition

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

Bielinski, Ashley R.; Boban, Mathew; He, Yang

2017-01-24

A method for tunable control of geometry in hyperbranched ZnO nanowire (NW) systems is reported, which enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition (ALD) was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angle for a variety ofmore » liquids, which is supported by mathematical models of structural superomniphobicity. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles, water: 172°/170°, hexadecane: 166°/156°, octane: 162°/145°, and heptane: 160°/130°. Low surface tension liquids were shown to bounce off the surface from a height of 7 cm without breaking through and wetting. This approach demonstrates the power of ALD as an enabling technique for hierarchical materials by design, spanning the macro, micro, and nano length scales.« less

Fabrication of a nano-cone array on a p-GaN surface for enhanced light extraction efficiency from GaN-based tunable wavelength LEDs.

PubMed

Soh, C B; Wang, B; Chua, S J; Lin, Vivian K X; Tan, Rayson J N; Tripathy, S

2008-10-08

We report on the fabrication of a nano-cone structured p-GaN surface for enhanced light extraction from tunable wavelength light emitting diodes (LEDs). Prior to p-contact metallization, self-assembled colloidal particles are deposited and used as a mask for plasma etching to create nano-cone structures on the p-GaN layer of LEDs. A well-defined periodic nano-cone array, with an average cone diameter of 300 nm and height of 150 nm, is generated on the p-GaN surface. The photoluminescence emission intensity recorded from the regions with the nano-cone array is increased by two times as compared to LEDs without surface patterning. The light output power from the LEDs with surface nano-cones shows significantly higher electroluminescence intensity at an injection current of 70 mA. This is due to the internal multiple scattering of light from the nano-cone sidewalls. Furthermore, we have shown that with an incorporation of InGaN nanostructures in the quantum well, the wavelength of these surface-patterned LEDs can be tuned from 517 to 488 nm with an increase in the injection current. This methodology may serve as a practical approach to increase the light extraction efficiency from wavelength tunable LEDs.

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

Zhuang, Jinda; Ju, Y. Sungtaek, E-mail: just@seas.ucla.edu

One major challenge in incorporating flexible electronics or optoelectronics on curved surfaces is the requirement of significant stretchability. We report a tunable platform for incorporating flexible and yet non-stretching device layers on a hemisphere. In this configuration, an array of planar petals contractively maps onto the surface of an inflatable hemisphere through elastocapillary interactions mediated by an interface liquid. A mechanical model is developed to elucidate the dependence of the conformality of the petal structures on their elastic modulus and thickness and the liquid surface tension. The modeling results are validated against experimental results obtained using petal structures of differentmore » thicknesses, restoring elastic spring elements of different spring constants, and liquids with different surface tension coefficients. Our platform will enable facile integration of non-stretching electronic and optoelectronic components prepared using established planar fabrication techniques on tunable hemispherical surfaces.« less

Simulation, fabrication, and characterization of a tunable electrowetting-based lens with a wedge-shaped PDMS dielectric layer.

PubMed

Moghaddam, Mohammadreza Salehi; Latifi, H; Shahraki, Hamidreza; Cheri, Mohammad Sadegh

2015-04-01

Microlenses with tunable focal length have wide applications in optofluidic devices. This work presents a numerical and experimental investigation on a tunable electrowetting-based concave lens. Optical properties such as focal length of the lens and visibility of images were investigated numerically and experimentally. A finite element analysis and a ZEMAX simulation were used for determination of surface profile and focal length of the lens. The results show that the theoretical surface profile and focal length of the lens are in good agreement with the experimental ones. The lens has a wide tuning focal length equal to 6.5 (cm). Because the polydimethylsiloxane (PDMS) layer is wedge shaped (as both the dielectric and hydrophobic layers), lower applied voltage is needed. A commercial program was used to find the focal length of the lens from maximum visibility value by tuning the applied voltage.

Deconvoluting the effects of surface chemistry and nanoscale topography: Pseudomonas aeruginosa biofilm nucleation on Si-based substrates.

PubMed

Zhang, Jing; Huang, Jinglin; Say, Carmen; Dorit, Robert L; Queeney, K T

2018-06-01

The nucleation of biofilms is known to be affected by both the chemistry and topography of the underlying substrate, particularly when topography includes nanoscale (<100 nm) features. However, determining the role of topography vs. chemistry is complicated by concomitant variation in both as a result of typical surface modification techniques. Analyzing the behavior of biofilm-forming bacteria exposed to surfaces with systematic, independent variation of both topography and surface chemistry should allow differentiation of the two effects. Silicon surfaces with reproducible nanotopography were created by anisotropic etching in deoxygenated water. Surface chemistry was varied independently to create hydrophilic (OH-terminated) and hydrophobic (alkyl-terminated) surfaces. The attachment and proliferation of Psuedomonas aeruginosa to these surfaces was characterized over a period of 12 h using fluorescence and confocal microscopy. The number of attached bacteria as well as the structural characteristics of the nucleating biofilm were influenced by both surface nanotopography and surface chemistry. In general terms, the presence of both nanoscale features and hydrophobic surface chemistry enhance bacterial attachment and colonization. However, the structural details of the resulting biofilms suggest that surface chemistry and topography interact differently on each of the four surface types we studied. Copyright © 2018 Elsevier Inc. All rights reserved.

Wavelength-Tunable IR Detector based on Suspended Bilayer Graphene Micro Ribbons

DTIC Science & Technology

2013-11-05

Substrates: Reduced Etching via Suppressed Catalytic Hydrogenation Using C2H4,” Chemistry of Materials , DOI : 10.1021/cm402052z (2013) 3. K. Kumar...studied the lesser known photophysics in CVD material . To this end we designed, fabricated, and characterized in Year One a device with suspended...optimization, we have discovered a new growth mode of two-lobed symmetrical curvilinear graphene domains. After optimization the CVD material quality was

Rhodium complexes as therapeutic agents.

PubMed

Ma, Dik-Lung; Wang, Modi; Mao, Zhifeng; Yang, Chao; Ng, Chan-Tat; Leung, Chung-Hang

2016-02-21

The landscape of inorganic medicinal chemistry has been dominated by the investigation of platinum, and to a lesser extent ruthenium, complexes over the past few decades. Recently, complexes based on other metal centers such as rhodium have attracted attention due to their tunable chemical and biological properties as well as distinct mechanisms of action. This perspective highlights recent examples of rhodium complexes that show diverse biological activities against various targets, including enzymes and protein-protein interactions.

Superhydrophobic photosensitizers. Mechanistic studies of (1)O2 generation in the plastron and solid/liquid droplet interface.

PubMed

Aebisher, David; Bartusik, Dorota; Liu, Yang; Zhao, Yuanyuan; Barahman, Mark; Xu, QianFeng; Lyons, Alan M; Greer, Alexander

2013-12-18

We describe here a physical-organic study of the first triphasic superhydrophobic sensitizer for photooxidations in water droplets. Control of synthetic parameters enables the mechanistic study of "borderline" two- and three-phase superhydrophobic sensitizer surfaces where (1)O2 is generated in compartments that are wetted, partially wetted, or remain dry in the plastron (i.e., air layer beneath the droplet). The superhydrophobic surface is synthesized by partially embedding silicon phthalocyanine (Pc) sensitizing particles to specific locations on polydimethylsiloxane (PDMS) posts printed in a square array (1 mm tall posts on 0.5 mm pitch). In the presence of red light and oxygen, singlet oxygen is formed on the superhydrophobic surface and reacts with 9,10-anthracene dipropionate dianion (1) within a freestanding water droplet to produce an endoperoxide in 54-72% yields. Control of the (1)O2 chemistry was achieved by the synthesis of superhydrophobic surfaces enriched with Pc particles either at the PDMS end-tips or at PDMS post bases. Much of the (1)O2 that reacts with anthracene 1 in the droplets was generated by the sensitizer "wetted" at the Pc particle/water droplet interface and gave the highest endoperoxide yields. About 20% of the (1)O2 can be introduced into the droplet from the plastron. The results indicate that the superhydrophobic sensitizer surface offers a unique system to study (1)O2 transfer routes where a balance of gas and liquid contributions of (1)O2 is tunable within the same superhydrophobic surface.

Superstretchable, Self-Healing Polymeric Elastomers with Tunable Properties

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

Cao, Peng-Fei; Li, Bingrui; Hong, Tao

Utilization of self-healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self-healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. In this paper, a series of urea functionalized poly(dimethyl siloxane)-based elastomers (U-PDMS-Es) are reported with extremely high stretchability, self-healing mechanical properties, and recoverable gas-separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross-linker offers tunable mechanical properties of the obtained U-PDMS-Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elasticmore » recovery. The U-PDMS-Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain-dependent elastic recovery behavior of U-PDMS-Es is also studied. After mechanical damage, the U-PDMS-Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. Lastly, the U-PDMS-Es are also demonstrated to exhibit recoverable gas-separation functionality with retained permeability/selectivity after being damaged.« less

Superstretchable, Self-Healing Polymeric Elastomers with Tunable Properties

DOE PAGES

Cao, Peng-Fei; Li, Bingrui; Hong, Tao; ...

2018-04-16

Utilization of self-healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self-healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. In this paper, a series of urea functionalized poly(dimethyl siloxane)-based elastomers (U-PDMS-Es) are reported with extremely high stretchability, self-healing mechanical properties, and recoverable gas-separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross-linker offers tunable mechanical properties of the obtained U-PDMS-Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elasticmore » recovery. The U-PDMS-Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain-dependent elastic recovery behavior of U-PDMS-Es is also studied. After mechanical damage, the U-PDMS-Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. Lastly, the U-PDMS-Es are also demonstrated to exhibit recoverable gas-separation functionality with retained permeability/selectivity after being damaged.« less

An experimental and theoretical investigation on the optical and photocatalytic properties of ZnS nanoparticles

NASA Astrophysics Data System (ADS)

La Porta, F. A.; Nogueira, A. E.; Gracia, Lourdes; Pereira, W. S.; Botelho, G.; Mulinari, T. A.; Andrés, Juan; Longo, E.

2017-04-01

From the viewpoints of materials chemistry and physical chemistry, crystal structure directly determines the electronic structure and furthermore their optical and photocatalytic properties. Zinc sulfide (ZnS) nanoparticles (NPs) with tunable photoluminescence (PL) emission and high photocatalytic activity have been obtained by means of a microwave-assisted solvothermal (MAS) method using different precursors (i.e., zinc nitrate (ZN), zinc chloride (ZC), or zinc acetate (ZA)). The morphologies, optical properties, and electronic structures of the as-synthesized ZnS NPs were characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) isotherms for N2 adsorption/desorption processes, diffuse reflectance spectroscopy (DRS), PL measurements and theoretical calculations. Density functional theory calculations were used to determine the geometries and electronic properties of bulk wurtzite (WZ) ZnS NPs and their (0001), (101 ̅0), (112 ̅0), (101 ̅1), and (101 ̅2) surfaces. The dependence of the PL emission behavior of ZnS NPs on the precursor was elucidated by examining the energy band structure and density of states. The method for degradation of Rhodamine B (RhB) was used as a probe reaction to investigate the photocatalytic activity of the as-Synthesised ZnS NPs under UV light irradiation. The PL behavior as well as photocatalytic activities of ZnS NPs were attributed to specific features of the structural and electronic structures. Increased photocatalytic degradation was observed for samples synthesized using different precursors in the following order: ZA

Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.

PubMed

Sohail, Manzar; De Marco, Roland; Jarolímová, Zdeňka; Pawlak, Marcin; Bakker, Eric; He, Ning; Latonen, Rose-Marie; Lindfors, Tom; Bobacka, Johan

2015-09-29

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.

Fabrication of tunable plasmonic 3D nanostructures for SERS applications

NASA Astrophysics Data System (ADS)

Ozbay, Ayse; Yuksel, Handan; Solmaz, Ramazan; Kahraman, Mehmet

2016-03-01

Surface-enhanced Raman scattering (SERS) is a powerful technique used for characterization of biological and nonbiological molecules and structures. Since plasmonic properties of the nanomaterials is one of the most important factor influencing SERS activity, tunable plasmonic properties (wavelength of the surface plasmons and magnitude of the electromagnetic field generated on the surface) of SERS substrates are crucial in SERS studies. SERS enhancement can be maximized by controlling of plasmonic properties of the nanomaterials. In this study, a novel approach to fabricate tunable plasmonic 3D nanostructures based on combination of soft lithography and nanosphere lithography is studied. Spherical latex particles having different diameters are uniformly deposited on glass slides with convective assembly method. The experimental parameters for the convective assembly are optimized by changing of latex spheres concentration, stage velocity and latex particles volume placed between to two glass slides that staying with a certain angle to each other. Afterwards, polydimethylsiloxane (PDMS) elastomer is poured on the deposited latex particles and cured to obtain nanovoids on the PDMS surfaces. The diameter and depth of the nanovoids on the PDMS surface are controlled by the size of the latex particles. Finally, fabricated nanovoid template on the PDMS surfaces are filled with the silver coating to obtain plasmonic 3D nanostructures. Characterization of the fabricated surfaces is performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). SERS performance of fabricated 3D plasmonic nanostructures will be evaluated using Raman reporter molecules.

Tunable random lasing behavior in plasmonic nanostructures

NASA Astrophysics Data System (ADS)

Yadav, Ashish; Zhong, Liubiao; Sun, Jun; Jiang, Lin; Cheng, Gary J.; Chi, Lifeng

2017-01-01

Random lasing is desired in plasmonics nanostructures through surface plasmon amplification. In this study, tunable random lasing behavior was observed in dye molecules attached with Au nanorods (NRs), Au nanoparticles (NPs) and Au@Ag nanorods (NRs) respectively. Our experimental investigations showed that all nanostructures i.e., Au@AgNRs, AuNRs & AuNPs have intensive tunable spectral effects. The random lasing has been observed at excitation wavelength 532 nm and varying pump powers. The best random lasing properties were noticed in Au@AgNRs structure, which exhibits broad absorption spectrum, sufficiently overlapping with that of dye Rhodamine B (RhB). Au@AgNRs significantly enhance the tunable spectral behavior through localized electromagnetic field and scattering. The random lasing in Au@AgNRs provides an efficient coherent feedback for random lasers.

Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

DOE PAGES

Welz, Oliver; Savee, John D.; Osborn, David L.; ...

2014-07-04

The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH 3) 2CCHCH 2OH) and isoprenol (3-methyl-3-buten-1-ol, CH 2C(CH 3)CH 2CH 2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant productsmore » arising from QOOH chemistry are observed. These results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O 2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O 2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O 2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO 2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

Superconducting selenides intercalated with organic molecules: synthesis, crystal structure, electric and magnetic properties, superconducting properties, and phase separation in iron based-chalcogenides and hybrid organic-inorganic superconductors

NASA Astrophysics Data System (ADS)

Krzton-Maziopa, Anna; Pesko, Edyta; Puzniak, Roman

2018-06-01

Layered iron-based superconducting chalcogenides intercalated with molecular species are the subject of intensive studies, especially in the field of solid state chemistry and condensed matter physics, because of their intriguing chemistry and tunable electric and magnetic properties. Considerable progress in the research, revealing superconducting inorganic–organic hybrid materials with transition temperatures to superconducting state, T c, up to 46 K, has been brought in recent years. These novel materials are synthesized by low-temperature intercalation of molecular species, such as solvates of alkali metals and nitrogen-containing donor compounds, into layered FeSe-type structure. Both the chemical nature as well as orientation of organic molecules between the layers of inorganic host, play an important role in structural modifications and may be used for fine tuning of superconducting properties. Furthermore, a variety of donor species compatible with alkali metals, as well as the possibility of doping also in the host structure (either on Fe or Se sites), makes this system quite flexible and gives a vast array of new materials with tunable electric and magnetic properties. In this review, the main aspects of intercalation chemistry are discussed with a particular attention paid to the influence of the unique nature of intercalating species on the crystal structure and physical properties of the hybrid inorganic–organic materials. To get a full picture of these materials, a comprehensive description of the most effective chemical and electrochemical methods, utilized for synthesis of intercalated species, with critical evaluation of their strong and weak points, related to feasibility of synthesis, phase purity, crystal size and morphology of final products, is included as well.

In vitro behavior of human mesenchymal stem cells on poly(N-isopropylacrylamide) based biointerfaces obtained by matrix assisted pulsed laser evaporation

NASA Astrophysics Data System (ADS)

Icriverzi, Madalina; Rusen, Laurentiu; Sima, Livia Elena; Moldovan, Antoniu; Brajnicov, Simona; Bonciu, Anca; Mihailescu, Natalia; Dinescu, Maria; Cimpean, Anisoara; Roseanu, Anca; Dinca, Valentina

2018-05-01

The use of smart coatings with tunable characteristics in bioengineering fields is directly correlated with the surface chemical and topographical properties, the method of preparation, and also with the type of cells implied for the specific application. In this work, a versatile surface modification technique based on the use of lasers (Matrix-Assisted Pulsed Laser Evaporation (MAPLE)) was used to yield poly(N-isopropylacrylamide) (pNIPAM) and its derivatives (amine, azide and amide terminated pNIPAM) functional and termoresponsive thin films. Surface properties of pNIPAM and its derivative films such as morphology, roughness and hydrophobic/hydrophilic character, as well as the thermoresponsive capacity were investigated by atomic force microscopy and contact angle measurements. The chemical characteristics of the pNIPAM based thin films were analysed by Fourier Transform Infrared Spectroscopy (FTIR). The chemical functionality was kept for all the samples obtained by MAPLE and the thermoresponse was demonstrated by the change in the contact angle and thickness values when the temperature was shifted from 37 °C to 24 °C for all the materials tested, with a smaller change for maleimide terminated pNIPAM. Biological assays performed in vitro (fluorescence microscopy and Scanning Electron Microscopy (SEM)) confirmed the conditioning of the early mesenchymal stem cell (MSC) growth by specific chemistry of the coatings. The cell imaging analysis revealed no cytotoxic effect of pNIPAM surfaces irrespective of type of functionalization. An increased proliferation rate of the cells grown on pNIPAM-azide surfaces and a lower cell density on pNIPAM-maleimide surfaces compared to the pNIPAM surfaces was observed, which can direct their use to potential surfaces in regenerative medicine approaches.

Plateau-Rayleigh Crystal Growth of Nanowire Heterostructures: Strain-Modified Surface Chemistry and Morphological Control in One, Two, and Three Dimensions.

PubMed

Day, Robert W; Mankin, Max N; Lieber, Charles M

2016-04-13

One-dimensional (1D) structures offer unique opportunities for materials synthesis since crystal phases and morphologies that are difficult or impossible to achieve in macroscopic crystals can be synthesized as 1D nanowires (NWs). Recently, we demonstrated one such phenomenon unique to growth on a 1D substrate, termed Plateau-Rayleigh (P-R) crystal growth, where periodic shells develop along a NW core to form diameter-modulated NW homostructures with tunable morphologies. Here we report a novel extension of the P-R crystal growth concept with the synthesis of heterostructures in which Ge (Si) is deposited on Si (Ge) 1D cores to generate complex NW morphologies in 1, 2, or 3D. Depositing Ge on 50 nm Si cores with a constant GeH4 pressure yields a single set of periodic shells, while sequential variation of GeH4 pressure can yield multimodulated 1D NWs with two distinct sets of shell periodicities. P-R crystal growth on 30 nm cores also produces 2D loop structures, where Ge (Si) shells lie primarily on the outside (inside) of a highly curved Si (Ge) core. Systematic investigation of shell morphology as a function of growth time indicates that Ge shells grow in length along positive curvature Si cores faster than along straight Si cores by an order of magnitude. Short Ge deposition times reveal that shells develop on opposite sides of 50 and 100 nm Si cores to form straight 1D morphologies but that shells develop on the same side of 20 nm cores to produce 2D loop and 3D spring structures. These results suggest that strain mediates the formation of 2 and 3D morphologies by altering the NW's surface chemistry and that surface diffusion of heteroatoms on flexible freestanding 1D substrates can facilitate this strain-mediated mechanism.

Electrodeposition on nanofibrous polymer scaffolds: Rapid mineralization, tunable calcium phosphate composition and topography

PubMed Central

He, Chuanglong; Xiao, Guiyong; Jin, Xiaobing; Sun, Chenghui; Ma, Peter X.

2011-01-01

We developed a straightforward, fast, and versatile technique to fabricate mineralized nanofibrous polymer scaffolds for bone regeneration in this work. Nanofibrous poly(l-lactic acid) scaffolds were fabricated using both electrospinning and phase separation techniques. An electrodeposition process was designed to deposit calcium phosphate on the nanofibrous scaffolds. Such scaffolds contain a high quality mineral coating on the fiber surface with tunable surface topography and chemical composition by varying the processing parameters, which can mimic the composition and structure of natural bone extracellular matrix and provide a more biocompatible interface for bone regeneration. PMID:21673827

Electronically controlled spoof localized surface plasmons on the corrugated ring with a shorting pin

NASA Astrophysics Data System (ADS)

Zhang, Chao; Zhou, Yong Jin

2018-07-01

We have demonstrated that spoof localized surface plasmons (LSPs) can be controlled by loading a shorting pin into the corrugated ring resonator in the microwave and terahertz (THz) frequencies. Electronical switchability and tunability of spoof LSPs have been achieved by mounting Schottky barrier diodes and varactor diodes across the slit around the shorting pin in the ground plane. An electronically tunable band-pass filter has been demostrated in the microwave frequencies. Such electronically controlled spoof LSPs devices can find more applications for highly integrated plasmonic circuits in microwave and THz frequencies.

Thermal annealing induced the tunable optical properties of silver thin films with linear variable thickness

NASA Astrophysics Data System (ADS)

Hong, Ruijin; Shao, Wen; Ji, Jialin; Tao, Chunxian; Zhang, Dawei

2018-06-01

Silver thin films with linear variable thickness were deposited at room temperature. The corresponding tunability of optical properties and Raman scattering intensity were realized by thermal annealing process. With the thickness increasing, the topography of as-annealed silver thin films was observed to develop from discontinued nanospheres into continuous structure with a redshift of the surface plasmon resonance wavelength in visible region. Both the various nanosphere sizes and states of aggregation of as-annealed silver thin films contributed to significantly increasing the sensitivity of surface enhanced Raman scattering (SERS).

Tunable, superconducting, surface-emitting teraherz source

DOEpatents

Welp, Ulrich [Lisle, IL; Koshelev, Alexei E [Bolingbrook, IL; Gray, Kenneth E [Evanston, IL; Kwok, Wai-Kwong [Evanston, IL; Vlasko-Vlasov, Vitalii [Downers Grove, IL

2009-10-27

A compact, solid-state THz source based on the driven Josephson vortex lattice in a highly anisotropic superconductor such as Bi.sub.2Sr.sub.2CaCu.sub.2O.sub.8 that allows cw emission at tunable frequency. A second order metallic Bragg grating is used to achieve impedance matching and to induce surface emission of THz-radiation from a Bi.sub.2Sr.sub.2CaCu.sub.2O.sub.8 sample. Steering of the emitted THz beam is accomplished by tuning the Josephson vortex spacing around the grating period using a superimposed magnetic control field.

Tunable, superconducting, surface-emitting teraherz source

DOEpatents

Welp, Ulrich; Koshelev, Alexei E.; Gray, Kenneth E.; Kwok, Wai-Kwong; Vlasko-Vlasov, Vitalii

2010-05-11

A compact, solid-state THz source based on the driven Josephson vortex lattice in a highly anisotropic superconductor such as Bi.sub.2Sr.sub.2CaCu.sub.2O.sub.8 that allows cw emission at tunable frequency. A second order metallic Bragg grating is used to achieve impedance matching and to induce surface emission of THz-radiation from a Bi.sub.2Sr.sub.2CaCu.sub.2O.sub.8 sample. Steering of the emitted THz beam is accomplished by tuning the Josephson vortex spacing around the grating period using a superimposed magnetic control field.

Meta-structure and tunable optical device including the same

DOEpatents

Han, Seunghoon; Papadakis, Georgia Theano; Atwater, Harry

2017-12-26

A meta-structure and a tunable optical device including the same are provided. The meta-structure includes a plurality of metal layers spaced apart from one another, an active layer spaced apart from the plurality of metal layers and having a carrier concentration that is tuned according to an electric signal applied to the active layer and the plurality of metal layers, and a plurality of dielectric layers spaced apart from one another and each having one surface contacting a metal layer among the plurality of metal layers and another surface contacting the active layer.

Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry

NASA Astrophysics Data System (ADS)

Qian, Elaine A.; Wixtrom, Alex I.; Axtell, Jonathan C.; Saebi, Azin; Jung, Dahee; Rehak, Pavel; Han, Yanxiao; Moully, Elamar Hakim; Mosallaei, Daniel; Chow, Sylvia; Messina, Marco S.; Wang, Jing Yang; Royappa, A. Timothy; Rheingold, Arnold L.; Maynard, Heather D.; Král, Petr; Spokoyny, Alexander M.

2017-04-01

The majority of biomolecules are intrinsically atomically precise, an important characteristic that enables rational engineering of their recognition and binding properties. However, imparting a similar precision to hybrid nanoparticles has been challenging because of the inherent limitations of existing chemical methods and building blocks. Here we report a new approach to form atomically precise and highly tunable hybrid nanomolecules with well-defined three-dimensionality. Perfunctionalization of atomically precise clusters with pentafluoroaryl-terminated linkers produces size-tunable rigid cluster nanomolecules. These species are amenable to facile modification with a variety of thiol-containing molecules and macromolecules. Assembly proceeds at room temperature within hours under mild conditions, and the resulting nanomolecules exhibit high stabilities because of their full covalency. We further demonstrate how these nanomolecules grafted with saccharides can exhibit dramatically improved binding affinity towards a protein. Ultimately, the developed strategy allows the rapid generation of precise molecular assemblies to investigate multivalent interactions.

Coumaraz-2-on-4-ylidene: Ambiphilic N-heterocyclic Carbenes with a Fine-Tunable Electronic Structure.

PubMed

Song, Hayoung; Kim, Hyunho; Lee, Eunsung

2018-05-16

Herein, a coumaraz-2-on-4-ylidene (1) as a new example of ambiphilic N-heterocyclic carbenes with fine tunable electronic properties is reported. The N-carbamic and aryl groups on carbene carbon provide exceptionally high electrophilicity and nucleophilicity simultaneously to the carbene center, as evidenced by the 77Se NMR chemical shifts of their selenoketone derivatives and the CO stretching strengths of their rhodium carbonyl complexes. Since the precursors of 1 could be synthesized from various functionalized Schiff bases in a practical and scalable manner, the electronic properties of 1 can be fine-tuned in quantitative and predictable way using the Hammett σ constant of the functional groups on aryl ring. The facile electronic tuning capability of 1 may be further applicable to eliciting novel properties in main-group and transition metal chemistry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene based terahertz phase modulators

NASA Astrophysics Data System (ADS)

Kakenov, N.; Ergoktas, M. S.; Balci, O.; Kocabas, C.

2018-07-01

Electrical control of amplitude and phase of terahertz radiation (THz) is the key technological challenge for high resolution and noninvasive THz imaging. The lack of active materials and devices hinders the realization of these imaging systems. Here, we demonstrate an efficient terahertz phase and amplitude modulation using electrically tunable graphene devices. Our device structure consists of electrolyte-gated graphene placed at quarter wavelength distance from a reflecting metallic surface. In this geometry, graphene operates as a tunable impedance surface which yields electrically controlled reflection phase. Terahertz time domain reflection spectroscopy reveals the voltage controlled phase modulation of π and the reflection modulation of 50 dB. To show the promises of our approach, we demonstrate a multipixel phase modulator array which operates as a gradient impedance surface.

Topological phase diagram and saddle point singularity in a tunable topological crystalline insulator

DOE PAGES

Neupane, Madhab; Xu, Su-Yang; Sankar, R.; ...

2015-08-20

Here we report the evolution of the surface electronic structure and surface material properties of a topological crystalline insulator (TCI), Pb 1more » $${-}$$xSnxSe, as a function of various material parameters including composition x, temperature T , and crystal structure. Our spectroscopic data demonstrate the electronic ground-state condition for the saddle point singularity, the tunability of surface chemical potential, and the surface states’ response to circularly polarized light. Our results show that each material parameter can tune the system between the trivial and topological phase in a distinct way, unlike that seen in Bi 2Se 3 and related compounds, leading to a rich topological phase diagram. Our systematic studies of the TCI Pb 1$${-}$$xSnxSe are a valuable materials guide to realize new topological phenomena.« less

Los Alamos Quantum Dots for Solar, Display Technology

ScienceCinema

Klimov, Victor

2018-05-01

Quantum dots are ultra-small bits of semiconductor matter that can be synthesized with nearly atomic precision via modern methods of colloidal chemistry. Their emission color can be tuned by simply varying their dimensions. Color tunability is combined with high emission efficiencies approaching 100 percent. These properties have recently become the basis of a new technology – quantum dot displays – employed, for example, in the newest generation of e-readers and video monitors.

Amine-derived synthetic approach to color-tunable InP/ZnS quantum dots with high fluorescent qualities

NASA Astrophysics Data System (ADS)

Song, Woo-Seuk; Lee, Hye-Seung; Lee, Ju Chul; Jang, Dong Seon; Choi, Yoonyoung; Choi, Moongoo; Yang, Heesun

2013-06-01

High-quality, Cd-free InP quantum dots (QDs) have been conventionally synthesized by exclusively selecting tris(trimethylsilyl)phosphine (P(TMS)3) as a phosphorus (P) precursor, which is problematic from the standpoint of green and economic chemistry. Thus, other synthetic chemistries adopting alternative P sources to P(TMS)3 have been introduced, however, they could not guarantee the production of satisfactorily fluorescence-efficient, color-pure InP QDs. In this study, the unprecedented controlled synthesis of a series of band-gap-tuned InP QDs is demonstrated through a hot-injection of a far safer and cheaper tris(dimethylamino)phosphine in the presence of a key coordinating solvent of oleylamine that enables successful QD nucleation/growth. Effects of the co-existence of Zn additive, the core growth temperature, and the amount of P source injected on the growth behaviors of InP QD are investigated. After ZnS overcoating by a successive injection of 1-dodecanethiol only, high-fluorescence-quality, green-to-red color emission-tunable core/shell QDs of InP/ZnS are obtained. The fluorescent characteristics of different color-emitting QDs desirably exhibit little fluctuations in quantum yield and emission bandwidth, specifically ranging 51-53 % and 60-64 nm, respectively. Lastly, the utility of the introduction of a secondary shelling process in rendering the QDs are more bright, photostable is also proved.

Strain engineered barium strontium titanate for tunable thin film resonators

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

Khassaf, H.; Khakpash, N.; Sun, F.

2014-05-19

Piezoelectric properties of epitaxial (001) barium strontium titanate (BST) films are computed as functions of composition, misfit strain, and temperature using a non-linear thermodynamic model. Results show that through adjusting in-plane strains, a highly adaptive rhombohedral ferroelectric phase can be stabilized at room temperature with outstanding piezoelectric response exceeding those of lead based piezoceramics. Furthermore, by adjusting the composition and the in-plane misfit, an electrically tunable piezoelectric response can be obtained in the paraelectric state. These findings indicate that strain engineered BST films can be utilized in the development of electrically tunable and switchable surface and bulk acoustic wave resonators.

Tunable emission in surface passivated Mn-ZnS nanophosphors and its application for Glucose sensing

NASA Astrophysics Data System (ADS)

Sharma, Manoj; Jain, Tarun; Singh, Sukhvir; Pandey, O. P.

2012-03-01

The present work describes the tunable emission in inorganic-organic hybrid NPs which can be useful for optoelectronic and biosensing applications. In this work, Mn- ZnS nanoparticles emitting various colors, including blue and orange, were synthesized by simple chemical precipitation method using chitosan as a capping agent. Earlier reports describe that emission color characteristics in nanoparticles are tuned by varying particle size and with doping concentration. Here in this article tunable emission has been achieved by varying excitation wavelength in a single sample. This tunable emission property with high emission intensity was further achieved by changing capping concentration keeping host Mn-ZnS concentration same. Tunable emission is explained by FRET mechanism. Commission Internationale de l'Eclairage (CIE) chromaticity coordinates shifts from (0.273, 0.20) and (0.344, 0.275) for same naocrystals by suitably tuning excitation energy from higher and lower ultra-violet (UV) range. Synthesized nanoparticles have been characterized by X-ray diffraction, SEM, HRTEM, UV- Visible absorption and PL spectroscopy for structural and optical studies. Using tunable emission property, these highly emissive nanoparticles functionalized with biocompatible polymer chitosan were further used for glucose sensing applications.

Understanding the influence of surface chemical states on the dielectric tunability of sputtered Ba0.5Sr0.5TiO3 thin films

NASA Astrophysics Data System (ADS)

Venkata Saravanan, K.; Raju, K. C. James

2014-03-01

The surface chemical states of RF-magnetron sputtered Ba0.5Sr0.5TiO3 (BST5) thin films deposited at different oxygen mixing percentage (OMP) was examined by x-ray photoelectron spectroscopy. The O1s XPS spectra indicate the existence of three kinds of oxygen species (dissociated oxygen ion O2 -, adsorbed oxide ion O- and lattice oxide ion O2-) on the films’ surface, which strongly depends on OMP. The presence of oxygen species other than lattice oxygen ion makes the films’ surface highly reactivity to atmospheric gases, resulting in the formation of undesired surface layers. The XPS results confirm the formation of surface nitrates for the films deposited under oxygen deficient atmosphere (OMP ≦̸ 25%), whereas the films deposited in oxygen rich atmosphere (OMP ≧̸ 75%) show the presence of metal-hydroxide. The influence of a surface dead layer on the tunable dielectric properties of BST5 films have been studied in detail and are reported. Furthermore, our observations indicate that an optimum ratio of Ar:O2 is essential for achieving desired material and dielectric properties in BST5 thin films. The films deposited at 50% OMP have the highest dielectric tunability of ~65% (@280 kV cm-1), with good ɛ r-E curve symmetry of 98% and low tan δ of 0.018. The figure of merit for these films is about 35, which is promising for frequency agile device applications.

PdHx entrapped in covalent triazine framework modulates selectivity in glycerol oxidation [Modulation of palladium activity and stability by a covalent triazine framework

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

Chan-Thaw, Carine E.; Villa, Alberto; Wang, Di

The confinement of a Pd nanoparticle within a nitrogen-containing covalent triazine framework (CTF) material was investigated to understand if the highly tunable CTF chemistry mediates the Pd catalytic properties through an ensemble effect with the CTF nitrogen atoms or a confinement effect within the CTF pores. The results surprisingly demonstrate that the CTF stabilizes the formation of 2.6 nm PdHx particles within the pores. These PdHx particles are very active for the liquid phase oxidation of glycerol due to the in situ formation of H2O2 which catalytically promotes the initial C-C cleavage. In addition the confined particles are stable overmore » many catalytic cycles whereas nanoparticles trapped outside of the pores loose activity rapidly. These results indicate that there is the potential to tune the CTF chemistry to significantly modify the chemistry of the catalytic metals.« less

PdHx entrapped in covalent triazine framework modulates selectivity in glycerol oxidation [Modulation of palladium activity and stability by a covalent triazine framework

DOE PAGES

Chan-Thaw, Carine E.; Villa, Alberto; Wang, Di; ...

2015-06-25

The confinement of a Pd nanoparticle within a nitrogen-containing covalent triazine framework (CTF) material was investigated to understand if the highly tunable CTF chemistry mediates the Pd catalytic properties through an ensemble effect with the CTF nitrogen atoms or a confinement effect within the CTF pores. The results surprisingly demonstrate that the CTF stabilizes the formation of 2.6 nm PdHx particles within the pores. These PdHx particles are very active for the liquid phase oxidation of glycerol due to the in situ formation of H2O2 which catalytically promotes the initial C-C cleavage. In addition the confined particles are stable overmore » many catalytic cycles whereas nanoparticles trapped outside of the pores loose activity rapidly. These results indicate that there is the potential to tune the CTF chemistry to significantly modify the chemistry of the catalytic metals.« less

Combined laser heating and tandem acousto-optical filter for two-dimensional temperature distribution on the surface of the heated microobject

NASA Astrophysics Data System (ADS)

Bykov, A. A.; Kutuza, I. B.; Zinin, P. V.; Machikhin, A. S.; Troyan, I. A.; Bulatov, K. M.; Batshev, V. I.; Mantrova, Y. V.; Gaponov, M. I.; Prakapenka, V. B.; Sharma, S. K.

2018-01-01

Recently it has been shown that it is possible to measure the two-dimensional distribution of the surface temperature of microscopic specimens. The main component of the system is a tandem imaging acousto-optical tunable filter synchronized with a video camera. In this report, we demonstrate that combining the laser heating system with a tandem imaging acousto-optical tunable filter allows measurement of the temperature distribution under laser heating of the platinum plates as well as a visualization of the infrared laser beam, that is widely used for laser heating in diamond anvil cells.

Engineering Silver Nanoparticles: Towards a Tunable Antimicrobial

NASA Astrophysics Data System (ADS)

Puppala, Hema Lakshmi

Overwhelming production of commercially available products containing silver nanoparticles (AgNPs) underscores the studies determining their fate in the environment. In order to regulate the use, assess the environmental impact and develop eco-responsible silver products, models that can predict AgNP toxicity based on physicochemical properties are vital. With that vision, this thesis developed well-characterized model libraries of uniform AgNPs stabilized with oleate in the range of 2-45 nm diameter with variable surface coating and investigated the dissolution properties that link AgNP structure to antimicrobial activity. High temperature organic synthesis allowed controlled growth of AgNPs (sigma<15%) by an Ostwald ripening mechanism in the first few hours, and followed by size dependent growth rates yielding uniform nanocrystals. Characterization of these materials revealed a crystalline nature, bidentate binding mode of oleate and non-oxidized pristine silver surface. Phase transfer of these AgNPs from organics to water was facilitated by encapsulation and ligand exchange methods using amphiphilic polymers and methoxy poly (ethylene glycol) (mPEGSH) respectively. Among these surface coatings, steric stabilization by mPEGSH not only helped retain their optical properties but also reduced the dissolution (<1(w/w)%) of AgNPs. This enhanced the stability in various environmentally relevant high ionic strength media (such as Hoaglands, EPA hard water and OECD medium), thereby increasing the shelf life. In addition, size, surface coating, pH of the medium and grafting density of the polymer mediated the dissolution of AgNPs. For instance, the rate of dissolution was decreased by 40% when the polymer coating possessed a mushroom conformation and increased with reducing core size. Analogous to dissolution, physicochemical properties also influenced the antimicrobial activity which were studied by minimum inhibitory concentration (MIC) and bactericidal efficacy assays. For example, surface passivation with mPEGSH prevented the oxidation of active silver atoms on the surface, and resulted in reduced toxicity against E. coli. Moreover citrate stabilized AgNPs when surface modified with mPEGSH had reduced toxicity, which was correlated with residual Ag+ in AgNP solution. Therefore this study demonstrates that processes in the environment that increase stability of AgNPs could make them more persistent due to low dissolution. Furthermore, the size and surface chemistry effects of AgNPs studied here make the intrinsic antimicrobial property of silver tunable and hence more versatile. This work also served as a material support for research on investigating toxicity of AgNPs to C. elegans, Daphnia Magna, Populus and Arabidopsis. In the future, this data will be used to develop nanomaterial bioavailability & environmental exposure (nanoBEE) models that predict the environmental impact of AgNPs.

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

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

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less

Bridging Zirconia Nodes within a Metal-Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires.

PubMed

Platero-Prats, Ana E; League, Aaron B; Bernales, Varinia; Ye, Jingyun; Gallington, Leighanne C; Vjunov, Aleksei; Schweitzer, Neil M; Li, Zhanyong; Zheng, Jian; Mehdi, B Layla; Stevens, Andrew J; Dohnalkova, Alice; Balasubramanian, Mahalingam; Farha, Omar K; Hupp, Joseph T; Browning, Nigel D; Fulton, John L; Camaioni, Donald M; Lercher, Johannes A; Truhlar, Donald G; Gagliardi, Laura; Cramer, Christopher J; Chapman, Karena W

2017-08-02

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis, and difference envelope density analysis, with electron microscopy imaging and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO x H y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield heterobimetallic metal-oxo nanowires. This bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering resistance of these clusters during the hydrogenation of light olefins.

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

DOE PAGES

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia; ...

2017-07-11

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less

Low-cost shape-control synthesis of porous carbon film on β″-alumina ceramics for Na-based battery application

NASA Astrophysics Data System (ADS)

Hu, Yingying; Wen, Zhaoyin; Wu, Xiangwei; Jin, Jun

2012-12-01

Porous carbon films with tunable pore structure to modify the β″-alumina electrolyte surface are fabricated through a low-cost and direct wet chemistry method with glucose and poly(methyl-methacrylate) (PMMA) as precursors. FTIR analysis confirms the effective connection between the carbohydrate and the pore-forming agent PMMA through hydrogen bonds. The experimental results indicate that the structural parameters of the porous carbon films, including mean pore size and film thickness, can be tuned simply by adjusting the amount of PMMA in the glucose/PMMA composite. This soft-template-assisted method could be readily extended to modify any other ceramic surfaces. The porous carbon films are demonstrated to greatly improve the wettability of the β″-alumina ceramics by molten sodium. Na/β″-alumina/Na cells are used to investigate the interfacial properties between sodium and the β″-alumina electrolyte. The results obtained at 350 °C reveal that the polarization behavior of the cell is alleviated by the porous coating. This work represents a successful method to coat ceramics with porous carbon and offers a promising solution to overcome the polarization problems of the sodium/β″-alumina interface in Na-based batteries.

Nano-optomechanical characterization of surface-plasmon-based tunable filter integrated with comb-drive actuator

NASA Astrophysics Data System (ADS)

Honma, H.; Mitsudome, M.; Ishida, M.; Sawada, K.; Takahashi, K.

2017-03-01

We report a tunable plasmonic color filter consisting of a metamaterial periodic grating and microelectromechanical systems (MEMS) actuator. An aluminum subwavelength grating is integrated with electrostatic comb-drive actuators to expand the metal subwavelength period, which allows continuous control of the excitation wavelength of surface plasmons (SPs). We develop a batch fabrication process by employing a liftoff technique using an electron beam resist altered by the electron dose depending on different aspect ratios (length/width) for various components such as the subwavelength grating, nanohinge flexural suspensions, and comb fingers. We successfully demonstrate a continuous shift in the excitation wavelength over the 514-635 nm range by nanopitch expansion. The design margin of the grating period for SP excitation is evaluated by comparing the experimental pitch variation and theoretically calculated values. The resonance frequency of the tunable filter is optically measured to be approximately 10 kHz. The optically and mechanically obtained values agree well with the theory of electrostatic actuation and finite-difference time-domain simulation.

Tunable Physical Properties of Ethylcellulose/Gelatin Composite Nanofibers by Electrospinning.

PubMed

Liu, Yuyu; Deng, Lingli; Zhang, Cen; Feng, Fengqin; Zhang, Hui

2018-02-28

In this work, the ethylcellulose/gelatin blends at various weight ratios in water/ethanol/acetic acid solution were electrospun to fabricate nanofibers with tunable physical properties. The solution compatibility was predicted based on Hansen solubility parameters and evaluated by rheological measurements. The physical properties were characterized by scanning electron microscopy, porosity, differential scanning calorimetry, thermogravimetry, Fourier transform infrared spectroscopy, and water contact angle. Results showed that the entangled structures among ethylcellulose and gelatin chains through hydrogen bonds gave rise to a fine morphology of the composite fibers with improved thermal stability. The fibers with higher gelatin ratio (75%), possessed hydrophilic surface (water contact angle of 53.5°), and adequate water uptake ability (1234.14%), while the fibers with higher ethylcellulose proportion (75%) tended to be highly water stable with a hydrophobic surface (water contact angle of 129.7°). This work suggested that the composite ethylcellulose/gelatin nanofibers with tunable physical properties have potentials as materials for bioactive encapsulation, food packaging, and filtration applications.

Coherent and tunable terahertz radiation from graphene surface plasmon polaritons excited by an electron beam

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

Liu, Shenggang, E-mail: liusg@uestc.edu.cn; Hu, Min; Chen, Xiaoxing

2014-05-19

Although surface plasmon polaritons (SPPs) resonance in graphene can be tuned in the terahertz regime, transforming such SPPs into coherent terahertz radiation has not been achieved. Here, we propose a graphene-based coherent terahertz radiation source with greatly enhanced intensity. The radiation works at room temperature, it is tunable and can cover the whole terahertz regime. The radiation intensity generated with this method is 400 times stronger than that from SPPs at a conventional dielectric or semiconducting surface and is comparable to that from the most advanced photonics source such as a quantum cascade laser. The physical mechanism for this strongmore » radiation is presented. The phase diagrams defining the parameters range for the occurrence of radiation is also shown.« less

Room-temperature processing of CdSe quantum dots with tunable sizes

NASA Astrophysics Data System (ADS)

Joo, So-Yeong; Jeong, Da-Woon; Lee, Chan-Gi; Kim, Bum-Sung; Park, Hyun-Su; Kim, Woo-Byoung

2017-06-01

In this work, CdSe quantum dots (QDs) with tunable sizes have been fabricated via photo-induced chemical etching at room temperature, and the related reaction mechanism was investigated. The surface of QDs was oxidized by the holes generated through photon irradiation of oxygen species, and the obtained oxide layer was dissolved in an aqueous solution of 3-amino-1-propanol (APOL) with an APOL:H2O volume ratio of 5:1. The generated electrons promoted QD surface interactions with amino groups, which ultimately passivated surface defects. The absorption and photoluminescence emission peaks of the produced QDs were clearly blue-shifted about 26 nm with increasing time, and the resulting quantum yield for an 8 h etched sample was increased from 20% to 26%, as compared to the initial sample.

Electrically tunable metasurface based on Mie-type dielectric resonators.

PubMed

Su, Zhaoxian; Zhao, Qian; Song, Kun; Zhao, Xiaopeng; Yin, Jianbo

2017-02-21

In this paper, we have designed a metasurface based on electrically tunable Mie-type resonators and theoretically demonstrated its tunable response to electromagnetic waves with varying frequency. The metasurface consists of disk-like ferroelectric resonators arrayed on a metal film and the upper surface of resonators is covered by ion gel film which is transparent for incident electromagnetic wave. Using the metal film and ion gel film as electrodes, the permittivity of the resonators can be adjusted by an external electric field and, as a result, the reflection phase of the resonators can be dynamically adjusted in a relatively wide range. By programmable controlling the electric field strength applied on resonators of metasurface, a 2π phase ramp can be realized and, thereby, the arbitrary reflection behavior of incident waves with varied frequency is obtained. Because of the tunability, this metasurface can also be used to design adaptive metasurface lens and carpet cloak.

Micro-optofluidic Lenses: A review

PubMed Central

Nguyen, Nam-Trung

2010-01-01

This review presents a systematic perspective on the development of micro-optofluidic lenses. The progress on the development of micro-optofluidic lenses are illustrated by example from recent literature. The advantage of micro-optofluidic lenses over solid lens systems is their tunability without the use of large actuators such as servo motors. Depending on the relative orientation of light path and the substrate surface, micro-optofluidic lenses can be categorized as in-plane or out-of-plane lenses. However, this review will focus on the tunability of the lenses and categorizes them according to the concept of tunability. Micro-optofluidic lenses can be either tuned by the liquid in use or by the shape of the lens. Micro-optofluidic lenses with tunable shape are categorized according to the actuation schemes. Typical parameters of micro-optofluidic lenses reported recently are compared and discussed. Finally, perspectives are given for future works in this field. PMID:20714369

Electrically tunable metasurface based on Mie-type dielectric resonators

PubMed Central

Su, Zhaoxian; Zhao, Qian; Song, Kun; Zhao, Xiaopeng; Yin, Jianbo

2017-01-01

In this paper, we have designed a metasurface based on electrically tunable Mie-type resonators and theoretically demonstrated its tunable response to electromagnetic waves with varying frequency. The metasurface consists of disk-like ferroelectric resonators arrayed on a metal film and the upper surface of resonators is covered by ion gel film which is transparent for incident electromagnetic wave. Using the metal film and ion gel film as electrodes, the permittivity of the resonators can be adjusted by an external electric field and, as a result, the reflection phase of the resonators can be dynamically adjusted in a relatively wide range. By programmable controlling the electric field strength applied on resonators of metasurface, a 2π phase ramp can be realized and, thereby, the arbitrary reflection behavior of incident waves with varied frequency is obtained. Because of the tunability, this metasurface can also be used to design adaptive metasurface lens and carpet cloak. PMID:28220861

Electrically tunable metasurface based on Mie-type dielectric resonators

NASA Astrophysics Data System (ADS)

Su, Zhaoxian; Zhao, Qian; Song, Kun; Zhao, Xiaopeng; Yin, Jianbo

2017-02-01

In this paper, we have designed a metasurface based on electrically tunable Mie-type resonators and theoretically demonstrated its tunable response to electromagnetic waves with varying frequency. The metasurface consists of disk-like ferroelectric resonators arrayed on a metal film and the upper surface of resonators is covered by ion gel film which is transparent for incident electromagnetic wave. Using the metal film and ion gel film as electrodes, the permittivity of the resonators can be adjusted by an external electric field and, as a result, the reflection phase of the resonators can be dynamically adjusted in a relatively wide range. By programmable controlling the electric field strength applied on resonators of metasurface, a 2π phase ramp can be realized and, thereby, the arbitrary reflection behavior of incident waves with varied frequency is obtained. Because of the tunability, this metasurface can also be used to design adaptive metasurface lens and carpet cloak.

Moth eye-inspired anti-reflective surfaces for improved IR optical systems & visible LEDs fabricated with colloidal lithography and etching.

PubMed

Chan, Lesley W; Morse, Daniel E; Gordon, Michael J

2018-05-08

Near- and sub-wavelength photonic structures are used by numerous organisms (e.g. insects, cephalopods, fish, birds) to create vivid and often dynamically-tunable colors, as well as create, manipulate, or capture light for vision, communication, crypsis, photosynthesis, and defense. This review introduces the physics of moth eye (ME)-like, biomimetic nanostructures and discusses their application to reduce optical losses and improve efficiency of various optoelectronic devices, including photodetectors, photovoltaics, imagers, and light emitting diodes. Light-matter interactions at structured and heterogeneous surfaces over different length scales are discussed, as are the various methods used to create ME-inspired surfaces. Special interest is placed on a simple, scalable, and tunable method, namely colloidal lithography with plasma dry etching, to fabricate ME-inspired nanostructures in a vast suite of materials. Anti-reflective surfaces and coatings for IR devices and enhancing light extraction from visible light emitting diodes are highlighted.

Ultrafast polarisation spectroscopy of photoinduced charges in a conjugated polymer

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

Bakulin, A A; Loosdrecht, P van; Pshenichnikov, M S

2009-07-31

Tunable optical parametric generators and amplifiers (OPA), proposed and developed by Akhmanov and his colleagues, have become the working horses in exploration of dynamical processes in physics, chemistry, and biology. In this paper, we demonstrate the possibility of using ultrafast polarisation-sensitive two-colour spectroscopy, performed with a set of two OPAs, to study charge photogeneration and transport in conjugated polymers and their donor-acceptor blends. (special issue devoted to the 80th birthday of S.A. Akhmanov)

Optimization of Strontium Titanate (SrTiO3) Thin Films Fabricated by Metal Organic Chemical Vapor Deposition (MOCVD) for Microwave-Tunable Devices

DTIC Science & Technology

2015-12-01

induced (non)stoichiometry on the structure, dielectric response, and thermal conductivity of SrTiO3 thin films. Chemistry of Materials. 2012;24:331...must be below a few percent. The external sources of loss, such as conductor interface losses and various losses that inevitably arise from device...epitaxy • Excellent control of film stoichiometry and thickness • Large area uniformity and potential for complex structure coating • Optimized

Synthesis of layer-tunable graphene: A combined kinetic implantation and thermal ejection approach

DOE PAGES

Wang, Gang; Zhang, Miao; Liu, Su; ...

2015-05-04

Layer-tunable graphene has attracted broad interest for its potentials in nanoelectronics applications. However, synthesis of layer-tunable graphene by using traditional chemical vapor deposition (CVD) method still remains a great challenge due to the complex experimental parameters and the carbon precipitation process. Herein, by performing ion implantation into a Ni/Cu bilayer substrate, the number of graphene layers, especially single or double layer, can be controlled precisely by adjusting the carbon ion implant fluence. The growth mechanism of the layer-tunable graphene is revealed by monitoring the growth process is observed that the entire implanted carbon atoms can be expelled towards the substratemore » surface and thus graphene with designed layer number can be obtained. Such a growth mechanism is further confirmed by theoretical calculations. The proposed approach for the synthesis of layer-tunable graphene offers more flexibility in the experimental conditions. Being a core technology in microelectronics processing, ion implantation can be readily implemented in production lines and is expected to expedite the application of graphene to nanoelectronics.« less

Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

DTIC Science & Technology

2015-12-21

SECURITY CLASSIFICATION OF: The overall goal of this project is to determine how electrode surface chemistry can be rationally designed to decrease...2015 Approved for Public Release; Distribution Unlimited Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for...ABSTRACT Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

Colloidal core-seeded semiconductor nanorods as fluorescent labels for in-vitro diagnostics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Chan, YinThai

2016-03-01

Colloidal semiconductor nanocrystals are ideal fluorophores for clinical diagnostics, therapeutics, and highly sensitive biochip applications due to their high photostability, size-tunable color of emission and flexible surface chemistry. The relatively recent development of core-seeded semiconductor nanorods showed that the presence of a rod-like shell can confer even more advantageous physicochemical properties than their spherical counterparts, such as large multi-photon absorption cross-sections and facet-specific chemistry that can be exploited to deposit secondary nanoparticles. It may be envisaged that these highly fluorescent nanorods can be integrated with large scale integrated (LSI) microfluidic systems that allow miniaturization and integration of multiple biochemical processes in a single device at the nanoliter scale, resulting in a highly sensitive and automated detection platform. In this talk, I will describe a LSI microfluidic device that integrates RNA extraction, reverse transcription to cDNA, amplification and target pull-down to detect histidine decarboxylase (HDC) gene directly from human white blood cells samples. When anisotropic colloidal semiconductor nanorods (NRs) were used as the fluorescent readout, the detection limit was found to be 0.4 ng of total RNA, which was much lower than that obtained using spherical quantum dots (QDs) or organic dyes. This was attributed to the large action cross-section of NRs and their high probability of target capture in a pull-down detection scheme. The combination of large scale integrated microfluidics with highly fluorescent semiconductor NRs may find widespread utility in point-of-care devices and multi-target diagnostics.

Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; Mahaffy, Paul R.

2011-01-01

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

Semiconductor detector with smoothly tunable effective thickness for the study of ionization loss by moderately relativistic electrons

NASA Astrophysics Data System (ADS)

Shchagin, A. V.; Shul'ga, N. F.; Trofymenko, S. V.; Nazhmudinov, R. M.; Kubankin, A. S.

2016-11-01

The possibility of measurement of electrons ionization loss in Si layer of smoothly tunable thickness is shown in the proof-of-principle experiment. The Si surface-barrier detector with the depleted layer thickness controlled by the value of high voltage power supply has been used. Ionization loss spectra for electrons emitted by radioactive source 207Bi are presented and discussed. Experimental results for the most probable ionization loss in the Landau spectral peak are compared with theoretical calculations. The possibility of research of evolution of electromagnetic field of ultra-relativistic particles traversing media interface with the use of detectors with smoothly tunable thickness is proposed.

Low Profile Tunable Dipole Antennas Using BST Varactors for Biomedical Applications

NASA Technical Reports Server (NTRS)

Cure, David; Weller, Thomas; Price, Tony; Miranda, Felix A.

2013-01-01

In this presentation a 2.4 GHz low profile (lambda45) tunable dipole antenna is evaluated in the presence of a human core model (HCM) body phantom. The antenna uses a frequency selective surface (FSS) with interdigital barium strontium titanate (BST) varactor-tuned unit cells and its performance is compared to a similar low profile antenna that uses an FSS with semiconductor varactor diodes. The measured data of the antenna demonstrate tunability from 2.2 GHz to 2.55 GHz in free space and impedance match improvement in the presence of a HCM at different distances. This antenna has smaller size, lower cost and less weight compared to the semiconductor varactor diode counterpart.

Continuously tunable solution-processed organic semiconductor DFB lasers pumped by laser diode.

PubMed

Klinkhammer, Sönke; Liu, Xin; Huska, Klaus; Shen, Yuxin; Vanderheiden, Sylvia; Valouch, Sebastian; Vannahme, Christoph; Bräse, Stefan; Mappes, Timo; Lemmer, Uli

2012-03-12

The fabrication and characterization of continuously tunable, solution-processed distributed feedback (DFB) lasers in the visible regime is reported. Continuous thin film thickness gradients were achieved by means of horizontal dipping of several conjugated polymer and blended small molecule solutions on cm-scale surface gratings of different periods. We report optically pumped continuously tunable laser emission of 13 nm in the blue, 16 nm in the green and 19 nm in the red spectral region on a single chip respectively. Tuning behavior can be described with the Bragg-equation and the measured thickness profile. The laser threshold is low enough that inexpensive laser diodes can be used as pump sources.

Low Profile Tunable Dipole Antenna Using BST Varactors for Biomedical Applications

NASA Technical Reports Server (NTRS)

Cure, David; Weller, Thomas M.; Miranda, Felix A.; Price, Tony

2013-01-01

In this paper a 2.4 GHz low profile (lambda/47) tunable dipole antenna is evaluated in the presence of a human core model (HCM) body phantom. The antenna uses a frequency selective surface (FSS) with interdigital barium strontium titanate (BST) varactor-tuned unit cells and its performance is compared to a similar low profile antenna that uses an FSS with semiconductor varactor diodes. The measured data of the antenna demonstrate tunability from 2.2 GHz to 2.55 GHz in free space and impedance match improvement in the presence of a HCM at different distances. This antenna has smaller size, lower cost and less weight compared to the semiconductor varactor diode counterpart.

Synthetic biology and biomimetic chemistry as converging technologies fostering a new generation of smart biosensors.

PubMed

Scognamiglio, Viviana; Antonacci, Amina; Lambreva, Maya D; Litescu, Simona C; Rea, Giuseppina

2015-12-15

Biosensors are powerful tunable systems able to switch between an ON/OFF status in response to an external stimulus. This extraordinary property could be engineered by adopting synthetic biology or biomimetic chemistry to obtain tailor-made biosensors having the desired requirements of robustness, sensitivity and detection range. Recent advances in both disciplines, in fact, allow to re-design the configuration of the sensing elements - either by modifying toggle switches and gene networks, or by producing synthetic entities mimicking key properties of natural molecules. The present review considered the role of synthetic biology in sustaining biosensor technology, reporting examples from the literature and reflecting on the features that make it a useful tool for designing and constructing engineered biological systems for sensing application. Besides, a section dedicated to bioinspired synthetic molecules as powerful tools to enhance biosensor potential is reported, and treated as an extension of the concept of biomimetic chemistry, where organic synthesis is used to generate artificial molecules that mimic natural molecules. Thus, the design of synthetic molecules, such as aptamers, biomimetics, molecular imprinting polymers, peptide nucleic acids, and ribozymes were encompassed as "products" of biomimetic chemistry. Copyright © 2015 Elsevier B.V. All rights reserved.

Development and understanding of multifunctional gold nanorings for photodynamic therapy of cancer

NASA Astrophysics Data System (ADS)

Hu, Yue

Gold nanostructures of various geometries and dimensions are being broadly explored in the fast expanding field of nanomedicine due to the unusual combination of biocompatibility, versatility of surface functionalization, and localized surface-plasmon resonance (LSPR). Examples of relevant applications include biomedical imaging, clinical diagnostics and therapeutics. Gold nanorings (Au NRs) are of particular interest because of their intricate structure and LSPR tunability over a wide wavelength range. A solution-based synthesis approach is yet to be developed, however, to allow exploration of Au NRs for basic and applied studies. This dissertation focuses on the fabrication, characterization, and evaluation of colloidal Au NRs for enhanced photodynamic therapy (PDT) of breast cancer cells. We have developed a novel synthesis strategy and associated pathways toward Au NRs by galvanic replacement reaction of Co nanoparticles (Co NPs) in HAuCl4 solution. We have shown that surface-chemistry mediated particle-particle interaction of the Co NPs that leads to their 1D chain-like assembly as sacrificial template is critically important for the growth of Au NRs. Otherwise, Au nanoshells or Au nanotubes may result. The Au NRs exhibit tunable LSPR wavelengths from visible to near-infrared (NIR) region via varying the aspect ratio, in agreement with our theoretical calculations using the finite-difference time domain (FDTD) method. A layer-by-layer (LbL) assembly method was used to load Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS4) photosensitizer (PS) onto the surface of Au NRs. We have revealed that the photosensitivity of AlPcS4 can be quenched unless desorbed from the surface of Au NRs in the cellular compartment. An eight-fold increase in PDT killing efficiency of human breast cancer cells (MDA-MB-231) has been achieved using LbL-assembled AlPcS4-Au NR complexes in comparison to AlPcS4 only or the mixture of AlPcS 4 and Au NRs. This strategy allows reliable delivery of PS to targeted cells and exploits the LSPR of Au NRs in NIR to generate elevated singlet oxygen species (1O2) for destruction of cancer cells. Furthermore, we have shown that Au NR-enhanced 1O2 generation could be optimized by proper combination of the LSPR wavelength of Au NRs and the spacing between AlPcS4 and Au NRs. Our research findings together with the mechanistic understanding have the potential to facilitate the clinical translation of Au NRs for greatly improved PDT efficacy of cancer treatment.

Optical performance of a PDMS tunable lens with automatically controlled applied stress

NASA Astrophysics Data System (ADS)

Cruz-Felix, Angel S.; Santiago-Alvarado, Agustín.; Hernández-Méndez, Arturo; Reyes-Pérez, Emilio R.; Tepichín-Rodriguez, Eduardo

2016-09-01

The advances in the field of adaptive optics and in the fabrication of tunable optical components capable to automatically modify their physical features are of great interest in areas like machine vision, imaging systems, ophthalmology, etc. Such components like tunable lenses are used to reduce the overall size of optical setups like in small camera systems and even to imitate some biological functions made by the human eye. In this direction, in the last years we have been working in the development and fabrication of PDMS-made tunable lenses and in the design of special mechanical mounting systems to manipulate them. A PDMS-made tunable lens was previously designed by us, following the scheme reported by Navarro et al. in 1985, in order to mimic the accommodation process made by the crystalline lens of the human eye. The design included a simulation of the application of radial stress onto the lens and it was shown that the effective focal length was indeed changed. In this work we show the fabrication process of this particular tunable lens and an optimized mechanism that is able to automatically change the curvature of both surfaces of the lens by the application of controlled stress. We also show results of a study and analysis of aberrations performed to the Solid Elastic Lens (SEL).

Nanosecond laser ablated copper superhydrophobic surface with tunable ultrahigh adhesion and its renewability with low temperature annealing

NASA Astrophysics Data System (ADS)

He, An; Liu, Wenwen; Xue, Wei; Yang, Huan; Cao, Yu

2018-03-01

Recently, metallic superhydrophobic surfaces with ultrahigh adhesion have got plentiful attention on account of their significance in scientific researches and industrial applications like droplet transport, drug delivery and novel microfluidic devices. However, the long lead time and transience hindered its in-depth development and industrial application. In this work, nanosecond laser ablation was carried out to construct grid of micro-grooves on copper surface, whereafter, by applying fast ethanol assisted low-temperature annealing, we obtained surface with superhydrophobicity and ultrahigh adhesion within hours. And the ultrahigh adhesion force was found tunable by varying the groove spacing. Using ultrasonic cleaning as the simulation of natural wear and tear in service, the renewability of superhydrophobicity was also investigated, and the result shows that the contact angle can rehabilitate promptly by the processing of ethanol assisted low-temperature annealing, which gives a promising fast and cheap circuitous strategy to realize the long wish durable metallic superhydrophobic surfaces in practical applications.

Reversible structural modulation of Fe-Pt bimetallic surfaces and its effect on reactivity.

PubMed

Ma, Teng; Fu, Qiang; Su, Hai-Yan; Liu, Hong-Yang; Cui, Yi; Wang, Zhen; Mu, Ren-Tao; Li, Wei-Xue; Bao, Xin-He

2009-05-11

Tunable surface: The surface structure of the Fe-Pt bimetallic catalyst can be reversibly modulated between the iron-oxide-rich Pt surface and the Pt-skin structure with subsurface Fe via alternating reduction and oxidation treatments (see figure). The regenerated active Pt-skin structure is active in reactions involving CO and/or O.

Enhanced mobility CsPbI 3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells

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

Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.

Here, we developed lead halide perovskite quantum dot (QD) films with tuned surface chemistry based on A-site cation halide salt (AX) treatments. QD perovskites offer colloidal synthesis and processing using industrially friendly solvents, which decouples grain growth from film deposition, and at present produce larger open-circuit voltages (V OC's) than thin-film perovskites. CsPbI 3 QDs, with a tunable bandgap between 1.75 and 2.13 eV, are an ideal top cell candidate for all-perovskite multijunction solar cells because of their demonstrated small V OC deficit. We show that charge carrier mobility within perovskite QD films is dictated by the chemical conditions atmore » the QD-QD junctions. The AX treatments provide a method for tuning the coupling between perovskite QDs, which is exploited for improved charge transport for fabricating high-quality QD films and devices. The AX treatments presented here double the film mobility, enabling increased photocurrent, and lead to a record certified QD solar cell efficiency of 13.43%.« less

Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells

PubMed Central

Zhou, Nanjia; Kim, Myung-Gil; Loser, Stephen; Smith, Jeremy; Yoshida, Hiroyuki; Guo, Xugang; Song, Charles; Jin, Hosub; Chen, Zhihua; Yoon, Seok Min; Freeman, Arthur J.; Chang, Robert P. H.; Facchetti, Antonio; Marks, Tobin J.

2015-01-01

In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor–inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance. PMID:26080437

Role of chondroitin sulphate tethered silk scaffold in cartilaginous disc tissue regeneration.

PubMed

Bhattacharjee, Maumita; Chawla, Shikha; Chameettachal, Shibu; Murab, Sumit; Bhavesh, Neel Sarovar; Ghosh, Sourabh

2016-04-12

Strategies for tissue engineering focus on scaffolds with tunable structure and morphology as well as optimum surface chemistry to simulate the anatomy and functionality of the target tissue. Silk fibroin has demonstrated its potential in supporting cartilaginous tissue formation both in vitro and in vivo. In this study, we investigate the role of controlled lamellar organization and chemical composition of biofunctionalized silk scaffolds in replicating the structural properties of the annulus region of an intervertebral disc using articular chondrocytes. Covalent attachment of chondroitin sulfate (CS) to silk is characterized. CS-conjugated silk constructs demonstrate enhanced cellular metabolic activity and chondrogenic redifferentiation potential with significantly improved mechanical properties over silk-only constructs. A matrix-assisted laser desorption ionization-time of flight analysis and protein-protein interaction studies help to generate insights into how CS conjugation can facilitate the production of disc associated matrix proteins, compared to a silk-only based construct. An in-depth understanding of the interplay between such extra cellular matrix associated proteins should help in designing more rational scaffolds for cartilaginous disc regeneration needs.

Effect of annealing on magnetic properties of Ni80Fe20 permalloy nanoparticles prepared by polyol method.

PubMed

Qin, G W; Pei, W L; Ren, Y P; Shimada, Y; Endo, Y; Yamaguchi, M; Okamoto, S; Kitakami, O

2011-12-01

Ni80Fe20 permalloy nanoparticles with narrow size distribution and homogeneous composition have been prepared by the polyol processing at 180 degrees C for 2 h and their particle sizes can be tunable in the size range of 20-440 nm by proper addition of K2PtCI4 agent. X-ray diffraction results show that the NiFe nanoparticles are of face centered cubic structure. The addition of K2PtCl4 does not affect the composition of NiFe NPs but decreases the particle size remarkably. Both saturation magnetization and coercivity of the as-prepared NiFe nanoparticles decrease with decreasing particle size. Annealed at 280 degrees C, however, the saturation magnetization of various sized NiFe nanoparticles increases drastically and approaches to the bulk for the -440 nm NiFe particles, and a maximum coercivity (-270 Oe) happens at a critical size of -50 nm. The magnetic property dependency of these NiFe nanoparticles on annealing has been discussed by considering the surface chemistry.

Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells

DOE PAGES

Zhou, Nanjia; Kim, Myung -Gil; Loser, Stephen; ...

2015-06-15

In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor– inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactivemore » materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Lastly, continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance.« less

In silico design of porous polymer networks: high-throughput screening for methane storage materials.

PubMed

Martin, Richard L; Simon, Cory M; Smit, Berend; Haranczyk, Maciej

2014-04-02

Porous polymer networks (PPNs) are a class of advanced porous materials that combine the advantages of cheap and stable polymers with the high surface areas and tunable chemistry of metal-organic frameworks. They are of particular interest for gas separation or storage applications, for instance, as methane adsorbents for a vehicular natural gas tank or other portable applications. PPNs are self-assembled from distinct building units; here, we utilize commercially available chemical fragments and two experimentally known synthetic routes to design in silico a large database of synthetically realistic PPN materials. All structures from our database of 18,000 materials have been relaxed with semiempirical electronic structure methods and characterized with Grand-canonical Monte Carlo simulations for methane uptake and deliverable (working) capacity. A number of novel structure-property relationships that govern methane storage performance were identified. The relationships are translated into experimental guidelines to realize the ideal PPN structure. We found that cooperative methane-methane attractions were present in all of the best-performing materials, highlighting the importance of guest interaction in the design of optimal materials for methane storage.

Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells.

PubMed

Zhou, Nanjia; Kim, Myung-Gil; Loser, Stephen; Smith, Jeremy; Yoshida, Hiroyuki; Guo, Xugang; Song, Charles; Jin, Hosub; Chen, Zhihua; Yoon, Seok Min; Freeman, Arthur J; Chang, Robert P H; Facchetti, Antonio; Marks, Tobin J

2015-06-30

In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor-inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance.

Enhanced mobility CsPbI 3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells

DOE PAGES

Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.; ...

2017-10-27

Here, we developed lead halide perovskite quantum dot (QD) films with tuned surface chemistry based on A-site cation halide salt (AX) treatments. QD perovskites offer colloidal synthesis and processing using industrially friendly solvents, which decouples grain growth from film deposition, and at present produce larger open-circuit voltages (V OC's) than thin-film perovskites. CsPbI 3 QDs, with a tunable bandgap between 1.75 and 2.13 eV, are an ideal top cell candidate for all-perovskite multijunction solar cells because of their demonstrated small V OC deficit. We show that charge carrier mobility within perovskite QD films is dictated by the chemical conditions atmore » the QD-QD junctions. The AX treatments provide a method for tuning the coupling between perovskite QDs, which is exploited for improved charge transport for fabricating high-quality QD films and devices. The AX treatments presented here double the film mobility, enabling increased photocurrent, and lead to a record certified QD solar cell efficiency of 13.43%.« less

The role of helium metastable states in radio-frequency driven helium-oxygen atmospheric pressure plasma jets: measurement and numerical simulation

NASA Astrophysics Data System (ADS)

Niemi, K.; Waskoenig, J.; Sadeghi, N.; Gans, T.; O'Connell, D.

2011-10-01

Absolute densities of metastable He(23S1) atoms were measured line-of-sight integrated along the discharge channel of a capacitively coupled radio-frequency driven atmospheric pressure plasma jet operated in technologically relevant helium-oxygen mixtures by tunable diode-laser absorption spectroscopy. The dependences of the He(23S1) density in the homogeneous-glow-like α-mode plasma with oxygen admixtures up to 1% were investigated. The results are compared with a one-dimensional numerical simulation, which includes a semi-kinetical treatment of the pronounced electron dynamics and the complex plasma chemistry (in total 20 species and 184 reactions). Very good agreement between measurement and simulation is found. The main formation mechanisms for metastable helium atoms are identified and analyzed, including their pronounced spatio-temporal dynamics. Penning ionization through helium metastables is found to be significant for plasma sustainment, while it is revealed that helium metastables are not an important energy carrying species into the jet effluent and therefore will not play a direct role in remote surface treatments.

Toxicity Evaluation of Engineered Nanomaterials (Phase 1 Studies)

DTIC Science & Technology

2012-01-01

Surface Chemistry on Cellular Response ...................................................................................................... 48...Gold Nanomaterial Solution Purity and Surface Chemistry Toxicity ................................................................. 18 Figure 7...Solution Purity and Surface Chemistry Control Although several studies have shown that both MPS and PEG are biocompatible, in order to ensure that

Nanorice Particles: Hybrid Plasmonic Nanostructures

NASA Technical Reports Server (NTRS)

Le, Fei (Inventor); Halas, Nancy J. (Inventor); Nordlander, Peter (Inventor); Brandl, Daniel (Inventor); Wang, Hui (Inventor)

2010-01-01

A new hybrid nanoparticle, i.e., a nanorice particle, which combines the intense local fields of nanorods with the highly tunable plasmon resonances of nanoshells, is described herein. This geometry possesses far greater structural tunability than previous nanoparticle geometries, along with much larger local field enhancements and far greater sensitivity as a surface plasmon resonance (SPR) nanosensor than presently known dielectric-conductive material nanostructures. In an embodiment, a nanoparticle comprises a prolate spheroid-shaped core having a first aspect ratio. The nanoparticle also comprises at least one conductive shell surrounding said prolate spheroid-shaped core. The nanoparticle has a surface plasmon resonance sensitivity of at least 600 nm RIU(sup.-1). Methods of making the disclosed nanorice particles are also described herein.

Enhanced and tunable electric dipole-dipole interactions near a planar metal film

NASA Astrophysics Data System (ADS)

Zhou, Lei-Ming; Yao, Pei-Jun; Zhao, Nan; Sun, Fang-Wen

2017-08-01

We investigate the enhanced electric dipole-dipole interaction of surface plasmon polaritons (SPPs) supported by a planar metal film waveguide. By taking two nitrogen-vacancy (NV) center electric dipoles in diamond as an example, both the coupling strength and collective relaxation of two dipoles are studied with the numerical Green Function method. Compared to two-dipole coupling on a planar surface, metal film provides stronger and tunable coupling coefficients. Enhancement of the interaction between coupled NV center dipoles could have applications in both quantum information and energy transfer investigation. Our investigation provides systematic results for experimental applications based on a dipole-dipole interaction mediated with SPPs on a planar metal film.

Experimental demonstration of tunable directional excitation of surface plasmon polaritons with a subwavelength metallic double slit

NASA Astrophysics Data System (ADS)

Li, Xiaowei; Tan, Qiaofeng; Bai, Benfeng; Jin, Guofan

2011-06-01

We demonstrate experimentally the directional excitation of surface plasmon polaritons (SPPs) on a metal film by a subwavelength double slit under backside illumination, based on the interference of SPPs generated by the two slits. By varying the incident angle, the SPPs can be tunably directed into two opposite propagating directions with a predetermined splitting ratio. Under certain incident angle, unidirectional SPP excitation can be achieved. This compact directional SPP coupler is potentially useful for many on-chip applications. As an example, we show the integration of the double-slit couplers with SPP Bragg mirrors, which can effectively realize selective coupling of SPPs into different ports in an integrated plasmonic chip.

Tunable and highly reproducible surface-enhanced Raman scattering substrates made from large-scale nanoparticle arrays based on periodically poled LiNbO3 templates

NASA Astrophysics Data System (ADS)

Liu, Xiaoyan; Kitamura, Kenji; Yu, Qiuming; Xu, Jiajie; Osada, Minoru; Takahiro, Nagata; Li, Jiangyu; Cao, Guozhong

2013-10-01

This work describes novel surface-enhanced Raman scattering (SERS) substrates based on ferroelectric periodically poled LiNbO3 templates. The templates comprise silver nanoparticles (AgNPs), the size and position of which are tailored by ferroelectric lithography. The substrate has uniform and large sampling areas that show SERS effective with excellent signal reproducibility, for which the fabrication protocol is advantageous in its simplicity. We demonstrate ferroelectric-based SERS substrates with particle sizes ranging from 30 to 70 nm and present tunable SERS effect from Raman active 4-mercaptopyridine molecules attached to AgNPs when excited by a laser source at 514 nm.

Electrically Tunable Nd:YAG waveguide laser based on Graphene

PubMed Central

Ma, Linan; Tan, Yang; Akhmadaliev, Shavkat; Zhou, Shengqiang; Chen, Feng

2016-01-01

We demonstrate a tunable hybrid Graphene-Nd:YAG cladding waveguide laser exploiting the electro-optic and the Joule heating effects of Graphene. A cladding Nd:YAG waveguide was fabricated by the ion irradiation. The multi-layer graphene were transferred onto the waveguide surface as the saturable absorber to get the Q-switched pulsed laser oscillation in the waveguide. Composing with appropriate electrodes, graphene based capacitance and heater were formed on the surface of the Nd:YAG waveguide. Through electrical control of graphene, the state of the hybrid waveguide laser was turned on or off. And the laser operation of the hybrid waveguide was electrically tuned between the continuous wave laser and the nanosecond pulsed laser. PMID:27833114

Unraveling atomic-level self-organization at the plasma-material interface

NASA Astrophysics Data System (ADS)

Allain, J. P.; Shetty, A.

2017-07-01

The intrinsic dynamic interactions at the plasma-material interface and critical role of irradiation-driven mechanisms at the atomic scale during exposure to energetic particles require a priori the use of in situ surface characterization techniques. Characterization of ‘active’ surfaces during modification at atomic-scale levels is becoming more important as advances in processing modalities are limited by an understanding of the behavior of these surfaces under realistic environmental conditions. Self-organization from exposure to non-equilibrium and thermalized plasmas enable dramatic control of surface morphology, topography, composition, chemistry and structure yielding the ability to tune material properties with an unprecedented level of control. Deciphering self-organization mechanisms of nanoscale morphology (e.g. nanodots, ripples) and composition on a variety of materials including: compound semiconductors, semiconductors, ceramics, polymers and polycrystalline metals via low-energy ion-beam assisted plasma irradiation are critical to manipulate functionality in nanostructured systems. By operating at ultra-low energies near the damage threshold, irradiation-driven defect engineering can be optimized and surface-driven mechanisms controlled. Tunability of optical, electronic, magnetic and bioactive properties is realized by reaching metastable phases controlled by atomic-scale irradiation-driven mechanisms elucidated by novel in situ diagnosis coupled to atomistic-level computational tools. Emphasis will be made on tailored surface modification from plasma-enhanced environments on particle-surface interactions and their subsequent modification of hard and soft matter interfaces. In this review, we examine current trends towards in situ and in operando surface and sub-surface characterization to unravel atomic-scale mechanisms at the plasma-material interface. This work will emphasize on recent advances in the field of plasma and ion-induced nanopatterning and nanostructuring as well as ultra-thin film deposition. Future outlook will examine the critical role of complementary surface-sensitive techniques and trends towards advances in both in situ and in operando tooling.

Self-Assembled N-Heterocyclic Carbene-Based Carboxymethylated Dextran Monolayers on Gold as a Tunable Platform for Designing Affinity-Capture Biosensor Surfaces.

PubMed

Li, Zhijun; Munro, Kim; Narouz, Mina R; Lau, Andrew; Hao, Hongxia; Crudden, Cathleen M; Horton, J Hugh

2018-05-30

Sensor surfaces play a predominant role in the development of optical biosensor technologies for the analysis of biomolecular interactions. Thiol-based self-assembled monolayers (SAMs) on gold have been widely used as linker layers for sensor surfaces. However, the degradation of the thiol-gold bond can limit the performance and durability of such surfaces, directly impacting their performance and cost-effectiveness. To this end, a new family of materials based on N-heterocyclic carbenes (NHCs) has emerged as an alternative for surface modification, capable of self-assembling onto a gold surface with higher affinity and superior stability as compared to the thiol-based systems. Here we demonstrate three applications of NHC SAMs supporting a dextran layer as a tunable platform for developing various affinity-capture biosensor surfaces. We describe the development and testing of NHC-based dextran biosensor surfaces modified with each of streptavidin, nitrilotriacetic acid, and recombinant Protein A. These affinity-capture sensor surfaces enable oriented binding of ligands for optimal performance in biomolecular assays. Together, the intrinsic high stability and flexible design of the NHC biosensing platforms show great promise and open up exciting possibilities for future biosensing applications.

Structural Dynamics of Carbon Dots in Water and N, N-Dimethylformamide Probed by All-Atom Molecular Dynamics Simulations.

PubMed

Paloncýová, Markéta; Langer, Michal; Otyepka, Michal

2018-04-10

Carbon dots (CDs), one of the youngest members of the carbon nanostructure family, are now widely experimentally studied for their tunable fluorescence properties, bleaching resistance, and biocompatibility. Their interaction with biomolecular systems has also been explored experimentally. However, many atomistic details still remain unresolved. Molecular dynamics (MD) simulations enabling atomistic and femtosecond resolutions simultaneously are a well-established tool of computational chemistry which can provide useful insights into investigated systems. Here we present a full procedure for performing MD simulations of CDs. We developed a builder for generating CDs of a desired size and with various oxygen-containing surface functional groups. Further, we analyzed the behavior of various CDs differing in size, surface functional groups, and degrees of functionalization by MD simulations. These simulations showed that surface functionalized CDs are stable in a water environment through the formation of an extensive hydrogen bonding network. We also analyzed the internal dynamics of individual layers of CDs and evaluated the role of surface functional groups on CD stability. We observed that carboxyl groups interconnected the neighboring layers and decreased the rate of internal rotations. Further, we monitored changes in the CD shape caused by an excess of charged carboxyl groups or carbonyl groups. In addition to simulations in water, we analyzed the behavior of CDs in the organic solvent DMF, which decreased the stability of pure CDs but increased the level of interlayer hydrogen bonding. We believe that the developed protocol, builder, and parameters will facilitate future studies addressing various aspects of structural features of CDs and nanocomposites containing CDs.

Flexible Teflon nanocone array surfaces with tunable superhydrophobicity for self-cleaning and aqueous droplet patterning.

PubMed

Toma, Mana; Loget, Gabriel; Corn, Robert M

2014-07-23

Tunable hydrophobic/hydrophilic flexible Teflon nanocone array surfaces were fabricated over large areas (cm(2)) by a simple two-step method involving the oxygen plasma etching of a colloidal monolayer of polystyrene beads on a Teflon film. The wettability of the nanocone array surfaces was controlled by the nanocone array dimensions and various additional surface modifications. The resultant Teflon nanocone array surfaces were hydrophobic and adhesive (a "gecko" type of surface on which a water droplet has a high contact angle but stays in place) with a contact angle that correlated with the aspect ratio/sharpness of the nanocones. The surfaces switched to a superhydrophobic or "lotus" type of surface when hierarchical nanostructures were created on Teflon nanocones by modifying them with a gold nanoparticle (AuNPs) film. The nanocone array surfaces could be made superhydrophobic with a maximum contact angle of 160° by the further modification of the AuNPs with an octadecanethiol (C18SH) monolayer. Additionally, these nanocone array surfaces became hydrophilic when the nanocone surfaces were sequentially modified with AuNPs and hydrophilic polydopamine (PDA) layers. The nanocone array surfaces were tested for two potential applications: self-cleaning superhydrophobic surfaces and for the passive dispensing of aqueous droplets onto hybrid superhydrophobic/hydrophilic microarrays.

Organic Chemistry in Two Dimensions: Surface-Functionalized Polymers and Self-Assembled Monolayer Films

DTIC Science & Technology

1988-09-01

surfaces as components of materials . In particular, we hope to develop the ability to rationalize and predict the macroscooic properties of surfaces...of much of the current research in areas such as materials science, condensed matter and device physics, and polymer physical chemistry. Surface...6 Underlying our program in surface chemistry is a broad interest in the prop- erties of organic surfaces as components of materials . In particular

Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition

DOE PAGES

Kiraly, Brian T.; Jacobberger, Robert M.; Mannix, Andrew J.; ...

2015-10-27

Epitaxially oriented wafer-scale graphene grown directly on semiconducting Ge substrates is of high interest for both fundamental science and electronic device applications. To date, however, this material system remains relatively unexplored structurally and electronically, particularly at the atomic scale. To further understand the nature of the interface between graphene and Ge, we utilize ultrahigh vacuum scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) along with Raman and X-ray photoelectron spectroscopy to probe interfacial atomic structure and chemistry. STS reveals significant differences in electronic interactions between graphene and Ge(110)/Ge(111), which is consistent with a model of stronger interaction on Ge(110)more » leading to epitaxial growth. Raman spectra indicate that the graphene is considerably strained after growth, with more point-to-point variation on Ge(111). Furthermore, this native strain influences the atomic structure of the interface by inducing metastable and previously unobserved Ge surface reconstructions following annealing. These nonequilibrium reconstructions cover >90% of the surface and, in turn, modify both the electronic and mechanical properties of the graphene overlayer. Finally, graphene on Ge(001) represents the extreme strain case, where graphene drives the reorganization of the Ge surface into [107] facets. From this study, it is clear that the interaction between graphene and the underlying Ge is not only dependent on the substrate crystallographic orientation, but is also tunable and strongly related to the atomic reconfiguration of the graphene–Ge interface.« less

Thermomechanical and chemical properties of porous W/liquid Li hybrid systems as plasma-facing self-healing surfaces

NASA Astrophysics Data System (ADS)

Kapat, Aveek; Lang, Eric; Neff, Anton; Allain, Jean Paul

2017-10-01

The environmental conditions at the plasma-material interface of a future nuclear fusion reactor interacting will be extreme. The incident plasma will carry heat fluxes of the order of 100's of MWm-2 and particle fluxes that can average 1024 m-2s-1. The fusion reactor wall would need to operate at high temperatures near 800 C and the incident energy of particles will vary from a few eV ions to MeV neutrons. A hybrid system, inspired by self-healing solid-state concepts, combines the ductile phase of liquid Li within a solid phase porous W. The liquid Li serves to control hydrogen retention and provide vapor shielding, within the framework of a tunable porosity to optimize edge plasma conditions [2]. Additionally, the porous interface can also provide for effective defect sinks for high duty cycle neutron damage. The surface chemistry of liquid Li on a porous surface varied with D irradiation is studied and its effect on retention. Prior results with refractory alloys have demonstrated effective wetting properties [3]. These hybrid systems, as well as traditional W samples, are bombarded with 500eV D2+and Ar+ at 230oC and 300oC. The Li, O, and C XPS peaks were examined and compared to controls. Additionally, the porous W is characterized for thermo-mechanical properties. Work supported by USDOE Contract DE- DE-SC0014267.

Self-assembled tunable networks of sticky colloidal particles

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

Demortiere, Arnaud; Snezhko, Oleksiy Alexey; Sapozhnikov, Maksim

Self-assembled tunable networks of microscopic polymer fibers ranging from wavy colloidal "fur" to highly interconnected networks are created from polymer systems and an applied electric field. The networks emerge via dynamic self-assembly in an alternating (ac) electric field from a non-aqueous suspension of "sticky" polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles.

Optical and Acoustic Device Applications of Ferroelastic Crystals

NASA Astrophysics Data System (ADS)

Meeks, Steven Wayne

This dissertation presents the discovery of a means of creating uniformly periodic domain gratings in a ferroelastic crystal of neodymium pentaphosphate (NPP). The uniform and non-uniform domain structures which can be created in NPP have the potential applications as tunable active gratings for lasers, tunable diffraction gratings, tunable Bragg reflection gratings, tunable acoustic filters, optical modulators, and optical domain wall memories. The interaction of optical and acoustic waves with ferroelastic domain walls in NPP is presented in detail. Acoustic amplitude reflection coefficients from a single domain wall in NPP are much larger than other ferroelastic-ferroelectrics such as gadolinium molybdate (GMO). Domain walls of NPP are used to make two demonstration acoustic devices: a tunable comb filter and a tunable delay line. The tuning process is accomplished by moving the position of the reflecting surface (the domain wall). A theory of the reflection of optical waves from NPP domain walls is discussed. The optical reflection is due to a change in the polarization of the wave, and not a change in the index, as the wave crosses the domain wall. Theoretical optical power reflection coefficients show good agreement with the experimentally measured values. The largest optical reflection coefficient of a single domain wall is at a critical angle and is 2.2% per domain wall. Techniques of injecting periodic and aperiodic domain walls into NPP are presented. The nucleation process of the uniformly periodic domain gratings in NPP is described in terms of a newly-discovered domain structure, namely the ferroelastic bubble. A ferroelastic bubble is the elastic analogue to the well-known magnetic bubble. The period of the uniformly periodic domain grating is tunable from 100 to 0.5 microns and the grating period may be tuned relatively rapidly. The Bragg efficiency of these tunable gratings is 77% for an uncoated crystal. Several demonstration devices which use these periodic structures are discussed. These devices are a tunable active grating laser (TAG laser), a tunable active grating (TAG), and a tunable acoustic bulk wave filter.

Thermosensitive Triterpenoid-Appended Polymers with Broad Temperature Tunability Regulated by Host-Guest Chemistry.

PubMed

Hao, Jie; Gao, Yuxia; Li, Ying; Yan, Qiang; Hu, Jun; Ju, Yong

2017-09-05

Thermoresponsive water-soluble polymers are of great importance since they typically show a lower critical solution temperature (LCST) in aqueous media. In this research, the LCST change in broad temperature ranges of copolymers composed of natural glycyrrhetinic acid (GA)-based methacrylate and N,N'-dimethylacrylamides (DMAs) was investigated as a function of the concentration and the content of GA pendants. By complexation of GA pendants with β-cyclodextrin (β-CD), a side-chain polypseudorotaxane was obtained, which exhibited a significant increase in the LCST of copolymers. Moreover, the precisely reversible control of the LCST behavior was realized through adding a competing guest molecule, sodium 1-admantylcarboxylate. This work illustrates a simple and effective approach to endow water-soluble polymers with broad temperature tunability and helps us further understand the effect of a biocompatible host-guest complementary β-CD/GA pair on the thermoresponsive process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multimodal transmission property in a liquid-filled photonic crystal fiber

NASA Astrophysics Data System (ADS)

Lin, Wei; Miao, Yinping; Song, Binbin; Zhang, Hao; Liu, Bo; Liu, Yange; Yan, Donglin

2015-02-01

The multimode interference (MMI) effect in a liquid-filled photonic crystal fiber (PCF) has been experimentally demonstrated by fully infiltrating the air-hole cladding of a solid-core PCF with the refractive index (RI) matching liquid whose RI is close to the silica background. Due to the weak mode confinement capability of the cladding region, several high-order modes are excited to establish the multimode interference effect. The multimode interferometer shows a good temperature tunability of 12.30 nm/K, which makes it a good candidate for a highly tunable optical filtering as well as temperature sensing applications. Furthermore, this MMI effect would have great promise in various applications such as highly sensitive multi-parameter sensing, tunable optically filtering, and surface-enhanced Raman scattering.

Sputtered (barium(x), strontium(1-x))titanate, BST, thin films on flexible copper foils for use as a non-linear dielectric

NASA Astrophysics Data System (ADS)

Laughlin, Brian James

Ferroelectric thin film dielectrics have a non-linear DC bias dependent permittivity and can be used as the dielectric between metal electrodes to make tunable Metal-Insulator-Metal (MIM) capacitors. Varactors can be used to change the resonance frequency of a circuit allowing high speed frequency switching intra- and inter-band. 2-D geometric arrays of circuitry, where resonant frequency is independently controlled by tunable elements in each section of the array, allow electromagnetic radiation to be focused and the wave front spatial trajectory controlled. BST thin films varactors allow large DC fields to be applied with modest voltages providing large tunabilities. If ferroelectric thin film based devices are to complement or supplant semiconductor varactors as tunable elements then devices must be synthesized using a low cost processing techniques. The Film on Foil process methodology for depositing BST thin films on copper foil substrates was used to create BST/Cu specimens. Sputtering conditions were determined via BST deposition on platinized silicon. Sputtered BST thin films were synthesized on Cu foil substrates and densified using high T, controlled pO2 anneals. XRD showed the absence of Cu2O in as-deposited, post crystallization annealed, and post "re-ox" annealed state. Data showed a polycrystalline BST microstructure with a 55--80 nm grain size and no copper oxidation. HRTEM imaging qualitatively showed evidence of an abrupt BST/Cu interface free from oxide formation. Dielectric properties of Cu/BST/Pt MIM devices were measured as a function of DC bias, frequency, and temperature. A permittivity of 725 was observed with tunability >3:1 while zero bias tan delta of 0.02 saturating to tan delta < 0.003 at high DC bias. No significant frequency dispersion was observed over five decades of frequency. Temperature dependent measurements revealed a broad ferroelectric transition with a maximum at -32°C which sustains a large tunability over -150°C to 150°C. Sputtered BST thin films on copper foils show comparable dielectric properties to CVD deposited films on platinized silicon substrates proving sputtered BST/Cu specimens can reproduce excellent properties using a more cost-effective processing approach. A concept for reducing the temperature dependence was explored. Stacks of multiple compositions of BST thin films were considered as an extension of core-shell structures to a thin film format. Temperature profiles of BST/Cu films were modeled and mathematically combined in simulations of multi-composition film stacks. Simulations showed singular composition BST thin films could meet X7R specifications if a film has a 292 K < TC < 330 K. Simulations of series connected film stacks show only modest temperature profile broadening. Parallel connected dual composition film stacks showed a 75°C temperature range with essentially flat capacitance by simulating compositions that create a DeltaTC = 283°C. Maximum permittivity and temperature profile shape independent of film thickness or composition were assumed for simulations. BST/Cu thickness and compositions series were fabricated and dielectric properties characterized. These studies showed films could be grown from 300 nm and approaching 1 mum without changing the dielectric temperature response. In studying BST composition, an increasing TC shift was observed when increasing Ba mole fraction in BST thin films while tunability >3:1 was maintained. These results provide a route for creating temperature stable capacitors using a BST/Cu embodiment. An effort to reduce surface roughness of copper foil substrates adversely impacted BST film integrity by impairing adhesion. XPS analysis of high surface roughness commercially obtained Cu foils revealed a surface treatment of Zn-Cu-O that was not present on smooth Cu, thus an investigation of surface chemistry was conducted. Sessile drop experiments were performed to characterize Cu-BST adhesion and the effects of metallic Zn and ZnO in this system. The study revealed the work of adhesion of Cu-BST, WCu-BSTa ≈ 0.60 J m-2, an intermediate value relative to noble metals commonly used as electrodes and substrates for electroceramics. Examination of metallic Zn-BST adhesion revealed a dramatic decrease of WZn-BSTa ≈ 0.13 J m-2, while increasing the content of Zn in metallic (Cux,Zn1-x) alloys monotonically reduced WCux,Zn1-x -BSTa . Conversely, a Cu-ZnO interface showed a large work of adhesion, WCu-ZnOa = 2.0 J m-2. These results indicate that a ZnO interlayer between the substrate Cu and the BST thin film provides adequate adhesion for robust films on flexible copper foil substrates. Additionally, this study provided characterization of adhesion for Zn-Al2O3 and Zn-BST; data that does not exist in the open literature. A process has been developed for preparing ultra-smooth copper foils by evaporation and subsequent peel-off of copper metal layers from glass slides. These 15 mum thick substrates exhibited roughness values between 1 and 2 nm RMS and 9 nm RMS over 25 mum2 and 100 mum2 analysis areas, respectively. The deposition and crystallization of BST layers on these ultra-smooth foils is demonstrated. The fully processed dielectric layers exhibited field tunability >5:1, and could withstand fields >750 kV cm-1. High field loss tangents below 0.007 were observed, making these materials excellent candidates for microwave devices. Finally, a process of lamination and contact lithography was used to demonstrate patterning of micron-scale features suitable for microwave circuit element designs.

Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

PubMed

Pegalajar-Jurado, Adoracion; Easton, Christopher D; Crawford, Russell J; McArthur, Sally L

2015-03-26

Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

Surface chemistry of InP ridge structures etched in Cl{sub 2}-based plasma analyzed with angular XPS

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

Bouchoule, Sophie, E-mail: sophie.bouchoule@lpn.cnrs.fr; Cambril, Edmond; Guilet, Stephane

2015-09-15

Two x-ray photoelectron spectroscopy configurations are proposed to analyze the surface chemistry of micron-scale InP ridge structures etched in chlorine-based inductively coupled plasma (ICP). Either a classical or a grazing configuration allows to retrieve information about the surface chemistry of the bottom surface and sidewalls of the etched features. The procedure is used to study the stoichiometry of the etched surface as a function of ridge aspect ratio for Cl{sub 2}/Ar and Cl{sub 2}/H{sub 2} plasma chemistries. The results show that the bottom surface and the etched sidewalls are P-rich, and indicate that the P-enrichment mechanism is rather chemically driven.more » Results also evidence that adding H{sub 2} to Cl{sub 2} does not necessarily leads to a more balanced surface stoichiometry. This is in contrast with recent experimental results obtained with the HBr ICP chemistry for which fairly stoichiometric surfaces have been obtained.« less

Impact of surface chemistry

PubMed Central

Somorjai, Gabor A.; Li, Yimin

2011-01-01

The applications of molecular surface chemistry in heterogeneous catalyst technology, semiconductor-based technology, medical technology, anticorrosion and lubricant technology, and nanotechnology are highlighted in this perspective. The evolution of surface chemistry at the molecular level is reviewed, and the key roles of surface instrumentation developments for in situ studies of the gas–solid, liquid–solid, and solid–solid interfaces under reaction conditions are emphasized. PMID:20880833

Multifunctional Hybrid Multilayer Gate Dielectrics with Tunable Surface Energy for Ultralow-Power Organic and Amorphous Oxide Thin-Film Transistors.

PubMed

Byun, Hye-Ran; You, Eun-Ah; Ha, Young-Geun

2017-03-01

For large-area, printable, and flexible electronic applications using advanced semiconductors, novel dielectric materials with excellent capacitance, insulating property, thermal stability, and mechanical flexibility need to be developed to achieve high-performance, ultralow-voltage operation of thin-film transistors (TFTs). In this work, we first report on the facile fabrication of multifunctional hybrid multilayer gate dielectrics with tunable surface energy via a low-temperature solution-process to produce ultralow-voltage organic and amorphous oxide TFTs. The hybrid multilayer dielectric materials are constructed by iteratively stacking bifunctional phosphonic acid-based self-assembled monolayers combined with ultrathin high-k oxide layers. The nanoscopic thickness-controllable hybrid dielectrics exhibit the superior capacitance (up to 970 nF/cm 2 ), insulating property (leakage current densities <10 -7 A/cm 2 ), and thermal stability (up to 300 °C) as well as smooth surfaces (root-mean-square roughness <0.35 nm). In addition, the surface energy of the hybrid multilayer dielectrics are easily changed by switching between mono- and bifunctional phosphonic acid-based self-assembled monolayers for compatible fabrication with both organic and amorphous oxide semiconductors. Consequently, the hybrid multilayer dielectrics integrated into TFTs reveal their excellent dielectric functions to achieve high-performance, ultralow-voltage operation (< ± 2 V) for both organic and amorphous oxide TFTs. Because of the easily tunable surface energy, the multifunctional hybrid multilayer dielectrics can also be adapted for various organic and inorganic semiconductors, and metal gates in other device configurations, thus allowing diverse advanced electronic applications including ultralow-power and large-area electronic devices.

Click hydrogels, microgels and nanogels: emerging platforms for drug delivery and tissue engineering.

PubMed

Jiang, Yanjiao; Chen, Jing; Deng, Chao; Suuronen, Erik J; Zhong, Zhiyuan

2014-06-01

Hydrogels, microgels and nanogels have emerged as versatile and viable platforms for sustained protein release, targeted drug delivery, and tissue engineering due to excellent biocompatibility, a microporous structure with tunable porosity and pore size, and dimensions spanning from human organs, cells to viruses. In the past decade, remarkable advances in hydrogels, microgels and nanogels have been achieved with click chemistry. It is a most promising strategy to prepare gels with varying dimensions owing to its high reactivity, superb selectivity, and mild reaction conditions. In particular, the recent development of copper-free click chemistry such as strain-promoted azide-alkyne cycloaddition, radical mediated thiol-ene chemistry, Diels-Alder reaction, tetrazole-alkene photo-click chemistry, and oxime reaction renders it possible to form hydrogels, microgels and nanogels without the use of potentially toxic catalysts or immunogenic enzymes that are commonly required. Notably, unlike other chemical approaches, click chemistry owing to its unique bioorthogonal feature does not interfere with encapsulated bioactives such as living cells, proteins and drugs and furthermore allows versatile preparation of micropatterned biomimetic hydrogels, functional microgels and nanogels. In this review, recent exciting developments in click hydrogels, microgels and nanogels, as well as their biomedical applications such as controlled protein and drug release, tissue engineering, and regenerative medicine are presented and discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dynamic biophotonics: female squid exhibit sexually dimorphic tunable leucophores and iridocytes.

PubMed

DeMartini, Daniel G; Ghoshal, Amitabh; Pandolfi, Erica; Weaver, Aaron T; Baum, Mary; Morse, Daniel E

2013-10-01

Loliginid squid use tunable multilayer reflectors to modulate the optical properties of their skin for camouflage and communication. Contained inside specialized cells called iridocytes, these photonic structures have been a model for investigations into bio-inspired adaptive optics. Here, we describe two distinct sexually dimorphic tunable biophotonic features in the commercially important species Doryteuthis opalescens: bright stripes of rainbow iridescence on the mantle just beneath each fin attachment and a bright white stripe centered on the dorsal surface of the mantle between the fins. Both of these cellular features are unique to the female; positioned in the same location as the conspicuously bright white testis in the male, they are completely switchable, transitioning between transparency and high reflectivity. The sexual dimorphism, location and tunability of these features suggest that they may function in mating or reproduction. These features provide advantageous new models for investigation of adaptive biophotonics. The intensely reflective cells of the iridescent stripes provide a greater signal-to-noise ratio than the adaptive iridocytes studied thus far, while the cells constituting the white stripe are adaptive leucophores--unique biological tunable broadband scatterers containing Mie-scattering organelles activated by acetylcholine, and a unique complement of reflectin proteins.

Advances in understanding the surface chemistry of lignocellulosic biomass via time-of-flight secondary ion mass spectrometry

DOE PAGES

Tolbert, Allison K.; Ragauskas, Arthur J.

2016-12-12

Overcoming the natural recalcitrance of lignocellulosic biomass is necessary in order to efficiently convert biomass into biofuels or biomaterials and many times this requires some type of chemical pretreatment and/or biological treatment. While bulk chemical analysis is the traditional method of determining the impact a treatment has on biomass, the chemistry on the surface of the sample can differ from the bulk chemistry. Specifically, enzymes and microorganisms bind to the surface of the biomass and their efficiency could be greatly impacted by the chemistry of the surface. Therefore, it is important to study and understand the chemistry of the biomassmore » at the surface. Time-of- flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool that can spectrally and spatially analyze the surface chemistry of a sample. This review discusses the advances in understanding lignocellulosic biomass surface chemistry using the ToF-SIMS by addressing the instrument parameters, biomass sample preparation, and characteristic lignocellulosic ion fragmentation peaks along with their typical location in the plant cell wall. Furthermore, the use of the ToF-SIMS in detecting chemical changes due to chemical pretreatments, microbial treatments, and physical or genetic modifications is discussed along with possible future applications of the instrument in lignocellulosic biomass studies.« less

Advances in understanding the surface chemistry of lignocellulosic biomass via time-of-flight secondary ion mass spectrometry

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

Tolbert, Allison K.; Ragauskas, Arthur J.

Overcoming the natural recalcitrance of lignocellulosic biomass is necessary in order to efficiently convert biomass into biofuels or biomaterials and many times this requires some type of chemical pretreatment and/or biological treatment. While bulk chemical analysis is the traditional method of determining the impact a treatment has on biomass, the chemistry on the surface of the sample can differ from the bulk chemistry. Specifically, enzymes and microorganisms bind to the surface of the biomass and their efficiency could be greatly impacted by the chemistry of the surface. Therefore, it is important to study and understand the chemistry of the biomassmore » at the surface. Time-of- flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool that can spectrally and spatially analyze the surface chemistry of a sample. This review discusses the advances in understanding lignocellulosic biomass surface chemistry using the ToF-SIMS by addressing the instrument parameters, biomass sample preparation, and characteristic lignocellulosic ion fragmentation peaks along with their typical location in the plant cell wall. Furthermore, the use of the ToF-SIMS in detecting chemical changes due to chemical pretreatments, microbial treatments, and physical or genetic modifications is discussed along with possible future applications of the instrument in lignocellulosic biomass studies.« less

Tunable Liquid Gradient Refractive Index (L-GRIN) lens with two degrees of freedom.

PubMed

Mao, Xiaole; Lin, Sz-Chin Steven; Lapsley, Michael Ian; Shi, Jinjie; Juluri, Bala Krishna; Huang, Tony Jun

2009-07-21

We report a tunable optofluidic microlens configuration named the Liquid Gradient Refractive Index (L-GRIN) lens for focusing light within a microfluidic device. The focusing of light was achieved through the gradient refractive index (GRIN) within the liquid medium, rather than via curved refractive lens surfaces. The diffusion of solute (CaCl(2)) between side-by-side co-injected microfluidic laminar flows was utilized to establish a hyperbolic secant (HS) refractive index profile to focus light. Tailoring the refractive index profile by adjusting the flow conditions enables not only tuning of the focal distance (translation mode), but also shifting of the output light direction (swing mode), a second degree of freedom that to our knowledge has yet to be accomplished for in-plane tunable microlenses. Advantages of the L-GRIN lens also include a low fluid consumption rate, competitive focusing performance, and high compatibility with existing microfluidic devices. This work provides a new strategy for developing integrative tunable microlenses for a variety of lab-on-a-chip applications.

Citrate chemistry and biology for biomaterials design.

PubMed

Ma, Chuying; Gerhard, Ethan; Lu, Di; Yang, Jian

2018-05-04

Leveraging the multifunctional nature of citrate in chemistry and inspired by its important role in biological tissues, a class of highly versatile and functional citrate-based materials (CBBs) has been developed via facile and cost-effective polycondensation. CBBs exhibiting tunable mechanical properties and degradation rates, together with excellent biocompatibility and processability, have been successfully applied in vitro and in vivo for applications ranging from soft to hard tissue regeneration, as well as for nanomedicine designs. We summarize in the review, chemistry considerations for CBBs design to tune polymer properties and to introduce functionality with a focus on the most recent advances, biological functions of citrate in native tissues with the new notion of degradation products as cell modulator highlighted, and the applications of CBBs in wound healing, nanomedicine, orthopedic, cardiovascular, nerve and bladder tissue engineering. Given the expansive evidence for citrate's potential in biology and biomaterial science outlined in this review, it is expected that citrate based materials will continue to play an important role in regenerative engineering. Copyright © 2018 Elsevier Ltd. All rights reserved.

On-Chip Electrolytic Chemistry for the Tuning of Graphene Devices

NASA Astrophysics Data System (ADS)

Schmucker, Scott; Ruppalt, Laura; Culbertson, James; Do, Jae Won; Lyding, Joseph; Robinson, Jeremy; Cress, Cory

2015-03-01

The inherent interfacial nature of two-dimensional materials has motivated the tuning of these films by choice of substrate or chemical functionalization. Such parameters are generally selected during fabrication, and therefore remain static during device operation. However, the possibility of dynamic chemistry in a tunable solid-state system will enable the development of new devices which fully leverage the rich chemistry of graphenic materials. Here, we fabricate a novel device for localized, dynamic doping and functionalization of graphene that is compatible with CMOS processing. The device is enabled by a top-gated, solid electrochemical cell designed with calcium fluoride (CaF2) substituting the oxide of a traditional MOSFET. When the CaF2 is gated, F flows from cathode to anode, segregating Ca and F. In this work, one electrode is graphene. When saturated with fluorine, graphene undergoes covalent modification, becoming a wide-bandgap semiconductor. In contrast, when functionalized with calcium or dilute fluorine, graphene is electron or hole doped, respectively. With transport, Raman, and XPS, we demonstrate this lithographically localized and reversible modulation of graphene's electronic and chemical character.

From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry.

PubMed

Müller, Achim; Gouzerh, Pierre

2012-11-21

Following Nature's lessons, today chemists can cross the boundary of the small molecule world to construct multifunctional and highly complex molecular nano-objects up to protein size and even cell-like nanosystems showing responsive sensing. Impressive examples emerge from studies of the solutions of some oxoanions of the early transition metals especially under reducing conditions which enable the controlled linking of metal-oxide building blocks. The latter are available from constitutional dynamic libraries, thus providing the option to generate multifunctional unique nanoscale molecular systems with exquisite architectures, which even opens the way towards adaptive and evolutive (Darwinian) chemistry. The present review presents the first comprehensive report of current knowledge (including synthesis aspects not discussed before) regarding the related giant metal-oxide clusters mainly of the type {Mo(57)M'(6)} (M' = Fe(III), V(IV)) (torus structure), {M(72)M'(30)} (M = Mo, M' = V(IV), Cr(III), Fe(III), Mo(V)), {M(72)Mo(60)} (M = Mo, W) (Keplerates), {Mo(154)}, {Mo(176)}, {Mo(248)} ("big wheels"), and {Mo(368)} ("blue lemon") - all having the important transferable pentagonal {(M)M(5)} groups in common. These discoveries expanded the frontiers of inorganic chemistry to the mesoscopic world, while there is probably no collection of discrete inorganic compounds which offers such a versatile chemistry and the option to study new phenomena of interdisciplinary interest. The variety of different properties of the sphere- and wheel-type metal-oxide-based clusters can directly be related to their unique architectures: The spherical Keplerate-type capsules having 20 crown-ether-type pores and tunable internal functionalities allow the investigation of confined matter as well as that of sphere-surface-supramolecular and encapsulation chemistry - including related new aspects of the biologically important hydrophobic effects - but also of nanoscale ion transport and separation. The wheel-type molybdenum-oxide clusters exhibiting complex landscapes do not only have well-defined reaction sites but also show unprecedented adaptability regarding the integration of various kinds of matter. Applications in different fields, e.g. in materials science and catalysis including those in small spaces, investigated by several groups, are discussed while possible directions for future work are outlined.

Electrowetting-based optics

NASA Astrophysics Data System (ADS)

Kuiper, S.; Hendriks, B. H. W.; Hayes, R. A.; Feenstra, B. J.; Baken, J. M. E.

2005-09-01

Electrowetting is electrostatic manipulation of liquids. It can be used to displace and deform volumes of polar liquids. A very promising application area is optics. The surface of a volume of liquid can be used as a tunable lens and displacement of the liquid can change the refraction, diffraction or transmission of light when passing through the liquid. In this paper we describe a selection of various tunable optical components that make use of electrowetting, ranging from refractive and diffractive lenses to diaphragms and displays.

From 1D to 3D: Tunable Sub-10 nm Gaps in Large Area Devices.

PubMed

Zhou, Ziwei; Zhao, Zhiyuan; Yu, Ye; Ai, Bin; Möhwald, Helmuth; Chiechi, Ryan C; Yang, Joel K W; Zhang, Gang

2016-04-20

Tunable sub-10 nm 1D nanogaps are fabricated based on nanoskiving. The electric field in different sized nanogaps is investigated theoretically and experimentally, yielding nonmonotonic dependence and an optimized gap-width (5 nm). 2D nanogap arrays are fabricated to pack denser gaps combining surface patterning techniques. Innovatively, 3D multistory nanogaps are built via a stacking procedure, processing higher integration, and much improved electric field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable UV Laser Photolysis of NF2: Quantum Yield for NF(a1 delta) Production.

DTIC Science & Technology

1988-05-25

UV Laser Photolysis of NF2: Quantum Yield for NF(a A) Production ’v0 LR. F. HEIDNER, H . HELVAJIAN , 4and J. B. KOFFEND Aerophysics Laboratory...experiments, the chemistry of NF2 with various hydrocarbons has been studied. It has also been shown that the addition-elimination reaction between H and NF2...COMPLI R LEN SP, 3 ,HAND L BE AM~ H O [ I , , i 1 CAIHOC IAM COOLED GaAs CAPACITANCE PHOTOTUIBE MANOMETER _ LENS /’~ ~L + . ANMEE _.... BANDPASS FILTER

Gold nanorods-silicone hybrid material films and their optical limiting property

NASA Astrophysics Data System (ADS)

Li, Chunfang; Qi, Yanhai; Hao, Xiongwen; Peng, Xue; Li, Dongxiang

2015-10-01

As a kind of new optical limiting materials, gold nanoparticles have optical limiting property owing to their optical nonlinearities induced by surface plasmon resonance (SPR). Gold nanorods (GNRs) possess transversal SPR absorption and tunable longitudinal SPR absorption in the visible and near-infrared region, so they can be used as potential optical limiting materials against tunable laser pulses. In this letter, GNRs were prepared using seed-mediated growth method and surface-modified by silica coating to obtain good dispersion in polydimethylsiloxane prepolymers. Then the silicone rubber films doped with GNRs were prepared after vulcanization, whose optical limiting property and optical nonlinearity were investigated. The silicone rubber samples doped with more GNRs were found to exhibit better optical limiting performance.

Mechanical stress-controlled tunable active frequency-selective surface

NASA Astrophysics Data System (ADS)

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

2017-01-01

This study proposes a tunable active frequency-selective surface (AFSS) realized by mechanically expanding or contracting a split-ring resonator (SRR) array. The proposed AFSS transfers mechanical stress from its elastic substrate to the top of the SRR, thereby achieving electromagnetic (EM) modulation without the need for an additional external power supply, meeting the requirements for the target application: the invisibility cloak. The operating mechanism of the proposed AFSS differs from those of other AFSSs, supporting modulations in arbitrary frequencies in the target range. The proposed stress-controlled or strain-induced EM modulation proves the existence of an identical and linear relationship between the strain gradient and the frequency shift, implying its suitability for other EM modulation ranges and applications.

Experimental demonstration of tunable directional excitation of surface plasmon polaritons with a subwavelength metallic double slit

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

Li Xiaowei; Tsinghua-Foxconn Nanotechnology Research Center, Tsinghua University, Beijing 100084; Tan Qiaofeng

2011-06-20

We demonstrate experimentally the directional excitation of surface plasmon polaritons (SPPs) on a metal film by a subwavelength double slit under backside illumination, based on the interference of SPPs generated by the two slits. By varying the incident angle, the SPPs can be tunably directed into two opposite propagating directions with a predetermined splitting ratio. Under certain incident angle, unidirectional SPP excitation can be achieved. This compact directional SPP coupler is potentially useful for many on-chip applications. As an example, we show the integration of the double-slit couplers with SPP Bragg mirrors, which can effectively realize selective coupling of SPPsmore » into different ports in an integrated plasmonic chip.« less

Tunable plasmonic nanocavity with Ge2Sb2Te5 film for directional launching of surface plasmons

NASA Astrophysics Data System (ADS)

Jeong, Hee-Dong; Hwang, Chi-Young; Kim, Hyuntai; Choi, Muhan; Lee, Seung-Yeol

2018-04-01

A tunable plasmonic nanocavity which consists of a metallic groove with submerged ultra-thin Ge2Sb2Te5 film is proposed for controlling the on/off characteristics of directional surface plasmon polaritions (SPPs) launching. Different mechanisms of launching SPPs using two orthogonal incident polarizations are investigated to reveal the SPP generation characteristics from the proposed nanocavity. By choosing the appropriate position of Ge2Sb2Te5 film, we report that the directional launching characteristics of SPPs can be controlled by changing the phase state of extremely small volume of Ge2Sb2Te5 film, which shows up to 37 dB of extinction ratio changing characteristics.

Trapping of drops by wetting defects

PubMed Central

't Mannetje, Dieter; Ghosh, Somnath; Lagraauw, Rudy; Otten, Simon; Pit, Arjen; Berendsen, Christian; Zeegers, Jos; van den Ende, Dirk; Mugele, Frieder

2014-01-01

Controlling the motion of drops on solid surfaces is crucial in many natural phenomena and technological processes including the collection and removal of rain drops, cleaning technology and heat exchangers. Topographic and chemical heterogeneities on solid surfaces give rise to pinning forces that can capture and steer drops in desired directions. Here we determine general physical conditions required for capturing sliding drops on an inclined plane that is equipped with electrically tunable wetting defects. By mapping the drop dynamics on the one-dimensional motion of a point mass, we demonstrate that the trapping process is controlled by two dimensionless parameters, the trapping strength measured in units of the driving force and the ratio between a viscous and an inertial time scale. Complementary experiments involving superhydrophobic surfaces with wetting defects demonstrate the general applicability of the concept. Moreover, we show that electrically tunable defects can be used to guide sliding drops along actively switchable tracks—with potential applications in microfluidics. PMID:24721935

Flexible coherent control of plasmonic spin-Hall effect.

PubMed

Xiao, Shiyi; Zhong, Fan; Liu, Hui; Zhu, Shining; Li, Jensen

2015-09-29

The surface plasmon polariton is an emerging candidate for miniaturizing optoelectronic circuits. Recent demonstrations of polarization-dependent splitting using metasurfaces, including focal-spot shifting and unidirectional propagation, allow us to exploit the spin degree of freedom in plasmonics. However, further progress has been hampered by the inability to generate more complicated and independent surface plasmon profiles for two incident spins, which work coherently together for more flexible and tunable functionalities. Here by matching the geometric phases of the nano-slots on silver to specific superimpositions of the inward and outward surface plasmon profiles for the two spins, arbitrary spin-dependent orbitals can be generated in a slot-free region. Furthermore, motion pictures with a series of picture frames can be assembled and played by varying the linear polarization angle of incident light. This spin-enabled control of orbitals is potentially useful for tip-free near-field scanning microscopy, holographic data storage, tunable plasmonic tweezers, and integrated optical components.

Three-Dimensional Porous Particles Composed of Curved, Two-Dimensional, Nano-Sized Layers for Li-Ion Batteries

NASA Technical Reports Server (NTRS)

Yushin, Gleb; Evanoff, Kara; Magasinski, Alexander

2012-01-01

Thin Si films coated on porous 3D particles composed of curved 2D graphene sheets have been synthesized utilizing techniques that allow for tunable properties. Since graphene exhibits specific surface area up to 100 times higher than carbon black or graphite, the deposition of the same mass of Si on graphene is much faster in comparison -- a factor which is important for practical applications. In addition, the distance between graphene layers is tunable and variation in the thickness of the deposited Si film is feasible. Both of these characteristics allow for optimization of the energy and power characteristics. Thicker films will allow higher capacity, but slower rate capabilities. Thinner films will allow more rapid charging, or higher power performance. In this innovation, uniform deposition of Si and C layers on high-surface area graphene produced granules with specific surface area (SSA) of 5 sq. m/g.

Role of Integrin Subunits in Mesenchymal Stem Cell Differentiation and Osteoblast Maturation on Graphitic Carbon-coated Microstructured Surfaces

PubMed Central

Olivares-Navarrete, Rene; Rodil, Sandra E.; Hyzy, Sharon L.; Dunn, Ginger R.; Almaguer-Flores, Argelia; Schwartz, Zvi; Boyan, Barbara D.

2015-01-01

Surface roughness, topography, chemistry, and energy promote osteoblast differentiation and increase osteogenic local factor production in vitro and bone-to-implant contact in vivo, but the mechanisms involved are not well understood. Knockdown of integrin heterodimer alpha2beta1 (α2β1) blocks the osteogenic effects of the surface, suggesting signaling by this integrin homodimer is required. The purpose of the present study was to separate effects of surface chemistry and surface structure on integrin expression by coating smooth or rough titanium (Ti) substrates with graphitic carbon, retaining surface morphology but altering surface chemistry. Ti surfaces (smooth [Ra<0.4μm], rough [Ra≥3.4μm]) were sputter-coated using a magnetron sputtering system with an ultrapure graphite target, producing a graphitic carbon thin film. Human mesenchymal stem cells and MG63 osteoblast-like cells had higher mRNA for integrin subunits α1, α2, αv, and β1 on rough surfaces in comparison to smooth, and integrin αv on graphitic-carbon-coated rough surfaces in comparison to Ti. Osteogenic differentiation was greater on rough surfaces in comparison to smooth, regardless of chemistry. Silencing integrins β1, α1, or α2 decreased osteoblast maturation on rough surfaces independent of surface chemistry. Silencing integrin αv decreased maturation only on graphitic carbon-coated surfaces, not on Ti. These results suggest a major role of the integrin β1 subunit in roughness recognition, and that integrin alpha subunits play a major role in surface chemistry recognition. PMID:25770999

Aptamer functionalized noble metal particles for bioanalytical and biomedical applications

NASA Astrophysics Data System (ADS)

Yasun, Emir

Noble metal particles, especially gold (Au) and silver (Ag) have been exploited in a broad range of biological applications due to their unique intrinsic features that depend on their physical appearance or optoelectronic properties, which can be tuned with the change in the size or shape of those particles. Thus, this tunability enables gold nanoparticles (AuNPs) to be used in biomedical diagnostic and therapeutical applications. In photothermal therapy applications, nanomaterials, which can absorb efficiently in NIR region, are utilized since the healthy tissue or cells can't absorb at this spectral region. Among AuNPs, gold nanorods (AuNRs) are one of the best candidates for hyperthermia therapy of cancer cells with their high absorption cross-sections and tunable absorption maxima in NIR region. When this unique optical property is combined with the specificity against cancer cells utilized by aptamer conjugations, AuNRs become to be one of the most important nanoparticles employed in both cancer cell sensing and therapy. However, one drawback of AuNRs is having the surfactant CTAB on their surface, which can cause nonspecificity and cytotoxicity. In this research, the side effects of CTAB are passivated by BSA modification, where the nonspecificity and cytotoxicity are dramatically decreased prior to the NIR treatment. Recognition of changes in the rare cancer protein abundances can lead the early diagnosis of cancer, so capturing these low abundance proteins has a great significance. In this research, firstly, aptamer conjugated AuNRs were used to capture 1ng of a-thrombin effectively from plasma samples as model system. Then both aptamer conjugated AuNRs and silver microspheres (SMSs) are used to capture the biomarker proteins of a colon cancer cell line, DLD-1. Gold and silver surfaces can easily be modified through thiolate chemistry, compared to the tedious modification steps for the magnetic particles, so more aptamer immobilization can be achieved for AuNRs and SMSs, which can increase the possibility of binding to the target protein. Furthermore, SMSs offer a novel separation method, gravitational separation owing to their heavy nature. In this way, there is no need for an external stimuli to separate the captured proteins and protein isolation can take only seconds.

Shrink-induced graphene sensor for alpha-fetoprotein detection with low-cost self-assembly and label-free assay

NASA Astrophysics Data System (ADS)

Sando, Shota; Zhang, Bo; Cui, Tianhong

2017-12-01

Combination of shrink induced nano-composites technique and layer-by-layer (LbL) self-assembled graphene challenges controlling surface morphology. Adjusting shrink temperature achieves tunability on graphene surface morphology on shape memory polymers, and it promises to be an alternative in fields of high-surface-area conductors and molecular detection. In this study, self-assembled graphene on a shrink polymer substrate exhibits nanowrinkles after heating. Induced nanowrinkles on graphene with different shrink temperature shows distinct surface roughness and wettability. As a result, it becomes more hydrophilic with higher shrink temperatures. The tunable wettability promises to be utilized in, for example, microfluidic devices. The graphene on shrink polymer also exhibits capability of being used in sensing applications for pH and alpha-fetoprotein (AFP) detection with advantages of label free and low cost, due to self-assembly technique, easy functionalization, and antigen-antibody reaction on graphene surface. The detection limit of AFP detection is down to 1 pg/mL, and therefore the sensor also has a significant potential for biosensing as it relies on low-cost self-assembly and label-free assay.

Temperature-tunable wettability on a bioinspired structured graphene surface for fog collection and unidirectional transport.

PubMed

Song, Yun-Yun; Liu, Yan; Jiang, Hao-Bo; Li, Shu-Yi; Kaya, Cigdem; Stegmaier, Thomas; Han, Zhi-Wu; Ren, Lu-Quan

2018-02-22

We designed a type of smart bioinspired wettable surface with tip-shaped patterns by combining polydimethylsiloxane (PDMS) and graphene (PDMS/G). The laser etched porous graphene surface can produce an obvious wettability change between 200 °C and 0 °C due to a change in aperture size and chemical components. We demonstrate that the cooperation of the geometrical structure and the controllable wettability play an important role in water gathering, and surfaces with tip-shaped wettability patterns can quickly drive tiny water droplets toward more wettable regions, so making a great contribution to the improvement of water collection efficiency. In addition, due to the effective cooperation between super hydrophobic and hydrophilic regions of the special tip-shaped pattern, unidirectional water transport on the 200 °C heated PDMS/G surface can be realized. This study offers a novel insight into the design of temperature-tunable materials with interphase wettability that may enhance fog collection efficiency in engineering liquid harvesting equipment, and realize unidirectional liquid transport, which could potentially be applied to the realms of microfluidics, medical devices and condenser design.

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

DOE PAGES

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.; ...

2017-07-31

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

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

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

PubMed

Pekkanen, Allison M; Mondschein, Ryan J; Williams, Christopher B; Long, Timothy E

2017-09-11

Supramolecular chemistry continues to experience widespread growth, as fine-tuned chemical structures lead to well-defined bulk materials. Previous literature described the roles of hydrogen bonding, ionic aggregation, guest/host interactions, and π-π stacking to tune mechanical, viscoelastic, and processing performance. The versatility of reversible interactions enables the more facile manufacturing of molded parts with tailored hierarchical structures such as tissue engineered scaffolds for biological applications. Recently, supramolecular polymers and additive manufacturing processes merged to provide parts with control of the molecular, macromolecular, and feature length scales. Additive manufacturing, or 3D printing, generates customizable constructs desirable for many applications, and the introduction of supramolecular interactions will potentially increase production speed, offer a tunable surface structure for controlling cell/scaffold interactions, and impart desired mechanical properties through reinforcing interlayer adhesion and introducing gradients or self-assembled structures. This review details the synthesis and characterization of supramolecular polymers suitable for additive manufacture and biomedical applications as well as the use of supramolecular polymers in additive manufacturing for drug delivery and complex tissue scaffold formation. The effect of supramolecular assembly and its dynamic behavior offers potential for controlling the anisotropy of the printed objects with exquisite geometrical control. The potential for supramolecular polymers to generate well-defined parts, hierarchical structures, and scaffolds with gradient properties/tuned surfaces provides an avenue for developing next-generation biomedical devices and tissue scaffolds.

Characterisation of the protein corona using tunable resistive pulse sensing: determining the change and distribution of a particle's surface charge.

PubMed

Blundell, Emma L C J; Healey, Matthew J; Holton, Elizabeth; Sivakumaran, Muttuswamy; Manstana, Sarabjit; Platt, Mark

2016-08-01

The zeta potential of the protein corona around carboxyl particles has been measured using tunable resistive pulse sensing (TRPS). A simple and rapid assay for characterising zeta potentials within buffer, serum and plasma is presented monitoring the change, magnitude and distribution of proteins on the particle surface. First, we measure the change in zeta potential of carboxyl-functionalised nanoparticles in solutions that contain biologically relevant concentrations of individual proteins, typically constituted in plasma and serum, and observe a significant difference in distributions and zeta values between room temperature and 37 °C assays. The effect is protein dependent, and the largest difference between the two temperatures is recorded for the γ-globulin protein where the mean zeta potential changes from -16.7 to -9.0 mV for 25 and 37 °C, respectively. This method is further applied to monitor particles placed into serum and/or plasma. A temperature-dependent change is again observed with serum showing a 4.9 mV difference in zeta potential between samples incubated at 25 and 37 °C; this shift was larger than that observed for samples in plasma (0.4 mV). Finally, we monitor the kinetics of the corona reorientation for particles initially placed into serum and then adding 5 % (V/V) plasma. The technology presented offers an interesting insight into protein corona structure and kinetics of formation measured in biologically relevant solutions, i.e. high protein, high salt levels, and its particle-by-particle analysis gives a measure of the distribution of particle zeta potential that may offer a better understanding of the behaviour of nanoparticles in solution. Graphical Abstract The relative velocity of a nanoparticle as it traverses a nanopore can be used to determine its zeta potential. Monitoring the changes in translocation speeds can therefore be used to follow changes to the surface chemistry/composition of 210 nm particles that were placed into protein rich solutions, serum and plasma. The particle-by-particle measurements allow the zeta potential and distribution of the particles to be characterised, illustrating the effects of protein concentration and temperature on the protein corona. When placed into a solution containing a mixture of proteins, the affinity of the protein to the particle's surface determines the corona structure, and is not dependent on the protein concentration.

Controllable asymmetric transmission via gap-tunable acoustic metasurface

NASA Astrophysics Data System (ADS)

Liu, Bingyi; Jiang, Yongyuan

2018-04-01

In this work, we utilize the acoustic gradient metasurface (AGM) of a bilayer configuration to realize the controllable asymmetric transmission. Relying on the adjustable gap between the two composing layers, the metasurface could switch from symmetric transmission to asymmetric transmission at a certain gap value. The underlying mechanism is attributed to the interference between the forward diffracted waves scattered by the surface bound waves at two air-AGM interfaces, which is apparently influenced by the interlayer distance. We further utilize the hybrid acoustic elements to construct the desired gradient metasurface with a tunable gap and validate the controllable asymmetric transmission with full-wave simulations. Our work provides the solution for actively controlling the transmission property of an acoustic element, which shows potential application in acoustic communication as a dynamic tunable acoustic diode.

Multiscale Simulations of ALD in Cross Flow Reactors

DOE PAGES

Yanguas-Gil, Angel; Libera, Joseph A.; Elam, Jeffrey W.

2014-08-13

In this study, we have developed a multiscale simulation code that allows us to study the impact of surface chemistry on the coating of large area substrates with high surface area/high aspect-ratio features. Our code, based on open-source libraries, takes advantage of the ALD surface chemistry to achieve an extremely efficient two-way coupling between reactor and feature length scales, and it can provide simulated quartz crystal microbalance and mass spectrometry data at any point of the reactor. By combining experimental surface characterization with simple analysis of growth profiles in a tubular cross flow reactor, we are able to extract amore » minimal set of reactions to effectively model the surface chemistry, including the presence of spurious CVD, to evaluate the impact of surface chemistry on the coating of large, high surface area substrates.« less

Development of Polydimethylsiloxane Substrates with Tunable Elastic Modulus to Study Cell Mechanobiology in Muscle and Nerve

PubMed Central

Palchesko, Rachelle N.; Zhang, Ling; Sun, Yan; Feinberg, Adam W.

2012-01-01

Mechanics is an important component in the regulation of cell shape, proliferation, migration and differentiation during normal homeostasis and disease states. Biomaterials that match the elastic modulus of soft tissues have been effective for studying this cell mechanobiology, but improvements are needed in order to investigate a wider range of physicochemical properties in a controlled manner. We hypothesized that polydimethylsiloxane (PDMS) blends could be used as the basis of a tunable system where the elastic modulus could be adjusted to match most types of soft tissue. To test this we formulated blends of two commercially available PDMS types, Sylgard 527 and Sylgard 184, which enabled us to fabricate substrates with an elastic modulus anywhere from 5 kPa up to 1.72 MPa. This is a three order-of-magnitude range of tunability, exceeding what is possible with other hydrogel and PDMS systems. Uniquely, the elastic modulus can be controlled independently of other materials properties including surface roughness, surface energy and the ability to functionalize the surface by protein adsorption and microcontact printing. For biological validation, PC12 (neuronal inducible-pheochromocytoma cell line) and C2C12 (muscle cell line) were used to demonstrate that these PDMS formulations support cell attachment and growth and that these substrates can be used to probe the mechanosensitivity of various cellular processes including neurite extension and muscle differentiation. PMID:23240031

Particle generator

DOEpatents

Hess, Wayne P.; Joly, Alan G.; Gerrity, Daniel P.; Beck, Kenneth M.; Sushko, Peter V.; Shlyuger, Alexander L.

2005-06-28

Energy tunable solid state sources of neutral particles are described. In a disclosed embodiment, a halogen particle source includes a solid halide sample, a photon source positioned to deliver photons to a surface of the halide, and a collimating means positioned to accept a spatially defined plume of hyperthermal halogen particles emitted from the sample surface.

Novel Design of Tunable Microlens with Lowered Driving Voltage and Iris with Conformal Antireflective Surface

NASA Astrophysics Data System (ADS)

Almoallem, Yousuf Dawood

Miniaturizing camera systems as required in many new compact devices places a severe restriction on the device size and power consumption. In modern life nowadays, a daily used compact devices like mobile phones and tablets must have some essential components such as single or multiple tiny cameras, as a component of micro-optical systems. In fact, for most of the current miniaturized cameras, optical power is varied based on the traditional situation where the distances between the lenses are mechanically varied relying on old-fashioned voice coil motors or equivalent mechanical drivers. Spatial and power consumption could be scaled down drastically with much faster response time when the revolutionary alternative liquid tunable microlens is utilized after acquiring a good understanding of microfluidics. The influence of interfacial tension as a key metric in controlling microfluidics systems (e.g. liquid microlens) has drawn considerable attention in biomedical, industrial, military fields over the past decade. Tunable microlenses overcome aforementioned concerns of miniaturizing optical systems and present a viable solution by tuning the focal length of lenses via, for example, variation in the lens curvature. Here, a novel tunable dielectrophoretic (DEP)-based tunable lens is presented. Out of many other mechanisms of tuning the lenses, the dielectric mechanism is especially promising since having the capability to achieve a faster response and overcome the electrolysis issue. Nonetheless, DEP usually requires high driving voltage levels. The proposed design is operating with a lowered voltage level and is based on a tunable dielectric liquid lens with a double-sided electrode design, unlike in the conventional scheme with a single-sided electrode design. The design methodology, geometrical analysis, device fabrication, simulation, and testing are demonstrated. Furthermore, the design, simulation, fabrication and characterization of a black-silicon (BSi) based iris is discussed. Reducing undesirable light stray reflections from surfaces is desired in many 3D optical elements, such as supporting optomechanical mounts, irises, optical filters, solar cells, and photolithography underlying layers. BSi (as antireflective nanostructures) provides a potential economic solution which is highly absorptive across the visible spectrum to replace many currently used yet expensive coating materials. Si nanowires (SiNW) were formed using a metal-assisted chemical (MAC) etching process to get a conformal antireflective property on the iris 3D structure including sharp tips and sidewalls. A significant reduction in undesirable light stray reflections was achieved as a result of successful implementation of the conformal antireflective surface on all facets of fabricated irises to eliminate undesirable light stray reflections.

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

PubMed Central

Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

2014-01-01

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70–90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties. PMID:25323067

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

NASA Astrophysics Data System (ADS)

Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

2014-10-01

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

Gold Nanoparticles with Externally Controlled, Reversible Shifts of Local Surface Plasmon Resonance Bands

PubMed Central

Yavuz, Mustafa S.; Jensen, Gary C.; Penaloza, David P.; Seery, Thomas A. P.; Pendergraph, Samuel A.; Rusling, James F.; Sotzing, Gregory A.

2010-01-01

We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

WATER CHEMISTRY ASSESSMENT METHODS

EPA Science Inventory

This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

Surface chemistry: Key to control and advance myriad technologies

PubMed Central

Yates, John T.; Campbell, Charles T.

2011-01-01

This special issue on surface chemistry is introduced with a brief history of the field, a summary of the importance of surface chemistry in technological applications, a brief overview of some of the most important recent developments in this field, and a look forward to some of its most exciting future directions. This collection of invited articles is intended to provide a snapshot of current developments in the field, exemplify the state of the art in fundamental research in surface chemistry, and highlight some possibilities in the future. Here, we show how those articles fit together in the bigger picture of this field. PMID:21245359

Airborne measurements of CO2 column concentrations made with a pulsed IPDA lidar using a multiple-wavelength-locked laser and HgCdTe APD detector

NASA Astrophysics Data System (ADS)

Abshire, James B.; Ramanathan, Anand K.; Riris, Haris; Allan, Graham R.; Sun, Xiaoli; Hasselbrack, William E.; Mao, Jianping; Wu, Stewart; Chen, Jeffrey; Numata, Kenji; Kawa, Stephan R.; Yang, Mei Ying Melissa; DiGangi, Joshua

2018-04-01

Here we report on measurements made with an improved CO2 Sounder lidar during the ASCENDS 2014 and 2016 airborne campaigns. The changes made to the 2011 version of the lidar included incorporating a rapidly wavelength-tunable, step-locked seed laser in the transmitter, using a much more sensitive HgCdTe APD detector and using an analog digitizer with faster readout time in the receiver. We also improved the lidar's calibration approach and the XCO2 retrieval algorithm. The 2014 and 2016 flights were made over several types of topographic surfaces from 3 to 12 km aircraft altitudes in the continental US. The results are compared to the XCO2 values computed from an airborne in situ sensor during spiral-down maneuvers. The 2014 results show significantly better performance and include measurement of horizontal gradients in XCO2 made over the Midwestern US that agree with chemistry transport models. The results from the 2016 airborne lidar retrievals show precisions of ˜ 0.7 parts per million (ppm) with 1 s averaging over desert surfaces, which is an improvement of about 8 times compared to similar measurements made in 2011. Measurements in 2016 were also made over fresh snow surfaces that have lower surface reflectance at the laser wavelengths. The results from both campaigns showed that the mean values of XCO2 retrieved from the lidar consistently agreed with those based on the in situ sensor to within 1 ppm. The improved precision and accuracy demonstrated in the 2014 and 2016 flights should benefit future airborne science campaigns and advance the technique's readiness for a space-based instrument.

Tunable hard X-ray spectrometer utilizing asymmetric planes of a quartz transmission crystal

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

Seely, John F., E-mail: seelyjf@gmail.com; Feldman, Uri; Henins, Albert

2016-05-15

A Cauchois type hard x-ray spectrometer was developed that utilizes the (301) diffraction planes at an asymmetric angle of 23.51° to the normal to the surface of a cylindrically curved quartz transmission crystal. The energy coverage is tunable by rotating the crystal and the detector arm, and spectra were recorded in the 8 keV to 20 keV range with greater than 2000 resolving power. The high resolution results from low aberrations enabled by the nearly perpendicular angle of the diffracted rays with the back surface of the crystal. By using other asymmetric planes of the same crystal and rotating tomore » selected angles, the spectrometer can operate with high resolution up to 50 keV.« less

Enhanced optical transmission through double-overlapped annular aperture array

NASA Astrophysics Data System (ADS)

Wang, Chaonan; Bai, Ming; Jin, Ming

2012-07-01

In this paper, transmission properties through an array of concentric or eccentric double-overlapped annular apertures (CDOAAs or EDOAAs) are investigated. It is demonstrated that local surface plasmon-assisted TE11-like modes in CDOAAs exhibit a blue shift with the increasing overlapped factor. For EDOAAs with asymmetric annular apertures in both directions, a new resonant peak can be excited at a larger wavelength using linearly polarised light, which corresponds to extreme field localisation around the narrowest gap attributed to the gap plasmons' excitation and is quite sensitive to the offset of the eccentric centre island. These properties provide a possible method to achieve multiplexed and tunable wavelength selection using different local surface plasmon resonances and are of significant potential applicable value to the designing of tunable optical devices.

Tunable antenna radome based on graphene frequency selective surface

NASA Astrophysics Data System (ADS)

Qu, Meijun; Rao, Menglou; Li, Shufang; Deng, Li

2017-09-01

In this paper, a graphene-based frequency selective surface (FSS) is proposed. The proposed FSS exhibits a tunable bandpass filtering characteristic due to the alterable conductivity of the graphene strips which is controlled by chemical potential. Based on the reconfigurable bandpass property of the proposed FSS, a cylindrical antenna radome is designed using the FSS unit cells. A conventional omnidirectional dipole can realize a two-beam directional pattern when it is placed into the proposed antenna radome. Forward and backward endfire radiations of the dipole loaded with the radome is realized by properly adjusting the chemical potential. The proposed antenna radome is extremely promising for beam-scanning in terahertz and mid-infrared plasmonic devices and systems when the gain of a conventional antenna needs to be enhanced.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles.

PubMed

Wu, Pae C; Khoury, Christopher G; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V; Vo-Dinh, Tuan; Brown, April S; Everitt, Henry O

2009-09-02

Size-controlled gallium nanoparticles deposited on sapphire were explored as alternative substrates to enhance Raman spectral signatures. Gallium's resilience following oxidation is inherently advantageous in comparison with silver for practical ex vacuo nonsolution applications. Ga nanoparticles were grown using a simple molecular beam epitaxy-based fabrication protocol, and monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry allowed the nanoparticles to be easily controlled for size. The Raman spectra obtained from cresyl fast violet (CFV) deposited on substrates with differing mean nanoparticle sizes represent the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Nonoptimized aggregate enhancement factors of approximately 80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles

PubMed Central

Wu, Pae C; Khoury, Christopher G.; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V.; Vo-Dinh, Tuan; Brown, April S.; Everitt, Henry O.

2009-01-01

Size-controlled gallium nanoparticles deposited on sapphire are explored as alternative substrates to enhance Raman spectral signatures. Gallium’s resilience following oxidation is inherently advantageous compared to silver for practical ex vacuo, non-solution applications. Ga nanoparticles are grown using a simple, molecular beam epitaxy-based fabrication protocol, and by monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry, the nanoparticles are easily controlled for size. Raman spectroscopy performed on cresyl fast violet (CFV) deposited on substrates of differing mean nanoparticle size represents the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Non-optimized aggregate enhancement factors of ~80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm. PMID:19655747

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

DOE PAGES

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura; ...

2016-10-19

One important advance in fluid surface control was the amphiphilic surfactant composed of coupled molecular structures (i.e., hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e., hard water). This disrupts surfactant function and requires extensive use of undesirable and expensive chelating additives. We show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel–Crafts acylation within single layer (SPP) zeolite catalysts. Finally, these alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

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

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura

2016-11-23

An important advance in fluid surface control was the amphiphilic surfactant comprised of coupled molecular structures (i.e. hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e. hard water), which disrupt surfactant function and require extensive use of undesirable and expensive chelating additives. Here we show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel-Crafts acylation within single layer (SPP) zeolite catalysts. These alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Design of tunable ultraviolet (UV) absorbance by controlling the Agsbnd Al co-sputtering deposition

NASA Astrophysics Data System (ADS)

Zhang, Xin-Yuan; Chen, Lei; Wang, Yaxin; Zhang, Yongjun; Yang, Jinghai; Choi, Hyun Chul; Jung, Young Mee

2018-05-01

Changing the structure and composition of a material can alter its properties; hence, the controlled fabrication of metal nanostructures plays a key role in a wide range of applications. In this study, the structure of Agsbnd Al ordered arrays fabricated by co-sputtering deposition onto a monolayer colloidal crystal significantly increased its ultraviolet (UV) absorbance owing to a tunable localized surface plasmon resonance (LSPR) effect. By increasing the spacing between two nanospheres and the content of aluminum, absorbance in the UV region could be changed from UVA (320-400 nm) to UVC (200-275 nm), and the LSPR peak in the visible region gradually shifted to the UV region. This provides the potential for surface-enhanced Raman scattering (SERS) in both the UV and visible regions.

Surface-enhanced Raman scattering on periodic metal nanotips with tunable sharpness.

PubMed

Linn, Nicholas C; Sun, Chih-Hung; Arya, Ajay; Jiang, Peng; Jiang, Bin

2009-06-03

This paper reports on a scalable bottom-up technology for producing periodic gold nanotips with tunable sharpness as surface-enhanced Raman scattering (SERS) substrates. Inverted silicon pyramidal pits, which are templated from non-close-packed colloidal crystals prepared by a spin-coating technology, are used as structural templates to replicate arrays of polymer nanopyramids with nanoscale sharp tips. The deposition of a thin layer of gold on the polymer nanopyramids leads to the formation of SERS-active substrates with a high enhancement factor (up to 10(8)). The thickness of the deposited metal determines the sharpness of the nanotips and the resulting Raman enhancement factor. Finite-element electromagnetic modeling shows that the nanotips can significantly enhance the local electromagnetic field and the sharpness of nanotips greatly affects the SERS enhancement.

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

2017-05-02

In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

Silver nanoparticles with tunable work functions

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

Wang, Pangpang, E-mail: pangpang@molecular-device.kyushu-u.ac.jp; Tanaka, Daisuke; Ryuzaki, Sou

To improve the efficiencies of electronic devices, materials with variable work functions are required to decrease the energy level differences at the interfaces between working layers. Here, we report a method to obtain silver nanoparticles with tunable work functions, which have the same silver core of 5 nm in diameter and are capped by myristates and 1-octanethoilates self-assembled monolayers, respectively. The silver nanoparticles capped by organic molecules can form a uniform two-dimensional sheet at air-water interface, and the sheet can be transferred on various hydrophobic substrates. The surface potential of the two-dimensional nanoparticle sheet was measured in terms of Kelvin probemore » force microscopy, and the work function of the sheet was then calculated from the surface potential value by comparing with a reference material. The exchange of the capping molecules results in a work function change of approximately 150–250 meV without affecting their hydrophobicity. We systematically discussed the origin of the work function difference and found it should come mainly from the anchor groups of the ligand molecules. The organic molecule capped nanoparticles with tunable work functions have a potential for the applications in organic electronic devices.« less

Systematic characterization of a 1550 nm microelectromechanical (MEMS)-tunable vertical-cavity surface-emitting laser (VCSEL) with 7.92 THz tuning range for terahertz photomixing systems

NASA Astrophysics Data System (ADS)

Haidar, M. T.; Preu, S.; Cesar, J.; Paul, S.; Hajo, A. S.; Neumeyr, C.; Maune, H.; Küppers, F.

2018-01-01

Continuous-wave (CW) terahertz (THz) photomixing requires compact, widely tunable, mode-hop-free driving lasers. We present a single-mode microelectromechanical system (MEMS)-tunable vertical-cavity surface-emitting laser (VCSEL) featuring an electrothermal tuning range of 64 nm (7.92 THz) that exceeds the tuning range of commercially available distributed-feedback laser (DFB) diodes (˜4.8 nm) by a factor of about 13. We first review the underlying theory and perform a systematic characterization of the MEMS-VCSEL, with particular focus on the parameters relevant for THz photomixing. These parameters include mode-hop-free CW tuning with a side-mode-suppression-ratio >50 dB, a linewidth as narrow as 46.1 MHz, and wavelength and polarization stability. We conclude with a demonstration of a CW THz photomixing setup by subjecting the MEMS-VCSEL to optical beating with a DFB diode driving commercial photomixers. The achievable THz bandwidth is limited only by the employed photomixers. Once improved photomixers become available, electrothermally actuated MEMS-VCSELs should allow for a tuning range covering almost the whole THz domain with a single system.

Phase-slope and phase measurements of tunable CW-THz radiation with terahertz comb for wide-dynamic-range, high-resolution, distance measurement of optically rough object.

PubMed

Yasui, Takeshi; Fujio, Makoto; Yokoyama, Shuko; Araki, Tsutomu

2014-07-14

Phase measurement of continuous-wave terahertz (CW-THz) radiation is a potential tool for direct distance and imaging measurement of optically rough objects due to its high robustness to optical rough surfaces. However, the 2π phase ambiguity in the phase measurement of single-frequency CW-THz radiation limits the dynamic range of the measured distance to the order of the wavelength used. In this article, phase-slope measurement of tunable CW-THz radiation with a THz frequency comb was effectively used to extend the dynamic range up to 1.834 m while maintaining an error of a few tens µm in the distance measurement of an optically rough object. Furthermore, a combination of phase-slope measurement of tunable CW-THz radiation and phase measurement of single-frequency CW-THz radiation enhanced the distance error to a few µm within the dynamic range of 1.834 m without any influence from the 2π phase ambiguity. The proposed method will be a powerful tool for the construction and maintenance of large-scale structures covered with optically rough surfaces.

Starch functionalized biodegradable semi-IPN as a pH-tunable controlled release platform for memantine.

PubMed

Ganguly, Sayan; Maity, Tushar; Mondal, Subhadip; Das, Poushali; Das, Narayan C

2017-02-01

Sequentially prepared semi-interpenetrating polymer network (semi-IPN) has been developed here via Michael type addition of acrylic acid (AA) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) on to starch. The semi-IPN hydrogel have proficiency in fast water imbibition towards gel network and swelling tunable character with pH alteration in ambient condition. The synthesized gel has been characterized by Fourier transformed infrared spectroscopy (FTIR) to confirm Michael type grafting of monomers on to starch. The surface morphology, observed from Scanning Electron Microscopy (SEM) exhibited corrugated rough surface on hydrogel which enhances the fast water uptake feature by anomalous Fickian case II diffusion mechanism. Grafting reaction also improves its thermal stability which has been confirmed by thermogravimetric analysis (TGA). Biodegradation study with hen egg lysozyme medium reveals the accelerated enzymatic scission of the starch backbone and progressive mass loss. Degradation of the hydrogel around 60% of its primary mass has been observed within 7days. The physicochemical characterizations of this hydrogel suggest this as a promising pH-tunable, biodegradable candidate for control drug delivery vehicle. Copyright © 2016 Elsevier B.V. All rights reserved.

Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

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

Limpens, Rens; Fujii, Minoru; Neale, Nathan R.

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Negligible Electronic Interaction between Photoexcited Electron-Hole Pairs and Free Electrons in Phosphorus-Boron Co-Doped Silicon Nanocrystals

DOE PAGES

Limpens, Rens; Neale, Nathan R; Fujii, Minoru; ...

2018-03-05

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

DOE PAGES

Limpens, Rens; Fujii, Minoru; Neale, Nathan R.; ...

2018-02-28

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Terahertz artificial birefringence and tunable phase shifter based on dielectric metasurface with compound lattice.

PubMed

Ji, Yun-Yun; Fan, Fei; Chen, Meng; Yang, Lei; Chang, Sheng-Jiang

2017-05-15

A dielectric metasurface with line-square compound lattice structure has been fabricated and demonstrated in the terahertz (THz) regime by the THz time-domain spectroscopy and numerical simulation. A polarization dependent electromagnetically induced transparency (EIT) effect is achieved in this metasurface due to the mode coupling and interference between the resonance modes in line and square subunits of the metasurface. Accompany with the EIT effect, a large artificial birefringence effect between two orthogonal polarization states is also observed in this compound metasurface, of which birefringence is over 0.6. Furthermore, the liquid crystals are filled on the surface of this dielectric metasurface to fabricate an electrically tunable THz LC phase shifter. The experimental results show that its tunable phase shift under the biased electric field reaches 0.33π, 1.8 times higher than the bare silicon, which confirms the enhancement role of THz microstructure on the LC phase shift in the THz regime. The large birefringence phase shift of this compound metasurface and its LC tunable phase shifter will be of great significance for potential applications in THz polarization and phase devices.

Tunable inverse topological heterostructure utilizing ( B i 1 - x I n x ) 2 S e 3 and multichannel weak-antilocalization effect

DOE PAGES

Brahlek, Matthew J.; Koirala, Nikesh; Liu, Jianpeng; ...

2016-03-10

In typical topological insulator (TI) systems the TI is bordered by a non-TI insulator, and the surrounding conventional insulators, including vacuum, are not generally treated as part of the TI system. Here, we implement a material system where the roles are reversed, and the topological surface states form around the non-TI (instead of the TI) layers. This is realized by growing a layer of the tunable non-TI (Bi 1-xIn x) 2Se 3 in between two layers of the TI Bi 2Se 3 using the atomically precise molecular beam epitaxy technique. On this tunable inverse topological platform, we systematically vary themore » thickness and the composition of the (Bi 1-xIn x) 2Se 3 layer and show that this tunes the coupling between the TI layers from strongly coupled metallic to weakly coupled, and finally to a fully decoupled insulating regime. This system can be used to probe the fundamental nature of coupling in TI materials and provides a tunable insulating layer for TI devices.« less

Experimental validation of tunable features in laser-induced plasma resonators

NASA Astrophysics Data System (ADS)

Colón Quiñones, Roberto A.; Cappelli, Mark A.

2017-08-01

Measurements are presented which examine the use of gaseous plasma elements as highly-tunable resonators. The resonator considered here is a laser-induced plasma kernel generated by focusing the fundamental output from a Q-switched Nd:YAG laser through a lens and into a gas at constant pressure. The near-ellipsoidal plasma element interacts with incoming microwave radiation through excitation of low-order, electric-dipole resonances similar to those seen in metallic spheres. The tunability of these elements stems from the dispersive nature of plasmas arising from their variable electron density, electron momentum transfer collision frequency, and the concomitant e↵ect of these properties on the excited surface plasmon resonance. Experiments were carried out in the Ku band of the microwave spectrum to characterize the scattering properties of these resonators for di↵erent values of electron density. The experimental results are compared with results from theoretical approximations and finite element method electromagnetic simulations. The described tunable resonators have the potential to be used as the building blocks in a new class of all-plasma metamaterials with fully three-dimensional structural flexibility.

Observation of Gate-Tunable Coherent Perfect Absorption of Terahertz Waves in Graphene

NASA Astrophysics Data System (ADS)

Kocabas, Coskun; Kakenov, Nurbek; Balci, Osman; Takan, Taylan; Ozkan, Vedat Ali; Altan, Hakan

We report experimental observation of electrically tunable coherent perfect absorption (CPA) of terahertz (THz) radiation in graphene. We develop a reflection-type tunable THz cavity formed by a large-area graphene layer, a metallic reflective electrode, and an electrolytic medium in between. Ionic gating in the THz cavity allows us to tune the Fermi energy of graphene up to 1 eV and to achieve a critical coupling condition at 2.8 THz with absorption of 100 %. With the enhanced THz absorption, we were able to measure the Fermi energy dependence of the transport scattering time of highly doped graphene. Furthermore, we demonstrate flexible active THz surfaces that yield large modulation in the THz reflectivity with low insertion losses. We anticipate that the gate-tunable CPA will lead to efficient active THz optoelectronics applications. This work was partially supported by the Scientific and Technological Research Council of Turkey (TUBITAK) Grant No. 114F379 and the European Research Council (ERC) Consolidator Grant ERC-682723 SmartGraphene. N.K. acknowledges the TUBITAK-BIDEB 2215.

Organic chemistry on solid surfaces

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zaera, Francisco

2006-07-01

Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed.

Electric Switching of Fluorescence Decay in Gold-Silica-Dye Nematic Nanocolloids Mediated by Surface Plasmons.

PubMed

Jiang, Li; Mundoor, Haridas; Liu, Qingkun; Smalyukh, Ivan I

2016-07-26

Tunable composite materials with interesting physical behavior can be designed through integrating unique optical properties of solid nanostructures with facile responses of soft matter to weak external stimuli, but this approach remains challenged by their poorly controlled coassembly at the mesoscale. Using scalable wet chemical synthesis procedures, we fabricated anisotropic gold-silica-dye colloidal nanostructures and then organized them into the device-scale (demonstrated for square-inch cells) electrically tunable composites by simultaneously invoking molecular and colloidal self-assembly. We show that the ensuing ordered colloidal dispersions of shape-anisotropic nanostructures exhibit tunable fluorescence decay rates and intensity. We characterize how these properties depend on low-voltage fields and polarization of both the excitation and emission light, demonstrating a great potential for the practical realization of an interesting breed of nanostructured composite materials.

Method and apparatus for enhancing laser absorption sensitivity

NASA Technical Reports Server (NTRS)

Webster, Christopher R. (Inventor)

1987-01-01

A simple optomechanical method and apparatus is described for substantially reducing the amplitude of unwanted multiple interference fringes which often limit the sensitivities of tunable laser absorption spectrometers. An exterior cavity is defined by partially transmissible surfaces such as a laser exit plate, a detector input, etc. That cavity is spoiled by placing an oscillating plate in the laser beam. For tunable diode laser spectroscopy in the mid-infrared region, a Brewster-plate spoiler allows the harmonic detection of absorptances of less than 10 to the -5 in a single laser scan. Improved operation is achieved without subtraction techniques, without complex laser frequency modulation, and without distortion of the molecular lineshape signal. The technique is applicable to tunable lasers operating from UV to IR wavelengths and in spectrometers which employ either short or long pathlengths, including the use of retroreflectors or multipass cells.

Mixed-Halide Perovskites with Stabilized Bandgaps.

PubMed

Xiao, Zhengguo; Zhao, Lianfeng; Tran, Nhu L; Lin, Yunhui Lisa; Silver, Scott H; Kerner, Ross A; Yao, Nan; Kahn, Antoine; Scholes, Gregory D; Rand, Barry P

2017-11-08

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (V OC ) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned V OC from 1.05 to 1.45 V in solar cells.

Frequency-tunable terahertz absorber with wire-based metamaterial and graphene

NASA Astrophysics Data System (ADS)

Xiong, Han; Jiang, Yan-Nan; Yang, Cheng; Zeng, Xiao-Ping

2018-01-01

We present a dynamically tunable metamaterial graphene absorber (MGA) in the terahertz regime. The unit cell of the proposed MGA consists of metal wire and graphene sheet over the grounded dielectric absorber. The MGA achieves frequency tunable characteristics via changing the chemical potential. In order to understand the absorption mechanism of this absorber, a simple equivalent circuit method has been proposed. Because the coupling between wire-based metamaterial and graphene is complicated and cannot be neglected an equivalent surface impedance was introduced and extracted for simplification. In addition to the chemical potential of graphene, the constitutive parameters of metal wire are also discussed in detail to completely understand how these factors affect the absorption properties. It is believed that this study may be useful for providing valuable guidance in the development of more advanced MGAs.

Electrically tunable graphene plasmonic quasicrystal metasurfaces for transformation optics

PubMed Central

Zeng, Chao; Liu, Xueming; Wang, Guoxi

2014-01-01

The past few years have witnessed tremendous achievements of transformation optics applied to metallic plasmonic systems. Due to the poor tunability of metals, however, the ultimate control over surface plasmons remains a challenge. Here we propose a new type of graphene plasmonic (GP) metasurfaces by shaping the dielectrics underneath monolayer graphene into specific photonic crystals. The radial and axial gradient-index (GRIN) lenses are implemented to demonstrate the feasibility and versatility of the proposal. It is found that the designed GP-GRIN lenses work perfectly well for focusing, collimating, and guiding the GP waves. Especially, they exhibit excellent performances in the THz regime as diverse as ultra-small focusing spot (λ0/60) and broadband electrical tunability. The proposed method offers potential opportunities in exploiting active transformational plasmonic elements operating at THz frequencies. PMID:25042132

Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

PubMed

Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

2018-03-07

Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

Polydopamine-based concentric nanoshells with programmable architectures and plasmonic properties.

PubMed

Choi, Chun Kit K; Zhuo, Xiaolu; Chiu, Yee Ting Elaine; Yang, Hongrong; Wang, Jianfang; Choi, Chung Hang Jonathan

2017-11-09

Nanoshells, classically comprising gold as the metallic component and silica as the dielectric material, are important for fundamental studies in nanoplasmonics. They also empower a myriad of applications, including sensing, energy harvesting, and cancer therapy. Yet, laborious preparation precludes the development of next-generation nanoshells with structural complexity, compositional diversity, and tailorable plasmonic behaviors. This work presents an efficient approach to the bottom-up assembly of concentric nanoshells. By employing polydopamine as the dielectric material and exploiting its intrinsic adhesiveness and pH-tunable surface charge, the growth of each shell only takes 3-4 hours at room temperature. A series of polydopamine-based concentric nanoshells with programmable nanogap thickness, elemental composition (gold and silver), and geometrical configuration (number of layers) is prepared, followed by extensive structural characterization. Four of the silver-containing nanostructures are newly reported. Systematic investigations into the plasmonic properties of concentric nanoshells as a function of their structural parameters further reveal multiple Fano resonances and local-field "hot spots", infrequently reported plasmonic features for individual nanostructures fabricated using bottom-up wet chemistry. These results establish materials design rules for engineering complex plasmon-based systems originating from the integration of multiple plasmonic elements into defined locations within a compact nanostructure.

Origin and tunability of unusually large surface capacitance in doped cerium oxide studied by ambient-pressure X-ray photoelectron spectroscopy

DOE PAGES

Gopal, Chirranjeevi Balaji; Gabaly, Farid El; McDaniel, Anthony H.; ...

2016-03-31

Here, the volumetric redox (chemical) capacitance of the surface of CeO 2–δ films is quantified in situ to be 100-fold larger than the bulk values under catalytically relevant conditions. Sm addition slightly lowers the surface oxygen nonstoichiometry, but effects a 10-fold enhancement in surface chemical capacitance by mitigating defect interactions, highlighting the importance of differential nonstoichiometry for catalysis.

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

Two-step fabrication of ZnO-PVP composites with tunable visible emissions

NASA Astrophysics Data System (ADS)

Agulto, Verdad C.; Empizo, Melvin John F.; Kawano, Keisuke; Minami, Yuki; Yamanoi, Kohei; Sarukura, Nobuhiko; Yago, Allan Christopher C.; Sarmago, Roland V.

2018-02-01

We report a two-step fabrication of zinc oxide-polyvinylpyrrolidone (ZnO-PVP) composites for potential phosphor-based applications. The composites are fabricated by initially preparing ZnO microrods using hydrothermal growth method and then dip-coating the microrods into aqueous PVP solutions with varying molar concentrations. The as-prepared ZnO microrods exhibit smooth surfaces and broad visible emissions, while the ZnO-PVP composites have pitted surfaces with shifted and reduced visible emissions. These changes in the structural and optical properties, which are found to depend on the PVP concentration, are attributed to the adsorption of PVP on the microrod surface. Although the surface morphology and visible emission are modified by PVP, the composites still maintain a hexagonal wurtzite crystal structure and near-band-edge ultraviolet (UV) emission similar with the as-prepared microrods. Our results therefore suggest that the ZnO-PVP composites can be used as phosphors that offer not only properties found in both ZnO and PVP but also tunable visible emissions which can be controlled during material fabrication.

Microelectrofluidic lens for variable curvature

NASA Astrophysics Data System (ADS)

Chang, Jong-hyeon; Lee, Eunsung; Jung, Kyu-Dong; Lee, Seungwan; Choi, Minseog; Kim, Woonbae

2012-10-01

This paper presents a tunable liquid lens based on microelectrofluidic technology which integrates electrowetting and microfluidics. In the novel microelectrofluidic lens (MEFL), electrowetting in the hydrophobic surface channel induces the Laplace pressure difference between two fluidic interfaces on the lens aperture and the surface channel. Then, the pressure difference makes the lens curvature tunable. The previous electrowetting lens in which the contact angle changes at the side wall has a certain limitation of the curvature variation because of the contact angle saturation. Although the contact angle saturation also appears in the surface channel of the MEFL, the low surface channel increases the Laplace pressure and it makes the MEFL to have full variation of the optical power possible. The magnitude of the applied voltage determines the lens curvature in the analog mode MEFL as well as the electrowetting lens. Digital operation is also possible when the control electrodes of the MEFL are patterned to have an array. It is expected that the proposed MEFL is able to be widely used because of its full variation of the optical power without the use of oil and digital operation with fast response.

Ion transport and selectivity in biomimetic nanopores with pH-tunable zwitterionic polyelectrolyte brushes.

PubMed

Zeng, Zhenping; Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2015-10-28

Inspired by nature, functionalized nanopores with biomimetic structures have attracted growing interests in using them as novel platforms for applications of regulating ion and nanoparticle transport. To improve these emerging applications, we study theoretically for the first time the ion transport and selectivity in short nanopores functionalized with pH tunable, zwitterionic polyelectrolyte (PE) brushes. In addition to background salt ions, the study takes into account the presence of H(+) and OH(-) ions along with the chemistry reactions between functional groups on PE chains and protons. Due to ion concentration polarization, the charge density of PE layers is not homogeneously distributed and depends significantly on the background salt concentration, pH, grafting density of PE chains, and applied voltage bias, thereby resulting in many interesting and unexpected ion transport phenomena in the nanopore. For example, the ion selectivity of the biomimetic nanopore can be regulated from anion-selective (cation-selective) to cation-selective (anion-selective) by diminishing (raising) the solution pH when a sufficiently small grafting density of PE chains, large voltage bias, and low background salt concentration are applied.

Characterization of a multi-module tunable EC-QCL system for mid-infrared biofluid spectroscopy for hospital use and personalized diabetes technology

NASA Astrophysics Data System (ADS)

Grafen, M.; Nalpantidis, K.; Ostendorf, A.; Ihrig, D.; Heise, H. M.

2016-03-01

Blood glucose monitoring systems are important point-of-care devices for the hospital and personalised diabetes technology. FTIR-spectrometers have been successfully employed for the development of continuous bed-side monitoring systems in combination with micro-dialysis. For implementation in miniaturised portable systems, external-cavity quantum cascade lasers (EC-QCL) are suited. An ultra-broadly tunable pulsed EC-QCL system, covering a spectral range from 1920 to 780 cm-1, has been characterised with regard to the spectral emission profiles and wavenumber scale accuracy. The measurement of glucose in aqueous solution is presented and problems with signal linearity using Peltier-cooled MCT-detectors are discussed. The use of larger optical sample pathlengths for attenuating the laser power in transmission measurements has recently been suggested and implemented, but implications for broad mid-infrared measurements have now been investigated. The utilization of discrete wavenumber variables as an alternative for sweep-tune measurements has also been studied and sparse multivariate calibration models intended for clinical chemistry applications are described for glucose and lactate.

Engineered Biomimetic Polymers as Tunable Agents for Controlling CaCO₃ Mineralization

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

Chen, Chun-Long; Qi, Jiahui; Zuckermann, Ronald N.

2011-01-01

In nature, living organisms use peptides and proteins to precisely control the nucleation and growth of inorganic minerals and sequester CO₂ via mineralization of CaCO₃. Here we report the exploitation of a novel class of sequence-specific non-natural polymers called peptoids as tunable agents that dramatically control CaCO₃ mineralization. We show that amphiphilic peptoids composed of hydrophobic and anionic monomers exhibit both a high degree of control over calcite growth morphology and an unprecedented 23-fold acceleration of growth at a peptoid concentration of only 50 nM, while acidic peptides of similar molecular weight exhibited enhancement factors of only ~2 or less.more » We further show that both the morphology and rate controls depend on peptoid sequence, side-chain chemistry, chain length, and concentration. These findings provide guidelines for developing sequence-specific non-natural polymers that mimic the functions of natural peptides or proteins in their ability to direct mineralization of CaCO₃, with an eye toward their application to sequestration of CO₂ through mineral trapping.« less

Colloidal nanocrystals for photoelectrochemical and photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Gadiyar, Chethana; Loiudice, Anna; Buonsanti, Raffaella

2017-02-01

Colloidal nanocrystals (NCs) are among the most modular and versatile nanomaterial platforms for studying emerging phenomena in different fields thanks to their superb compositional and morphological tunability. A promising, yet challenging, application involves the use of colloidal NCs as light absorbers and electrocatalysts for water splitting. In this review we discuss how the tunability of these materials is ideal to understand the complex phenomena behind storing energy in chemical bonds and to optimize performance through structural and compositional modification. First, we describe the colloidal synthesis method as a means to achieve a high degree of control over single material NCs and NC heterostructures, including examples of the role of the ligands in modulating size and shape. Next, we focus on the use of NCs as light absorbers and catalysts to drive both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), together with some of the challenges related to the use of colloidal NCs as model systems and/or technological solution in water splitting. We conclude with a broader prospective on the use of colloidal chemistry for new material discovery.

Spatially controlled immobilisation of biomolecules: A complete approach in green chemistry

NASA Astrophysics Data System (ADS)

Grinenval, Eva; Nonglaton, Guillaume; Vinet, Françoise

2014-01-01

The development of 'green' sensors is a challenging task in the field of biomolecule sensing, for example in the detection of cardiac troponin-I (cTnI). In the present work a complete approach in green chemistry was developed to create chemically active patterns for the immobilisation of biological probes. This key technology is discussed on the basis of the twelve green chemistry principles, and is a combination of surface patterning by spotting and surface chemistries modified by molecular vapour deposition. The (1H,1H,2H,2H)-perfluorodecyltrichlorosilane (FDTS) was used as a novel anti-adsorption layer while the 3,4-epoxybutyltrimethoxysilane (EBTMOS) was used to immobilise probes. Oligonucleotides and the anti-cTnI antibody were studied. The spatially controlled immobilisation of probes was characterised by fluorescence. The demonstrated surface modification has broad applications in areas such as diagnostics and bio-chemical sensing. Moreover, the environmental impacts of surface patterning and surface chemistry were discussed from a 'greenness' point of view.

Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

PubMed

Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

2016-10-01

Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Capacity of mesoporous bioactive glass nanoparticles to deliver therapeutic molecules

NASA Astrophysics Data System (ADS)

El-Fiqi, Ahmed; Kim, Tae-Hyun; Kim, Meeju; Eltohamy, Mohamed; Won, Jong-Eun; Lee, Eun-Jung; Kim, Hae-Won

2012-11-01

Inorganic bioactive nanomaterials are attractive for hard tissue regeneration, including nanocomponents for bone replacement composites and nanovehicles for delivering therapeutics. Bioactive glass nanoparticles (BGn) have recently gained potential usefulness as bone and tooth regeneratives. Here we demonstrate the capacity of the BGn with mesopores to load and deliver therapeutic molecules (drugs and particularly genes). Spherical BGn with sizes of 80-90 nm were produced to obtain 3-5 nm sized mesopores through a sono-reacted sol-gel process. A simulated body fluid test of the mesoporous BGn confirmed their excellent apatite forming ability and the cellular toxicity study demonstrated their good cell viability up to 100 μg ml-1. Small molecules like chemical drug (Na-ampicillin) and gene (small interfering RNA; siRNA) were introduced as model drugs considering the mesopore size of the nanoparticles. Moreover, amine-functionalization allowed switchable surface charge property of the BGn (from -20-30 mV to +20-30 mV). Loading of ampicillin or siRNA saturated within a few hours (~2 h) and reflected the mesopore structure. While the ampicillin released relatively rapidly (~12 h), the siRNA continued to release up to 3 days with almost zero-order kinetics. The siRNA-nanoparticles were easily taken up by the cells, with a transfection efficiency as high as ~80%. The silencing effect of siRNA delivered from the BGn, as examined by using bcl-2 model gene, showed dramatic down-regulation (~15% of control), suggesting the potential use of BGn as a new class of nanovehicles for genes. This, in conjunction with other attractive properties, including size- and mesopore-related high surface area and pore volume, tunable surface chemistry, apatite-forming ability, good cell viability and the possible ion-related stimulatory effects, will potentiate the usefulness of the BGn in hard tissue regeneration.Inorganic bioactive nanomaterials are attractive for hard tissue regeneration, including nanocomponents for bone replacement composites and nanovehicles for delivering therapeutics. Bioactive glass nanoparticles (BGn) have recently gained potential usefulness as bone and tooth regeneratives. Here we demonstrate the capacity of the BGn with mesopores to load and deliver therapeutic molecules (drugs and particularly genes). Spherical BGn with sizes of 80-90 nm were produced to obtain 3-5 nm sized mesopores through a sono-reacted sol-gel process. A simulated body fluid test of the mesoporous BGn confirmed their excellent apatite forming ability and the cellular toxicity study demonstrated their good cell viability up to 100 μg ml-1. Small molecules like chemical drug (Na-ampicillin) and gene (small interfering RNA; siRNA) were introduced as model drugs considering the mesopore size of the nanoparticles. Moreover, amine-functionalization allowed switchable surface charge property of the BGn (from -20-30 mV to +20-30 mV). Loading of ampicillin or siRNA saturated within a few hours (~2 h) and reflected the mesopore structure. While the ampicillin released relatively rapidly (~12 h), the siRNA continued to release up to 3 days with almost zero-order kinetics. The siRNA-nanoparticles were easily taken up by the cells, with a transfection efficiency as high as ~80%. The silencing effect of siRNA delivered from the BGn, as examined by using bcl-2 model gene, showed dramatic down-regulation (~15% of control), suggesting the potential use of BGn as a new class of nanovehicles for genes. This, in conjunction with other attractive properties, including size- and mesopore-related high surface area and pore volume, tunable surface chemistry, apatite-forming ability, good cell viability and the possible ion-related stimulatory effects, will potentiate the usefulness of the BGn in hard tissue regeneration. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr31775c

High-speed mid-infrared hyperspectral imaging using quantum cascade lasers

NASA Astrophysics Data System (ADS)

Kelley, David B.; Goyal, Anish K.; Zhu, Ninghui; Wood, Derek A.; Myers, Travis R.; Kotidis, Petros; Murphy, Cara; Georgan, Chelsea; Raz, Gil; Maulini, Richard; Müller, Antoine

2017-05-01

We report on a standoff chemical detection system using widely tunable external-cavity quantum cascade lasers (ECQCLs) to illuminate target surfaces in the mid infrared (λ = 7.4 - 10.5 μm). Hyperspectral images (hypercubes) are acquired by synchronously operating the EC-QCLs with a LN2-cooled HgCdTe camera. The use of rapidly tunable lasers and a high-frame-rate camera enables the capture of hypercubes with 128 x 128 pixels and >100 wavelengths in <0.1 s. Furthermore, raster scanning of the laser illumination allowed imaging of a 100-cm2 area at 5-m standoff. Raw hypercubes are post-processed to generate a hypercube that represents the surface reflectance relative to that of a diffuse reflectance standard. Results will be shown for liquids (e.g., silicone oil) and solid particles (e.g., caffeine, acetaminophen) on a variety of surfaces (e.g., aluminum, plastic, glass). Signature spectra are obtained for particulate loadings of RDX on glass of <1 μg/cm2.

Tunable Nanoantennas for Surface Enhanced Infrared Absorption Spectroscopy by Colloidal Lithography and Post-Fabrication Etching

NASA Astrophysics Data System (ADS)

Chen, Kai; Duy Dao, Thang; Nagao, Tadaaki

2017-03-01

We fabricated large-area metallic (Al and Au) nanoantenna arrays on Si substrates using cost-effective colloidal lithography with different micrometer-sized polystyrene spheres. Variation of the sphere size leads to tunable plasmon resonances in the middle infrared (MIR) range. The enhanced near-fields allow us to detect the surface phonon polaritons in the natural SiO2 thin layers. We demonstrated further tuning capability of the resonances by employing dry etching of the Si substrates with the nanoantennas acting as the etching masks. The effective refractive index of the nanoantenna surroundings is efficiently decreased giving rise to blueshifts of the resonances. In addition, partial removal of the Si substrates elevates the nanoantennas from the high-refractive-index substrates making more enhanced near-fields accessible for molecular sensing applications as demonstrated here with surface-enhanced infrared absorption (SEIRA) spectroscopy for a thin polymer film. We also directly compared the plasmonic enhancement from the Al and Au nanoantenna arrays.

Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups

NASA Astrophysics Data System (ADS)

La, Yunju; Park, Chiyoung; Shin, Tae Joo; Joo, Sang Hoon; Kang, Sebyung; Kim, Kyoung Taek

2014-06-01

Analogous to the complex membranes found in cellular organelles, such as the endoplasmic reticulum, the inverse cubic mesophases of lipids and their colloidal forms (cubosomes) possess internal networks of water channels arranged in crystalline order, which provide a unique nanospace for membrane-protein crystallization and guest encapsulation. Polymeric analogues of cubosomes formed by the direct self-assembly of block copolymers in solution could provide new polymeric mesoporous materials with a three-dimensionally organized internal maze of large water channels. Here we report the self-assembly of amphiphilic dendritic-linear block copolymers into polymer cubosomes in aqueous solution. The presence of precisely defined bulky dendritic blocks drives the block copolymers to form spontaneously highly curved bilayers in aqueous solution. This results in the formation of colloidal inverse bicontinuous cubic mesophases. The internal networks of water channels provide a high surface area with tunable surface functional groups that can serve as anchoring points for large guests such as proteins and enzymes.

Flexible coherent control of plasmonic spin-Hall effect

PubMed Central

Xiao, Shiyi; Zhong, Fan; Liu, Hui; Zhu, Shining; Li, Jensen

2015-01-01

The surface plasmon polariton is an emerging candidate for miniaturizing optoelectronic circuits. Recent demonstrations of polarization-dependent splitting using metasurfaces, including focal-spot shifting and unidirectional propagation, allow us to exploit the spin degree of freedom in plasmonics. However, further progress has been hampered by the inability to generate more complicated and independent surface plasmon profiles for two incident spins, which work coherently together for more flexible and tunable functionalities. Here by matching the geometric phases of the nano-slots on silver to specific superimpositions of the inward and outward surface plasmon profiles for the two spins, arbitrary spin-dependent orbitals can be generated in a slot-free region. Furthermore, motion pictures with a series of picture frames can be assembled and played by varying the linear polarization angle of incident light. This spin-enabled control of orbitals is potentially useful for tip-free near-field scanning microscopy, holographic data storage, tunable plasmonic tweezers, and integrated optical components. PMID:26415636

Nanoporous Gold Nanocomposites as a Versatile Platform for Plasmonic Engineering and Sensing

PubMed Central

Zhao, Fusheng; Zeng, Jianbo; Shih, Wei-Chuan

2017-01-01

Plasmonic metal nanostructures have shown great potential in sensing applications. Among various materials and structures, monolithic nanoporous gold disks (NPGD) have several unique features such as three-dimensional (3D) porous network, large surface area, tunable plasmonic resonance, high-density hot-spots, and excellent architectural integrity and environmental stability. They exhibit a great potential in surface-enhanced spectroscopy, photothermal conversion, and plasmonic sensing. In this work, interactions between smaller colloidal gold nanoparticles (AuNP) and individual NPGDs are studied. Specifically, colloidal gold nanoparticles with different sizes are loaded onto NPGD substrates to form NPG hybrid nanocomposites with tunable plasmonic resonance peaks in the near-infrared spectral range. Newly formed plasmonic hot-spots due to the coupling between individual nanoparticles and NPG disk have been identified in the nanocomposites, which have been experimentally studied using extinction and surface-enhanced Raman scattering. Numerical modeling and simulations have been employed to further unravel various coupling scenarios between AuNP and NPGDs. PMID:28657586

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

2016-08-01

The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

Submillimeter Planetary Atmospheric Chemistry Exploration Sounder

NASA Technical Reports Server (NTRS)

Schlecht, Erich T.; Allen, Mark A.; Gill, John J.; Choonsup, Lee; Lin, Robert H.; Sin, Seth; Mehdi, Imran; Siegel, Peter H.; Maestrini, Alain

2013-01-01

Planetary Atmospheric Chemistry Exploration Sounder (SPACES), a high-sensitivity laboratory breadboard for a spectrometer targeted at orbital planetary atmospheric analysis. The frequency range is 520 to 590 GHz, with a target noise temperature sensitivity of 2,500 K for detecting water, sulfur compounds, carbon compounds, and other atmospheric constituents. SPACES is a prototype for a powerful tool for the exploration of the chemistry and dynamics of any planetary atmosphere. It is fundamentally a single-pixel receiver for spectral signals emitted by the relevant constituents, intended to be fed by a fixed or movable telescope/antenna. Its front-end sensor translates the received signal down to the 100-MHz range where it can be digitized and the data transferred to a spectrum analyzer for processing, spectrum generation, and accumulation. The individual microwave and submillimeter wave components (mixers, LO high-powered amplifiers, and multipliers) of SPACES were developed in cooperation with other programs, although with this type of instrument in mind. Compared to previous planetary and Earth science instruments, its broad bandwidth (approx. =.13%) and rapid tunability (approx. =.10 ms) are new developments only made possible recently by the advancement in submillimeter circuit design and processing at JPL.

THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

EPA Science Inventory

In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

A Self Consistent RF Discharge, Plasma Chemistry and Surface Model for Plasma Enhanced Chemical Vapor Deposition

DTIC Science & Technology

1988-06-30

consists of three submodels for the electron kinetics, plasma chemistry , and surface deposition kinetics for a-Si:H deposited from radio frequency...properties. Plasma enhanced, Chemical vapor deposition, amorphous silicon, Modeling, Electron kinetics, Plasma chemistry , Deposition kinetics, Rf discharge, Silane, Film properties, Silicon.

DNA Meter: Energy Tunable, Quantitative Hybridization Assay

PubMed Central

Braunlin, William; Völker, Jens; Plum, G. Eric; Breslauer, Kenneth J.

2015-01-01

We describe a novel hybridization assay that employs a unique class of energy tunable, bulge loop-containing competitor strands (C*) that hybridize to a probe strand (P). Such initial “pre-binding” of a probe strand modulates its effective “availability” for hybridizing to a target site (T). More generally, the assay described here is based on competitive binding equilibria for a common probe strand (P) between such tunable competitor strands (C*) and a target strand (T). We demonstrate that loop variable, energy tunable families of C*P complexes exhibit enhanced discrimination between targets and mismatched targets, thereby reducing false positives/negatives. We refer to a C*P complex between a C* competitor single strand and the probe strand as a “tuning fork,” since the C* strand exhibits branch points (forks) at the duplex-bulge interfaces within the complex. By varying the loop to create families of such “tuning forks,” one can construct C*P “energy ladders” capable of resolving small differences within the target that may be of biological/functional consequence. The methodology further allows quantification of target strand concentrations, a determination heretofore not readily available by conventional hybridization assays. The dual ability of this tunable assay to discriminate and quantitate targets provides the basis for developing a technology we refer to as a “DNA Meter.” Here we present data that establish proof-of-principle for an in solution version of such a DNA Meter. We envision future applications of this tunable assay that incorporate surface bound/spatially resolved DNA arrays to yield enhanced discrimination and sensitivity. PMID:23529692

Green synthesis of biocompatible gold nanocrystals with tunable surface plasmon resonance using garlic phytochemicals.

PubMed

Menon, Deepthy; Basanth, Amritha; Retnakumari, Archana; Manzoor, K; Nair, Shantikumar V

2012-12-01

Synthesis of biocompatible gold nanoparticles having tunable optical absorbance finds immense use in biomedical applications such as cancer diagnosis and photothermal therapy. Hence, it is imperative to develop environment and bio-friendly green chemical processes that aid in preparing gold nanoparticles with tunable optical properties. In the present work, phytochemicals present in the medicinal herb, viz., garlic, were used to provide the dual effects of reduction of gold salts to gold nanoparticles as well as stabilization, in a single step process. The optical tunability of nanogold with respect to concentration of precursor and volume of garlic extract, processing conditions of garlic, its differing molecular weight fractions, reaction time and temperature has been demonstrated. The presence of a range of anisotropic nanogold including nanotriangles, nanorods and nanospheres as evident from TEM endows the colloid with a tunable optical absorption, specifically into the near infrared region. In vitro stability studies of the colloidal suspension in various media including saline, BSA, histidine and PBS showed that gold nanoparticles did not aggregate with time or differing pH conditions. The role of the garlic phytochemicals in providing stability against agglomeration was also substantiated by FTIR studies. Cytotoxicity studies performed using spherical and anisotropic gold nanoparticles on MCF-7 and L929 cell lines proved the biocompatibility of the material up to high doses of 500 microg/ml. The present work highlights the role of garlic phytochemicals in preparing biocompatible metallic gold nanoparticles with tunable optical properties and good in vitro stability, suggesting its potential use for molecular imaging or therapeutic nanomedicines.

A New Smart Surface-Enhanced Raman Scattering Sensor Based on pH-Responsive Polyacryloyl Hydrazine Capped Ag Nanoparticles

NASA Astrophysics Data System (ADS)

Yuan, Shuai; Ge, Fengyan; Zhou, Man; Cai, Zaisheng; Guang, Shanyi

2017-08-01

A novel pH-responsive Ag@polyacryloyl hydrazide (Ag@PAH) nanoparticle for the first time as a surface-enhanced Raman scattering (SERS) substrate was prepared without reducing agent and end-capping reagent. Ag@PAH nanoparticles exhibited an excellent tunable detecting performance in the range from pH = 4 to pH = 9. This is explained that the swelling-shrinking behavior of responsive PAH can control the distance between Ag NPs and the target molecules under external pH stimuli, resulting in the tunable LSPR and further controlled SERS. Furthermore, Ag@PAH nanoparticles possessed an ultra-sensitive detecting ability and the detection limit of Rhodamine 6G reduced to 10-12 M. These advantages qualified Ag@PAH NP as a promising smart SERS substrate in the field of trace analysis and sensors.

Cooperative effect of pH-dependent ion transport within two symmetric-structured nanochannels.

PubMed

Meng, Zheyi; Chen, Yang; Li, Xiulin; Xu, Yanglei; Zhai, Jin

2015-04-15

A novel and simple design is introduced to construct bichannel nanofluid diodes by combining two poly(ethylene terephthalate) (PET) films with columnar nanochannel arrays varying in size or in surface charge. This type of bichannel device performs obvious ion current rectification, and the pH-dependent tunability and degree of rectification can be improved by histidine modification. The origin of the ion current rectification and its pH-dependent tunability are attributed to the cooperative effect of the two columnar half-channels and the applied bias on the mobile ions. As a result of surface groups on the bichannel being charged with different polarities or degrees at different pH values, the function of the bichannel device can be converted from a nanofluid diode to a normal nanochannel or to a reverse diode.

Broadband and efficient plasmonic control in the near-infrared and visible via strong interference of surface plasmon polaritons.

PubMed

Gan, C H; Nash, G R

2013-11-01

Broadband and tunable control of surface plasmon polaritons in the near-infrared and visible spectrum is demonstrated theoretically and numerically with a pair of phased nanoslits. We establish, with simulations supported by a coupled wave model, that by dividing the incident power equally between two input channels, the maximum plasmon intensity deliverable to either side of the nanoslit pair is twice that for an isolated slit. For a broadband source, a compact device with nanoslit separation of the order of a tenth of the wavelength is shown to steer nearly all the generated plasmons to one side for the same phase delay, thereby achieving a broadband unidirectional plasmon launcher. The reported effect can be applied to the design of ultra-broadband and efficient tunable plasmonic devices.

Chemoresponsive Colloidosomes via Ag⁺ Soldering of Surface-Assembled Nanoparticle Monolayers.

PubMed

Liu, Miao; Tian, Qian; Li, Yulin; You, Bo; Xu, An; Deng, Zhaoxiang

2015-04-28

Colloidosomes with a hollow interior and a porous plasmonic shell are highly desired for many applications including nanoreactors, surface-enhanced Raman scattering (SERS), photothermal therapy, and controlled drug release. We herein report a silica nanosphere-templated electrostatic self-assembly in conjunction with a newly developed Ag(+) soldering to fabricate gold colloidosomes toward multifunctionality and stimuli-responsibility. The gold colloidosomes are capable of capturing a nanosized object and releasing it via structural dissociation upon responding to a biochemical input (GSH, glutathione) at a concentration close to its cellular level. In addition, the colloidosomes have a tunable nanoporous shell composed of strongly coupled gold nanoparticles, which exhibit broadened near-infrared plasmon resonance. These features along with the simplicity and high tunability of the fabrication process make the gold colloidosomes quite promising for applications in a chemical or cellular environment.

Highly Tunable Complementary Micro/Submicro-Nanopatterned Surfaces Combining Block Copolymer Self-Assembly and Colloidal Lithography.

PubMed

Chang, Tongxin; Du, Binyang; Huang, Haiying; He, Tianbai

2016-08-31

Two kinds of large-area ordered and highly tunable micro/submicro-nanopatterned surfaces in a complementary manner were successfully fabricated by elaborately combining block copolymer self-assembly and colloidal lithography. Employing a monolayer of polystyrene (PS) colloidal spheres assembled on top as etching mask, polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) or polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) micelle films were patterned into micro/submicro patches by plasma etching, which could be further transferred into micropatterned metal nanoarrays by subsequent metal precursor loading and a second plasma etching. On the other hand, micro/submicro-nanopatterns in a complementary manner were generated via preloading a metal precursor in initial micelle films before the assembly of PS colloidal spheres on top. Both kinds of micro/submicro-nanopatterns showed good fidelity at the micro/submicroscale and nanoscale; meanwhile, they could be flexibly tuned by the sample and processing parameters. Significantly, when the PS colloidal sphere size was reduced to 250 nm, a high-resolution submicro-nanostructured surface with 3-5 metal nanoparticles in each patch or a single-nanoparticle interconnected honeycomb network was achieved. Moreover, by applying gold (Au) nanoparticles as anchoring points, micronanopatterned Au arrays can serve as a flexible template to pattern bovine serum albumin (BSA) molecules. This facile and cost-effective approach may provide a novel platform for fabrication of micropatterned nanoarrays with high tunability and controllability, which are promising in the applications of biological and microelectronic fields.

Superhydrophobic, carbon-infiltrated carbon nanotubes on Si and 316L stainless steel with tunable geometry

NASA Astrophysics Data System (ADS)

Stevens, Kimberly A.; Esplin, Christian D.; Davis, Taylor M.; Butterfield, D. Jacob; Ng, Philip S.; Bowden, Anton E.; Jensen, Brian D.; Iverson, Brian D.

2018-05-01

The use of carbon nanotubes to create superhydrophobic coatings has been considered due to their ability to offer a relatively uniform nanostructure. However, carbon nanotubes (CNTs) may be considered delicate with a typical diameter of tens of nanometers for a multi-walled CNT; as-grown carbon nanotubes often require the addition of a thin-film hydrophobic coating to render them superhydrophobic. Furthermore, fine control over the diameter of the as-grown CNTs or the overall nanostructure is difficult. This work demonstrates the utility of using carbon infiltration to layer amorphous carbon on multi-walled nanotubes to improve structural integrity and achieve superhydrophobic behavior with tunable geometry. These carbon-infiltrated carbon nanotube (CICNT) surfaces exhibit an increased number of contact points between neighboring tubes, resulting in a composite structure with improved mechanical stability. Additionally, the native surface can be rendered superhydrophobic with a vacuum pyrolysis treatment, with contact angles as high as 160° and contact angle hysteresis on the order of 1°. The CICNT diameter, static contact angle, sliding angle, and contact angle hysteresis were examined for varying levels of carbon-infiltration to determine the effect of infiltration on superhydrophobicity. The same superhydrophobic behavior and tunable geometry were also observed with CICNTs grown directly on stainless steel without an additional catalyst layer. The ability to tune the geometry while maintaining superhydrophobic behavior offers significant potential in condensation heat transfer, anti-icing, microfluidics, anti-microbial surfaces, and other bio-applications where control over the nanostructure is beneficial.

PLZT Electrooptic Ceramic Photonic Devices for Surface-Normal Operation in Trenches Cut Across Arrays of Optical Fiber

NASA Astrophysics Data System (ADS)

Hirabayashi, Katsuhiko

2005-03-01

Simple Pb_1-x La_x(Zr_y Ti_z)_1-x/4 O3 (PLZT) electrooptic ceramic photonic device arrays for surface-normal operation have been developed for application to polarization-controller arrays and Fabry-Pérot tunable filter arrays. These arrays are inserted in trenches cut across fiber arrays. Each element of the arrayed structure corresponds to one optical beam and takes the form of a cell. Each sidewall of the cell (width: 50-80 μm) is coated to form an electrode. The arrays have 16 elements at a pitch of 250 μm. The phase modulator has about 1 dB of loss and a half-wavelength voltage of 120 V. A cascade of two PLZT phase modulators (thickness: 300 μm), with each attached to a polyimide lambda/2 plate (thickness:15 μm), is capable of converting an arbitrary polarization to the transverse-electric (TE) or transverse-magnetic (TM) polarization. The response time is 1 μs. The Fabry-Pérot tunable filters have a thickness of 50 μm . The front and back surfaces of each cell are coated by 99%-reflective mirror. The free spectral range (FSR) of the filters is about 10 nm, tunable range is about 10 nm, loss is 2.2 dB, and finesse is 150. The tuning speed of these devices is high, taking only 1 μs.

2013 Chemical reactions at surfaces. Surfaces in Energy and the Environment. Gordon Research Conference and Gordon Research Seminar (April 28 - May 3, 2013 - Les Diablerets, Switzerland)

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

Stair, Peter C.

presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments.

The effects of atmospheric chemistry on radiation budget in the Community Earth Systems Model

NASA Astrophysics Data System (ADS)

Choi, Y.; Czader, B.; Diao, L.; Rodriguez, J.; Jeong, G.

2013-12-01

The Community Earth Systems Model (CESM)-Whole Atmosphere Community Climate Model (WACCM) simulations were performed to study the impact of atmospheric chemistry on the radiation budget over the surface within a weather prediction time scale. The secondary goal is to get a simplified and optimized chemistry module for the short time period. Three different chemistry modules were utilized to represent tropospheric and stratospheric chemistry, which differ in how their reactions and species are represented: (1) simplified tropospheric and stratospheric chemistry (approximately 30 species), (2) simplified tropospheric chemistry and comprehensive stratospheric chemistry from the Model of Ozone and Related Chemical Tracers, version 3 (MOZART-3, approximately 60 species), and (3) comprehensive tropospheric and stratospheric chemistry (MOZART-4, approximately 120 species). Our results indicate the different details in chemistry treatment from these model components affect the surface temperature and impact the radiation budget.

Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

ERIC Educational Resources Information Center

White, J. M.; Campbell, Charles T.

1980-01-01

Provides background data on surface chemistry as an emerging discipline. Highlights the important role which surfaces play in catalysis by focusing on the catalyzed oxidation of carbon monoxide. Provides a demonstration of how surfaces exert their influences in heterogeneous phenomena and illustrates how experimental problems in this field are…

Hydration and Thermal Expansion in Anatase Nanoparticles

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

Zhu, He; Li, Qiang; Ren, Yang

A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

Graphene based tunable fractal Hilbert curve array broadband radar absorbing screen for radar cross section reduction

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

Huang, Xianjun, E-mail: xianjun.huang@manchester.ac.uk; College of Electronic Science and Engineering, National University of Defense Technology, Changsha 410073; Hu, Zhirun

2014-11-15

This paper proposes a new type of graphene based tunable radar absorbing screen. The absorbing screen consists of Hilbert curve metal strip array and chemical vapour deposition (CVD) graphene sheet. The graphene based screen is not only tunable when the chemical potential of the graphene changes, but also has broadband effective absorption. The absorption bandwidth is from 8.9GHz to 18.1GHz, ie., relative bandwidth of more than 68%, at chemical potential of 0eV, which is significantly wider than that if the graphene sheet had not been employed. As the chemical potential varies from 0 to 0.4eV, the central frequency of themore » screen can be tuned from 13.5GHz to 19.0GHz. In the proposed structure, Hilbert curve metal strip array was designed to provide multiple narrow band resonances, whereas the graphene sheet directly underneath the metal strip array provides tunability and averagely required surface resistance so to significantly extend the screen operation bandwidth by providing broadband impedance matching and absorption. In addition, the thickness of the screen has been optimized to achieve nearly the minimum thickness limitation for a nonmagnetic absorber. The working principle of this absorbing screen is studied in details, and performance under various incident angles is presented. This work extends applications of graphene into tunable microwave radar cross section (RCS) reduction applications.« less

Tunable dielectric properties of Barium Magnesium Niobate (BMN) doped Barium Strontium Titanate (BST) thin films by magnetron sputtering

NASA Astrophysics Data System (ADS)

Alema, Fikadu; Reinholz, Aaron; Pokhodnya, Konstantin

2013-03-01

We report on the tunable dielectric properties of Mg and Nb co-doped Ba0.45Sr0.55TiO3 (BST) thin film prepared by the magnetron sputtering using BST target (pure and doped with BaMg0.33Nb0.67O3 (BMN)) on Pt/TiO2/SiO2/Al2O3 4'' wafers at 700 °C under oxygen atmosphere. The electrical measurements are conducted on 2432 metal-ferroelectric-metal capacitors using Pt as the top and bottom electrode. The crystalline structure, microstructure, and surface morphology of the films are analyzed and correlated to the films dielectric properties. The BMN doped and undoped BST films have shown tunabilities of 48% and 52%; and leakage current densities of 2.2x10-6 A/cm2 and 3.7x10-5 A/cm2, respectively at 0.5 MV/cm bias field. The results indicate that the BMN doped film exhibits a lower leakage current with no significant decrease in tunability. Due to similar electronegativity and ionic radii, it was suggested that both Mg2+ (accepter-type) and Nb5+ (donor-type) dopants substitutTi4+ ion in BST. The improvement in the film dielectric losses and leakage current with insignificant loss of tunability is attributed to the adversary effects of Mg2+ and Nb5+ in BST.

Near-field spectroscopic investigation of dual-band heavy fermion metamaterials.

PubMed

Gilbert Corder, Stephanie N; Chen, Xinzhong; Zhang, Shaoqing; Hu, Fengrui; Zhang, Jiawei; Luan, Yilong; Logan, Jack A; Ciavatti, Thomas; Bechtel, Hans A; Martin, Michael C; Aronson, Meigan; Suzuki, Hiroyuki S; Kimura, Shin-Ichi; Iizuka, Takuya; Fei, Zhe; Imura, Keiichiro; Sato, Noriaki K; Tao, Tiger H; Liu, Mengkun

2017-12-22

Broadband tunability is a central theme in contemporary nanophotonics and metamaterials research. Combining metamaterials with phase change media offers a promising approach to achieve such tunability, which requires a comprehensive investigation of the electromagnetic responses of novel materials at subwavelength scales. In this work, we demonstrate an innovative way to tailor band-selective electromagnetic responses at the surface of a heavy fermion compound, samarium sulfide (SmS). By utilizing the intrinsic, pressure sensitive, and multi-band electron responses of SmS, we create a proof-of-principle heavy fermion metamaterial, which is fabricated and characterized using scanning near-field microscopes with <50 nm spatial resolution. The optical responses at the infrared and visible frequency ranges can be selectively and separately tuned via modifying the occupation of the 4f and 5d band electrons. The unique pressure, doping, and temperature tunability demonstrated represents a paradigm shift for nanoscale metamaterial and metasurface design.

Tunable antireflection from conformal Al-doped ZnO films on nanofaceted Si templates

PubMed Central

2014-01-01

Photon harvesting by reducing reflection loss is the basis of photovoltaic devices. Here, we show the efficacy of Al-doped ZnO (AZO) overlayer on ion beam-synthesized nanofaceted silicon for suppressing reflection loss. In particular, we demonstrate thickness-dependent tunable antireflection (AR) from conformally grown AZO layer, showing a systematic shift in the reflection minima from ultraviolet to visible to near-infrared ranges with increasing thickness. Tunable AR property is understood in light of depth-dependent refractive index of nanofaceted silicon and AZO overlayer. This improved AR property significantly increases the fill factor of such textured heterostructures, which reaches its maximum for 60-nm AZO compared to the ones based on planar silicon. This thickness matches with the one that shows the maximum reduction in surface reflectance. PACS 81.07.-b; 42.79.Wc; 81.16.Rf; 81.15.Cd PMID:24808799

A tunable plasmonic nano-antenna based on metal–graphene double-nanorods

NASA Astrophysics Data System (ADS)

Dong, Zhewei; Sun, Chen; Si, Jiangnan; Deng, Xiaoxu

2018-05-01

A tunable plasmonic antenna based on metal–graphene nanostructures is proposed in the mid-infrared region, composed of two identical gold nanorods placed on separated graphene sheets. The unidirectional side scattering of the plasmonic antenna achieved by the constructive and destructive interference of the localized surface plasmon resonances (LSPR) of the nanorods is investigated using finite-difference time-domain solutions and is theoretically analyzed based on a two point dipole model. The scattering directivity peak of the plasmonic antenna is red-shifted linearly with increasing refractive index of the environment. The scattering direction from the plasmonic antenna is switched actively by tuning the LSPRs of the nanorods with the Fermi energies of the separated graphene sheets. The refractive index sensitivity and active tunable scattering direction of the plasmonic antenna provides a promising application to manipulate light at the nanoscale in the fields of bio-sensing and optoelectronic devices.

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

PubMed Central

Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

2015-01-01

The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

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

Gilbert Corder, Stephanie N.; Chen, Xinzhong; Zhang, Shaoqing

Broadband tunability is a central theme in contemporary nanophotonics and metamaterials research. Combining metamaterials with phase change media offers a promising approach to achieve such tunability, which requires a comprehensive investigation of the electromagnetic responses of novel materials at subwavelength scales. In this work, we demonstrate an innovative way to tailor band-selective electromagnetic responses at the surface of a heavy fermion compound, samarium sulfide (SmS). By utilizing the intrinsic, pressure sensitive, and multi-band electron responses of SmS, we create a proof-of-principle heavy fermion metamaterial, which is fabricated and characterized using scanning near-field microscopes with < 50 nm spatial resolution. Themore » optical responses at the infrared and visible frequency ranges can be selectively and separately tuned via modifying the occupation of the 4f and 5d band electrons. The unique pressure, doping, and temperature tunability demonstrated represents a paradigm shift for nanoscale metamaterial and metasurface design.« less

Near-field spectroscopic investigation of dual-band heavy fermion metamaterials

DOE PAGES

Gilbert Corder, Stephanie N.; Chen, Xinzhong; Zhang, Shaoqing; ...

2017-12-22

Broadband tunability is a central theme in contemporary nanophotonics and metamaterials research. Combining metamaterials with phase change media offers a promising approach to achieve such tunability, which requires a comprehensive investigation of the electromagnetic responses of novel materials at subwavelength scales. In this work, we demonstrate an innovative way to tailor band-selective electromagnetic responses at the surface of a heavy fermion compound, samarium sulfide (SmS). By utilizing the intrinsic, pressure sensitive, and multi-band electron responses of SmS, we create a proof-of-principle heavy fermion metamaterial, which is fabricated and characterized using scanning near-field microscopes with < 50 nm spatial resolution. Themore » optical responses at the infrared and visible frequency ranges can be selectively and separately tuned via modifying the occupation of the 4f and 5d band electrons. The unique pressure, doping, and temperature tunability demonstrated represents a paradigm shift for nanoscale metamaterial and metasurface design.« less

Turbulent Mixing Chemistry in Disks

NASA Astrophysics Data System (ADS)

Semenov, D.; Wiebe, D.

2006-11-01

A gas-grain chemical model with surface reaction and 1D/2D turbulent mixing is available for protoplanetary disks and molecular clouds. Current version is based on the updated UMIST'95 database with gas-grain interactions (accretion, desorption, photoevaporation, etc.) and modified rate equation approach to surface chemistry (see also abstract for the static chemistry code).

Tunable infrared absorption and visible transparency of colloidal aluminum-doped zinc oxide nanocrystals.

PubMed

Buonsanti, Raffaella; Llordes, Anna; Aloni, Shaul; Helms, Brett A; Milliron, Delia J

2011-11-09

Plasmonic nanocrystals have been attracting a lot of attention both for fundamental studies and different applications, from sensing to imaging and optoelectronic devices. Transparent conductive oxides represent an interesting class of plasmonic materials in addition to metals and vacancy-doped semiconductor quantum dots. Herein, we report a rational synthetic strategy of high-quality colloidal aluminum-doped zinc oxide nanocrystals. The presence of substitutional aluminum in the zinc oxide lattice accompanied by the generation of free electrons is proved for the first time by tunable surface plasmon absorption in the infrared region both in solution and in thin films.

Experimental demonstration of a ferroelectric liquid crystal tunable filter for fast demodulation of FBG sensors

NASA Astrophysics Data System (ADS)

Mathews, Sunish; Semenova, Yuliya; Rajan, Ginu; Farrell, Gerald

2009-05-01

A discretely tunable Surface-Stabilized Ferroelectric Liquid Crystal based Lyot Filter, with tuning speeds in the order of microseconds, is demonstrated experimentally as a channel dropper for the demodulation of multiple Fibre Bragg Grating sensors. The 3-stage Lyot Filter designed and experimentally verified can be used together with the high-speed ratiometric wavelength measurement system employing a fibre bend loss edge filter. Such systems can be used for the demodulation of distributed Fibre Bragg Grating sensors employed in applications such as structural monitoring, industrial sensing and haptic telerobotic surgical systems.

What's on the Surface? Physics and Chemistry of Delta-Doped Surfaces

NASA Technical Reports Server (NTRS)

Hoenk, Michael

2011-01-01

Outline of presentation: 1. Detector surfaces and the problem of stability 2. Delta-doped detectors 3. Physics of Delta-doped Silicon 4. Chemistry of the Si-SiO2 Interface 5. Physics and Chemistry of Delta-doped Surfaces a. Compensation b. Inversion c. Quantum exclusion. Conclusions: 1. Quantum confinement of electrons and holes dominates the behavior of delta-doped surfaces. 2. Stability of delta-doped detectors: Delta-layer creates an approx 1 eV tunnel barrier between bulk and surface. 3. At high surface charge densities, Tamm-Shockley states form at the surface. 4. Surface passivation by quantum exclusion: Near-surface delta-layer suppresses T-S trapping of minority carriers. 5. The Si-SiO2 interface compensates the surface 6. For delta-layers at intermediate depth, surface inversion layer forms 7. Density of Si-SiO2 interface charge can be extremely high (>10(exp 14)/sq cm)

Application of tunable diode laser absorption spectroscopy in the detection of oxygen

NASA Astrophysics Data System (ADS)

Zhou, Xin; Jin, Xing

2015-10-01

Most aircrafts is driven by chemic energy which is released in the combustion process. For improving the capability of engine and controlling the running on-time, the processes of fuel physics and chemistry need to be analysis by kinds of high quality sensor. In the research of designing and improving the processes of fuel physics and chemistry, the concentration, temperature and velocity of kinds of gas in the combustor need to be detected and measured. In addition, these engines and research equipments are always in the harsh environment of high temperature, high pressure and high speed. The harsh environment needs the sensor to be high reliability, well repetition, no cross- sensitivity between gases, and the traditional measurement system can't satisfy the metrical requirement well. Tunable diode laser absorption spectroscopy (TDLAS) analytic measurement technology can well satisfy the measurement in the harsh environment, which can support the whole measurement plan and high quality measurement system. Because the TDLAS sensor has the excellence of small bulk, light weight, high reliability and well specifically measurement, the TDLAS measurement technology has wide prospects. Different from most measurements, only a beam of laser can be pass through the measured environment by TDLAS, and the measurement equipment needn't be set in the harsh environment. So, the TDLAS equipment can't be interrupted by the measured equipment. The ability of subsistence in the harsh environment is very valuable, especially in the measurement on the subject of aerospace with environment of high speed, combustion and plasma. This paper focuses on the collecting the articles on the subject of oxygen detection of TDLAS. By analyzing the research and results of the articles, we conclude the central issues, difficulties and results. And we can get some instructive conclusions.

Nanostructured PEG-based hydrogels with tunable physical properties for gene delivery to human mesenchymal stem cells.

PubMed

Li, Yan; Yang, Chuan; Khan, Majad; Liu, Shaoqiong; Hedrick, James L; Yang, Yi-Yan; Ee, Pui-Lai R

2012-09-01

Effective delivery of DNA to direct cell behavior in a well defined three dimensional scaffold offers a superior approach in tissue engineering. In this study, we synthesized biodegradable nanostructured hydrogels with tunable physical properties for cell and gene delivery. The hydrogels were formed via Michael addition chemistry by reacting a four-arm acrylate-terminated PEG with a four-arm thiol-functionalized PEG. Nanosized micelles self-assembled from the amphiphilic PEG-b-polycarbonate diblock copolymer, having reactive end-groups, were chemically incorporated into the hydrogel networks at various contents. The use of Michael addition chemistry allows for in situ hydrogel formation under the physiological conditions. Mechanical property analysis of the hydrogels revealed a correlation between the content of micelles and the storage modulus of the hydrogels. Internal morphology of hydrogels was observed using a field emission scanning electron microscope, which showed that the number and/or size of the pores in the hydrogel increased with increasing micelle content due to reduced crosslinking degree. There exists an optimal micelle content for cell proliferation and gene transfection. MTT assays demonstrated the highest cell viability in the hydrogel with 20% micelles. The gene expression level in hMSCs in the hydrogel with 20% micelles was also significantly higher than that in the hydrogel without micelles. The enhanced cell viability and gene expression in the hydrogel with the optimized micelle content are likely attributed to the physical properties that provide a better environment for cell-matrix interactions. Therefore, incorporating micelles into the hydrogel is a good strategy to control cellular behavior in 3-D through changes in physical properties of the microenvironment. Copyright © 2012 Elsevier Ltd. All rights reserved.

A functionalized poly(ethylene glycol)-based bioassay surface chemistry that facilitates bio-immobilization and inhibits non-specific protein, bacterial, and mammalian cell adhesion

PubMed Central

Harbers, Gregory M.; Emoto, Kazunori; Greef, Charles; Metzger, Steven W.; Woodward, Heather N.; Mascali, James J.; Grainger, David W.; Lochhead, Michael J.

2008-01-01

This paper describes a new bioassay surface chemistry that effectively inhibits non-specific biomolecular and cell binding interactions, while providing a capacity for specific immobilization of desired biomolecules. Poly(ethylene glycol) (PEG) as the primary component in nonfouling film chemistry is well-established, but the multicomponent formulation described here is unique in that it (1) is applied in a single, reproducible, solution-based coating step; (2) can be applied to diverse substrate materials without the use of special primers; and (3) is readily functionalized to provide specific attachment chemistries. Surface analysis data are presented, detailing surface roughness, polymer film thickness, and film chemistry. Protein non-specific binding assays demonstrate significant inhibition of serum, fibrinogen, and lysozyme adsorption to coated glass, indium tin oxide, and tissue culture polystyrene dishes. Inhibition of S. aureus and K. pneumoniae microbial adhesion in a microfluidic flow cell, and inhibition of fibroblast cell adhesion from serum-based cell culture is shown. Effective functionalization of the coating is demonstrated by directing fibroblast adhesion to polymer surfaces activated with an RGD peptide. Batch-to-batch reproducibility data are included. The in situ cross-linked PEG-based coating chemistry is unique in its formulation, and its surface properties are attractive for a broad range of in vitro bioassay applications. PMID:18815622

Effect of material flexibility on the thermodynamics and kinetics of hydrophobically induced evaporation of water.

PubMed

Altabet, Y Elia; Haji-Akbari, Amir; Debenedetti, Pablo G

2017-03-28

The evaporation of water induced by confinement between hydrophobic surfaces has received much attention due to its suggested functional role in numerous biophysical phenomena and its importance as a general mechanism of hydrophobic self-assembly. Although much progress has been made in understanding the basic physics of hydrophobically induced evaporation, a comprehensive understanding of the substrate material features (e.g., geometry, chemistry, and mechanical properties) that promote or inhibit such transitions remains lacking. In particular, comparatively little research has explored the relationship between water's phase behavior in hydrophobic confinement and the mechanical properties of the confining material. Here, we report the results of extensive molecular simulations characterizing the rates, free energy barriers, and mechanism of water evaporation when confined between model hydrophobic materials with tunable flexibility. A single-order-of-magnitude reduction in the material's modulus results in up to a nine-orders-of-magnitude increase in the evaporation rate, with the corresponding characteristic time decreasing from tens of seconds to tens of nanoseconds. Such a modulus reduction results in a 24-orders-of-magnitude decrease in the reverse rate of condensation, with time scales increasing from nanoseconds to tens of millions of years. Free energy calculations provide the barriers to evaporation and confirm our previous theoretical predictions that making the material more flexible stabilizes the confined vapor with respect to liquid. The mechanism of evaporation involves surface bubbles growing/coalescing to form a subcritical gap-spanning tube, which then must grow to cross the barrier.

Engineering graphene and TMDs based van der Waals heterostructures for photovoltaic and photoelectrochemical solar energy conversion.

PubMed

Li, Changli; Cao, Qi; Wang, Faze; Xiao, Yequan; Li, Yanbo; Delaunay, Jean-Jacques; Zhu, Hongwei

2018-05-08

Graphene and two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant interest due to their unique properties that cannot be obtained in their bulk counterparts. These atomically thin 2D materials have demonstrated strong light-matter interactions, tunable optical bandgap structures and unique structural and electrical properties, rendering possible the high conversion efficiency of solar energy with a minimal amount of active absorber material. The isolated 2D monolayer can be stacked into arbitrary van der Waals (vdWs) heterostructures without the need to consider lattice matching. Several combinations of 2D/3D and 2D/2D materials have been assembled to create vdWs heterojunctions for photovoltaic (PV) and photoelectrochemical (PEC) energy conversion. However, the complex, less-constrained, and more environmentally vulnerable interface in a vdWs heterojunction is different from that of a conventional, epitaxially grown heterojunction, engendering new challenges for surface and interface engineering. In this review, the physics of band alignment, the chemistry of surface modification and the behavior of photoexcited charge transfer at the interface during PV and PEC processes will be discussed. We will present a survey of the recent progress and challenges of 2D/3D and 2D/2D vdWs heterojunctions, with emphasis on their applicability to PV and PEC devices. Finally, we will discuss emerging issues yet to be explored for 2D materials to achieve high solar energy conversion efficiency and possible strategies to improve their performance.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

NASA Astrophysics Data System (ADS)

Wilmsmeyer, Amanda R.; Gordon, Wesley O.; Davis, Erin Durke; Mantooth, Brent A.; Lalain, Teri A.; Morris, John R.

2014-01-01

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces.

PubMed

Wilmsmeyer, Amanda R; Gordon, Wesley O; Davis, Erin Durke; Mantooth, Brent A; Lalain, Teri A; Morris, John R

2014-01-01

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

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

Wilmsmeyer, Amanda R.; Morris, John R.; Gordon, Wesley O.

2014-01-15

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry tomore » study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.« less

Ultrasensitive Surface-Enhanced Raman Spectroscopy Detection Based on Amorphous Molybdenum Oxide Quantum Dots.

PubMed

Li, Hao; Xu, Qun; Wang, Xuzhe; Liu, Wei

2018-06-07

Surface-enhanced Raman spectroscopy (SERS) based on plasmonic semiconductive material has been proved to be an efficient tool to detect trace of substances, while the relatively weak plasmon resonance compared with noble metal materials restricts its practical application. Herein, for the first time a facile method to fabricate amorphous H x MoO 3 quantum dots with tunable plasmon resonance is developed by a controlled oxidization route. The as-prepared amorphous H x MoO 3 quantum dots show tunable plasmon resonance in the region of visible and near-infrared light. Moreover, the tunability induced by SC CO 2 is analyzed by a molecule kinetic theory combined with a molecular thermodynamic model. More importantly, the ultrahigh enhancement factor of amorphous H x MoO 3 quantum dots detecting on methyl blue can be up to 9.5 × 10 5 with expending the limit of detection to 10 -9 m. Such a remarkable porperty can also be found in this H x MoO 3 -based sensor with Rh6G and RhB as probe molecules, suggesting that the amorphous H x MoO 3 quantum dot is an efficient candidate for SERS on molecule detection in high precision. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

NASA Technical Reports Server (NTRS)

Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

2009-01-01

Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

The behavior of MC3T3-E1 cells on chitosan/poly-L-lysine composite films: effect of nanotopography, surface chemistry, and wettability.

PubMed

Zheng, Zhenhuan; Zhang, Ling; Kong, Lijun; Wang, Aijun; Gong, Yandao; Zhang, Xiufang

2009-05-01

In the present work, a series of composite films were produced from chitosan/poly-L-lysine blend solutions. The surface topography, chemistry, and wettability of composite films were characterized by atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and contact angle assay, respectively. For all composite films, blending with poly-L-lysine induced changes in surface chemistry and wettability. Interestingly, it was also found that increasing poly-L-lysine weight fraction in blend solutions could result in different nanoscaled surface topographic features, which displayed particle-, granule-, or fiber-dominant morphologies. MC3T3-E1 osteoblast-like cells were cultured on all composite films to evaluate the effects of surface nanotopography, chemistry, and wettability on cell behavior. The observations indicated that MC3T3-E1 cell behavior was affected by surface topography, chemistry, and wettability simultaneously and that cells showed strong responses to surface topography. On fiber-dominant surface, cells fully spread with obvious cytoskeleton organization and exhibited significantly higher level of adhesion and proliferation compared with particle- or granule-dominant surfaces. Furthermore, fiber-dominant surface also induced greater expression of mature osteogenic marker osteocalcin and higher mineralization based on RT-PCR and von Kossa staining. The results suggest that topographic modification of chitosan substratum at the nanoscale may be exploited in regulating cell behavior for its applications in tissue engineering.

NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Dynamically tunable extraordinary light absorption in monolayer graphene

NASA Astrophysics Data System (ADS)

Safaei, Alireza; Chandra, Sayan; Vázquez-Guardado, Abraham; Calderon, Jean; Franklin, Daniel; Tetard, Laurene; Zhai, Lei; Leuenberger, Michael N.; Chanda, Debashis

2017-10-01

The high carrier mobility of graphene makes it an attractive material for electronics, however, graphene's application for optoelectronic systems is limited due to its low optical absorption. We present a cavity-coupled nanopatterned graphene absorber designed to sustain temporal and spatial overlap between localized surface plasmon resonance and cavity modes, thereby resulting in enhanced absorption up to an unprecedented value of theoretically (60 %) and experimentally measured (45 %) monolayer graphene in the technologically relevant 8-12-μm atmospheric transparent infrared imaging band. We demonstrate a wide electrostatic tunability of the absorption band (˜2 μ m ) by modifying the Fermi energy. The proposed device design allows enhanced absorption and dynamic tunability of chemical vapor deposition grown low carrier mobility graphene which provides a significant advantage over previous strategies where absorption enhancement was limited to exfoliated high carrier mobility graphene. We developed an analytical model that incorporates the coupling of the graphene electron and substrate phonons, providing valuable and instructive insights into the modified plasmon-phonon dispersion relation necessary to interpret the experimental observations. Such gate voltage and cavity tunable enhanced absorption in chemical vapor deposited large area monolayer graphene paves the path towards the scalable development of ultrasensitive infrared photodetectors, modulators, and other optoelectronic devices.

NASA Tech Briefs, July 2013

NASA Technical Reports Server (NTRS)

2013-01-01

Dielectrophoresis-Based Particle Sensor Using Nanoelectrode Arrays; Multi-Dimensional Damage Detection for Surfaces and Structures; ULTRA: Underwater Localization for Transit and Reconnaissance Autonomy; Autonomous Cryogenic Leak Detector for Improving Launch Site Operations; Submillimeter Planetary Atmospheric Chemistry Exploration Sounder; Method for Reduction of Silver Biocide Plating on Metal Surfaces; Silicon Micromachined Microlens Array for THz Antennas; Forward-Looking IED Detector Ground Penetrating Radar; Fully Printed, Flexible, Phased Array Antenna for Lunar Surface Communication, Battery Charge Equalizer with Transformer Array; An Efficient, Highly Flexible Multi-Channel Digital Downconverter Architecture; Dimmable Electronic Ballast for a Gas Discharge Lamp; Conductive Carbon Nanotube Inks for Use with Desktop Inkjet Printing Technology; Enhanced Schapery Theory Software Development for Modeling Failure of Fiber-Reinforced Laminates; High-Performance, Low-Temperature-Operating, Long-Lifetime Aerospace Lubricants; Carbon Nanotube Microarrays Grown on Nanoflake Substrates; Differential Muon Tomography to Continuously Monitor Changes in the Composition of Subsurface Fluids; Microgravity Drill and Anchor System; 20 Granular Media-Based Tunable Passive Vibration Suppressor; 21 Miga Aero Actuator and 2D Machined Mechanical Binary Latch; Micro-XRF for In Situ Geological Exploration of Other Planets; Hydrogen-Enhanced Lunar Oxygen Extraction and Storage Using Only Solar Power; Uplift of Ionospheric Oxygen Ions During Extreme Magnetic Storms; Miniaturized, High-Speed, Modulated X-Ray Source; Hollow-Fiber Spacesuit Water Membrane Evaporator 25 High-Power Single-Mode 2.65-micrometers InGaAsSb/AlInGaAsSb Diode Lasers; Optical Device for Converting a Laser Beam Into Two Co-aligned but Oppositely Directed Beams; A Hybrid Fiber/Solid-State Regenerative Amplifier with Tunable Pulse Widths for Satellite Laser Ranging; X-Ray Diffractive Optics; SynGenics Optimization System (SynOptSys); 29 CFD Script for Rapid TPS Damage Assessment; radEq Add-On Module for CFD Solver Loci-CHEM; Science Opportunity Analyzer (SOA) Version 8; 30 Autonomous Byte Stream Randomizer; Distributed Engine Control Empirical/Analytical Verification Tools; Dynamic Server-Based KML Code Generator Method for Level-of-Detail Traversal of Geospatial Data; Automated Planning of Science Products Based on Nadir Overflights and Alerts for Onboard and Ground Processing; Linked Autonomous Interplanetary Satellite Orbit Navigation; Risk-Constrained Dynamic Programming for Optimal Mars Entry, Descent, and Landing; Scheduling Operations for Massive Heterogeneous Clusters; Deepak Condenser Model (DeCoM); Flight Software Math Library; Recirculating 1-K-Pot for Pulse-Tube Cryostats; 35 Method for Processing Lunar Regolith Using Microwaves; Wells for In Situ Extraction of Volatiles from Regolith (WIEVR); and Estimating the Backup Reaction Wheel Orientation Using Reaction Wheel Spin Rates Flight Telemetry from a Spacecraft.

Study on Manipulations of Fluids in Micro-scale and Their Applications in Physical, Bio/chemistry

NASA Astrophysics Data System (ADS)

Zhou, Bingpu

Microfluidics is a highly interdisciplinary research field which manipulates, controls and analyzes fluids in micro-scale for physical and bio/chemical applications. In this thesis, several aspects of fluid manipulations in micro-scale were studied, discussed and employed for demonstrations of practical utilizations. To begin with, mixing in continuous flow microfluidic was raised and investigated. A simple method for mixing actuation based on magnetism was proposed and realized via integration of magnetically functionalized micropillar arrays inside the microfluidic channel.With such technique, microfluidic mixing could be swiftly switched on and off via simple application or retraction of the magnetic field. Thereafter, in Chapter 3 we mainly focused on how to establish stable while tunable concentration gradients inside microfluidic network using a simple design. The proposed scheme could also be modified with on-chip pneumatic actuated valve to realize pulsatile/temporal concentration gradients simultaneously in ten microfluidic branches. We further applied such methodology to obtain roughness gradients onPolydimethylsiloxane (PDMS) surface via combinations of the microfluidic network andphoto-polymerizations. The obtained materials were utilized in parallel cell culture to figure out the relationship between substrate morphologies and the cell behaviors. In the second part of this work, we emphasized on manipulations on microdroplets insidethe microfluidic channel and explored related applications in bio/chemical aspects. Firstly, microdroplet-based microfluidic universal logic gates were successfully demonstrated vialiquid-electronic hybrid divider. For application based on such novel scheme of control lable droplet generation, on-demand chemical reaction within paired microdroplets was presented using IF logic gate. Followed by this, another important operation of microdroplet - splitting -was investigated. Addition lateral continuous flow was applied at the bifurcation as a mediumto controllably divide microdroplets with highly tunable splitting ratios. Related physical mechanism was proposed and such approach was adopted further for rapid synthesis of multi-scale microspheres.

Synthesis of photodegradable hydrogels as dynamically tunable cell culture platforms

PubMed Central

Kloxin, April M.; Tibbitt, Mark W.; Anseth, Kristi S.

2013-01-01

We describe a detailed procedure to create photolabile, poly(ethylene glycol)-based (PEG) hydrogels and manipulate material properties in situ. The cytocompatible chemistry and degradation process enable dynamic, tunable changes for applications in 2D or 3D cell culture. The materials are created by synthesizing an o-nitrobenzylether-based photodegradable monomer that can be coupled to primary amines. Here, we provide coupling procedures to PEG-bis-amine to form a photodegradable crosslinker or to the fibronectin-derived peptide RGDS to form a photoreleasable tether. Hydrogels are synthesized with the photodegradable crosslinker in the presence or absence of cells, allowing direct encapsulation or seeding on surfaces. Cell-material interactions can be probed in 2D or 3D by spatiotemporally controlling the gel microenvironment, which allows unique experiments to be performed to monitor cell response to changes in their niche. Degradation is readily achieved with cytocompatible wavelengths of low intensity flood irradiation (365 to 420 nm) in minutes or with highintensity laser irradiation (405 nm) in seconds. In this protocol, synthesis and purification of the photodegradable monomers take approximately 2 weeks, but can be substantially shortened by purchasing the o-nitrobenzylether precursor. Preparation of the sterile solutions for hydrogel fabrication takes hours, while the reaction to form the final hydrogel is complete in minutes. Hydrogel degradation occurs on-demand, in seconds to minutes, with user-directed light exposure. This comprehensive protocol is useful for controlling peptide presentation and substrate modulus during cell culture on or within an elastic matrix. These PEG-based materials are useful for probing the dynamic influence of cell-cell and cell-material interactions on cell function in 2D or 3D. While other protocols are available for controlling peptide presentation or modulus, few allow manipulation of material properties in situ and in the presence of cells down to the micrometer scale. PMID:21127482

Two-Photon Microscopy Analysis of Gold Nanoparticle Uptake in 3D Cell Spheroids.

PubMed

Rane, Tushar D; Armani, Andrea M

2016-01-01

Nanomaterials can be synthesized from a wide range of material systems in numerous morphologies, creating an extremely diverse portfolio. As result of this tunability, these materials are emerging as a new class of nanotherapeutics and imaging agents. One particularly interesting nanomaterial is the gold nanoparticle. Due to its inherent biocompatibility and tunable photothermal behavior, it has made a rapid transition from the lab setting to in vivo testing. In most nanotherapeutic applications, the efficacy of the agent is directly related to the target of interest. However, the optimization of the AuNP size and shape for efficacy in vitro, prior to testing in in vivo models of a disease, has been largely limited to two dimensional monolayers of cells. Two dimensional cell cultures are unable to reproduce conditions experienced by AuNP in the body. In this article, we systematically investigate the effect of different properties of AuNP on the penetration depth into 3D cell spheroids using two-photon microscopy. The 3D spheroids are formed from the HCT116 cell line, a colorectal carcinoma cell line. In addition to studying different sizes and shapes of AuNPs, we also study the effect of an oligo surface chemistry. There is a significant difference between AuNP uptake profiles in the 2D monolayers of cells as compared to the 3D cell spheroids. Additionally, the range of sizes and shapes studied here also exhibit marked differences in uptake penetration depth and efficacy. Finally, our results demonstrate that two-photon microscopy enables quantitative AuNP localization and concentration data to be obtained at the single spheroid level without fluorescent labeling of the AuNP, thus, providing a viable technique for large scale screening of AuNP properties in 3D cell spheroids as compared to tedious and time consuming techniques like electron microscopy.

Synergistic Enhancement of Enzyme Performance and Resilience via Orthogonal Peptide-Protein Chemistry Enabled Multilayer Construction.

PubMed

Zhang, Xue-Jian; Wang, Xiao-Wei; Sun, Jiaxing; Su, Chao; Yang, Shuguang; Zhang, Wen-Bin

2018-05-16

Protein immobilization is critical to utilize their unique functions in diverse applications. Herein, we report that orthogonal peptide-protein chemistry enabled multilayer construction can facilitate the incorporation of various folded structural domains, including calmodulin in different states, affibody and dihydrofolate reductase (DHFR). An extended conformation is found to be the most advantageous for steady film growth. The resulting protein thin films exhibit sensitive and selective responsive behaviors to bio-signals (Ca2+, TFP, NADPH, etc.) and fully maintain the catalytic activity of DHFR. The approach is applicable to different substrates such as hydrophobic gold and hydrophilic silica microparticles. The DHFR enzyme can be immobilized onto silica microparticles with tunable amounts. The multi-layer set-up exhibits a synergistic enhancement of DHFR activity with increasing number of bilayers and also makes the embedded DHFR more resilient to lyophilization. Therefore, this is a convenient and versatile method for protein immobilization with potential benefits of synergistic enhancement in enzyme performance and resilience.

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Tang, Jing; Aldalbahi, Ali; Torad, Nagy L; Yamauchi, Yusuke

2015-04-20

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation for surface resistance of yttrium-barium-copper-oxide thin films on various substrates for microwave applications

NASA Astrophysics Data System (ADS)

Yao, Hongjun

High temperature superconducting (HTS) materials such as YBCO (Yttrium-Barium-Copper-Oxide) are very attractive in microwave applications because of their extremely low surface resistance. In the proposed all-HTS tunable filter, a layer of HTS thin film on a very thin substrate (100 mum) is needed to act as the toractor that can be rotated to tune the frequency. In order to provide more substrate candidates that meet both electrical and mechanical requirements for this special application, surface resistance of YBCO thin films on various substrates was measured using microstrip ring resonator method. For alumina polycrystalline substrate, a layer of YSZ (Yttrium stabilized Zirconia) was deposited using IBAD (ion beam assisted deposition) method prior to YBCO deposition. The surface resistance of the YBCO thin film on alumina was found to be 22 mO due to high-angle grain boundary problem caused by the mixed in-plane orientations and large FWHM (full width at half maximum) of the thin film. For YBCO thin films on a YSZ single crystal substrate, the surface resistance showed even higher value of 30 mO because of the mixed in-plane orientation problem. However, by annealing the substrate in 200 Torr oxygen at 730°C prior to deposition, the in-plane orientation of YBCO thin films can be greatly improved. Therefore, the surface resistance decreased to 1.4 mO, which is still more than an order higher than the reported best value. The YBCO thin films grown on LaAlO3 single crystal substrate showed perfect in-plane orientation with FWHM less 1°. The surface resistance was as low as 0.032 mO. A tunable spiral resonator made of YBCO thin film on LaAlO3 single crystal substrate demonstrated that the resonant frequency can be tuned in a rang as large as 500 MHz by changing the gap between toractor and substrate. The Q-factor was more than 12,000, which ensured the extraordinarily high sensitivity for the proposed all-HTS tunable filter.

Controllable Broadband Optical Transparency and Wettability Switching of Temperature-Activated Solid/Liquid-Infused Nanofibrous Membranes.

PubMed

Manabe, Kengo; Matsubayashi, Takeshi; Tenjimbayashi, Mizuki; Moriya, Takeo; Tsuge, Yosuke; Kyung, Kyu-Hong; Shiratori, Seimei

2016-09-29

Inspired by biointerfaces, such as the surfaces of lotus leaves and pitcher plants, researchers have developed innovative strategies for controlling surface wettability and transparency. In particular, great success has been achieved in obtaining low adhesion and high transmittance via the introduction of a liquid layer to form liquid-infused surfaces. Furthermore, smart surfaces that can change their surface properties according to external stimuli have recently attracted substantial interest. As some of the best-performing smart surface materials, slippery liquid-infused porous surfaces (SLIPSs), which are super-repellent, demonstrate the successful achievement of switchable adhesion and tunable transparency that can be controlled by a graded mechanical stimulus. However, despite considerable efforts, producing temperature-responsive, super-repellent surfaces at ambient temperature and pressure remains difficult because of the use of nonreactive lubricant oil as a building block in previously investigated repellent surfaces. Therefore, the present study focused on developing multifunctional materials that dynamically adapt to temperature changes. Here, we demonstrate temperature-activated solidifiable/liquid paraffin-infused porous surfaces (TA-SLIPSs) whose transparency and control of water droplet movement at room temperature can be simultaneously controlled. The solidification of the paraffin changes the surface morphology and the size of the light-transmission inhibitor in the lubricant layer; as a result, the control over the droplet movement and the light transmittance at different temperatures is dependent on the solidifiable/liquid paraffin mixing ratio. Further study of such temperature-responsive, multifunctional systems would be valuable for antifouling applications and the development of surfaces with tunable optical transparency for innovative medical applications, intelligent windows, and other devices.

Fabrication of hexagonal star-shaped and ring-shaped patterns arrays by Mie resonance sphere-lens-lithography

NASA Astrophysics Data System (ADS)

Liu, Xianchao; Wang, Jun; Li, Ling; Gou, Jun; Zheng, Jie; Huang, Zehua; Pan, Rui

2018-05-01

Mie resonance sphere-lens-lithography has proved to be a good candidate for fabrication of large-area tunable surface nanopattern arrays. Different patterns on photoresist surface are obtained theoretically by adjusting optical coupling among neighboring spheres with different gap sizes. The effect of light reflection from the substrate on the pattern produced on the photoresist with a thin thickness is also discussed. Sub-micron hexagonal star-shaped and ring-shaped patterns arrays are achieved with close-packed spheres arrays and spheres arrays with big gaps, respectively. Changing of star-shaped vertices is induced by different polarization of illumination. Experimental results agree well with the simulation. By using smaller resonance spheres, sub-400 nm star-shaped and ring-shaped patterns can be realized. These tunable patterns are different from results of previous reports and have enriched pattern morphology fabricated by sphere-lens-lithography, which can find application in biosensor and optic devices.

Thin-film topological insulators for continuously tunable terahertz absorption

NASA Astrophysics Data System (ADS)

West, D.; Zhang, S. B.

2018-02-01

One of the defining characteristics of a three-dimensional topological insulator (TI) is the appearance of a Dirac cone on its surface when it creates an interface with vacuum. For thin film TIs, however, the Dirac cones on opposite surfaces interact forming a small gap. For the case of three quintuple layers of Bi2Se3, we show that this gap can be continuously tuned between 128 meV and 0 meV with the application of modest perpendicular electric fields of less than 30 meV Å-1. Through both the Hamiltonian model and first-principles density functional theory calculations, we show that the inherent nonlinearity in realistic Dirac cone interaction leads to a gap which can be continuously tuned through the application of an external electric field. This tunability, coupled with the high optical absorption of thin film TIs, make this a very promising platform for terahertz and infrared detection.

Electrowetting Controlled Tunable Liquid Microlens

NASA Astrophysics Data System (ADS)

Krupenkin, Tom; Yang, Shu

2002-03-01

Electrowetting potentially provides a convenient way to control the shape and position of the liquid droplet on a rigid substrate. However, the effectiveness of this method relies strongly on the precise control of the surface properties of the substrate. Here we present a tunable liquid microlens capable of adjusting the position of its focal spot in all three dimensions. The microlens consists of a droplet of a transparent conductive liquid placed on a dielectric substrate with a hydrophobic coating. By varying the voltage applied to the structure, both the position and the curvature of the microlens can be changed. The influence of the bulk and surface properties of the materials on the microlens behavior is experimentally investigated and supported by theoretical calculations. Some of the potential problems associated with the stick-slip behavior and contact angle hysteresis are outlined and possible ways to prevent them are suggested.

A New Smart Surface-Enhanced Raman Scattering Sensor Based on pH-Responsive Polyacryloyl Hydrazine Capped Ag Nanoparticles.

PubMed

Yuan, Shuai; Ge, Fengyan; Zhou, Man; Cai, Zaisheng; Guang, Shanyi

2017-08-14

A novel pH-responsive Ag@polyacryloyl hydrazide (Ag@PAH) nanoparticle for the first time as a surface-enhanced Raman scattering (SERS) substrate was prepared without reducing agent and end-capping reagent. Ag@PAH nanoparticles exhibited an excellent tunable detecting performance in the range from pH = 4 to pH = 9. This is explained that the swelling-shrinking behavior of responsive PAH can control the distance between Ag NPs and the target molecules under external pH stimuli, resulting in the tunable LSPR and further controlled SERS. Furthermore, Ag@PAH nanoparticles possessed an ultra-sensitive detecting ability and the detection limit of Rhodamine 6G reduced to 10 -12  M. These advantages qualified Ag@PAH NP as a promising smart SERS substrate in the field of trace analysis and sensors.

Tunable surface acoustic wave device based on acoustoelectric interaction in ZnO/GaN heterostructures

NASA Astrophysics Data System (ADS)

Li, Rui; Reyes, Pavel I.; Ragavendiran, Sowmya; Shen, H.; Lu, Yicheng

2015-08-01

A tunable surface acoustic wave (SAW) device is developed on a multilayer structure which consists of an n-type semiconductor ZnO layer and a Ni-doped piezoelectric ZnO layer deposited on a GaN/c-Al2O3 substrate. The unique acoustic dispersion relationship between ZnO and GaN generates the multi-mode SAW response in this structure, facilitating high frequency operation. A dc bias voltage is applied to a Ti/Au gate layer deposited on the path of SAW delay line to modulate the electrical conductivity for tuning the acoustic velocity. For devices operating at 1.25 GHz, a maximum SAW velocity change of 0.9% is achieved, equivalent to the frequency change of 11.2 MHz. This voltage-controlled frequency tuning device has potential applications in resettable sensors, adaptive signal processing, and secure wireless communication.

Room-temperature Synthesis of Amorphous Molybdenum Oxide Nanodots with Tunable Localized Surface Plasmon Resonances.

PubMed

Zhu, Chuanhui; Xu, Qun; Ji, Liang; Ren, Yumei; Fang, Mingming

2017-12-05

Two-dimensional (2D) semiconductors have recently emerged as a remarkable class of plasmonic alternative to conventional noble metals. However, tuning of their plasmonic resonances towards different wavelengths in the visible-light region with physical or chemical methods still remains challenging. In this work, we design a simple room-temperature chemical reaction route to synthesize amorphous molybdenum oxide (MoO 3-x ) nanodots that exhibit strong localized surface plasmon resonances (LSPR) in the visible and near-infrared region. Moreover, tunable plasmon resonances can be achieved in a wide range with the changing surrounding solvent, and accordingly the photoelectrocatalytic activity can be optimized with the varying LSPR peaks. This work boosts the light-matter interaction at the nanoscale and could enable photodetectors, sensors, and photovoltaic devices in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctional mussel-inspired copolymerized epigallocatechin gallate (EGCG)/arginine coating: the potential as an ad-layer for vascular materials.

PubMed

Luo, Rifang; Tang, Linlin; Xie, Lingxia; Wang, Jin; Huang, Nan; Wang, Yunbing

2016-12-01

Surface properties are considered to be important factors in addressing proper functionalities. In this paper, a multifunctional mussel-inspired coating was prepared via the direct copolymerization of epigallocatechin gallate (EGCG) and arginine. The coating formation was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectra. The EGCG/arginine coating contained diverse functional groups like amines, phenols and carboxyls, whose densities were also tunable. Such mussel-inspired coating could also be applied as an ad-layer for its secondary reactivity, demonstrated by quartz crystal microbalance technique. Moreover, the tunable surface density of phenols showed potential ability in modulating endothelial cell and smooth muscle cell viability. The coatings rich in phenols presented excellent free radical scavenging property. Current results strongly indicated the potential of EGCG/arginine coatings to be applied as an ad-layer for vascular materials.

Tunable ultra-broadband polarization filter based on three-core resonance of the fluid-infiltrated and gold-coated photonic crystal fiber

NASA Astrophysics Data System (ADS)

Liu, Yingchao; Chen, Hailiang; Ma, Mingjian; Zhang, Wenxun; Wang, Yujun; Li, Shuguang

2018-03-01

We propose a tunable ultra-broadband polarization filter based on three-core resonance of the fluid-infiltrated and gold-coated high birefringent photonic crystal fiber (HB-PCF). Gold film was applied to the inner walls of two cladding air holes and surface plasmon polaritons were generated on its surface. The two gold-coated cladding air holes acted as two defective cores. As the phase matching condition was satisfied, light transmitted in the fiber core and coupled to the two defective cores. The three-core PCF supported three super modes in two orthogonal polarization directions. The coupling characteristics among these modes were investigated using the finite-element method. We found that the coupling wavelengths and strength between these guided modes can be tuned by altering the structural parameters of the designed HB-PCF, such as the size of the voids, thickness of the gold-films and liquid infilling pattern. Under the optimized structural parameters, a tunable broadband polarization filter was realized. For one liquid infilling pattern, we obtained a broadband polarization filter which filtered out the light in y-polarization direction at the wavelength of 1550 nm. For another liquid infilling pattern, we filtered out light in the x-polarization direction at the wavelength of 1310 nm. Our studies on the designed HB-PCF made contributions to the further devising of tunable broadband polarization filters, which are extensively used in telecommunication and sensor systems. Project supported by the National Natural Science Foundation of China (Grant Nos. 61505175 and 61475134) and the Natural Science Foundation of Hebei Province (Grant Nos. F2017203110 and F2017203193).

Varifocal liquid lens based on microelectrofluidic technology.

PubMed

Chang, Jong-hyeon; Jung, Kyu-Dong; Lee, Eunsung; Choi, Minseog; Lee, Seungwan; Kim, Woonbae

2012-11-01

This Letter presents a tunable liquid lens based on microelectrofluidic technology. In the microelectrofluidic lens (MEFL), electrowetting in the hydrophobic surface channel induces the Laplace pressure difference between two fluidic interfaces on the lens aperture and the surface channel. Then, the pressure difference makes the lens curvature tunable. In spite of the contact angle saturation, the narrow surface channel increases the Laplace pressure to have a wide range of optical power variation in the MEFL. The magnitude of the applied voltage determines the lens curvature in the analog mode MEFL. Digital operation is also possible when the control electrodes of the MEFL are patterned to have an array. The lens aperture and maximum surface channel diameter were designed to 3.2 mm and 6.4 mm, respectively, with a channel height of 0.2 mm for an optical power range between +210 and -30 D. By switching the control electrodes, the averaged transit time in steps and turnaround time were as low as 2.4 ms and 16.5 ms, respectively, in good agreement with the simulation results. It is expected that the proposed MEFL may be widely used with advantages of wide variation of the optical power with fast and precise controllability in a digital manner.

Investigating the Effect of Nanoscale Changes on the Chemistry and Energetics of Nanocrystals with a Novel Photoemission Spectroscopy Methodology

NASA Astrophysics Data System (ADS)

Liao, Michael W.

This dissertation explores the effect of nanometer-scale changes in structure on the energetics of photocatalytic and photovoltaic materials. Of particular interest are semiconductor nanocrystals (NCs), which have interesting chemical properties that lead to novel structures and applications. Chief among these properties are quantum confinement and the high surface area-to-volume ratio, which allow for chemical tuning of the energetics and structure of NCs. This tunable energetic landscape has led to increasing application of NCs in various areas of research, including solar energy conversion, light-emitting diode technologies, and photocatalysis. However, spectroscopic methods to determine the energetics of NCs have not been well developed, due to chemical complexities of relevant NCs such as polydispersity, capping ligand effects, core-shell structures, and other chemical modifications. In this work, we demonstrate and expand the utility of photoelectron spectroscopy (PES) to probe the energetics of NCs by considering the physical processes that lead to background and secondary photoemission to enhance photoemission from the sample of interest. A new methodology for the interpretation of UP spectra was devised in order to emphasize the minute changes to the UP spectra line shape that arise from nanoscopic changes to the NCs. We applied various established subtractions that correct for photon source satellites, secondary photoelectrons, and substrate photoemission. We then investigated the effect of ligand surface coverage on the surface chemistry and density of states at the top of valence band (VB). We systematically removed ligands by increasing numbers of purification steps for two diameters of NCs and found that doing so increased photoemission density at the top of the VB, which is due to undercoordinated surface atoms. Deeper VB structure was also altered, possibly due to reorganization of the atoms in the NC. Using the new UPS interpretation methodology, we examined the evolution of the valence band energy (EVB) of CdSe NCs as it was modified from spherical NC to rod to Au-NP tipped nanorod (NR). We also employed potential-modulated attenuated total reflectance spectroscopy (PM-ATR) to probe the conduction band energy (ECB) of the series. The EVB decreased with each modification, which is predicted with a band-bending model. This trend was also observed in the ECB, as revealed by spectroelectrochemistry, along with the appearance of new metal-semiconductor states in the band gap. UPS was finally used to investigate the even more complex Pt-NP tipped CdSe CdS core shell NR heterostructure. The addition of the CdS shell decreases the EVB relative to CdSe, as expected from common cation II-VI compounds. The Pt-NC increases the EVB, which, like the Au-CdSe NR, is predicted by employing a band-bending model. XPS revealed that PtSx-like chemical states were formed near the CdS-Pt interface. These experiments, along with the improved UP spectra interpretation methodology, demonstrate the wealth of information regarding surface chemistry and energetics that can be obtained with PES which can be applied to not only NCs, but also to metal oxide or molecular thin films.

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

ATR-FTIR Spectroscopy in the Undergraduate Chemistry Laboratory: Part II--A Physical Chemistry Laboratory Experiment on Surface Adsorption

ERIC Educational Resources Information Center

Schuttlefield, Jennifer D.; Larsen, Sarah C.; Grassian, Vicki H.

2008-01-01

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy is a useful technique for measuring the infrared spectra of solids and liquids as well as probing adsorption on particle surfaces. The use of FTIR-ATR spectroscopy in organic and inorganic chemistry laboratory courses as well as in undergraduate research was presented…

Tunable far infrared studies of molecular parameters in support of stratospheric measurements

NASA Technical Reports Server (NTRS)

Chance, K. V.; Nolt, Ira G.; Radostitz, J. V.; Park, K.

1990-01-01

The purpose of this research is to make precise, fully line-resolved measurements of molecular parameters that are necessary for the analysis of spectra obtained in far infrared field measurement programs. These measurements make it possible to accurately analyze the data from field measurements to obtain atmospheric concentration profiles of key trace gases involved in the ozone chemistry. The research objectives include: measurements of pressure broadening of molecular lines of OH, O2, O3, HCl, and H2O, their temperature dependence, and, when possible, the pressure-induced frequency shifts of the lines; measurements of line positions of radical species, such as HO2.

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

NASA Astrophysics Data System (ADS)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

A facile route to steady redox-modulated nitroxide spin-labeled surfaces based on diazonium chemistry.

PubMed

Cougnon, Charles; Boisard, Séverine; Cador, Olivier; Dias, Marylène; Levillain, Eric; Breton, Tony

2013-05-18

A TEMPO derivative was covalently grafted onto carbon and gold surfaces via the diazonium chemistry. The acid-dependent redox properties of the nitroxyl group were exploited to elaborate electro-switchable magnetic surfaces. ESR characterization demonstrated the reversible and permanent magnetic character of the material.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of `polar ice' mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm `carbonyl' absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes.

Structure and performance of dielectric films based on self-assembled nanocrystals with a high dielectric constant.

PubMed

Huang, Limin; Liu, Shuangyi; Van Tassell, Barry J; Liu, Xiaohua; Byro, Andrew; Zhang, Henan; Leland, Eli S; Akins, Daniel L; Steingart, Daniel A; Li, Jackie; O'Brien, Stephen

2013-10-18

Self-assembled films built from nanoparticles with a high dielectric constant are attractive as a foundation for new dielectric media with increased efficiency and range of operation, due to the ability to exploit nanofabrication techniques and emergent electrical properties originating from the nanoscale. However, because the building block is a discrete one-dimensional unit, it becomes a challenge to capture potential enhancements in dielectric performance in two or three dimensions, frequently due to surface effects or the presence of discontinuities. This is a recurring theme in nanoparticle film technology when applied to the realm of thin film semiconductor and device electronics. We present the use of chemically synthesized (Ba,Sr)TiO3 nanocrystals, and a novel deposition-polymerization technique, as a means to fabricate the dielectric layer. The effective dielectric constant of the film is tunable according to nanoparticle size, and effective film dielectric constants of up to 34 are enabled. Wide area and multilayer dielectrics of up to 8 cm(2) and 190 nF are reported, for which the building block is an 8 nm nanocrystal. We describe models for assessing dielectric performance, and distinct methods for improving the dielectric constant of a nanocrystal thin film. The approach relies on evaporatively driven assembly of perovskite nanocrystals with uniform size distributions in a tunable 7-30 nm size range, coupled with the use of low molecular weight monomer/polymer precursor chemistry that can infiltrate the porous nanocrystal thin film network post assembly. The intercrystal void space (low k dielectric volume fraction) is minimized, while simultaneously promoting intercrystal connectivity and maximizing volume fraction of the high k dielectric component. Furfuryl alcohol, which has good affinity to the surface of (Ba,Sr)TiO3 nanocrystals and miscibility with a range of solvents, is demonstrated to be ideal for the production of nanocomposites. The nanocrystal/furfuryl alcohol dispersions are suitable for the fabrication of thin films by chemical deposition techniques, including spin-coating, printing or a spraying process. To demonstrate the application of this technique to device fabrication, a multilayer capacitor with capacitance of 0.83 nF mm(-2) at 1 MHz is presented.

HEKATE-A novel grazing incidence neutron scattering concept for the European Spallation Source.

PubMed

Glavic, Artur; Stahn, Jochen

2018-03-01

Structure and magnetism at surfaces and buried interfaces on the nanoscale can only be accessed by few techniques, one of which is grazing incidence neutron scattering. While the technique has its strongest limitation in a low signal and large background, due to the low scattering probability and need for high resolution, it can be expected that the high intensity of the European Spallation Source in Lund, Sweden, will make many more such studies possible, warranting a dedicated beamline for this technique. We present an instrument concept, Highly Extended K range And Tunable Experiment (HEKATE), for surface scattering that combines the advantages of two Selene neutron guides with unique capabilities of spatially separated distinct wavelength frames. With this combination, it is not only possible to measure large specular reflectometry ranges, even on free liquid surfaces, but also to use two independent incident beams with tunable sizes and resolutions that can be optimized for the specifics of the investigated samples. Further the instrument guide geometry is tuned for reduction of high energy particle background and only uses low to moderate supermirror coatings for high reliability and affordable cost.

HEKATE—A novel grazing incidence neutron scattering concept for the European Spallation Source

NASA Astrophysics Data System (ADS)

Glavic, Artur; Stahn, Jochen

2018-03-01

Structure and magnetism at surfaces and buried interfaces on the nanoscale can only be accessed by few techniques, one of which is grazing incidence neutron scattering. While the technique has its strongest limitation in a low signal and large background, due to the low scattering probability and need for high resolution, it can be expected that the high intensity of the European Spallation Source in Lund, Sweden, will make many more such studies possible, warranting a dedicated beamline for this technique. We present an instrument concept, Highly Extended K range And Tunable Experiment (HEKATE), for surface scattering that combines the advantages of two Selene neutron guides with unique capabilities of spatially separated distinct wavelength frames. With this combination, it is not only possible to measure large specular reflectometry ranges, even on free liquid surfaces, but also to use two independent incident beams with tunable sizes and resolutions that can be optimized for the specifics of the investigated samples. Further the instrument guide geometry is tuned for reduction of high energy particle background and only uses low to moderate supermirror coatings for high reliability and affordable cost.

Tunable multiband polarization conversion and manipulation in vanadium dioxide-based asymmetric chiral metamaterial

NASA Astrophysics Data System (ADS)

Song, Shichao; Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Zhang, Zuojun; Gao, Ping; Luo, Xiangang

2018-04-01

Tunable multiband polarization conversion and manipulation are achieved by introducing vanadium dioxide (VO2) into a planar spiral asymmetric chiral metamaterial. Numerical simulations demonstrate that when VO2 is in the insulating state, circularly polarized electromagnetic waves are emitted at two distinct resonant frequencies. When VO2 is in the metallic state, the number of resonant frequencies changes from two to four. In addition, the initial left-handed and right-handed circularly polarized transmitted waves correspondingly transform into right and left ones. Moreover, the surface current distributions are studied in order to investigate the transformation behaviors of both the insulating and metallic states.

Photonic polymer-blend structures and method for making

DOEpatents

Barnes, Michael D.

2004-06-29

The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

A tunable lighting system integrated by inorganic and transparent organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Zhang, Jing-jing; Zhang, Tao; Jin, Ya-fang; Liu, Shi-shen; Yuan, Shi-dong; Cui, Zhao; Zhang, Li; Wang, Wei-hui

2014-05-01

A tunable surface-emitting integrated lighting system is constructed using a combination of inorganic light-emitting diodes (LEDs) and transparent organic LEDs (OLEDs). An RB two-color LED is used to supply red and blue light emission, and a green organic LED is used to supply green light emission. Currents of the LED and OLED are tuned to produce a white color, showing different Commission Internationale d'Eclairage (CIE) chromaticity coordinates and correlated color temperatures with a wide adjustable range. Such an integration can compensate for the lack of the LED's luminance uniformity and the transparent OLED's luminance intensity.

Non-Uniform Bias Enhancement of a Varactor-Tuned FSS used with a Low Profile 2.4 GHz Dipole Antenna

NASA Technical Reports Server (NTRS)

Cure, David; Weller, Thomas M.; Miranda, Felix A.

2012-01-01

In this paper a low profile antenna using a nonuniformly biased varactor-tuned frequency selective surface (FSS) is presented. The tunable FSS avoids the use of vias and has a simplified DC bias network. The voltages to the DC bias ports can be varied independently allowing adjustment in the frequency response and enhanced radiation properties. The measured data demonstrate tunability from 2.15 GHz to 2.63 GHz with peak efficiencies that range from 50% to 90% and instantaneous bandwidths of 50 MHz to 280 MHz within the tuning range. The total antenna thickness is approximately lambda/45.

Magnetically tunable unidirectional waveguide based on magnetic photonic crystals

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

Tong, Weiwei; Wang, Jiafu, E-mail: wangjiafu1981@126.com, E-mail: qushaobo@mail.xjtu.edu.cn; Wang, Jun

2016-08-01

In this letter, we presented a magnetically tunable ferrite-loaded unidirectional waveguide based on magnetic photonic crystals. Two rows of ferrite rods are symmetrically arranged near the two lateral sides of the rectangular waveguide, where they are biased with static magnetic fields with the same amplitude and opposite directions along the rod axis. Since the magnetic one-way transmission is induced by the magnetic surface plasmon resonance, the operating band of the unidirectional waveguide can be tuned by changing the biased magnetic field intensity. To validate the design, a prototype was fabricated and measured. Both the simulation and experiment results verify themore » unidirectional transmission property.« less

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

DOE PAGES

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang; ...

2017-09-14

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

PubMed

Szakal, Christopher; McCarthy, James A; Ugelow, Melissa S; Konicek, Andrew R; Louis, Kacie; Yezer, Benjamin; Herzing, Andrew A; Hamers, Robert J; Holbrook, R David

2012-07-01

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.

Tunable thiol-epoxy shape memory polymer foams

NASA Astrophysics Data System (ADS)

Ellson, Gregory; Di Prima, Matthew; Ware, Taylor; Tang, Xiling; Voit, Walter

2015-05-01

Shape memory polymers (SMPs) are uniquely suited to a number of applications due to their shape storage and recovery abilities and the wide range of available chemistries. However, many of the desired performance properties are tied to the polymer chemistry which can make optimization difficult. The use of foaming techniques is one way to tune mechanical response of an SMP without changing the polymer chemistry. In this work, a novel thiol-epoxy SMP was foamed using glass microspheres (40 and 50% by volume Q-Cel 6019), using expandable polymer microspheres (1% 930 DU 120), and by a chemical blowing agent (1% XOP-341). Each approach created SMP foam with a differing density and microstructure from the others. Thermal and thermomechanical analysis was performed to observe the behavioral difference between the foaming techniques and to confirm that the glass transition (Tg) was relatively unchanged near 50 °C while the glassy modulus varied from 19.1 to 345 MPa and the rubbery modulus varied from 0.04 to 2.2 MPa. The compressive behavior of the foams was characterized through static compression testing at different temperatures, and cyclic compression testing at Tg. Constrained shape recovery testing showed a range of peak recovery stress from 5 MPa for the syntactic Q-Cel foams to ˜0.1 MPa for the chemically blown XOP-341 foam. These results showed that multiple foaming approaches can be used with a novel SMP to vary the mechanical response independent of Tg and polymer chemistry.

Colloidal characterization of ultrafine silicon carbide and silicon nitride powders

NASA Technical Reports Server (NTRS)

Whitman, Pamela K.; Feke, Donald L.

1986-01-01

The effects of various powder treatment strategies on the colloid chemistry of aqueous dispersions of silicon carbide and silicon nitride are examined using a surface titration methodology. Pretreatments are used to differentiate between the true surface chemistry of the powders and artifacts resulting from exposure history. Silicon nitride powders require more extensive pretreatment to reveal consistent surface chemistry than do silicon carbide powders. As measured by titration, the degree of proton adsorption from the suspending fluid by pretreated silicon nitride and silicon carbide powders can both be made similar to that of silica.

On the use of SPM to probe the interplay between polymer surface chemistry and polymer surface mechanics

NASA Astrophysics Data System (ADS)

Brogly, Maurice; Noel, Olivier; Awada, Houssein; Castelein, Gilles

2007-03-01

Adhesive properties of a polymer surface results from the complex contribution of surface chemistry and activation of sliding and dissipating mechanisms within the polymer surface layer. The purpose of this study is to dissociate the different contributions (chemical and mechanical) included in an AFM force-distance curve in order to establish relationships between the surface viscoelastic properties of the polymer, the surface chemistry of functionalized polymer surfaces and the adhesive forces, as determined by C-AFM experiments. Indeed we are interested in the measurements of local attractive or adhesive forces in AFM contact mode, of controlled chemical and mechanical model substrates. In order to investigate the interplay between mechanical or viscoelastic mechanisms and surface chemistry during the tip - polymer contact, we achieved force measurements on model PDMS polymer networks, whose surfaces are chemically controlled with the same functional groups as before (silicon substrates). On the basis of AFM nano-indentation experiments, surface Young moduli have been determined. The results show that the viscoelastic contribution is dominating in the adhesion force measurement. We propose an original model, which express the local adhesion force to the energy dissipated within the contact and the surface properties of the material (thermodynamic work of adhesion). Moreover we show that the dissipation function is related to Mc, the mass between crosslinks of the network.

Ab Initio-Based Predictions of Hydrocarbon Combustion Chemistry

DTIC Science & Technology

2015-07-15

There are two prime objectives of the research. One is to develop and apply efficient methods for using ab initio potential energy surfaces (PESs...31-Mar-2015 Approved for Public Release; Distribution Unlimited Final Report: Ab Initio -Based Predictions of Hydrocarbon Combustion Chemistry The...Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 hydrocarbon combustion, ab initio quantum chemistry, potential energy surfaces, chemical

Control of the microstructure and surface chemistry of graphene aerogels via pH and time manipulation by a hydrothermal method.

PubMed

García-Bordejé, E; Víctor-Román, S; Sanahuja-Parejo, O; Benito, A M; Maser, W K

2018-02-15

Three-dimensional graphene aerogels of controlled pore size have emerged as an important platform for several applications such as energy storage or oil-water separation. The aerogels of reduced graphene oxide are mouldable and light weight, with a porosity up to 99.9%, consisting mainly of macropores. Graphene aerogel preparation by self-assembly in the liquid phase is a promising strategy due to its tunability and sustainability. For graphene aerogels prepared by a hydrothermal method, it is known that the pH value has an impact on their properties but it is unclear how pH affects the auto-assembly process leading to the final properties. We have monitored the time evolution of the chemical and morphological properties of aerogels as a function of the initial pH value. In the hydrothermal treatment process, the hydrogel is precipitated earlier and with lower oxygen content for basic pH values (∼13 wt% O) than for acidic pH values (∼20 wt% O). Moreover, ∼7 wt% of nitrogen is incorporated on the graphene nanosheets at basic pH generated by NH 3 addition. To our knowledge, there is no precedent showing that the pH value affects the microstructure of graphene nanosheets, which become more twisted and bent for the more intensive deoxygenation occurring at basic pH. The bent nanosheets attained at pH = 11 reduce the stacking by the basal planes and they connect via the borders, hence leading eventually to higher pore volumes. In contrast, the flatter graphene nanosheets attained under acidic pH entail more stacking and higher oxygen content after a long hydrothermal treatment. The gravimetric absorption capacity of non-polar solvents scales directly with the pore volume. The aerogels have proved to be highly selective, recyclable and robust for the absorption of nonpolar solvents in water. The control of the porous structure and surface chemistry by manipulation of pH and time will also pave the way for other applications such as supercapacitors or batteries.

Tunable Diode Laser Atomic Absorption Spectroscopy for Detection of Potassium under Optically Thick Conditions.

PubMed

Qu, Zhechao; Steinvall, Erik; Ghorbani, Ramin; Schmidt, Florian M

2016-04-05

Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer-Lambert's law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950-1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.

Simultaneous in situ measurements and diurnal variations of NO, NO2, O3, jNO2, CH4, H2O, and CO2 in the 40- to 26-km region using an open path tunable diode laser spectrometer

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; May, Randy D.

1987-01-01

Simultaneous in situ measurements of temperature, pressure, and the NO, NO2, O3, jNO2, CH4, H2O, and CO2 concentrations were conducted in the 40- to 26-km region of the stratosphere using the JPL Balloon-borne Laser In Situ Sensor, a tunable diode laser absorption spectrometer. The NO, NO2, CH4, H2O, and CO2 concentration measurements generally show good agreement with previous observations, with a tendency for somewhat lower NO2 amounts. Measured O3 concentrations at 38 km agree well with comparable measurements from in situ UV photometers, but at 28 km they are lower by about 10 percent and agree more closely with the solar backscattered UV data. A decline was found in NO2 during the night over a 5-km altitude range, which implies either lower NO2 postsunset profiles, or an NO2 decay rate that is significantly higher than current model predictions that use N2O5 chemistry.

Tunable inversion symmetry to control indirect-to-direct band gaps transitions

NASA Astrophysics Data System (ADS)

Lu, Xue-Zeng; Rondinelli, James M.

2018-05-01

Electric-field tunable indirect-to-direct band gap transitions occur in thin-film silicon and transition metal dichalcogenides; however, they remain challenging to access in three-dimensional transition metal oxides. Very recently, an unusual polar-to-nonpolar phase transition under epitaxial strain was discovered in A3B2O7 hybrid improper ferroelectrics (HIFs), which supports controllable dielectric anisotropy and magnetization. Here we examine HIF (ABO3) 1/(A'BO3) 1 superlattices and AA'BB' O6 double perovskites and predict a competing nonpolar antiferroelectric phase, demonstrating it is hidden in hybrid improper ferroelectrics exhibiting corner-connected B O6 octahedra. Furthermore, we show the transition between the polar and nonpolar phases enables an in-plane electric field to control the indirect-to-direct band gap transition at the phase boundary in the (ABO3) 1/(A'BO3) 1 superlattices and AA'BB' O6 double perovskites, which may be tuned through static strain or chemical substitution. Our findings establish HIFs as a functional electronics class from which to realize direct gap materials and enables the integration of a broader palette of chemistries and compounds for linear and nonlinear optical applications.

Hydrolytically degradable poly(ethylene glycol) hydrogel scaffolds with tunable degradation and mechanical properties

PubMed Central

Zustiak, Silviya P.

2011-01-01

The objective of this work was to create three-dimensional (3D) hydrogel matrices with defined mechanical properties, as well as tunable degradability for use in applications involving protein delivery and cell encapsulation. Thus, we report the synthesis and characterization of a novel hydrolytically degradable poly(ethylene glycol) (PEG) hydrogel composed of PEG vinyl sulfone (PEG-VS) cross-linked with PEG-diester-dithiol. Unlike previously reported degradable PEG-based hydrogels, these materials are homogeneous in structure, fully hydrophilic and have highly specific cross-linking chemistry. We characterized hydrogel degradation and associated trends in mechanical properties, i.e., storage modulus (G′), swelling ratio (QM), and mesh size (ξ). Degradation time and the monitored mechanical properties of the hydrogel correlated with cross-linker molecular weight, cross-linker functionality, and total polymer density; these properties changed predictably as degradation proceeded (G′ decreased, whereas QM and ξ increased) until the gels reached complete degradation. Balb/3T3 fibroblast adhesion and proliferation within the 3D hydrogel matrices were also verified. In sum, these unique properties indicate that the reported degradable PEG hydrogels are well poised for specific applications in protein and cell delivery to repair soft tissue. PMID:20355705

Precision platform for convex lens-induced confinement microscopy

NASA Astrophysics Data System (ADS)

Berard, Daniel; McFaul, Christopher M. J.; Leith, Jason S.; Arsenault, Adriel K. J.; Michaud, François; Leslie, Sabrina R.

2013-10-01

We present the conception, fabrication, and demonstration of a versatile, computer-controlled microscopy device which transforms a standard inverted fluorescence microscope into a precision single-molecule imaging station. The device uses the principle of convex lens-induced confinement [S. R. Leslie, A. P. Fields, and A. E. Cohen, Anal. Chem. 82, 6224 (2010)], which employs a tunable imaging chamber to enhance background rejection and extend diffusion-limited observation periods. Using nanopositioning stages, this device achieves repeatable and dynamic control over the geometry of the sample chamber on scales as small as the size of individual molecules, enabling regulation of their configurations and dynamics. Using microfluidics, this device enables serial insertion as well as sample recovery, facilitating temporally controlled, high-throughput measurements of multiple reagents. We report on the simulation and experimental characterization of this tunable chamber geometry, and its influence upon the diffusion and conformations of DNA molecules over extended observation periods. This new microscopy platform has the potential to capture, probe, and influence the configurations of single molecules, with dramatically improved imaging conditions in comparison to existing technologies. These capabilities are of immediate interest to a wide range of research and industry sectors in biotechnology, biophysics, materials, and chemistry.

Ce3+-Doped garnet phosphors: composition modification, luminescence properties and applications.

PubMed

Xia, Zhiguo; Meijerink, Andries

2017-01-03

Garnets have the general formula of A 3 B 2 C 3 O 12 and form a wide range of inorganic compounds, occurring both naturally (gemstones) and synthetically. Their physical and chemical properties are closely related to the structure and composition. In particular, Ce 3+ -doped garnet phosphors have a long history and are widely applied, ranging from flying spot cameras, lasers and phosphors in fluorescent tubes to more recent applications in white light LEDs, as afterglow materials and scintillators for medical imaging. Garnet phosphors are unique in their tunability of the luminescence properties through variations in the {A}, [B] and (C) cation sublattice. The flexibility in phosphor composition and the tunable luminescence properties rely on design and synthesis strategies for new garnet compositions with tailor-made luminescence properties. It is the aim of this review to discuss the variation in luminescence properties of Ce 3+ -doped garnet materials in relation to the applications. This review will provide insight into the relation between crystal chemistry and luminescence for the important class of Ce 3+ -doped garnet phosphors. It will summarize previous research on the structural design and optical properties of garnet phosphors and also discuss future research opportunities in this field.

Quercetin conjugated poly(β-amino esters) nanogels for the treatment of cellular oxidative stress.

PubMed

Gupta, Prachi; Authimoolam, Sundar P; Hilt, J Zach; Dziubla, Thomas D

2015-11-01

PβAE polymers have emerged as highly promising candidates for biomedical and drug delivery applications owing to their tunable, degradable and pH sensitive properties. These polymeric systems can serve as prodrug carriers for the delivery of bioactive compounds which suffer from poor aqueous solubility, low bioavailability and are biologically unstable, such as the antioxidant, quercetin. Using acrylate functionalized quercetin, it is possible to incorporate the polyphenol into the backbone of the polymer matrix, permitting slow release of the intact molecule which is perfectly timed with the polymer degradation. While formulating these quercetin conjugated PβAE matrix into nanocarriers would allow for multiple delivery routes (oral, intravenous, inhalation etc.), well known oil-water nano-emulsion formulation methods are not amenable to the crosslinked hydrolytically sensitive nanoparticle/nanogel. In this work, a single-phase reaction-precipitation method was developed to formulate quercetin conjugated PβAE nanogels (QNG) via reaction of acrylated quercetin (4-5 acrylate groups) with a secondary diamine under dilute conditions using acetonitrile as the reaction medium, resulting in a self-stabilized suspension. The proposed approach permits the post synthesis modification of the spherical nanogels with a PEGylated coating, enhancing their aqueous stability and stealth characteristics. Nanogel size was controlled by varying feed reactant concentrations, achieving drug loadings of 25-38wt%. Uniform release of quercetin over 45-48h was observed upon PβAE ester hydrolysis under physiological conditions with its retained antioxidant activity over the extended times. Here we present the first demonstration of using poly(beta amino ester) chemistry to form nanogels composed of a bioactive polyphenol for the control of cellular oxidative stress. Previous nanogel and nanoparticle approaches, which use a water phase, are not readily amenable to PBAE chemistry due to their hydrolytic sensitivity. Here we demonstrate a simple approach to control particle size, modify surface chemistry and achieve highly regulated controlled release of active antioxidants, which can protect cells against external oxidative stress signals. This work has importance in the area of controlling material biocompatibility through augmenting the antioxidant status of cells. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The impact of surface chemistry on the performance of localized solar-driven evaporation system

PubMed Central

Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-01-01

This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation. PMID:26337561

The impact of surface chemistry on the performance of localized solar-driven evaporation system.

PubMed

Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-09-04

This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

Surface chemistry driven actuation in nanoporous gold

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

Biener, J; Wittstock, A; Zepeda-Ruiz, L

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry driven actuation can be realized in high surface area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes in the order of a few tenths of a percent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into amore » mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.« less

Molecular Rotors

DTIC Science & Technology

2006-10-31

microwave signal processing components, and micro-fluidic devices. The projected involved the preparation, surface mounting, and characterization of...Guisinger, R. Basu, and M. C. Hersam, “Atomic-level characterization and control of free radical surface chemistry using scanning tunneling microscopy...Basu, and M. C. Hersam, “Atomic level characterization and control of organosilicon surface chemistry using scanning tunneling microscopy,” presented

Surface chemistry and moisture sorption properties of wood coated with multifunctional alkoxysilanes by sol-gel process

Treesearch

Mandla A. Tshabalala; Peter Kingshott; Mark R. VanLandingham; David Plackett

2003-01-01

Sol-gel surface deposition of a hydrophobic polysiloxane coating on wood was accomplished by using a mixture of a low molecular weight multifunctional alkoxysilane, methyltrimethoxysilane (MTMOS), and a high molecular weight multifunctional alkoxysilane, hexadecyltrimethoxysilane (HDTMOS). Investigation of the surface chemistry and morphology of the wood specimens by...

Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

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

Yoon, Yeohoon; Du, Yingge; Garcia, Juan C.

2015-02-02

Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absencemore » of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas. We also postulate that the entire nearest subsurface region could be voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.« less

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

PubMed

Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

2016-07-01

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Hydrofluoric Acid Etching Time on Titanium Topography, Chemistry, Wettability, and Cell Adhesion

PubMed Central

Zahran, R.; Rosales Leal, J. I.; Rodríguez Valverde, M. A.; Cabrerizo Vílchez, M. A.

2016-01-01

Titanium implant surface etching has proven an effective method to enhance cell attachment. Despite the frequent use of hydrofluoric (HF) acid, many questions remain unresolved, including the optimal etching time and its effect on surface and biological properties. The objective of this study was to investigate the effect of HF acid etching time on Ti topography, surface chemistry, wettability, and cell adhesion. These data are useful to design improved acid treatment and obtain an improved cell response. The surface topography, chemistry, dynamic wetting, and cell adhesiveness of polished Ti surfaces were evaluated after treatment with HF acid solution for 0, 2; 3, 5, 7, or 10 min, revealing a time-dependent effect of HF acid on their topography, chemistry, and wetting. Roughness and wetting increased with longer etching time except at 10 min, when roughness increased but wetness decreased. Skewness became negative after etching and kurtosis tended to 3 with longer etching time. Highest cell adhesion was achieved after 5–7 min of etching time. Wetting and cell adhesion were reduced on the highly rough surfaces obtained after 10-min etching time. PMID:27824875

Surface Functionalization of Exosomes Using Click Chemistry

PubMed Central

2015-01-01

A method for conjugation of ligands to the surface of exosomes was developed using click chemistry. Copper-catalyzed azide alkyne cycloaddition (click chemistry) is ideal for biocojugation of small molecules and macromolecules to the surface of exosomes, due to fast reaction times, high specificity, and compatibility in aqueous buffers. Exosomes cross-linked with alkyne groups using carbodiimide chemistry were conjugated to a model azide, azide-fluor 545. Conjugation had no effect on the size of exosomes, nor was there any change in the extent of exosome adherence/internalization with recipient cells, suggesting the reaction conditions were mild on exosome structure and function. We further investigated the extent of exosomal protein modification with alkyne groups. Using liposomes with surface alkyne groups of a similar size and concentration to exosomes, we estimated that approximately 1.5 alkyne groups were present for every 150 kDa of exosomal protein. PMID:25220352

Tunable geometric Fano resonances in a metal/insulator stack

NASA Astrophysics Data System (ADS)

Grotewohl, Herbert

We present a theoretical analysis of surface-plasmon-mediated mode-coupling in a planar thin film metal/insulator stack. The spatial overlap of a surface plasmon polariton (SPP) and a waveguide mode results in a Fano interference analog. Tuning of the material parameters effects the modes and output fields of the system. Lastly, the intensity and phase sensitivity of the system are compared to a standard surface plasmon resonance (SPR). We begin with background information on Fano interference, an interference effect between two indistinguishable pathways. Originally described for autoionization, we discuss the analogs in other systems. We discuss the features of Fano interference in the mode diagrams, and the Fano resonance observed in the output field. The idea of a geometric Fano resonance (GFR) occurring in the angular domain is presented. Background information on surface plasmon polaritons is covered next. The dielectric properties of metals and how they relate to surface plasmons is first reviewed. The theoretical background of SPPs on an infinite planar surface is covered. The modes of a two planar interface metal/insulator stack are reviewed and the leaky properties of the waveguide are shown in the reflectance. We solve for modes of a three interface metal/insulator stack and shows an avoided crossing in the modes indicative of Fano interference. We observe the asymmetric Fano resonance in the angular domain in the reflectance. The tunability of the material parameters tunes the GFR of the system. The GFR tuning is explored and different Fano lineshapes are observed. We also observe a reversal of the asymmetry Fano lineshape, attributed to the relate phase interactions of the non-interacting modes. The phase of the GFR is calculated and discussed for the variations of the parameters. The reflected field is explored as the insulator permittivities are varied. As the waveguide permittivity is varied, we show there is little response from the system. As the exterior permittivity is varied, the reflectance exhibits the geometric Fano resonance and the tunability of the lineshape is explored. Finally, we calculate the sensitivities of our metal/insulator stack to changes in the permittivity and compare them to the sensitivities of SPRs.

Development of a portable petroleum by-products chemical sensor : phase III and IV.

DOT National Transportation Integrated Search

2009-08-21

Semiconductor quantum dots (QDs) are considered to have potential for chemical sensing application : because of their high surface to volume ratio and unique size tunable properties like : photoluminescence (PL). However, our study revealed for the f...

Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

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

Not Available

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

Reconfigurable all-dielectric metasurface based on tunable chemical systems in aqueous solution.

PubMed

Yang, Xiaoqing; Zhang, Di; Wu, Shiyue; Yin, Yang; Li, Lanshuo; Cao, Kaiyuan; Huang, Kama

2017-06-09

Dynamic control transmission and polarization properties of electromagnetic (EM) wave propagation is investigated using chemical reconfigurable all-dielectric metasurface. The metasurface is composed of cross-shaped periodical teflon tubes and inner filled chemical systems (i.e., mixtures and chemical reaction) in aqueous solution. By tuning the complex permittivity of chemical systems, the reconfigurable metasurface can be easily achieved. The transmission properties of different incident polarized waves (i.e., linear and circular polarization) were simulated and experimentally measured for static ethanol solution as volume ratio changed. Both results indicated this metasurface can serve as either tunable FSS (Frequency Selective Surface) or tunable linear-to-circular/cross Polarization Converter at required frequency range. Based on the reconfigurable laws obtained from static solutions, we developed a dynamic dielectric system and researched a typical chemical reaction with time-varying permittivity filled in the tubes experimentally. It provides new ways for realizing automatic reconfiguration of metasurface by chemical reaction system with given variation laws of permittivity.

Graphene-Based Flexible and Transparent Tunable Capacitors.

PubMed

Man, Baoyuan; Xu, Shicai; Jiang, Shouzheng; Liu, Aihua; Gao, Shoubao; Zhang, Chao; Qiu, Hengwei; Li, Zhen

2015-12-01

We report a kind of electric field tunable transparent and flexible capacitor with the structure of graphene-Bi1.5MgNb1.5O7 (BMN)-graphene. The graphene films with low sheet resistance were grown by chemical vapor deposition. The BMN thin films were fabricated on graphene by using laser molecular beam epitaxy technology. Compared to BMN films grown on Au, the samples on graphene substrates show better quality in terms of crystallinity, surface morphology, leakage current, and loss tangent. By transferring another graphene layer, we fabricated flexible and transparent capacitors with the structure of graphene-BMN-graphene. The capacitors show a large dielectric constant of 113 with high dielectric tunability of ~40.7 % at a bias field of 1.0 MV/cm. Also, the capacitor can work stably in the high bending condition with curvature radii as low as 10 mm. This flexible film capacitor has a high optical transparency of ~90 % in the visible light region, demonstrating their potential application for a wide range of flexible electronic devices.

Integrated Method for Purification and Single-Particle Characterization of Lentiviral Vector Systems by Size Exclusion Chromatography and Tunable Resistive Pulse Sensing.

PubMed

Heider, Susanne; Muzard, Julien; Zaruba, Marianne; Metzner, Christoph

2017-07-01

Elements derived from lentiviral particles such as viral vectors or virus-like particles are commonly used for biotechnological and biomedical applications, for example in mammalian protein expression, gene delivery or therapy, and vaccine development. Preparations of high purity are necessary in most cases, especially for clinical applications. For purification, a wide range of methods are available, from density gradient centrifugation to affinity chromatography. In this study we have employed size exclusion columns specifically designed for the easy purification of extracellular vesicles including exosomes. In addition to viral marker protein and total protein analysis, a well-established single-particle characterization technology, termed tunable resistive pulse sensing, was employed to analyze fractions of highest particle load and purity and characterize the preparations by size and surface charge/electrophoretic mobility. With this study, we propose an integrated platform combining size exclusion chromatography and tunable resistive pulse sensing for monitoring production and purification of viral particles.

Toward tunable band gap and tunable dirac point in bilayer graphene with molecular doping.

PubMed

Yu, Woo Jong; Liao, Lei; Chae, Sang Hoon; Lee, Young Hee; Duan, Xiangfeng

2011-11-09

The bilayer graphene has attracted considerable attention for potential applications in future electronics and optoelectronics because of the feasibility to tune its band gap with a vertical displacement field to break the inversion symmetry. Surface chemical doping in bilayer graphene can induce an additional offset voltage to fundamentally affect the vertical displacement field and the band gap opening in bilayer graphene. In this study, we investigate the effect of chemical molecular doping on band gap opening in bilayer graphene devices with single or dual gate modulation. Chemical doping with benzyl viologen molecules modulates the displacement field to allow the opening of a transport band gap and the increase of the on/off ratio in the bilayer graphene transistors. Additionally, Fermi energy level in the opened gap can be rationally controlled by the amount of molecular doping to obtain bilayer graphene transistors with tunable Dirac points, which can be readily configured into functional devices, such as complementary inverters.

Tunable magnetic properties by interfacial manipulation of L1(0)-FePt perpendicular ultrathin film with island-like structures.

PubMed

Feng, C; Wang, S G; Yang, M Y; Zhang, E; Zhan, Q; Jiang, Y; Li, B H; Yu, G H

2012-02-01

Based on interfacial manipulation of the MgO single crystal substrate and non-magnetic AIN compound, a L1(0)-FePt perpendicular ultrathin film with the structure of MgO/FePt-AIN/Ta was designed, prepared, and investigated. The film is comprised of L1(0)-FePt "magnetic islands," which exhibits a perpendicular magnetic anisotropy (PMA), tunable coercivity (Hc), and interparticle exchange coupling (IEC). The MgO substrate promotes PMA of the film because of interfacial control of the FePt lattice orientation. The AIN compound is doped to increase the difference of surface energy between FePt layer and MgO substrate and to suppress the growth of FePt grains, which takes control of island growth mode of FePt atoms. The AIN compound also acts as isolator of L1(0)-FePt islands to pin the sites of FePt domains, resulting in the tunability of Hc and IEC of the films.

Tunable Fano Resonance and Plasmon-Exciton Coupling in Single Au Nanotriangles on Monolayer WS2 at Room Temperature.

PubMed

Wang, Mingsong; Krasnok, Alex; Zhang, Tianyi; Scarabelli, Leonardo; Liu, He; Wu, Zilong; Liz-Marzán, Luis M; Terrones, Mauricio; Alù, Andrea; Zheng, Yuebing

2018-05-01

Tunable Fano resonances and plasmon-exciton coupling are demonstrated at room temperature in hybrid systems consisting of single plasmonic nanoparticles deposited on top of the transition metal dichalcogenide monolayers. By using single Au nanotriangles (AuNTs) on monolayer WS 2 as model systems, Fano resonances are observed from the interference between a discrete exciton band of monolayer WS 2 and a broadband plasmonic mode of single AuNTs. The Fano lineshape depends on the exciton binding energy and the localized surface plasmon resonance strength, which can be tuned by the dielectric constant of surrounding solvents and AuNT size, respectively. Moreover, a transition from weak to strong plasmon-exciton coupling with Rabi splitting energies of 100-340 meV is observed by rationally changing the surrounding solvents. With their tunable plasmon-exciton interactions, the proposed WS 2 -AuNT hybrids can open new pathways to develop active nanophotonic devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental demonstrations in audible frequency range of band gap tunability and negative refraction in two-dimensional sonic crystal.

PubMed

Pichard, Hélène; Richoux, Olivier; Groby, Jean-Philippe

2012-10-01

The propagation of audible acoustic waves in two-dimensional square lattice tunable sonic crystals (SC) made of square cross-section infinitely rigid rods embedded in air is investigated experimentally. The band structure is calculated with the plane wave expansion (PWE) method and compared with experimental measurements carried out on a finite extend structure of 200 cm width, 70 cm depth and 15 cm height. The structure is made of square inclusions of 5 cm side with a periodicity of L = 7.5 cm placed inbetween two rigid plates. The existence of tunable complete band gaps in the audible frequency range is demonstrated experimentally by rotating the scatterers around their vertical axis. Negative refraction is then analyzed by use of the anisotropy of the equi-frequency surface (EFS) in the first band and of a finite difference time domain (FDTD) method. Experimental results finally show negative refraction in the audible frequency range.

Highly tunable quantum Hall far-infrared photodetector by use of GaAs/Al{sub x}Ga{sub 1−x}As-graphene composite material

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

Tang, Chiu-Chun; Ling, D. C.; Chi, C. C.

2014-11-03

We have developed a highly tunable, narrow band far-infrared (FIR) photodetector which utilizes the characteristic merits of graphene and two-dimensional electron gas (2DEG) in GaAs/Al{sub x}Ga{sub 1−x}As heterostructure in the Quantum Hall states (QHS). The heterostructure surface is covered with chemical vapor-deposited graphene, which functions as a transparent top-gate to vary the electron density of the 2DEG. FIR response observed in the vicinity of integer QH regime can be effectively tuned in a wide range of 27–102 cm{sup −1} with a bias voltage less than −1 V. In addition, we have found that the presence of graphene can genuinely modulate the photoresponse.more » Our results demonstrate a promising direction for realizing a tunable long-wavelength FIR detector using QHS in GaAs 2DEG/ graphene composite material.« less

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

PubMed Central

Alhamami, Mays; Doan, Huu; Cheng, Chil-Hung

2014-01-01

Metal-organic frameworks (MOFs) are a new class of microporous materials that possess framework flexibility, large surface areas, “tailor-made” framework functionalities, and tunable pore sizes. These features empower MOFs superior performances and broader application spectra than those of zeolites and phosphine-based molecular sieves. In parallel with designing new structures and new chemistry of MOFs, the observation of unique breathing behaviors upon adsorption of gases or solvents stimulates their potential applications as host materials in gas storage for renewable energy. This has attracted intense research energy to understand the causes at the atomic level, using in situ X-ray diffraction, calorimetry, Fourier transform infrared spectroscopy, and molecular dynamics simulations. This article is developed in the following order: first to introduce the definition of MOFs and the observation of their framework flexibility. Second, synthesis routes of MOFs are summarized with the emphasis on the hydrothermal synthesis, owing to the environmental-benign and economically availability of water. Third, MOFs exhibiting breathing behaviors are summarized, followed by rationales from thermodynamic viewpoint. Subsequently, effects of various functionalities on breathing behaviors are appraised, including using post-synthetic modification routes. Finally, possible framework spatial requirements of MOFs for yielding breathing behaviors are highlighted as the design strategies for new syntheses. PMID:28788614

Hybrid nanostructures of well-organized arrays of colloidal quantum dots and a self-assembled monolayer of gold nanoparticles for enhanced fluorescence

NASA Astrophysics Data System (ADS)

Liu, Xiaoying; McBride, Sean P.; Jaeger, Heinrich M.; Nealey, Paul F.

2016-07-01

Hybrid nanomaterials comprised of well-organized arrays of colloidal semiconductor quantum dots (QDs) in close proximity to metal nanoparticles (NPs) represent an appealing system for high-performance, spectrum-tunable photon sources with controlled photoluminescence. Experimental realization of such materials requires well-defined QD arrays and precisely controlled QD-metal interspacing. This long-standing challenge is tackled through a strategy that synergistically combines lateral confinement and vertical stacking. Lithographically generated nanoscale patterns with tailored surface chemistry confine the QDs into well-organized arrays with high selectivity through chemical pattern directed assembly, while subsequent coating with a monolayer of close-packed Au NPs introduces the plasmonic component for fluorescence enhancement. The results show uniform fluorescence emission in large-area ordered arrays for the fabricated QD structures and demonstrate five-fold fluorescence amplification for red, yellow, and green QDs in the presence of the Au NP monolayer. Encapsulation of QDs with a silica shell is shown to extend the design space for reliable QD/metal coupling with stronger enhancement of 11 times through the tuning of QD-metal spatial separation. This approach provides new opportunities for designing hybrid nanomaterials with tailored array structures and multiple functionalities for applications such as multiplexed optical coding, color display, and quantum transduction.

Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates

PubMed Central

Jackson, J. B.; Halas, N. J.

2004-01-01

Au and Ag nanoshells are investigated as substrates for surface-enhanced Raman scattering (SERS). We find that SERS enhancements on nanoshell films are dramatically different from those observed on colloidal aggregates, specifically that the Raman enhancement follows the plasmon resonance of the individual nanoparticles. Comparative finite difference time domain calculations of fields at the surface of smooth and roughened nanoshells reveal that surface roughness contributes only slightly to the total enhancement. SERS enhancements as large as 2.5 × 1010 on Ag nanoshell films for the nonresonant molecule p-mercaptoaniline are measured. PMID:15608058

Low temperature surface chemistry and nanostructures

NASA Astrophysics Data System (ADS)

Sergeev, G. B.; Shabatina, T. I.

2002-03-01

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.

Emphasizing the role of surface chemistry on hydrophobicity and cell adhesion behavior of polydimethylsiloxane/TiO2 nanocomposite films.

PubMed

Yousefi, Seyedeh Zahra; Tabatabaei-Panah, Pardis-Sadat; Seyfi, Javad

2018-07-01

Improving the bioinertness of materials is of great importance for developing biomedical devices that contact human tissues. The main goal of this study was to establish correlations among surface morphology, roughness and chemistry with hydrophobicity and cell adhesion in polydimethylsiloxane (PDMS) nanocomposites loaded with titanium dioxide (TiO 2 ) nanoparticles. Firstly, wettability results showed that the nanocomposite loaded with 30 wt.% of TiO 2 exhibited a superhydrophobic behavior; however, the morphology and roughness analysis proved that there was no discernible difference between the surface structures of samples loaded with 20 and 30 wt.% of nanoparticles. Both cell culture and MTT assay experiments showed that, despite the similarity between the surface structures, the sample loaded with 30 wt.% nanoparticles exhibits the greatest reduction in the cell viability (80%) as compared with the pure PDMS film. According to the X-ray photoelectron spectroscopy results, the remarkable reduction in cell viability of the superhydrophobic sample could be majorly attributed to the role of surface chemistry. The obtained results emphasize the importance of adjusting the surface properties especially surface chemistry to gain the optimum cell adhesion behavior. Copyright © 2018 Elsevier B.V. All rights reserved.

Size tunable gold nanorods evenly distributed in the channels of mesoporous silica.

PubMed

Li, Zhi; Kübel, Christian; Pârvulescu, Vasile I; Richards, Ryan

2008-06-01

Uniformly distributed gold nanorods in mesoporous silica were synthesized in situ by performing a seed-mediated growth process in the channels of SBA-15 which functions as a hard-template to confine the diameter of gold nanorods. By changing the amount of gold precursor, gold nanorods were prepared with a fixed diameter (6-7 nm) and tunable aspect ratios from 3 to 30. Transmission electron microscope and electron tomography were utilized to visualize the gold nanorods supported on one piece of SBA-15 segment and showed a fairly uniform 3-dimensional distribution of gold nanorods within the SBA-15 channels. The longitudinal plasmon resonances of the gold nanorods/SBA-15 composites analyzed by diffuse reflectance UV-vis spectra were found to be tunable depending on the length of gold nanorods. No significant decrease in surface area and/or pore size of the composite was found after growth, indicating the growth process did not disrupt the open mesoporous structure of SBA-15. The combination of the tunable size of the nanorods and their 3-dimensional distribution within the open supporting matrix makes the gold nanorods/SBA-15 composites interesting candidates to systematically study the influence of the aspect ratio of gold nanorods on their properties and potential applications, i.e., catalyst, optical polarizer, and ultrasensitive medical imaging technique.

A photo-excited broadband to dual-band tunable terahertz prefect metamaterial polarization converter

NASA Astrophysics Data System (ADS)

Zhu, Jianfeng; Yang, Yang; Li, Shufang

2018-04-01

A new and simple design of photo-excited broadband to dual-band tunable terahertz (THz) metamaterial cross polarization converter is proposed in this paper. The tunable converter is a sandwich structure with the center-cut cross-shaped metallic patterned structure as a resonator, the middle dielectric layer as a spacer and the bottom metallic film as the ground. The conductivity of the photoconductive semiconductor (Silicon) filled in the gap of the cross-shaped metallic resonator can be tuned by the incident pump power, leading to an easy modulation of the electromagnetic response of the proposed converter. The results show that the proposed cross-polarization converter can be tuned from a broadband with polarization conversion ratio (PCR) beyond 95% (1.86-2.94 THz) to dual frequency bands (fl = 1 . 46 THz &fh = 2 . 9 THz). The conversion peaks can reach 99.9% for the broadband and, 99.5% (fl) and 99.7% (fh) for the dual-band, respectively. Most importantly, numerical simulations demonstrate that the broadband/dual-band polarization conversion mechanism of the converter originates from the localized surface plasmon modes, which make the design simple and different from previous designs. With these good features, the proposed broadband to dual-band tunable polarization converter is expected to be used in widespread applications.

Pressure sensitive microparticle adhesion through biomimicry of the pollen-stigma interaction.

PubMed

Lin, Haisheng; Qu, Zihao; Meredith, J Carson

2016-03-21

Many soft biomimetic synthetic adhesives, optimized to support macroscopic masses (∼kg), have been inspired by geckos, insects and other animals. Far less work has investigated bioinspired adhesion that is tuned to micro- and nano-scale sizes and forces. However, such adhesive forces are extremely important in the adhesion of micro- and nanoparticles to surfaces, relevant to a wide range of industrial and biological systems. Pollens, whose adhesion is critical to plant reproduction, are an evolutionary-optimized system for biomimicry to engineer tunable adhesion between particles and micro-patterned soft matter surfaces. In addition, the adhesion of pollen particles is relevant to topics as varied as pollinator ecology, transport of allergens, and atmospheric phenomena. We report the first observation of structurally-derived pressure-sensitive adhesion of a microparticle by using the sunflower pollen and stigma surfaces as a model. This strong, pressure-sensitive adhesion results from interlocking between the pollen's conical spines and the stigma's receptive papillae. Inspired by this behavior, we fabricated synthetic polymeric patterned surfaces that mimic the stigma surface's receptivity to pollen. These soft mimics allow the magnitude of the pressure-sensitive response to be tuned by adjusting the size and spacing of surface features. These results provide an important new insight for soft material adhesion based on bio-inspired principles, namely that ornamented microparticles and micro-patterned surfaces can be designed with complementarity that enable a tunable, pressure-sensitive adhesion on the microparticle size and length scale.

Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Loeffler, Mark J.

2012-01-01

Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

Tunable circuit for tunable capacitor devices

DOEpatents

Rivkina, Tatiana; Ginley, David S.

2006-09-19

A tunable circuit (10) for a capacitively tunable capacitor device (12) is provided. The tunable circuit (10) comprises a tunable circuit element (14) and a non-tunable dielectric element (16) coupled to the tunable circuit element (16). A tunable capacitor device (12) and a method for increasing the figure of merit in a tunable capacitor device (12) are also provided.

Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency.

PubMed

Kong, Ming; Li, Yuanzhi; Chen, Xiong; Tian, Tingting; Fang, Pengfei; Zheng, Feng; Zhao, Xiujian

2011-10-19

TiO(2) nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO(2) nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.

Giant magnetoresistive biosensors for molecular diagnosis: surface chemistry and assay development

NASA Astrophysics Data System (ADS)

Yu, Heng; Osterfeld, Sebastian J.; Xu, Liang; White, Robert L.; Pourmand, Nader; Wang, Shan X.

2008-08-01

Giant magnetoresistive (GMR) biochips using magnetic nanoparticle as labels were developed for molecular diagnosis. The sensor arrays consist of GMR sensing strips of 1.5 μm or 0.75 μm in width. GMR sensors are exquisitely sensitive yet very delicate, requiring ultrathin corrosion-resistive passivation and efficient surface chemistry for oligonucleotide probe immobilization. A mild and stable surface chemistry was first developed that is especially suitable for modifying delicate electronic device surfaces, and a practical application of our GMR biosensors was then demonstrated for detecting four most common human papillomavirus (HPV) subtypes in plasmids. We also showed that the DNA hybridization time could potentially be reduced from overnight to about ten minutes using microfluidics.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

PubMed Central

2016-01-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of ‘polar ice’ mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm ‘carbonyl’ absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes. PMID:28083090

3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

ERIC Educational Resources Information Center

Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

2015-01-01

Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

Estimating the Analytical and Surface Enhancement Factors in Surface-Enhanced Raman Scattering (SERS): A Novel Physical Chemistry and Nanotechnology Laboratory Experiment

ERIC Educational Resources Information Center

Pavel, Ioana E.; Alnajjar, Khadijeh S.; Monahan, Jennifer L.; Stahler, Adam; Hunter, Nora E.; Weaver, Kent M.; Baker, Joshua D.; Meyerhoefer, Allie J.; Dolson, David A.

2012-01-01

A novel laboratory experiment was successfully implemented for undergraduate and graduate students in physical chemistry and nanotechnology. The main goal of the experiment was to rigorously determine the surface-enhanced Raman scattering (SERS)-based sensing capabilities of colloidal silver nanoparticles (AgNPs). These were quantified by…

Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

PubMed

Ryan, Robert G; Stacey, Alastair; O'Donnell, Kane M; Ohshima, Takeshi; Johnson, Brett C; Hollenberg, Lloyd C L; Mulvaney, Paul; Simpson, David A

2018-04-18

Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

PEG-nanotube liquid crystals as templates for construction of surfactant-free gold nanorods.

PubMed

Kameta, Naohiro; Shiroishi, Hidenobu

2018-05-03

Lyotropic liquid crystals, in which nanotubes coated with polyethylene glycol were aligned side-by-side in aqueous dispersions, acted as templates for the construction of surfactant-free gold nanorods with controllable diameters, functionalizable surfaces, and tunable optical properties.

Improving Ionic Conductivity and Lithium-Ion Transference Number in Lithium-Ion Battery Separators.

PubMed

Zahn, Raphael; Lagadec, Marie Francine; Hess, Michael; Wood, Vanessa

2016-12-07

The microstructure of lithium-ion battery separators plays an important role in separator performance; however, here we show that a geometrical analysis falls short in predicting the lithium-ion transport in the electrolyte-filled pore space. By systematically modifying the surface chemistry of a commercial polyethylene separator while keeping its microstructure unchanged, we demonstrate that surface chemistry, which alters separator-electrolyte interactions, influences ionic conductivity and lithium-ion transference number. Changes in separator surface chemistry, particularly those that increase lithium-ion transference numbers can reduce voltage drops across the separator and improve C-rate capability.

Aromatic, Alphatic, Enigmatic: The Chemistry of Titan

NASA Astrophysics Data System (ADS)

Horst, Sarah

2017-10-01

The extraordinary complexity of Titan’s atmospheric chemistry far surpasses that of any other solar system atmosphere. With its thick N2 atmosphere and stable bodies of liquid on its surface, Titan also possesses many physical processes that are similar to those that occur on Earth. The connection between Titan’s surface and atmosphere is unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan’s atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan’s atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. I will review our current understanding of chemistry on Titan forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I will conclude with some of the questions that remain after Cassini-Huygens.

Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

NASA Astrophysics Data System (ADS)

Yonata, B.; Nasrudin, H.

2018-01-01

A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

NASA Technical Reports Server (NTRS)

Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

1991-01-01

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

The Interaction of UV-Laser Radiation with Metal and Semiconductor Surfaces

DTIC Science & Technology

1992-05-26

order of magnitude larger than the typical widths of non- 43 R.C. Weast, ed., Handbook of Chemistry and Physics, p. D-185 (CRC Press, 1986). 25 resonant...fundamental chemistry and practical applications of laser chemical processing techniques involved photofragmentation of relatively 28 simple metal-alkyl...pressure of the gas was monitored with a capacitance manometer. A variety of techniques were used in this work to examine the surface-phase chemistry and

Defect states at organic-inorganic interfaces: Insight from first principles calculations for pentaerythritol tetranitrate on MgO surface

NASA Astrophysics Data System (ADS)

Tsyshevsky, Roman V.; Rashkeev, Sergey N.; Kuklja, Maija M.

2015-07-01

Light-responsive organic-inorganic interfaces offer experimental opportunities that are otherwise difficult to achieve. Since laser light can be manipulated very precisely, it becomes possible to engineer selective, predictive, and highly controlled interface properties. Photochemistry of organic-inorganic energetic interfaces is a rapidly emerging research field in which energy absorption and interface stability mechanisms have yet to be established. To explore the interaction of the laser irradiation with molecular materials, we performed first principle calculations of a prototype organic-inorganic interface between a nitroester (pentaerythritol tetranitrate, PETN, C5H8N4O12) and a magnesium oxide (MgO) surface. We found that the light absorption is defined by the band alignment between interface components and interfacial charge transfer coupled with electronic states in the band gap, generated by oxide surface defects. Hence the choice of an oxide substrate and its morphology makes the optical absorption tunable and governs both the energy accumulation and energy release at the interface. The obtained results offer a possible consistent interpretation of experiments on selective laser initiation of energetic materials, which reported that the presence of metal oxide additives triggered the photoinitiation by excitation energy much lower than the band gap. We suggest that PETN photodecomposition is catalyzed by oxygen vacancies (F0 centers) at the MgO surface. Our conclusions predict ways for a complete separation of thermo- and photo-stimulated interface chemistry of molecular materials, which is imperative for highly controllable fast decomposition and was not attainable before. The methodology described here can be applied to any type of molecular material/wide band gap dielectric interfaces. It provides a solid basis for novel design and targeted improvements of organic-inorganic interfaces with desired properties that promise to enable vastly new concepts of energy storage and conversion, photocatalysis, and molecular electronics.

Chemistry Division: Annual progress report for period ending March 31, 1987

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

Not Available

1987-08-01

This report is divided into the following sections: coal chemistry; aqueous chemistry at high temperatures and pressures; geochemistry of crustal processes to high temperatures and pressures; chemistry of advanced inorganic materials; structure and dynamics of advanced polymeric materials; chemistry of transuranium elements and compounds; separations chemistry; reactions and catalysis in molten salts; surface science related to heterogeneous catalysis; electron spectroscopy; chemistry related to nuclear waste disposal; computational modeling of security document printing; and special topics. (DLC)

An oxidized liquid metal-based microfluidic platform for tunable electronic device applications.

PubMed

Li, Guangyong; Parmar, Mitesh; Lee, Dong-Weon

2015-02-07

Easy movement of oxidized Galinstan in microfluidic channels is a promising way for the wide application of the non-toxic liquid metal. In this paper, two different surface modification techniques (physical and chemical) are reported, which dramatically improve the non-wetting characteristics of oxidized Galinstan in the microfluidic channel. In the physical technique, normal paper textures are transferred to the inner wall of polydimethylsiloxane (PDMS) channels and four types of nanoparticles are then coated on the surface of the wall for further improvement of the non-wetting characteristics. Highest advancing angle of 167° and receding angle of 151° are achieved on the paper-textured PDMS with titanium oxide (TiO2) nanoparticles. In the chemical technique, three types of inorganic acids are employed to generate dual-scale structures on the PDMS surface. The inner wall surface treated with sulfuric acid (H2SO4) shows the highest contact angle of 167° and a low hysteresis of ~14° in the dynamic measurement. Creating, transporting, separating and merging of oxidized Galinstan droplets are successfully demonstrated in the fabricated PDMS microfluidic channels. After optimization of these modification techniques, the potential application of tunable capacitors and electronic filters is realized by using liquid metal-based microfluidic devices.

Miniature electrically tunable rotary dual-focus lenses

NASA Astrophysics Data System (ADS)

Zou, Yongchao; Zhang, Wei; Lin, Tong; Chau, Fook Siong; Zhou, Guangya

2016-03-01

The emerging dual-focus lenses are drawing increasing attention recently due to their wide applications in both academia and industries, including laser cutting systems, microscopy systems, and interferometer-based surface profilers. In this paper, a miniature electrically tunable rotary dual-focus lens is developed. Such a lens consists of two optical elements, each having an optical flat surface and one freeform surface. The two freeform surfaces are initialized with the governing equation Ar2θ (A is the constant to be determined, r and θ denote the radii and angles in the polar coordinate system) and then optimized by ray tracing technique with additional Zernike polynomial terms for aberration correction. The freeform surfaces are achieved by a single-point diamond turning technique and then a PDMS-based replication process is utilized to materialize the final lens elements. To drive the two coaxial elements to rotate independently, two MEMS thermal rotary actuators are developed and fabricated by a standard MUMPs process. The experimental results show that the MEMS thermal actuator provides a maximum rotation angle of about 8.2 degrees with an input DC voltage of 6.5 V, leading to a wide tuning range for both the two focal lengths of the lens. Specifically, one focal length can be tuned from about 30 mm to 20 mm while the other one can be adjusted from about 30 mm to 60 mm.

Effect of material flexibility on the thermodynamics and kinetics of hydrophobically induced evaporation of water

PubMed Central

Altabet, Y. Elia; Haji-Akbari, Amir; Debenedetti, Pablo G.

2017-01-01

The evaporation of water induced by confinement between hydrophobic surfaces has received much attention due to its suggested functional role in numerous biophysical phenomena and its importance as a general mechanism of hydrophobic self-assembly. Although much progress has been made in understanding the basic physics of hydrophobically induced evaporation, a comprehensive understanding of the substrate material features (e.g., geometry, chemistry, and mechanical properties) that promote or inhibit such transitions remains lacking. In particular, comparatively little research has explored the relationship between water’s phase behavior in hydrophobic confinement and the mechanical properties of the confining material. Here, we report the results of extensive molecular simulations characterizing the rates, free energy barriers, and mechanism of water evaporation when confined between model hydrophobic materials with tunable flexibility. A single-order-of-magnitude reduction in the material’s modulus results in up to a nine-orders-of-magnitude increase in the evaporation rate, with the corresponding characteristic time decreasing from tens of seconds to tens of nanoseconds. Such a modulus reduction results in a 24-orders-of-magnitude decrease in the reverse rate of condensation, with time scales increasing from nanoseconds to tens of millions of years. Free energy calculations provide the barriers to evaporation and confirm our previous theoretical predictions that making the material more flexible stabilizes the confined vapor with respect to liquid. The mechanism of evaporation involves surface bubbles growing/coalescing to form a subcritical gap-spanning tube, which then must grow to cross the barrier. PMID:28289194

Cucurbit[n]uril-Based Microcapsules Self-Assembled within Microfluidic Droplets: A Versatile Approach for Supramolecular Architectures and Materials

PubMed Central

2017-01-01

Conspectus Microencapsulation is a fundamental concept behind a wide range of daily applications ranging from paints, adhesives, and pesticides to targeted drug delivery, transport of vaccines, and self-healing concretes. The beauty of microfluidics to generate microcapsules arises from the capability of fabricating monodisperse and micrometer-scale droplets, which can lead to microcapsules/particles with fine-tuned control over size, shape, and hierarchical structure, as well as high reproducibility, efficient material usage, and high-throughput manipulation. The introduction of supramolecular chemistry, such as host–guest interactions, endows the resultant microcapsules with stimuli-responsiveness and self-adjusting capabilities, and facilitates hierarchical microstructures with tunable stability and porosity, leading to the maturity of current microencapsulation industry. Supramolecular architectures and materials have attracted immense attention over the past decade, as they open the possibility to obtain a large variety of aesthetically pleasing structures, with myriad applications in biomedicine, energy, sensing, catalysis, and biomimicry, on account of the inherent reversible and adaptive nature of supramolecular interactions. As a subset of supramolecular interactions, host–guest molecular recognition involves the formation of inclusion complexes between two or more moieties, with specific three-dimensional structures and spatial arrangements, in a highly controllable and cooperative manner. Such highly selective, strong yet dynamic interactions could be exploited as an alternative methodology for programmable and controllable engineering of supramolecular architectures and materials, exploiting reversible interactions between complementary components. Through the engineering of molecular structures, assemblies can be readily functionalized based on host–guest interactions, with desirable physicochemical characteristics. In this Account, we summarize the current state of development in the field of monodisperse supramolecular microcapsules, fabricated through the integration of traditional microfluidic techniques and interfacial host–guest chemistry, specifically cucurbit[n]uril (CB[n])-mediated host–guest interactions. Three different strategies, colloidal particle-driven assembly, interfacial condensation-driven assembly and electrostatic interaction-driven assembly, are classified and discussed in detail, presenting the methodology involved in each microcapsule formation process. We highlight the state-of-the-art in design and control over structural complexity with desirable functionality, as well as promising applications, such as cargo delivery stemming from the assembled microcapsules. On account of its dynamic nature, the CB[n]-mediated host–guest complexation has demonstrated efficient response toward various external stimuli such as UV light, pH change, redox chemistry, and competitive guests. Herein, we also demonstrate different microcapsule modalities, which are engineered with CB[n] host–guest chemistry and also can be disrupted with the aid of external stimuli, for triggered release of payloads. In addition to the overview of recent achievements and current limitations of these microcapsules, we finally summarize several perspectives on tunable cargo loading and triggered release, directions, and challenges for this technology, as well as possible strategies for further improvement, which will lead to substainitial progress of host–guest chemistry in supramolecular architectures and materials. PMID:28075551

The Effects of Interactive Stratospheric Chemistry on Antarctic and Southern Ocean Climate Change in an AOGCM

NASA Technical Reports Server (NTRS)

Li, Feng; Newman, Paul; Pawson, Steven; Waugh, Darryn

2014-01-01

Stratospheric ozone depletion has played a dominant role in driving Antarctic climate change in the last decades. In order to capture the stratospheric ozone forcing, many coupled atmosphere-ocean general circulation models (AOGCMs) prescribe the Antarctic ozone hole using monthly and zonally averaged ozone field. However, the prescribed ozone hole has a high ozone bias and lacks zonal asymmetry. The impacts of these biases on model simulations, particularly on Southern Ocean and the Antarctic sea ice, are not well understood. The purpose of this study is to determine the effects of using interactive stratospheric chemistry instead of prescribed ozone on Antarctic and Southern Ocean climate change in an AOGCM. We compare two sets of ensemble simulations for the 1960-2010 period using different versions of the Goddard Earth Observing System 5 - AOGCM: one with interactive stratospheric chemistry, and the other with prescribed monthly and zonally averaged ozone and 6 other stratospheric radiative species calculated from the interactive chemistry simulations. Consistent with previous studies using prescribed sea surface temperatures and sea ice concentrations, the interactive chemistry runs simulate a deeper Antarctic ozone hole and consistently larger changes in surface pressure and winds than the prescribed ozone runs. The use of a coupled atmosphere-ocean model in this study enables us to determine the impact of these surface changes on Southern Ocean circulation and Antarctic sea ice. The larger surface wind trends in the interactive chemistry case lead to larger Southern Ocean circulation trends with stronger changes in northerly and westerly surface flow near the Antarctica continent and stronger upwelling near 60S. Using interactive chemistry also simulates a larger decrease of sea ice concentrations. Our results highlight the importance of using interactive chemistry in order to correctly capture the influences of stratospheric ozone depletion on climate change over Antarctic and the Southern Ocean.

Bandwidth broadening of a graphene-based circular polarization converter by phase compensation.

PubMed

Gao, Xi; Yang, Wanli; Cao, Weiping; Chen, Ming; Jiang, Yannan; Yu, Xinhua; Li, Haiou

2017-10-02

We present a broadband tunable circular polarization converter composed of a single graphene sheet patterned with butterfly-shaped holes, a dielectric spacer, and a 7-layer graphene ground plane. It can convert a linearly polarized wave into a circularly polarized wave in reflection mode. The polarization converter can be dynamically tuned by varying the Fermi energy of the single graphene sheet. Furthermore, the 7-layer graphene acting as a ground plane can modulate the phase of its reflected wave by controlling the Femi energy, which provides constructive interference condition at the surface of the single graphene sheet in a broad bandwidth and therefore significantly broadens the tunable bandwidth of the proposed polarization converter.

Correlations between the interfacial chemistry and current-voltage behavior of n-GaAs/liquid junctions

NASA Technical Reports Server (NTRS)

Tufts, Bruce J.; Casagrande, Louis G.; Lewis, Nathan S.; Grunthaner, Frank J.

1990-01-01

Correlations between the surface chemistry of etched, (100) oriented n-GaAs electrodes and their subsequent photoelectrochemical behavior have been probed by high-resolution X-ray photoelectron spectroscopy. GaAs photoanodes were chemically treated to prepare either an oxide-free near stoichiometric surface, a surface enriched in zero-valent arsenic or a substrate-oxide terminated surface. The current-voltage (I-V) behavior of each surface type was subsequently monitored in contact with several electrolytes.

Various fates of neuronal progenitor cells observed on several different chemical functional groups

NASA Astrophysics Data System (ADS)

Liu, Xi; Wang, Ying; He, Jin; Wang, Xiu-Mei; Cui, Fu-Zhai; Xu, Quan-Yuan

2011-12-01

Neuronal progenitor cells cultured on gold-coated glass surfaces modified by different chemical functional groups, including hydroxyl (-OH), carboxyl (-COOH), amino (-NH2), bromo (-Br), mercapto (-SH), - Phenyl and methyl (-CH3), were studied here to investigate the influence of surface chemistry on the cells' adhesion, morphology, proliferation and functional gene expression. Focal adhesion staining indicated in the initial culture stage cells exhibited morphological changes in response to different chemical functional groups. Cells cultured on -NH2 grafted surface displayed focal adhesion plaque and flattened morphology and had the largest contact area. However, their counter parts on -CH3 grafted surface displayed no focal adhesion and rounded morphology and had the smallest contact area. After 6 days culture, the proliferation trend was as follows: -NH2 > -SH> -COOH> - Phenyl > - Br > -OH> -CH3. To determine the neural functional properties of the cells affected by surface chemistry, the expression of glutamate decarboxylase (GAD67), nerve growth factor (NGF) and brainderived neurotrophic factor (BDNF) were characterized. An increase of GAD67 expression was observed on -NH2, -COOH and -SH grafted surfaces, while no increase in NGF and BDNF expression was observed on any chemical surfaces. These results highlight the importance of surface chemistry in the fate determination of neuronal progenitor cells, and suggest that surface chemistry must be considered in the design of biomaterials for neural tissue engineering.

Modification of heterogeneous chemistry by complex substrate morphology

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

Henson, B.F.; Buelow, S.J.; Robinson, J.M.

1998-12-31

This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous reaction with a surface. Typically the surface exists as a dispersion or matrix of particulate matter or pores, and a determination of the heterogeneous chemistry of the system must address the extent to which the complexity of the environmental surface affects the reaction rates. Reactions that are of current interest are the series of chlorine nitrate reactions important in polar ozone depletion. The authors have applied surfacemore » spectroscopic techniques developed at LANL to address the chemistry of chlorine nitrate reactions on porous nitric and sulfuric acid ice surfaces as a model study of the measurement of complex, heterogeneous reaction rates. The result of the study is an experimental determination of the surface coverage of one adsorbed reagent and a mechanism of reactivity based on the dependence of this coverage on temperature and vapor pressure. The resulting mechanism allows the first comprehensive modeling of chlorine nitrate reaction probability data from several laboratories.« less

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry.

PubMed

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf

2017-11-20

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two-step reaction mechanism-1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom-shows that it mirrors acid-catalyzed ether cleavage in solution. The O-Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell-Evans-Polanyi principle. Electron rearrangement during C-O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S N 2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.

PubMed

Finlayson-Pitts, Barbara J

2009-09-28

While particles have significant deleterious impacts on human health, visibility and climate, quantitative understanding of their formation, composition and fates remains problematic. Indeed, in many cases, even qualitative understanding is lacking. One area of particular uncertainty is the nature of particle surfaces and how this determines interactions with gases in the atmosphere, including water, which is important for cloud formation and properties. The focus in this Perspective article is on some chemistry relevant to airborne particles and especially to reactions occurring on their surfaces. The intent is not to provide a comprehensive review, but rather to highlight a few selected examples of interface chemistry involving inorganic and organic species that may be important in the lower atmosphere. This includes sea salt chemistry, nitrate and nitrite ion photochemistry, organics on surfaces and heterogeneous reactions of oxides of nitrogen on proxies for airborne mineral dust and boundary layer surfaces. Emphasis is on the molecular level understanding that can only be gained by fully integrating experiment and theory to elucidate these complex systems.

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Dateo, Christopher e.; Schwenke, David W.; Halicioglu, Timur; Huo, winifred M.

2005-01-01

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. Study of the highly nonequilibrium rotational distribution of a nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into an atmosphere containing methane. A study of the etching of a Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

Wang, Dun-You; Stallcop, James R.; Dateo, Christopher E.; Schwenke, David W.; Haliciogiu, Timur; Huo, Winifred

2004-01-01

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. The study of the highly nonequilibrium rotational distribution of nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence the rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into a methane containing atmosphere. A study of the etching of Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

Static Chemistry in Disks or Clouds

NASA Astrophysics Data System (ADS)

Semenov, D.; Wiebe, D.

2006-11-01

This FORTRAN77 code can be used to model static, time-dependent chemistry in ISM and circumstellar disks. Current version is based on the OSU'06 gas-grain astrochemical network with all updates to the reaction rates, and includes surface chemistry from Hasegawa & Herbst (1993) and Hasegawa, Herbst, and Leung (1992). Surface chemistry can be modeled either with the standard rate equation approach or modified rate equation approach (useful in disks). Gas-grain interactions include sticking of neutral molecules to grains, dissociative recombination of ions on grains as well as thermal, UV, X-ray, and CRP-induced desorption of frozen species. An advanced X-ray chemistry and 3 grain sizes with power-law size distribution are also included. An deuterium extension to this chemical model is available.

Why surface chemistry matters for QD–QD resonance energy transfer

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

Hoffman, Jacob B.; Alam, Rabeka; Kamat, Prashant V.

Resonance energy transfer (RET) has been shown to occur in films of semiconductor quantum dots (QDs) with variation in QD composition and size. When coupled with charge carrier transfer, RET could provide a complementary strategy for light harvesting in QD based solid state photovoltaic devices. Due to a direct dependence on the optical properties of the donor and acceptor, QD surface chemistry plays a drastic role in determining the efficiency of RET. Here, the impact of QD surface chemistry on RET in QD films was investigated using a pair of different sized CdSe QDs spin-cast onto a glass substrate. Themore » effects of QD surface passivation on RET were studied by removing surface ligands through QD washing and adding an insulating ZnS shell. In addition, QD films were subjected to solid state ligand exchanges with thiolated ligands in order to mimic a layer-by-layer deposition method commonly used in the construction of QD photovoltaics. These solid state ligand exchanges exhibit drastic quenching of RET in the films. As a result, these experiments highlight the importance of understanding surface chemistry when designing photovoltaics that utilize RET.« less

Why surface chemistry matters for QD–QD resonance energy transfer

DOE PAGES

Hoffman, Jacob B.; Alam, Rabeka; Kamat, Prashant V.

2017-01-12

Resonance energy transfer (RET) has been shown to occur in films of semiconductor quantum dots (QDs) with variation in QD composition and size. When coupled with charge carrier transfer, RET could provide a complementary strategy for light harvesting in QD based solid state photovoltaic devices. Due to a direct dependence on the optical properties of the donor and acceptor, QD surface chemistry plays a drastic role in determining the efficiency of RET. Here, the impact of QD surface chemistry on RET in QD films was investigated using a pair of different sized CdSe QDs spin-cast onto a glass substrate. Themore » effects of QD surface passivation on RET were studied by removing surface ligands through QD washing and adding an insulating ZnS shell. In addition, QD films were subjected to solid state ligand exchanges with thiolated ligands in order to mimic a layer-by-layer deposition method commonly used in the construction of QD photovoltaics. These solid state ligand exchanges exhibit drastic quenching of RET in the films. As a result, these experiments highlight the importance of understanding surface chemistry when designing photovoltaics that utilize RET.« less

Covalent Surface Modifications of Carbon Nanotubes.

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

Pavia Sanders, Adriana; O'Bryan, Greg

A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

Broadband infrared light emitting waveguides based on UV curable PbS quantum dot composites

NASA Astrophysics Data System (ADS)

Shen, Kai; Baig, Sarfaraz; Jiang, Guomin; Paik, Young-hun; Kim, Sung Jin; Wang, Michael R.

2018-02-01

We present herein the active PbS-photopolymer waveguide fabricated by vacuum assisted microfluidic (VAM) soft lithography technique. The PbS Quantum Dots (QDs) were synthesized using colloidal chemistry methods with tunable sizes and emission wavelengths, resulting in efficient light emission around 1000 nm center wavelength. The PbS QDs have demonstrated much better solubility in our newly synthesized UV curable polymer than SU-8 photoresist, verified by Photoluminescence (PL) testing. Through refractive index control, the PbS QDs-polymer core material and polymer cladding material can efficiently confine the infrared emitting light with a broad spectral bandwidth of 180 nm. Both single-mode and multi-mode light emitting waveguides have been realized.

Soft Chemistry, Coloring and Polytypism in Filled Tetrahedral Semiconductors: Toward Enhanced Thermoelectric and Battery Materials.

PubMed

White, Miles A; Medina-Gonzalez, Alan M; Vela, Javier

2018-03-12

Filled tetrahedral semiconductors are a rich family of compounds with tunable electronic structure, making them ideal for applications in thermoelectrics, photovoltaics, and battery anodes. Furthermore, these materials crystallize in a plethora of related structures that are very close in energy, giving rise to polytypism through the manipulation of synthetic parameters. This Minireview highlights recent advances in the solution-phase synthesis and nanostructuring of these materials. These methods enable the synthesis of metastable phases and polytypes that were previously unobtainable. Additionally, samples synthesized in solution phase have enhanced thermoelectric performance due to their decreased grain size. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A concise review on smart polymers for controlled drug release.

PubMed

Aghabegi Moghanjoughi, Arezou; Khoshnevis, Dorna; Zarrabi, Ali

2016-06-01

Design and synthesis of efficient drug delivery systems are of critical importance in health care management. Innovations in materials chemistry especially in polymer field allows introduction of advanced drug delivery systems since polymers could provide controlled release of drugs in predetermined doses over long periods, cyclic and tunable dosages. To this end, researchers have taken advantages of smart polymers since they can undergo large reversible, chemical, or physical fluctuations as responses to small changes in environmental conditions, for instance, in pH, temperature, light, and phase transition. The present review aims to highlight various kinds of smart polymers, which are used in controlled drug delivery systems as well as mechanisms of action and their applications.

Progress towards synthetic chlorins with graded polarity, conjugatable substituents, and wavelength tunability

DOE PAGES

Ra, Doyoung; Gauger, Kelly A.; Muthukumaran, Kannan; ...

2015-04-01

Advances in chlorin synthetic chemistry now enable the de novo preparation of diverse chlorin-containing molecular architectures. Five distinct molecular designs have been explored here, including hydrophobic bioconjugatable (oxo)chlorins; a hydrophilic bioconjugatable chlorin; a trans-ethynyl/iodochlorin building block; a set of chlorins bearing electron-rich (methoxy, dimethylamino, methylthio) groups at the 3-position; and a set of ten 3,13-disubstituted chlorins chiefly bearing groups with extended π-moieties. Altogether 23 new chlorins (17 targets, 6 intermediates) have been prepared. Lastly, the challenge associated with molecular designs that encompass the combination of “hydrophilic, bioconjugatable and wavelength-tunable” chiefly resides in the nature of the hydrophilic unit.

Fabrication of nitric oxide-releasing polyurethane glucose sensor membranes

PubMed Central

Koh, Ahyeon; Riccio, Daniel A.; Sun, Bin; Carpenter, Alexis W.; Nichols, Scott P.; Schoenfisch, Mark H.

2011-01-01

Despite clear evidence that polymeric nitric oxide (NO) release coatings reduce the foreign body response (FBR) and may thus improve the analytical performance of in vivo continuous glucose monitoring devices when used as sensor membranes, the compatibility of the NO release chemistry with that required for enzymatic glucose sensing remains unclear. Herein, we describe the fabrication and characterization of NO-releasing polyurethane sensor membranes using NO donor-modified silica vehicles embedded within the polymer. In addition to demonstrating tunable NO release as a function of the NO donor silica scaffold and polymer compositions and concentrations, we describe the impact of the NO release vehicle and its release kinetics on glucose sensor performance. PMID:21795038

COSMIC-RAY-MEDIATED FORMATION OF BENZENE ON THE SURFACE OF SATURN'S MOON TITAN

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

Zhou Li; Zheng Weijun; Kaiser, Ralf I.

2010-08-01

The aromatic benzene molecule (C{sub 6}H{sub 6})-a central building block of polycyclic aromatic hydrocarbon molecules-is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C{sub 2}H{sub 2}) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two ordersmore » of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene.« less

Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires

PubMed Central

2016-01-01

The tunable properties of molecular materials place them among the favorites for a variety of future generation devices. In addition, to maintain the current trend of miniaturization of those devices, a departure from the present top-down production methods may soon be required and self-assembly appears among the most promising alternatives. On-surface synthesis unites the promises of molecular materials and of self-assembly, with the sturdiness of covalently bonded structures: an ideal scenario for future applications. Following this idea, we report the synthesis of functional extended nanowires by self-assembly. In particular, the products correspond to one-dimensional organic semiconductors. The uniaxial alignment provided by our substrate templates allows us to access with exquisite detail their electronic properties, including the full valence band dispersion, by combining local probes with spatial averaging techniques. We show how, by selectively doping the molecular precursors, the product’s energy level alignment can be tuned without compromising the charge carrier’s mobility. PMID:26841052

Fluids by design using chaotic surface waves to create a metafluid that is Newtonian, thermal, and entirely tunable

PubMed Central

Welch, Kyle J.; Liebman-Peláez, Alexander; Corwin, Eric I.

2016-01-01

In conventional fluids, viscosity depends on temperature according to a strict relationship. To change this relationship, one must change the molecular nature of the fluid. Here, we create a metafluid whose properties are derived not from the properties of molecules but rather from chaotic waves excited on the surface of vertically agitated water. By making direct rheological measurements of the flow properties of our metafluid, we show that it has independently tunable viscosity and temperature, a quality that no conventional fluid possesses. We go on to show that the metafluid obeys the Einstein relation, which relates many-body response (viscosity) to single-particle dynamics (diffusion) and is a fundamental result in equilibrium thermal systems. Thus, our metafluid is wholly consistent with equilibrium thermal physics, despite being markedly nonequilibrium. Taken together, our results demonstrate a type of material that retains equilibrium physics while simultaneously allowing for direct programmatic control over material properties. PMID:27621467

Fluidic Grooves on Doped-Ice Surface as Size-Tunable Channels

PubMed Central

Inagawa, Arinori; Harada, Makoto; Okada, Tetsuo

2015-01-01

We propose a new principle for fabrication of size-tunable fluidic nano- and microchannels with a ubiquitous green material, water. Grooves filled with a solution are spontaneously formed on the surface of ice when an appropriate dopant is incorporated. Sucrose doping allows the development of grooves with lengths of 300 μm along the boundaries of ice crystal grains. This paper focuses on controlling the size of the liquid-filled groove and reveals its applicability to size-selective differentiation of nano- and micromaterials. The width of this groove can be varied in a range of 200 nm to 4 μm by adjusting the working temperature of the frozen platform. The channel dimension is reproducible as long as the same frozen condition is employed. We demonstrate the size-selective entrapment of particles as well as the state evaluation of DNA by controlling the physical interference of the ice wall with the electrophoretic migration of particles. PMID:26601703

Tunable liquid optics: electrowetting-controlled liquid mirrors based on self-assembled Janus tiles.

PubMed

Bucaro, Michael A; Kolodner, Paul R; Taylor, J Ashley; Sidorenko, Alex; Aizenberg, Joanna; Krupenkin, Tom N

2009-04-09

In this paper, we describe a tunable, high-reflectivity optofluidic device based on self-assembly of anisotropically functionalized hexagonal micromirrors (Janus tiles) on the surface of an oil droplet to create a concave liquid mirror. The liquid mirror is deposited on a patterned transparent electrode that allows the focal length and axial position to be electrically controlled. The mirror is mechanically robust and retains its integrity even at high levels of vibrational excitation of the interface. The use of reflection instead of refraction overcomes the limited available refractive-index contrast between pairs of density-matched liquids, allowing stronger focusing than is possible for a liquid lens of the same geometry. This approach is compatible with optical instruments that could provide novel functionality-for example, a dynamic 3D projector, i.e., a light source which can scan an image onto a moving, nonplanar focal surface. Janus tiles with complex optical properties can be manufactured using our approach, thus potentially enabling a wide range of novel optical elements.

Tunable liquid optics: electrowetting-controlled liquid mirrors based on self-assembled Janus tiles

NASA Astrophysics Data System (ADS)

Krupenkin, Tom; Bucaro, Mike; Kolodner, Paul; Taylor, Ashley; Sidorenko, Alex; Aizenberg, Joanna

2009-03-01

In this work we describe a tunable, high-reflectivity optofluidic device based on self-assembly of anisotropically-functionalized hexagonal micromirrors (Janus tiles) on the surface of an oil droplet to create a concave liquid mirror. The liquid mirror is deposited on a patterned transparent electrode that allows the focal length and axial position to be electrically controlled. The mirror is mechanically robust and retains its integrity even at high levels of vibrational excitation of the interface. The use of reflection instead of refraction overcomes the limited available refractive-index contrast between pairs of density-matched liquids, allowing stronger focusing than is possible for a liquid lens of the same geometry. This approach is compatible with optical instruments that could provide novel functionality - for example, a dynamic 3D projector; i.e., a light source which can scan an image onto a moving, non-planar focal surface. Janus tiles with complex optical properties can be manufactured using our approach, thus potentially enabling a wide range of novel optical elements.

Electro-Mechanical Simulation of a Large Aperture MOEMS Fabry-Perot Tunable Filter

NASA Technical Reports Server (NTRS)

Kuhn, Jonathan L.; Barclay, Richard B.; Greenhouse, Matthew A.; Mott, D. Brent; Satyapal, Shobita; Powers, Edward I. (Technical Monitor)

2000-01-01

We are developing a micro-machined electrostatically actuated Fabry-Perot tunable filter with a large clear aperture for application in high through-put wide-field imaging spectroscopy and lidar systems. In the first phase of this effort, we are developing key components based on coupled electro-mechanical simulations. In particular, the movable etalon plate design leverages high coating stresses to yield a flat surface in drum-head tension over a large diameter (12.5 mm). In this approach, the cylindrical silicon movable plate is back etched, resulting in an optically coated membrane that is suspended from a thick silicon support ring. Understanding the interaction between the support ring, suspended membrane, and coating is critical to developing surfaces that are flat to within stringent etalon requirements. In this work, we present the simulations used to develop the movable plate, spring suspension system, and electrostatic actuation mechanism. We also present results from tests of fabricated proof of concept components.

Observation of Fermi arcs in the type-II Weyl semimetal candidate WTe 2

DOE PAGES

Wu, Yun; Mou, Daixiang; Jo, Na Hyun; ...

2016-09-14

We use ultrahigh resolution, tunable, vacuum ultraviolet laser angle-resolved photoemission spectroscopy (ARPES) to study the electronic properties of WTe 2, a material that was predicted to be a type-II Weyl semimetal. The Weyl fermion states in WTe 2 were proposed to emerge at the crossing points of electron and hole pockets, and Fermi arcs connecting electron and hole pockets would be visible in the spectral function on (001) surface. Here we report the observation of such Fermi arcs in WTe 2 confirming the theoretical predictions. This provides strong evidence for type-II Weyl semimetallic states in WTe 2. Here, we alsomore » find that trivial and topological domains coexist on the same surface of the sample due to the presence of inhomogeneous strain detected by scanning electron microscopy data. This is in agreement with the theoretical prediction that strain can drive this system from topological Weyl to trivial semimetal. WTe 2 therefore provides a tunable playground for studying exotic topological quantum effects.« less

Fluidic Grooves on Doped-Ice Surface as Size-Tunable Channels

NASA Astrophysics Data System (ADS)

Inagawa, Arinori; Harada, Makoto; Okada, Tetsuo

2015-11-01

We propose a new principle for fabrication of size-tunable fluidic nano- and microchannels with a ubiquitous green material, water. Grooves filled with a solution are spontaneously formed on the surface of ice when an appropriate dopant is incorporated. Sucrose doping allows the development of grooves with lengths of 300 μm along the boundaries of ice crystal grains. This paper focuses on controlling the size of the liquid-filled groove and reveals its applicability to size-selective differentiation of nano- and micromaterials. The width of this groove can be varied in a range of 200 nm to 4 μm by adjusting the working temperature of the frozen platform. The channel dimension is reproducible as long as the same frozen condition is employed. We demonstrate the size-selective entrapment of particles as well as the state evaluation of DNA by controlling the physical interference of the ice wall with the electrophoretic migration of particles.

Surface charge tunability as a powerful strategy to control electrostatic interaction for high efficiency silencing, using tailored oligopeptide-modified poly(beta-amino ester)s (PBAEs).

PubMed

Dosta, Pere; Segovia, Nathaly; Cascante, Anna; Ramos, Victor; Borrós, Salvador

2015-07-01

Here we present an extended family of pBAEs that incorporate terminal oligopeptide moieties synthesized from both positive and negative amino acids. Polymer formulations of mixtures of negative and positive oligopeptide-modified pBAEs are capable of condensing siRNA into discrete nanoparticles. We have demonstrated that efficient delivery of nucleic acids in a cell-type dependent manner can be achieved by careful control of the pBAE formulation. In addition, our approach of adding differently charged oligopeptides to the termini of poly(β-amino ester)s is of great interest for the design of tailored complexes having specific features, such as tuneable zeta potential. We anticipate that this surface charge tunability may be a powerful strategy to control unwanted electrostatic interactions, while preserving high silencing efficiency and reduced toxicity. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stretchable and Tunable Microtectonic ZnO-Based Sensors and Photonics.

PubMed

Gutruf, Philipp; Zeller, Eike; Walia, Sumeet; Nili, Hussein; Sriram, Sharath; Bhaskaran, Madhu

2015-09-16

The concept of realizing electronic applications on elastically stretchable "skins" that conform to irregularly shaped surfaces is revolutionizing fundamental research into mechanics and materials that can enable high performance stretchable devices. The ability to operate electronic devices under various mechanically stressed states can provide a set of unique functionalities that are beyond the capabilities of conventional rigid electronics. Here, a distinctive microtectonic effect enabled oxygen-deficient, nanopatterned zinc oxide (ZnO) thin films on an elastomeric substrate are introduced to realize large area, stretchable, transparent, and ultraportable sensors. The unique surface structures are exploited to create stretchable gas and ultraviolet light sensors, where the functional oxide itself is stretchable, both of which outperform their rigid counterparts under room temperature conditions. Nanoscale ZnO features are embedded in an elastomeric matrix function as tunable diffraction gratings, capable of sensing displacements with nanometre accuracy. These devices and the microtectonic oxide thin film approach show promise in enabling functional, transparent, and wearable electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of Fermi arcs in the type-II Weyl semimetal candidate WTe 2

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

Wu, Yun; Mou, Daixiang; Jo, Na Hyun

We use ultrahigh resolution, tunable, vacuum ultraviolet laser angle-resolved photoemission spectroscopy (ARPES) to study the electronic properties of WTe 2, a material that was predicted to be a type-II Weyl semimetal. The Weyl fermion states in WTe 2 were proposed to emerge at the crossing points of electron and hole pockets, and Fermi arcs connecting electron and hole pockets would be visible in the spectral function on (001) surface. Here we report the observation of such Fermi arcs in WTe 2 confirming the theoretical predictions. This provides strong evidence for type-II Weyl semimetallic states in WTe 2. Here, we alsomore » find that trivial and topological domains coexist on the same surface of the sample due to the presence of inhomogeneous strain detected by scanning electron microscopy data. This is in agreement with the theoretical prediction that strain can drive this system from topological Weyl to trivial semimetal. WTe 2 therefore provides a tunable playground for studying exotic topological quantum effects.« less