Design principles and fundamental trade-offs in biomimetic light harvesting

International Nuclear Information System (INIS)

Sarovar, Mohan; Birgitta Whaley, K

2013-01-01

Recent developments in synthetic and supramolecular chemistry have created opportunities to design organic systems with tailored nanoscale structure for various technological applications. A key application area is the capture of light energy and its conversion into electrochemical or chemical forms for photovoltaic or sensing applications. In this work we consider cylindrical assemblies of chromophores that model structures produced by several supramolecular techniques. Our study is especially guided by the versatile structures produced by virus-templated assembly. We use a multi-objective optimization framework to determine design principles and limitations in light harvesting performance for such assemblies, both in the presence and absence of disorder. We identify a fundamental trade-off in cylindrical assemblies that is encountered when attempting to maximize both efficiency of energy transfer and absorption bandwidth. We also rationalize the optimal design strategies and provide explanations for why various structures provide optimal performance. Most importantly, we find that the optimal design strategies depend on the amount of energetic and structural disorder in the system. The aim of these studies is to develop a program of quantum-informed rational design for construction of organic assemblies that have the same degree of tailored nanoscale structure as biological photosynthetic light harvesting complexes, and consequently have the potential to reproduce their remarkable light harvesting performance. (paper)

Three-Dimensional Self-Assembled Photonic Crystal Waveguide

Science.gov (United States)

Baek, Kang-Hyun

Photonic crystals (PCs), two- or three-dimensionally periodic, artificial, and dielectric structures, have a specific forbidden band for electromagnetic waves, referred to as photonic bandgap (PBG). The PBG is analogous to the electronic bandgap in natural crystal structures with periodic atomic arrangement. A well-defined and embedded planar, line, or point defect within the PCs causes a break in its structural periodicity, and introduces a state in the PBG for light localization. It offers various applications in integrated optics and photonics including optical filters, sharp bending light guides and very low threshold lasers. Using nanofabrication processes, PCs of the 2-D slab-type and 3-D layer-by-layer structures have been investigated widely. Alternatively, simple and low-cost self-assembled PCs with full 3-D PBG, inverse opals, have been suggested. A template with face centered cubic closed packed structure, opal, may initially be built by self-assembly of colloidal spheres, and is selectively removed after infiltrating high refractive index materials into the interstitials of spheres. In this dissertation, the optical waveguides utilizing the 3-D self-assembled PCs are discussed. The waveguides were fabricated by microfabrication technology. For high-quality colloidal silica spheres and PCs, reliable synthesis, self-assembly, and characterization techniques were developed. Its theoretical and experimental demonstrations are provided and correlated. They suggest that the self-assembled PCs with PBG are feasible for the applications in integrated optics and photonics.

Self-reverse-biased solar panel optical receiver for simultaneous visible light communication and energy harvesting.

Science.gov (United States)

Shin, Won-Ho; Yang, Se-Hoon; Kwon, Do-Hoon; Han, Sang-Kook

2016-10-31

We propose a self-reverse-biased solar panel optical receiver for energy harvesting and visible light communication. Since the solar panel converts an optical component into an electrical component, it provides both energy harvesting and communication. The signal component can be separated from the direct current component, and these components are used for communication and energy harvesting. We employed a self-reverse-biased receiver circuit to improve the communication and energy harvesting performance. The reverse bias on the solar panel improves the responsivity and response time. The proposed system achieved 17.05 mbps discrete multitone transmission with a bit error rate of 1.1 x 10-3 and enhanced solar energy conversion efficiency.

Efficient light harvesting from flexible perovskite solar cells under indoor white light-emitting diode illumination

NARCIS (Netherlands)

Lucarelli, G.; Di Giacomo, F.; Zardetto, V.; Creatore, M.; Brown, T.M.

2017-01-01

This is the first report of an investigation on flexible perovskite solar cells for artificial light harvesting by using a white light-emitting diode (LED) lamp as a light source at 200 and 400 lx, values typically found in indoor environments. Flexible cells were developed using either

Light-assisted, templated self-assembly of gold nanoparticle chains.

Science.gov (United States)

Jaquay, Eric; Martínez, Luis Javier; Huang, Ningfeng; Mejia, Camilo A; Sarkar, Debarghya; Povinelli, Michelle L

2014-09-10

We experimentally demonstrate the technique of light-assisted, templated self-assembly (LATS) to trap and assemble 200 nm diameter gold nanoparticles. We excite a guided-resonance mode of a photonic-crystal slab with 1.55 μm laser light to create an array of optical traps. Unlike our previous demonstration of LATS with polystyrene particles, we find that the interparticle interactions play a significant role in the resulting particle patterns. Despite a two-dimensionally periodic intensity profile in the slab, the particles form one-dimensional chains whose orientations can be controlled by the incident polarization of the light. The formation of chains can be understood in terms of a competition between the gradient force due to the excitation of the mode in the slab and optical binding between particles.

Long range excitonic transport in a biomimetic system inspired by the bacterial light-harvesting apparatus

Energy Technology Data Exchange (ETDEWEB)

Harel, Elad [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208 (United States)

2012-05-07

Photosynthesis, the process by which energy from sunlight drives cellular metabolism, relies on a unique organization of light-harvesting and reaction center complexes. Recently, the organization of light-harvesting LH2 complexes and dimeric reaction center-light-harvesting I-PufX core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy [S. Bahatyrova et al., Nature (London) 430, 1058 (2004)]. Here, we discuss optimal exciton transfer in a biomimetic system closely modeled on the structure of LH2 and its organization within the membrane using a Markovian quantum model with dissipation and trapping added phenomenologically. In a deliberate manner, we neglect the high level detail of the bacterial light-harvesting complex and its interaction with the phonon bath in order to elucidate a set of design principles that may be incorporated in artificial pigment-scaffold constructs in a supramolecular assembly. We show that our scheme reproduces many of the most salient features found in their natural counterpart and may be largely explained by simple electrostatic considerations. Most importantly, we show that quantum effects act primarily to enforce robustness with respect to spatial and spectral disorder between and within complexes. The implications of such an arrangement are discussed in the context of biomimetic photosynthetic analogs capable of transferring energy efficiently across tens to hundreds of nanometers.

Long range excitonic transport in a biomimetic system inspired by the bacterial light-harvesting apparatus

International Nuclear Information System (INIS)

Harel, Elad

2012-01-01

Photosynthesis, the process by which energy from sunlight drives cellular metabolism, relies on a unique organization of light-harvesting and reaction center complexes. Recently, the organization of light-harvesting LH2 complexes and dimeric reaction center-light-harvesting I-PufX core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy [S. Bahatyrova et al., Nature (London) 430, 1058 (2004)]. Here, we discuss optimal exciton transfer in a biomimetic system closely modeled on the structure of LH2 and its organization within the membrane using a Markovian quantum model with dissipation and trapping added phenomenologically. In a deliberate manner, we neglect the high level detail of the bacterial light-harvesting complex and its interaction with the phonon bath in order to elucidate a set of design principles that may be incorporated in artificial pigment-scaffold constructs in a supramolecular assembly. We show that our scheme reproduces many of the most salient features found in their natural counterpart and may be largely explained by simple electrostatic considerations. Most importantly, we show that quantum effects act primarily to enforce robustness with respect to spatial and spectral disorder between and within complexes. The implications of such an arrangement are discussed in the context of biomimetic photosynthetic analogs capable of transferring energy efficiently across tens to hundreds of nanometers.

Energy transfer and clustering of photosynthetic light-harvesting complexes in reconstituted lipid membranes

International Nuclear Information System (INIS)

Dewa, Takehisa; Sumino, Ayumi; Watanabe, Natsuko; Noji, Tomoyasu; Nango, Mamoru

2013-01-01

Highlights: ► Photosynthetic light-harvesting complexes were reconstituted into lipid membranes. ► Energy transfers between light-harvesting complexes were examined. ► Atomic force microscopy indicated cluster formation of light-harvesting complexes. ► Efficient energy transfer was observed for the clustered complexes in the membranes. - Abstract: In purple photosynthetic bacteria, light-harvesting complex 2 (LH2) and light harvesting/reaction centre core complex (LH1-RC) play the key roles of capturing and transferring light energy and subsequent charge separation. These photosynthetic apparatuses form a supramolecular assembly; however, how the assembly influences the efficiency of energy conversion is not yet clear. We addressed this issue by evaluating the energy transfer in reconstituted photosynthetic protein complexes LH2 and LH1-RC and studying the structures and the membrane environment of the LH2/LH1-RC assemblies, which had been embedded into various lipid bilayers. Thus, LH2 and LH1-RC from Rhodopseudomonas palustris 2.1.6 were reconstituted in phosphatidylglycerol (PG), phosphatidylcholine (PC), and phosphatidylethanolamine (PE)/PG/cardiolipin (CL). Efficient energy transfer from LH2 to LH1-RC was observed in the PC and PE/PG/CL membranes. Atomic force microscopy revealed that LH2 and LH1-RC were heterogeneously distributed to form clusters in the PC and PE/PG/CL membranes. The results indicated that the phospholipid species influenced the cluster formation of LH2 and LH1-RC as well as the energy transfer efficiency

Energy transfer and clustering of photosynthetic light-harvesting complexes in reconstituted lipid membranes

Energy Technology Data Exchange (ETDEWEB)

Dewa, Takehisa, E-mail: takedewa@nitech.ac.jp [Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Japan Science and Technology, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012 (Japan); Sumino, Ayumi; Watanabe, Natsuko; Noji, Tomoyasu [Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Nango, Mamoru, E-mail: nango@nitech.ac.jp [Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

2013-06-20

Highlights: ► Photosynthetic light-harvesting complexes were reconstituted into lipid membranes. ► Energy transfers between light-harvesting complexes were examined. ► Atomic force microscopy indicated cluster formation of light-harvesting complexes. ► Efficient energy transfer was observed for the clustered complexes in the membranes. - Abstract: In purple photosynthetic bacteria, light-harvesting complex 2 (LH2) and light harvesting/reaction centre core complex (LH1-RC) play the key roles of capturing and transferring light energy and subsequent charge separation. These photosynthetic apparatuses form a supramolecular assembly; however, how the assembly influences the efficiency of energy conversion is not yet clear. We addressed this issue by evaluating the energy transfer in reconstituted photosynthetic protein complexes LH2 and LH1-RC and studying the structures and the membrane environment of the LH2/LH1-RC assemblies, which had been embedded into various lipid bilayers. Thus, LH2 and LH1-RC from Rhodopseudomonas palustris 2.1.6 were reconstituted in phosphatidylglycerol (PG), phosphatidylcholine (PC), and phosphatidylethanolamine (PE)/PG/cardiolipin (CL). Efficient energy transfer from LH2 to LH1-RC was observed in the PC and PE/PG/CL membranes. Atomic force microscopy revealed that LH2 and LH1-RC were heterogeneously distributed to form clusters in the PC and PE/PG/CL membranes. The results indicated that the phospholipid species influenced the cluster formation of LH2 and LH1-RC as well as the energy transfer efficiency.

Biogenesis of light harvesting proteins.

Science.gov (United States)

Dall'Osto, Luca; Bressan, Mauro; Bassi, Roberto

2015-09-01

The LHC family includes nuclear-encoded, integral thylakoid membrane proteins, most of which coordinate chlorophyll and xanthophyll chromophores. By assembling with the core complexes of both photosystems, LHCs form a flexible peripheral moiety for enhancing light-harvesting cross-section, regulating its efficiency and providing protection against photo-oxidative stress. Upon its first appearance, LHC proteins underwent evolutionary diversification into a large protein family with a complex genetic redundancy. Such differentiation appears as a crucial event in the adaptation of photosynthetic organisms to changing environmental conditions and land colonization. The structure of photosystems, including nuclear- and chloroplast-encoded subunits, presented the cell with a number of challenges for the control of the light harvesting function. Indeed, LHC-encoding messages are translated in the cytosol, and pre-proteins imported into the chloroplast, processed to their mature size and targeted to the thylakoids where are assembled with chromophores. Thus, a tight coordination between nuclear and plastid gene expression, in response to environmental stimuli, is required to adjust LHC composition during photoacclimation. In recent years, remarkable progress has been achieved in elucidating structure, function and regulatory pathways involving LHCs; however, a number of molecular details still await elucidation. In this review, we will provide an overview on the current knowledge on LHC biogenesis, ranging from organization of pigment-protein complexes to the modulation of gene expression, import and targeting to the photosynthetic membranes, and regulation of LHC assembly and turnover. Genes controlling these events are potential candidate for biotechnological applications aimed at optimizing light use efficiency of photosynthetic organisms. This article is part of a Special Issue entitled: Chloroplast biogenesis. Copyright © 2015 Elsevier B.V. All rights reserved.

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

NARCIS (Netherlands)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were

Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning.

Science.gov (United States)

Jin, Hyeong Min; Park, Dae Yong; Jeong, Seong-Jun; Lee, Gil Yong; Kim, Ju Young; Mun, Jeong Ho; Cha, Seung Keun; Lim, Joonwon; Kim, Jun Soo; Kim, Kwang Ho; Lee, Keon Jae; Kim, Sang Ouk

2017-08-01

One of the fundamental challenges encountered in successful incorporation of directed self-assembly in sub-10 nm scale practical nanolithography is the process compatibility of block copolymers with a high Flory-Huggins interaction parameter (χ). Herein, reliable, fab-compatible, and ultrafast directed self-assembly of high-χ block copolymers is achieved with intense flash light. The instantaneous heating/quenching process over an extremely high temperature (over 600 °C) by flash light irradiation enables large grain growth of sub-10 nm scale self-assembled nanopatterns without thermal degradation or dewetting in a millisecond time scale. A rapid self-assembly mechanism for a highly ordered morphology is identified based on the kinetics and thermodynamics of the block copolymers with strong segregation. Furthermore, this novel self-assembly mechanism is combined with graphoepitaxy to demonstrate the feasibility of ultrafast directed self-assembly of sub-10 nm nanopatterns over a large area. A chemically modified graphene film is used as a flexible and conformal light-absorbing layer. Subsequently, transparent and mechanically flexible nanolithography with a millisecond photothermal process is achieved leading the way for roll-to-roll processability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembly as a design tool for the integration of photonic structures into excitonic solar cells

KAUST Repository

Guldin, S.

2011-09-20

One way to successfully enhance light harvesting of excitonic solar cells is the integration of optical elements that increase the photon path length in the light absorbing layer. Device architectures which incorporate structural order in form of one- or three-dimensional refractive index lattices can lead to the localization of light in specific parts of the spectrum, while retaining the cell\\'s transparency in others. Herein, we present two routes for the integration of photonic crystals (PCs) into dye-sensitized solar cells (DSCs). In both cases, the self-assembly of soft matter plays a key role in the fabrication process of the TiO2 electrode. One approach relies on a combination of colloidal self-assembly and the self-assembly of block copolymers, resulting in a double layer dye-sensitized solar cell with increased light absorption from the 3D PC element. An alternative route is based on the fact that the refractive index of the mesoporous layer can be finely tuned by the interplay between block copolymer self-assembly and hydrolytic TiO2 sol-gel chemistry. Alternating deposition of high and low refractive index layers enables the integration of a 1D PC into a DSC.

An artificial light-harvesting array constructed from multiple Bodipy dyes.

Science.gov (United States)

Ziessel, Raymond; Ulrich, Gilles; Haefele, Alexandre; Harriman, Anthony

2013-07-31

An artificial light-harvesting array, comprising 21 discrete chromophores arranged in a rational manner, has been synthesized and characterized fully. The design strategy follows a convergent approach that leads to a molecular-scale funnel, having an effective chromophore concentration of 0.6 M condensed into ca. 55 nm(3), able to direct the excitation energy to a focal point. A cascade of electronic energy-transfer steps occurs from the rim to the focal point, with the rate slowing down as the exciton moves toward its ultimate target. Situated midway along each branch of the V-shaped array, two chromophoric relays differ only slightly in terms of their excitation energies, and this situation facilitates reverse energy transfer. Thus, the excitation energy becomes spread around the array, a situation reminiscent of a giant holding pattern for the photon that can sample many different chromophores before being trapped by the terminal acceptor. At high photon flux under conditions of relatively slow off-load to a device, such as a solar cell, electronic energy transfer encounters one or more barriers that hinder forward progress of the exciton and thereby delays arrival of the second photon. Preliminary studies have addressed the ability of the array to function as a sensitizer for amorphous silicon solar cells.

Current progress and challenges in engineering viable artificial leaf for solar water splitting

Directory of Open Access Journals (Sweden)

Phuc D. Nguyen

2017-12-01

Full Text Available Large scale production of H2, a clean fuel, can be realized with just water and solar light energy by employing a viable energy conversion device called artificial leaf. In this tutorial review, we discuss on advances achieved recently and technical challenges remained toward the creation of such a leaf. Development of key components like catalysts for water electrolysis process and light harvester for harvesting solar energy as well as strategies being developed for assembling these components to create a complete artificial leaf will be highlighted.

Layer by layer assembly of gold nanoparticles and graphene via Langmuir Blodgett method for efficient light-harvesting in photocatalytic applications

International Nuclear Information System (INIS)

Shakir, Imran; Ali, Zahid; Kang, Dae Joon

2014-01-01

Highlights: • Layer by layer assembly of gold nanoparticles and graphene. • Efficient visible light photocatalysis. • Plasmonic resonances by nanoparticles are utilized for visible light scattering. • Electron scavenging reaction. • Easy handling and recycling. - Abstract: The synthesis of a photocatalyst that is highly active under visible light is one of the most challenging tasks for solar-energy utilization. Here we report a multilayer assembly of gold nanoparticles and graphene that offers dual functionality to efficiently harness visible photons. Firstly, plasmonic resonances by gold nanoparticles are utilized for visible light scattering; secondly the electron scavenging reaction is enhanced by the gold nanoparticles trapping the electrons that are injected from the dye into the graphene. Moreover, the structure is in the form of a thin film, which demonstrates the potential for easy handling and recycling. Precise control over light harvesting and the photocatalytic response is achieved by controlling the number of layers

Layer by layer assembly of gold nanoparticles and graphene via Langmuir Blodgett method for efficient light-harvesting in photocatalytic applications

Energy Technology Data Exchange (ETDEWEB)

Shakir, Imran, E-mail: shakir@skku.edu [Deanship of scientific research, College of Engineering, King Saud University, PO-BOX 800, Riyadh 11421 (Saudi Arabia); Ali, Zahid [BK 21 Physics Research Division, Department of Energy Science, Institute of Basic Sciences, SKKU Advanced Institute of Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); National Institute of Lasers and Optronics, Islamabad (Pakistan); Kang, Dae Joon [BK 21 Physics Research Division, Department of Energy Science, Institute of Basic Sciences, SKKU Advanced Institute of Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

2014-12-25

Highlights: • Layer by layer assembly of gold nanoparticles and graphene. • Efficient visible light photocatalysis. • Plasmonic resonances by nanoparticles are utilized for visible light scattering. • Electron scavenging reaction. • Easy handling and recycling. - Abstract: The synthesis of a photocatalyst that is highly active under visible light is one of the most challenging tasks for solar-energy utilization. Here we report a multilayer assembly of gold nanoparticles and graphene that offers dual functionality to efficiently harness visible photons. Firstly, plasmonic resonances by gold nanoparticles are utilized for visible light scattering; secondly the electron scavenging reaction is enhanced by the gold nanoparticles trapping the electrons that are injected from the dye into the graphene. Moreover, the structure is in the form of a thin film, which demonstrates the potential for easy handling and recycling. Precise control over light harvesting and the photocatalytic response is achieved by controlling the number of layers.

Spiropyran-Decorated SiO₂-Pt Janus Micromotor: Preparation and Light-Induced Dynamic Self-Assembly and Disassembly.

Science.gov (United States)

Zhang, Qilu; Dong, Renfeng; Chang, Xueyi; Ren, Biye; Tong, Zhen

2015-11-11

The controlled self-assembly of self-propelled Janus micromotors may give the micromotors some potential applications in many fields. In this work, we design a kind of SiO2-Pt Janus catalytic micromotor functionalized by spiropyran (SP) moieties on the surface of the SiO2 hemisphere. The spiropyran-modified SiO2-Pt Janus micromotor exhibits autonomous self-propulsion in the presence of hydrogen peroxide fuel in N,N-dimethylformamide (DMF)/H2O (1:1 in volume) mixture. We demonstrate that the self-propelled Janus micromotors can dynamically assemble into multiple motors because of the electrostatic attractions and π-π stacking between MC molecules induced by UV light irradiation (λ = 365 nm) and also quickly disassemble into mono motors when the light is switched to green light (λ = 520 nm) for the first time. Furthermore, the assembled Janus motors can move together automatically with different motion patterns propelled by the hydrogen peroxide fuels upon UV irradiation. The work provides a new approach not only to the development of the potential application of Janus motors but also to the fundamental science of reversible self-assembly and disassembly of Janus micromotors.

Directed formation of micro- and nanoscale patterns of functional light-harvesting LH2 complexes.

Science.gov (United States)

Reynolds, Nicholas P; Janusz, Stefan; Escalante-Marun, Maryana; Timney, John; Ducker, Robert E; Olsen, John D; Otto, Cees; Subramaniam, Vinod; Leggett, Graham J; Hunter, C Neil

2007-11-28

The precision placement of the desired protein components on a suitable substrate is an essential prelude to any hybrid "biochip" device, but a second and equally important condition must also be met: the retention of full biological activity. Here we demonstrate the selective binding of an optically active membrane protein, the light-harvesting LH2 complex from Rhodobacter sphaeroides, to patterned self-assembled monolayers at the micron scale and the fabrication of nanometer-scale patterns of these molecules using near-field photolithographic methods. In contrast to plasma proteins, which are reversibly adsorbed on many surfaces, the LH2 complex is readily patterned simply by spatial control of surface polarity. Near-field photolithography has yielded rows of light-harvesting complexes only 98 nm wide. Retention of the native optical properties of patterned LH2 molecules was demonstrated using in situ fluorescence emission spectroscopy.

Light-assisted templated self assembly using photonic crystal slabs.

Science.gov (United States)

Mejia, Camilo A; Dutt, Avik; Povinelli, Michelle L

2011-06-06

We explore a technique which we term light-assisted templated self-assembly. We calculate the optical forces on colloidal particles over a photonic crystal slab. We show that exciting a guided resonance mode of the slab yields a resonantly-enhanced, attractive optical force. We calculate the lateral optical forces above the slab and predict that stably trapped periodic patterns of particles are dependent on wavelength and polarization. Tuning the wavelength or polarization of the light source may thus allow the formation and reconfiguration of patterns. We expect that this technique may be used to design all-optically reconfigurable photonic devices.

Self-Assembled Local Artificial Substrates of GaAs on Si Substrate

Directory of Open Access Journals (Sweden)

Frigeri C

2010-01-01

Full Text Available Abstract We propose a self-assembling procedure for the fabrication of GaAs islands by Droplet Epitaxy on silicon substrate. Controlling substrate temperature and amount of supplied gallium is possible to tune the base size of the islands from 70 up to 250 nm and the density from 107 to 109 cm−2. The islands show a standard deviation of base size distribution below 10% and their shape evolves changing the aspect ratio from 0.3 to 0.5 as size increases. Due to their characteristics, these islands are suitable to be used as local artificial substrates for the integration of III–V quantum nanostructures directly on silicon substrate.

Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles

Science.gov (United States)

Chen, Yihuang; Wang, Zewei; He, Yanjie; Yoon, Young Jun; Jung, Jaehan; Zhang, Guangzhao; Lin, Zhiqun

2018-02-01

The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.

Light-Harvesting Organic Nanocrystals Capable of Photon Upconversion.

Science.gov (United States)

Li, Li; Zeng, Yi; Yu, Tianjun; Chen, Jinping; Yang, Guoqiang; Li, Yi

2017-11-23

Harvesting and converting low energy photons into higher ones through upconversion have great potential in solar energy conversion. A light-harvesting nanocrystal assembled from 9,10-distyrylanthracene and palladium(II) meso-tetraphenyltetrabenzoporphyrin as the acceptor and the sensitizer, respectively effects red-to-green upconversion under incoherent excitation of low power density. An upconversion quantum yield of 0.29±0.02 % is obtained upon excitation with 640 nm laser of 120 mW cm -2 . The well-organized packing of acceptor molecules with aggregation-induced emission in the nanocrystals dramatically reduces the nonradiative decay of the excited acceptor, benefits the triplet-triplet annihilation (TTA) upconversion and guides the consequent upconverted emission. This work provides a straightforward strategy to develop light-harvesting nanocrystals based on TTA upconversion, which is attractive for energy conversion and photonic applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors.

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C A; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C. A.; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L.

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Carotenoid deactivation in an artificial light-harvesting complex via a vibrationally hot ground state

International Nuclear Information System (INIS)

Savolainen, Janne; Buckup, Tiago; Hauer, Juergen; Jafarpour, Aliakbar; Serrat, Carles; Motzkus, Marcus; Herek, Jennifer L.

2009-01-01

Ultrafast relaxation of a carotenoid in an artificial light-harvesting complex has been studied by transient absorption spectroscopy. The transient signal amplitudes at several wavelengths as well as the amplitudes of the underlying species associated spectra (SAS) are analysed for several excitation energies ranging over more than two orders of magnitude (10 nJ/pulse up to 3000 nJ/pulse). Our analysis shows that the contribution from the so-called S* signal on the long-wavelength side of the first allowed S 0 → S 2 transition has a markedly different excitation energy dependence and saturation behaviour than the electronic excited state S 1 . These observations are modelled and explained in terms of a two-photon excitation of a vibrationally hot ground state via an impulsive stimulated Raman scattering (ISRS). The experimental observations of the varying pulse energy dependencies of different excited state species are supported by an analysis based on a density-matrix formalism

Self-Assembled Core-Shell CdTe/Poly(3-hexylthiophene) Nanoensembles as Novel Donor-Acceptor Light-Harvesting Systems.

Science.gov (United States)

Istif, Emin; Kagkoura, Antonia; Hernandez-Ferrer, Javier; Stergiou, Anastasios; Skaltsas, Theodosis; Arenal, Raul; Benito, Ana M; Maser, Wolfgang K; Tagmatarchis, Nikos

2017-12-27

The self-assembly of novel core-shell nanoensembles consisting of regioregular poly(3-hexylthiophene) nanoparticles (P3HT NPs ) of 100 nm as core and semiconducting CdTe quantum dots (CdTe QDs ) as shell with a thickness of a few tens of nanometers was accomplished by employing a reprecipitation approach. The structure, morphology, and composition of CdTe QDs /P3HT NPs nanoensembles were confirmed by high-resolution scanning transmission microscopy and dynamic light-scattering studies. Intimate interface contact between the CdTe QDs shell and the P3HT NPs core leads to the stabilization of the CdTe QDs /P3HT NPs nanoensemble as probed by the steady-state absorption spectroscopy. Effective quenching of the characteristic photoluminescence of CdTe QDs at 555 nm, accompanied by simultaneous increase in emission of P3HT NPs at 660 and 720 nm, reveals photoinduced charge-transfer processes. Probing the redox properties of films of CdTe QDs /P3HT NPs further proves the formation of a stabilized core-shell system in the solid state. Photoelectrochemical assays on CdTe QDs /P3HT NPs films show a reversible on-off photoresponse at a bias voltage of +0.8 V with a 3 times increased photocurrent compared to CdTe QDs . The improved charge separation is directly related to the unique core-shell configuration, in which the outer CdTe QDs shell forces the P3HT NPs core to effectively act as electron acceptor. The creation of novel donor-acceptor core-shell hybrid materials via self-assembly is transferable to other types of conjugated polymers and semiconducting nanoparticles. This work, therefore, opens new pathways for the design of improved optoelectronic devices.

Light-driven self-assembly of hetero-shaped gold nanorods

Science.gov (United States)

Liaw, Jiunn-Woei; Chao, Hsueh-Yu; Huang, Cheng-Wei; Kuo, Mao-Kuen

2018-01-01

Light-driven self-assembly and coalescence of two nearby hetero-shaped gold nanorods (GNRs) with different lengths are studied theoretically. The optical forces and torques, in terms of Maxwell's stress tensor, upon these GNRs provided by a linearly polarized (LP) plane wave are analyzed using the multiple multipole (MMP) method. Numerical results show that the optical torque dominates their alignments and the optical force their attraction. The most likely outcome of the plasmon-mediated light-matter interaction is wavelength dependent. Three different coalescences of the two GNRs could be induced by a LP light in three different wavelength regimes, respectively. For example, the side-by-side coalescence of two GNRs with radius of 15 nm and different lengths (120 and 240 nm) is induced in water as irradiated by a LP light at 633 nm, the T-shaped one at 1064 nm, and the end-to-end one at 1700 nm. The plasmonic attractive force and heating power densities inside GNRs with different gaps are also studied; the smaller the gap, the larger the attractive force and heating power. The results imply that the plasmonic coalescence and heating of two discrete GNRs may cause the local fusion at the junction of the assembly and the subsequent annealing (even recrystallization). Because the heating makes the two discrete GNRs fused to become a new nanostructure, the plasmonic coalescence of optical manipulation is irreversible.

Engineering a Light-Attenuating Artificial Iris

Science.gov (United States)

Shareef, Farah J.; Sun, Shan; Kotecha, Mrignayani; Kassem, Iris; Azar, Dimitri; Cho, Michael

2016-01-01

Purpose Discomfort from light exposure leads to photophobia, glare, and poor vision in patients with congenital or trauma-induced iris damage. Commercial artificial iris lenses are static in nature to provide aesthetics without restoring the natural iris's dynamic response to light. A new photo-responsive artificial iris was therefore developed using a photochromic material with self-adaptive light transmission properties and encased in a transparent biocompatible polymer matrix. Methods The implantable artificial iris was designed and engineered using Photopia, a class of photo-responsive materials (termed naphthopyrans) embedded in polyethylene. Photopia was reshaped into annular disks that were spin-coated with polydimethylsiloxane (PDMS) to form our artificial iris lens of controlled thickness. Results Activated by UV and blue light in approximately 5 seconds with complete reversal in less than 1 minute, the artificial iris demonstrates graded attenuation of up to 40% of visible and 60% of UV light. There optical characteristics are suitable to reversibly regulate the incident light intensity. In vitro cell culture experiments showed up to 60% cell death within 10 days of exposure to Photopia, but no significant cell death observed when cultured with the artificial iris with protective encapsulation. Nuclear magnetic resonance spectroscopy confirmed these results as there was no apparent leakage of potentially toxic photochromic material from the ophthalmic device. Conclusions Our artificial iris lens mimics the functionality of the natural iris by attenuating light intensity entering the eye with its rapid reversible change in opacity and thus potentially providing an improved treatment option for patients with iris damage. PMID:27116547

Engineering a Light-Attenuating Artificial Iris.

Science.gov (United States)

Shareef, Farah J; Sun, Shan; Kotecha, Mrignayani; Kassem, Iris; Azar, Dimitri; Cho, Michael

2016-04-01

Discomfort from light exposure leads to photophobia, glare, and poor vision in patients with congenital or trauma-induced iris damage. Commercial artificial iris lenses are static in nature to provide aesthetics without restoring the natural iris's dynamic response to light. A new photo-responsive artificial iris was therefore developed using a photochromic material with self-adaptive light transmission properties and encased in a transparent biocompatible polymer matrix. The implantable artificial iris was designed and engineered using Photopia, a class of photo-responsive materials (termed naphthopyrans) embedded in polyethylene. Photopia was reshaped into annular disks that were spin-coated with polydimethylsiloxane (PDMS) to form our artificial iris lens of controlled thickness. Activated by UV and blue light in approximately 5 seconds with complete reversal in less than 1 minute, the artificial iris demonstrates graded attenuation of up to 40% of visible and 60% of UV light. There optical characteristics are suitable to reversibly regulate the incident light intensity. In vitro cell culture experiments showed up to 60% cell death within 10 days of exposure to Photopia, but no significant cell death observed when cultured with the artificial iris with protective encapsulation. Nuclear magnetic resonance spectroscopy confirmed these results as there was no apparent leakage of potentially toxic photochromic material from the ophthalmic device. Our artificial iris lens mimics the functionality of the natural iris by attenuating light intensity entering the eye with its rapid reversible change in opacity and thus potentially providing an improved treatment option for patients with iris damage.

PS2013 Satellite Workshop on Photosynthetic Light-Harvesting Systems

Energy Technology Data Exchange (ETDEWEB)

Niederman, Robert A. [Rutgers Univ., New Brunswick, NJ (United States); Blankenship, Robert E. [Washington Univ., St. Louis, MO (United States); Frank, Harry A. [Univ. of Connecticut, Storrs, CT (United States)

2015-02-07

These funds were used for partial support of the PS2013 Satellite Workshop on Photosynthetic Light-Harvesting Systems, that was held on 8-11 August, 2013, at Washington University, St. Louis, MO. This conference, held in conjunction with the 16th International Congress on Photosynthesis/St. Louis, continued a long tradition of light-harvesting satellite conferences that have been held prior to the previous six international photosynthesis congresses. In this Workshop, the basis was explored for the current interest in replacing fossil fuels with energy sources derived form direct solar radiation, coupled with light-driven electron transport in natural photosynthetic systems and how they offer a valuable blueprint for conversion of sunlight to useful energy forms. This was accomplished through sessions on the initial light-harvesting events in the biological conversion of solar energy to chemically stored energy forms, and how these natural photosynthetic processes serve as a guide to the development of robust bio-hybrid and artificial systems for solar energy conversion into both electricity or chemical fuels. Organized similar to a Gordon Research Conference, a lively, informal and collegial setting was established, highlighting the exchange of exciting new data and unpublished results from ongoing studies. A significant amount of time was set aside for open discussion and interactive poster sessions, with a special session devoted to oral presentations by talented students and postdoctoral fellows judged to have the best posters. This area of research has seen exceptionally rapid progress in recent years, with the availability of a number of antenna protein structures at atomic resolution, elucidation of the molecular surface architecture of native photosynthetic membranes by atomic force microscopy and the maturing of ultrafast spectroscopic and molecular biological techniques for the investigation and manipulation of photosynthetic systems. The conferees

Multicomponent and Dissipative Self-Assembly Approaches : Towards functional materials

NARCIS (Netherlands)

Boekhoven, J.

2012-01-01

The use of self-assembly has proven to be a powerful approach to create smart and functional materials and has led to a vast variety of successful examples. However, the full potential of self-assembly has not been reached. Despite the number of successful artificial materials based on

Toward a molecular programming language for algorithmic self-assembly

Science.gov (United States)

Patitz, Matthew John

Self-assembly is the process whereby relatively simple components autonomously combine to form more complex objects. Nature exhibits self-assembly to form everything from microscopic crystals to living cells to galaxies. With a desire to both form increasingly sophisticated products and to understand the basic components of living systems, scientists have developed and studied artificial self-assembling systems. One such framework is the Tile Assembly Model introduced by Erik Winfree in 1998. In this model, simple two-dimensional square 'tiles' are designed so that they self-assemble into desired shapes. The work in this thesis consists of a series of results which build toward the future goal of designing an abstracted, high-level programming language for designing the molecular components of self-assembling systems which can perform powerful computations and form into intricate structures. The first two sets of results demonstrate self-assembling systems which perform infinite series of computations that characterize computably enumerable and decidable languages, and exhibit tools for algorithmically generating the necessary sets of tiles. In the next chapter, methods for generating tile sets which self-assemble into complicated shapes, namely a class of discrete self-similar fractal structures, are presented. Next, a software package for graphically designing tile sets, simulating their self-assembly, and debugging designed systems is discussed. Finally, a high-level programming language which abstracts much of the complexity and tedium of designing such systems, while preventing many of the common errors, is presented. The summation of this body of work presents a broad coverage of the spectrum of desired outputs from artificial self-assembling systems and a progression in the sophistication of tools used to design them. By creating a broader and deeper set of modular tools for designing self-assembling systems, we hope to increase the complexity which is

Triazolobithiophene Light Absorbing Self-Assembled Monolayers: Synthesis and Mass Spectrometry Applications

Directory of Open Access Journals (Sweden)

Denis Séraphin

2011-10-01

Full Text Available The synthesis of five light absorbing triazolobithiophenic thiols, which were utilized for producing self-assembled monolayers (SAMs on gold surfaces, is presented. The monolayer formation was monitored by cyclic voltammetry, indicating excellent surface coverage. The new triazolobithiophenic compounds exhibited an absorption maximum around 340 nm, which is close to the emission wavelength of a standard nitrogen laser. Consequently these compounds could be used to aid ionization in laser desorption mass spectrometry (MS.

CH3 NH3 PbBr3 Perovskite Nanocrystals as Efficient Light-Harvesting Antenna for Fluorescence Resonance Energy Transfer.

Science.gov (United States)

Muthu, Chinnadurai; Vijayan, Anuja; Nair, Vijayakumar C

2017-05-04

Hybrid perovskites have created enormous research interest as a low-cost material for high-performance photovoltaic devices, light-emitting diodes, photodetectors, memory devices and sensors. Perovskite materials in nanocrystal form that display intense luminescence due to the quantum confinement effect were found to be particularly suitable for most of these applications. However, the potential use of perovskite nanocrystals as a light-harvesting antenna for possible applications in artificial photosynthesis systems is not yet explored. In the present work, we study the light-harvesting antenna properties of luminescent methylammonium lead bromide (CH 3 NH 3 PbBr 3 )-based perovskite nanocrystals using fluorescent dyes (rhodamine B, rhodamine 101, and nile red) as energy acceptors. Our studies revealed that CH 3 NH 3 PbBr 3 nanocrystals are an excellent light-harvesting antenna, and efficient fluorescence resonance energy transfer occurs from the nanocrystals to fluorescent dyes. Further, the energy transfer efficiency is found to be highly dependent on the number of anchoring groups and binding ability of the dyes to the surface of the nanocrystals. These observations may have significant implications for perovskite-based light-harvesting devices and their possible use in artificial photosynthesis systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design strategies for self-assembly of discrete targets

International Nuclear Information System (INIS)

Madge, Jim; Miller, Mark A.

2015-01-01

Both biological and artificial self-assembly processes can take place by a range of different schemes, from the successive addition of identical building blocks to hierarchical sequences of intermediates, all the way to the fully addressable limit in which each component is unique. In this paper, we introduce an idealized model of cubic particles with patterned faces that allows self-assembly strategies to be compared and tested. We consider a simple octameric target, starting with the minimal requirements for successful self-assembly and comparing the benefits and limitations of more sophisticated hierarchical and addressable schemes. Simulations are performed using a hybrid dynamical Monte Carlo protocol that allows self-assembling clusters to rearrange internally while still providing Stokes-Einstein-like diffusion of aggregates of different sizes. Our simulations explicitly capture the thermodynamic, dynamic, and steric challenges typically faced by self-assembly processes, including competition between multiple partially completed structures. Self-assembly pathways are extracted from the simulation trajectories by a fully extendable scheme for identifying structural fragments, which are then assembled into history diagrams for successfully completed target structures. For the simple target, a one-component assembly scheme is most efficient and robust overall, but hierarchical and addressable strategies can have an advantage under some conditions if high yield is a priority

Aerosolized droplet mediated self-assembly of photosynthetic pigment analogues and deposition onto substrates.

Science.gov (United States)

Shah, Vivek B; Biswas, Pratim

2014-02-25

Self-assembled photosynthetic molecules have a high extinction coefficient and a broad absorption in the infrared region, and these properties can be used to improve the efficiency of solar cells. We have developed a single-step method for the self-assembly of synthetic chlorin molecules (analogues of native bacteriochlorophylls) in aerosolized droplets, containing a single solvent and two solvents, to synthesize biomimetic light-harvesting structures. In the single-solvent approach, assembly is promoted by a concentration-driven process due to evaporation of the solvent. The peak absorbance of Zn(II) 3-(1-hydroxyethyl)-10-phenyl-13(1)-oxophorbine (1) in methanol shifted from 646 nm to 725 nm (∼ 80 nm shift) after assembly, which is comparable to the shift observed in the naturally occurring assembly of bacteriochlorophyll c. Although assembly is thermodynamically favorable, the kinetics of self-assembly play an important role, and this was demonstrated by varying the initial concentration of the pigment monomer. To overcome kinetic limitations, a two-solvent approach using a volatile solvent (tetrahydrofuran) in which the dye is soluble and a less volatile solvent (ethanol) in which the dye is sparingly soluble was demonstrated to be effective. The effect of molecular structure is demonstrated by spraying the sterically hindered Zn(II) 3-(1-hydroxyethyl)-10-mesityl-13(1)-oxophorbine (2), which is an analogue of 1, under similar conditions. The results illustrate a valuable and facile aerosol-based method for the formation of films of supramolecular assemblies.

Self-assembled Block Copolymer Membranes with Bioinspired Artificial Channels

KAUST Repository

Sutisna, Burhannudin

2018-04-01

Nature is an excellent design that inspires scientists to develop smart systems. In the realm of separation technology, biological membranes have been an ideal model for synthetic membranes due to their ultrahigh permeability, sharp selectivity, and stimuliresponse. In this research, fabrications of bioinspired membranes from block copolymers were studied. Membranes with isoporous morphology were mainly prepared using selfassembly and non-solvent induced phase separation (SNIPS). An effective method that can dramatically shorten the path for designing new isoporous membranes from block copolymers via SNIPS was first proposed by predetermining a trend line computed from the solvent properties, interactions and copolymer block sizes of previously-obtained successful systems. Application of the method to new copolymer systems and fundamental studies on the block copolymer self-assembly were performed. Furthermore, the manufacture of bioinspired membranes was explored using (1) poly(styrene-b-4-hydroxystyrene-b-styrene) (PS-b-PHS-b-PS), (2) poly(styrene-bbutadiene- b-styrene) (PS-b-PB-b-PS) and (3) poly(styrene-b-γ-benzyl-L-glutamate) (PSb- PBLG) copolymers via SNIPS. The structure formation was investigated using smallangle X-ray scattering (SAXS) and time-resolved grazing-Incidence SAXS. The PS-b- PHS-b-PS membranes showed preferential transport for proteins, presumably due to the hydrogen bond interactions within the channels, electrostatic attraction, and suitable pore dimension. Well-defined nanochannels with pore sizes of around 4 nm based on PS-b- PB-b-PS copolymers could serve as an excellent platform to fabricate bioinspired channels due to the modifiable butadiene blocks. Photolytic addition of thioglycolic acid was demonstrated without sacrificing the self-assembled morphology, which led to a five-fold increase in water permeance compared to that of the unmodified. Membranes with a unique feather-like structure and a lamellar morphology for dialysis and

Study of the spectra of silica colloidal crystals with assembled silver obtained from a photolysis method

Science.gov (United States)

Li, Wenjiang; He, Jinglong; He, Sailing

2005-02-01

The colorful artificial 3D silica colloidal crystals (opal) were prepared through self-assembly of silica spheres in the visible frequency range. We directly synthesized nano silver particles in the void of the silica artificial opal film using the photolysis of silver nitrate under UV light, nano silver particles were self-deposited around the surface of silica sphere. The shifts of the stop band of the artificial crystals after exposing different time under UV light were studied. Synthetic silica opal with three-dimensional (3D) structure is potentially useful for the development of diffractive optical devices, micro mechanical systems, and sensory elements because photonic band gaps obtained from self-assembled closely packed periodic structures.

Interference lithographic nanopatterning of plant and bacterial light-harvesting complexes on gold substrates

Energy Technology Data Exchange (ETDEWEB)

Patole, S.; Vasilev, C.; El-Zubir, O.; Wang, L.; Johnson, M. P.; Cadby, A. J.; Leggett, G. J.; Hunter, C. N.

2015-05-15

We describe a facile approach for nanopatterning of photosynthetic light-harvesting complexes over macroscopic areas, and use optical spectroscopy to demonstrate retention of native properties by both site-specifically and non-specifically attached photosynthetic membrane proteins. A Lloyd's mirror dual-beam interferometer was used to expose self-assembled monolayers of amine-terminated alkylthiolates on gold to laser irradiation. Following exposure, photo-oxidized adsorbates were replaced by oligo(ethylene glycol) terminated thiols, and the remaining intact amine-functionalized regions were used for attachment of the major light-harvesting chlorophyll–protein complex from plants, LHCII. These amine patterns could be derivatized with nitrilotriacetic acid (NTA), so that polyhistidine-tagged bacteriochlorophyll–protein complexes from phototrophic bacteria could be attached with a defined surface orientation. By varying parameters such as the angle between the interfering beams and the laser irradiation dose, it was possible to vary the period and widths of NTA and amine-functionalized lines on the surfaces; periods varied from 1200 to 240 nm and linewidths as small as 60 nm (λ/4) were achieved. This level of control over the surface chemistry was reflected in the surface topology of the protein nanostructures imaged by atomic force microscopy; fluorescence imaging and spectral measurements demonstrated that the surface-attached proteins had retained their native functionality.

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

Energy Technology Data Exchange (ETDEWEB)

Perlík, Václav; Seibt, Joachim; Šanda, František; Mančal, Tomáš [Institute of Physics, Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 5, Prague 121 16 (Czech Republic); Cranston, Laura J.; Cogdell, Richard J. [Institute of Molecular Cell and System Biology, College of Medical, Veterinary and Life Sciences, University of Glasgow, Glasgow Biomedical Research Centre, 120 University Place, Glasgow G12 8TA, Scotland (United Kingdom); Lincoln, Craig N.; Hauer, Jürgen, E-mail: juergen.hauer@tuwien.ac.at [Photonics Institute, Vienna University of Technology, Gusshausstrasse 27, 1040 Vienna (Austria); Savolainen, Janne [Department of Physical Chemistry II, Ruhr-University Bochum, 44780 Bochum (Germany)

2015-06-07

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

International Nuclear Information System (INIS)

Perlík, Václav; Seibt, Joachim; Šanda, František; Mančal, Tomáš; Cranston, Laura J.; Cogdell, Richard J.; Lincoln, Craig N.; Hauer, Jürgen; Savolainen, Janne

2015-01-01

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems

Managing lifelike behavior in a dynamic self-assembled system

Science.gov (United States)

Ropp, Chad; Bachelard, Nicolas; Wang, Yuan; Zhang, Xiang

Self-organization can arise outside of thermodynamic equilibrium in a process of dynamic self-assembly. This is observed in nature, for example in flocking birds, but can also be created artificially with non-living entities. Such dynamic systems often display lifelike properties, including the ability to self-heal and adapt to environmental changes, which arise due to the collective and often complex interactions between the many individual elements. Such interactions are inherently difficult to predict and control, and limit the development of artificial systems. Here, we report a fundamentally new method to manage dynamic self-assembly through the direct external control of collective phenomena. Our system consists of a waveguide filled with mobile scattering particles. These particles spontaneously self-organize when driven by a coherent field, self-heal when mechanically perturbed, and adapt to changes in the drive wavelength. This behavior is governed by particle interactions that are completely mediated by coherent wave scattering. Compared to hydrodynamic interactions which lead to compact ordered structures, our system displays sinusoidal degeneracy and many different steady-state geometries that can be adjusted using the external field.

Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

Science.gov (United States)

Yip, Hin-Lap

Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

Stereochemistry in subcomponent self-assembly.

Science.gov (United States)

Castilla, Ana M; Ramsay, William J; Nitschke, Jonathan R

2014-07-15

CONSPECTUS: As Pasteur noted more than 150 years ago, asymmetry exists in matter at all organization levels. Biopolymers such as proteins or DNA adopt one-handed conformations, as a result of the chirality of their constituent building blocks. Even at the level of elementary particles, asymmetry exists due to parity violation in the weak nuclear force. While the origin of homochirality in living systems remains obscure, as does the possibility of its connection with broken symmetries at larger or smaller length scales, its centrality to biomolecular structure is clear: the single-handed forms of bio(macro)molecules interlock in ways that depend upon their handednesses. Dynamic artificial systems, such as helical polymers and other supramolecular structures, have provided a means to study the mechanisms of transmission and amplification of stereochemical information, which are key processes to understand in the context of the origins and functions of biological homochirality. Control over stereochemical information transfer in self-assembled systems will also be crucial for the development of new applications in chiral recognition and separation, asymmetric catalysis, and molecular devices. In this Account, we explore different aspects of stereochemistry encountered during the use of subcomponent self-assembly, whereby complex structures are prepared through the simultaneous formation of dynamic coordinative (N → metal) and covalent (N═C) bonds. This technique provides a useful method to study stereochemical information transfer processes within metal-organic assemblies, which may contain different combinations of fixed (carbon) and labile (metal) stereocenters. We start by discussing how simple subcomponents with fixed stereogenic centers can be incorporated in the organic ligands of mononuclear coordination complexes and communicate stereochemical information to the metal center, resulting in diastereomeric enrichment. Enantiopure subcomponents were then

Directed Self-Assembly of Nanodispersions

Energy Technology Data Exchange (ETDEWEB)

Furst, Eric M [University of Delaware

2013-11-15

Directed self-assembly promises to be the technologically and economically optimal approach to industrial-scale nanotechnology, and will enable the realization of inexpensive, reproducible and active nanostructured materials with tailored photonic, transport and mechanical properties. These new nanomaterials will play a critical role in meeting the 21st century grand challenges of the US, including energy diversity and sustainability, national security and economic competitiveness. The goal of this work was to develop and fundamentally validate methods of directed selfassembly of nanomaterials and nanodispersion processing. The specific aims were: 1. Nanocolloid self-assembly and interactions in AC electric fields. In an effort to reduce the particle sizes used in AC electric field self-assembly to lengthscales, we propose detailed characterizations of field-driven structures and studies of the fundamental underlying particle interactions. We will utilize microscopy and light scattering to assess order-disorder transitions and self-assembled structures under a variety of field and physicochemical conditions. Optical trapping will be used to measure particle interactions. These experiments will be synergetic with calculations of the particle polarizability, enabling us to both validate interactions and predict the order-disorder transition for nanocolloids. 2. Assembly of anisotropic nanocolloids. Particle shape has profound effects on structure and flow behavior of dispersions, and greatly complicates their processing and self-assembly. The methods developed to study the self-assembled structures and underlying particle interactions for dispersions of isotropic nanocolloids will be extended to systems composed of anisotropic particles. This report reviews several key advances that have been made during this project, including, (1) advances in the measurement of particle polarization mechanisms underlying field-directed self-assembly, and (2) progress in the

Controlling Light Harvesting with Light

NARCIS (Netherlands)

Gwizdala, M.S.; Berera, R.; Kirilovsky, D.; van Grondelle, R.; Kruger, T.P.J.

2016-01-01

When exposed to intense sunlight, all organisms performing oxygenic photosynthesis implement various photoprotective strategies to prevent potentially lethal photodamage. The rapidly responding photoprotective mechanisms, occurring in the light-harvesting pigment-protein antennae, take effect within

Directed assembly of functional light harvesting antenna complexes onto chemically patterned surfaces

International Nuclear Information System (INIS)

Escalante, Maryana; Maury, Pascale; Bruinink, Christiaan M; Werf, Kees van der; Olsen, John D; Timney, John A; Huskens, Jurriaan; Hunter, C Neil; Subramaniam, Vinod; Otto, Cees

2008-01-01

We report the directed assembly of the photosynthetic membrane proteins LH1 and LH2 isolated from the purple bacterium Rhodobacter sphaeroides onto chemically patterned substrates. Nanoimprint lithography was used to pattern discrete regions of amino- and fluoro-terminated or poly(ethylene glycol) self-assembled monolayers onto a glass substrate. Densely packed layers of assembled protein complexes were observed with atomic force microscopy. The protein complexes attached selectively to the amino-terminated regions by electrostatic interactions. Spectral images generated with a hybrid scanning probe and fluorescence microscope confirmed that the patterned proteins retained their native optical signatures

Directed assembly of functional light harvesting antenna complexes onto chemically patterned surfaces

Energy Technology Data Exchange (ETDEWEB)

Escalante, Maryana [Biophysical Engineering Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Maury, Pascale [Molecular Nanofabrication Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Bruinink, Christiaan M [Molecular Nanofabrication Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Werf, Kees van der [Biophysical Engineering Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Olsen, John D [Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN (United Kingdom); Timney, John A [Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN (United Kingdom); Huskens, Jurriaan [Molecular Nanofabrication Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Hunter, C Neil [Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN (United Kingdom); Subramaniam, Vinod [Biophysical Engineering Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Otto, Cees [Biophysical Engineering Group, MESA and Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands)

2008-01-16

We report the directed assembly of the photosynthetic membrane proteins LH1 and LH2 isolated from the purple bacterium Rhodobacter sphaeroides onto chemically patterned substrates. Nanoimprint lithography was used to pattern discrete regions of amino- and fluoro-terminated or poly(ethylene glycol) self-assembled monolayers onto a glass substrate. Densely packed layers of assembled protein complexes were observed with atomic force microscopy. The protein complexes attached selectively to the amino-terminated regions by electrostatic interactions. Spectral images generated with a hybrid scanning probe and fluorescence microscope confirmed that the patterned proteins retained their native optical signatures.

Self-assembly surface modified indium-tin oxide anodes for single-layer light-emitting diodes

CERN Document Server

Morgado, J; Charas, A; Matos, M; Alcacer, L; Cacialli, F

2003-01-01

We study the effect of indium-tin oxide surface modification by self assembling of highly polar molecules on the performance of single-layer light-emitting diodes (LEDs) fabricated with polyfluorene blends and aluminium cathodes. We find that the efficiency and light-output of such LEDs is comparable to, and sometimes better than, the values obtained for LEDs incorporating a hole injection layer of poly(3,4-ethylene dioxythiophene) doped with polystyrene sulphonic acid. This effect is attributed to the dipole-induced work function modification of indium-tin oxide.

Self-assembly surface modified indium-tin oxide anodes for single-layer light-emitting diodes

International Nuclear Information System (INIS)

Morgado, Jorge; Barbagallo, Nunzio; Charas, Ana; Matos, Manuel; Alcacer, Luis; Cacialli, Franco

2003-01-01

We study the effect of indium-tin oxide surface modification by self assembling of highly polar molecules on the performance of single-layer light-emitting diodes (LEDs) fabricated with polyfluorene blends and aluminium cathodes. We find that the efficiency and light-output of such LEDs is comparable to, and sometimes better than, the values obtained for LEDs incorporating a hole injection layer of poly(3,4-ethylene dioxythiophene) doped with polystyrene sulphonic acid. This effect is attributed to the dipole-induced work function modification of indium-tin oxide

Light induced assembly and self-sorting of silica microparticles

NARCIS (Netherlands)

Vilanova Garcia, N.; De Feijter, I.; Teunissen, A.J.P.; Voets, I.K.

2018-01-01

To tailor the properties of colloidal materials, precise control over the self-assembly of their constituents is a prerequisite. Here, we govern the assembly of silica particles by functionalization with supramolecular moieties which interact with each other via directional and reversible hydrogen

Peptide-oligonucleotide conjugates as nanoscale building blocks for assembly of an artificial three-helix protein mimic

DEFF Research Database (Denmark)

Lou, Chenguang; Martos-Maldonado, Manuel C.; Madsen, Charlotte Stahl

2016-01-01

Peptide-based structures can be designed to yield artificial proteins with specific folding patterns and functions. Template-based assembly of peptide units is one design option, but the use of two orthogonal self-assembly principles, oligonucleotide triple helix and a coiled coil protein domain ...

Beta-Sheet-Forming, Self-Assembled Peptide Nanomaterials towards Optical, Energy, and Healthcare Applications.

Science.gov (United States)

Kim, Sungjin; Kim, Jae Hong; Lee, Joon Seok; Park, Chan Beum

2015-08-12

Peptide self-assembly is an attractive route for the synthesis of intricate organic nanostructures that possess remarkable structural variety and biocompatibility. Recent studies on peptide-based, self-assembled materials have expanded beyond the construction of high-order architectures; they are now reporting new functional materials that have application in the emerging fields such as artificial photosynthesis and rechargeable batteries. Nevertheless, there have been few reviews particularly concentrating on such versatile, emerging applications. Herein, recent advances in the synthesis of self-assembled peptide nanomaterials (e.g., cross β-sheet-based amyloid nanostructures, peptide amphiphiles) are selectively reviewed and their new applications in diverse, interdisciplinary fields are described, ranging from optics and energy storage/conversion to healthcare. The applications of peptide-based self-assembled materials in unconventional fields are also highlighted, such as photoluminescent peptide nanostructures, artificial photosynthetic peptide nanomaterials, and lithium-ion battery components. The relation of such functional materials to the rapidly progressing biomedical applications of peptide self-assembly, which include biosensors/chips and regenerative medicine, are discussed. The combination of strategies shown in these applications would further promote the discovery of novel, functional, small materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticulate hollow TiO2 fibers as light scatterers in dye-sensitized solar cells: layer-by-layer self-assembly parameters and mechanism.

Science.gov (United States)

Rahman, Masoud; Tajabadi, Fariba; Shooshtari, Leyla; Taghavinia, Nima

2011-04-04

Hollow structures show both light scattering and light trapping, which makes them promising for dye-sensitized solar cell (DSSC) applications. In this work, nanoparticulate hollow TiO(2) fibers are prepared by layer-by-layer (LbL) self-assembly deposition of TiO(2) nanoparticles on natural cellulose fibers as template, followed by thermal removal of the template. The effect of LbL parameters such as the type and molecular weight of polyelectrolyte, number of dip cycles, and the TiO(2) dispersion (amorphous or crystalline sol) are investigated. LbL deposition with weak polyelectrolytes (polyethylenimine, PEI) gives greater nanoparticle deposition yield compared to strong polyelectrolytes (poly(diallyldimethylammonium chloride), PDDA). Decreasing the molecular weight of the polyelectrolyte results in more deposition of nanoparticles in each dip cycle with narrower pore size distribution. Fibers prepared by the deposition of crystalline TiO(2) nanoparticles show higher surface area and higher pore volume than amorphous nanoparticles. Scattering coefficients and backscattering properties of fibers are investigated and compared with those of commercial P25 nanoparticles. Composite P25-fiber films are electrophoretically deposited and employed as the photoanode in DSSC. Photoelectrochemical measurements showed an increase of around 50% in conversion efficiency. By employing the intensity-modulated photovoltage and photocurrent spectroscopy methods, it is shown that the performance improvement due to addition of fibers is mostly due to the increase in light-harvesting efficiency. The high surface area due to the nanoparticulate structure and strong light harvesting due to the hollow structure make these fibers promising scatterers in DSSCs. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adaptive integration of daylight and artificial lighting

DEFF Research Database (Denmark)

Petersen, Kjell Yngve

2016-01-01

Daylight is dynamic and dependent upon weather conditions; unfolding with both subtle and dramatic variations in qualities of light. Through a building’s apertures, daylight creates a connection between the space inside and the world outside. The aperture or window itself constitutes the frame...... with the world. In contrast to fluctuating daylight, a specific distinctive feature of artificial light has been – until very recently – its constancy in colour and intensity. However, by virtue of the technological convertibility of LEDs in concert with digital control systems, LEDs are capable of dynamically...... producing variations in colour and intensity in ways that correspond to our experiences of the daylight. Daylight and artificial lighting are thus positioned in a new relationship to one another. Metaphorically, one can think of the adaptive software as ‘digital weather’ – as a self-generating and shifting...

Nanomaterial processing using self-assembly-bottom-up chemical and biological approaches

International Nuclear Information System (INIS)

Thiruvengadathan, Rajagopalan; Gangopadhyay, Keshab; Gangopadhyay, Shubhra; Korampally, Venumadhav; Ghosh, Arkasubhra; Chanda, Nripen

2013-01-01

Nanotechnology is touted as the next logical sequence in technological evolution. This has led to a substantial surge in research activities pertaining to the development and fundamental understanding of processes and assembly at the nanoscale. Both top-down and bottom-up fabrication approaches may be used to realize a range of well-defined nanostructured materials with desirable physical and chemical attributes. Among these, the bottom-up self-assembly process offers the most realistic solution toward the fabrication of next-generation functional materials and devices. Here, we present a comprehensive review on the physical basis behind self-assembly and the processes reported in recent years to direct the assembly of nanoscale functional blocks into hierarchically ordered structures. This paper emphasizes assembly in the synthetic domain as well in the biological domain, underscoring the importance of biomimetic approaches toward novel materials. In particular, two important classes of directed self-assembly, namely, (i) self-assembly among nanoparticle–polymer systems and (ii) external field-guided assembly are highlighted. The spontaneous self-assembling behavior observed in nature that leads to complex, multifunctional, hierarchical structures within biological systems is also discussed in this review. Recent research undertaken to synthesize hierarchically assembled functional materials have underscored the need as well as the benefits harvested in synergistically combining top-down fabrication methods with bottom-up self-assembly. (review article)

Improving Light Extraction of Organic Light-Emitting Devices by Attaching Nanostructures with Self-Assembled Photonic Crystal Patterns

Directory of Open Access Journals (Sweden)

Kai-Yu Peng

2014-01-01

Full Text Available A single-monolayered hexagonal self-assembled photonic crystal (PC pattern fabricated onto polyethylene terephthalate (PET films by using simple nanosphere lithography (NSL method has been demonstrated in this research work. The patterned nanostructures acted as a scattering medium to extract the trapped photons from substrate mode of optical-electronic device for improving the overall external quantum efficiency of the organic light-emitting diodes (OLEDs. With an optimum latex concentration, the distribution of self-assembled polystyrene (PS nanosphere patterns on PET films can be easily controlled by adjusting the rotation speed of spin-coater. After attaching the PS nanosphere array brightness enhancement film (BEF sheet as a photonic crystal pattern onto the device, the luminous intensity of OLEDs in the normal viewing direction is 161% higher than the one without any BEF attachment. The electroluminescent (EL spectrum of OLEDs with PS patterned BEF attachment also showed minor color offset and superior color stabilization characteristics, and thus it possessed the potential applications in all kinds of display technology and solid-state optical-electronic devices.

Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

KAUST Repository

Patil, Sachin; Moosa, Basem; Alsaiari, Shahad; Alamoudi, Kholod; Alshamsan, Aws; Almailk, Abdulaziz; Adil, Karim; Eddaoudi, Mohamed; Khashab, Niveen M.

2016-01-01

Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond

Artificial Nacre from Supramolecular Assembly of Graphene Oxide.

Science.gov (United States)

Wang, Yang; Li, Ting; Ma, Piming; Zhang, Shengwen; Zhang, Hongji; Du, Mingliang; Xie, Yi; Chen, Mingqing; Dong, Weifu; Ming, Weihua

2018-06-14

Inspired by the "brick-and-mortar" structure and remarkable mechanical performance of nacre, many efforts have been devoted to fabricating nacre-mimicking materials. Herein, a class of graphene oxide (GO) based artificial nacre material with quadruple hydrogen-bonding interactions was fabricated by functionalization of polydopamine-capped graphene oxide (PDG) with 2-ureido-4[1 H]-pyrimidinone (UPy) self-complementary quadruple hydrogen-bonding units followed by supramolecular assembly process. The artificial nacre displays a strict "brick-and-mortar" structure, with PDG nanosheets as the brick and UPy units as the mortar. The resultant nanocomposite shows an excellent balance of strength and toughness. Because of the strong strengthening via quadruple hydrogen bonding, the tensile strength and toughness can reach 325.6 ± 17.8 MPa and 11.1 ± 1.3 MJ m -3 , respectively, thus exceeding natural nacre, and reaching 3.6 and 10 times that of a pure GO artificial nacre. Furthermore, after further H 2 O treatment, the resulting H 2 O-treated PDG-UPy actuator displays significant bending actuations when driven by heat. This work provides a pathway for the development of artificial nacre for their potential applications in energy conversion, temperature sensor, and thermo-driven actuator.

Biogeography of photosynthetic light-harvesting genes in marine phytoplankton.

Directory of Open Access Journals (Sweden)

Thomas S Bibby

Full Text Available BACKGROUND: Photosynthetic light-harvesting proteins are the mechanism by which energy enters the marine ecosystem. The dominant prokaryotic photoautotrophs are the cyanobacterial genera Prochlorococcus and Synechococcus that are defined by two distinct light-harvesting systems, chlorophyll-bound protein complexes or phycobilin-bound protein complexes, respectively. Here, we use the Global Ocean Sampling (GOS Project as a unique and powerful tool to analyze the environmental diversity of photosynthetic light-harvesting genes in relation to available metadata including geographical location and physical and chemical environmental parameters. METHODS: All light-harvesting gene fragments and their metadata were obtained from the GOS database, aligned using ClustalX and classified phylogenetically. Each sequence has a name indicative of its geographic location; subsequent biogeographical analysis was performed by correlating light-harvesting gene budgets for each GOS station with surface chlorophyll concentration. CONCLUSION/SIGNIFICANCE: Using the GOS data, we have mapped the biogeography of light-harvesting genes in marine cyanobacteria on ocean-basin scales and show that an environmental gradient exists in which chlorophyll concentration is correlated to diversity of light-harvesting systems. Three functionally distinct types of light-harvesting genes are defined: (1 the phycobilisome (PBS genes of Synechococcus; (2 the pcb genes of Prochlorococcus; and (3 the iron-stress-induced (isiA genes present in some marine Synechococcus. At low chlorophyll concentrations, where nutrients are limited, the Pcb-type light-harvesting system shows greater genetic diversity; whereas at high chlorophyll concentrations, where nutrients are abundant, the PBS-type light-harvesting system shows higher genetic diversity. We interpret this as an environmental selection of specific photosynthetic strategy. Importantly, the unique light-harvesting system isiA is found

Selective internalization of self-assembled artificial oil bodies by HER2/neu-positive cells

International Nuclear Information System (INIS)

Chiang, Chung-Jen; Lin, Che-Chin; Lin, Li-Jen; Chang, Chih-Hsiang; Chao, Yun-Peng

2011-01-01

A novel delivery carrier was developed using artificial oil bodies (AOBs). Plant seed oil bodies (OBs) consist of a triacylglycerol matrix surrounded by a monolayer of phospholipids embedded with the storage protein oleosin (Ole). Ole consists of a central hydrophobic domain with two amphiphatic arms that extrude from the surface of OBs. In this study, a bivalent anti-HER2/neu affibody domain (ZH2) was fused with Ole at the C terminus. After overproduction in Escherichia coli, the fusion protein (Ole-ZH2) was recovered to assemble AOBs. The size of self-assembled AOBs was tailored by varying the oil/Ole-ZH2 ratio and pH to reach a nanoscale. Upon co-incubation with tumor cells, the nanoscale AOBs encapsulated with a hydrophobic fluorescence dye were selectively internalized by HER2/neu-overexpressing cells and displayed biocompatibility with the cells. In addition, the ZH2-mediated endosomal entry of AOBs occurred in a time- and AOB dose-dependent manner. The internalization efficiency was as high as 90%. The internalized AOBs disintegrated at the non-permissive pH (e.g. in acidic endosomes) and the cargo dye was released. Results of in vitro study revealed a sustained and prolonged release profile. Taken together, our findings indicate the potential of AOBs as a delivery carrier.

Reconstitution of chlorophyll a/b light-harvesting complexes: xanthophyll-dependent assembly and energy transfer

Energy Technology Data Exchange (ETDEWEB)

Plumley, F.G.; Schmidt, G.W.

1987-01-01

A method for in vitro reconstitution of the chlorophyll a/b light-harvesting complex from LiDodSO/sub 4//heat-denatured or acetone-extracted photosynthetic membranes has been developed. Characterization of the minimum components necessary for the functional organization or pigments in these membrane complexes reveals that xanthophylls are essential structural components.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly

Science.gov (United States)

Stewart, Elizabeth J.; Ganesan, Mahesh; Younger, John G.; Solomon, Michael J.

2015-01-01

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism. PMID:26272750

The role of energy losses in photosynthetic light harvesting

Science.gov (United States)

Krüger, T. P. J.; van Grondelle, R.

2017-07-01

Photosynthesis operates at the bottom of the food chain to convert the energy of light into carbohydrates at a remarkable global rate of about 130 TW. Nonetheless, the overall photosynthetic process has a conversion efficiency of a few percent at best, significantly less than bottom-up photovoltaic cells. The primary photosynthetic steps, consisting of light harvesting and charge separation, are often presented as having near-unity quantum efficiency but this holds only true under ideal conditions. In this review, we discuss the importance of energy loss mechanisms to establish robustness in photosynthetic light harvesting. Thermal energy dissipation of light-harvesting complexes (LHCs) in different environments is investigated and the relationships and contrasts between concentration quenching of high pigment concentrations, photoprotection (non-photochemical quenching), quenching due to protein aggregation, and fluorescence blinking are discussed. The role of charge-transfer states in light harvesting and energy dissipation is highlighted and the importance of controlled protein structural disorder to switch the light-harvesting antennae between effective light harvesters and efficient energy quenchers is underscored. The main LHC of plants, LHCII, is used as a prime example.

Preparation and self-assembly of amphiphilic polylysine dendrons

DEFF Research Database (Denmark)

Mirsharghi, Sahar; Knudsen, Kenneth D.; Bagherifam, Shahla

2016-01-01

Polylysine dendrons with lipid tails prepared by divergent solid-phase synthesis showed self-assembling properties in aqueous solutions., Herein, we present the synthesis of new amphiphilic polylysine dendrons with variable alkyl chain lengths (C1–C18) at the C-terminal. The dendrons were...... synthesized in moderate to quantitative yields by divergent solid-phase synthesis (SPS) employing an aldehyde linker. The self-assembling properties of the dendrons in aqueous solutions were studied by small angle neutron scattering (SANS) and dynamic light scattering (DLS). The self-assembling properties...... were influenced by the length of the alkyl chain and the generation number (Gn). Increasing the temperature and concentration did not have significant impact on the hydrodynamic diameter, but the self-assembling properties were influenced by the pH value. This demonstrated the need for positively...

Crystal structure of spinach major light-harvesting complex at 2.72Å resolution

Science.gov (United States)

Liu, Zhenfeng; Yan, Hanchi; Wang, Kebin; Kuang, Tingyun; Zhang, Jiping; Gui, Lulu; An, Xiaomin; Chang, Wenrui

2004-03-01

The major light-harvesting complex of photosystem II (LHC-II) serves as the principal solar energy collector in the photosynthesis of green plants and presumably also functions in photoprotection under high-light conditions. Here we report the first X-ray structure of LHC-II in icosahedral proteoliposome assembly at atomic detail. One asymmetric unit of a large R32 unit cell contains ten LHC-II monomers. The 14 chlorophylls (Chl) in each monomer can be unambiguously distinguished as eight Chla and six Chlb molecules. Assignment of the orientation of the transition dipole moment of each chlorophyll has been achieved. All Chlb are located around the interface between adjacent monomers, and together with Chla they are the basis for efficient light harvesting. Four carotenoid-binding sites per monomer have been observed. The xanthophyll-cycle carotenoid at the monomer-monomer interface may be involved in the non-radiative dissipation of excessive energy, one of the photoprotective strategies that have evolved in plants.

The role of energy losses in photosynthetic light harvesting

International Nuclear Information System (INIS)

Krüger, T P J; Van Grondelle, R

2017-01-01

Photosynthesis operates at the bottom of the food chain to convert the energy of light into carbohydrates at a remarkable global rate of about 130 TW. Nonetheless, the overall photosynthetic process has a conversion efficiency of a few percent at best, significantly less than bottom-up photovoltaic cells. The primary photosynthetic steps, consisting of light harvesting and charge separation, are often presented as having near-unity quantum efficiency but this holds only true under ideal conditions. In this review, we discuss the importance of energy loss mechanisms to establish robustness in photosynthetic light harvesting. Thermal energy dissipation of light-harvesting complexes (LHCs) in different environments is investigated and the relationships and contrasts between concentration quenching of high pigment concentrations, photoprotection (non-photochemical quenching), quenching due to protein aggregation, and fluorescence blinking are discussed. The role of charge-transfer states in light harvesting and energy dissipation is highlighted and the importance of controlled protein structural disorder to switch the light-harvesting antennae between effective light harvesters and efficient energy quenchers is underscored. The main LHC of plants, LHCII, is used as a prime example. (topical review)

Opal-like Multicolor Appearance of Self-Assembled Photonic Array.

Science.gov (United States)

Arnon, Zohar A; Pinotsi, Dorothea; Schmidt, Matthias; Gilead, Sharon; Guterman, Tom; Sadhanala, Aditya; Ahmad, Shahab; Levin, Aviad; Walther, Paul; Kaminski, Clemens F; Fändrich, Marcus; Kaminski Schierle, Gabriele S; Adler-Abramovich, Lihi; Shimon, Linda J W; Gazit, Ehud

2018-06-20

Molecular self-assembly of short peptide building blocks leads to the formation of various material architectures that may possess unique physical properties. Recent studies had confirmed the key role of biaromaticity in peptide self-assembly, with the diphenylalanine (FF) structural family as an archetypal model. Another significant direction in the molecular engineering of peptide building blocks is the use of fluorenylmethoxycarbonyl (Fmoc) modification, which promotes the assembly process and may result in nanostructures with distinctive features and macroscopic hydrogel with supramolecular features and nanoscale order. Here, we explored the self-assembly of the protected, noncoded fluorenylmethoxycarbonyl-β,β-diphenyl-Ala-OH (Fmoc-Dip) amino acid. This process results in the formation of elongated needle-like crystals with notable aromatic continuity. By altering the assembly conditions, arrays of spherical particles were formed that exhibit strong light scattering. These arrays display vivid coloration, strongly resembling the appearance of opal gemstones. However, unlike the Rayleigh scattering effect produced by the arrangement of opal, the described optical phenomenon is attributed to Mie scattering. Moreover, by controlling the solution evaporation rate, i.e., the assembly kinetics, we were able to manipulate the resulting coloration. This work demonstrates a bottom-up approach, utilizing self-assembly of a protected amino acid minimal building block, to create arrays of organic, light-scattering colorful surfaces.

Single-molecule exploration of photoprotective mechanisms in light-harvesting complexes

NARCIS (Netherlands)

Yang, Hsiang Yu; Schlau-Cohen, Gabriela S.; Gwizdala, Michal; Krüger, Tjaart; Xu, Pengqi; Croce, Roberta; Van Grondelle, Rienk; Moerner, W. E.

2015-01-01

Plants harvest sunlight by converting light energy to electron flow through the primary events in photosynthesis. One important question is how the light harvesting machinery adapts to fluctuating sunlight intensity. As a result of various regulatory processes, efficient light harvesting and

Self-assembly of self-assembled molecular triangles

Indian Academy of Sciences (India)

While the solution state structure of 1 can be best described as a trinuclear complex, in the solidstate well-fashioned intermolecular - and CH- interactions are observed. Thus, in the solid-state further self-assembly of already self-assembled molecular triangle is witnessed. The triangular panels are arranged in a linear ...

A comparative spectroscopic and kinetic study of photoexcitations in detergent-isolated and membrane-embedded LH2 light-harvesting complexes.

Science.gov (United States)

Freiberg, Arvi; Rätsep, Margus; Timpmann, Kõu

2012-08-01

Integral membrane proteins constitute more than third of the total number of proteins present in organisms. Solubilization with mild detergents is a common technique to study the structure, dynamics, and catalytic activity of these proteins in purified form. However beneficial the use of detergents may be for protein extraction, the membrane proteins are often denatured by detergent solubilization as a result of native lipid membrane interactions having been modified. Versatile investigations of the properties of membrane-embedded and detergent-isolated proteins are, therefore, required to evaluate the consequences of the solubilization procedure. Herein, the spectroscopic and kinetic fingerprints have been established that distinguish excitons in individual detergent-solubilized LH2 light-harvesting pigment-protein complexes from them in the membrane-embedded complexes of purple photosynthetic bacteria Rhodobacter sphaeroides. A wide arsenal of spectroscopic techniques in visible optical range that include conventional broadband absorption-fluorescence, fluorescence anisotropy excitation, spectrally selective hole burning and fluorescence line-narrowing, and transient absorption-fluorescence have been applied over broad temperature range between physiological and liquid He temperatures. Significant changes in energetics and dynamics of the antenna excitons upon self-assembly of the proteins into intracytoplasmic membranes are observed, analyzed, and discussed. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial. Copyright © 2011. Published by Elsevier B.V.

Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly.

Science.gov (United States)

Kimizuka, Nobuo; Yanai, Nobuhiro; Morikawa, Masa-Aki

2016-11-29

The self-assembly of functional molecules into ordered molecular assemblies and the fulfillment of potentials unique to their nanotomesoscopic structures have been one of the central challenges in chemistry. This Feature Article provides an overview of recent progress in the field of molecular self-assembly with the focus on the triplet-triplet annihilation-based photon upconversion (TTA-UC) and supramolecular storage of photon energy. On the basis of the integration of molecular self-assembly and photon energy harvesting, triplet energy migration-based TTA-UC has been achieved in varied molecular systems. Interestingly, some molecular self-assemblies dispersed in solution or organogels revealed oxygen barrier properties, which allowed TTA-UC even under aerated conditions. The elements of molecular self-assembly were also introduced to the field of molecular solar thermal fuel, where reversible photoliquefaction of ionic crystals to ionic liquids was found to double the molecular storage capacity with the simultaneous pursuit of switching ionic conductivity. A future prospect in terms of innovating molecular self-assembly toward molecular systems chemistry is also discussed.

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Brondijk, J.J.; Li, X.; Akkerman, H.B.; Blom, P.W.M.; Boer, B. de [University of Groningen, Molecular Electronics, Zernike Institute for Advanced Materials, Groningen (Netherlands)

2009-04-15

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only {proportional_to}1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly(p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays. (orig.)

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

Science.gov (United States)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

2009-04-01

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only ˜1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly( p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays.

{beta}-Carotene to bacteriochlorophyll c energy transfer in self-assembled aggregates mimicking chlorosomes

Energy Technology Data Exchange (ETDEWEB)

Alster, J. [Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 121 16 Praha (Czech Republic); Polivka, T. [Institute of Physical Biology, University of South Bohemia, Zamek 136, 373 33 Nove Hrady (Czech Republic); Biology Centre, Academy of Sciences of the Czech Republic, Branisovska 31, 370 05 Ceske Budejovice (Czech Republic); Arellano, J.B. [Instituto de Recursos Naturales y Agrobiologia de Salamanca (IRNASA-CSIC), Apdo. 257, 37071 Salamanca (Spain); Chabera, P. [Institute of Physical Biology, University of South Bohemia, Zamek 136, 373 33 Nove Hrady (Czech Republic); Vacha, F. [Institute of Physical Biology, University of South Bohemia, Zamek 136, 373 33 Nove Hrady (Czech Republic); Biology Centre, Academy of Sciences of the Czech Republic, Branisovska 31, 370 05 Ceske Budejovice (Czech Republic); Psencik, J., E-mail: psencik@karlov.mff.cuni.cz [Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 121 16 Praha (Czech Republic); Institute of Physical Biology, University of South Bohemia, Zamek 136, 373 33 Nove Hrady (Czech Republic)

2010-07-19

Carotenoids are together with bacteriochlorophylls important constituents of chlorosomes, the light-harvesting antennae of green photosynthetic bacteria. Majority of bacteriochlorophyll molecules form self-assembling aggregates inside the chlorosomes. Aggregates of bacteriochlorophylls with optical properties similar to those of chlorosomes can also be prepared in non-polar organic solvents or in aqueous environments when a suitable non-polar molecule is added. In this work, the ability of {beta}-carotene to induce aggregation of bacteriochlorophyll c in aqueous buffer was studied. Excitation relaxation and energy transfer in the carotenoid-bacteriochlorophyll assemblies were measured using femtosecond and nanosecond transient absorption spectroscopy. A fast, {approx}100-fs energy transfer from the S{sub 2} state of {beta}-carotene to bacteriochlorophyll c was revealed, while no evidence for significant energy transfer from the S{sub 1} state was found. Picosecond formation of the carotenoid triplet state (T{sub 1}) was observed, which was likely generated by singlet homo-fission from the S{sub 1} state of {beta}-carotene.

Building polyhedra by self-assembly: theory and experiment.

Science.gov (United States)

Kaplan, Ryan; Klobušický, Joseph; Pandey, Shivendra; Gracias, David H; Menon, Govind

2014-01-01

We investigate the utility of a mathematical framework based on discrete geometry to model biological and synthetic self-assembly. Our primary biological example is the self-assembly of icosahedral viruses; our synthetic example is surface-tension-driven self-folding polyhedra. In both instances, the process of self-assembly is modeled by decomposing the polyhedron into a set of partially formed intermediate states. The set of all intermediates is called the configuration space, pathways of assembly are modeled as paths in the configuration space, and the kinetics and yield of assembly are modeled by rate equations, Markov chains, or cost functions on the configuration space. We review an interesting interplay between biological function and mathematical structure in viruses in light of this framework. We discuss in particular: (i) tiling theory as a coarse-grained description of all-atom models; (ii) the building game-a growth model for the formation of polyhedra; and (iii) the application of these models to the self-assembly of the bacteriophage MS2. We then use a similar framework to model self-folding polyhedra. We use a discrete folding algorithm to compute a configuration space that idealizes surface-tension-driven self-folding and analyze pathways of assembly and dominant intermediates. These computations are then compared with experimental observations of a self-folding dodecahedron with side 300 μm. In both models, despite a combinatorial explosion in the size of the configuration space, a few pathways and intermediates dominate self-assembly. For self-folding polyhedra, the dominant intermediates have fewer degrees of freedom than comparable intermediates, and are thus more rigid. The concentration of assembly pathways on a few intermediates with distinguished geometric properties is biologically and physically important, and suggests deeper mathematical structure.

Hydrazine-mediated construction of nanocrystal self-assembly materials.

Science.gov (United States)

Zhou, Ding; Liu, Min; Lin, Min; Bu, Xinyuan; Luo, Xintao; Zhang, Hao; Yang, Bai

2014-10-28

Self-assembly is the basic feature of supramolecular chemistry, which permits to integrate and enhance the functionalities of nano-objects. However, the conversion of self-assembled structures to practical materials is still laborious. In this work, on the basis of studying one-pot synthesis, spontaneous assembly, and in situ polymerization of aqueous semiconductor nanocrystals (NCs), NC self-assembly materials are produced and applied to design high performance white light-emitting diode (WLED). In producing self-assembly materials, the additive hydrazine (N2H4) is curial, which acts as the promoter to achieve room-temperature synthesis of aqueous NCs by favoring a reaction-controlled growth, as the polyelectrolyte to weaken inter-NC electrostatic repulsion and therewith facilitate the one-dimensional self-assembly, and in particular as the bifunctional monomers to polymerize with mercapto carboxylic acid-modified NCs via in situ amidation reaction. This strategy is versatile for mercapto carboxylic acid-modified aqueous NCs, for example CdS, CdSe, CdTe, CdSe(x)Te(1-x), and Cd(y)Hg(1-y)Te. Because of the multisite modification with carboxyl, the NCs act as macromonomers, thus producing cross-linked self-assembly materials with excellent thermal, solvent, and photostability. The assembled NCs preserve strong luminescence and avoid unpredictable fluorescent resonance energy transfer, the main problem in design WLED from multiple NC components. These advantages allow the fabrication of NC-based WLED with high color rendering index (86), high luminous efficacy (41 lm/W), and controllable color temperature.

Self-assembling electroactive hydrogels for flexible display technology

Energy Technology Data Exchange (ETDEWEB)

Jones, Scott L; Wong, Kok Hou; Ladouceur, Francois [School of Electrical Engineering and Telecommunications, University of NSW, Sydney, NSW, 2052 (Australia); Thordarson, Pall, E-mail: f.ladouceur@unsw.edu.a [School of Chemistry, University of NSW, Sydney, NSW, 2052 (Australia)

2010-12-15

We have assessed the potential of self-assembling hydrogels for use in conformal displays. The self-assembling process can be used to alter the transparency of the material to all visible light due to scattering by fibres. The reversible transition is shown to be of low energy by differential scanning calorimetry. For use in technology it is imperative that this transition is controlled electrically. We have thus synthesized novel self-assembling hydrogelator molecules which contain an electroactive group. The well-known redox couple of anthraquinone/anthrahydroquinone has been used as the hydrophobic component for a series of small molecule gelators. They are further functionalized with peptide combinations of L-phenylalanine and glycine to provide the hydrophilic group to complete 'head-tail' models of self-assembling gels. The gelation and electroactive characteristics of the series were assessed. Cyclic voltammetry shows the reversible redox cycle to be only superficially altered by functionalization. Additionally, spectroelectrochemical measurements show a reversible transparency and colour change induced by the redox process.

Self-assembling electroactive hydrogels for flexible display technology

International Nuclear Information System (INIS)

Jones, Scott L; Wong, Kok Hou; Ladouceur, Francois; Thordarson, Pall

2010-01-01

We have assessed the potential of self-assembling hydrogels for use in conformal displays. The self-assembling process can be used to alter the transparency of the material to all visible light due to scattering by fibres. The reversible transition is shown to be of low energy by differential scanning calorimetry. For use in technology it is imperative that this transition is controlled electrically. We have thus synthesized novel self-assembling hydrogelator molecules which contain an electroactive group. The well-known redox couple of anthraquinone/anthrahydroquinone has been used as the hydrophobic component for a series of small molecule gelators. They are further functionalized with peptide combinations of L-phenylalanine and glycine to provide the hydrophilic group to complete 'head-tail' models of self-assembling gels. The gelation and electroactive characteristics of the series were assessed. Cyclic voltammetry shows the reversible redox cycle to be only superficially altered by functionalization. Additionally, spectroelectrochemical measurements show a reversible transparency and colour change induced by the redox process.

Revealing Linear Aggregates of Light Harvesting Antenna Proteins in Photosynthetic Membranes

OpenAIRE

He, Yufan; Zeng, Xiaohua; Mukherjee, Saptarshi; Rajapaksha, Suneth; Kaplan, Samuel; Lu, H. Peter

2010-01-01

How light energy is harvested in a natural photosynthetic membrane through energy transfer is closely related to the stoichiometry and arrangement of light harvesting antenna proteins in the membrane. The specific photosynthetic architecture facilitates a rapid and efficient energy transfer among the light harvesting proteins (LH2 and LH1) and to the reaction center. Here we report the identification of linear aggregates of light harvesting proteins, LH2, in the photosynthetic membranes under...

The family of light-harvesting-related proteins (LHCs, ELIPs, HLIPs): was the harvesting of light their primary function?

Science.gov (United States)

Montané, M H; Kloppstech, K

2000-11-27

Light-harvesting complex proteins (LHCs) and early light-induced proteins (ELIPs) are essential pigment-binding components of the thylakoid membrane and are encoded by one of the largest and most complex higher plant gene families. The functional diversification of these proteins corresponded to the transition from extrinsic (phycobilisome-based) to intrinsic (LHC-based) light-harvesting antenna systems during the evolution of chloroplasts from cyanobacteria, yet the functional basis of this diversification has been elusive. Here, we propose that the original function of LHCs and ELIPs was not to collect light and to transfer its energy content to the reaction centers but to disperse the absorbed energy of light in the form of heat or fluorescence. These energy-dispersing proteins are believed to have originated in cyanobacteria as one-helix, highly light-inducible proteins (HLIPs) that later acquired four helices through two successive gene duplication steps. We suggest that the ELIPs arose first in this succession, with a primary function in energy dispersion for protection of photosynthetic pigments from photo-oxidation. We consider the LHC I and II families as more recent and very successful evolutionary additions to this family that ultimately attained a new function, thereby replacing the ancestral extrinsic light-harvesting system. Our model accounts for the non-photochemical quenching role recently shown for higher plant psbS proteins.

Artificial light and nocturnal activity in gammarids

Directory of Open Access Journals (Sweden)

Elizabeth K. Perkin

2014-03-01

Full Text Available Artificial light is gaining attention as a potential stressor to aquatic ecosystems. Artificial lights located near streams increase light levels experienced by stream invertebrates and we hypothesized light would depress night drift rates. We also hypothesized that the effect of light on drift rates would decrease over time as the invertebrates acclimated to the new light level over the course of one month’s exposure. These hypotheses were tested by placing Gammarus spp. in eight, 75 m × 1 m artificial flumes. One flume was exposed to strong (416 lx artificial light at night. This strong light created a gradient between 4.19 and 0.04 lx over the neighboring six artificial flumes, while a control flume was completely covered with black plastic at night. Night-time light measurements taken in the Berlin area confirm that half the flumes were at light levels experienced by urban aquatic invertebrates. Surprisingly, no light treatment affected gammarid drift rates. In contrast, physical activity measurements of in situ individually caged G. roeseli showed they increased short-term activity levels in nights of complete darkness and decreased activity levels in brightly lit flumes. Both nocturnal and diurnal drift increased, and day drift rates were unexpectadly higher than nocturnal drift.

[Self-assembly tissue engineering fibrocartilage model of goat temporomandibular joint disc].

Science.gov (United States)

Kang, Hong; Li, Zhen-Qiang; Bi, Yan-Da

2011-06-01

To construct self-assembly fibrocartilage model of goat temporomandibular joint disc and observe the biological characteristics of the self-assembled fibrocartilage constructs, further to provide a basis for tissue engineering of the temporomandibular joint disc and other fibrocartilage. Cells from temporomandibular joint discs of goats were harvested and cultured. 5.5 x 10(6) cells were seeded in each agarose well with diameter 5 mm x depth 10 mm, daily replace of medium, cultured for 2 weeks. One day after seeding, goat temporomandibular joint disc cells in agarose wells were gathered and began to self-assemble into a disc-shaped base, then gradually turned into a round shape. When cultured for 2 weeks, hematoxylin-eosin staining was conducted and observed that cells were round and wrapped around by the matrix. Positive Safranin-O/fast green staining for glycosaminoglycans was observed throughout the entire constructs, and picro-sirius red staining was examined and distribution of numerous type I collagen was found. Immunohistochemistry staining demonstrated brown yellow particles in cytoplasm and around extracellular matrix, which showed self-assembly construct can produce type I collagen as native temporomandibular joint disc tissue. Production of extracellular matrix in self-assembly construct as native temporomandibular joint disc tissue indicates that the use of agarose wells to construct engineered temporomandibular joint disc will be possible and practicable.

Cooperative effects of fibronectin matrix assembly and initial cell-substrate adhesion strength in cellular self-assembly.

Science.gov (United States)

Brennan, James R; Hocking, Denise C

2016-03-01

organize cells into modular building blocks for artificial tissue fabrication. Fibronectin is an ECM protein that plays a key role in tissue formation during embryonic development. Additionally, the cell-mediated process of converting soluble fibronectin into insoluble, ECM-associated fibrils has been shown to initiate cellular self-assembly in vitro. In this study, we examine the relationship between the strength of cell-substrate adhesions and the ability of fibronectin fibril assembly to induce cellular self-assembly. Our results indicate that substrate composition and density play cooperative roles with cell-mediated fibronectin matrix assembly to control the transition of cells from 2D monolayers into 3D multicellular aggregates. Results of this study provide a quantitative approach to build predictive models of cellular self-assembly, as well as a simple cell-culture platform to produce biomimetic units for modular tissue engineering. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Light + architecture. Daylight - artificial light - energy; Licht + Architektur. Tageslicht - Kunstlicht - Energie

Energy Technology Data Exchange (ETDEWEB)

NONE

2009-07-01

The symposium intends to provide scientific and technical fundamentals for room lighting with daylight. Daylight deflection systems and artificial light control systems were analyzed for this purpose, and a catalogue of criteria was established. Planners were given tools for projecting daylight control systems. Builder-owners received the fundamentals for economic assessment of combined daylight and artificial light illumination systems, while industrial producers obtained information for further development to maturity and for marketing of daylight-dependent artificial light control systems. (GL)

Artificial light pollution increases nocturnal vigilance in peahens.

Science.gov (United States)

Yorzinski, Jessica L; Chisholm, Sarah; Byerley, Sydney D; Coy, Jeanee R; Aziz, Aisyah; Wolf, Jamie A; Gnerlich, Amanda C

2015-01-01

Artificial light pollution is drastically changing the sensory environments of animals. Even though many animals are now living in these changed environments, the effect light pollution has on animal behavior is poorly understood. We investigated the effect of light pollution on nocturnal vigilance in peahens (Pavo cristatus). Captive peahens were exposed to either artificial lighting or natural lighting at night. We employed a novel method to record their vigilance behavior by attaching accelerometers to their heads and continuously monitoring their large head movements. We found that light pollution significantly increases nocturnal vigilance in peahens. Furthermore, the birds faced a trade-off between vigilance and sleep at night: peahens that were more vigilant spent less time sleeping. Given the choice, peahens preferred to roost away from high levels of artificial lighting but showed no preference for roosting without artificial lighting or with low levels of artificial lighting. Our study demonstrates that light pollution can have a substantial impact on animal behavior that can potentially result in fitness consequences.

Workplane Illuminance Estimation for Robust Daylight Harvesting Lighting Control

NARCIS (Netherlands)

Zhang, S.; Birru, D.

2012-01-01

Daylight harvesting lighting controls can provide significant energysavings in daylit spaces. However, their performance is affected bythe changing lighting distribution in the space due to window treatments and the sun. Such impacts reduce the field performance of daylight harvesting dimming

Continuous light-emitting Diode (LED) lighting for improving food quality

OpenAIRE

Lu, C; Bian, Z

2016-01-01

Lighting-emitting diodes (LEDs) have shown great potential for plant growth and development, with higher luminous efficiency and positive impact compared with other artificial lighting. The combined effects of red/blue or/and green, and white LED light on plant growth and physiology, including chlorophyll fluorescence, nitrate content and phytochemical concentration before harvest, were investigated. The results showed that continuous light (CL)\\ud exposure at pre-harvest can effectively redu...

Ground-State Electronic Structure of RC-LH1 and LH2 Pigment Assemblies of Purple Bacteria via the EBF-MO Method.

Science.gov (United States)

Shrestha, Kushal; Jakubikova, Elena

2015-08-20

Light-harvesting antennas are protein-pigment complexes that play a crucial role in natural photosynthesis. The antenna complexes absorb light and transfer energy to photosynthetic reaction centers where charge separation occurs. This work focuses on computational studies of the electronic structure of the pigment networks of light-harvesting complex I (LH1), LH1 with the reaction center (RC-LH1), and light-harvesting complex II (LH2) found in purple bacteria. As the pigment networks of LH1, RC-LH1, and LH2 contain thousands of atoms, conventional density functional theory (DFT) and ab initio calculations of these systems are not computationally feasible. Therefore, we utilize DFT in conjunction with the energy-based fragmentation with molecular orbitals method and a semiempirical approach employing the extended Hückel model Hamiltonian to determine the electronic properties of these pigment assemblies. Our calculations provide a deeper understanding of the electronic structure of natural light-harvesting complexes, especially their pigment networks, which could assist in rational design of artificial photosynthetic devices.

Adaptation of light-harvesting functions of unicellular green algae to different light qualities.

Science.gov (United States)

Ueno, Yoshifumi; Aikawa, Shimpei; Kondo, Akihiko; Akimoto, Seiji

2018-05-28

Oxygenic photosynthetic organisms perform photosynthesis efficiently by distributing captured light energy to photosystems (PSs) at an appropriate balance. Maintaining photosynthetic efficiency under changing light conditions requires modification of light-harvesting and energy-transfer processes. In the current study, we examined how green algae regulate their light-harvesting functions in response to different light qualities. We measured low-temperature time-resolved fluorescence spectra of unicellular green algae Chlamydomonas reinhardtii and Chlorella variabilis cells grown under different light qualities. By observing the delayed fluorescence spectra, we demonstrated that both types of green algae primarily modified the associations between light-harvesting chlorophyll protein complexes (LHCs) and PSs (PSII and PSI). Under blue light, Chlamydomonas transferred more energy from LHC to chlorophyll (Chl) located far from the PSII reaction center, while energy was transferred from LHC to PSI via different energy-transfer pathways in Chlorella. Under green light, both green algae exhibited enhanced energy transfer from LHCs to both PSs. Red light induced fluorescence quenching within PSs in Chlamydomonas and LHCs in Chlorella. In Chlorella, energy transfer from PSII to PSI appears to play an important role in balancing excitation between PSII and PSI.

Upright nanopyramid structured cover glass with light harvesting and self-cleaning effects for solar cell applications

International Nuclear Information System (INIS)

Amalathas, Amalraj Peter; Alkaisi, Maan M

2016-01-01

In this paper, we demonstrate the effect of upright nanopyramid (UNP) structured cover glass with light harvesting and self-cleaning functions on the device performance of monocrystalline Si solar cells. The UNP structures were fabricated on the surface of the glass substrate by simple, high throughput and low cost UV nanoimprint lithography, using a Si master mold with inverted nanopyramid (INP) structures. The diffuse transmittance and haze ratio values were significantly increased for UNP patterned glass, especially in the wavelength range 300–600 nm compared to the bare glass; this implies that antireflection and strong light scattering are due to the UNP structures. By replacing a bare cover glass with UNP patterned glass, the power conversion efficiency of the monocrystalline Si solar cell was substantially enhanced by about 10.97%; this is mainly due to the increased short-circuit current density J SC of 32.39 mA cm −2 compared to the reference cell with bare cover glass (i.e. J SC   =  31.60 mA cm −2 ). In addition, unlike the bare cover glass (i.e. θ CA ∼ 36°), the fluorinated UNP structured cover glass exhibited a hydrophobic surface with a water contact angle ( θ CA ) of ∼132° and excellent self-cleaning of dust particles by rolling down water droplets. (paper)

Artificial light pollution increases nocturnal vigilance in peahens

Directory of Open Access Journals (Sweden)

Jessica L. Yorzinski

2015-08-01

Full Text Available Artificial light pollution is drastically changing the sensory environments of animals. Even though many animals are now living in these changed environments, the effect light pollution has on animal behavior is poorly understood. We investigated the effect of light pollution on nocturnal vigilance in peahens (Pavo cristatus. Captive peahens were exposed to either artificial lighting or natural lighting at night. We employed a novel method to record their vigilance behavior by attaching accelerometers to their heads and continuously monitoring their large head movements. We found that light pollution significantly increases nocturnal vigilance in peahens. Furthermore, the birds faced a trade-off between vigilance and sleep at night: peahens that were more vigilant spent less time sleeping. Given the choice, peahens preferred to roost away from high levels of artificial lighting but showed no preference for roosting without artificial lighting or with low levels of artificial lighting. Our study demonstrates that light pollution can have a substantial impact on animal behavior that can potentially result in fitness consequences.

Toward three-dimensional microelectronic systems: directed self-assembly of silicon microcubes via DNA surface functionalization.

Science.gov (United States)

Lämmerhardt, Nico; Merzsch, Stephan; Ledig, Johannes; Bora, Achyut; Waag, Andreas; Tornow, Marc; Mischnick, Petra

2013-07-02

The huge and intelligent processing power of three-dimensional (3D) biological "processors" like the human brain with clock speeds of only 0.1 kHz is an extremely fascinating property, which is based on a massively parallel interconnect strategy. Artificial silicon microprocessors are 7 orders of magnitude faster. Nevertheless, they do not show any indication of intelligent processing power, mostly due to their very limited interconnectivity. Massively parallel interconnectivity can only be realized in three dimensions. Three-dimensional artificial processors would therefore be at the root of fabricating artificially intelligent systems. A first step in this direction would be the self-assembly of silicon based building blocks into 3D structures. We report on the self-assembly of such building blocks by molecular recognition, and on the electrical characterization of the formed assemblies. First, planar silicon substrates were functionalized with self-assembling monolayers of 3-aminopropyltrimethoxysilane for coupling of oligonucleotides (single stranded DNA) with glutaric aldehyde. The oligonucleotide immobilization was confirmed and quantified by hybridization with fluorescence-labeled complementary oligonucleotides. After the individual processing steps, the samples were analyzed by contact angle measurements, ellipsometry, atomic force microscopy, and fluorescence microscopy. Patterned DNA-functionalized layers were fabricated by microcontact printing (μCP) and photolithography. Silicon microcubes of 3 μm edge length as model objects for first 3D self-assembly experiments were fabricated out of silicon-on-insulator (SOI) wafers by a combination of reactive ion etching (RIE) and selective wet etching. The microcubes were then surface-functionalized using the same protocol as on planar substrates, and their self-assembly was demonstrated both on patterned silicon surfaces (88% correctly placed cubes), and to cube aggregates by complementary DNA

The Self-Assembly of Nanogold for Optical Metamaterials

Science.gov (United States)

Nidetz, Robert A.

2011-12-01

Optical metamaterials are an emerging field that enables manipulation of light like never before. Producing optical metamaterials requires sub-wavelength building blocks. The focus here was to develop methods to produce building blocks for metamaterials from nanogold. Electron-beam lithography was used to define an aminosilane patterned chemical template in order to electrostatically self-assemble citrate-capped gold nanoparticles. Equilibrium self-assembly was achieved in 20 minutes by immersing chemical templates into gold nanoparticle solutions. The number of nanoparticles that self-assembled on an aminosilane dot was controlled by manipulating the diameters of the dots and nanoparticles. Adding salt to the nanoparticle solution enabled the nanoparticles to self-assemble in greater numbers on the same sized dot. However, the preparation of the nanoparticle solution containing salt was sensitive to spikes in the salt concentration which led to aggregation of the nanoparticles and non-specific deposition. Gold nanorods were also electrostatically self-assembled. Polyelectrolyte-coated gold nanorods were patterned with limited success. A polyelectrolyte chemical template also patterned gold nanorods, but the gold nanorods preferred to pattern on the edges of the pattern. Ligand-exchanged gold nanorods displayed the best self-assembly, but suffered from slow kinetics. Self-assembled gold nanoparticles were cross-linked with poly(diallyldimethylammonium chloride). The poly(diallyldimethylammonium chloride) allowed additional nanoparticles to pattern on top of the already patterned nanoparticles. Cross-linked nanoparticles were lifted-off of the substrate by sonication in a sodium hydroxide solution. The presence of van der Waals forces and/or amine bonding prevent the nanogold from lifting-off without sonication. A good-solvent evaporation process was used to self-assemble poly(styrene) coated gold nanoparticles into spherical microbead assemblies. The use of larger

Amphiphilic copolymers based on polyoxazoline and grape seed vegetable oil derivatives: self-assemblies and dynamic light scattering

Energy Technology Data Exchange (ETDEWEB)

Travelet, Christophe, E-mail: Christophe.Travelet@cermav.cnrs.fr [Universite Joseph Fourier (UJF), Institut de Chimie Moleculaire de Grenoble (ICMG-FR 2607 CNRS), PolyNat Carnot institute, Arcane LabEx, domaine universitaire de Grenoble, Centre de Recherches sur les Macromolecules Vegetales - CERMAV-UPR 5301 CNRS (France); Stemmelen, Mylene; Lapinte, Vincent [Universite de Montpellier II, Institut Charles Gerhardt Montpellier (UMR 5253 CNRS-UM2-UM1-ENSCM), equipe ingenierie et architectures macromoleculaires (France); Dubreuil, Frederic [Universite Joseph Fourier (UJF), Institut de Chimie Moleculaire de Grenoble (ICMG-FR 2607 CNRS), PolyNat Carnot institute, Arcane LabEx, domaine universitaire de Grenoble, Centre de Recherches sur les Macromolecules Vegetales - CERMAV-UPR 5301 CNRS (France); Robin, Jean-Jacques [Universite de Montpellier II, Institut Charles Gerhardt Montpellier (UMR 5253 CNRS-UM2-UM1-ENSCM), equipe ingenierie et architectures macromoleculaires (France); and others

2013-06-15

The self-assembly in solution of original structures of amphiphilic partially natural copolymers based on polyoxazoline [more precisely poly(2-methyl-2-oxazoline) (POx)] and grape seed vegetable oil derivatives (linear, T-, and trident-structure) is investigated. The results show that such systems are found, using dynamic light scattering (DLS), to spontaneously self-organize into monomodal, narrow-size, and stable nanoparticles in aqueous medium. The obtained hydrodynamic diameters (D{sub h}) range from 8.6 to 32.5 nm. Specifically, such size increases strongly with increasing natural block (i.e., lipophilic species) length due to higher hydrophobic interactions (from 10.1 nm for C{sub 19} to 19.2 nm for C{sub 57}). Furthermore, increasing the polyoxazoline (i.e., hydrophilic block) length leads to a moderate linear increase of the D{sub h}-values. Therefore, the first-order size effect comes from the natural lipophilic block, whereas the characteristic size can be tuned more finely (i.e., in a second-order) by choosing appropriately the polyoxazoline length. The DLS results in terms of characteristic size are corroborated using nanoparticle tracking analysis (NTA), and also by atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging where well-defined spherical and individual nanoparticles exhibit a very good mechanical resistance upon drying. Moreover, changing the lipophilic block architecture from linear to T-shape, while keeping the same molar mass, generates a branching and thus a shrinking by a factor of 2 of the nanoparticle volume, as observed by DLS. In this paper, it is clearly shown that the self-assemblies of amphiphilic block copolymer obtained from grape seed vegetable oil derivatives (sustainable renewable resources) as well as their tunability are of great interest for biomass valorization at the nanoscale level [continuation of the article by Stemmelen et al. (Polym Chem 4:1445-1458, 2013)].Graphical Abstract

Amphiphilic copolymers based on polyoxazoline and grape seed vegetable oil derivatives: self-assemblies and dynamic light scattering

International Nuclear Information System (INIS)

Travelet, Christophe; Stemmelen, Mylène; Lapinte, Vincent; Dubreuil, Frédéric; Robin, Jean-Jacques

2013-01-01

The self-assembly in solution of original structures of amphiphilic partially natural copolymers based on polyoxazoline [more precisely poly(2-methyl-2-oxazoline) (POx)] and grape seed vegetable oil derivatives (linear, T-, and trident-structure) is investigated. The results show that such systems are found, using dynamic light scattering (DLS), to spontaneously self-organize into monomodal, narrow-size, and stable nanoparticles in aqueous medium. The obtained hydrodynamic diameters (D h ) range from 8.6 to 32.5 nm. Specifically, such size increases strongly with increasing natural block (i.e., lipophilic species) length due to higher hydrophobic interactions (from 10.1 nm for C 19 to 19.2 nm for C 57 ). Furthermore, increasing the polyoxazoline (i.e., hydrophilic block) length leads to a moderate linear increase of the D h -values. Therefore, the first-order size effect comes from the natural lipophilic block, whereas the characteristic size can be tuned more finely (i.e., in a second-order) by choosing appropriately the polyoxazoline length. The DLS results in terms of characteristic size are corroborated using nanoparticle tracking analysis (NTA), and also by atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging where well-defined spherical and individual nanoparticles exhibit a very good mechanical resistance upon drying. Moreover, changing the lipophilic block architecture from linear to T-shape, while keeping the same molar mass, generates a branching and thus a shrinking by a factor of 2 of the nanoparticle volume, as observed by DLS. In this paper, it is clearly shown that the self-assemblies of amphiphilic block copolymer obtained from grape seed vegetable oil derivatives (sustainable renewable resources) as well as their tunability are of great interest for biomass valorization at the nanoscale level [continuation of the article by Stemmelen et al. (Polym Chem 4:1445–1458, 2013)].Graphical AbstractAmphiphilic copolymers based

Human factors and safety issues associated with actinide retrieval from spent light water reactor fuel assemblies

International Nuclear Information System (INIS)

Spelt, P.F.

1992-01-01

A major problem in environmental restoration and waste management is the disposition of used fuel assemblies from the many light water reactors in the United States, which present a radiation hazard to those whose job is to dispose of them, with a similar threat to the general environment associated with long-term storage in fuel repositories around the country. Actinides resident in the fuel pins as a result of their use in reactor cores constitute a significant component of this hazard. Recently, the Department of Energy has initiated an Actinide Recycle Program to study the feasibility of using pyrochemical (molten salt) processes to recover actinides from the spent fuel assemblies of commercial reactors. This project concerns the application of robotics technology to the operation and maintenance functions of a plant whose objective is to recover actinides from spent fuel assemblies, and to dispose of the resulting hardware and chemical components from this process. Such a procedure involves a number of safety and human factors issues. The purpose of the project is to explore the use of robotics and artificial intelligence to facilitate accomplishment of the program goals while maintaining the safety of the humans doing the work and the integrity of the environment. This project will result in a graphic simulation on a Silicon Graphics workstation as a proof of principle demonstration of the feasibility of using robotics along with an intelligent operator interface. A major component of the operator-system interface is a hybrid artificial intelligence system developed at Oak Ridge National Laboratory, which combines artificial neural networks and an expert system into a hybrid, self-improving computer-based system interface. 10 refs

Penguin colony attendance under artificial lights for ecotourism.

Science.gov (United States)

Rodríguez, Airam; Holmberg, Ross; Dann, Peter; Chiaradia, André

2018-03-30

Wildlife watching is an emerging ecotourism activity around the world. In Australia and New Zealand, night viewing of little penguins attracts hundreds of thousands of visitors per year. As penguins start coming ashore after sunset, artificial lighting is essential to allow visitors to view them in the dark. This alteration of the nightscape warrants investigation for any potential effects of artificial lighting on penguin behavior. We experimentally tested how penguins respond to different light wavelengths (colors) and intensities to examine effects on the colony attendance behavior at two sites on Phillip Island, Australia. At one site, nocturnal artificial illumination has been used for penguin viewing for decades, whereas at the other site, the only light is from the natural night sky. Light intensity did not affect colony attendance behaviors of penguins at the artificially lit site, probably due to penguin habituation to lights. At the not previously lit site, penguins preferred lit paths over dark paths to reach their nests. Thus, artificial light might enhance penguin vision at night and consequently it might reduce predation risk and energetic costs of locomotion through obstacle and path detection. Although penguins are faithful to their path, they can be drawn to artificial lights at small spatial scale, so light pollution could attract penguins to undesirable lit areas. When artificial lighting is required, we recommend keeping lighting as dim and time-restricted as possible to mitigate any negative effects on the behavior of penguins and their natural habitat. © 2018 Wiley Periodicals, Inc.

Hybrid nanogenerators for low frequency vibration energy harvesting and self-powered wireless locating

Science.gov (United States)

Yuan, Ying; Zhang, Hulin; Wang, Jie; Xie, Yuhang; Khan, Saeed Ahmed; Jin, Long; Yan, Zhuocheng; Huang, Long; Pan, Taisong; Yang, Weiqing; Lin, Yuan

2018-01-01

Hybrid energy harvesters based on different physical effects is fascinating, but a rational design for multiple energy harvesting is challenging. In this work, a spring-magnet oscillator-based triboelectric-electromagnetic generator (EMG) with a solar cell cap is proposed. A power was produced by a triboelectric nanogenerator (TENG) and an EMG independently or simultaneously by using a shared spring-magnet oscillator. The oscillator configuration enables versatile energy harvesting with the excellent size scalability and self-packaged structure which can perform well at low frequency ranging from 3.5 to 5 Hz. The solar cell cap mounted above the oscillator can harvest solar energy. Under vibrations at the frequency of 4 Hz, the TENG and the EMG produced maximum output power of 5.46 nW cm-3 and 378.79 μW cm-3, respectively. The generated electricity by the hybrid nanogenerator can be stored in a capacitor or Li-ion battery, which is capable of powering a wireless locator for real-time locating data reporting to a personal cell phone. The light-weight and handy hybrid nanogenerator can directly light a caution light or play as a portable flashlight by shaking hands at night.

Self-assembled nanostructures

CERN Document Server

Zhang, Jin Z; Liu, Jun; Chen, Shaowei; Liu, Gang-yu

2003-01-01

Nanostructures refer to materials that have relevant dimensions on the nanometer length scales and reside in the mesoscopic regime between isolated atoms and molecules in bulk matter. These materials have unique physical properties that are distinctly different from bulk materials. Self-Assembled Nanostructures provides systematic coverage of basic nanomaterials science including materials assembly and synthesis, characterization, and application. Suitable for both beginners and experts, it balances the chemistry aspects of nanomaterials with physical principles. It also highlights nanomaterial-based architectures including assembled or self-assembled systems. Filled with in-depth discussion of important applications of nano-architectures as well as potential applications ranging from physical to chemical and biological systems, Self-Assembled Nanostructures is the essential reference or text for scientists involved with nanostructures.

Selective intercalation of six ligands molecules in a self-assembled triple helix

NARCIS (Netherlands)

Mateos timoneda, Miguel; Kerckhoffs, J.M.C.A.; Reinhoudt, David; Crego Calama, Mercedes

2007-01-01

The addition of a ligand molecule to an artificial self-assembled triple helix leads to the selective intercalation of two hydrogen-bonded trimers in specific binding pockets. Furthermore, the triple helix suffers large conformational rearrangements in order to accommodate the ligand molecules in a

Bio-Photoelectrochemical Solar Cells Incorporating Reaction Center and Reaction Center Plus Light Harvesting Complexes

Science.gov (United States)

Yaghoubi, Houman

onto Au electrodes via surface exposed cysteine residues. This resulted in photocurrent densities as large as ~600 nA cm-2 while still the incident photon to generated electron quantum efficiency was as low as %3 x 10-4. 2- The second approach is to immobilize wild type RCs of Rhodobacter sphaeroides on the surface of a Au underlying electrode using self-assembled monolayers of carboxylic acid terminated oligomers and cytochrome c charge mediating layers, with a preferential orientation from the primary electron donor site. This approach resulted in EQE of up to 0.06%, which showed 200 times efficiency improvement comparing to the first approach. In the third approach, instead of isolated protein complexes, RCs plus light harvesting (LH) complexes were employed for a better photon absorption. Direct attachment of RC-LH1 complexes on Au working electrodes, resulted in 0.21% EQE which showed 3.5 times efficiency improvement over the second approach (700 times higher than the first approach). The main impact of this work is the harnessing of biological RCs for efficient energy harvesting in man-made structures. Specifically, the results in this work will advance the application of RCs in devices for energy harvesting and will enable a better understanding of bio and nanomaterial interfaces, thereby advancing the application of biological materials in electronic devices. At the end, this work offers general guidelines that can serve to improve the performance of bio-hybrid solar cells.

Light extraction improvement of InGaN light-emitting diodes with large-area highly ordered ITO nanobowls photonic crystal via self-assembled nanosphere lithography

Directory of Open Access Journals (Sweden)

Kui Wu

2013-09-01

Full Text Available The InGaN multiple quantum well light-emitting diodes (LEDs with different sizes of indium-tin-oxide (ITO nanobowl photonic crystal (PhC structure has been fabricated using self-assembled monolayer nanosphere lithography. The light output power (LOP of PhC LEDs (at 350 mA has been enhanced by 63.5% and the emission divergence exhibits a 28.8° reduction compared to conventional LEDs without PhC structure. Current-Voltage curves have shown that these PhC structures on ITO layer will not degrade the LED electrical properties. The finite-difference time-domain simulation (FDTD has also been performed for light extraction and emission characteristics, which is consistent with the experimental results.

UV/Vis and NIR Light-Responsive Spiropyran Self-Assembled Monolayers

NARCIS (Netherlands)

Ivashenko, Oleksii; Herpt, Jochem T. van; Feringa, Ben L.; Rudolf, Petra; Browne, Wesley R.

2013-01-01

Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SEAS), and X-ray photoelectron spectroscopies (XPS). The SAMs

Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

KAUST Repository

Patil, Sachin

2016-06-29

Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible light irradiation leading up to 90% of gene silencing in live cells.

Atmosphere self-cleaning under humidity conditions and influence of the snowflakes and artificial light interaction for water dissociation simulated by the means of COMSOL

Science.gov (United States)

Cocean, A.; Cocean, I.; Cazacu, M. M.; Bulai, G.; Iacomi, F.; Gurlui, S.

2018-06-01

The self-cleaning of the atmosphere under humidity conditions is observed due to the change in emission intensity when chemical traces are investigated with DARLIOES - the advanced LIDAR based on space- and time-resolved RAMAN and breakdown spectroscopy in conditions of consistent humidity of atmosphere. The determination was performed during the night, in the wintertime under conditions of high humidity and snowfall, in urban area of Iasi. The change in chemical composition of the atmosphere detected was assumed to different chemical reactions involving presence of the water. Water dissociation that was registered during spectral measurements is explained by a simulation of the interaction between artificial light and snowflakes - virtually designed in a spherical geometry - in a wet air environment, using COMSOL Multiphysics software. The aim of the study is to explain the decrease or elimination of some of the toxic trace chemical compounds in the process of self-cleaning in other conditions than the sun light interaction for further finding application for air cleaning under artificial conditions.

A smart mobile pouch as a biomechanical energy harvester towards self-powered smart wireless power transfer applications.

Science.gov (United States)

Chandrasekhar, Arunkumar; Alluri, Nagamalleswara Rao; Sudhakaran, M S P; Mok, Young Sun; Kim, Sang-Jae

2017-07-20

A Smart Mobile Pouch Triboelectric Nanogenerator (SMP-TENG) is introduced as a promising eco-friendly approach for scavenging biomechanical energy for powering next generation intelligent devices and smart phones. This is a cost-effective and robust method for harvesting energy from human motion, by utilizing worn fabrics as a contact material. The SMP-TENG is capable of harvesting energy in two operational modes: lateral sliding and vertical contact and separation. Moreover, the SMP-TENG can also act as a self-powered emergency flashlight and self-powered pedometer during normal human motion. A wireless power transmission setup integrated with SMP-TENG is demonstrated. This upgrades the traditional energy harvesting device into a self-powered wireless power transfer SMP-TENG. The wirelessly transferred power can be used to charge a Li-ion battery and light LEDs. The SMP-TENG opens a wide range of opportunities in the field of self-powered devices and low maintenance energy harvesting systems for portable and wearable electronic gadgets.

Fabrication of bioinspired nanostructured materials via colloidal self-assembly

Science.gov (United States)

Huang, Wei-Han

Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher

The xanthophylls in light-harvesting complex II of higher plants: light harvesting and triplet quenching.

NARCIS (Netherlands)

Peterman, E.J.G.; Gradinaru, C.C.; Calkoen, F.; Borst, J.C.; van Grondelle, R.; van Amerongen, H.

1997-01-01

A spectral and functional assignment of the xanthophylls in monomeric and trimeric light-harvesting complex II of green plants has been obtained using HPLC analysis of the pigment composition, laser-flash induced triplet- minus-singlet, fluorescence excitation, and absorption spectra. It is shown

Fabrication of Thermo-Responsive Molecular Layers from Self-Assembling Elastin-Like Oligopeptides Containing Cell-Binding Domain for Tissue Engineering

Directory of Open Access Journals (Sweden)

Tomoyuki Koga

2015-01-01

Full Text Available Novel thermo-responsive elastin-like oligopeptides containing cell-binding epitope (Arg-Gly-Asp-Ser sequence; arginine-glycine-aspartic acid-serine (RGDS-elastin-like peptides (ELP and RGDS-deg-ELP; were newly prepared as building blocks of self-assembled molecular layer for artificial extra cellular matrix. A detailed analysis of the conformation of the oligo(ELPs in water and their self-assembling behavior onto hydrophobic surfaces were performed by using circular dichroism, Fourier transform infrared spectroscopy (FTIR, atomic force microscopy and water contact angle measurements. The experimental results revealed that both oligo(ELPs self-assembled onto hydrophobic surfaces and formed molecular layers based on their thermo-responsive conformational change from hydrous random coil to dehydrated β-turn structure. Effective cell adhesion and spreading behaviors were observed on these self-assembled oligo(ELP layers. In addition, attached cells were found to be recovered successfully as a cell-sheet by temperature-induced disassembly of oligo(ELP layer. This achievement provides an important insight to construct novel oligopeptide-based nano-surfaces for the design of smart artificial extra-cellular matrix.

CMOS indoor light energy harvesting system for wireless sensing applications

CERN Document Server

Ferreira Carvalho, Carlos Manuel

2016-01-01

This book discusses in detail the CMOS implementation of energy harvesting.  The authors describe an integrated, indoor light energy harvesting system, based on a controller circuit that dynamically and automatically adjusts its operation to meet the actual light circumstances of the environment where the system is placed.  The system is intended to power a sensor node, enabling an autonomous wireless sensor network (WSN). Although designed to cope with indoor light levels, the system is also able to work with higher levels, making it an all-round light energy harvesting system.  The discussion includes experimental data obtained from an integrated manufactured prototype, which in conjunction with a photovoltaic (PV) cell, serves as a proof of concept of the desired energy harvesting system.  ·         Discusses several energy sources which can be used to power energy harvesting systems and includes an overview of PV cell technologies  ·         Includes an introduction to voltage step-...

OligArch: A software tool to allow artificially expanded genetic information systems (AEGIS to guide the autonomous self-assembly of long DNA constructs from multiple DNA single strands

Directory of Open Access Journals (Sweden)

Kevin M. Bradley

2014-08-01

Full Text Available Synthetic biologists wishing to self-assemble large DNA (L-DNA constructs from small DNA fragments made by automated synthesis need fragments that hybridize predictably. Such predictability is difficult to obtain with nucleotides built from just the four standard nucleotides. Natural DNA's peculiar combination of strong and weak G:C and A:T pairs, the context-dependence of the strengths of those pairs, unimolecular strand folding that competes with desired interstrand hybridization, and non-Watson–Crick interactions available to standard DNA, all contribute to this unpredictability. In principle, adding extra nucleotides to the genetic alphabet can improve the predictability and reliability of autonomous DNA self-assembly, simply by increasing the information density of oligonucleotide sequences. These extra nucleotides are now available as parts of artificially expanded genetic information systems (AEGIS, and tools are now available to generate entirely standard DNA from AEGIS DNA during PCR amplification. Here, we describe the OligArch (for "oligonucleotide architecting" software, an application that permits synthetic biologists to engineer optimally self-assembling DNA constructs from both six- and eight-letter AEGIS alphabets. This software has been used to design oligonucleotides that self-assemble to form complete genes from 20 or more single-stranded synthetic oligonucleotides. OligArch is therefore a key element of a scalable and integrated infrastructure for the rapid and designed engineering of biology.

Light harvesting complexes of Chromera velia, photosynthetic relative of apicomplexan parasites

KAUST Repository

Tichý, Josef

2013-06-01

The structure and composition of the light harvesting complexes from the unicellular alga Chromera velia were studied by means of optical spectroscopy, biochemical and electron microscopy methods. Two different types of antennae systems were identified. One exhibited a molecular weight (18-19 kDa) similar to FCP (fucoxanthin chlorophyll protein) complexes from diatoms, however, single particle analysis and circular dichroism spectroscopy indicated similarity of this structure to the recently characterized XLH antenna of xanthophytes. In light of these data we denote this antenna complex CLH, for "Chromera Light Harvesting" complex. The other system was identified as the photosystem I with bound Light Harvesting Complexes (PSI-LHCr) related to the red algae LHCI antennae. The result of this study is the finding that C. velia, when grown in natural light conditions, possesses light harvesting antennae typically found in two different, evolutionary distant, groups of photosynthetic organisms. © 2013 Elsevier B.V. All rights reserved.

Fabrication and properties of light-emitting diodes based on self-assembled multilayers of poly(phenylene vinylene)

Science.gov (United States)

Fou, A. C.; Onitsuka, O.; Ferreira, M.; Rubner, M. F.; Hsieh, B. R.

1996-05-01

Light-emitting diodes have been fabricated from self-assembled multilayers of poly(p-phenylene vinylene) (PPV) and two different polyanions; polystyrene sulfonic acid (SPS) and polymethacrylic acid (PMA). The type of polyanion used to assemble the multilayer thin films was found to dramatically influence the behavior and performance of devices fabricated with indium tin oxide and aluminum electrodes. Light-emitting devices fabricated from PMA/PPV multilayers were found to exhibit luminance levels in the range of 20-60 cd/m2, a thickness dependent turn-on voltage and classical rectifying behavior with rectification ratios greater than 105. In sharp contrast, the devices based on SPS/PPV exhibited near symmetric current-voltage curves, thickness independent turn-on voltages and much lower luminance levels. The significant difference in device behavior observed between these two systems is primarily due to a doping effect induced either chemically or electrochemically by the sulfonic acid groups of SPS. It was also found that the performance of these devices depends on the type of layer that is in contact with the Al top electrode thereby making it possible to manipulate device efficiency at the molecular level.

Light and architecture. Daylight - artificial light - energy; Licht und Architektur. Tageslicht - Kunstlicht - Energie

Energy Technology Data Exchange (ETDEWEB)

Wambsganss, M. (ed.) [ip5 ingenieurpartnerschaft, Karlsruhe (Germany)]|[Fachhochschule Rosenheim (Germany)

2007-07-01

The symposium intends to provide scientific and technical fundamentals for room lighting with daylight. Daylight deflection systems and artificial light control systems were analyzed for this purpose, and a catalogue of criteria was established. Planners were given tools for projecting daylight control systems. Builder-owners received the fundamentals for economic assessment of combined daylight and artificial light illumination systems, while industrial producers obtained information for further development to maturity and for marketing of daylight-dependent artificial light control systems. (GL)

Micellar Self-Assembly of Recombinant Resilin-/Elastin-Like Block Copolypeptides.

Science.gov (United States)

Weitzhandler, Isaac; Dzuricky, Michael; Hoffmann, Ingo; Garcia Quiroz, Felipe; Gradzielski, Michael; Chilkoti, Ashutosh

2017-08-14

Reported here is the synthesis of perfectly sequence defined, monodisperse diblock copolypeptides of hydrophilic elastin-like and hydrophobic resilin-like polypeptide blocks and characterization of their self-assembly as a function of structural parameters by light scattering, cryo-TEM, and small-angle neutron scattering. A subset of these diblock copolypeptides exhibit lower critical solution temperature and upper critical solution temperature phase behavior and self-assemble into spherical or cylindrical micelles. Their morphologies are dictated by their chain length, degree of hydrophilicity, and hydrophilic weight fraction of the ELP block. We find that (1) independent of the length of the corona-forming ELP block there is a minimum threshold in the length of the RLP block below which self-assembly does not occur, but that once that threshold is crossed, (2) the RLP block length is a unique molecular parameter to independently tune self-assembly and (3) increasing the hydrophobicity of the corona-forming ELP drives a transition from spherical to cylindrical morphology. Unlike the self-assembly of purely ELP-based block copolymers, the self-assembly of RLP-ELPs can be understood by simple principles of polymer physics relating hydrophilic weight fraction and polymer-polymer and polymer-solvent interactions to micellar morphology, which is important as it provides a route for the de novo design of desired nanoscale morphologies from first principles.

Design principles of natural light-harvesting as revealed by single molecule spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Krüger, T.P.J., E-mail: tjaart.kruger@up.ac.za [Department of Physics, University of Pretoria, Private bag X20, Hatfield 0028 (South Africa); Grondelle, R. van [Department of Physics and Astronomy, VU University Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands)

2016-01-01

Biology offers a boundless source of adaptation, innovation, and inspiration. A wide range of photosynthetic organisms exist that are capable of harvesting solar light in an exceptionally efficient way, using abundant and low-cost materials. These natural light-harvesting complexes consist of proteins that strongly bind a high density of chromophores to capture solar photons and rapidly transfer the excitation energy to the photochemical reaction centre. The amount of harvested light is also delicately tuned to the level of solar radiation to maintain a constant energy throughput at the reaction centre and avoid the accumulation of the products of charge separation. In this Review, recent developments in the understanding of light-harvesting by plants will be discussed, based on results obtained from single molecule spectroscopy studies. Three design principles of the main light-harvesting antenna of plants will be highlighted: (a) fine, photoactive control over the intrinsic protein disorder to efficiently use intrinsically available thermal energy dissipation mechanisms; (b) the design of the protein microenvironment of a low-energy chromophore dimer to control the amount of shade absorption; (c) the design of the exciton manifold to ensure efficient funneling of the harvested light to the terminal emitter cluster.

From self-organization to self-assembly: a new materialism?

Science.gov (United States)

Vincent, Bernadette Bensaude

2016-09-01

While self-organization has been an integral part of academic discussions about the distinctive features of living organisms, at least since Immanuel Kant's Critique of Judgement, the term 'self-assembly' has only been used for a few decades as it became a hot research topic with the emergence of nanotechnology. Could it be considered as an attempt at reducing vital organization to a sort of assembly line of molecules? Considering the context of research on self-assembly I argue that the shift of attention from self-organization to self-assembly does not really challenge the boundary between chemistry and biology. Self-assembly was first and foremost investigated in an engineering context as a strategy for manufacturing without human intervention and did not raise new perspectives on the emergence of vital organization itself. However self-assembly implies metaphysical assumptions that this paper tries to disentangle. It first describes the emergence of self-assembly as a research field in the context of materials science and nanotechnology. The second section outlines the metaphysical implications and will emphasize a sharp contrast between the ontology underlying two practices of self-assembly developed under the umbrella of synthetic biology. And unexpectedly, we shall see that chemists are less on the reductionist side than most synthetic biologists. Finally, the third section ventures some reflections on the kind of design involved in self-assembly practices.

Molecular Motions in Functional Self-Assembled Nanostructures

Directory of Open Access Journals (Sweden)

Jean-Marc Saiter

2013-01-01

Full Text Available The construction of “smart” materials able to perform specific functions at the molecular scale through the application of various stimuli is highly attractive but still challenging. The most recent applications indicate that the outstanding flexibility of self-assembled architectures can be employed as a powerful tool for the development of innovative molecular devices, functional surfaces and smart nanomaterials. Structural flexibility of these materials is known to be conferred by weak intermolecular forces involved in self-assembly strategies. However, some fundamental mechanisms responsible for conformational lability remain unexplored. Furthermore, the role played by stronger bonds, such as coordination, ionic and covalent bonding, is sometimes neglected while they can be employed readily to produce mechanically robust but also chemically reversible structures. In this review, recent applications of structural flexibility and molecular motions in self-assembled nanostructures are discussed. Special focus is given to advanced materials exhibiting significant performance changes after an external stimulus is applied, such as light exposure, pH variation, heat treatment or electromagnetic field. The crucial role played by strong intra- and weak intermolecular interactions on structural lability and responsiveness is highlighted.

Role of self-assembly coated Er3+: YAlO3/TiO2 in intimate coupling of visible-light-responsive photocatalysis and biodegradation reactions

International Nuclear Information System (INIS)

Dong, Shanshan; Dong, Shuangshi; Tian, Xiadi; Xu, Zhengxue; Ma, Dongmei; Cui, Bin; Ren, Nanqi; Rittmann, Bruce E.

2016-01-01

Highlights: • First study on intimate coupling of photocatalysis & biodegradation by visible light. • Self-assembly was used to coat Er 3+ : YAlO 3 /TiO 2 on the sponge carriers. • Fewer accumulated intermediates & higher phenol removal for VPCB than VPC or B alone. • Self-regulation in VPCB contributes to the high degradation efficiency. - Abstract: Conventionally used ultraviolet light can result in dissolved organic carbon (DOC) increasing and biofilm damage in intimate coupling of photocatalysis and biodegradation (ICPB). Visible-light-responsive photocatalysis offers an alternative for achieving ICPB. In this study, composite-cubes were developed using self-assembly to coat a thin and even layer of visible-light-responsive photocatalyst (Er 3+ : YAlO 3 /TiO 2 ) on sponge-type carriers, followed by biofilm cultivation. The degradations of phenol (50 mg L −1 ) were compared for four protocols in circulating beds: adsorption (AD), visible-light-responsive photocatalysis (VPC), biodegradation (B), and intimately coupled visible-light-responsive photocatalysis and biodegradation (VPCB). The phenol and DOC removal efficiencies using VPCB in 16 h were 99.8% and 65.2%, respectively, i.e., higher than those achieved using VPC (71.6% and 50.0%) or B (99.4% and 58.2%). The phenol removal of 96.3% could be obtained even after 3 additional cycles. The 6.17-min intermediate detected by HPLC, continuously accumulated for VPC, appeared at 1–6 h and then was completely removed for VPCB in 10 h. ICPB was further illustrated in that most of the biofilm was protected in the carrier interiors, with less protection on the carrier exterior in VPCB. A self-regulation mechanism that helped photocatalyst exposure to visible-light irradiation was identified, promoting the combined photocatalysis and biodegradation.

Artificial light and quantum order in systems of screened dipoles

International Nuclear Information System (INIS)

Wen Xiaogang

2003-01-01

The origin of light is an unsolved mystery in nature. Recently, it was suggested that light may originate from a new kind of order, quantum order. To test this idea in experiments, we study systems of screened magnetic/electric dipoles in two-dimensional (2D) and 3D lattices. We show that our models contain an artificial light-a photonlike collective excitation. We discuss how to design realistic devices that realize our models. We show that the 'speed of light' and the 'fine-structure constant' of the artificial light can be tuned in our models. The properties of artificial atoms (bound states of pairs of artificial charges) are also discussed. The existence of artificial light (as well as artificial electron) in condensed-matter systems suggests that elementary particles, such as light and electron, may not be elementary. They may be collective excitations of quantum order in our vacuum. In our model, light is realized as a fluctuation of string-nets and charges as the ends of open strings (or nodes of string nets)

Three-Dimensionally Isotropic Negative Refractive Index Materials from Block Copolymer Self-Assembled Chiral Gyroid Networks

KAUST Repository

Hur, Kahyun

2011-10-17

Metamaterials are engineered artificial materials that offer new functionalities such as super-resolution imaging and cloaking. Calculations of the photonic properties of three-dimensionally isotropic metamaterials with cubic double gyroid and alternating gyroid morphologies from block copolymer self-assembly are presented.

Chemical reactions directed Peptide self-assembly.

Science.gov (United States)

Rasale, Dnyaneshwar B; Das, Apurba K

2015-05-13

Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

Artificial light alters natural regimes of night-time sky brightness

Science.gov (United States)

Davies, Thomas W.; Bennie, Jonathan; Inger, Richard; Gaston, Kevin J.

2013-01-01

Artificial light is globally one of the most widely distributed forms of anthropogenic pollution. However, while both the nature and ecological effects of direct artificial lighting are increasingly well documented, those of artificial sky glow have received little attention. We investigated how city lights alter natural regimes of lunar sky brightness using a novel ten month time series of measurements recorded across a gradient of increasing light pollution. In the city, artificial lights increased sky brightness to levels six times above those recorded in rural locations, nine and twenty kilometers away. Artificial lighting masked natural monthly and seasonal regimes of lunar sky brightness in the city, and increased the number and annual regime of full moon equivalent hours available to organisms during the night. The changes have potentially profound ecological consequences.

Impact of cationic surfactant on the self-assembly of sodium caseinate.

Science.gov (United States)

Vinceković, Marko; Curlin, Marija; Jurašin, Darija

2014-08-27

The impact of a cationic surfactant, dodecylammonium chloride (DDACl), on the self-assembly of sodium caseinate (SC) has been investigated by light scattering, zeta potential, and rheological measurements as well as by microscopy (transmission electron and confocal laser scanning microscopy). In SC dilute solutions concentration-dependent self-assembly proceeds through the formation of spherical associates and their aggregation into elongated structures composed of connected spheres. DDACl interacts with SC via its hydrophilic and hydrophobic groups, inducing changes in SC self-assembled structures. These changes strongly depend on the surfactant aggregation states (monomeric or micellar) as well as concentration ratio of both components, leading to the formation of soluble and insoluble complexes of nano- to microdimensions. DDACl monomers interact with SC self-assembled entities in a different way compared to their micelles. Surfactant monomers form soluble complexes (similar to surfactant mixed micelles) at lower SC concentration but insoluble gelatinous complexes at higher SC concentration. At surfactant micellar concentration soluble complexes with casein chains wrapped around surfactant micelles are formed. This study suggests that the use of proper cationic surfactant concentration will allow modification and control of structural changes of SC self-assembled entities.

Self-Assembly of Organic Ferroelectrics by Evaporative Dewetting: A Case of β-Glycine.

Science.gov (United States)

Seyedhosseini, Ensieh; Romanyuk, Konstantin; Vasileva, Daria; Vasilev, Semen; Nuraeva, Alla; Zelenovskiy, Pavel; Ivanov, Maxim; Morozovska, Anna N; Shur, Vladimir Ya; Lu, Haidong; Gruverman, Alexei; Kholkin, Andrei L

2017-06-14

Self-assembly of ferroelectric materials attracts significant interest because it offers a promising fabrication route to novel structures useful for microelectronic devices such as nonvolatile memories, integrated sensors/actuators, or energy harvesters. In this work, we demonstrate a novel approach for self-assembly of organic ferroelectrics (as exemplified by ferroelectric β-glycine) using evaporative dewetting, which allows forming quasi-regular arrays of nano- and microislands with preferred orientation of polarization axes. Surprisingly, self-assembled islands are crystallographically oriented in a radial direction from the center of organic "grains" formed during dewetting process. The kinetics of dewetting process follows the t -1/2 law, which is responsible for the observed polygon shape of the grain boundaries and island coverage as a function of radial position. The polarization in ferroelectric islands of β-glycine is parallel to the substrate and switchable under a relatively small dc voltage applied by the conducting tip of piezoresponse force microscope. Significant size effect on polarization is observed and explained within the Landau-Ginzburg-Devonshire phenomenological formalism.

Detailed simulations of lighting conditions in office rooms lit by daylight and artificial light

DEFF Research Database (Denmark)

Iversen, Anne

In this thesis the effect on the annual artificial lighting demand is investigated by employing detailed simulations of lighting conditions in office rooms lit by daylight and artificial. The simulations of the artificial lighting demand is accomplished through daylight simulations in Radiance....... The detailed simulations includes studies of the resolution of different weather data sets in climate-based daylight modeling. Furthermore, influence of the electrical lighting demand by simulating with dynamic occupancy patterns is studied. Finally the thesis explores the influence of obstructions in an urban...... canyon on the daylight availability within the buildings, and hence on the energy consumption for artificial lights. The results from the thesis demonstrates that the effect on the outcome of the daylight simulations when simulating with typical weather data files for the location of Copenhagen...

Combined scanning probe and light scattering characterization of multi-stage self-assembly of targeted liposome-based delivery systems

International Nuclear Information System (INIS)

Farkas, N; Dagata, J A; Yang, C; Rait, A; Pirollo, K F; Chang, E H

2011-01-01

The mean size and size distribution of a targeted nanoparticle delivery system (NDS) strongly influences the intrinsic stability and functionality of this molecular complex, affects its performance as a systemic drug delivery platform and ultimately determines its efficacy toward early detection and treatment of cancer. Since its components undergo significant reorganization during multiple stages of self-assembly, it is essential to monitor the size and stability of the complex throughout the NDS formulation in order to ensure its potency and manufacturability prior to entering clinical trials. This work combines scanning probe microscopy (SPM) and dynamic light scattering (DLS) techniques to obtain quantitative and reliable size measurements of the NDS, and to investigate how variations in the NDS formulation or self-assembly process impact the size, structure and functionality of the complex with various therapeutic and diagnostic agent payloads. These combined SPM and DLS methods, when implemented at an early stage of the NDS formulation, present a potential measurement approach to facilitate drug discovery and development, optimization and quality control during manufacturing of the NDS

USE OF ARTIFICIAL LIGHT IN MUSHROOM CULTIVATION

Directory of Open Access Journals (Sweden)

N. L. Poyedinok

2013-12-01

Full Text Available Artificial light is used in greenhouses to increase productivity and quality of agricultural and ornamental plants. Despite the awareness of the fact that light also plays important role in the life of nonhotosynthetic organisms, such as fungi, its using in their biotechnology cultivation is currently limited. Science has quite a large amount information about the influence of artificial light of different nature on morphogenesis, metabolic processes and productivity of more than 100 species of fungi, many of which are valuable producers of biologically active compounds. Themechanisms of photoreactions of various fungi, which is an integral part of a purposeful photoregulation their activity in biotechnological processes are described. The analysis of the researches and of the experience of their practical application allows predicting potential of using artificial light in mushroom growing industry, as well as in creating highly productive, environmentally clean technologies of targeted synthesis of the final product.

Self-Assembly of Infinite Structures

Directory of Open Access Journals (Sweden)

Scott M. Summers

2009-06-01

Full Text Available We review some recent results related to the self-assembly of infinite structures in the Tile Assembly Model. These results include impossibility results, as well as novel tile assembly systems in which shapes and patterns that represent various notions of computation self-assemble. Several open questions are also presented and motivated.

Mechanical Self-Assembly Science and Applications

CERN Document Server

2013-01-01

Mechanical Self-Assembly: Science and Applications introduces a novel category of self-assembly driven by mechanical forces. This book discusses self-assembly in various types of small material structures including thin films, surfaces, and micro- and nano-wires, as well as the practice's potential application in micro and nanoelectronics, MEMS/NEMS, and biomedical engineering. The mechanical self-assembly process is inherently quick, simple, and cost-effective, as well as accessible to a large number of materials, such as curved surfaces for forming three-dimensional small structures. Mechanical self-assembly is complementary to, and sometimes offer advantages over, the traditional micro- and nano-fabrication. This book also: Presents a highly original aspect of the science of self-assembly Describes the novel methods of mechanical assembly used to fabricate a variety of new three-dimensional material structures in simple and cost-effective ways Provides simple insights to a number of biological systems and ...

Energy transfer dynamics from individual semiconductor nanoantennae to dye molecules with implication to light-harvesting nanosystems

Science.gov (United States)

Shan, Guangcun; Hu, Mingjun; Yan, Ze; Li, Xin; Huang, Wei

2018-03-01

Semiconductor nanocrystals can be used as nanoscale optical antennae to photoexcite individual dye molecules in an ensemble via energy transfer mechanism. The theoretical framework developed by Förster and others describes how electronic excitation migrates in the photosynthetic apparatus of plants, algae, and bacteria from light absorbing pigments to reaction centers where light energy is utilized for the eventual conversion into chemical energy. Herein we investigate the effect of the average donor-acceptor spacing on the time-resolved fluorescence intensity and dynamics of single donor-acceptor pairs with the dye acceptor concentration decreasing by using quantum Monte-Carlo simulation of FRET dynamics. Our results validated that the spatial disorder controlling the microscopic energy transfer rates accounts for the scatter in donor fluorescence lifetimes and intensities, which provides a new design guideline for artificial light-harvesting nanosystems.

Enhancing Self-Assembly in Cellulose Nanocrystal Suspensions Using High-Permittivity Solvents.

Science.gov (United States)

Bruckner, Johanna R; Kuhnhold, Anja; Honorato-Rios, Camila; Schilling, Tanja; Lagerwall, Jan P F

2016-09-27

Helical liquid crystal self-assembly in suspensions of cellulose nanocrystals (CNCs), bioderived nanorods exhibiting excellent mechanical and optical properties, opens attractive routes to sustainable production of advanced functional materials. For convenience, in most studies until now, the CNCs were suspended in water, leaving a knowledge gap concerning the influence of the solvent. Using a novel approach for aggregation-free solvent exchange in CNC suspensions, here we show that protic solvents with a high dielectric permittivity εr significantly speed up self-assembly (from days to hours) at high CNC mass fraction and reduce the concentration dependence of the helix period (variation reducing from more than 30 μm to less than 1 μm). Moreover, our computer simulations indicate that the degree of order at constant CNC content increases with increasing εr, leading to a shorter pitch and a reduced threshold for liquid crystallinity. In low-εr solvents, the onset of long-range orientational order is coupled to kinetic arrest, preventing the formation of a helical superstructure. Our results show that the choice of solvent is a powerful parameter for tuning the behavior of CNC suspensions, enhancing our ability to control the self-assembly and thereby harvesting valuable novel cellulose-based materials.

Self-assembled nanomaterials for photoacoustic imaging

Science.gov (United States)

Wang, Lei; Yang, Pei-Pei; Zhao, Xiao-Xiao; Wang, Hao

2016-01-01

In recent years, extensive endeavors have been paid to construct functional self-assembled nanomaterials for various applications such as catalysis, separation, energy and biomedicines. To date, different strategies have been developed for preparing nanomaterials with diversified structures and functionalities via fine tuning of self-assembled building blocks. In terms of biomedical applications, bioimaging technologies are urgently calling for high-efficient probes/contrast agents for high-performance bioimaging. Photoacoustic (PA) imaging is an emerging whole-body imaging modality offering high spatial resolution, deep penetration and high contrast in vivo. The self-assembled nanomaterials show high stability in vivo, specific tolerance to sterilization and prolonged half-life stability and desirable targeting properties, which is a kind of promising PA contrast agents for biomedical imaging. Herein, we focus on summarizing recent advances in smart self-assembled nanomaterials with NIR absorption as PA contrast agents for biomedical imaging. According to the preparation strategy of the contrast agents, the self-assembled nanomaterials are categorized into two groups, i.e., the ex situ and in situ self-assembled nanomaterials. The driving forces, assembly modes and regulation of PA properties of self-assembled nanomaterials and their applications for long-term imaging, enzyme activity detection and aggregation-induced retention (AIR) effect for diagnosis and therapy are emphasized. Finally, we conclude with an outlook towards future developments of self-assembled nanomaterials for PA imaging.

Self-assembled nanomaterials for photoacoustic imaging.

Science.gov (United States)

Wang, Lei; Yang, Pei-Pei; Zhao, Xiao-Xiao; Wang, Hao

2016-02-07

In recent years, extensive endeavors have been paid to construct functional self-assembled nanomaterials for various applications such as catalysis, separation, energy and biomedicines. To date, different strategies have been developed for preparing nanomaterials with diversified structures and functionalities via fine tuning of self-assembled building blocks. In terms of biomedical applications, bioimaging technologies are urgently calling for high-efficient probes/contrast agents for high-performance bioimaging. Photoacoustic (PA) imaging is an emerging whole-body imaging modality offering high spatial resolution, deep penetration and high contrast in vivo. The self-assembled nanomaterials show high stability in vivo, specific tolerance to sterilization and prolonged half-life stability and desirable targeting properties, which is a kind of promising PA contrast agents for biomedical imaging. Herein, we focus on summarizing recent advances in smart self-assembled nanomaterials with NIR absorption as PA contrast agents for biomedical imaging. According to the preparation strategy of the contrast agents, the self-assembled nanomaterials are categorized into two groups, i.e., the ex situ and in situ self-assembled nanomaterials. The driving forces, assembly modes and regulation of PA properties of self-assembled nanomaterials and their applications for long-term imaging, enzyme activity detection and aggregation-induced retention (AIR) effect for diagnosis and therapy are emphasized. Finally, we conclude with an outlook towards future developments of self-assembled nanomaterials for PA imaging.

Migratory bats respond to artificial green light with positive phototaxis.

Directory of Open Access Journals (Sweden)

Christian C Voigt

Full Text Available Artificial light at night is spreading worldwide at unprecedented rates, exposing strictly nocturnal animals such as bats to a novel anthropogenic stressor. Previous studies about the effect of artificial light on bats focused almost exclusively on non-migratory species, yet migratory animals such as birds are known to be largely affected by light pollution. Thus, we conducted a field experiment to evaluate if bat migration is affected by artificial light at night. In late summer, we presented artificial green light of 520 nm wavelength to bats that were migrating south along the shoreline of the Baltic Sea. Using a light on-off treatment, we observed that the activity of Pipistrellus nathusii and P. pygmaeus, the two most abundant migratory species at our site, increased by more than 50% in the light-on compared to the light-off treatment. We observed an increased number of feeding buzzes during the light-on compared to the light-off treatment for P. nathusii. However, feeding activity was low in general and did not increase disproportionately during the light-on treatment in relation to the overall echolocation call activity of bats. Further, P. nathusii were attracted towards the green light at a distance of about 23 m, which is way beyond the echolocation detection range for insects of Nathusius' bats. We therefore infer that migratory bats were not attracted to artificial green light because of high insect densities, but instead by positive phototaxis. We conclude that artificial light at night may potentially impact bat migration in a yet unrecognized way.

3D Programmable Micro Self Assembly

National Research Council Canada - National Science Library

Bohringer, Karl F; Parviz, Babak A; Klavins, Eric

2005-01-01

.... We have developed a "self assembly tool box" consisting of a range of methods for micro-scale self-assembly in 2D and 3D We have shown physical demonstrations of simple 3D self-assemblies which lead...

Natural strategies for photosynthetic light harvesting

NARCIS (Netherlands)

Croce, R.; van Amerongen, H.

2014-01-01

Photosynthetic organisms are crucial for life on Earth as they provide food and oxygen and are at the basis of most energy resources. They have a large variety of light-harvesting strategies that allow them to live nearly everywhere where sunlight can penetrate. They have adapted their pigmentation

Molecular self-assembly advances and applications

CERN Document Server

Dequan, Alex Li

2012-01-01

In the past several decades, molecular self-assembly has emerged as one of the main themes in chemistry, biology, and materials science. This book compiles and details cutting-edge research in molecular assemblies ranging from self-organized peptide nanostructures and DNA-chromophore foldamers to supramolecular systems and metal-directed assemblies, even to nanocrystal superparticles and self-assembled microdevices

Synthesis and Self-Assembly of Chiral Cylindrical Molecular Complexes: Functional Heterogeneous Liquid-Solid Materials Formed by Helicene Oligomers

Directory of Open Access Journals (Sweden)

Nozomi Saito

2018-01-01

Full Text Available Chiral cylindrical molecular complexes of homo- and hetero-double-helices derived from helicene oligomers self-assemble in solution, providing functional heterogeneous liquid-solid materials. Gels and liotropic liquid crystals are formed by fibril self-assembly in solution; molecular monolayers and fibril films are formed by self-assembly on solid surfaces; gels containing gold nanoparticles emit light; silica nanoparticles aggregate and adsorb double-helices. Notable dynamics appears during self-assembly, including multistep self-assembly, solid surface catalyzed double-helix formation, sigmoidal and stairwise kinetics, molecular recognition of nanoparticles, discontinuous self-assembly, materials clocking, chiral symmetry breaking and homogeneous-heterogeneous transitions. These phenomena are derived from strong intercomplex interactions of chiral cylindrical molecular complexes.

Nonequilibrium carrier dynamics in self-assembled InGaAs quantum dots

International Nuclear Information System (INIS)

Wesseli, M.; Ruppert, C.; Trumm, S.; Betz, M.; Krenner, H.J.; Finley, J.J.

2006-01-01

Carrier dynamics in InGaAs/GaAs quantum dots is analyzed with highly sensitive femtosecond transmission spectroscopy. In a first step, measurements on a large ensemble of nanoislands reveal the dynamical electronic filling of quantum dots from the surrounding wetting layer. Most interestingly, we find a spin-preserving phonon mediated scattering into fully localized states within a few picoseconds. Then, individual artificial atoms are isolated with metallic shadow masks. For the first time, a single self-assembled quantum dot is addressed in an ultrafast transmission experiment. We find bleaching signals in the order of 10 -5 that arise from individual interband transitions of one quantum dot. As a result, we have developed an ultrafast optical tool for both manipulation and read-out of a single self-assembled quantum dot. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Complex epsilon-near-zero metamaterials for broadband light harvesting systems

KAUST Repository

Bonifazi, Marcella; Tian, Yi; Fratalocchi, Andrea

2018-01-01

We engineered an epsilon-near-zero (ENZ) material from suitably disordered metallic nanostructures. We create a new class of dispersionless composite materials that efficiently harnesses white light. By means of Atomic Force Microscopy (AFM) and Photoluminescence (PLE) measurements we experimentally demonstrate that this nanomaterial increases up to a record value the absorption of ultra-thin light harvesting films at visible and infrared wavelengths. Moreover, we obtained a 170% broadband increase of the external quantum efficiency (EQE) when these ENZ materials are inserted in an energy-harvesting module. We developed an inexpensive electrochemical deposition process that enables large-scale production of this material for energy-harvesting applications.

Complex epsilon-near-zero metamaterials for broadband light harvesting systems

KAUST Repository

Bonifazi, Marcella

2018-02-17

We engineered an epsilon-near-zero (ENZ) material from suitably disordered metallic nanostructures. We create a new class of dispersionless composite materials that efficiently harnesses white light. By means of Atomic Force Microscopy (AFM) and Photoluminescence (PLE) measurements we experimentally demonstrate that this nanomaterial increases up to a record value the absorption of ultra-thin light harvesting films at visible and infrared wavelengths. Moreover, we obtained a 170% broadband increase of the external quantum efficiency (EQE) when these ENZ materials are inserted in an energy-harvesting module. We developed an inexpensive electrochemical deposition process that enables large-scale production of this material for energy-harvesting applications.

Water ordering controls the dynamic equilibrium of micelle-fibre formation in self-assembly of peptide amphiphiles.

Science.gov (United States)

Deshmukh, Sanket A; Solomon, Lee A; Kamath, Ganesh; Fry, H Christopher; Sankaranarayanan, Subramanian K R S

2016-08-24

Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides remains elusive. Here, we use a multistage atomistic-coarse-grained approach, complemented by circular dichroism/infrared spectroscopy and dynamic light scattering experiments to highlight the dual nature of water in driving the self-assembly of peptide amphiphiles (PAs). We show computationally that water cage formation and breakage near the hydrophobic groups control the fusion dynamics and aggregation of PAs in the micellar stage. Simulations also suggest that enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards the fibre phase and stimulates structure and order during the PA assembly into nanofibres. Experiments validate our simulation findings; the measured infrared O-H bond stretching frequency is reminiscent of an ice-like bond which suggests that the solvated water becomes increasingly ordered with time in the assembled peptide network, thus shedding light on the role of water in a self-assembly process.

Single-molecule exploration of photoprotective mechanisms in light-harvesting complexes

Science.gov (United States)

Yang, Hsiang-Yu; Schlau-Cohen, Gabriela S.; Gwizdala, Michal; Krüger, Tjaart; Xu, Pengqi; Croce, Roberta; van Grondelle, Rienk; Moerner, W. E.

2015-03-01

Plants harvest sunlight by converting light energy to electron flow through the primary events in photosynthesis. One important question is how the light harvesting machinery adapts to fluctuating sunlight intensity. As a result of various regulatory processes, efficient light harvesting and photoprotection are balanced. Some of the biological steps in the photoprotective processes have been extensively studied and physiological regulatory factors have been identified. For example, the effect of lumen pH in changing carotenoid composition has been explored. However, the importance of photophysical dynamics in the initial light-harvesting steps and its relation to photoprotection remain poorly understood. Conformational and excited-state dynamics of multi-chromophore pigment-protein complexes are often difficult to study and limited information can be extracted from ensemble-averaged measurements. To address the problem, we use the Anti-Brownian ELectrokinetic (ABEL) trap to investigate the fluorescence from individual copies of light-harvesting complex II (LHCII), the primary antenna protein in higher plants, in a solution-phase environment. Perturbative surface immobilization or encapsulation schemes are avoided, and therefore the intrinsic dynamics and heterogeneity in the fluorescence of individual proteins are revealed. We perform simultaneous measurements of fluorescence intensity (brightness), excited-state lifetime, and emission spectrum of single trapped proteins. By analyzing the correlated changes between these observables, we identify forms of LHCII with different fluorescence intensities and excited-state lifetimes. The distinct forms may be associated with different energy dissipation mechanisms in the energy transfer chain. Changes of relative populations in response to pH and carotenoid composition are observed, which may extend our understanding of the molecular mechanisms of photoprotection.

Protein Structural Deformation Induced Lifetime Shortening of Photosynthetic Bacteria Light-Harvesting Complex LH2 Excited State

OpenAIRE

Chen, Xing-Hai; Zhang, Lei; Weng, Yu-Xiang; Du, Lu-Chao; Ye, Man-Ping; Yang, Guo-Zhen; Fujii, Ritsuko; Rondonuwu, Ferdy S.; Koyama, Yasushi; Wu, Yi-Shi; Zhang, J. P.

2005-01-01

Photosynthetic bacterial light-harvesting antenna complex LH2 was immobilized on the surface of TiO2 nanoparticles in the colloidal solution. The LH2/TiO2 assembly was investigated by the time-resolved spectroscopic methods. The excited-state lifetimes for carotenoid-containing and carotenoidless LH2 have been measured, showing a decrease in the excited-state lifetime of B850 when LH2 was immobilized on TiO2. The possibility that the decrease of the LH2 excited-state lifetime being caused by ...

Fabrication of Scalable Indoor Light Energy Harvester and Study for Agricultural IoT Applications

International Nuclear Information System (INIS)

Watanabe, M; Nakamura, A; Kunii, A; Kusano, K; Futagawa, M

2015-01-01

A scalable indoor light energy harvester was fabricated by microelectromechanical system (MEMS) and printing hybrid technology and evaluated for agricultural IoT applications under different environmental input power density conditions, such as outdoor farming under the sun, greenhouse farming under scattered lighting, and a plant factory under LEDs. We fabricated and evaluated a dye- sensitized-type solar cell (DSC) as a low cost and “scalable” optical harvester device. We developed a transparent conductive oxide (TCO)-less process with a honeycomb metal mesh substrate fabricated by MEMS technology. In terms of the electrical and optical properties, we achieved scalable harvester output power by cell area sizing. Second, we evaluated the dependence of the input power scalable characteristics on the input light intensity, spectrum distribution, and light inlet direction angle, because harvested environmental input power is unstable. The TiO 2 fabrication relied on nanoimprint technology, which was designed for optical optimization and fabrication, and we confirmed that the harvesters are robust to a variety of environments. Finally, we studied optical energy harvesting applications for agricultural IoT systems. These scalable indoor light harvesters could be used in many applications and situations in smart agriculture. (paper)

Fabrication of Scalable Indoor Light Energy Harvester and Study for Agricultural IoT Applications

Science.gov (United States)

Watanabe, M.; Nakamura, A.; Kunii, A.; Kusano, K.; Futagawa, M.

2015-12-01

A scalable indoor light energy harvester was fabricated by microelectromechanical system (MEMS) and printing hybrid technology and evaluated for agricultural IoT applications under different environmental input power density conditions, such as outdoor farming under the sun, greenhouse farming under scattered lighting, and a plant factory under LEDs. We fabricated and evaluated a dye- sensitized-type solar cell (DSC) as a low cost and “scalable” optical harvester device. We developed a transparent conductive oxide (TCO)-less process with a honeycomb metal mesh substrate fabricated by MEMS technology. In terms of the electrical and optical properties, we achieved scalable harvester output power by cell area sizing. Second, we evaluated the dependence of the input power scalable characteristics on the input light intensity, spectrum distribution, and light inlet direction angle, because harvested environmental input power is unstable. The TiO2 fabrication relied on nanoimprint technology, which was designed for optical optimization and fabrication, and we confirmed that the harvesters are robust to a variety of environments. Finally, we studied optical energy harvesting applications for agricultural IoT systems. These scalable indoor light harvesters could be used in many applications and situations in smart agriculture.

Strategies for Efficient Charge Separation and Transfer in Artificial Photosynthesis of Solar Fuels.

Science.gov (United States)

Xu, Yuxing; Li, Ailong; Yao, Tingting; Ma, Changtong; Zhang, Xianwen; Shah, Jafar Hussain; Han, Hongxian

2017-11-23

Converting sunlight to solar fuels by artificial photosynthesis is an innovative science and technology for renewable energy. Light harvesting, photogenerated charge separation and transfer (CST), and catalytic reactions are the three primary steps in the processes involved in the conversion of solar energy to chemical energy (SE-CE). Among the processes, CST is the key "energy pump and delivery" step in determining the overall solar-energy conversion efficiency. Efficient CST is always high priority in designing and assembling artificial photosynthesis systems for solar-fuel production. This Review not only introduces the fundamental strategies for CST but also the combinatory application of these strategies to five types of the most-investigated semiconductor-based artificial photosynthesis systems: particulate, Z-scheme, hybrid, photoelectrochemical, and photovoltaics-assisted systems. We show that artificial photosynthesis systems with high SE-CE efficiency can be rationally designed and constructed through combinatory application of these strategies, setting a promising blueprint for the future of solar fuels. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Light-Controlled Swarming and Assembly of Colloidal Particles

Directory of Open Access Journals (Sweden)

Jianhua Zhang

2018-02-01

Full Text Available Swarms and assemblies are ubiquitous in nature and they can perform complex collective behaviors and cooperative functions that they cannot accomplish individually. In response to light, some colloidal particles (CPs, including light active and passive CPs, can mimic their counterparts in nature and organize into complex structures that exhibit collective functions with remote controllability and high temporospatial precision. In this review, we firstly analyze the structural characteristics of swarms and assemblies of CPs and point out that light-controlled swarming and assembly of CPs are generally achieved by constructing light-responsive interactions between CPs. Then, we summarize in detail the recent advances in light-controlled swarming and assembly of CPs based on the interactions arisen from optical forces, photochemical reactions, photothermal effects, and photoisomerizations, as well as their potential applications. In the end, we also envision some challenges and future prospects of light-controlled swarming and assembly of CPs. With the increasing innovations in mechanisms and control strategies with easy operation, low cost, and arbitrary applicability, light-controlled swarming and assembly of CPs may be employed to manufacture programmable materials and reconfigurable robots for cooperative grasping, collective cargo transportation, and micro- and nanoengineering.

Self-Assembly, Pattern Formation and Growth Phenomena in Nano-Systems

CERN Document Server

Nepomnyashchy, Alexander A

2006-01-01

Nano-science and nano-technology are rapidly developing scientific and technological areas that deal with physical, chemical and biological processes that occur on nano-meter scale – one millionth of a millimeter. Self-organization and pattern formation play crucial role on nano-scales and promise new, effective routes to control various nano-scales processes. This book contains lecture notes written by the lecturers of the NATO Advanced Study Institute "Self-Assembly, Pattern Formation and Growth Phenomena in Nano-Systems" that took place in St Etienne de Tinee, France, in the fall 2004. They give examples of self-organization phenomena on micro- and nano-scale as well as examples of the interplay between phenomena on nano- and macro-scales leading to complex behavior in various physical, chemical and biological systems. They discuss such fascinating nano-scale self-organization phenomena as self-assembly of quantum dots in thin solid films, pattern formation in liquid crystals caused by light, self-organi...

Inverse Problem in Self-assembly

Science.gov (United States)

Tkachenko, Alexei

2012-02-01

By decorating colloids and nanoparticles with DNA, one can introduce highly selective key-lock interactions between them. This leads to a new class of systems and problems in soft condensed matter physics. In particular, this opens a possibility to solve inverse problem in self-assembly: how to build an arbitrary desired structure with the bottom-up approach? I will present a theoretical and computational analysis of the hierarchical strategy in attacking this problem. It involves self-assembly of particular building blocks (``octopus particles''), that in turn would assemble into the target structure. On a conceptual level, our approach combines elements of three different brands of programmable self assembly: DNA nanotechnology, nanoparticle-DNA assemblies and patchy colloids. I will discuss the general design principles, theoretical and practical limitations of this approach, and illustrate them with our simulation results. Our crucial result is that not only it is possible to design a system that has a given nanostructure as a ground state, but one can also program and optimize the kinetic pathway for its self-assembly.

Bola-amphiphile self-assembly

DEFF Research Database (Denmark)

Svaneborg, Carsten

2012-01-01

Bola-amphiphiles are rod-like molecules where both ends of the molecule likes contact with water, while the central part of the molecule dislikes contact with water. What do such molecules do when they are dissolved in water? They self-assemble into micelles. This is a Dissipartive particle...... dynamics simulation of this self-assembly behaviour....

Tuning of metal work functions with self-assembled monolayers

NARCIS (Netherlands)

de Boer, B; Hadipour, A; Mandoc, MM; van Woudenbergh, T; Blom, PWM

2005-01-01

Work functions of gold and silver are varied by over 1.4 and 1.7 eV, respectively, by using self-assembled monolayers. Using these modified electrodes, the hole current in a poly(2-methoxy-5-(2'-ethylhexyloxy)- 1,4-phenylene vinylene) light-emitting diode is tuned by more than six orders of

Self-assembled biomimetic nanoreactors I: Polymeric template

Science.gov (United States)

McTaggart, Matt; Malardier-Jugroot, Cecile; Jugroot, Manish

2015-09-01

The variety of nanoarchitectures made feasible by the self-assembly of alternating copolymers opens new avenues for biomimicry. Indeed, self-assembled structures allow the development of nanoreactors which combine the efficiency of high surface area metal active centres to the effect of confinement due to the very small cavities generated by the self-assembly process. A novel self-assembly of high molecular weight alternating copolymers is characterized in the present study. The self-assembly is shown to organize into nanosheets, providing a 2 nm hydrophobic cavity with a 1D confinement.

Multivalent protein assembly using monovalent self-assembling building blocks

NARCIS (Netherlands)

Petkau - Milroy, K.; Sonntag, M.H.; Colditz, A.; Brunsveld, L.

2013-01-01

Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard

Self-assembled tunable photonic hyper-crystals.

Science.gov (United States)

Smolyaninova, Vera N; Yost, Bradley; Lahneman, David; Narimanov, Evgenii E; Smolyaninov, Igor I

2014-07-16

We demonstrate a novel artificial optical material, the "photonic hyper-crystal", which combines the most interesting features of hyperbolic metamaterials and photonic crystals. Similar to hyperbolic metamaterials, photonic hyper-crystals exhibit broadband divergence in their photonic density of states due to the lack of usual diffraction limit on the photon wave vector. On the other hand, similar to photonic crystals, hyperbolic dispersion law of extraordinary photons is modulated by forbidden gaps near the boundaries of photonic Brillouin zones. Three dimensional self-assembly of photonic hyper-crystals has been achieved by application of external magnetic field to a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing.

Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

Science.gov (United States)

Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

2017-04-18

chains from self-assembly. The handedness of the twisted lamella can be determined by using rotation experiment of polarized light microscopy (PLM). Similar to the self-assembly of BCPs*, the examined results suggest the homochiral evolution in the crystallized chiral polylactides. The results presented in this Account demonstrate the notable progress in the spectral and morphological determination for the examination of molecular, conformational, and hierarchical chirality in self-assembled twisted superstructures of chiral polymers and helical phases of block copolymers and suggest the attainability of homochiral evolution in the self-assembly of chiral homopolymers and BCPs*. The suggested methodologies for the understanding of the mechanisms of the chirality transfer at different length scales provide the approaches to give Supporting Information for disclosing the mysteries of the homochiral evolution from molecular level.

Unknown Aspects of Self-Assembly of PbS Microscale Superstructures

Science.gov (United States)

Querejeta-Fernández, Ana; Hernández-Garrido, Juan C.; Yang, Hengxi; Zhou, Yunlong; Varela, Aurea; Parras, Marina; Calvino-Gámez, José J.; González-Calbet, Jose M.; Green, Peter F.; Kotov, Nicholas A.

2012-01-01

A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints this field requires advancements in three principle directions: a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and micro-levels of organization; b) understanding of disassembly/deconstruction processes; and c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: 1) nucleation of early PbS NPs with an average diameter of 31 nm; 2) assembly into 100–500 nm octahedral mesocrystals; 3) assembly into 1000–2500 nm hyperbranched stars; 4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; 5) deconstruction into rods and cubooctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern–determining forces that include vander Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy harvesting devices which require organization of PbS components at multiple scales. PMID:22515512

Enhanced Light Harvesting in Dye-Sensitized Solar Cell Using External Lightguide

Directory of Open Access Journals (Sweden)

Chi-Hui Chien

2011-01-01

Full Text Available An external lightguide (EL for enhancing the light-harvesting efficiency of dye-sensitized solar cells (DSSCs was designed and developed. The EL attached to the exterior of a DSSC photoelectrode directed light on a dye-covered nanoporous TiO2 film (D-NTF of the photoelectrode. Experimental tests confirmed that the EL increased the light-harvesting efficiency of a DSSC with an active area of 0.25 cm2 by 30.69%. Photocurrent density and the power conversion efficiency were also increased by 38.12% and 25.09%, respectively.

Role of self-assembly coated Er{sup 3+}: YAlO{sub 3}/TiO{sub 2} in intimate coupling of visible-light-responsive photocatalysis and biodegradation reactions

Energy Technology Data Exchange (ETDEWEB)

Dong, Shanshan [Key Lab of Groundwater Resources and Environment, Ministry of Education, Jilin University, Changchun 130021 (China); Dong, Shuangshi, E-mail: dongshuangshi@gmail.com [Key Lab of Groundwater Resources and Environment, Ministry of Education, Jilin University, Changchun 130021 (China); Tian, Xiadi; Xu, Zhengxue; Ma, Dongmei; Cui, Bin [Key Lab of Groundwater Resources and Environment, Ministry of Education, Jilin University, Changchun 130021 (China); Ren, Nanqi, E-mail: rnq@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (SKLUWRE, HIT), Harbin 150090 (China); Rittmann, Bruce E. [Swette Center for Environmetal Technology, Biodesign Institute at Arizona State University, Tempe, AZ, 85287-5701 (United States)

2016-01-25

Highlights: • First study on intimate coupling of photocatalysis & biodegradation by visible light. • Self-assembly was used to coat Er{sup 3+}: YAlO{sub 3}/TiO{sub 2} on the sponge carriers. • Fewer accumulated intermediates & higher phenol removal for VPCB than VPC or B alone. • Self-regulation in VPCB contributes to the high degradation efficiency. - Abstract: Conventionally used ultraviolet light can result in dissolved organic carbon (DOC) increasing and biofilm damage in intimate coupling of photocatalysis and biodegradation (ICPB). Visible-light-responsive photocatalysis offers an alternative for achieving ICPB. In this study, composite-cubes were developed using self-assembly to coat a thin and even layer of visible-light-responsive photocatalyst (Er{sup 3+}: YAlO{sub 3}/TiO{sub 2}) on sponge-type carriers, followed by biofilm cultivation. The degradations of phenol (50 mg L{sup −1}) were compared for four protocols in circulating beds: adsorption (AD), visible-light-responsive photocatalysis (VPC), biodegradation (B), and intimately coupled visible-light-responsive photocatalysis and biodegradation (VPCB). The phenol and DOC removal efficiencies using VPCB in 16 h were 99.8% and 65.2%, respectively, i.e., higher than those achieved using VPC (71.6% and 50.0%) or B (99.4% and 58.2%). The phenol removal of 96.3% could be obtained even after 3 additional cycles. The 6.17-min intermediate detected by HPLC, continuously accumulated for VPC, appeared at 1–6 h and then was completely removed for VPCB in 10 h. ICPB was further illustrated in that most of the biofilm was protected in the carrier interiors, with less protection on the carrier exterior in VPCB. A self-regulation mechanism that helped photocatalyst exposure to visible-light irradiation was identified, promoting the combined photocatalysis and biodegradation.

A Hybrid Indoor Ambient Light and Vibration Energy Harvester for Wireless Sensor Nodes

Directory of Open Access Journals (Sweden)

Hua Yu

2014-05-01

Full Text Available To take advantage of applications where both light and vibration energy are available, a hybrid indoor ambient light and vibration energy harvesting scheme is proposed in this paper. This scheme uses only one power conditioning circuit to condition the combined output power harvested from both energy sources so as to reduce the power dissipation. In order to more accurately predict the instantaneous power harvested from the solar panel, an improved five-parameter model for small-scale solar panel applying in low light illumination is presented. The output voltage is increased by using the MEMS piezoelectric cantilever arrays architecture. It overcomes the disadvantage of traditional MEMS vibration energy harvester with low voltage output. The implementation of the maximum power point tracking (MPPT for indoor ambient light is implemented using analog discrete components, which improves the whole harvester efficiency significantly compared to the digital signal processor. The output power of the vibration energy harvester is improved by using the impedance matching technique. An efficient mechanism of energy accumulation and bleed-off is also discussed. Experiment results obtained from an amorphous-silicon (a-Si solar panel of 4.8 × 2.0 cm2 and a fabricated piezoelectric MEMS generator of 11 × 12.4 mm2 show that the hybrid energy harvester achieves a maximum efficiency around 76.7%.

Exploring single chain amphiphile self-assembly and their possible roles in light transduction

DEFF Research Database (Denmark)

Monnard, Pierre-Alain

2011-01-01

Self-assembled structures of single-chain amphiphiles have been used as hosts for biochemical, and chemical reactions. Their use as models for protocells (i.e., precursors to the first biological cells) has been extensively researched by various groups because the availability of single chain......: the medium composition in terms of ionic strengths and the medium physical parameters, such as temperature, significantly influence the formation of structures, as well as their subsequent stability. In addition, membranes composed of a single amphiphile type seem to be implausible as no potential amphiphile...... source studied to date can supply one single type of amphiphile at concentrations conducive to self-assembly. Mixtures of single-chain amphiphiles were therefore proposed to better model primitive membranes and potentially enhance their structural integrity1-3. Recently, we have established that complex...

Energy transfer dynamics in Light-Harvesting Dendrimers

Science.gov (United States)

Melinger, Joseph S.; McMorrow, Dale; Kleiman, Valeria D.

2002-03-01

We explore energy transfer dynamics in light-harvesting phenylacetylene symmetric and asymmetric dendrimers. Femtosecond pump-probe spectroscopy is used to probe the ultrafast dynamics of electronic excitations in these dendrimers. The backbone of the macromolecule consists of branches of increasing conjugation length, creating an energy gradient, which funnels energy to an accepting perylene trap. In the case of the symmetric dendrimer (nanostar), the energy transfer efficiency is known to approach nearly unity, although the nature and timescale of the energy transfer process is still unknown. For the asymmetric dendrimers, energy transfer efficiencies are very high, with the possibility of more complex transfer processes. We experimentally monitor the transport of excitons through the light-harvesting dendrimer. The transients show a number of components, with timescales ranging from <300fs to several tens of picoseconds, revealing the complex photophysics taking place in these macromolecules. We interpret our results in terms of the Förster mechanism in which energy transfer occurs through dipole-dipole interactions.

Self-assembling chimeric polypeptide-doxorubicin conjugate nanoparticles that abolish tumours after a single injection

Science.gov (United States)

Andrew Mackay, J.; Chen, Mingnan; McDaniel, Jonathan R.; Liu, Wenge; Simnick, Andrew J.; Chilkoti, Ashutosh

2009-12-01

New strategies to self-assemble biocompatible materials into nanoscale, drug-loaded packages with improved therapeutic efficacy are needed for nanomedicine. To address this need, we developed artificial recombinant chimeric polypeptides (CPs) that spontaneously self-assemble into sub-100-nm-sized, near-monodisperse nanoparticles on conjugation of diverse hydrophobic molecules, including chemotherapeutics. These CPs consist of a biodegradable polypeptide that is attached to a short Cys-rich segment. Covalent modification of the Cys residues with a structurally diverse set of hydrophobic small molecules, including chemotherapeutics, leads to spontaneous formation of nanoparticles over a range of CP compositions and molecular weights. When used to deliver chemotherapeutics to a murine cancer model, CP nanoparticles have a fourfold higher maximum tolerated dose than free drug, and induce nearly complete tumour regression after a single dose. This simple strategy can promote co-assembly of drugs, imaging agents and targeting moieties into multifunctional nanomedicines.

Self-assembling peptide semiconductors

Science.gov (United States)

Tao, Kai; Makam, Pandeeswar; Aizen, Ruth; Gazit, Ehud

2017-01-01

Semiconductors are central to the modern electronics and optics industries. Conventional semiconductive materials bear inherent limitations, especially in emerging fields such as interfacing with biological systems and bottom-up fabrication. A promising candidate for bioinspired and durable nanoscale semiconductors is the family of self-assembled nanostructures comprising short peptides. The highly ordered and directional intermolecular π-π interactions and hydrogen-bonding network allow the formation of quantum confined structures within the peptide self-assemblies, thus decreasing the band gaps of the superstructures into semiconductor regions. As a result of the diverse architectures and ease of modification of peptide self-assemblies, their semiconductivity can be readily tuned, doped, and functionalized. Therefore, this family of electroactive supramolecular materials may bridge the gap between the inorganic semiconductor world and biological systems. PMID:29146781

Equilibrium polymerization models of re-entrant self-assembly

Science.gov (United States)

Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Redox-Active Carbohydrate-Coated Nanoparticles: Self-Assembly of a Cyclodextrin-Polystyrene Glycopolymer with Tetrazine-Naphthalimide.

Science.gov (United States)

Gross, Andrew J; Haddad, Raoudha; Travelet, Christophe; Reynaud, Eric; Audebert, Pierre; Borsali, Redouane; Cosnier, Serge

2016-11-15

The controlled self-assembly of precise and well-defined photochemically and electrochemically active carbohydrate-coated nanoparticles offers the exciting prospect of biocompatible catalysts for energy storage/conversion and biolabeling applications. Here an aqueous nanoparticle system has been developed with a versatile outer layer for host-guest molecule encapsulation via β-cyclodextrin inclusion complexes. A β-cyclodextrin-modified polystyrene polymer was first obtained by copper nanopowder click chemistry. The glycopolymer enables self-assembly and controlled encapsulation of tetrazine-naphthalimide, as a model redox-active agent, into nanoparticles via nanoprecipitation. Cyclodextrin host-guest interactions permit encapsulation and internanoparticle cross-linking for the formation of fluorescent compound and clustered self-assemblies with chemically reversible electroactivity in aqueous solution. Light scattering experiments revealed stable particles with hydrodynamic diameters of 138 and 654 nm for nanoparticles prepared with tetrazine, of which 95% of the nanoparticles represent the smaller objects by number. Dynamic light scattering revealed differences as a function of preparation method in terms of size, 3-month stability, polydispersity, radius of gyration, and shape factor. Individual self-assemblies were visualized by atomic force microscopy and fluorescence microscopy and monitored in real-time by nanoparticle tracking analysis. UV-vis and fluorescence spectra provided insight into the optical properties and critical evidence for host-guest encapsulation as evidenced by solvachromatism and enhanced tetrazine uptake. Cyclic voltammetry was used to investigate the electrochemical properties and provided further support for encapsulation and an estimate of the tetrazine loading capacity in tandem with light scattering data.

Light-emitting self-assembled peptide nucleic acids exhibit both stacking interactions and Watson-Crick base pairing.

Science.gov (United States)

Berger, Or; Adler-Abramovich, Lihi; Levy-Sakin, Michal; Grunwald, Assaf; Liebes-Peer, Yael; Bachar, Mor; Buzhansky, Ludmila; Mossou, Estelle; Forsyth, V Trevor; Schwartz, Tal; Ebenstein, Yuval; Frolow, Felix; Shimon, Linda J W; Patolsky, Fernando; Gazit, Ehud

2015-04-01

The two main branches of bionanotechnology involve the self-assembly of either peptides or DNA. Peptide scaffolds offer chemical versatility, architectural flexibility and structural complexity, but they lack the precise base pairing and molecular recognition available with nucleic acid assemblies. Here, inspired by the ability of aromatic dipeptides to form ordered nanostructures with unique physical properties, we explore the assembly of peptide nucleic acids (PNAs), which are short DNA mimics that have an amide backbone. All 16 combinations of the very short di-PNA building blocks were synthesized and assayed for their ability to self-associate. Only three guanine-containing di-PNAs-CG, GC and GG-could form ordered assemblies, as observed by electron microscopy, and these di-PNAs efficiently assembled into discrete architectures within a few minutes. The X-ray crystal structure of the GC di-PNA showed the occurrence of both stacking interactions and Watson-Crick base pairing. The assemblies were also found to exhibit optical properties including voltage-dependent electroluminescence and wide-range excitation-dependent fluorescence in the visible region.

Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

Science.gov (United States)

Ruiz-Osés, M; Gonzalez-Lakunza, N; Silanes, I; Gourdon, A; Arnau, A; Ortega, J E

2006-12-28

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

Science.gov (United States)

Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

2015-09-30

We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

Onset of self-assembly

International Nuclear Information System (INIS)

Chitanvis, S.M.

1998-01-01

We have formulated a theory of self-assembly based on the notion of local gauge invariance at the mesoscale. Local gauge invariance at the mesoscale generates the required long-range entropic forces responsible for self-assembly in binary systems. Our theory was applied to study the onset of mesostructure formation above a critical temperature in estane, a diblock copolymer. We used diagrammatic methods to transcend the Gaussian approximation and obtain a correlation length ξ∼(c-c * ) -γ , where c * is the minimum concentration below which self-assembly is impossible, c is the current concentration, and γ was found numerically to be fairly close to 2/3. The renormalized diffusion constant vanishes as the critical concentration is approached, indicating the occurrence of critical slowing down, while the correlation function remains finite at the transition point. copyright 1998 The American Physical Society

Artificial night lighting inhibits feeding in moths

NARCIS (Netherlands)

Langevelde, Van Frank; Grunsven, Van Roy H.A.; Veenendaal, Elmar M.; Fijen, Thijs P.M.

2017-01-01

One major, yet poorly studied, change in the environment is nocturnal light pollution, which strongly alters habitats of nocturnally active species. Artificial night lighting is often considered as driving force behind rapid moth population declines in severely illuminated countries. To understand

Molecular Factors Controlling Photosynthetic Light Harvesting by Carotenoids

Czech Academy of Sciences Publication Activity Database

Polívka, Tomáš; Frank, H.A.

2010-01-01

Roč. 43, č. 8 (2010), s. 1125-1134 ISSN 0001-4842 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * energy transfer * photosynthesis * light-harvesting Subject RIV: BO - Biophysics Impact factor: 21.840, year: 2010

Self-assembled nanomaterials based on beta (β"3) tetrapeptides

International Nuclear Information System (INIS)

Seoudi, Rania S; Hinds, Mark G; Wilson, David J D; Adda, Christopher G; Mechler, Adam; Del Borgo, Mark; Aguilar, Marie-Isabel; Perlmutter, Patrick

2016-01-01

β "3-amino acid based polypeptides offer a unique starting material for the design of self-assembled nanostructures such as fibres and hierarchical dendritic assemblies, due to their well-defined helical geometry in which the peptide side chains align at 120° due to the 3.0–3.1 residue pitch of the helix. In a previous work we have described the head-to-tail self-assembly of N-terminal acetylated β "3-peptides into infinite helical nanorods that was achieved by designing a bioinspired supramolecular self-assembly motif. Here we describe the effect of consecutively more polar side chains on the self-assembly characteristics of β "3-tetrapeptides Ac-β "3Ala-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[ALIA]), Ac-β "3Ser-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[SLIA]) and Ac-β "3Lys-β "3Leu-β "3Ile-β "3Glu (Ac-β"3[KLIE]). β "3-tetrapeptides complete 1 1/3 turns of the helix: thus in the oligomeric form the side chain positions shift 120° with each added monomer, forming a regular periodic pattern along the nanorod. Dynamic light scattering (DLS) measurements confirmed that these peptides self-assemble even in highly polar solvents such as water and DMSO, while diffusion-ordered NMR spectroscopy revealed the presence of a substantial monomeric population. Temperature dependence of the size distribution in DLS measurements suggests a dynamic equilibrium between monomers and oligomers. Solution casting produced distinct fibrillar deposits after evaporating the solvent. In the case of the apolar Ac-β "3[ALIA] the longitudinal helix morphology gives rise to geometrically defined (∼70°) junctions between fibres, forming a mesh that opens up possibilities for applications e.g. in tissue scaffolding. The deposits of polar Ac-β "3[SLIA] and Ac-β "3[KLIE] exhibit fibres in regular parallel alignment over surface areas in the order of 10 μm. (paper)

Self-assembled DNA Structures for Nanoconstruction

Science.gov (United States)

Yan, Hao; Yin, Peng; Park, Sung Ha; Li, Hanying; Feng, Liping; Guan, Xiaoju; Liu, Dage; Reif, John H.; LaBean, Thomas H.

2004-09-01

In recent years, a number of research groups have begun developing nanofabrication methods based on DNA self-assembly. Here we review our recent experimental progress to utilize novel DNA nanostructures for self-assembly as well as for templates in the fabrication of functional nano-patterned materials. We have prototyped a new DNA nanostructure known as a cross structure. This nanostructure has a 4-fold symmetry which promotes its self-assembly into tetragonal 2D lattices. We have utilized the tetragonal 2D lattices as templates for highly conductive metallic nanowires and periodic 2D protein nano-arrays. We have constructed and characterized a DNA nanotube, a new self-assembling superstructure composed of DNA tiles. We have also demonstrated an aperiodic DNA lattice composed of DNA tiles assembled around a long scaffold strand; the system translates information encoded in the scaffold strand into a specific and reprogrammable barcode pattern. We have achieved metallic nanoparticle linear arrays templated on self-assembled 1D DNA arrays. We have designed and demonstrated a 2-state DNA lattice, which displays expand/contract motion switched by DNA nanoactuators. We have also achieved an autonomous DNA motor executing unidirectional motion along a linear DNA track.

Artificial light at night inhibits mating in a Geometrid moth

NARCIS (Netherlands)

van Geffen, Koert G.; van Eck, Emiel; de Boer, Rens A.; van Grunsven, Roy H.A.; Salis, Lucia; Berendse, Frank; Veenendaal, Elmar M.

2015-01-01

* Levels of artificial night lighting are increasing rapidly worldwide, subjecting nocturnal organisms to a major change in their environment. Many moth species are strongly attracted to sources of artificial night lighting, with potentially severe, yet poorly studied, consequences for development,

Artificial light at night inhibits mating in a Geometrid moth

NARCIS (Netherlands)

Geffen, van K.G.; Eck, van E.; Boer, de R.; Grunsven, van R.H.A.; Salis, F.; Berendse, F.; Veenendaal, E.M.

2015-01-01

1.Levels of artificial night lighting are increasing rapidly worldwide, subjecting nocturnal organisms to a major change in their environment. Many moth species are strongly attracted to sources of artificial night lighting, with potentially severe, yet poorly studied, consequences for development,

A 3D Optical Metamaterial Made by Self-Assembly

KAUST Repository

Vignolini, Silvia

2011-10-24

Optical metamaterials have unusual optical characteristics that arise from their periodic nanostructure. Their manufacture requires the assembly of 3D architectures with structure control on the 10-nm length scale. Such a 3D optical metamaterial, based on the replication of a self-assembled block copolymer into gold, is demonstrated. The resulting gold replica has a feature size that is two orders of magnitude smaller than the wavelength of visible light. Its optical signature reveals an archetypal Pendry wire metamaterial with linear and circular dichroism. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A 3D Optical Metamaterial Made by Self-Assembly

KAUST Repository

Vignolini, Silvia; Yufa, Nataliya A.; Cunha, Pedro S.; Guldin, Stefan; Rushkin, Ilia; Stefik, Morgan; Hur, Kahyun; Wiesner, Ulrich; Baumberg, Jeremy J.; Steiner, Ullrich

2011-01-01

Optical metamaterials have unusual optical characteristics that arise from their periodic nanostructure. Their manufacture requires the assembly of 3D architectures with structure control on the 10-nm length scale. Such a 3D optical metamaterial, based on the replication of a self-assembled block copolymer into gold, is demonstrated. The resulting gold replica has a feature size that is two orders of magnitude smaller than the wavelength of visible light. Its optical signature reveals an archetypal Pendry wire metamaterial with linear and circular dichroism. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compact passively self-tuning energy harvesting for rotating applications

International Nuclear Information System (INIS)

Gu, Lei; Livermore, Carol

2012-01-01

This paper presents a compact, passive, self-tuning energy harvester for rotating applications. The harvester rotates in the vertical plane and is comprised of two beams: a relatively rigid piezoelectric generating beam and a narrow, flexible driving beam with a tip mass mounted at the end. The mass impacts the generating beam repeatedly under the influence of gravity to drive generation. Centrifugal force from the rotation modifies the resonant frequency of the flexible driving beam and the frequency response of the harvester. An analytical model that captures the harvester system's resonant frequency as a function of rotational speed is used to guide the detailed design. With an optimized design, the resonant frequency of the harvester substantially matches the frequency of the rotation over a wide frequency range from 4 to 16.2 Hz. A prototype of the passive self-tuning energy harvester using a lead zirconate titanate generating beam achieved a power density of 30.8 µW cm −3 and a more than 11 Hz bandwidth, which is much larger than the 0.8 Hz bandwidth calculated semi-empirically for a similar but untuned harvester. Passive tuning was also demonstrated using the more robust and reliable but less efficient polymer polyvinylidene fluoride for the generating beam

Self assembly of rectangular shapes on concentration programming and probabilistic tile assembly models.

Science.gov (United States)

Kundeti, Vamsi; Rajasekaran, Sanguthevar

2012-06-01

Efficient tile sets for self assembling rectilinear shapes is of critical importance in algorithmic self assembly. A lower bound on the tile complexity of any deterministic self assembly system for an n × n square is [Formula: see text] (inferred from the Kolmogrov complexity). Deterministic self assembly systems with an optimal tile complexity have been designed for squares and related shapes in the past. However designing [Formula: see text] unique tiles specific to a shape is still an intensive task in the laboratory. On the other hand copies of a tile can be made rapidly using PCR (polymerase chain reaction) experiments. This led to the study of self assembly on tile concentration programming models. We present two major results in this paper on the concentration programming model. First we show how to self assemble rectangles with a fixed aspect ratio ( α:β ), with high probability, using Θ( α + β ) tiles. This result is much stronger than the existing results by Kao et al. (Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008) and Doty (Randomized self-assembly for exact shapes. In: proceedings of the 50th annual IEEE symposium on foundations of computer science (FOCS), IEEE, Atlanta. pp 85-94, 2009)-which can only self assembly squares and rely on tiles which perform binary arithmetic. On the other hand, our result is based on a technique called staircase sampling . This technique eliminates the need for sub-tiles which perform binary arithmetic, reduces the constant in the asymptotic bound, and eliminates the need for approximate frames (Kao et al. Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008). Our second result applies staircase sampling on the equimolar concentration programming model (The tile complexity of linear assemblies. In: proceedings of the 36th international colloquium automata, languages and programming: Part I on ICALP '09, Springer-Verlag, pp 235

Light-harvesting organic photoinitiators of polymerization.

Science.gov (United States)

Lalevée, Jacques; Tehfe, Mohamad-Ali; Dumur, Frédéric; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Fouassier, Jean-Pierre

2013-02-12

Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembling membranes and related methods thereof

Science.gov (United States)

Capito, Ramille M; Azevedo, Helena S; Stupp, Samuel L

2013-08-20

The present invention relates to self-assembling membranes. In particular, the present invention provides self-assembling membranes configured for securing and/or delivering bioactive agents. In some embodiments, the self-assembling membranes are used in the treatment of diseases, and related methods (e.g., diagnostic methods, research methods, drug screening).

Large branched self-assembled DNA complexes

International Nuclear Information System (INIS)

Tosch, Paul; Waelti, Christoph; Middelberg, Anton P J; Davies, A Giles

2007-01-01

Many biological molecules have been demonstrated to self-assemble into complex structures and networks by using their very efficient and selective molecular recognition processes. The use of biological molecules as scaffolds for the construction of functional devices by self-assembling nanoscale complexes onto the scaffolds has recently attracted significant attention and many different applications in this field have emerged. In particular DNA, owing to its inherent sophisticated self-organization and molecular recognition properties, has served widely as a scaffold for various nanotechnological self-assembly applications, with metallic and semiconducting nanoparticles, proteins, macromolecular complexes, inter alia, being assembled onto designed DNA scaffolds. Such scaffolds may typically contain multiple branch-points and comprise a number of DNA molecules selfassembled into the desired configuration. Previously, several studies have used synthetic methods to produce the constituent DNA of the scaffolds, but this typically constrains the size of the complexes. For applications that require larger self-assembling DNA complexes, several tens of nanometers or more, other techniques need to be employed. In this article, we discuss a generic technique to generate large branched DNA macromolecular complexes

Biocompatible and Biomimetic Self-Assembly of Functional Nanostructures

Science.gov (United States)

2010-02-28

evaporation induced self-assembly of aqueous silica precursors with a biologically compatible surfactant, glycerol monooleate ( GMO ) via dip-coating...film is first deposited, it has a relatively low contact angle with water and remains in a semi-solid state. Upon exposure to UV/ozone, the GMO begins...Figure 8. A) Water contact angle of a GMO -templated silica film as a function of UV light and ozone exposure time, B) Localization of fluorescently

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

Science.gov (United States)

Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

2014-11-04

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

On the solution self-assembly of nanocolloidal brushes: insights from simulations

International Nuclear Information System (INIS)

Striolo, Alberto

2008-01-01

The synthesis of novel nanoparticles with exceptional properties continues to stimulate the search for advanced applications in fields as diverse as solar energy harvesting and polymer reinforcement. It is widely recognized that to practically exploit the promised benefits it is necessary to guide the assembly of the various nanoparticles into well-defined supra-molecular structures. Towards this goal, we report Monte Carlo simulation results for the self-assembly of spherical nanoparticles in implicit solvent. The nanoparticles interact solely via dispersive interactions, modeled as square-well potentials. To control the morphology of the self-assembled aggregates, side chains are grafted on specific locations on the nanoparticle surface (i.e., on the equator, on the tropics, on the entire tropical region, or uniformly on the nanoparticle surface). The results are discussed in terms of average cluster size, probability of observing aggregates of given size, and aggregate radius of gyration and asphericity as a function of the aggregate size. The parameters of interest are the solution conditions and the nanoparticle volume fraction (always in the dilute regime). As shown in previous reports (e.g., Striolo 2007 Small 3 628), the nanoparticles form insoluble agglomerates in the absence of the side chains. When the side chains are long and uniformly distributed on the nanoparticles, these remain individually dispersed in solution. More importantly, when the side chains are grafted on selected locations on the nanoparticles, these self-assemble, yielding structures composed of up to 7-10 nanoparticles. The number of grafted side chains is the parameter that predominantly determines the average aggregate size, while the aggregate morphology can be tuned by appropriately controlling the distribution and length of the grafted side chains.

Assembling RNA Nanoparticles.

Science.gov (United States)

Xiao, Shou-Jun

2017-01-01

RNA nanoparticles are designed and self-assembled according to noncanonical interactions of naturally conserved RNA motifs and/or canonical Watson-Crick base-pairing interactions, which have potential applications in gene therapy and nanomedicine. These artificially engineered nanoparticles are mainly synthesized from in vitro transcribed RNAs, purified by denaturing and native polyacrylamide gel electrophoresis (PAGE), and characterized with native PAGE, AFM, and TEM technologies. The protocols of in vitro transcription, denaturing and native PAGE, and RNA nanoparticle self-assembly are described in detail.

Self-assembled cellulose materials for biomedicine: A review.

Science.gov (United States)

Yang, Jisheng; Li, Jinfeng

2018-02-01

Cellulose-based materials have reached a growing interest for the improvement of biomedicine, due to their good biocompatibility, biodegradability, and low toxicity. Self-assembly is a spontaneous process by which organized structures with particular functions and properties could be obtained without additional complicated processing steps. This article describes the modifications, properties and applications of cellulose and its derivatives, which including a detailed review of representative types of solvents such as NMMO, DMAc/LiCl, some molten salt hydrates, some aqueous solutions of metal complexes, ionic liquids and NaOH-water system etc. The modifications were frequently performed by esterification, etherification, ATRP, RAFT, ROP and other novel methods. Stimuli-responsive cellulose-based materials, such as temperature-, pH-, light- and redox-responsive, were synthesized for their superior performance. Additionally, the applications of cellulose-based materials which can self-assemble into micelles, vesicles and other aggregates, for drug/gene delivery, bioimaging, biosensor, are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon anti-bunching

NARCIS (Netherlands)

Wientjes, E.; Renger, J.; Curto, A.G.; Cogdell, R.; Hulst, van N.F.

2014-01-01

The nature of the highly efficient energy transfer in photosynthetic light-harvesting complexes is a subject of intense research. Unfortunately, the low fluorescence efficiency and limited photostability hampers the study of individual light-harvesting complexes at ambient conditions. Here we

Self-Organization and the Self-Assembling Process in Tissue Engineering

Science.gov (United States)

Eswaramoorthy, Rajalakshmanan; Hadidi, Pasha; Hu, Jerry C.

2015-01-01

In recent years, the tissue engineering paradigm has shifted to include a new and growing subfield of scaffoldless techniques which generate self-organizing and self-assembling tissues. This review aims to provide a cogent description of this relatively new research area, with special emphasis on applications toward clinical use and research models. Particular emphasis is placed on providing clear definitions of self-organization and the self-assembling process, as delineated from other scaffoldless techniques in tissue engineering and regenerative medicine. Significantly, during formation, self-organizing and self-assembling tissues display biological processes similar to those that occur in vivo. These help lead to the recapitulation of native tissue morphological structure and organization. Notably, functional properties of these tissues also approach native tissue values; some of these engineered tissues are already in clinical trials. This review aims to provide a cohesive summary of work in this field, and to highlight the potential of self-organization and the self-assembling process to provide cogent solutions to current intractable problems in tissue engineering. PMID:23701238

Self-assembled systems of water soluble metal 8-hydroxyquinolates with surfactants and conjugated polyelectrolytes

DEFF Research Database (Denmark)

Burrows, Hugh D.; Costa, Telma; Luisa Ramos, M.

2016-01-01

We have studied the interaction of 8-hydroxyquinoline-5-sulfonate (8-HQS) with the metal ions Al(III) and Zn(II) in aqueous solution in the presence of tetraalkylammonium surfactants using UV/vis absorption, fluorescence, NMR spectroscopy and electrical conductivity measurements, complemented by ...... assembly between the conjugated polyelectrolyte and the metal/8-HQS complex, as demonstrated by electronic energy transfer. The potential of these systems in sensing, light harvesting, and electron injection/transport layers in organic semiconductor devices is discussed....

Dielectrophoretic self-assembly of polarized light emitting poly(9,9-dioctylfluorene) nanofibre arrays

International Nuclear Information System (INIS)

O'Riordan, A; Iacopino, D; Lovera, P; Floyd, L; Reynolds, K; Redmond, G

2011-01-01

Conjugated polymer based 1D nanostructures are attractive building blocks for future opto-electronic nanoscale devices and systems. However, a critical challenge remains the lack of manipulation methods that enable controlled and reliable positioning and orientation of organic nanostructures in a fast, reliable and scalable manner. To address this challenge, we explore dielectrophoretic assembly of discrete poly(9,9-dioctylfluorene) nanofibres and demonstrate site selective assembly and orientation of these fibres. Nanofibre arrays were assembled preferentially at receptor electrode edges, being aligned parallel to the applied electric field with a high order parameter fit (∼0.9) and exhibiting an emission dichroic ratio of ∼ 4.0. As such, the dielectrophoretic method represents a fast, reliable and scalable self-assembly approach for manipulation of 1D organic nanostructures. The ability to fabricate nanofibre arrays in this manner could be potentially important for exploration and development of future nanoscale opto-electronic devices and systems.

Unique double concentric ring organization of light harvesting complexes in Gemmatimonas phototrophica.

Directory of Open Access Journals (Sweden)

Marko Dachev

2017-12-01

Full Text Available The majority of life on Earth depends directly or indirectly on the sun as a source of energy. The initial step of photosynthesis is facilitated by light-harvesting complexes, which capture and transfer light energy into the reaction centers (RCs. Here, we analyzed the organization of photosynthetic (PS complexes in the bacterium G. phototrophica, which so far is the only phototrophic representative of the bacterial phylum Gemmatimonadetes. The isolated complex has a molecular weight of about 800 ± 100 kDa, which is approximately 2 times larger than the core complex of Rhodospirillum rubrum. The complex contains 62.4 ± 4.7 bacteriochlorophyll (BChl a molecules absorbing in 2 distinct infrared absorption bands with maxima at 816 and 868 nm. Using femtosecond transient absorption spectroscopy, we determined the energy transfer time between these spectral bands as 2 ps. Single particle analyses of the purified complexes showed that they were circular structures with an outer diameter of approximately 18 nm and a thickness of 7 nm. Based on the obtained, we propose that the light-harvesting complexes in G. phototrophica form 2 concentric rings surrounding the type 2 RC. The inner ring (corresponding to the B868 absorption band is composed of 15 subunits and is analogous to the inner light-harvesting complex 1 (LH1 in purple bacteria. The outer ring is composed of 15 more distant BChl dimers with no or slow energy transfer between them, resulting in the B816 absorption band. This completely unique and elegant organization offers good structural stability, as well as high efficiency of light harvesting. Our results reveal that while the PS apparatus of Gemmatimonadetes was acquired via horizontal gene transfer from purple bacteria, it later evolved along its own pathway, devising a new arrangement of its light harvesting complexes.

Ultrafast Energy Transfer in an Artificial Photosynthetic Antenna

Directory of Open Access Journals (Sweden)

van Grondelle R.

2013-03-01

Full Text Available We temporally resolved energy transfer kinetics in an artificial light-harvesting dyad composed of a phthalocyanine covalently linked to a carotenoid. Upon carotenoid photo-excitation, energy transfers within ≈100fs (≈52% efficiency to the phthalocyanine.

Physical principles for DNA tile self-assembly.

Science.gov (United States)

Evans, Constantine G; Winfree, Erik

2017-06-19

DNA tiles provide a promising technique for assembling structures with nanoscale resolution through self-assembly by basic interactions rather than top-down assembly of individual structures. Tile systems can be programmed to grow based on logical rules, allowing for a small number of tile types to assemble large, complex assemblies that can retain nanoscale resolution. Such algorithmic systems can even assemble different structures using the same tiles, based on inputs that seed the growth. While programming and theoretical analysis of tile self-assembly often makes use of abstract logical models of growth, experimentally implemented systems are governed by nanoscale physical processes that can lead to very different behavior, more accurately modeled by taking into account the thermodynamics and kinetics of tile attachment and detachment in solution. This review discusses the relationships between more abstract and more physically realistic tile assembly models. A central concern is how consideration of model differences enables the design of tile systems that robustly exhibit the desired abstract behavior in realistic physical models and in experimental implementations. Conversely, we identify situations where self-assembly in abstract models can not be well-approximated by physically realistic models, putting constraints on physical relevance of the abstract models. To facilitate the discussion, we introduce a unified model of tile self-assembly that clarifies the relationships between several well-studied models in the literature. Throughout, we highlight open questions regarding the physical principles for DNA tile self-assembly.

Biomedical Applications of Self-Assembling Peptides

NARCIS (Netherlands)

Radmalekshahi, Mazda; Lempsink, Ludwijn; Amidi, Maryam; Hennink, Wim E.; Mastrobattista, Enrico

2016-01-01

Self-assembling peptides have gained increasing attention as versatile molecules to generate diverse supramolecular structures with tunable functionality. Because of the possibility to integrate a wide range of functional domains into self-assembling peptides including cell attachment sequences,

Submolecular Gates Self-Assemble for Hot-Electron Transfer in Proteins.

Science.gov (United States)

Filip-Granit, Neta; Goldberg, Eran; Samish, Ilan; Ashur, Idan; van der Boom, Milko E; Cohen, Hagai; Scherz, Avigdor

2017-07-27

Redox reactions play key roles in fundamental biological processes. The related spatial organization of donors and acceptors is assumed to undergo evolutionary optimization facilitating charge mobilization within the relevant biological context. Experimental information from submolecular functional sites is needed to understand the organization strategies and driving forces involved in the self-development of structure-function relationships. Here we exploit chemically resolved electrical measurements (CREM) to probe the atom-specific electrostatic potentials (ESPs) in artificial arrays of bacteriochlorophyll (BChl) derivatives that provide model systems for photoexcited (hot) electron donation and withdrawal. On the basis of computations we show that native BChl's in the photosynthetic reaction center (RC) self-assemble at their ground-state as aligned gates for functional charge transfer. The combined computational and experimental results further reveal how site-specific polarizability perpendicular to the molecular plane enhances the hot-electron transport. Maximal transport efficiency is predicted for a specific, ∼5 Å, distance above the center of the metalized BChl, which is in remarkably close agreement with the distance and mutual orientation of corresponding native cofactors. These findings provide new metrics and guidelines for analysis of biological redox centers and for designing charge mobilizing machines such as artificial photosynthesis.

Controllable self-assembly of sodium caseinate with a zwitterionic vitamin-derived bolaamphiphile.

Science.gov (United States)

Sun, Li-Hui; Sun, Yu-Long; Yang, Li-Jun; Zhang, Jian; Chen, Zhong-Xiu

2013-11-06

The control of self-assembly of sodium caseinate (SC) including the formation of mixed layers, microspheres, or nanoparticles is highly relevant to the microstructure of food and the design of promising drug delivery systems. In this paper, we designed a structure-switchable zwitterionic bolaamphiphile, 1,12-diaminododecanediorotate (DDO), from orotic acid, which has special binding sites and can guide the self-assembly of SC. Complexation between SC and DDO was investigated using dynamic light scattering, transmission electron microscopy, differential scanning calorimetry, and fluorescence spectra measurements. Monomeric DDO was bound to the negatively charged sites on the SC micelle and made the structure of SC more compact with decreased electrostatic repulsion between the head groups. Vesicular DDO led to reassociation of vesicles with enlarged size via preferable hydrophobic interactions. Moreover, the aggregation between SC and DDO was found to be temperature-dependent and reversible. This research provides an effective way to control the reversible self-assembly of SC by the zwitterionic vitamin-derived bolaamphiphile.

Energy harvesting for self-powered aerostructure actuation

Science.gov (United States)

Bryant, Matthew; Pizzonia, Matthew; Mehallow, Michael; Garcia, Ephrahim

2014-04-01

This paper proposes and experimentally investigates applying piezoelectric energy harvesting devices driven by flow induced vibrations to create self-powered actuation of aerostructure surfaces such as tabs, flaps, spoilers, or morphing devices. Recently, we have investigated flow-induced vibrations and limit cycle oscillations due to aeroelastic flutter phenomena in piezoelectric structures as a mechanism to harvest energy from an ambient fluid flow. We will describe how our experimental investigations in a wind tunnel have demonstrated that this harvested energy can be stored and used on-demand to actuate a control surface such as a trailing edge flap in the airflow. This actuated control surface could take the form of a separate and discrete actuated flap, or could constitute rotating or deflecting the oscillating energy harvester itself to produce a non-zero mean angle of attack. Such a rotation of the energy harvester and the associated change in aerodynamic force is shown to influence the operating wind speed range of the device, its limit cycle oscillation (LCO) amplitude, and its harvested power output; hence creating a coupling between the device's performance as an energy harvester and as a control surface. Finally, the induced changes in the lift, pitching moment, and drag acting on a wing model are quantified and compared for a control surface equipped with an oscillating energy harvester and a traditional, static control surface of the same geometry. The results show that when operated in small amplitude LCO the energy harvester adds negligible aerodynamic drag.

Reflection and extinction of light by self-assembled monolayers of a quinque-thiophene derivative: A coherent scattering approach

Energy Technology Data Exchange (ETDEWEB)

Gholamrezaie, Fatemeh; Meskers, Stefan C. J., E-mail: s.c.j.meskers@tue.nl [Molecular Materials and Nanosystems and Institute of Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Leeuw, Dago M. de [Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany)

2016-06-07

Scattering matrix theory is used to describe resonant optical properties of molecular monolayers. Three types of coupling are included: exciton-exciton, exciton-photon, and exciton-phonon coupling. We use the K-matrix formalism, developed originally to describe neutron scattering spectra in nuclear physics to compute the scattering of polaritons by phonons. This perturbation approach takes into account the three couplings and allows one to go beyond molecular exciton theory without the need of introducing additional boundary conditions for the polariton. We demonstrate that reflection, absorption, and extinction of light by 2D self-assembled monolayers of molecules containing quinque-thiophene chromophoric groups can be calculated. The extracted coherence length of the Frenkel exciton is discussed.

Self-assembled nanogaps for molecular electronics.

Science.gov (United States)

Tang, Qingxin; Tong, Yanhong; Jain, Titoo; Hassenkam, Tue; Wan, Qing; Moth-Poulsen, Kasper; Bjørnholm, Thomas

2009-06-17

A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO2:Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during self-assembly and the gap length was determined by the molecule length. The gold nanorods and gold nanoparticles, respectively covalently bonded at the two ends of the molecule, had very small dimensions, e.g. a width of approximately 20 nm, and hence were expected to minimize the screening effect. The ultra-long conducting SnO2:Sb nanowires provided the bridge to connect one of the electrodes of the molecular device (gold nanoparticle) to the external circuit. The tip of the atomic force microscope (AFM) was contacted onto the other electrode (gold nanorod) for the electrical measurement of the OPV device. The conductance measurement confirmed that the self-assembly of the molecules and the subsequent self-assembly of the gold nanorods was a feasible method for the fabrication of the nanogap of the molecular devices.

Self-assembled nanogaps for molecular electronics

International Nuclear Information System (INIS)

Tang Qingxin; Tong Yanhong; Jain, Titoo; Hassenkam, Tue; Moth-Poulsen, Kasper; Bjoernholm, Thomas; Wan Qing

2009-01-01

A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO 2 :Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during self-assembly and the gap length was determined by the molecule length. The gold nanorods and gold nanoparticles, respectively covalently bonded at the two ends of the molecule, had very small dimensions, e.g. a width of ∼20 nm, and hence were expected to minimize the screening effect. The ultra-long conducting SnO 2 :Sb nanowires provided the bridge to connect one of the electrodes of the molecular device (gold nanoparticle) to the external circuit. The tip of the atomic force microscope (AFM) was contacted onto the other electrode (gold nanorod) for the electrical measurement of the OPV device. The conductance measurement confirmed that the self-assembly of the molecules and the subsequent self-assembly of the gold nanorods was a feasible method for the fabrication of the nanogap of the molecular devices.

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates

Directory of Open Access Journals (Sweden)

Yujiao Xie

2018-03-01

Full Text Available New amphiphilic liquid crystal (LC polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR spectrum, 1H NMR, gel permeation chromatographic (GPC, thermogravimetric analysis (TGA, differential scanning calorimetry (DSC, polarizing optical microscope (POM, and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td, glass temperature (Tg, and isotropic temperature (Ti increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX, together with drug release tracking, were evaluated by dynamic light scattering (DLS, SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications.

Spin State As a Probe of Vesicle Self-Assembly

OpenAIRE

Kim, Sanghoon; Bellouard, Christine; Eastoe, Julian; Canilho, Nadia; Rogers, Sarah E; Ihiawakrim, Dris; Ersen, Ovidiu; Pasc, Andreea

2016-01-01

A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compo...

Synthetic Self-Assembled Materials in Biological Environments

NARCIS (Netherlands)

Versluis, F.; van Esch, J.H.; Eelkema, R.

2016-01-01

Synthetic self-assembly has long been recognized as an excellent approach for the formation of ordered structures on the nanoscale. Although the development of synthetic self-assembling materials has often been inspired by principles observed in nature (e.g., the assembly of lipids, DNA,

Biomimetic light-harvesting funnels for re-directioning of diffuse light.

Science.gov (United States)

Pieper, Alexander; Hohgardt, Manuel; Willich, Maximilian; Gacek, Daniel Alexander; Hafi, Nour; Pfennig, Dominik; Albrecht, Andreas; Walla, Peter Jomo

2018-02-14

Efficient sunlight harvesting and re-directioning onto small areas has great potential for more widespread use of precious high-performance photovoltaics but so far intrinsic solar concentrator loss mechanisms outweighed the benefits. Here we present an antenna concept allowing high light absorption without high reabsorption or escape-cone losses. An excess of randomly oriented pigments collects light from any direction and funnels the energy to individual acceptors all having identical orientations and emitting ~90% of photons into angles suitable for total internal reflection waveguiding to desired energy converters (funneling diffuse-light re-directioning, FunDiLight). This is achieved using distinct molecules that align efficiently within stretched polymers together with others staying randomly orientated. Emission quantum efficiencies can be >80% and single-foil reabsorption energy funneling, dipole re-orientation, and ~1.5-2 nm nearest donor-acceptor transfer occurs within hundreds to ~20 ps. Single-molecule 3D-polarization experiments confirm nearly parallel emitters. Stacked pigment selection may allow coverage of the entire solar spectrum.

Self-assembly of cyclodextrins

DEFF Research Database (Denmark)

Fülöp, Z.; Kurkov, S.V.; Nielsen, T.T.

2012-01-01

The design of functional cyclodextrin (CD) nanoparticles is a developing area in the field of nanomedicine. CDs can not only help in the formation of drug carriers but also increase the local concentration of drugs at the site of action. CD monomers form aggregates by self-assembly, a tendency...... that increases upon formation of inclusion complexes with lipophilic drugs. However, the stability of such aggregates is not sufficient for parenteral administration. In this review CD polymers and CD containing nanoparticles are categorized, with focus on self-assembled CD nanoparticles. It is described how...

Tuning peptide self-assembly by an in-tether chiral center

Science.gov (United States)

Hu, Kuan; Xiong, Wei; Li, Hu; Zhang, Pei-Yu; Yin, Feng; Zhang, Qianling; Jiang, Fan; Li, Zigang

2018-01-01

The self-assembly of peptides into ordered nanostructures is important for understanding both peptide molecular interactions and nanotechnological applications. However, because of the complexity and various self-assembling pathways of peptide molecules, design of self-assembling helical peptides with high controllability and tunability is challenging. We report a new self-assembling mode that uses in-tether chiral center-induced helical peptides as a platform for tunable peptide self-assembly with good controllability. It was found that self-assembling behavior was governed by in-tether substitutional groups, where chirality determined the formation of helical structures and aromaticity provided the driving force for self-assembly. Both factors were essential for peptide self-assembly to occur. Experiments and theoretical calculations indicate long-range crystal-like packing in the self-assembly, which was stabilized by a synergy of interpeptide π-π and π-sulfur interactions and hydrogen bond networks. In addition, the self-assembled peptide nanomaterials were demonstrated to be promising candidate materials for applications in biocompatible electrochemical supercapacitors.

Influence of pre-harvest red light irradiation on main phytochemicals and antioxidant activity of Chinese kale sprouts.

Science.gov (United States)

Deng, Mingdan; Qian, Hongmei; Chen, Lili; Sun, Bo; Chang, Jiaqi; Miao, Huiying; Cai, Congxi; Wang, Qiaomei

2017-05-01

The effects of pre-harvest red light irradiation on main healthy phytochemicals as well as antioxidant activity of Chinese kale sprouts during postharvest storage were investigated. 6-day-old sprouts were treated by red light for 24h before harvest and sampled for further analysis of nutritional quality on the first, second and third day after harvest. The results indicated that red light exposure notably postponed the degradation of aliphatic, indole, and total glucosinolates during postharvest storage. The vitamin C level was remarkably higher in red light treated sprouts on the first and second day after harvest when compared with the control. In addition, red light treatment also enhanced the accumulation of total phenolics and maintained higher level of antioxidant activity than the control. All above results suggested that pre-harvest red light treatment might provide a new strategy to maintain the nutritive value of Chinese kale sprouts during postharvest storage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-assembly of highly efficient, broadband plasmonic absorbers for solar steam generation.

Science.gov (United States)

Zhou, Lin; Tan, Yingling; Ji, Dengxin; Zhu, Bin; Zhang, Pei; Xu, Jun; Gan, Qiaoqiang; Yu, Zongfu; Zhu, Jia

2016-04-01

The study of ideal absorbers, which can efficiently absorb light over a broad range of wavelengths, is of fundamental importance, as well as critical for many applications from solar steam generation and thermophotovoltaics to light/thermal detectors. As a result of recent advances in plasmonics, plasmonic absorbers have attracted a lot of attention. However, the performance and scalability of these absorbers, predominantly fabricated by the top-down approach, need to be further improved to enable widespread applications. We report a plasmonic absorber which can enable an average measured absorbance of ~99% across the wavelengths from 400 nm to 10 μm, the most efficient and broadband plasmonic absorber reported to date. The absorber is fabricated through self-assembly of metallic nanoparticles onto a nanoporous template by a one-step deposition process. Because of its efficient light absorption, strong field enhancement, and porous structures, which together enable not only efficient solar absorption but also significant local heating and continuous stream flow, plasmonic absorber-based solar steam generation has over 90% efficiency under solar irradiation of only 4-sun intensity (4 kW m(-2)). The pronounced light absorption effect coupled with the high-throughput self-assembly process could lead toward large-scale manufacturing of other nanophotonic structures and devices.

Self-assembled ultra small ZnO nanocrystals for dye-sensitized solar cell application

Energy Technology Data Exchange (ETDEWEB)

Patra, Astam K.; Dutta, Arghya; Bhaumik, Asim, E-mail: msab@iacs.res.in

2014-07-01

We demonstrate a facile chemical approach to produce self-assembled ultra-small mesoporous zinc oxide nanocrystals using sodium salicylate (SS) as a template under hydrothermal conditions. These ZnO nanomaterials have been successfully fabricated as a photoanode for the dye-sensitized solar cell (DSSC) in the presence of N719 dye and iodine–triiodide electrolyte. The structural features, crystallinity, purity, mesophase and morphology of the nanostructure ZnO are investigated by several characterization tools. N{sub 2} sorption analysis revealed high surface areas (203 m{sup 2} g{sup −1}) and narrow pore size distributions (5.1–5.4 nm) for different samples. The mesoporous structure and strong photoluminescence facilitates the high dye loading at the mesoscopic void spaces and light harvesting in DSSC. By utilizing this ultra-small ZnO photoelectrode with film thickness of about 7 μm in the DSSC with an open-circuit voltage (V{sub OC}) of 0.74 V, short-circuit current density (J{sub SC}) of 3.83 mA cm{sup −2} and an overall power conversion efficiency of 1.12% has been achieved. - Graphical abstract: Ultra-small ZnO nanocrystals have been synthesized with sodium salicylate as a template and using it as a photoanode in a dye-sensitized solar cell 1.12% power conversion efficiency has been observed. - Highlights: • Synthesis of self-assembled ultra-small mesoporous ZnO nanocrystals by using sodium salicylate as a template. • Mesoporous ZnO materials have high BET surface areas and void space. • ZnO nanoparticles serve as a photoanode for the dye-sensitized solar cell (DSSC). • Using ZnO nanocrystals as photoelectrode power conversion efficiency of 1.12% has been achieved.

Discrete redox signaling pathways regulate photosynthetic light-harvesting and chloroplast gene transcription.

Directory of Open Access Journals (Sweden)

John F Allen

Full Text Available In photosynthesis in chloroplasts, two related regulatory processes balance the actions of photosystems I and II. These processes are short-term, post-translational redistribution of light-harvesting capacity, and long-term adjustment of photosystem stoichiometry initiated by control of chloroplast DNA transcription. Both responses are initiated by changes in the redox state of the electron carrier, plastoquinone, which connects the two photosystems. Chloroplast Sensor Kinase (CSK is a regulator of transcription of chloroplast genes for reaction centres of the two photosystems, and a sensor of plastoquinone redox state. We asked whether CSK is also involved in regulation of absorbed light energy distribution by phosphorylation of light-harvesting complex II (LHC II. Chloroplast thylakoid membranes isolated from a CSK T-DNA insertion mutant and from wild-type Arabidopsis thaliana exhibit similar light- and redox-induced (32P-labelling of LHC II and changes in 77 K chlorophyll fluorescence emission spectra, while room-temperature chlorophyll fluorescence emission transients from Arabidopsis leaves are perturbed by inactivation of CSK. The results indicate indirect, pleiotropic effects of reaction centre gene transcription on regulation of photosynthetic light-harvesting in vivo. A single, direct redox signal is transmitted separately to discrete transcriptional and post-translational branches of an integrated cytoplasmic regulatory system.

Polymorphism of lipid self-assembly systems

International Nuclear Information System (INIS)

Takahashi, Hiroshi

2002-01-01

When lipid molecules are dispersed into an aqueous medium, various self-organized structures are formed, depending on conditions (temperature, concentration, etc), in consequence of the amphipathic nature of the molecules. In addition, lipid self-assembly systems exhibit polymorphic phase transition behavior. Since lipids are one of main components of biomembranes, studies on the structure and thermodynamic properties of lipid self-assembly systems are fundamentally important for the consideration of the stability of biomembranes. (author)

A new building block for DNA network formation by self-assembly and polymerase chain reaction.

Science.gov (United States)

Bußkamp, Holger; Keller, Sascha; Robotta, Marta; Drescher, Malte; Marx, Andreas

2014-01-01

The predictability of DNA self-assembly is exploited in many nanotechnological approaches. Inspired by naturally existing self-assembled DNA architectures, branched DNA has been developed that allows self-assembly to predesigned architectures with dimensions on the nanometer scale. DNA is an attractive material for generation of nanostructures due to a plethora of enzymes which modify DNA with high accuracy, providing a toolbox for many different manipulations to construct nanometer scaled objects. We present a straightforward synthesis of a rigid DNA branching building block successfully used for the generation of DNA networks by self-assembly and network formation by enzymatic DNA synthesis. The Y-shaped 3-armed DNA construct, bearing 3 primer strands is accepted by Taq DNA polymerase. The enzyme uses each arm as primer strand and incorporates the branched construct into large assemblies during PCR. The networks were investigated by agarose gel electrophoresis, atomic force microscopy, dynamic light scattering, and electron paramagnetic resonance spectroscopy. The findings indicate that rather rigid DNA networks were formed. This presents a new bottom-up approach for DNA material formation and might find applications like in the generation of functional hydrogels.

Dual-Hop VLC/RF Transmission System with Energy Harvesting Relay under Delay Constraint

KAUST Repository

Rakia, Tamer

2017-02-09

In this paper, we introduce a dual-hop visible light communication (VLC) / radio frequency (RF) transmission system to extend the coverage of indoor VLC systems. The relay between the two hops is able to harvest light energy from different artificial light sources and sunlight entering the room. The relay receives data packet over a VLC channel and uses the harvested energy to retransmit it to a mobile terminal over an RF channel. We develop a novel statistical model for the harvested electrical power and analyze the probability of data packet loss. We define a system design parameter (α ∈ [0, 1)) that controls the time dedicated for excess energy harvesting and data packet retransmission. It was found that the parameter has an optimal value which minimizes the packet loss probability. Further more, this optimal value is independent of the RF channel path loss. However, optimal showed inverse dependence on the packet size.

Role of ions in the regulation of light-harvesting

Directory of Open Access Journals (Sweden)

Radek Kana

2016-12-01

Full Text Available Regulation of photosynthetic light harvesting in the thylakoids is one of the major key factors affecting the efficiency of photosynthesis. Thylakoid membrane is negatively charged and influences both the structure and the function of the primarily photosynthetic reactions through its electrical double layer. Further, there is a heterogeneous organization of soluble ions (K+, Mg2+, Cl- attached to the thylakoid membrane that, together with fixed charges (negatively charged amino acids, lipids, provides an electrical field. The electrical double layer is affected by the valence of the ions and interferes with the regulation of state transitions, protein interactions, and excitation energy spillover from Photosystem II to Photosystem I. These effects are reflected in changes in the intensity of chlorophyll a fluorescence, which is also a measure of photoprotective non-photochemical quenching of the excited state of chlorophyll a. A triggering of non-photochemical quenching proceeds via lumen acidification and is coupled to the export of positive counter-ions (Mg2+, K+ to the stroma or/and negative ions (e.g., Cl- into the lumen. The effect of protons and anions in the lumen and of the cations (Mg2+, K+ in the stroma are, thus, functionally tightly interconnected. In this review, we discuss the consequences of the model of electrical double layer, proposed by James Barber (J. Barber (1980 Biochim Biophys Acta 594:253-308 in light of light-harvesting regulation. Further, we explain differences between electrostatic screening and neutralization, and we emphasize the opposite effect of monovalent (K+ and divalent (Mg2+ ions on light-harvesting and on screening of the negative charges on the thylakoid membrane; this effect needs to be incorporated in all future models of photosynthetic regulation by ion channels and transporters.

Day-light-controlled artificial lighting a potential energy saver": right interior light by sky luninance trracking

NARCIS (Netherlands)

Rutten, A.J.F.; Mills, Evan

1991-01-01

The energy consumption in office buildings can considerably be cut, if daylight is used as task lighting. A conservative estimate - starting from existing knowledge and calculation methods - gives a potential saving of 460 GWh a year or 46 % of the electricity costs for artificial lighting in Dutch

From isolated light-harvesting complexes to the thylakoid membrane: a single-molecule perspective

Science.gov (United States)

Gruber, J. Michael; Malý, Pavel; Krüger, Tjaart P. J.; Grondelle, Rienk van

2018-01-01

The conversion of solar radiation to chemical energy in plants and green algae takes place in the thylakoid membrane. This amphiphilic environment hosts a complex arrangement of light-harvesting pigment-protein complexes that absorb light and transfer the excitation energy to photochemically active reaction centers. This efficient light-harvesting capacity is moreover tightly regulated by a photoprotective mechanism called non-photochemical quenching to avoid the stress-induced destruction of the catalytic reaction center. In this review we provide an overview of single-molecule fluorescence measurements on plant light-harvesting complexes (LHCs) of varying sizes with the aim of bridging the gap between the smallest isolated complexes, which have been well-characterized, and the native photosystem. The smallest complexes contain only a small number (10-20) of interacting chlorophylls, while the native photosystem contains dozens of protein subunits and many hundreds of connected pigments. We discuss the functional significance of conformational dynamics, the lipid environment, and the structural arrangement of this fascinating nano-machinery. The described experimental results can be utilized to build mathematical-physical models in a bottom-up approach, which can then be tested on larger in vivo systems. The results also clearly showcase the general property of biological systems to utilize the same system properties for different purposes. In this case it is the regulated conformational flexibility that allows LHCs to switch between efficient light-harvesting and a photoprotective function.

Equation of State for Phospholipid Self-Assembly

DEFF Research Database (Denmark)

Marsh, Derek

2016-01-01

Phospholipid self-assembly is the basis of biomembrane stability. The entropy of transfer from water to self-assembled micelles of lysophosphatidylcholines and diacyl phosphatidylcholines with different chain lengths converges to a common value at a temperature of 44°C. The corresponding enthalpies...... of transfer converge at ∼-18°C. An equation of state for the free energy of self-assembly formulated from this thermodynamic data depends on the heat capacity of transfer as the sole parameter needed to specify a particular lipid. For lipids lacking calorimetric data, measurement of the critical micelle...

Hierarchical self-assembly of a bow-shaped molecule bearing self-complementary hydrogen bonding sites into extended supramolecular assemblies.

Science.gov (United States)

Ikeda, Masato; Nobori, Tadahito; Schmutz, Marc; Lehn, Jean-Marie

2005-01-07

The bow-shaped molecule 1 bearing a self-complementary DAAD-ADDA (D=donor A=acceptor) hydrogen-bonding array generates, in hydrocarbon solvents, highly ordered supramolecular sheet aggregates that subsequently give rise to gels by formation of an entangled network. The process of hierarchical self-assembly of compound 1 was investigated by the concentration and temperature dependence of UV-visible and (1)H NMR spectra, fluorescence spectra, and electron microscopy data. The temperature dependence of the UV-visible spectra indicates a highly cooperative process for the self-assembly of compound 1 in decaline. The electron micrograph of the decaline solution of compound 1 (1.0 mM) revealed supramolecular sheet aggregates forming an entangled network. The selected area electronic diffraction patterns of the supramolecular sheet aggregates were typical for single crystals, indicative of a highly ordered assembly. The results exemplify the generation, by hierarchical self-assembly, of highly organized supramolecular materials presenting novel collective properties at each level of organization.

Layer-by-layer assembled TiO2 films with high ultraviolet light-shielding property

International Nuclear Information System (INIS)

Li, Xiaozhou; Wang, Lin; Pei, Yuxin; Jiang, Jinqiang

2014-01-01

Ultraviolet (UV) B is hazardous to human, plants and animals. With the rapid growth of ozone holes over the earth, the exploration of optical materials that can cut off harmful UV radiation is important. In this work, fusiform TiO 2 nanoparticles were synthesized by a hydrothermal synthesis method. The thin films assembled with TiO 2 nanoparticles and oppositely charged polyelectrolytes were fabricated via a layer-by-layer assembly method. The fabrication of poly(ethylene imine) (PEI)/TiO 2 multilayer films was verified by ultraviolet–visible spectra measurements, scanning electron microscopy and atomic force microscopy. The as-prepared PEI/TiO 2 multilayer films can effectively absorb harmful UVB light and filter off visible light. Most importantly, the PEI/TiO 2 films can be deposited directly on various kinds of hydrophilic substrates such as quartz, glass, silicon and hydrophobic substrates such as polystyrene, polypropylene, polyethylene and polymethyl methacrylate when the hydrophilic substrates were modified to obtain a hydrophilic surface. - Highlights: • PEI/TiO 2 films were fabricated via a layer-by-layer self-assembly method. • The films could effectively absorb harmful UVB light and filter off visible light. • The films could deposit directly on either hydrophilic or hydrophobic substrates

Colloidal Self-Assembly Driven by Deformability & Near-Critical Phenomena

NARCIS (Netherlands)

Evers, C.H.J.|info:eu-repo/dai/nl/338775188

2016-01-01

Self-assembly is the spontaneous formation of patterns or structures without human intervention. This thesis aims to increase our understanding of self-assembly. In self-assembly of proteins, the building blocks are very small and complex. Consequently, grasping the basic principles that drive the

Self-assembly of amorphous biophotonic nanostructures by phase separation

Energy Technology Data Exchange (ETDEWEB)

Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar; Mochrie, Simon G.J.; Cao, Hui; Prum, Richard O.; (Yale)

2009-04-23

Some of the most vivid colors in the animal kingdom are created not by pigments, but by wavelength-selective scattering of light from nanostructures. Here we investigate quasi-ordered nanostructures of avian feather barbs which produce vivid non-iridescent colors. These {beta}-keratin and air nanostructures are found in two basic morphologies: tortuous channels and amorphous packings of spheres. Each class of nanostructure is isotropic and has a pronounced characteristic length scale of variation in composition. These local structural correlations lead to strong backscattering over a narrow range of optical frequencies and little variation with angle of incidence. Such optical properties play important roles in social and sexual communication. To be effective, birds need to precisely control the development of these nanoscale structures, yet little is known about how they grow. We hypothesize that multiple lineages of birds have convergently evolved to exploit phase separation and kinetic arrest to self-assemble spongy color-producing nanostructures in feather barbs. Observed avian nanostructures are strikingly similar to those self-assembled during the phase separation of fluid mixtures; the channel and sphere morphologies are characteristic of phase separation by spinodal decomposition and nucleation and growth, respectively. These unstable structures are locked-in by the kinetic arrest of the {beta}-keratin matrix, likely through the entanglement or cross-linking of supermolecular {beta}-keratin fibers. Using the power of self-assembly, birds can robustly realize a diverse range of nanoscopic morphologies with relatively small physical and chemical changes during feather development.

A Two-Piece Derivative of a Group I Intron RNA as a Platform for Designing Self-Assembling RNA Templates to Promote Peptide Ligation

Directory of Open Access Journals (Sweden)

Takahiro Tanaka

2012-01-01

Full Text Available Multicomponent RNA-peptide complexes are attractive from the viewpoint of artificial design of functional biomacromolecular systems. We have developed self-folding and self-assembling RNAs that serve as templates to assist chemical ligation between two reactive peptides with RNA-binding capabilities. The design principle of previous templates, however, can be applied only to limited classes of RNA-binding peptides. In this study, we employed a two-piece derivative of a group I intron RNA from the Tetrahymena large subunit ribosomal RNA (LSU rRNA as a platform for new template RNAs. In this group I intron-based self-assembling platform, modules for the recognition of substrate peptides can be installed independently from modules holding the platform structure. The new self-assembling platform allows us to expand the repertoire of substrate peptides in template RNA design.

Sky luminance research imperative for adequate ciontrol of temporary supplementary artificial lighting installations

NARCIS (Netherlands)

Rutten, A.J.F.

1994-01-01

The energy consumption in Dutch office buildings can be cut considerably if daylight is used as task lighting. A conservative estimate gives a potential saving of 46% on the electricity costs for artificial lighting. The problem of photo-electric control of artificial lighting supplementing the

Optimum Assembly Sequence Planning System Using Discrete Artificial Bee Colony Algorithm

Directory of Open Access Journals (Sweden)

Özkan Özmen

2018-01-01

Full Text Available Assembly refers both to the process of combining parts to create a structure and to the product resulting therefrom. The complexity of this process increases with the number of pieces in the assembly. This paper presents the assembly planning system design (APSD program, a computer program developed based on a matrix-based approach and the discrete artificial bee colony (DABC algorithm, which determines the optimum assembly sequence among numerous feasible assembly sequences (FAS. Specifically, the assembly sequences of three-dimensional (3D parts prepared in the computer-aided design (CAD software AutoCAD are first coded using the matrix-based methodology and the resulting FAS are assessed and the optimum assembly sequence is selected according to the assembly time optimisation criterion using DABC. The results of comparison of the performance of the proposed method with other methods proposed in the literature verify its superiority in finding the sequence with the lowest overall time. Further, examination of the results of application of APSD to assemblies consisting of parts in different numbers and shapes shows that it can select the optimum sequence from among hundreds of FAS.

Design and fabrication of self-powered micro-harvesters rotating and vibrated micro-power systems

CERN Document Server

Pan, C T; Lin, Liwei; Chen, Ying-Chung

2013-01-01

Presents the latest methods for designing and fabricating self-powered micro-generators and energy harvester systems Design and Fabrication of Self-Powered Micro-Harvesters introduces the latest trends of self-powered generators and energy harvester systems, including the design, analysis and fabrication of micro power systems. Presented in four distinct parts, the authors explore the design and fabrication of: vibration-induced electromagnetic micro-generators; rotary electromagnetic micro-generators; flexible piezo-micro-generator with various widths; and PVDF electrospunpiezo-energy with

Effect of spectral composition of artificial light on the attraction of moths

NARCIS (Netherlands)

Langevelde, van F.; Ettema, J.A.; Donners, M.; Wallis de Vries, M.F.; Groenendijk, D.

2011-01-01

During the last decades, artificial night lighting has increased globally, which largely affected many plant and animal species. So far, current research highlights the importance of artificial light with smaller wavelengths in attracting moths, yet the effect of the spectral composition of

Three-Dimensional Calcium Alginate Hydrogel Assembly via TiOPc-Based Light-Induced Controllable Electrodeposition

Directory of Open Access Journals (Sweden)

Yang Liu

2017-06-01

Full Text Available Artificial reconstruction of three-dimensional (3D hydrogel microstructures would greatly contribute to tissue assembly in vitro, and has been widely applied in tissue engineering and drug screening. Recent technological advances in the assembly of functional hydrogel microstructures such as microfluidic, 3D bioprinting, and micromold-based 3D hydrogel fabrication methods have enabled the formation of 3D tissue constructs. However, they still lack flexibility and high efficiency, which restrict their application in 3D tissue constructs. Alternatively, we report a feasible method for the fabrication and reconstruction of customized 3D hydrogel blocks. Arbitrary hydrogel microstructures were fabricated in situ via flexible and rapid light-addressable electrodeposition. To demonstrate the versatility of this method, the higher-order assembly of 3D hydrogel blocks was investigated using a constant direct current (DC voltage (6 V applied between two electrodes for 20–120 s. In addition to the plane-based two-dimensional (2D assembly, hierarchical structures—including multi-layer 3D hydrogel structures and vessel-shaped structures—could be assembled using the proposed method. Overall, we developed a platform that enables researchers to construct complex 3D hydrogel microstructures efficiently and simply, which has the potential to facilitate research on drug screening and 3D tissue constructs.

Spin State As a Probe of Vesicle Self-Assembly.

Science.gov (United States)

Kim, Sanghoon; Bellouard, Christine; Eastoe, Julian; Canilho, Nadia; Rogers, Sarah E; Ihiawakrim, Dris; Ersen, Ovidiu; Pasc, Andreea

2016-03-02

A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution of surfactants between the bilayers and the aqueous bulk.

Quantifying quality in DNA self-assembly

Science.gov (United States)

Wagenbauer, Klaus F.; Wachauf, Christian H.; Dietz, Hendrik

2014-01-01

Molecular self-assembly with DNA is an attractive route for building nanoscale devices. The development of sophisticated and precise objects with this technique requires detailed experimental feedback on the structure and composition of assembled objects. Here we report a sensitive assay for the quality of assembly. The method relies on measuring the content of unpaired DNA bases in self-assembled DNA objects using a fluorescent de-Bruijn probe for three-base ‘codons’, which enables a comparison with the designed content of unpaired DNA. We use the assay to measure the quality of assembly of several multilayer DNA origami objects and illustrate the use of the assay for the rational refinement of assembly protocols. Our data suggests that large and complex objects like multilayer DNA origami can be made with high strand integration quality up to 99%. Beyond DNA nanotechnology, we speculate that the ability to discriminate unpaired from paired nucleic acids in the same macromolecule may also be useful for analysing cellular nucleic acids. PMID:24751596

Self assembly of organic nanostructures and dielectrophoretic assembly of inorganic nanowires.

Science.gov (United States)

Dholakia, Geetha; Kuo, Steven; Allen, E. L.

2007-03-01

Self assembly techniques enable the organization of organic molecules into nanostructures. Currently engineering strategies for efficient assembly and routine integration of inorganic nanoscale objects into functional devices is very limited. AC Dielectrophoresis is an efficient technique to manipulate inorganic nanomaterials into higher dimensional structures. We used an alumina template based sol-gel synthesis method for the growth of various metal oxide nanowires with typical diameters of 100-150 nm, ranging in length from 3-10 μm. Here we report the dielectrophoretic assembly of TiO2 nanowires, an important material for photocatalysis and photovoltaics, onto interdigitated devices. Self assembly in organic nanostructures and its dependence on structure and stereochemistry of the molecule and dielectrophoretic field dependence in the assembly of inorganic nanowires will be compared and contrasted. Tunneling spectroscopy and DOS of these nanoscale systems will also be discussed.

Centrioles: Some Self-Assembly Required

OpenAIRE

Song, Mi Hye; Miliaras, Nicholas B.; Peel, Nina; O'Connell, Kevin F.

2008-01-01

Centrioles play an important role in organizing microtubules and are precisely duplicated once per cell cycle. New (daughter) centrioles typically arise in association with existing (mother) centrioles (canonical assembly), suggesting that mother centrioles direct the formation of daughter centrioles. However, under certain circumstances, centrioles can also self-assemble free of an existing centriole (de novo assembly). Recent work indicates that the canonical and de novo pathways utilize a ...

Self-assembly of active amphiphilic Janus particles

Science.gov (United States)

Mallory, S. A.; Alarcon, F.; Cacciuto, A.; Valeriani, C.

2017-12-01

In this article, we study the phenomenology of a two dimensional dilute suspension of active amphiphilic Janus particles. We analyze how the morphology of the aggregates emerging from their self-assembly depends on the strength and the direction of the active forces. We systematically explore and contrast the phenomenologies resulting from particles with a range of attractive patch coverages. Finally, we illustrate how the geometry of the colloids and the directionality of their interactions can be used to control the physical properties of the assembled active aggregates and suggest possible strategies to exploit self-propulsion as a tunable driving force for self-assembly.

Evidence for coherent mixing of excited and charge-transfer states in the major plant light-harvesting antenna, LHCII

NARCIS (Netherlands)

Ramanan, Charusheela; Ferretti, Marco; van Roon, Henny; Novoderezhkin, Vladimir I.; van Grondelle, Rienk

2017-01-01

LHCII, the major light harvesting antenna from plants, plays a dual role in photosynthesis. In low light it is a light-harvester, while in high light it is a quencher that protects the organism from photodamage. The switching mechanism between these two orthogonal conditions is mediated by protein

Tissue engineering by self-assembly and bio-printing of living cells

International Nuclear Information System (INIS)

Jakab, Karoly; Marga, Francoise; Forgacs, Gabor; Norotte, Cyrille; Murphy, Keith; Vunjak-Novakovic, Gordana

2010-01-01

Biofabrication of living structures with desired topology and functionality requires the interdisciplinary effort of practitioners of the physical, life and engineering sciences. Such efforts are being undertaken in many laboratories around the world. Numerous approaches are pursued, such as those based on the use of natural or artificial scaffolds, decellularized cadaveric extracellular matrices and, most lately, bioprinting. To be successful in this endeavor, it is crucial to provide in vitro micro-environmental clues for the cells resembling those in the organism. Therefore, scaffolds, populated with differentiated cells or stem cells, of increasing complexity and sophistication are being fabricated. However, no matter how sophisticated scaffolds are, they can cause problems stemming from their degradation, eliciting immunogenic reactions and other a priori unforeseen complications. It is also being realized that ultimately the best approach might be to rely on the self-assembly and self-organizing properties of cells and tissues and the innate regenerative capability of the organism itself, not just simply prepare tissue and organ structures in vitro followed by their implantation. Here we briefly review the different strategies for the fabrication of three-dimensional biological structures, in particular bioprinting. We detail a fully biological, scaffoldless, print-based engineering approach that uses self-assembling multicellular units as bio-ink particles and employs early developmental morphogenetic principles, such as cell sorting and tissue fusion. (topical review)

Tissue engineering by self-assembly and bio-printing of living cells

Energy Technology Data Exchange (ETDEWEB)

Jakab, Karoly; Marga, Francoise; Forgacs, Gabor [Department of Physics and Astronomy, University of Missouri, Columbia, MO 65211 (United States); Norotte, Cyrille [Department of Biology, University of Missouri, Columbia, MO 65211 (United States); Murphy, Keith [Organovo, Inc., 5871 Oberlin Drive, San Diego, CA 92121 (United States); Vunjak-Novakovic, Gordana, E-mail: forgacsg@missouri.ed [Department of Biomedical Engineering, Columbia University, New York, NY 10032 (United States)

2010-06-15

Biofabrication of living structures with desired topology and functionality requires the interdisciplinary effort of practitioners of the physical, life and engineering sciences. Such efforts are being undertaken in many laboratories around the world. Numerous approaches are pursued, such as those based on the use of natural or artificial scaffolds, decellularized cadaveric extracellular matrices and, most lately, bioprinting. To be successful in this endeavor, it is crucial to provide in vitro micro-environmental clues for the cells resembling those in the organism. Therefore, scaffolds, populated with differentiated cells or stem cells, of increasing complexity and sophistication are being fabricated. However, no matter how sophisticated scaffolds are, they can cause problems stemming from their degradation, eliciting immunogenic reactions and other a priori unforeseen complications. It is also being realized that ultimately the best approach might be to rely on the self-assembly and self-organizing properties of cells and tissues and the innate regenerative capability of the organism itself, not just simply prepare tissue and organ structures in vitro followed by their implantation. Here we briefly review the different strategies for the fabrication of three-dimensional biological structures, in particular bioprinting. We detail a fully biological, scaffoldless, print-based engineering approach that uses self-assembling multicellular units as bio-ink particles and employs early developmental morphogenetic principles, such as cell sorting and tissue fusion. (topical review)

The self-assembly of monodisperse nanospheres within microtubes

International Nuclear Information System (INIS)

Zheng Yuebing; Juluri, Bala Krishna; Huang, Tony Jun

2007-01-01

Self-assembled monodisperse nanospheres within microtubes have been fabricated and characterized. In comparison with colloidal crystals formed on planar substrates, colloidal nanocrystals self-assembled in microtubes demonstrate high spatial symmetry in their optical transmission and reflection properties. The dynamic self-assembly process inside microtubes is investigated by combining temporal- and spatial-spectrophotometric measurements. The understanding of this process is achieved through both experimentally recorded reflection spectra and finite difference time domain (FDTD)-based simulation results

Energy savings due to daylight and artificial lighting integration in office buildings in hot climate

Energy Technology Data Exchange (ETDEWEB)

Al-Ashwal, Nagib T. [Sana' a University, Sana' a (Yemen); Budaiwi, Ismail M. [King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia)

2011-07-01

Reducing energy consumption while maintaining acceptable environmental quality in buildings has been a challenging task for building professionals. In office buildings, artificial lighting systems are a major consumer of energy and can significantly contribute to building cooling load. Furthermore, although reliable, artificial lighting does not necessarily provide the required quality of lighting. Significant improvement in lighting quality and energy consumption can be achieved by proper integration of daylight and artificial lighting. The objective of this study is to investigate the energy performance of office buildings resulting from daylight and artificial lighting integration in hot climates. A parametric analysis is conducted to find the impact of different window design parameters, including window area, height and glazing type, on building energy performance. Results have shown that as much as 35% reduction in lighting energy consumption and 13% reduction in total energy consumption can be obtained when proper daylighting and artificial lighting integration is achieved.

Data from: Artificial night lighting inhibits feeding in moths

NARCIS (Netherlands)

Langevelde, van F.; Grunsven, van R.H.A.; Veenendaal, E.M.; Fijen, T.P.M.

2017-01-01

One major, yet poorly studied, change in the environment is nocturnal light pollution, which strongly alters habitats of nocturnally active species. Artificial night lighting is often considered as driving force behind rapid moth population declines in severely illuminated countries. To understand

Quantitative computational models of molecular self-assembly in systems biology.

Science.gov (United States)

Thomas, Marcus; Schwartz, Russell

2017-05-23

Molecular self-assembly is the dominant form of chemical reaction in living systems, yet efforts at systems biology modeling are only beginning to appreciate the need for and challenges to accurate quantitative modeling of self-assembly. Self-assembly reactions are essential to nearly every important process in cell and molecular biology and handling them is thus a necessary step in building comprehensive models of complex cellular systems. They present exceptional challenges, however, to standard methods for simulating complex systems. While the general systems biology world is just beginning to deal with these challenges, there is an extensive literature dealing with them for more specialized self-assembly modeling. This review will examine the challenges of self-assembly modeling, nascent efforts to deal with these challenges in the systems modeling community, and some of the solutions offered in prior work on self-assembly specifically. The review concludes with some consideration of the likely role of self-assembly in the future of complex biological system models more generally.

Silver nanoprisms self-assembly on differently functionalized silica surface

International Nuclear Information System (INIS)

Pilipavicius, J; Chodosovskaja, A; Beganskiene, A; Kareiva, A

2015-01-01

In this work colloidal silica/silver nanoprisms (NPRs) composite coatings were made. Firstly colloidal silica sols were synthesized by sol-gel method and produced coatings on glass by dip-coating technique. Next coatings were silanized by (3-Aminopropyl)triethoxysilane (APTES), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (AEAPTMS), (3- Mercaptopropyl)trimethoxysilane (MPTMS). Silver NPRs where synthesized via seed-mediated method and high yield of 94±15 nm average edge length silver NPRs were obtained with surface plasmon resonance peak at 921 nm. Silica-Silver NPRs composite coatings obtained by selfassembly on silica coated-functionalized surface. In order to find the most appropriate silanization way for Silver NPRs self-assembly, the composite coatings were characterized by scanning electron microscopy (SEM), dynamic light scattering (DLS), water contact angle (CA) and surface free energy (SFE) methods. Results have showed that surface functionalization is necessary to achieve self-assembled Ag NPRs layer. MPTMS silanized coatings resulted sparse distribution of Ag NPRs. Most homogeneous, even distribution composite coatings obtained on APTES functionalized silica coatings, while AEAPTMS induced strong aggregation of Silver NPRs

Filamentous phages as building blocks for reconfigurable and hierarchical self-assembly

Science.gov (United States)

Gibaud, Thomas

2017-12-01

Filamentous bacteriophages such as fd-like viruses are monodisperse rod-like colloids that have well defined properties of diameter, length, rigidity, charge and chirality. Engineering these viruses leads to a library of colloidal rods, which can be used as building blocks for reconfigurable and hierarchical self-assembly. Their condensation in an aqueous solution with additive polymers, which act as depletants to induce attraction between the rods, leads to a myriad of fluid-like micronic structures ranging from isotropic/nematic droplets, colloid membranes, achiral membrane seeds, twisted ribbons, π-wall, pores, colloidal skyrmions, Möbius anchors, scallop membranes to membrane rafts. These structures, and the way that they shape-shift, not only shed light on the role of entropy, chiral frustration and topology in soft matter, but also mimic many structures encountered in different fields of science. On the one hand, filamentous phages being an experimental realization of colloidal hard rods, their condensation mediated by depletion interactions constitutes a blueprint for the self-assembly of rod-like particles and provides a fundamental foundation for bio- or material-oriented applications. On the other hand, the chiral properties of the viruses restrict the generalities of some results but vastly broaden the self-assembly possibilities.

High efficiency light harvesting by carotenoids in the LH2 complex from photosynthetic bacteria: unique adaptation to growth under low-light conditions.

Science.gov (United States)

Magdaong, Nikki M; LaFountain, Amy M; Greco, Jordan A; Gardiner, Alastair T; Carey, Anne-Marie; Cogdell, Richard J; Gibson, George N; Birge, Robert R; Frank, Harry A

2014-09-25

Rhodopin, rhodopinal, and their glucoside derivatives are carotenoids that accumulate in different amounts in the photosynthetic bacterium, Rhodoblastus (Rbl.) acidophilus strain 7050, depending on the intensity of the light under which the organism is grown. The different growth conditions also have a profound effect on the spectra of the bacteriochlorophyll (BChl) pigments that assemble in the major LH2 light-harvesting pigment-protein complex. Under high-light conditions the well-characterized B800-850 LH2 complex is formed and accumulates rhodopin and rhodopin glucoside as the primary carotenoids. Under low-light conditions, a variant LH2, denoted B800-820, is formed, and rhodopinal and rhodopinal glucoside are the most abundant carotenoids. The present investigation compares and contrasts the spectral properties and dynamics of the excited states of rhodopin and rhodopinal in solution. In addition, the systematic differences in pigment composition and structure of the chromophores in the LH2 complexes provide an opportunity to explore the effect of these factors on the rate and efficiency of carotenoid-to-BChl energy transfer. It is found that the enzymatic conversion of rhodopin to rhodopinal by Rbl. acidophilus 7050 grown under low-light conditions results in nearly 100% carotenoid-to-BChl energy transfer efficiency in the LH2 complex. This comparative analysis provides insight into how photosynthetic systems are able to adapt and survive under challenging environmental conditions.

Centrioles: some self-assembly required.

Science.gov (United States)

Song, Mi Hye; Miliaras, Nicholas B; Peel, Nina; O'Connell, Kevin F

2008-12-01

Centrioles play an important role in organizing microtubules and are precisely duplicated once per cell cycle. New (daughter) centrioles typically arise in association with existing (mother) centrioles (canonical assembly), suggesting that mother centrioles direct the formation of daughter centrioles. However, under certain circumstances, centrioles can also selfassemble free of an existing centriole (de novo assembly). Recent work indicates that the canonical and de novo pathways utilize a common mechanism and that a mother centriole spatially constrains the self-assembly process to occur within its immediate vicinity. Other recently identified mechanisms further regulate canonical assembly so that during each cell cycle, one and only one daughter centriole is assembled per mother centriole.

DNAzyme-Based Logic Gate-Mediated DNA Self-Assembly.

Science.gov (United States)

Zhang, Cheng; Yang, Jing; Jiang, Shuoxing; Liu, Yan; Yan, Hao

2016-01-13

Controlling DNA self-assembly processes using rationally designed logic gates is a major goal of DNA-based nanotechnology and programming. Such controls could facilitate the hierarchical engineering of complex nanopatterns responding to various molecular triggers or inputs. Here, we demonstrate the use of a series of DNAzyme-based logic gates to control DNA tile self-assembly onto a prescribed DNA origami frame. Logic systems such as "YES," "OR," "AND," and "logic switch" are implemented based on DNAzyme-mediated tile recognition with the DNA origami frame. DNAzyme is designed to play two roles: (1) as an intermediate messenger to motivate downstream reactions and (2) as a final trigger to report fluorescent signals, enabling information relay between the DNA origami-framed tile assembly and fluorescent signaling. The results of this study demonstrate the plausibility of DNAzyme-mediated hierarchical self-assembly and provide new tools for generating dynamic and responsive self-assembly systems.

Freezing-induced self-assembly of amphiphilic molecules

Science.gov (United States)

Albouy, P. A.; Deville, S.; Fulkar, A.; Hakouk, K.; Impéror-Clerc, M.; Klotz, M.; Liu, Q.; Marcellini, M.; Perez, J.

The self-assembly of amphiphilic molecules usually takes place in a liquid phase, near room temperature. Here, using small angle X-ray scattering (SAXS) experiments performed in real time, we show that freezing of aqueous solutions of copolymer amphiphilic molecules can induce self-assembly below 0{\\deg}C.

Toward understanding as photosynthetic biosignatures: light harvesting and energy transfer calculation

Science.gov (United States)

Komatsu, Y.; Umemura, M.; Shoji, M.; Shiraishi, K.; Kayanuma, M.; Yabana, K.

2014-03-01

Among several proposed biosignatures, red edge is a direct evidence of photosynthetic life if it is detected (Kiang et al 2007). Red edge is a sharp change in reflectance spectra of vegetation in NIR region (about 700-750 nm). The sign of red edge is observed by Earthshine or remote sensing (Wolstencroft & Raven 2002, Woolf et al 2002). But, why around 700-750 nm? The photosynthetic organisms on Earth have evolved to optimize the sunlight condition. However, if we consider about photosynthetic organism on extrasolar planets, they should have developed to utilize the spectra of its principal star. Thus, it is not strange even if it shows different vegetation spectra. In this study, we focused on the light absorption mechanism of photosynthetic organisms on Earth and investigated the fundamental properties of the light harvesting mechanisms, which is the first stage for the light absorption. Light harvesting complexes contain photosynthetic pigments like chlorophylls. Effective light absorption and the energy transfer are accomplished by the electronic excitations of collective photosynthetic pigments. In order to investigate this mechanism, we constructed an energy transfer model by using a dipole-dipole approximation for the interactions between electronic excitations. Transition moments and transition energies of each pigment are calculated at the time-dependent density functional theory (TDDFT) level (Marques & Gross 2004). Quantum dynamics simulation for the excitation energy transfer was calculated by the Liouvelle's equation. We adopted the model to purple bacteria, which has been studied experimentally and known to absorb lower energy. It is meaningful to focus on the mechanism of this bacteria, since in the future mission, M planets will become a important target. We calculated the oscillator strengths in one light harvesting complex and confirmed the validity by comparing to the experimental data. This complex is made of an inner and an outer ring. The

Oxide nanostructures through self-assembly

Science.gov (United States)

Aggarwal, S.; Ogale, S. B.; Ganpule, C. S.; Shinde, S. R.; Novikov, V. A.; Monga, A. P.; Burr, M. R.; Ramesh, R.; Ballarotto, V.; Williams, E. D.

2001-03-01

A prominent theme in inorganic materials research is the creation of uniformly flat thin films and heterostructures over large wafers, which can subsequently be lithographically processed into functional devices. This letter proposes an approach that will lead to thin film topographies that are directly counter to the above-mentioned philosophy. Recent years have witnessed considerable research activity in the area of self-assembly of materials, stimulated by observations of self-organized behavior in biological systems. We have fabricated uniform arrays of nonplanar surface features by a spontaneous assembly process involving the oxidation of simple metals, especially under constrained conditions on a variety of substrates, including glass and Si. In this letter we demonstrate the pervasiveness of this process through examples involving the oxidation of Pd, Cu, Fe, and In. The feature sizes can be controlled through the grain size and thickness of the starting metal thin film. Finally, we demonstrate how such submicron scale arrays can serve as templates for the design and development of self-assembled, nanoelectronic devices.

Dynamics of self-assembled cytosine nucleobases on graphene

Science.gov (United States)

Saikia, Nabanita; Johnson, Floyd; Waters, Kevin; Pandey, Ravindra

2018-05-01

Molecular self-assembly of cytosine (C n ) bases on graphene was investigated using molecular dynamics methods. For free-standing C n bases, simulation conditions (gas versus aqueous) determine the nature of self-assembly; the bases prefer to aggregate in the gas phase and are stabilized by intermolecular H-bonds, while in the aqueous phase, the water molecules disrupt base-base interactions, which facilitate the formation of π-stacked domains. The substrate-induced effects, on the other hand, find the polarity and donor-acceptor sites of the bases to govern the assembly process. For example, in the gas phase, the assembly of C n bases on graphene displays short-range ordered linear arrays stabilized by the intermolecular H-bonds. In the aqueous phase, however, there are two distinct configurations for the C n bases assembly on graphene. For the first case corresponding to low surface coverage, the bases are dispersed on graphene and are isolated. The second configuration archetype is disordered linear arrays assembled with medium and high surface coverage. The simulation results establish the role of H-bonding, vdW π-stacking, and the influence of graphene surface towards the self-assembly. The ability to regulate the assembly into well-defined patterns can aid in the design of self-assembled nanostructures for the next-generation DNA based biosensors and nanoelectronic devices.

Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles

Science.gov (United States)

Zhang, Ting; Zhou, Li-Peng; Guo, Xiao-Qing; Cai, Li-Xuan; Sun, Qing-Fu

2017-06-01

Container-molecules are attractive to chemists due to their unique structural characteristics comparable to enzymes and receptors in nature. We report here a family of artificial self-assembled macrocyclic containers that feature induced-fit transformations in response to different anionic guests. Five metal-organic macrocycles with empirical formula of MnL2n (M=Metal L=Ligand n=3, 4, 5, 6, 7) are selectively obtained starting from one simple benzimidazole-based ligand and square-planar palladium(II) ions, either by direct anion-adaptive self-assembly or induced-fit transformations. Hydrogen-bonding interactions between the inner surface of the macrocycles and the anionic guests dictate the shape and size of the product. A comprehensive induced-fit transformation map across all the MnL2n species is drawn, with a representative reconstitution process from Pd7L14 to Pd3L6 traced in detail, revealing a gradual ring-shrinking mechanism. We envisage that these macrocyclic molecules with adjustable well-defined hydrogen-bonding pockets will find wide applications in molecular sensing or catalysis.

Self-Assembly in the Ferritin Nano-Cage Protein Superfamily

Directory of Open Access Journals (Sweden)

Yu Zhang

2011-08-01

Full Text Available Protein self-assembly, through specific, high affinity, and geometrically constraining protein-protein interactions, can control and lead to complex cellular nano-structures. Establishing an understanding of the underlying principles that govern protein self-assembly is not only essential to appreciate the fundamental biological functions of these structures, but could also provide a basis for their enhancement for nano-material applications. The ferritins are a superfamily of well studied proteins that self-assemble into hollow cage-like structures which are ubiquitously found in both prokaryotes and eukaryotes. Structural studies have revealed that many members of the ferritin family can self-assemble into nano-cages of two types. Maxi-ferritins form hollow spheres with octahedral symmetry composed of twenty-four monomers. Mini-ferritins, on the other hand, are tetrahedrally symmetric, hollow assemblies composed of twelve monomers. This review will focus on the structure of members of the ferritin superfamily, the mechanism of ferritin self-assembly and the structure-function relations of these proteins.

Ultrafine luminescent structures through nanoparticle self-assembly

International Nuclear Information System (INIS)

Prabhakaran, K; Goetzinger, S; Shafi, K V P M; Mazzei, A; Schietinger, S; Benson, O

2006-01-01

We report the fabrication of ultrafine structures consisting of regular arrays of nanoemitters through the self-assembly of luminescent nanoparticles on a silicon wafer. Nanoparticles of yttrium aluminium garnet (YAG) doped with Eu 3+ ions were synthesized by a sonochemical technique. These particles, suspended in ethanol, are introduced onto a pre-patterned silicon wafer, covered with a thin oxide layer. On annealing the sample in an ultrahigh-vacuum chamber, the nanoparticles self-assemble along the pattern. We demonstrate this 'chemical lithography' by assembling the nanoparticles along a variety of patterns. We believe that such self-organized nanopatterning of functional structures is important for the realization of nanodevices

Regulating DNA Self-assembly by DNA-Surface Interactions.

Science.gov (United States)

Liu, Longfei; Li, Yulin; Wang, Yong; Zheng, Jianwei; Mao, Chengde

2017-12-14

DNA self-assembly provides a powerful approach for preparation of nanostructures. It is often studied in bulk solution and involves only DNA-DNA interactions. When confined to surfaces, DNA-surface interactions become an additional, important factor to DNA self-assembly. However, the way in which DNA-surface interactions influence DNA self-assembly is not well studied. In this study, we showed that weak DNA-DNA interactions could be stabilized by DNA-surface interactions to allow large DNA nanostructures to form. In addition, the assembly can be conducted isothermally at room temperature in as little as 5 seconds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

KAUST Repository

Guldin, Stefan; Kolle, Mathias; Stefik, Morgan; Langford, Richard; Eder, Dominik; Wiesner, Ulrich; Steiner, Ullrich

2011-01-01

Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

KAUST Repository

Guldin, Stefan

2011-07-06

Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum transport through complex networks - from light-harvesting proteins to semiconductor devices

Energy Technology Data Exchange (ETDEWEB)

Kreisbeck, Christoph

2012-06-18

Electron transport through small systems in semiconductor devices plays an essential role for many applications in micro-electronics. One focus of current research lies on establishing conceptually new devices based on ballistic transport in high mobility AlGaAs/AlGa samples. In the ballistic regime, the transport characteristics are determined by coherent interference effects. In order to guide experimentalists to an improved device design, the characterization and understanding of intrinsic device properties is crucial. We develop a time-dependent approach that allows us to simulate experimentally fabricated, complex devicegeometries with an extension of up to a few micrometers. Particularly, we explore the physical origin of unexpected effects that have been detected in recent experiments on transport through Aharonov-Bohm waveguide-interferometers. Such interferometers can be configured as detectors for transfer properties of embedded quantum systems. We demonstrate that a four-terminal waveguide-ring is a suitable setup for measuring the transmission phase of a harmonic quantum dot. Quantum effects are not restricted exclusively to artificial devices but have been found in biological systems as well. Pioneering experiments reveal quantum effects in light-harvesting complexes, the building blocks of photosynthesis. We discuss the Fenna-Matthews-Olson complex, which is a network of coupled bacteriochlorophylls. It acts as an energy wire in the photosynthetic apparatus of green sulfur bacteria. Recent experimental findings suggest that energy transfer takes place in the form of coherent wave-like motion, rather than through classical hopping from one bacteriochlorophyll to the next. However, the question of why and how coherent transfer emerges in light-harvesting complexes is still open. The challenge is to merge seemingly contradictory features that are observed in experiments on two-dimensional spectroscopy into a consistent theory. Here, we provide such a

Self-assembly of coiled coil peptides into nanoparticles vs 2-d plates: effects of assembly pathway

Science.gov (United States)

Kim, Kyunghee; Pochan, Darrin

Molecular solution assembly, or self-assembly, is a process by which ordered nanostructures or patterns are formed by non-covalent interactions during assembly. Biomimicry, the use of bioinspired molecules or biologically relevant materials, is an important area of self-assembly research with peptides serving a critical role as molecular tools. The morphology of peptide assemblies can be controlled by adjusting solution conditions such as the concentration of peptides, the temperature, and pH. Herein, spherical nanostructures, which have potential for creating an encapsulation system, are formed by self-assembly when coiled coil peptides are combined in solution. These peptides are homotrimeric and heterodimeric coiled-coil bundles and the homotrimer is connected with each of heterodimer through their external surfaces via disulfide bonds. The resultant covalent constructs could co-assemble into complementary trimeric hubs, respectively. The two peptide constructs are directly mixed and assembled in solution in order to produce either spherical particles or 2-d plates depending on the solution conditions and kinetic pathway of assembly. In particular, structural changes of the self-assembled peptides are explored by control of the thermal history of the assembly solution.

Self-assembling segmented coiled tubing

Science.gov (United States)

Raymond, David W.

2016-09-27

Self-assembling segmented coiled tubing is a concept that allows the strength of thick-wall rigid pipe, and the flexibility of thin-wall tubing, to be realized in a single design. The primary use is for a drillstring tubular, but it has potential for other applications requiring transmission of mechanical loads (forces and torques) through an initially coiled tubular. The concept uses a spring-loaded spherical `ball-and-socket` type joint to interconnect two or more short, rigid segments of pipe. Use of an optional snap ring allows the joint to be permanently made, in a `self-assembling` manner.

Layer-by-layer assembled TiO{sub 2} films with high ultraviolet light-shielding property

Energy Technology Data Exchange (ETDEWEB)

Li, Xiaozhou [College of Science, Northwest A and F University, Yangling, Shaanxi 712100 (China); Wang, Lin, E-mail: wanglin0317@nwsuaf.edu.cn [College of Science, Northwest A and F University, Yangling, Shaanxi 712100 (China); Pei, Yuxin [College of Science, Northwest A and F University, Yangling, Shaanxi 712100 (China); Jiang, Jinqiang [State Key Lab of Applied Surface and Colloid Chemistry, College of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi' an 710062 (China)

2014-11-28

Ultraviolet (UV) B is hazardous to human, plants and animals. With the rapid growth of ozone holes over the earth, the exploration of optical materials that can cut off harmful UV radiation is important. In this work, fusiform TiO{sub 2} nanoparticles were synthesized by a hydrothermal synthesis method. The thin films assembled with TiO{sub 2} nanoparticles and oppositely charged polyelectrolytes were fabricated via a layer-by-layer assembly method. The fabrication of poly(ethylene imine) (PEI)/TiO{sub 2} multilayer films was verified by ultraviolet–visible spectra measurements, scanning electron microscopy and atomic force microscopy. The as-prepared PEI/TiO{sub 2} multilayer films can effectively absorb harmful UVB light and filter off visible light. Most importantly, the PEI/TiO{sub 2} films can be deposited directly on various kinds of hydrophilic substrates such as quartz, glass, silicon and hydrophobic substrates such as polystyrene, polypropylene, polyethylene and polymethyl methacrylate when the hydrophilic substrates were modified to obtain a hydrophilic surface. - Highlights: • PEI/TiO{sub 2} films were fabricated via a layer-by-layer self-assembly method. • The films could effectively absorb harmful UVB light and filter off visible light. • The films could deposit directly on either hydrophilic or hydrophobic substrates.

Surface Tension Directed Fluidic Self-Assembly of Semiconductor Chips across Length Scales and Material Boundaries

Directory of Open Access Journals (Sweden)

Shantonu Biswas

2016-03-01

Full Text Available This publication provides an overview and discusses some challenges of surface tension directed fluidic self-assembly of semiconductor chips which are transported in a liquid medium. The discussion is limited to surface tension directed self-assembly where the capture, alignment, and electrical connection process is driven by the surface free energy of molten solder bumps where the authors have made a contribution. The general context is to develop a massively parallel and scalable assembly process to overcome some of the limitations of current robotic pick and place and serial wire bonding concepts. The following parts will be discussed: (2 Single-step assembly of LED arrays containing a repetition of a single component type; (3 Multi-step assembly of more than one component type adding a sequence and geometrical shape confinement to the basic concept to build more complex structures; demonstrators contain (3.1 self-packaging surface mount devices, and (3.2 multi-chip assemblies with unique angular orientation. Subsequently, measures are discussed (4 to enable the assembly of microscopic chips (10 μm–1 mm; a different transport method is introduced; demonstrators include the assembly of photovoltaic modules containing microscopic silicon tiles. Finally, (5 the extension to enable large area assembly is presented; a first reel-to-reel assembly machine is realized; the machine is applied to the field of solid state lighting and the emerging field of stretchable electronics which requires the assembly and electrical connection of semiconductor devices over exceedingly large area substrates.

An Exploration into Integrating Daylight and Artificial Light via an Observational Instrument

DEFF Research Database (Denmark)

Petersen, Kjell Yngve; Søndergaard, Karin

2015-01-01

An Exploration into Integrating Daylight and Artificial Light via an Observational Instrument Daylight is dynamic and dependent upon weather conditions; unfolding with both subtle and dramatic variations in qualities of light. Through a building’s apertures, daylight creates a connection between...... abstract and blurred phenomena, these diffused luminous reflections rouse us into interactions with the world. In this book we are interested in identifying the qualitative parameters involved in the integration of dynamic artificial lighting and daylight; the latter being already highly dynamic by nature...... that examine how the dynamic artificial lighting in the observational instrument unfolds during the changing of the daylight situations that are generated by the weather outside. This research employs the concept of coupling between interior and exterior, in order to identify a spectrum of design parameters...

Artificial light at night alters trophic interactions of intertidal invertebrates.

Science.gov (United States)

Underwood, Charlotte N; Davies, Thomas W; Queirós, Ana M

2017-07-01

Despite being globally widespread in coastal regions, the impacts of light pollution on intertidal ecosystems has received little attention. Intertidal species exhibit many night-time-dependent ecological strategies, including feeding, reproduction, orientation and predator avoidance, which are likely negatively affected by shifting light regimes, as has been observed in terrestrial and aquatic taxa. Coastal lighting may shape intertidal communities through its influence on the nocturnal foraging activity of dogwhelks (Nucella lapillus), a widespread predatory mollusc that structures biodiversity in temperate rocky shores. In the laboratory, we investigated whether the basal and foraging activity of this predator was affected by exposure to night-time lighting both in the presence and absence of olfactory predator cues (Carcinus maenas, common shore crab). Assessments of dogwhelks' behavioural responses to night-time white LED lighting were performed on individuals that had been acclimated to night-time white LED lighting conditions for 16 days and individuals that had not previously been exposed to artificial light at night. Dogwhelks acclimated to night-time lighting exhibited natural refuge-seeking behaviour less often compared to control animals, but were more likely to respond to and handle prey irrespective of whether olfactory predator cues were present. These responses suggest night-time lighting likely increased the energetic demand of dogwhelks through stress, encouraging foraging whenever food was available, regardless of potential danger. Contrastingly, whelks not acclimated under night-time lighting were more likely to respond to the presence of prey under artificial light at night when olfactory predator cues were present, indicating an opportunistic shift towards the use of visual instead of olfactory cues in risk evaluation. These results demonstrate that artificial night-time lighting influences the behaviour of intertidal fauna such that the

Artificial night light alters nocturnal prey interception outcomes for morphologically variable spiders

Directory of Open Access Journals (Sweden)

Suet Wai Yuen

2017-12-01

Full Text Available Artificial night light has the potential to significantly alter visually-dependent species interactions. However, examples of disruptions of species interactions through changes in light remain rare and how artificial night light may alter predator–prey relationships are particularly understudied. In this study, we examined whether artificial night light could impact prey attraction and interception in Nephila pilipes orb weaver spiders, conspicuous predators who make use of yellow color patterns to mimic floral resources and attract prey to their webs. We measured moth prey attraction and interception responses to treatments where we experimentally manipulated the color/contrast of spider individuals in the field (removed yellow markings and also set up light manipulations. We found that lit webs had lower rates of moth interception than unlit webs. Spider color, however, had no clear impact on moth interception or attraction rates in lit nor unlit webs. The results show that night light can reduce prey interception for spiders. Additionally, this study highlights how environmental and morphological variation can complicate simple predictions of ecological light pollution’s disruption of species interactions.

Artificial night light alters nocturnal prey interception outcomes for morphologically variable spiders.

Science.gov (United States)

Yuen, Suet Wai; Bonebrake, Timothy C

2017-01-01

Artificial night light has the potential to significantly alter visually-dependent species interactions. However, examples of disruptions of species interactions through changes in light remain rare and how artificial night light may alter predator-prey relationships are particularly understudied. In this study, we examined whether artificial night light could impact prey attraction and interception in Nephila pilipes orb weaver spiders, conspicuous predators who make use of yellow color patterns to mimic floral resources and attract prey to their webs. We measured moth prey attraction and interception responses to treatments where we experimentally manipulated the color/contrast of spider individuals in the field (removed yellow markings) and also set up light manipulations. We found that lit webs had lower rates of moth interception than unlit webs. Spider color, however, had no clear impact on moth interception or attraction rates in lit nor unlit webs. The results show that night light can reduce prey interception for spiders. Additionally, this study highlights how environmental and morphological variation can complicate simple predictions of ecological light pollution's disruption of species interactions.

Live visualizations of single isolated tubulin protein self-assembly via tunneling current: effect of electromagnetic pumping during spontaneous growth of microtubule.

Science.gov (United States)

Sahu, Satyajit; Ghosh, Subrata; Fujita, Daisuke; Bandyopadhyay, Anirban

2014-12-03

As we bring tubulin protein molecules one by one into the vicinity, they self-assemble and entire event we capture live via quantum tunneling. We observe how these molecules form a linear chain and then chains self-assemble into 2D sheet, an essential for microtubule, --fundamental nano-tube in a cellular life form. Even without using GTP, or any chemical reaction, but applying particular ac signal using specially designed antenna around atomic sharp tip we could carry out the self-assembly, however, if there is no electromagnetic pumping, no self-assembly is observed. In order to verify this atomic scale observation, we have built an artificial cell-like environment with nano-scale engineering and repeated spontaneous growth of tubulin protein to its complex with and without electromagnetic signal. We used 64 combinations of plant, animal and fungi tubulins and several doping molecules used as drug, and repeatedly observed that the long reported common frequency region where protein folds mechanically and its structures vibrate electromagnetically. Under pumping, the growth process exhibits a unique organized behavior unprecedented otherwise. Thus, "common frequency point" is proposed as a tool to regulate protein complex related diseases in the future.

Artificial neural networks for spatial distribution of fuel assemblies in reload of PWR reactors

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Edyene; Castro, Victor F.; Velásquez, Carlos E.; Pereira, Claubia, E-mail: claubia@nuclear.ufmg.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Programa de Pós-Graduação em Ciências e Técnicas Nucleares

2017-07-01

An artificial neural network methodology is being developed in order to find an optimum spatial distribution of the fuel assemblies in a nuclear reactor core during reload. The main bounding parameter of the modelling was the neutron multiplication factor, k{sub ef{sub f}}. The characteristics of the network are defined by the nuclear parameters: cycle, burnup, enrichment, fuel type, and average power peak of each element. These parameters were obtained by the ORNL nuclear code package SCALE6.0. As for the artificial neural network, the ANN Feedforward Multi{sub L}ayer{sub P}erceptron with various layers and neurons were constructed. Three algorithms were used and tested: LM (Levenberg-Marquardt), SCG (Scaled Conjugate Gradient) and BayR (Bayesian Regularization). Artificial neural network have implemented using MATLAB 2015a version. As preliminary results, the spatial distribution of the fuel assemblies in the core using a neural network was slightly better than the standard core. (author)

Artificial neural networks for spatial distribution of fuel assemblies in reload of PWR reactors

International Nuclear Information System (INIS)

Oliveira, Edyene; Castro, Victor F.; Velásquez, Carlos E.; Pereira, Claubia

2017-01-01

An artificial neural network methodology is being developed in order to find an optimum spatial distribution of the fuel assemblies in a nuclear reactor core during reload. The main bounding parameter of the modelling was the neutron multiplication factor, k ef f . The characteristics of the network are defined by the nuclear parameters: cycle, burnup, enrichment, fuel type, and average power peak of each element. These parameters were obtained by the ORNL nuclear code package SCALE6.0. As for the artificial neural network, the ANN Feedforward Multi L ayer P erceptron with various layers and neurons were constructed. Three algorithms were used and tested: LM (Levenberg-Marquardt), SCG (Scaled Conjugate Gradient) and BayR (Bayesian Regularization). Artificial neural network have implemented using MATLAB 2015a version. As preliminary results, the spatial distribution of the fuel assemblies in the core using a neural network was slightly better than the standard core. (author)

Estimation Methodology for the Electricity Consumption with the Daylight- and Occupancy-Controlled Artificial Lighting

DEFF Research Database (Denmark)

Larsen, Olena Kalyanova; Jensen, Rasmus Lund; Strømberg, Ida Kristine

2017-01-01

Artificial lighting represents 15-30% of the total electricity consumption in buildings in Scandinavia. It is possible to avoid a large share of electricity use for lighting by application of daylight control systems for artificial lighting. Existing methodology for estimation of electricity...... consumption with application of such control systems in Norway is based on Norwegian standard NS 3031:2014 and can only provide results from a rough estimate. This paper aims to introduce a new estimation methodology for the electricity usage with the daylight- and occupancy-controlled artificial lighting...

Spontaneous Assembly of Exopolymers from Phytoplankton

Directory of Open Access Journals (Sweden)

Yong-Xue Ding

2009-01-01

Full Text Available Phytoplankton exopolymeric substances (EPS contribute significantly to the dissolved organic car bon (DOC pool in the ocean, playing crucial roles in the surface ocean car bon cycle. Recent studies have demonstrated that ~10% of marine DOC can self-assemble as microgels through electro static Ca bonds providing hotspots of enriched microbial substrate. How ever, the question whether EPS can self-assemble and the formation mechanisms for EPS microgels have not been examined. Here were port that EPS from three representative phytoplankton species, Synechococcus, Emiliania huxleyi, and Skeletonema costatum can spontaneously self assemble in artificial sea water (ASW, forming microscopic gels of ~ 3 - 4 __m in diameter. Different from the marine DOC polymers assembly, these EPS samples can self-assemble in Ca2+-free ASW. Further experiments from fluorescence enhancement and chemical composition analysis confirmed the existence of fair amounts of hydrophobic domains in these EPS samples. These results suggest that hydrophobic interactions play a key role in the assembly of EPS from these three species of marine phytoplankton.

Mitochondrial damage and cytoskeleton reorganization in human dermal fibroblasts exposed to artificial visible light similar to screen-emitted light.

Science.gov (United States)

Rascalou, Adeline; Lamartine, Jérôme; Poydenot, Pauline; Demarne, Frédéric; Bechetoille, Nicolas

2018-05-05

Artificial visible light is everywhere in modern life. Social communication confronts us with screens of all kinds, and their use is on the rise. We are therefore increasingly exposed to artificial visible light, the effects of which on skin are poorly known. The purpose of this study was to model the artificial visible light emitted by electronic devices and assess its effect on normal human fibroblasts. The spectral irradiance emitted by electronic devices was optically measured and equipment was developed to accurately reproduce such artificial visible light. Effects on normal human fibroblasts were analyzed on human genome microarray-based gene expression analysis. At cellular level, visualization and image analysis were performed on the mitochondrial network and F-actin cytoskeleton. Cell proliferation, ATP release and type I procollagen secretion were also measured. We developed a device consisting of 36 LEDs simultaneously emitting blue, green and red light at distinct wavelengths (450 nm, 525 nm and 625 nm) with narrow spectra and equivalent radiant power for the three colors. A dose of 99 J/cm 2 artificial visible light was selected so as not to induce cell mortality following exposure. Microarray analysis revealed 2984 light-modulated transcripts. Functional annotation of light-responsive genes revealed several enriched functions including, amongst others, the "mitochondria" and "integrin signaling" categories. Selected results were confirmed by real-time quantitative PCR, analyzing 24 genes representing these two categories. Analysis of micro-patterned culture plates showed marked fragmentation of the mitochondrial network and disorganization of the F-actin cytoskeleton following exposure. Functionally, there was considerable impairment of cell growth and spread, ATP release and type I procollagen secretion in exposed fibroblasts. Artificial visible light induces drastic molecular and cellular changes in normal human fibroblasts. This may impede

Optically nonlinear energy transfer in light-harvesting dendrimers

OpenAIRE

Andrews, David; Bradshaw, DS

2004-01-01

Dendrimeric polymers are the subject of intense research activity geared towards their implementation in nanodevice applications such as energy harvesting systems,organic light-emitting diodes, photosensitizers, low-threshold lasers, and quantum logic elements, etc. A recent development in this area has been the construction of dendrimers specifically designed to exhibit novel forms of optical nonlinearity, exploiting the unique properties of these materials at high levels of photon flux. Sta...

Spin effects in InAs self-assembled quantum dots

Directory of Open Access Journals (Sweden)

Brasil Maria

2011-01-01

Full Text Available Abstract We have studied the polarized resolved photoluminescence in an n-type resonant tunneling diode (RTD of GaAs/AlGaAs which incorporates a layer of InAs self-assembled quantum dots (QDs in the center of a GaAs quantum well (QW. We have observed that the QD circular polarization degree depends on applied voltage and light intensity. Our results are explained in terms of the tunneling of minority carriers into the QW, carrier capture by InAs QDs and bias-controlled density of holes in the QW.

Magnetic self-assembly of small parts

Science.gov (United States)

Shetye, Sheetal B.

Modern society's propensity for miniaturized end-user products is compelling electronic manufacturers to assemble and package different micro-scale, multi-technology components in more efficient and cost-effective manners. As the size of the components gets smaller, issues such as part sticking and alignment precision create challenges that slow the throughput of conventional robotic pick-n-place systems. As an alternative, various self-assembly approaches have been proposed to manipulate micro to millimeter scale components in a parallel fashion without human or robotic intervention. In this dissertation, magnetic self-assembly (MSA) is demonstrated as a highly efficient, completely parallel process for assembly of millimeter scale components. MSA is achieved by integrating permanent micromagnets onto component bonding surfaces using wafer-level microfabrication processes. Embedded bonded powder methods are used for fabrication of the magnets. The magnets are then magnetized using pulse magnetization methods, and the wafers are then singulated to form individual components. When the components are randomly mixed together, self-assembly occurs when the intermagnetic forces overcome the mixing forces. Analytical and finite element methods (FEM) are used to study the force interactions between the micromagnets. The multifunctional aspects of MSA are presented through demonstration of part-to-part and part-to-substrate assembly of 1 mm x 1mm x 0.5 mm silicon components. Part-to-part assembly is demonstrated by batch assembly of free-floating parts in a liquid environment with the assembly yield of different magnetic patterns varying from 88% to 90% in 20 s. Part-to-substrate assembly is demonstrated by assembling an ordered array onto a fixed substrate in a dry environment with the assembly yield varying from 86% to 99%. In both cases, diverse magnetic shapes/patterns are used to control the alignment and angular orientation of the components. A mathematical model is

Self-assembled software and method of overriding software execution

Science.gov (United States)

Bouchard, Ann M.; Osbourn, Gordon C.

2013-01-08

A computer-implemented software self-assembled system and method for providing an external override and monitoring capability to dynamically self-assembling software containing machines that self-assemble execution sequences and data structures. The method provides an external override machine that can be introduced into a system of self-assembling machines while the machines are executing such that the functionality of the executing software can be changed or paused without stopping the code execution and modifying the existing code. Additionally, a monitoring machine can be introduced without stopping code execution that can monitor specified code execution functions by designated machines and communicate the status to an output device.

Superhydrophobic and transparent coatings prepared by self-assembly of dual-sized silica particles

Science.gov (United States)

Xu, Qian-Feng; Wang, Jian-Nong

2010-06-01

Superhydrophobic and transparent coatings have been prepared by self-assembly of dual-sized silica particles from a mixed dispersion. The desirable micro/nano hierarchical structure for superhydrophobicity is constructed simply by adjusting the size and ratio of the dual-sized particles without organic/inorganic templates. The transparency of the prepared coatings is also researched, and the light scattering can be reduced by lowering the ratio of big sub-micro particles while the superhydrophobicity maintains unchanged. When nano particles with a diameter of 50 nm and sub-micro particles with a diameter of 350 nm are assembled, a superhydrophobic property with a water contact angle of 161° is achieved. Additionally, the coated glass is also very transparent. The highest transmittance of the coated glass can reach 85%. Compared to traditional colloid self-assembly approach, which often involves dozens of steps of layer-by-layer processing and organic/inorganic templates, the present approach is much simpler and has advantages for large-scale coating.

Understanding emergent functions in self-assembled fibrous networks

Science.gov (United States)

Sinko, Robert; Keten, Sinan

2015-09-01

Understanding self-assembly processes of nanoscale building blocks and characterizing their properties are both imperative for designing new hierarchical, network materials for a wide range of structural, optoelectrical, and transport applications. Although the characterization and choices of these material building blocks have been well studied, our understanding of how to precisely program a specific morphology through self-assembly still must be significantly advanced. In the recent study by Xie et al (2015 Nanotechnology 26 205602), the self-assembly of end-functionalized nanofibres is investigated using a coarse-grained molecular model and offers fundamental insight into how to control the structural morphology of nanofibrous networks. Varying nanoscale networks are observed when the molecular interaction strength is changed and the findings suggest that self-assembly through the tuning of molecular interactions is a key strategy for designing nanostructured networks with specific topologies.

Elucidating dominant pathways of the nano-particle self-assembly process.

Science.gov (United States)

Zeng, Xiangze; Li, Bin; Qiao, Qin; Zhu, Lizhe; Lu, Zhong-Yuan; Huang, Xuhui

2016-09-14

Self-assembly processes play a key role in the fabrication of functional nano-structures with widespread application in drug delivery and micro-reactors. In addition to the thermodynamics, the kinetics of the self-assembled nano-structures also play an important role in determining the formed structures. However, as the self-assembly process is often highly heterogeneous, systematic elucidation of the dominant kinetic pathways of self-assembly is challenging. Here, based on mass flow, we developed a new method for the construction of kinetic network models and applied it to identify the dominant kinetic pathways for the self-assembly of star-like block copolymers. We found that the dominant pathways are controlled by two competing kinetic parameters: the encounter time Te, characterizing the frequency of collision and the transition time Tt for the aggregate morphology change from rod to sphere. Interestingly, two distinct self-assembly mechanisms, diffusion of an individual copolymer into the aggregate core and membrane closure, both appear at different stages (with different values of Tt) of a single self-assembly process. In particular, the diffusion mechanism dominates the middle-sized semi-vesicle formation stage (with large Tt), while the membrane closure mechanism dominates the large-sized vesicle formation stage (with small Tt). Through the rational design of the hydrophibicity of the copolymer, we successfully tuned the transition time Tt and altered the dominant self-assembly pathways.

Self-assembling triblock proteins for biofunctional surface modification

Science.gov (United States)

Fischer, Stephen E.

Despite the tremendous promise of cell/tissue engineering, significant challenges remain in engineering functional scaffolds to precisely regulate the complex processes of tissue growth and development. As the point of contact between the cells and the scaffold, the scaffold surface plays a major role in mediating cellular behaviors. In this dissertation, the development and utility of self-assembling, artificial protein hydrogels as biofunctional surface modifiers is described. The design of these recombinant proteins is based on a telechelic triblock motif, in which a disordered polyelectrolyte central domain containing embedded bioactive ligands is flanked by two leucine zipper domains. Under moderate conditions of temperature and pH, the leucine zipper end domains form amphiphilic alpha-helices that reversibly associate into homo-trimeric aggregates, driving hydrogel formation. Moreover, the amphiphilic nature of these helical domains enables surface adsorption to a variety of scaffold materials to form biofunctional protein coatings. The nature and stability of these coatings in various solution conditions, and their interaction with mammalian cells is the primary focus of this dissertation. In particular, triblock protein coatings functionalized with cell recognition sequences are shown to produce well-defined surfaces with precise control over ligand density. The impact of this is demonstrated in multiple cell types through ligand density-dependent cell-substrate interactions. To improve the stability of these physically self-assembled coatings, two covalent crosslinking strategies are described---one in which a zero-length chemical crosslinker (EDC) is utilized and a second in which disulfide bonds are engineered into the recombinant proteins. These targeted crosslinking approaches are shown to increase the stability of surface adsorbed protein layers with minimal effect on the presentation of many bioactive ligands. Finally, to demonstrate the versatility

Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

Science.gov (United States)

Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

Science.gov (United States)

Lin, Tao

Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

Light harvesting complexes of Chromera velia, photosynthetic relative of apicomplexan parasites

KAUST Repository

Tichý , Josef; Gardian, Zdenko; Bí na, David; Koní k, Peter; Litví n, Radek V.; Herbstová , Miroslava; Pain, Arnab; Vá cha, František

2013-01-01

The structure and composition of the light harvesting complexes from the unicellular alga Chromera velia were studied by means of optical spectroscopy, biochemical and electron microscopy methods. Two different types of antennae systems were

Generic concept to program the time domain of self-assemblies with a self-regulation mechanism.

Science.gov (United States)

Heuser, Thomas; Steppert, Ann-Kathrin; Lopez, Catalina Molano; Zhu, Baolei; Walther, Andreas

2015-04-08

Nature regulates complex structures in space and time via feedback loops, kinetically controlled transformations, and under energy dissipation to allow non-equilibrium processes. Although man-made static self-assemblies realize excellent control over hierarchical structures via molecular programming, managing their temporal destiny by self-regulation is a largely unsolved challenge. Herein, we introduce a generic concept to control the time domain by programming the lifetimes of switchable self-assemblies in closed systems. We conceive dormant deactivators that, in combination with fast promoters, enable a unique kinetic balance to establish an autonomously self-regulating, transient pH-state, whose duration can be programmed over orders of magnitude-from minutes to days. Coupling this non-equilibrium state to pH-switchable self-assemblies allows predicting their assembly/disassembly fate in time, similar to a precise self-destruction mechanism. We demonstrate a platform approach by programming self-assembly lifetimes of block copolymers, nanoparticles, and peptides, enabling dynamic materials with a self-regulation functionality.

Two dimensional self-assembly zinc porphyrin and zinc phthalocyanine heterojunctions with record high power conversion efficiencies

Science.gov (United States)

Yu, Junting; Jiang, Zhou; Hao, Yifan; Zhu, Qianhong; Zhao, Mingliang; Jiang, Xue; Zhao, Jijun

2018-06-01

Compared to inorganic solar cells, the power conversion efficiencies (PCEs) of organic solar cells are much lower, but they are compensated by many merits such as lower cost, less weight, and tunable structures, making them prospective for further applications. Porphyrin and phthalocyanine are the two most significant materials for organic solar cells due to their strong light-absorbing properties and semiconductor characteristics. However, there is little research on the 2D heterojunction solar cells based on these two materials, meanwhile the PCEs of them are still low. Here we have self-assembled several 2D zinc porphyrins (ZnPors) and performed first-principles simulation to demonstrate their good stability, suitable light harvesting, and high charge carrier mobility. By perfectly matching lattice constants and molecular energy levels between those 2D ZnPors and our previous proposed zinc phthalocyanines (ZnPcs), 11 type-II organic heterojunctions are constructed to further improve their charge separation capability. Those advantages endow 2D ZnPors and ZnPcs appreciable PCEs for solar cells. Among them, the theoretical PCE of 2D ZnPors/ZnPcs heterojunctions achieves as high as 19.84%, which exceeds all reported organic solar cells, and even approaches the PCEs of inorganic solar cells. These results indicate that our 2D ZnPors and 2D ZnPcs are good candidate materials for future organic solar cells.

Plants lacking the main light-harvesting complex retain photosystem II macro-organization.

Science.gov (United States)

Ruban, A V; Wentworth, M; Yakushevska, A E; Andersson, J; Lee, P J; Keegstra, W; Dekker, J P; Boekema, E J; Jansson, S; Horton, P

2003-02-06

Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts. Several light-harvesting antenna complexes are organized precisely in the PSII macrostructure-the major trimeric complexes (LHCII) that bind 70% of PSII chlorophyll and three minor monomeric complexes-which together form PSII supercomplexes. The antenna complexes are essential for collecting sunlight and regulating photosynthesis, but the relationship between these functions and their molecular architecture is unresolved. Here we report that antisense Arabidopsis plants lacking the proteins that form LHCII trimers have PSII supercomplexes with almost identical abundance and structure to those found in wild-type plants. The place of LHCII is taken by a normally minor and monomeric complex, CP26, which is synthesized in large amounts and organized into trimers. Trimerization is clearly not a specific attribute of LHCII. Our results highlight the importance of the PSII macrostructure: in the absence of one of its main components, another protein is recruited to allow it to assemble and function.

Controllable synthesis of Bi{sub 2}WO{sub 6} nanoplate self-assembled hierarchical erythrocyte microspheres via a one-pot hydrothermal reaction with enhanced visible light photocatalytic activity

Energy Technology Data Exchange (ETDEWEB)

Yang, Zhenya; Huang, Lin; Xie, Yanyu; Lin, Zheguan; Fan, Yunyan; Liu, Dan; Chen, Lu; Zhang, Zizhong, E-mail: z.zhang@fzu.edu.cn; Wang, Xuxu

2017-05-01

Highlights: • Bi{sub 2}WO{sub 6} hierarchical erythrocyte structure was designed by F{sup −}-assisted one-pot reaction. • Erythrocyte structure enhanced the visible-light photocatalytic activity of Bi{sub 2}WO{sub 6}. • Superoxide radical anions and h{sup +} were the main active species for RhB degradation. - Abstract: This work provides a simple approach of the F{sup −}-assisted one-pot hydrothermal reaction to successfully synthesize Bi{sub 2}WO{sub 6} hierarchical erythrocyte microspheres. The importance role of F{sup −} was systematically investigated by comparing different type of halogen ions, hydrothermal temperature and time. The possible growth mechanism of Bi{sub 2}WO{sub 6} hierarchical structures was proposed. The hierarchical erythrocytes were formed through the well-ordered and oriented self-assembly of thin Bi{sub 2}WO{sub 6} nanoplate primary subunits. F{sup −} ions were absorbed on Bi{sub 2}WO{sub 6} nanoplate surface to suppress the nanoplate stack but to induce a self-assembly through the edge interaction of Bi{sub 2}WO{sub 6} nanoplates into erythrocyte-like hierarchical microspheres superstructures. This erythrocyte structure narrowed the band gap energy and enhanced the visible-light photocatalytic activity of Bi{sub 2}WO{sub 6}. Moreover, superoxide radical anions and h{sup +} were revealed as the main active species responding for the RhB degradation on Bi{sub 2}WO{sub 6} under visible light irradiation.

Charged triblock copolymer self-assembly into charged micelles

Science.gov (United States)

Chen, Yingchao; Zhang, Ke; Zhu, Jiahua; Wooley, Karen; Pochan, Darrin; Department of Material Science; Engineering University of Delaware Team; Department of Chemistry Texas A&M University Collaboration

2011-03-01

Micelles were formed through the self-assembly of amphiphlic block copolymer poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA-PMA-PS). ~Importantly, the polymer is complexed with diamine molecules in pure THF solution prior to water titration solvent processing-a critical aspect in the control of final micelle geometry. The addition of diamine triggers acid-base complexation ~between the carboxylic acid PAA side chains and amines. ~Remarkably uniform spheres were found to form close-packed patterns when forced into dried films and thin, solvated films when an excess of amine was used in the polymer assembly process. Surface properties and structural features of these hexagonal-packed spherical micelles with charged corona have been explored by various characterization methods including Transmission Electron Microscopy (TEM), cryogenic TEM, z-potential analysis and Dynamic Light Scattering. The forming mechanism for this pattern and morphology changes against external stimulate such as salt will be discussed.

Green grasses as light harvesters in dye sensitized solar cells

Science.gov (United States)

Shanmugam, Vinoth; Manoharan, Subbaiah; Sharafali, A.; Anandan, Sambandam; Murugan, Ramaswamy

2015-01-01

Chlorophylls, the major pigments presented in plants are responsible for the process of photosynthesis. The working principle of dye sensitized solar cell (DSSC) is analogous to natural photosynthesis in light-harvesting and charge separation. In a similar way, natural dyes extracted from three types of grasses viz. Hierochloe Odorata (HO), Torulinium Odoratum (TO) and Dactyloctenium Aegyptium (DA) were used as light harvesters in dye sensitized solar cells (DSSCs). The UV-Vis absorption spectroscopy, Fourier transform infrared (FT-IR), and liquid chromatography-mass spectrometry (LC-MS) were used to characterize the dyes. The electron transport mechanism and internal resistance of the DSSCs were investigated by the electrochemical impedance spectroscopy (EIS). The performance of the cells fabricated with the grass extract shows comparable efficiencies with the reported natural dyes. Among the three types of grasses, the DSSC fabricated with the dye extracted from Hierochloe Odorata (HO) exhibited the maximum efficiency. LC-MS investigations indicated that the dominant pigment present in HO dye was pheophytin a (Pheo a).

Teaching the Absorption of Light Colours Using an Artificial Rainbow

Science.gov (United States)

Yurumezoglu, Kemal; Isik, Hakan; Arikan, Gizem; Kabay, Gozde

2015-01-01

This paper presents an experimental activity based on the absorption of light colours by pigments. The activity is constructed using a stepwise design and offers an opportunity for students and teachers to compare and generalize the interactions between light and pigment colours. The light colours composing an artificial rainbow produced in the…

Bioinspired synthesis and self-assembly of hybrid organic–inorganic nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Zhang, Honghu [Iowa State Univ., Ames, IA (United States)

2016-12-17

Nature is replete with complex organic–inorganic hierarchical materials of diverse yet specific functions. These materials are intricately designed under physiological conditions through biomineralization and biological self-assembly processes. Tremendous efforts have been devoted to investigating mechanisms of such biomineralization and biological self-assembly processes as well as gaining inspiration to develop biomimetic methods for synthesis and self-assembly of functional nanomaterials. In this work, we focus on the bioinspired synthesis and self-assembly of functional inorganic nanomaterials templated by specialized macromolecules including proteins, DNA and polymers. The in vitro biomineralization process of the magnetite biomineralizing protein Mms6 has been investigated using small-angle X-ray scattering. Templated by Mms6, complex magnetic nanomaterials can be synthesized on surfaces and in the bulk. DNA and synthetic polymers have been exploited to construct macroscopic two- and three-dimensional (2D and 3D) superlattices of gold nanocrystals. Employing X-ray scattering and spectroscopy techniques, the self-assembled structures and the self-assembly mechanisms have been studied, and theoretical models have been developed. Our results show that specialized macromolecules including proteins, DNA and polymers act as effective templates for synthesis and self-assembly of nanomaterials. These bottom-up approaches provide promising routes to fabricate hybrid organic–inorganic nanomaterials with rationally designed hierarchical structures, targeting specific functions.

Prodrugs as self-assembled hydrogels: a new paradigm for biomaterials.

Science.gov (United States)

Vemula, Praveen Kumar; Wiradharma, Nikken; Ankrum, James A; Miranda, Oscar R; John, George; Karp, Jeffrey M

2013-12-01

Prodrug-based self-assembled hydrogels represent a new class of active biomaterials that can be harnessed for medical applications, in particular the design of stimuli responsive drug delivery devices. In this approach, a promoiety is chemically conjugated to a known-drug to generate an amphiphilic prodrug that is capable of forming self-assembled hydrogels. Prodrug-based self-assembled hydrogels are advantageous as they alter the solubility of the drug, enhance drug loading, and eliminate the use of harmful excipients. In addition, self-assembled prodrug hydrogels can be designed to undergo controlled drug release or tailored degradation in response to biological cues. Herein we review the development of prodrug-based self-assembled hydrogels as an emerging class of biomaterials that overcome several common limitations encountered in conventional drug delivery. Published by Elsevier Ltd.

Resource Allocation for Outdoor Visible Light Communications with Energy Harvesting Capabilities

KAUST Repository

Abdelhady, Amr Mohamed Abdelaziz; Amin, Osama; Chaaban, Anas; Alouini, Mohamed-Slim

2018-01-01

Visible light communication (VLC) is a promising technology that can support high data rate services for outdoor mass gathering night events while permitting energy harvesting. In this paper, a VLC system is considered where a transmitter sends data

Self-assembly of silica microparticles in magnetic multiphase flows: Experiment and simulation

Science.gov (United States)

Li, Xiang; Niu, Xiao-Dong; Li, You; Chen, Mu-Feng

2018-04-01

Dynamic self-assembly, especially self-assembly under magnetic field, is vital not only for its marvelous phenomenon but also for its mechanisms. Revealing the underlying mechanisms is crucial for a deeper understanding of self-assembly. In this paper, several magnetic induced self-assembly experiments by using the mixed magnetic multiphase fluids comprised of silica microspheres were carried out. The relations of the strength of external magnetic field, the inverse magnetorheological effect, and the structures of self-assembled particles were investigated. In addition, a momentum-exchanged immersed boundary-based lattice Boltzmann method (MEIB-LBM) for modeling multi-physical coupling multiphase flows was employed to numerically study the magnetic induced self-assembly process in detail. The present work showed that the external magnetic field can be used to control the form of self-assembly of nonmagnetic microparticles in a chain-like structure, and the self-assembly process can be classified into four stages with magnetic hysteresis, magnetization of nonmagnetic microparticles, self-assembly in chain-like structures, and the stable chain state. The combination of experimental and numerical results could offer a method to control the self-assembled nonmagnetic microparticles, which can provide the technical and theoretical support for the design and fabrication of micro/nanomaterials.

Identifying the nature of surface chemical modification for directed self-assembly of block copolymers

Directory of Open Access Journals (Sweden)

Laura Evangelio

2017-09-01

Full Text Available In recent years, block copolymer lithography has emerged as a viable alternative technology for advanced lithography. In chemical-epitaxy-directed self-assembly, the interfacial energy between the substrate and each block copolymer domain plays a key role on the final ordering. Here, we focus on the experimental characterization of the chemical interactions that occur at the interface built between different chemical guiding patterns and the domains of the block copolymers. We have chosen hard X-ray high kinetic energy photoelectron spectroscopy as an exploration technique because it provides information on the electronic structure of buried interfaces. The outcome of the characterization sheds light onto key aspects of directed self-assembly: grafted brush layer, chemical pattern creation and brush/block co-polymer interface.

Energy Harvesting - Wireless Sensor Networks for Indoors Applications Using IEEE 802.11

DEFF Research Database (Denmark)

Fafoutis, Xenofon; Sørensen, Thomas; Madsen, Jan

2014-01-01

The paper investigates the feasibility of using IEEE 802.11 in energy harvesting low-power sensing applications. The investigation is based on a prototype carbon dioxide sensor node that is powered by artificial indoors light. The wireless communication module of the sensor node is based on the RTX......4100 module. RTX4100 incorporates a wireless protocol that duty-cycles the radio while being compatible with IEEE 802.11 access points. The presented experiments demonstrate sustainable operation but indicate a trade-off between the benefits of using IEEE 802.11 in energy harvesting applications...

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd- Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Directory of Open Access Journals (Sweden)

Mphilisi M. Mahlambi

2012-01-01

Full Text Available Metal-ion- (Ag, Co, Ni and Pd doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL self-assembly technique using a poly(styrene sulfonate sodium salt (PSS and poly(allylamine hydrochloride (PAH polyelectrolyte system. Solid diffuse reflectance (SDR studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM, the thin films had a porous morphology and the atomic force microscope (AFM studies showed “rough” surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation. The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5 reusability cycles.

Self-assembled nanogaps for molecular electronics

DEFF Research Database (Denmark)

Tang, Qingxin; Tong, Yanhong; Jain, Titoo

2009-01-01

A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO2:Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during se...

DNA-Based Self-Assembly of Fluorescent Nanodiamonds.

Science.gov (United States)

Zhang, Tao; Neumann, Andre; Lindlau, Jessica; Wu, Yuzhou; Pramanik, Goutam; Naydenov, Boris; Jelezko, Fedor; Schüder, Florian; Huber, Sebastian; Huber, Marinus; Stehr, Florian; Högele, Alexander; Weil, Tanja; Liedl, Tim

2015-08-12

As a step toward deterministic and scalable assembly of ordered spin arrays we here demonstrate a bottom-up approach to position fluorescent nanodiamonds (NDs) with nanometer precision on DNA origami structures. We have realized a reliable and broadly applicable surface modification strategy that results in DNA-functionalized and perfectly dispersed NDs that were then self-assembled in predefined geometries. With optical studies we show that the fluorescence properties of the nitrogen-vacancy color centers in NDs are preserved during surface modification and DNA assembly. As this method allows the nanoscale arrangement of fluorescent NDs together with other optically active components in complex geometries, applications based on self-assembled spin lattices or plasmon-enhanced spin sensors as well as improved fluorescent labeling for bioimaging could be envisioned.

Self-assembly from milli- to nanoscales: methods and applications

International Nuclear Information System (INIS)

Mastrangeli, M; Celis, J-P; Abbasi, S; Varel, C; Böhringer, K F; Van Hoof, C

2009-01-01

The design and fabrication techniques for microelectromechanical systems (MEMS) and nanodevices are progressing rapidly. However, due to material and process flow incompatibilities in the fabrication of sensors, actuators and electronic circuitry, a final packaging step is often necessary to integrate all components of a heterogeneous microsystem on a common substrate. Robotic pick-and-place, although accurate and reliable at larger scales, is a serial process that downscales unfavorably due to stiction problems, fragility and sheer number of components. Self-assembly, on the other hand, is parallel and can be used for device sizes ranging from millimeters to nanometers. In this review, the state-of-the-art in methods and applications for self-assembly is reviewed. Methods for assembling three-dimensional (3D) MEMS structures out of two-dimensional (2D) ones are described. The use of capillary forces for folding 2D plates into 3D structures, as well as assembling parts onto a common substrate or aggregating parts to each other into 2D or 3D structures, is discussed. Shape matching and guided assembly by magnetic forces and electric fields are also reviewed. Finally, colloidal self-assembly and DNA-based self-assembly, mainly used at the nanoscale, are surveyed, and aspects of theoretical modeling of stochastic assembly processes are discussed. (topical review)

Ternary self-assemblies in water

DEFF Research Database (Denmark)

Hill, Leila R.; Blackburn, Octavia A.; Jones, Michael W.

2013-01-01

The self-assembly of higher order structures in water is realised by using the association of 1,3-biscarboxylates to binuclear meta-xylyl bridged DO3A complexes. Two dinicotinate binding sites are placed at a right-angle in a rhenium complex, which is shown to form a 1 : 2 complex with α,α'-bis(E......The self-assembly of higher order structures in water is realised by using the association of 1,3-biscarboxylates to binuclear meta-xylyl bridged DO3A complexes. Two dinicotinate binding sites are placed at a right-angle in a rhenium complex, which is shown to form a 1 : 2 complex with α...

Order from the disorder: hierarchical nanostructures self-assembled from the gas phase (Conference Presentation)

Science.gov (United States)

Di Fonzo, Fabio

2017-02-01

The assembly of nanoscale building blocks in engineered mesostructures is one of the fundamental goals of nanotechnology. Among the various processes developed to date, self-assembly emerges as one of the most promising, since it relays solely on basic physico-chemical forces. Our research is focused on a new type of self-assembly strategy from the gas-phase: Scattered Ballistic Deposition (SBD). SBD arises from the interaction of a supersonic molecular beam with a static gas and enables the growth of quasi-1D hierarchical mesostructures. Overall, they resemble a forest composed of individual, high aspect-ratio, tree-like structures, assembled from amorphous or crystalline nanoparticles. SBD is a general occurring phenomenon and can be obtained with different vapour or cluster sources. In particular, SBD by Pulsed Laser Deposition is a convenient physical vapor technique that allows the generation of supersonic plasma jets from any inorganic material irrespective of melting temperature, preserving even the most complex stoichiometries. One of the advantages of PLD over other vapour deposition techniques is extremely wide operational pressure range, from UHV to ambient pressure. These characteristics allowed us to develop quasi-1D hierarchical nanostructures from different transition metal oxides, semiconductors and metals. The precise control offered by the SBD-PLD technique over material properties at the nanoscale allowed us to fabricate ultra-thin, high efficiency hierarchical porous photonic crystals with Bragg reflectivity up to 85%. In this communication we will discuss the application of these materials to solar energy harvesting and storage, stimuli responsive photonic crystals and smart surfaces with digital control of their wettability behaviour.

Self-recognition in the coordination driven self-assembly of 2-D polygons.

Science.gov (United States)

Addicott, Chris; Das, Neeladri; Stang, Peter J

2004-08-23

Self-recognition in the transition-metal-mediated self-assembly of some 2-D polygons is presented. Prolonged heating of two or three organoplatinum reagents with 4,4'-dipyridyl in aqueous acetone results in the predominant formation of a rectangle, triangle, and/or square. All mixtures are characterized with NMR and electrospray ionization mass spectrometry (ESIMS). Despite the potential for ill-defined oligomeric products, these mixed ligand systems prefer to self-assemble into discrete species.

Self-assembly of inorganic nanoparticles: Ab ovo

Science.gov (United States)

Kotov, Nicholas A.

2017-09-01

There are numerous remarkable studies related to the self-organization of polymers, coordination compounds, microscale particles, biomolecules, macroscale particles, surfactants, and reactive molecules on surfaces. The focus of this paper is on the self-organization of nanoscale inorganic particles or simply nanoparticles (NPs). Although there are fascinating and profound discoveries made with other self-assembling structures, the ones involving NPs deserve particular attention because they (a) are omnipresent in Nature; (b) have relevance to numerous disciplines (physics, chemistry, biology, astronomy, Earth sciences, and others); (c) embrace most of the features, geometries, and intricacies observed for the self-organization of other chemical species; (d) offer new tools for studies of self-organization phenomena; and (e) have a large economic impact, extending from energy and construction industries, to optoelectronics, biomedical technologies, and food safety. Despite the overall success of the field it is necessary to step back from its multiple ongoing research venues and consider two questions: What is self-assembly of nanoparticles? and Why do we need to study it? The reason to bring them up is to achieve greater scientific depth in the understanding of these omnipresent phenomena and, perhaps, deepen their multifaceted impact. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

Bio-assembled, piezoelectric prawn shell made self-powered wearable sensor for non-invasive physiological signal monitoring

Science.gov (United States)

Ghosh, Sujoy Kumar; Mandal, Dipankar

2017-03-01

A human interactive self-powered wearable sensor is designed using waste by-product prawn shells. The structural origin of intrinsic piezoelectric characteristics of bio-assembled chitin nanofibers has been investigated. It allows the prawn shell to make a tactile sensor that performs also as a highly durable mechanical energy harvester/nanogenerator. The feasibility and fundamental physics of self-powered consumer electronics even from human perception is highlighted by prawn shells made nanogenerator (PSNG). High fidelity and non-invasive monitoring of vital signs, such as radial artery pulse wave and coughing actions, may lead to the potential use of PSNG for early intervention. It is presumed that PSNG has enormous future aspects in real-time as well as remote health care assessment.

Cooperative light-induced molecular movements of highly ordered azobenzene self-assembled monolayers.

Science.gov (United States)

Pace, Giuseppina; Ferri, Violetta; Grave, Christian; Elbing, Mark; von Hänisch, Carsten; Zharnikov, Michael; Mayor, Marcel; Rampi, Maria Anita; Samorì, Paolo

2007-06-12

Photochromic systems can convert light energy into mechanical energy, thus they can be used as building blocks for the fabrication of prototypes of molecular devices that are based on the photomechanical effect. Hitherto a controlled photochromic switch on surfaces has been achieved either on isolated chromophores or within assemblies of randomly arranged molecules. Here we show by scanning tunneling microscopy imaging the photochemical switching of a new terminally thiolated azobiphenyl rigid rod molecule. Interestingly, the switching of entire molecular 2D crystalline domains is observed, which is ruled by the interactions between nearest neighbors. This observation of azobenzene-based systems displaying collective switching might be of interest for applications in high-density data storage.

Enabling complex nanoscale pattern customization using directed self-assembly.

Science.gov (United States)

Doerk, Gregory S; Cheng, Joy Y; Singh, Gurpreet; Rettner, Charles T; Pitera, Jed W; Balakrishnan, Srinivasan; Arellano, Noel; Sanders, Daniel P

2014-12-16

Block copolymer directed self-assembly is an attractive method to fabricate highly uniform nanoscale features for various technological applications, but the dense periodicity of block copolymer features limits the complexity of the resulting patterns and their potential utility. Therefore, customizability of nanoscale patterns has been a long-standing goal for using directed self-assembly in device fabrication. Here we show that a hybrid organic/inorganic chemical pattern serves as a guiding pattern for self-assembly as well as a self-aligned mask for pattern customization through cotransfer of aligned block copolymer features and an inorganic prepattern. As informed by a phenomenological model, deliberate process engineering is implemented to maintain global alignment of block copolymer features over arbitrarily shaped, 'masking' features incorporated into the chemical patterns. These hybrid chemical patterns with embedded customization information enable deterministic, complex two-dimensional nanoscale pattern customization through directed self-assembly.

A protochlorophyllide light-harvesting complex involved in de-etiolation of higher plants

International Nuclear Information System (INIS)

Reinbothe, C.; Lebedev, N.; Reinbothe, S.

1999-01-01

When etiolated angiosperm seedlings break through the soil after germination, they are immediately exposed to sunlight, but at this stage they are unable to perform photosynthesis1. In the absence of chlorophyll a and chlorophyll b, two other porphyrin species cooperate as the basic light-harvesting structure of etiolated plants. Protochlorophyllide a and protochlorophyllide b (ref. 2) form supramolecular complexes with NADPH and two closely related NADPH:protochlorophyllide oxidoreductase (POR) proteins—PORA and PORB (ref. 3)—in the prolamellar body of etioplasts. Here we report that these light-harvesting POR–protochlorophyllide complexes, named LHPP, are essential for the establishment of the photosynthetic apparatus and also confer photoprotection on the plant. They collect sunlight for rapid chlorophyll a biosynthesis and, simultaneously, dissipate excess light energy in the bulk of non-photoreducible protochlorophyllide b. Based on this dual function, it seems that LHPP provides the link between skotomorphogenesis and photosynthesis that is required for efficient de-etiolation

Protein structural deformation induced lifetime shortening of photosynthetic bacteria light-harvesting complex LH2 excited state.

Science.gov (United States)

Chen, Xing-Hai; Zhang, Lei; Weng, Yu-Xiang; Du, Lu-Chao; Ye, Man-Ping; Yang, Guo-Zhen; Fujii, Ritsuko; Rondonuwu, Ferdy S; Koyama, Yasushi; Wu, Yi-Shi; Zhang, J P

2005-06-01

Photosynthetic bacterial light-harvesting antenna complex LH2 was immobilized on the surface of TiO(2) nanoparticles in the colloidal solution. The LH2/TiO(2) assembly was investigated by the time-resolved spectroscopic methods. The excited-state lifetimes for carotenoid-containing and carotenoidless LH2 have been measured, showing a decrease in the excited-state lifetime of B850 when LH2 was immobilized on TiO(2). The possibility that the decrease of the LH2 excited-state lifetime being caused by an interfacial electron transfer reaction between B850 and the TiO(2) nanoparticle was precluded experimentally. We proposed that the observed change in the photophysical properties of LH2 when assembled onto TiO(2) nanoparticles is arising from the interfacial-interaction-induced structural deformation of the LH2 complex deviating from an ellipse of less eccentric to a more eccentric ellipse, and the observed phenomenon can be accounted by an elliptical exciton model. Experiment by using photoinactive SiO(2) nanoparticle in place of TiO(2) and core complex LH1 instead of LH2 provide further evidence to the proposed mechanism.

Self-assembled Nanomaterials for Chemotherapeutic Applications

Science.gov (United States)

Shieh, Aileen

The self-assembly of short designed peptides into functional nanostructures is becoming a growing interest in a wide range of fields from optoelectronic devices to nanobiotechnology. In the medical field, self-assembled peptides have especially attracted attention with several of its attractive features for applications in drug delivery, tissue regeneration, biological engineering as well as cosmetic industry and also the antibiotics field. We here describe the self-assembly of peptide conjugated with organic chromophore to successfully deliver sequence independent micro RNAs into human non-small cell lung cancer cell lines. The nanofiber used as the delivery vehicle is completely non-toxic and biodegradable, and exhibit enhanced permeability effect for targeting malignant tumors. The transfection efficiency with nanofiber as the delivery vehicle is comparable to that of the commercially available RNAiMAX lipofectamine while the toxicity is significantly lower. We also conjugated the peptide sequence with camptothecin (CPT) and observed the self-assembly of nanotubes for chemotherapeutic applications. The peptide scaffold is non-toxic and biodegradable, and drug loading of CPT is high, which minimizes the issue of systemic toxicity caused by extensive burden from the elimination of drug carriers. In addition, the peptide assembly drastically increases the solubility and stability of CPT under physiological conditions in vitro, while active CPT is gradually released from the peptide chain under the slight acidic tumor cell environment. Cytotoxicity results on human colorectal cancer cells and non-small cell lung cancer cell lines display promising anti-cancer properties compared to the parental CPT drug, which cannot be used clinically due to its poor solubility and lack of stability in physiological conditions. Moreover, the peptide sequence conjugated with 5-fluorouracil formed a hydrogel with promising topical chemotherapeutic applications that also display

Mapping lightscapes: spatial patterning of artificial lighting in an urban landscape.

Science.gov (United States)

Hale, James D; Davies, Gemma; Fairbrass, Alison J; Matthews, Thomas J; Rogers, Christopher D F; Sadler, Jon P

2013-01-01

Artificial lighting is strongly associated with urbanisation and is increasing in its extent, brightness and spectral range. Changes in urban lighting have both positive and negative effects on city performance, yet little is known about how its character and magnitude vary across the urban landscape. A major barrier to related research, planning and governance has been the lack of lighting data at the city extent, particularly at a fine spatial resolution. Our aims were therefore to capture such data using aerial night photography and to undertake a case study of urban lighting. We present the finest scale multi-spectral lighting dataset available for an entire city and explore how lighting metrics vary with built density and land-use. We found positive relationships between artificial lighting indicators and built density at coarse spatial scales, whilst at a local level lighting varied with land-use. Manufacturing and housing are the primary land-use zones responsible for the city's brightly lit areas, yet manufacturing sites are relatively rare within the city. Our data suggests that efforts to address light pollution should broaden their focus from residential street lighting to include security lighting within manufacturing areas.

Morphology and Pattern Control of Diphenylalanine Self-Assembly via Evaporative Dewetting.

Science.gov (United States)

Chen, Jiarui; Qin, Shuyu; Wu, Xinglong; Chu, And Paul K

2016-01-26

Self-assembled peptide nanostructures have unique physical and biological properties and promising applications in electrical devices and functional molecular recognition. Although solution-based peptide molecules can self-assemble into different morphologies, it is challenging to control the self-assembly process. Herein, controllable self-assembly of diphenylalanine (FF) in an evaporative dewetting solution is reported. The fluid mechanical dimensionless numbers, namely Rayleigh, Marangoni, and capillary numbers, are introduced to control the interaction between the solution and FF molecules in the self-assembly process. The difference in the film thickness reflects the effects of Rayleigh and Marangoni convection, and the water vapor flow rate reveals the role of viscous fingering in the emergence of aligned FF flakes. By employing dewetting, various FF self-assembled patterns, like concentric and spokelike, and morphologies, like strips and hexagonal tubes/rods, can be produced, and there are no significant lattice structural changes in the FF nanostructures.

Quantum coherence spectroscopy reveals complex dynamics in bacterial light-harvesting complex 2 (LH2).

Science.gov (United States)

Harel, Elad; Engel, Gregory S

2012-01-17

Light-harvesting antenna complexes transfer energy from sunlight to photosynthetic reaction centers where charge separation drives cellular metabolism. The process through which pigments transfer excitation energy involves a complex choreography of coherent and incoherent processes mediated by the surrounding protein and solvent environment. The recent discovery of coherent dynamics in photosynthetic light-harvesting antennae has motivated many theoretical models exploring effects of interference in energy transfer phenomena. In this work, we provide experimental evidence of long-lived quantum coherence between the spectrally separated B800 and B850 rings of the light-harvesting complex 2 (LH2) of purple bacteria. Spectrally resolved maps of the detuning, dephasing, and the amplitude of electronic coupling between excitons reveal that different relaxation pathways act in concert for optimal transfer efficiency. Furthermore, maps of the phase of the signal suggest that quantum mechanical interference between different energy transfer pathways may be important even at ambient temperature. Such interference at a product state has already been shown to enhance the quantum efficiency of transfer in theoretical models of closed loop systems such as LH2.

Synthesis and Functional Reconstitution of Light-Harvesting Complex II into Polymeric Membrane Architectures.

Science.gov (United States)

Zapf, Thomas; Tan, Cherng-Wen Darren; Reinelt, Tobias; Huber, Christoph; Shaohua, Ding; Geifman-Shochat, Susana; Paulsen, Harald; Sinner, Eva-Kathrin

2015-12-01

One of most important processes in nature is the harvesting and dissipation of solar energy with the help of light-harvesting complex II (LHCII). This protein, along with its associated pigments, is the main solar-energy collector in higher plants. We aimed to generate stable, highly controllable, and sustainable polymer-based membrane systems containing LHCII-pigment complexes ready for light harvesting. LHCII was produced by cell-free protein synthesis based on wheat-germ extract, and the successful integration of LHCII and its pigments into different membrane architectures was monitored. The unidirectionality of LHCII insertion was investigated by protease digestion assays. Fluorescence measurements indicated chlorophyll integration in the presence of LHCII in spherical as well as planar bilayer architectures. Surface plasmon enhanced fluorescence spectroscopy (SPFS) was used to reveal energy transfer from chlorophyll b to chlorophyll a, which indicates native folding of the LHCII proteins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How nature designs light-harvesting antenna systems: design principles and functional realization in chlorophototrophic prokaryotes

Science.gov (United States)

Bryant, Donald A.; Canniffe, Daniel P.

2018-02-01

Chlorophyll-based phototrophs, or chlorophototrophs, convert light energy into stored chemical potential energy using two types of photochemical reaction center (RC), denoted type-1 and type-2. After excitation with light, a so-called special pair of chlorophylls in the RC is oxidized, and an acceptor is reduced. To ensure that RCs function at maximal rates in diffuse and variable light conditions, chlorophototrophs have independently evolved diverse light-harvesting antenna systems to rapidly and efficiently transfer that energy to the RCs. Energy transfer between weakly coupled chromophores is generally believed to proceed by resonance energy transfer, a dipole-induced-dipole process that was initially described theoretically by Förster. Nature principally optimizes three parameters in antenna systems: the distance separating the donor and acceptor chromophores, the relative orientations of those chromophores, and the spectral overlap between the donor and the acceptor chromophores. However, there are other important biological parameters that nature has optimized, and some common themes emerge from comparisons of different antenna systems. This tutorial considers structural and functional characteristics of three fundamentally different light-harvesting antenna systems of chlorophotrophic bacteria: phycobilisomes of cyanobacteria, the light-harvesting complexes (LH1 and LH2) of purple bacteria, and chlorosomes of green bacteria. Phycobilisomes are generally considered to represent an antenna system in which the chromophores are weakly coupled, while the strongly coupled bacteriochlorophyll molecules in LH1 and LH2 are strongly coupled and are better described by exciton theory. Chlorosomes can contain up to 250 000 bacteriochlorophyll molecules, which are very strongly coupled and form supramolecular, nanotubular arrays. The general and specific principles that have been optimized by natural selection during the evolution of these diverse light-harvesting

Selective Surface Acoustic Wave-Based Organophosphorus Sensor Employing a Host-Guest Self-Assembly Monolayer of β-Cyclodextrin Derivative

Directory of Open Access Journals (Sweden)

Yong Pan

2015-07-01

Full Text Available Self-assembly and molecular imprinting technologies are very attractive technologies for the development of artificial recognition systems and provide chemical recognition based on need and not happenstance. In this paper, we employed a b-cyclodextrin derivative surface acoustic wave (SAW chemical sensor for detecting the chemical warfare agents (CWAs sarin (O-Isoprophyl methylphosphonofluoridate, GB. Using sarin acid (isoprophyl hydrogen methylphosphonate as an imprinting template, mono[6-deoxy-6-[(mercaptodecamethylenethio

Conjugated material self-assembly : towards supramolecular electronics

NARCIS (Netherlands)

Leclère, P.E.L.G.; Surin, M.; Cavallini, M.; Jonkheijm, P.; Henze, O.; Schenning, A.P.H.J.; Biscarini, F.; Grimsdale, A.C.; Feast, W.J.; Meijer, E.W.; Müllen, K.; Brédas, J.L.; Lazzaroni, R.

2004-01-01

Properties of organic electronic materials in solid-state are determined as individual molecules and molecular assembly. It is essential to optimize conjugated materials to control performance of molecular assembly that constitute electronic devices such as light-emitting diodes and solar cells, and

Construction of Supramolecular Architectures via Self-assembly

Institute of Scientific and Technical Information of China (English)

Takeharu; Haino

2007-01-01

1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).

Quantitative self-assembly prediction yields targeted nanomedicines

Science.gov (United States)

Shamay, Yosi; Shah, Janki; Işık, Mehtap; Mizrachi, Aviram; Leibold, Josef; Tschaharganeh, Darjus F.; Roxbury, Daniel; Budhathoki-Uprety, Januka; Nawaly, Karla; Sugarman, James L.; Baut, Emily; Neiman, Michelle R.; Dacek, Megan; Ganesh, Kripa S.; Johnson, Darren C.; Sridharan, Ramya; Chu, Karen L.; Rajasekhar, Vinagolu K.; Lowe, Scott W.; Chodera, John D.; Heller, Daniel A.

2018-02-01

Development of targeted nanoparticle drug carriers often requires complex synthetic schemes involving both supramolecular self-assembly and chemical modification. These processes are generally difficult to predict, execute, and control. We describe herein a targeted drug delivery system that is accurately and quantitatively predicted to self-assemble into nanoparticles based on the molecular structures of precursor molecules, which are the drugs themselves. The drugs assemble with the aid of sulfated indocyanines into particles with ultrahigh drug loadings of up to 90%. We devised quantitative structure-nanoparticle assembly prediction (QSNAP) models to identify and validate electrotopological molecular descriptors as highly predictive indicators of nano-assembly and nanoparticle size. The resulting nanoparticles selectively targeted kinase inhibitors to caveolin-1-expressing human colon cancer and autochthonous liver cancer models to yield striking therapeutic effects while avoiding pERK inhibition in healthy skin. This finding enables the computational design of nanomedicines based on quantitative models for drug payload selection.

Structural Polymorphism in a Self-Assembled Tri-Aromatic Peptide System.

Science.gov (United States)

Brown, Noam; Lei, Jiangtao; Zhan, Chendi; Shimon, Linda J W; Adler-Abramovich, Lihi; Wei, Guanghong; Gazit, Ehud

2018-04-24

Self-assembly is a process of key importance in natural systems and in nanotechnology. Peptides are attractive building blocks due to their relative facile synthesis, biocompatibility, and other unique properties. Diphenylalanine (FF) and its derivatives are known to form nanostructures of various architectures and interesting and varied characteristics. The larger triphenylalanine peptide (FFF) was found to self-assemble as efficiently as FF, forming related but distinct architectures of plate-like and spherical nanostructures. Here, to understand the effect of triaromatic systems on the self-assembly process, we examined carboxybenzyl-protected diphenylalanine (z-FF) as a minimal model for such an arrangement. We explored different self-assembly conditions by changing solvent compositions and peptide concentrations, generating a phase diagram for the assemblies. We discovered that z-FF can form a variety of structures, including nanowires, fibers, nanospheres, and nanotoroids, the latter were previously observed only in considerably larger or co-assembly systems. Secondary structure analysis revealed that all assemblies possessed a β-sheet conformation. Additionally, in solvent combinations with high water ratios, z-FF formed rigid and self-healing hydrogels. X-ray crystallography revealed a "wishbone" structure, in which z-FF dimers are linked by hydrogen bonds mediated by methanol molecules, with a 2-fold screw symmetry along the c-axis. All-atom molecular dynamics (MD) simulations revealed conformations similar to the crystal structure. Coarse-grained MD simulated the assembly of the peptide into either fibers or spheres in different solvent systems, consistent with the experimental results. This work thus expands the building block library for the fabrication of nanostructures by peptide self-assembly.

Macroscopic magnetic Self assembly

NARCIS (Netherlands)

Löthman, Per Arvid

2018-01-01

Exploring the macroscopic scale's similarities to the microscale is part and parcel of this thesis as reflected in the research question: what can we learn about the microscopic scale by studying the macroscale? Investigations of the environment in which the self-assembly takes place, and the

Fatal attraction of short-tailed shearwaters to artificial lights.

Directory of Open Access Journals (Sweden)

Airam Rodríguez

Full Text Available Light pollution is increasing around the world and altering natural nightscapes with potential ecological and evolutionary consequences. A severe ecological perturbation caused by artificial lights is mass mortalities of organisms, including seabird fledglings that are attracted to lights at night on their first flights to the sea. Here, we report on the number of fledging short-tailed shearwaters Ardenna tenuirostris found grounded in evening and morning rescue patrols conducted at Phillip Island, Australia, during a 15-year period (1999-2013. We assessed factors affecting numbers of grounded birds and mortality including date, moon phase, wind direction and speed, number of visitors and holiday periods. We also tested experimentally if birds were attracted to lights by turning the lights off on a section of the road. Of 8871 fledglings found, 39% were dead or dying. This mortality rate was 4-8 times higher than reported elsewhere for other shearwater species, probably because searching for fledglings was part of our systematic rescue effort rather than the opportunistic rescue used elsewhere. Thus, it suggests that light-induced mortality of seabirds is usually underestimated. We rescued more birds (dead and alive in peak fledging, moonless and windy nights. Mortality increased through the fledging period, in the mornings and with increased traffic on holiday periods. Turning the road lights off decreased the number of grounded birds (dead and alive. While moon, wind and time are uncontrolled natural constraints, we demonstrated that reduction of light pollution and better traffic management can mitigate artificial light-induced mortality.

Green grasses as light harvesters in dye sensitized solar cells.

Science.gov (United States)

Shanmugam, Vinoth; Manoharan, Subbaiah; Sharafali, A; Anandan, Sambandam; Murugan, Ramaswamy

2015-01-25

Chlorophylls, the major pigments presented in plants are responsible for the process of photosynthesis. The working principle of dye sensitized solar cell (DSSC) is analogous to natural photosynthesis in light-harvesting and charge separation. In a similar way, natural dyes extracted from three types of grasses viz. Hierochloe Odorata (HO), Torulinium Odoratum (TO) and Dactyloctenium Aegyptium (DA) were used as light harvesters in dye sensitized solar cells (DSSCs). The UV-Vis absorption spectroscopy, Fourier transform infrared (FT-IR), and liquid chromatography-mass spectrometry (LC-MS) were used to characterize the dyes. The electron transport mechanism and internal resistance of the DSSCs were investigated by the electrochemical impedance spectroscopy (EIS). The performance of the cells fabricated with the grass extract shows comparable efficiencies with the reported natural dyes. Among the three types of grasses, the DSSC fabricated with the dye extracted from Hierochloe Odorata (HO) exhibited the maximum efficiency. LC-MS investigations indicated that the dominant pigment present in HO dye was pheophytin a (Pheo a). Copyright © 2014 Elsevier B.V. All rights reserved.

Minimalistic peptide supramolecular co-assembly: expanding the conformational space for nanotechnology.

Science.gov (United States)

Makam, Pandeeswar; Gazit, Ehud

2018-05-21

Molecular self-assembly is a ubiquitous process in nature and central to bottom-up nanotechnology. In particular, the organization of peptide building blocks into ordered supramolecular structures has gained much interest due to the unique properties of the products, including biocompatibility, chemical and structural diversity, robustness and ease of large-scale synthesis. In addition, peptides, as short as dipeptides, contain all the molecular information needed to spontaneously form well-ordered structures at both the nano- and the micro-scale. Therefore, peptide supramolecular assembly has been effectively utilized to produce novel materials with tailored properties for various applications in the fields of material science, engineering, medicine, and biology. To further expand the conformational space of peptide assemblies in terms of structural and functional complexity, multicomponent (two or more) peptide supramolecular co-assembly has recently evolved as a promising extended approach, similar to the structural diversity of natural sequence-defined biopolymers (proteins) as well as of synthetic covalent co-polymers. The use of this methodology was recently demonstrated in various applications, such as nanostructure physical dimension control, the creation of non-canonical complex topologies, mechanical strength modulation, the design of light harvesting soft materials, fabrication of electrically conducting devices, induced fluorescence, enzymatic catalysis and tissue engineering. In light of these significant advancements in the field of peptide supramolecular co-assembly in the last few years, in this tutorial review, we provide an updated overview and future prospects of this emerging subject.

Hierarchical Formation of Fibrillar and Lamellar Self-Assemblies from Guanosine-Based Motifs

Directory of Open Access Journals (Sweden)

Paolo Neviani

2010-01-01

Full Text Available Here we investigate the supramolecular polymerizations of two lipophilic guanosine derivatives in chloroform by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties.

pH-Sensitive Reversible Programmed Targeting Strategy by the Self-Assembly/Disassembly of Gold Nanoparticles.

Science.gov (United States)

Ma, Jinlong; Hu, Zhenpeng; Wang, Wei; Wang, Xinyu; Wu, Qiang; Yuan, Zhi

2017-05-24

A reversible programmed targeting strategy could achieve high tumor accumulation due to its long blood circulation time and high cellular internalization. Here, targeting ligand-modified poly(ethylene glycol) (PEG-ligand), dibutylamines (Bu), and pyrrolidinamines (Py) were introduced on the surface of gold nanoparticles (Au NPs) for reversible shielding/deshielding of the targeting ligands by pH-responsive self-assembly. Hydrophobic interaction and steric repulsion are the main driving forces for the self-assembly/disassembly of Au NPs. The precise self-assembly (pH ≥ 7.2) and disassembly (pH ≤ 6.8) of Au NPs with different ligands could be achieved by fine-tuning the modifying molar ratio of Bu and Py (R m ), which followed the formula R m = 1/(-0.0013X 2 + 0.0323X + 1), in which X is the logarithm of the partition coefficient of the targeting ligand. The assembled/disassembled behavior of Au NPs at pH 7.2 and 6.8 was confirmed by transmission electron microscopy and dynamic light scattering. Enzyme-linked immunosorbent assays and cellular uptake studies showed that the ligands could be buried inside the assembly and exposed when disassembled. More importantly, this process was reversible, which provides the possibility of prolonging blood circulation by shielding ligands associated with the NPs that were effused from tumor tissue.

Strategies to enhance the excitation energy-transfer efficiency in a light-harvesting system using the intra-molecular charge transfer character of carotenoids

Energy Technology Data Exchange (ETDEWEB)

Yukihira, Nao [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Sugai, Yuko [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Fujiwara, Masazumi [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Kosumi, Daisuke [Institute of Pulsed Power Science; Kumamoto University; Kumamoto; Japan; Iha, Masahiko [South Product Co. Ltd.; Uruma-shi; Japan; Sakaguchi, Kazuhiko [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Katsumura, Shigeo [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Gardiner, Alastair T. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Cogdell, Richard J. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Hashimoto, Hideki [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan

2017-01-01

Fucoxanthin is a carotenoid that is mainly found in light-harvesting complexes from brown algae and diatoms. Due to the presence of a carbonyl group attached to polyene chains in polar environments, excitation produces an excited intra-molecular charge transfer. This intra-molecular charge transfer state plays a key role in the highly efficient (~95%) energy-transfer from fucoxanthin to chlorophyllain the light-harvesting complexes from brown algae. In purple bacterial light-harvesting systems the efficiency of excitation energy-transfer from carotenoids to bacteriochlorophylls depends on the extent of conjugation of the carotenoids. In this study we were successful, for the first time, in incorporating fucoxanthin into a light-harvesting complex 1 from the purple photosynthetic bacterium,Rhodospirillum rubrumG9+ (a carotenoidless strain). Femtosecond pump-probe spectroscopy was applied to this reconstituted light-harvesting complex in order to determine the efficiency of excitation energy-transfer from fucoxanthin to bacteriochlorophyllawhen they are bound to the light-harvesting 1 apo-proteins.

Micelles versus Ribbons: How Congeners Drive the Self-Assembly of Acidic Sophorolipid Biosurfactants.

Science.gov (United States)

Dhasaiyan, Prabhu; Le Griel, Patrick; Roelants, Sophie; Redant, Emile; Van Bogaert, Inge N A; Prevost, Sylvain; Prasad, B L V; Baccile, Niki

2017-03-17

Sophorolipids (SLs), a class of microbially derived biosurfactants, are reported by different research groups to have different self-assembled structures (either micelles or giant ribbons) under the same conditions. Here we explore the reasons behind these contradictory results and attribute these differences to the role of specific congeners that are present in minute quantities. We show that a sample composed of a majority of oleic acid (C18:1) sophorolipid in the presence of only 0.5 % (or more) of congeners with stearic acid (C18:0) or linoleic acid (C18:2) results in the formation of micelles that are stable over long periods of time. Conversely, the presence of only 10 to 15 % of congeners with a stearic acid chain gives fibrillar structures instead of micelles. To study the mechanisms responsible, oleic acid SLs devoid of any other congeners were prepared. Very interestingly, this sample can self-assemble into either micelles or fibers depending on minute modifications to the self-assembly conditions. The findings are supported by light scattering, small-angle X-ray scattering, transmission electron microscopy under cryogenic conditions, high-pressure liquid chromatography, and NMR spectroscopy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembly behaviour of conjugated terthiophene surfactants in water

NARCIS (Netherlands)

van Rijn, Patrick; Janeliunas, Dainius; Brizard, Aurelie M.; Stuart, Marc C. A.; Koper, Ger J. M.; Eelkema, Rienk; van Esch, Jan H.

2011-01-01

Conjugated self-assembled systems in water are of great interest because of their potential application in biocompatible supramolecular electronics, but so far their supramolecular chemistry remains almost unexplored. Here we present amphiphilic terthiophenes as a general self-assembling platform

Self-organized pattern formation upon femtosecond laser ablation by circularly polarized light

International Nuclear Information System (INIS)

Varlamova, Olga; Costache, Florenta; Reif, Juergen; Bestehorn, Michael

2006-01-01

Surface ripples generation upon femtosecond laser ablation is attributed to self-organized structure formation from instability. We report that linear arrangements are observed not only for linearly polarized light but also for ablation with circularly polarized light. Long ordered chains of spherical nanoparticles, reminding of bead-strings are almost parallel but exhibit typical non-linear dynamics features such as bifurcations. In a first attempt to understand the self-assembly, we rely on models recently developed for the description of similar structures upon ion beam erosion and for the simulation of instabilities in thin liquid films. Our picture describes an unstable surface layer, non-uniformly eroded through Coulomb repulsion between individual positive charges

Self-Assembly of Spider Silk-Fusion Proteins Comprising Enzymatic and Fluorescence Activity.

Science.gov (United States)

Humenik, Martin; Mohrand, Madeleine; Scheibel, Thomas

2018-04-18

The recombinant spider silk protein eADF4(C16) was genetically fused either with esterase 2 (EST2) or green fluorescent protein (GFP). The fusions EST-eADF4(C16) and GFP-eADF4(C16) were spectroscopically investigated and showed native structures of EST and GFP. The structural integrity was confirmed by the enzymatic activity of EST and the fluorescence of GFP. The spider silk moiety retained its intrinsically unstructured conformation in solution and the self-assembly into either nanofibrils or nanoparticles could be controlled by the concentration of phosphate. Particles, however, showed significantly lower activity of the EST and GFP domains likely caused by a steric hindrance. However, upon self-assembly of EST-eADF4(C16) and GFP-eADF4(C16) into fibrils the protein activities were retained. In general, the fusion of globular enzymes with the spider silk domain allows the generation of fibrous biomaterials with catalytic or light emitting properties.

Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles.

Science.gov (United States)

Wang, Chao; Wang, Zhiqiang; Zhang, Xi

2012-04-17

The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting

Mesoscopic Self-Assembly: A Shift to Complexity

Directory of Open Access Journals (Sweden)

Massimo eMastrangeli

2015-06-01

Full Text Available By focusing on the construction of thermodynamically stable structures, the self-assembly of mesoscopic systems has proven capable of formidable achievements in the bottom-up engineering of micro- and nanosystems. Yet, inspired by an analogous evolution in supramolecular chemistry, synthetic mesoscopic self-assembly may have a lot more ahead, within reach of a shift toward fully three-dimensional architectures, collective interactions of building blocks and kinetic control. All over these challenging fronts, complexity holds the key.

Self-assembly based plasmonic arrays tuned by atomic layer deposition for extreme visible light absorption.

Science.gov (United States)

Hägglund, Carl; Zeltzer, Gabriel; Ruiz, Ricardo; Thomann, Isabell; Lee, Han-Bo-Ram; Brongersma, Mark L; Bent, Stacey F

2013-07-10

Achieving complete absorption of visible light with a minimal amount of material is highly desirable for many applications, including solar energy conversion to fuel and electricity, where benefits in conversion efficiency and economy can be obtained. On a fundamental level, it is of great interest to explore whether the ultimate limits in light absorption per unit volume can be achieved by capitalizing on the advances in metamaterial science and nanosynthesis. Here, we combine block copolymer lithography and atomic layer deposition to tune the effective optical properties of a plasmonic array at the atomic scale. Critical coupling to the resulting nanocomposite layer is accomplished through guidance by a simple analytical model and measurements by spectroscopic ellipsometry. Thereby, a maximized absorption of light exceeding 99% is accomplished, of which up to about 93% occurs in a volume-equivalent thickness of gold of only 1.6 nm. This corresponds to a record effective absorption coefficient of 1.7 × 10(7) cm(-1) in the visible region, far exceeding those of solid metals, graphene, dye monolayers, and thin film solar cell materials. It is more than a factor of 2 higher than that previously obtained using a critically coupled dye J-aggregate, with a peak width exceeding the latter by 1 order of magnitude. These results thereby substantially push the limits for light harvesting in ultrathin, nanoengineered systems.

On the theory of frequency-shifted secondary emission of light-harvesting molecular systems

International Nuclear Information System (INIS)

Morozov, V.A.

2001-01-01

The expressions are obtained for the intensity of the frequency-shifted secondary emission of a chromophore playing the role of a reaction center in the simplest model three-chromophore molecular 'light-harvesting' antenna, which is constructed and oriented in space so that the incident photons coherently excite two of its chromophore pigments. The quantum-field formalism was used, which takes into account the generalized (quantum-electrodynamic) dipole-dipole, as well as radiative and nonradiative dissipative interactions between pigments and the reaction center of the antenna. The special features of the excitation spectrum of the Raman scattering line and the frequency-shifted fluorescence spectrum of the reaction center of the molecular antenna under study are discussed. A comparison of the expressions obtained for the excitation and fluorescence spectra and with the corresponding expressions obtained for a bichromophore molecular system, which differs from a three-chromophore antenna by the absence of one of the pigments, revealed the properties of the mechanism of action of light-harvesting molecular antennas that have not been found earlier. In particular, it is shown that 'the light-harvesting' caused by the collective dissipative interactions of pigments with the reaction center of the antenna can substantially exceed a sum of contributions from separate pigments

An Inductorless Self-Controlled Rectifier for Piezoelectric Energy Harvesting.

Science.gov (United States)

Lu, Shaohua; Boussaid, Farid

2015-11-19

This paper presents a high-efficiency inductorless self-controlled rectifier for piezoelectric energy harvesting. High efficiency is achieved by discharging the piezoelectric device (PD) capacitance each time the current produced by the PD changes polarity. This is achieved automatically without the use of delay lines, thereby making the proposed circuit compatible with any type of PD. In addition, the proposed rectifier alleviates the need for an inductor, making it suitable for on-chip integration. Reported experimental results show that the proposed rectifier can harvest up to 3.9 times more energy than a full wave bridge rectifier.

An Inductorless Self-Controlled Rectifier for Piezoelectric Energy Harvesting

Directory of Open Access Journals (Sweden)

Shaohua Lu

2015-11-01

Full Text Available This paper presents a high-efficiency inductorless self-controlled rectifier for piezoelectric energy harvesting. High efficiency is achieved by discharging the piezoelectric device (PD capacitance each time the current produced by the PD changes polarity. This is achieved automatically without the use of delay lines, thereby making the proposed circuit compatible with any type of PD. In addition, the proposed rectifier alleviates the need for an inductor, making it suitable for on-chip integration. Reported experimental results show that the proposed rectifier can harvest up to 3.9 times more energy than a full wave bridge rectifier.

Opto-electronic devices with nanoparticles and their assemblies

Science.gov (United States)

Nguyen, Chieu Van

Nanotechnology is a fast growing field; engineering matters at the nano-meter scale. A key nanomaterial is nanoparticles (NPs). These sub-wavelength (background noise. The second device is based on a one-dimensional (1-D) self-directed self-assembly of Au NPs mediated by dielectric materials. Depending on the coverage density of the Au NPs assembly deposited on the device, electronic emission was observed at ultra-low bias of 40V, leading to low-power plasma generation in air at atmospheric pressure. Light emitted from the plasma is apparent to the naked eyes. Similarly, 1-D self-assembly of Au NPs mediated by iron oxide was fabricated and exhibits ferro-magnetic behavior. The multi-functional 1-D self-assembly of Au NPs has great potential in modern electronics such as solid state lighting, plasma-based nanoelectronics, and memory devices.

Harvesting a short rotation forest

Energy Technology Data Exchange (ETDEWEB)

Perttu, K L [ed.

1984-12-01

Willow and Sallow, considered of great interest for Swedish conditions, present new problems in harvesting. Traditional logging techniques offer few elements of equipment or methods. Light whips may be comminuted to a bulk product, easy to handle, difficult to store, requiring a hot logging system - and requiring a heavy, powerful harvester. Aggregating the material introduces an intermediate wood-fuel unit, suitable for storing, transport and infeed into any comminuter. If the harvester produced billets it would require less energy for its operation and it may be used for other purposes such as pre-commercial thinning or row thinning during the growing season. A few groups of designers have worked on analyses of requirements and possible solutions. Test rigs for severing and bundling were built and evaluated. Public funding was made available for design work on harvesters. Five groups were selected to produce layout designs of large and small harvesters. An evaluation procedure was performed, leading to selection of two concepts, slightly reworked from their original shapes. One is a large self-propelled front-sutting harvester, the other is a harvesting unit to be mounted on a suitable farm tractor. With 3 refs.

The non-covalent decoration of self-assembling protein fibers.

Science.gov (United States)

Mahmoud, Zahra N; Grundy, Daniel J; Channon, Kevin J; Woolfson, Derek N

2010-10-01

The design of self-assembling fibers presents challenges in basic science, and has potential for developing materials for applications in areas such as tissue engineering. A contemporary issue in the field is the construction of multi-component, functionalized systems. Previously, we have developed peptide-based fibers, the SAF system, that comprises two complementary peptides, which affords considerable control over assembly and morphology. Here we present a straightforward route to functionalizing the SAFs with small molecules and, subsequently, other moieties. This is achieved via non-covalent recruitment of charged peptide tags, which offers advantages such as further control, reversibility, and future prospects for developing recombinant tags. We demonstrate the concept by appending fluorescent labels and biotin (and thence gold nanoparticles) to the peptides, and visualising the resulting decorated SAFs by light and electron microscopy. The peptide tags bind in the nm-mum range, and show specificity compared with control peptides, and for the SAFs over similar alpha-helix-based peptide fibers. 2010 Elsevier Ltd. All rights reserved.

Self-assembling peptide-based building blocks in medical applications

Energy Technology Data Exchange (ETDEWEB)

Acar, Handan; Srivastava, Samanvaya; Chung, Eun Ji; Schnorenberg, Mathew R.; Barrett, John C.; LaBelle, James L.; Tirrell, Matthew

2017-02-01

Peptides and peptide-conjugates, comprising natural and synthetic building blocks, are an increasingly popular class of biomaterials. Self-assembled nanostructures based on peptides and peptide-conjugates offer advantages such as precise selectivity and multifunctionality that can address challenges and limitations in the clinic. In this review article, we discuss recent developments in the design and self-assembly of various nanomaterials based on peptides and peptide-conjugates for medical applications, and categorize them into two themes based on the driving forces of molecular self-assembly. First, we present the self-assembled nanostructures driven by the supramolecular interactions between the peptides, with or without the presence of conjugates. The studies where nanoassembly is driven by the interactions between the conjugates of peptide-conjugates are then presented. Particular emphasis is given to in vivo studies focusing on therapeutics, diagnostics, immune modulation and regenerative medicine. Finally, challenges and future perspectives are presented.

Synthesis and Characterization of Self-Assembled Nanogels Made of Pullulan

Directory of Open Access Journals (Sweden)

Sílvia A. Ferreira

2011-03-01

Full Text Available Self-assembled nanogels made of hydrophobized pullulan were obtained using a versatile, simple, reproducible and low-cost method. In a first reaction pullulan was modified with hydroxyethyl methacrylate or vinyl methacrylate, further modified in the second step with hydrophobic 1-hexadecanethiol, resulting as an amphiphilic material, which self-assembles in water via the hydrophobic interaction among alkyl chains. Structural features, size, shape, surface charge and stability of the nanogels were studied using hydrogen nuclear magnetic resonance, fluorescence spectroscopy, cryo-field emission scanning electron microscopy and dynamic light scattering. Above the critical aggregation concentration spherical polydisperse macromolecular micelles revealed long-term colloidal stability in aqueous medium, with a nearly neutral negative surface charge and mean hydrodynamic diameter in the range 100–400 nm, depending on the polymer degree of substitution. Good size stability was observed when nanogels were exposed to potential destabilizing pH conditions. While the size stability of the nanogel made of pullulan with vinyl methacrylate and more hydrophobic chains grafted was affected by the ionic strength and urea, nanogel made of pullulan with hydroxyethyl methacrylate and fewer hydrophobic chains grafted remained stable.

Watching Nanoscale Self-Assembly Kinetics of Gold Prisms in Liquids

Science.gov (United States)

Kim, Juyeong; Ou, Zihao; Jones, Matthew R.; Chen, Qian

We use liquid-phase transmission electron microscopy to watch self-assembly of gold triangular prisms into polymer-like structures. The in situ dynamics monitoring enabled by liquid-phase transmission electron microscopy, single nanoparticle tracking, and the marked conceptual similarity between molecular reactions and nanoparticle self-assembly combined elucidate the following mechanistic understanding: a step-growth polymerization based assembly statistics, kinetic pathways sampling particle curvature dependent energy minima and their interconversions, and directed assembly into polymorphs (linear or cyclic chains) through in situ modulation of the prism bonding geometry. Our study bridges the constituent kinetics on the molecular and nanoparticle length scales, which enriches the design rules in directed self-assembly of anisotropic nanoparticles.

Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

Science.gov (United States)

Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

2015-08-01

Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple Distributed Smart Microgrids with a Self-Autonomous, Energy Harvesting Wireless Sensor Network

DEFF Research Database (Denmark)

Guerrero, Josep M.; Kheng Tan, Yen

2012-01-01

The chapter covers the smart wireless sensors for microgrids, as well as the energy harvesting technology used to sustain the operations of these sensors. Last, a case study on the multiple distributed smart microgrids with a self-autonomous, energy harvesting wireless sensor network is presented....

Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.

Science.gov (United States)

Iwaura, Rika; Yui, Hiroharu; Someya, Yuu; Ohnishi-Kameyama, Mayumi

2014-01-05

We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT. Copyright © 2013 Elsevier B.V. All rights reserved.

Controlling Self-Assembly in Al(110) Homoepitaxy

Science.gov (United States)

Tiwary, Yogesh; Fichthorn, Kristen

2010-03-01

Homoepitaxial growth on Al(110) exhibits nanoscale self-assembly into huts with well-defined (100) and (111) facets [1]. Although some of the diffusion mechanisms underlying this kinetic self-assembly were identified and incorporated into a two-dimensional model [2], we used density-functional theory (DFT) to identify many other mechanisms that are needed to describe the three-dimensional assembly seen experimentally [3]. We developed a three-dimensional kinetic Monte Carlo (KMC) model of Al(110) homoepitaxy. The inputs to the model were obtained from DFT [3,4]. Our model is in agreement with experimentally observed trends for this system. We used KMC to predict self-assembly under various growth conditions. To achieve precise placement of Al nanohuts, we simulated thermal-field-directed assembly [5]. Our results indicate that this technique can be used to create uniform arrays of nanostructures. [1] F. Buatier de Mongeot, W. Zhu, A. Molle, R. Buzio, C. Boragno, U. Valbusa, E. Wang, and Z. Zhang, Phys. Rev. Lett. 91, 016102 (2003). [2] W. Zhu, F. Buatier de Mongeot, U. Valbusa, E. G. Wang, and Z. Y. Zhang, Phys. Rev. Lett. 92, 106102 (2004). [3] Y. Tiwary and K. A. Fichthorn, submitted to Phys. Rev. B. [4] Y. Tiwary and K. A. Fichthorn, Phys. Rev. B 78, 205418 (2008). [5] C. Zhang and R. Kalyanaraman, Appl. Phys. Lett. 83, 4827 (2003).

Reviving Vibration Energy Harvesting and Self-Powered Sensing by a Triboelectric Nanogenerator

KAUST Repository

Chen, Jun

2017-10-10

Vibration energy harvesting and sensing is a traditional and growing research field in which various working mechanisms and designs have been developed for an improved performance. Relying on a coupling effect of contact electrification and electrostatic induction, in the past 5 years, triboelectric nanogenerator (TENG) has been applied as a fundamentally new technology to revive the field of vibration energy harvesting and self-powered sensing, especially for low-frequency vibrations such as human motion, automobile, machine, and bridge vibrations. The demonstrated instantaneous energy conversion efficiency of ∼70% and a total efficiency up to 85% distinguished TENG from traditional techniques. In this article, both TENG-enabled vibration energy harvesting and self-powered active sensing are comprehensively reviewed. Moving toward future development, problems pressing for solutions and onward research directions are also posed to deliver a coherent picture.

Electrodynamic tailoring of self-assembled three-dimensional electrospun constructs

Science.gov (United States)

Reis, Tiago C.; Correia, Ilídio J.; Aguiar-Ricardo, Ana

2013-07-01

The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive electrostatic forces between the positively charged aerial fibers and the already collected ones, which tend to acquire a negatively charged network oriented towards the nozzle. The in situ polarization degree is strengthened by higher amounts of clustered fibers, and therefore the initial high density fibrous regions are the preliminary motifs for the self-assembly mechanism. As such regions increase their in situ polarization electrostatic repulsive forces will appear, favoring a competitive growth of these self-assembled fibrous clusters. Highly polarized regions will evidence higher distances between consecutive micro-assembled fibers (MAFs). Different processing parameters - deposition time, electric field intensity, concentration of polymer solution, environmental temperature and relative humidity - were evaluated in an attempt to control material's design.The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive

Light Harvesting for Organic Photovoltaics

Science.gov (United States)

2016-01-01

The field of organic photovoltaics has developed rapidly over the last 2 decades, and small solar cells with power conversion efficiencies of 13% have been demonstrated. Light absorbed in the organic layers forms tightly bound excitons that are split into free electrons and holes using heterojunctions of electron donor and acceptor materials, which are then extracted at electrodes to give useful electrical power. This review gives a concise description of the fundamental processes in photovoltaic devices, with the main emphasis on the characterization of energy transfer and its role in dictating device architecture, including multilayer planar heterojunctions, and on the factors that impact free carrier generation from dissociated excitons. We briefly discuss harvesting of triplet excitons, which now attracts substantial interest when used in conjunction with singlet fission. Finally, we introduce the techniques used by researchers for characterization and engineering of bulk heterojunctions to realize large photocurrents, and examine the formed morphology in three prototypical blends. PMID:27951633

Integrating DNA strand-displacement circuitry with DNA tile self-assembly

Science.gov (United States)

Zhang, David Yu; Hariadi, Rizal F.; Choi, Harry M.T.; Winfree, Erik

2013-01-01

DNA nanotechnology has emerged as a reliable and programmable way of controlling matter at the nanoscale through the specificity of Watson–Crick base pairing, allowing both complex self-assembled structures with nanometer precision and complex reaction networks implementing digital and analog behaviors. Here we show how two well-developed frameworks, DNA tile self-assembly and DNA strand-displacement circuits, can be systematically integrated to provide programmable kinetic control of self-assembly. We demonstrate the triggered and catalytic isothermal self-assembly of DNA nanotubes over 10 μm long from precursor DNA double-crossover tiles activated by an upstream DNA catalyst network. Integrating more sophisticated control circuits and tile systems could enable precise spatial and temporal organization of dynamic molecular structures. PMID:23756381

Self-Assembly of Colloidal Particles

Indian Academy of Sciences (India)

is self-assembly where one engineers interaction between nanoscopic building blocks so ..... big question in the field how this microscopic chirality of the virus gets translated ... shape emerges due to a competition between the surface tension.

Balancing the intermolecular forces in peptide amphiphiles for controlling self-assembly transitions.

Science.gov (United States)

Buettner, C J; Wallace, A J; Ok, S; Manos, A A; Nicholl, M J; Ghosh, A; Tweedle, M F; Goldberger, J E

2017-06-21

While the influence of alkyl chain length and headgroup size on self-assembly behaviour has been well-established for simple surfactants, the rational control over the pH- and concentration-dependent self-assembly behaviour in stimuli responsive peptides remains an elusive goal. Here, we show that different amphiphilic peptides can have similar self-assembly phase diagrams, providing the relative strengths of the attractive and repulsive forces are balanced. Using palmitoyl-YYAAEEEEK(DO3A:Gd)-NH 2 and palmitoyl-YAAEEEEK(DO3A:Gd)-NH 2 as controls, we show that reducing hydrophobic attractive forces through fewer methylene groups in the alkyl chain will lead to a similar self-assembly phase diagram as increasing the electrostatic repulsive forces via the addition of a glutamic acid residue. These changes allow creation of self-assembled MRI vehicles with slightly different micelle and nanofiber diameters but with minimal changes in the spin-lattice T 1 relaxivity. These findings reveal a powerful strategy to design self-assembled vehicles with different sizes but with similar self-assembly profiles.

Self-assembled domain structures: From micro- to nanoscale

Directory of Open Access Journals (Sweden)

Vladimir Shur

2015-06-01

Full Text Available The recent achievements in studying the self-assembled evolution of micro- and nanoscale domain structures in uniaxial single crystalline ferroelectrics lithium niobate and lithium tantalate have been reviewed. The results obtained by visualization of static domain patterns and kinetics of the domain structure by different methods from common optical microscopy to more sophisticated scanning probe microscopy, scanning electron microscopy and confocal Raman microscopy, have been discussed. The kinetic approach based on various nucleation processes similar to the first-order phase transition was used for explanation of the domain structure evolution scenarios. The main mechanisms of self-assembling for nonequilibrium switching conditions caused by screening ineffectiveness including correlated nucleation, domain growth anisotropy, and domain–domain interaction have been considered. The formation of variety of self-assembled domain patterns such as fractal-type, finger and web structures, broad domain boundaries, and dendrites have been revealed at each of all five stages of domain structure evolution during polarization reversal. The possible applications of self-assembling for micro- and nanodomain engineering were reviewed briefly. The review covers mostly the results published by our research group.

Self-assembly of silver nanoparticles and bacteriophage

Directory of Open Access Journals (Sweden)

Santi Scibilia

2016-03-01

Full Text Available Biohybrid nanostructured materials, composed of both inorganic nanoparticles and biomolecules, offer prospects for many new applications in extremely diverse fields such as chemistry, physics, engineering, medicine and nanobiotechnology. In the recent years, Phage display technique has been extensively used to generate phage clones displaying surface peptides with functionality towards organic materials. Screening and selection of phage displayed material binding peptides has attracted great interest because of their use for development of hybrid materials with multiple functionalities. Here, we present a self-assembly approach for the construction of hybrid nanostructured networks consisting of M13 P9b phage clone, specific for Pseudomonas aeruginosa, selected by Phage display technology, directly assembled with silver nanoparticles (AgNPs, previously prepared by pulsed laser ablation. These networks are characterized by UV–vis optical spectroscopy, scanning/transmission electron microscopies and Raman spectroscopy. We investigated the influence of different ions and medium pH on self-assembly by evaluating different phage suspension buffers. The assembly of these networks is controlled by electrostatic interactions between the phage pVIII major capsid proteins and the AgNPs. The formation of the AgNPs-phage networks was obtained only in two types of tested buffers at a pH value near the isoelectric point of each pVIII proteins displayed on the surface of the clone. This systematic study allowed to optimize the synthesis procedure to assembly AgNPs and bacteriophage. Such networks find application in the biomedical field of advanced biosensing and targeted gene and drug delivery. Keywords: Phage display, Silver nanoparticles, Self-assembly, Hybrid architecture, Raman spectroscopy

Driven self-assembly of hard nanoplates on soft elastic shells

International Nuclear Information System (INIS)

Zhang Yao-Yang; Hua Yun-Feng; Deng Zhen-Yu

2015-01-01

The driven self-assembly behaviors of hard nanoplates on soft elastic shells are investigated by using molecular dynamics (MD) simulation method, and the driven self-assembly structures of adsorbed hard nanoplates depend on the shape of hard nanoplates and the bending energy of soft elastic shells. Three main structures for adsorbed hard nanoplates, including the ordered aggregation structures of hard nanoplates for elastic shells with a moderate bending energy, the collapsed structures for elastic shells with a low bending energy, and the disordered aggregation structures for hard shells, are observed. The self-assembly process of adsorbed hard nanoplates is driven by the surface tension of the elastic shell, and the shape of driven self-assembly structures is determined on the basis of the minimization of the second moment of mass distribution. Meanwhile, the deformations of elastic shells can be controlled by the number of adsorbed rods as well as the length of adsorbed rods. This investigation can help us understand the complexity of the driven self-assembly of hard nanoplates on elastic shells. (paper)

Amyloid Fibrils as Building Blocks for Natural and Artificial Functional Materials.

Science.gov (United States)

Knowles, Tuomas P J; Mezzenga, Raffaele

2016-08-01

Proteinaceous materials based on the amyloid core structure have recently been discovered at the origin of biological functionality in a remarkably diverse set of roles, and attention is increasingly turning towards such structures as the basis of artificial self-assembling materials. These roles contrast markedly with the original picture of amyloid fibrils as inherently pathological structures. Here we outline the salient features of this class of functional materials, both in the context of the functional roles that have been revealed for amyloid fibrils in nature, as well as in relation to their potential as artificial materials. We discuss how amyloid materials exemplify the emergence of function from protein self-assembly at multiple length scales. We focus on the connections between mesoscale structure and material function, and demonstrate how the natural examples of functional amyloids illuminate the potential applications for future artificial protein based materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new construction technique for tissue-engineered heart valves using the self-assembly method.

Science.gov (United States)

Tremblay, Catherine; Ruel, Jean; Bourget, Jean-Michel; Laterreur, Véronique; Vallières, Karine; Tondreau, Maxime Y; Lacroix, Dan; Germain, Lucie; Auger, François A

2014-11-01

Tissue engineering appears as a promising option to create new heart valve substitutes able to overcome the serious drawbacks encountered with mechanical substitutes or tissue valves. The objective of this article is to present the construction method of a new entirely biological stentless aortic valve using the self-assembly method and also a first assessment of its behavior in a bioreactor when exposed to a pulsatile flow. A thick tissue was created by stacking several fibroblast sheets produced with the self-assembly technique. Different sets of custom-made templates were designed to confer to the thick tissue a three-dimensional (3D) shape similar to that of a native aortic valve. The construction of the valve was divided in two sequential steps. The first step was the installation of the thick tissue in a flat preshaping template followed by a 4-week maturation period. The second step was the actual cylindrical 3D forming of the valve. The microscopic tissue structure was assessed using histological cross sections stained with Masson's Trichrome and Picrosirius Red. The thick tissue remained uniformly populated with cells throughout the construction steps and the dense extracellular matrix presented corrugated fibers of collagen. This first prototype of tissue-engineered heart valve was installed in a bioreactor to assess its capacity to sustain a light pulsatile flow at a frequency of 0.5 Hz. Under the light pulsed flow, it was observed that the leaflets opened and closed according to the flow variations. This study demonstrates that the self-assembly method is a viable option for the construction of complex 3D shapes, such as heart valves, with an entirely biological material.

A Theoretical and Experimental Study of DNA Self-assembly

Science.gov (United States)

Chandran, Harish

The control of matter and phenomena at the nanoscale is fast becoming one of the most important challenges of the 21st century with wide-ranging applications from energy and health care to computing and material science. Conventional top-down approaches to nanotechnology, having served us well for long, are reaching their inherent limitations. Meanwhile, bottom-up methods such as self-assembly are emerging as viable alternatives for nanoscale fabrication and manipulation. A particularly successful bottom up technique is DNA self-assembly where a set of carefully designed DNA strands form a nanoscale object as a consequence of specific, local interactions among the different components, without external direction. The final product of the self-assembly process might be a static nanostructure or a dynamic nanodevice that performs a specific function. Over the past two decades, DNA self-assembly has produced stunning nanoscale objects such as 2D and 3D lattices, polyhedra and addressable arbitrary shaped substrates, and a myriad of nanoscale devices such as molecular tweezers, computational circuits, biosensors and molecular assembly lines. In this dissertation we study multiple problems in the theory, simulations and experiments of DNA self-assembly. We extend the Turing-universal mathematical framework of self-assembly known as the Tile Assembly Model by incorporating randomization during the assembly process. This allows us to reduce the tile complexity of linear assemblies. We develop multiple techniques to build linear assemblies of expected length N using far fewer tile types than previously possible. We abstract the fundamental properties of DNA and develop a biochemical system, which we call meta-DNA, based entirely on strands of DNA as the only component molecule. We further develop various enzyme-free protocols to manipulate meta-DNA systems and provide strand level details along with abstract notations for these mechanisms. We simulate DNA circuits by

3D Orthogonal Woven Triboelectric Nanogenerator for Effective Biomechanical Energy Harvesting and as Self-Powered Active Motion Sensors.

Science.gov (United States)

Dong, Kai; Deng, Jianan; Zi, Yunlong; Wang, Yi-Cheng; Xu, Cheng; Zou, Haiyang; Ding, Wenbo; Dai, Yejing; Gu, Bohong; Sun, Baozhong; Wang, Zhong Lin

2017-10-01

The development of wearable and large-area energy-harvesting textiles has received intensive attention due to their promising applications in next-generation wearable functional electronics. However, the limited power outputs of conventional textiles have largely hindered their development. Here, in combination with the stainless steel/polyester fiber blended yarn, the polydimethylsiloxane-coated energy-harvesting yarn, and nonconductive binding yarn, a high-power-output textile triboelectric nanogenerator (TENG) with 3D orthogonal woven structure is developed for effective biomechanical energy harvesting and active motion signal tracking. Based on the advanced 3D structural design, the maximum peak power density of 3D textile can reach 263.36 mW m -2 under the tapping frequency of 3 Hz, which is several times more than that of conventional 2D textile TENGs. Besides, its collected power is capable of lighting up a warning indicator, sustainably charging a commercial capacitor, and powering a smart watch. The 3D textile TENG can also be used as a self-powered active motion sensor to constantly monitor the movement signals of human body. Furthermore, a smart dancing blanket is designed to simultaneously convert biomechanical energy and perceive body movement. This work provides a new direction for multifunctional self-powered textiles with potential applications in wearable electronics, home security, and personalized healthcare. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of light transmission through optical fiber-to-fiber connector assemblies

International Nuclear Information System (INIS)

Chung, M.; Gutowski, M.; Adams, M.; Solomon, J.

1998-01-01

Optical fiber-to-fiber connectors are now being used widely in particle tracking detectors. We describe the properties of the connectors, their production, and measurements of the light transmission through the gap of the connector assembly. We studied light transmission for various types of connectors illuminated by several different light sources. The light transmission was found to be dependent on the angular distribution of the light rays passing through a connector assembly. Two arrangements were studied, a point source and a diffuse source. A green LED with a diffuser is believed to best reproduce the angular distributions of light in the real detector applications. We also studied the transmission as a function of the index of refraction of the optical couplants. The light transmission depends on the index of refraction of an optical couplant placed in the gap, and improves as it approaches the index of refraction of the fiber core. Light transmissions of 80%∼88% were obtained without any optical couplant in the connector gap and transmissions of 89%∼99% with various optical couplants. A Monte Carlo study using measured light distributions from a fiber end produced a reasonable agreement with the transmission measurements made on a connector assembly

Study of light transmission through optical fiber-to-fiber connector assemblies

International Nuclear Information System (INIS)

Chung, M.; Gutowski, M.; Adams, M.; Solomon, J.

1998-01-01

Optical fiber-to-fiber connectors are now being used widely in particle tracking detectors. We describe the properties of the connectors, their production, and measurements of the light transmission through the gap of the connector assembly. We studied light transmission for various types of connectors illuminated by several different light sources. The light transmission was found to be dependent on the angular distribution of the light rays passing through a connector assembly. Two arrangements were studied, a point source and a diffuse source. A green LED with a diffuser is believed to best reproduce the angular distributions of light in the real detector applications. We also studied the transmission as a function of the index of refraction of the optical couplants. The light transmission depends on the index of refraction of an optical couplant placed in the gap, and improves as it approaches the index of refraction of the fiber core. Light transmissions of 80%∼88% were obtained without any optical couplant in the connector gap and transmissions of 89%∼99% with various optical couplants. A Monte Carlo study using measured light distributions from a fiber end produced a reasonable agreement with the transmission measurements made on a connector assembly. copyright 1998 American Institute of Physics

Functional self-assembled lipidic systems derived from renewable resources.

Science.gov (United States)

Silverman, Julian R; Samateh, Malick; John, George

2016-01-01

Self-assembled lipidic amphiphile systems can create a variety of multi-functional soft materials with value-added properties. When employing natural reagents and following biocatalytic syntheses, self-assembling monomers may be inherently designed for degradation, making them potential alternatives to conventional and persistent polymers. By using non-covalent forces, self-assembled amphiphiles can form nanotubes, fibers, and other stimuli responsive architectures prime for further applied research and incorporation into commercial products. By viewing these lipid derivatives under a lens of green principles, there is the hope that in developing a structure-function relationship and functional smart materials that research may remain safe, economic, and efficient.

Balancing photosynthetic light-harvesting and light-utilization capacities in potato leaf tissue during acclimation to different growth temperatures

Science.gov (United States)

Steffen, K. L.; Wheeler, R. M.; Arora, R.; Palta, J. P.; Tibbitts, T. W.

1995-01-01

We investigated the effect of temperature during growth and development on the relationship between light-harvesting capacity, indicated by chlorophyll concentration, and light-utilization potential, indicated by light- and bicarbonate-saturated photosynthetic oxygen evolution, in Solanum tuberosum L. cv. Norland. Clonal plantlets were transplanted and grown at 20 degrees C for 2 weeks before transfer to 12, 16, 20, 24 and 28 degrees C for 6 weeks. After 4 weeks of the temperature treatments, leaf tissue fresh weights per area were one-third higher in plants grown at 12 degrees C vs those grown at 28 degrees C. Conversely, chlorophyll content per area in tissue grown at 12 degrees C was less than one-half of that of tissue grown at 28 degrees C at 4 weeks. Photosynthetic capacity measured at a common temperature of 20 degrees C and expressed on a chlorophyll basis was inversely proportional to growth temperature. Leaf tissue from plants grown at 12 degrees C for 4 weeks had photosynthetic rates that were 3-fold higher on a chlorophyll basis than comparable tissue from plants grown at 28 degrees C. These results suggest that the relationship between light-harvesting capacity and light-utilization potential varies 3-fold in response to the growth temperatures examined. The role of this response in avoidance of photoinhibition is discussed.

Self-assembled three-dimensional chiral colloidal architecture

Science.gov (United States)

Ben Zion, Matan Yah; He, Xiaojin; Maass, Corinna C.; Sha, Ruojie; Seeman, Nadrian C.; Chaikin, Paul M.

2017-11-01

Although stereochemistry has been a central focus of the molecular sciences since Pasteur, its province has previously been restricted to the nanometric scale. We have programmed the self-assembly of micron-sized colloidal clusters with structural information stemming from a nanometric arrangement. This was done by combining DNA nanotechnology with colloidal science. Using the functional flexibility of DNA origami in conjunction with the structural rigidity of colloidal particles, we demonstrate the parallel self-assembly of three-dimensional microconstructs, evincing highly specific geometry that includes control over position, dihedral angles, and cluster chirality.

Identification of Factors Promoting HBV Capsid Self-Assembly by Assembly-Promoting Antivirals.

Science.gov (United States)

Rath, Soumya Lipsa; Liu, Huihui; Okazaki, Susumu; Shinoda, Wataru

2018-02-26

Around 270 million individuals currently live with hepatitis B virus (HBV) infection. Heteroaryldihydropyrimidines (HAPs) are a family of antivirals that target the HBV capsid protein and induce aberrant self-assembly. The capsids formed resemble the native capsid structure but are unable to propagate the virus progeny because of a lack of RNA/DNA. Under normal conditions, self-assembly is initiated by the viral genome. The mode of action of HAPs, however, remains largely unknown. In this work, using molecular dynamics simulations, we attempted to understand the action of HAP by comparing the dynamics of capsid proteins with and without HAPs. We found that the inhibitor is more stable in higher oligomers. It retains its stability in the hexamer throughout 1 μs of simulation. Our results also show that the inhibitor might help in stabilizing the C-terminus, the HBc 149-183 arginine-rich domain of the capsid protein. The C-termini of dimers interact with each other, assisted by the HAP inhibitor. During capsid assembly, the termini are supposed to directly interact with the viral genome, thereby suggesting that the viral genome might work in a similar way to stabilize the capsid protein. Our results may help in understanding the underlying molecular mechanism of HBV capsid self-assembly, which should be crucial for exploring new drug targets and structure-based drug design.

Activity patterns during food provisioning are affected by artificial light in free living great tits (Parus major.

Directory of Open Access Journals (Sweden)

Mieke Titulaer

Full Text Available Artificial light may have severe ecological consequences but there is limited experimental work to assess these consequences. We carried out an experimental study on a wild population of great tits (Parus major to assess the impact of light pollution on daily activity patterns during the chick provisioning period. Pairs that were provided with a small light outside their nest box did not alter the onset, cessation or duration of their working day. There was however a clear effect of artificial light on the feeding rate in the second half of the nestling period: when provided with artificial light females increased their feeding rate when the nestlings were between 9 and 16 days old. Artificial light is hypothesised to have affected the perceived photoperiod of either the parents or the offspring which in turn led to increased parental care. This may have negative fitness consequences for the parents, and light pollution may thus create an ecological trap for breeding birds.

Illumination properties and energy savings of a solar fiber optic lighting system balanced by artificial lights

OpenAIRE

Lingfors, David

2013-01-01

A solar fiber optic lighting system, SP3 from the Swedish company Parans Solar Lighting AB, has been installed in a study area/corridor test site. A collector is tracking the sun during daytime, focusing the direct sun irradiance via Fresnel lenses into optical fibers, which guide the solar light into the building. The illumination properties of the system have been characterized. The energy saving due to reduced need of artificial lighting have been calculated and methods for balancing the a...

Energy conversion in natural and artificial photosynthesis.

Science.gov (United States)

McConnell, Iain; Li, Gonghu; Brudvig, Gary W

2010-05-28

Modern civilization is dependent upon fossil fuels, a nonrenewable energy source originally provided by the storage of solar energy. Fossil-fuel dependence has severe consequences, including energy security issues and greenhouse gas emissions. The consequences of fossil-fuel dependence could be avoided by fuel-producing artificial systems that mimic natural photosynthesis, directly converting solar energy to fuel. This review describes the three key components of solar energy conversion in photosynthesis: light harvesting, charge separation, and catalysis. These processes are compared in natural and in artificial systems. Such a comparison can assist in understanding the general principles of photosynthesis and in developing working devices, including photoelectrochemical cells, for solar energy conversion. 2010 Elsevier Ltd. All rights reserved.

A Novel Strategy for Synthesis of Gold Nanoparticle Self Assemblies

NARCIS (Netherlands)

Verma, Jyoti; Lal, Sumit; van Veen, Henk A.; van Noorden, Cornelis J. F.

2014-01-01

Gold nanoparticle self assemblies are one-dimensional structures of gold nanoparticles. Gold nanoparticle self assemblies exhibit unique physical properties and find applications in the development of biosensors. Methodologies currently available for lab-scale and commercial synthesis of gold

Optically nonlinear energy transfer in light-harvesting dendrimers

Science.gov (United States)

Andrews, David L.; Bradshaw, David S.

2004-08-01

Dendrimeric polymers are the subject of intense research activity geared towards their implementation in nanodevice applications such as energy harvesting systems, organic light-emitting diodes, photosensitizers, low-threshold lasers, and quantum logic elements, etc. A recent development in this area has been the construction of dendrimers specifically designed to exhibit novel forms of optical nonlinearity, exploiting the unique properties of these materials at high levels of photon flux. Starting from a thorough treatment of the underlying theory based on the principles of molecular quantum electrodynamics, it is possible to identify and characterize several optically nonlinear mechanisms for directed energy transfer and energy pooling in multichromophore dendrimers. Such mechanisms fall into two classes: first, those where two-photon absorption by individual donors is followed by transfer of the net energy to an acceptor; second, those where the excitation of two electronically distinct but neighboring donor groups is followed by a collective migration of their energy to a suitable acceptor. Each transfer process is subject to minor dissipative losses. In this paper we describe in detail the balance of factors and the constraints that determines the favored mechanism, which include the excitation statistics, structure of the energy levels, laser coherence factors, chromophore selection rules and architecture, possibilities for the formation of delocalized excitons, spectral overlap, and the overall distribution of donors and acceptors. Furthermore, it transpires that quantum interference between different mechanisms can play an important role. Thus, as the relative importance of each mechanism determines the relevant nanophotonic characteristics, the results reported here afford the means for optimizing highly efficient light-harvesting dendrimer devices.

Design and self-assembly of simple coat proteins for artificial viruses

NARCIS (Netherlands)

Hernandez-Garcia, Armando; Kraft, Daniela J.; Janssen, Anne F J; Bomans, Paul H H; Sommerdijk, Nico A J M; Thies-Weesie, Dominique M E; Favretto, Marco E.; Brock, Roland; De Wolf, Frits A.; Werten, Marc W T; Van Der Schoot, Paul; Stuart, Martien Cohen; De Vries, Renko

2014-01-01

Viruses are among the simplest biological systems and are highly effective vehicles for the delivery of genetic material into susceptible host cells1. Artificial viruses can be used as model systems for providing insights into natural viruses and can be considered a testing ground for developing

Crystal-Structure-Guided Design of Self-Assembling RNA Nanotriangles.

Science.gov (United States)

Boerneke, Mark A; Dibrov, Sergey M; Hermann, Thomas

2016-03-14

RNA nanotechnology uses RNA structural motifs to build nanosized architectures that assemble through selective base-pair interactions. Herein, we report the crystal-structure-guided design of highly stable RNA nanotriangles that self-assemble cooperatively from short oligonucleotides. The crystal structure of an 81 nucleotide nanotriangle determined at 2.6 Å resolution reveals the so-far smallest circularly closed nanoobject made entirely of double-stranded RNA. The assembly of the nanotriangle architecture involved RNA corner motifs that were derived from ligand-responsive RNA switches, which offer the opportunity to control self-assembly and dissociation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-‘‘factory’’ for self-assembled peptide nanostructures

DEFF Research Database (Denmark)

Castillo, Jaime; Rodriguez-Trujíllo, Romén; Gauthier, Sébastian

2011-01-01

This study describes an integrated micro ‘‘factory’’ for the preparation of biological self-assembled peptide nanotubes and nanoparticles on a polymer chip, yielding controlled growth conditions. Self-assembled peptides constitute attractive building blocks for the fabrication of biological...... nanostructures due to the mild conditions of their synthesis process. This biological material can form nanostructures in a rapid way and the synthesis method is less expensive as compared to that of carbon nanotubes or silicon nanowires. The present article thus reports on the on-chip fabrication of self-assembled...

Supramolecular ribbons from amphiphilic trisamides self-assembly.

Science.gov (United States)

García, Fátima; Buendía, Julia; Sánchez, Luis

2011-08-05

Two amphiphilic C(3)-symmetric OPE-based trisamides have been synthesized and their self-assembling features investigated in solution and on surface. Variable-temperature UV-vis experiments demonstrate the cooperative supramolecular polymerization of these trisamides that self-assemble by the operation of triple C═O···H-N H-bonding arrays between the amide functional groups and π-π stacking between the aromatic units. The helical organization of the aggregates has been demonstrated by circular dichroism at a concentration as low as 1 × 10(-4) M in acetonitrile. In the reported trisamides, the large hydrophobic aromatic core acts as a solvophobic module impeding the interaction between the polar TEG chains and the amide H-bonds. This strategy makes unnecessary the separation of the amide functional groups to the polar tri(ethylene glycol) chains by paraffinic fragments. Achiral trisamide 1 self-assembles into flat ribbon-like structures that experience an amplification of chirality by the addition of a small amount of chiral 2 that generates twisted stripes.

Plants lacking the main light-harvesting complex retain photosystem II macro-organization

NARCIS (Netherlands)

Ruban, A.V.; Wentworth, M.; Yakushevska, A.E.; Andersson, J.; Lee, P.J.; Keegstra, W.; Dekker, J.P.; Boekema, E.J.; Jansson, S.; Horton, P.

2003-01-01

Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts. Several light-harvesting antenna complexes are organized precisely in the

Plants lacking the main light-harvesting complex retain photosystem II macro-organization

NARCIS (Netherlands)

Ruban, AV; Wentworth, M; Yakushevska, AE; Andersson, J; Lee, PJ; Keegstra, W; Dekker, JP; Boekema, EJ; Jansson, S; Horton, P

2003-01-01

Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts(1). Several light-harvesting antenna complexes are organized precisely in the

Pigment structure in the FCP-like light-harvesting complex from Chromera velia

Czech Academy of Sciences Publication Activity Database

Llansola-Portoles, M.J.; Uragami, C.; Pacsal, A.; Bína, David; Litvín, Radek; Robert, B.

2016-01-01

Roč. 1857, č. 11 (2016), s. 1759-1765 ISSN 0005-2728 R&D Projects: GA ČR GBP501/12/G055 Institutional support: RVO:60077344 Keywords : Photosynthesis * Chlorophylls * Carotenoids * Light harvesting complex Subject RIV: CE - Biochemistry Impact factor: 4.932, year: 2016

Self-Assembled Monolayers of CdSe Nanocrystals on Doped GaAs Substrates

DEFF Research Database (Denmark)

Marx, E.; Ginger, D.S.; Walzer, Karsten

2002-01-01

This letter reports the self-assembly and analysis of CdSe nanocrystal monolayers on both p- and a-doped GaAs substrates. The self-assembly was performed using a 1,6-hexanedithiol self-assembled monolayer (SAM) to link CdSe nanocrystals to GaAs substrates. Attenuated total reflection Fourier tran...

Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

Science.gov (United States)

Das, Santu; Kumar, Saurabh; Mallick, Apabrita; Roy, Soumyajit

2015-09-01

Topological transformation manifested in inorganic materials shows manifold possibilities. In our present work, we show a clear topological transformation in a soft-oxometalate (SOM) system which was formed from its polyoxometalate (POM) precursor [PMo12@Mo72Fe30]. This topological transformation was observed due to time dependent competitive self-assembly of two different length scale soft-oxometalate moieties formed from this two-component host-guest reaction. We characterized different morphologies by scanning electron microscopy, electron dispersive scattering spectroscopy, dynamic light scattering, horizontal attenuated total reflection-infrared spectroscopy and Raman spectroscopy. The predominant structure is selected by its size in a sort of supramolecular Darwinian competition in this process and is described here.

Nanospheres Prepared by Self-Assembly of Random Copolymers in Supercritical Carbon Dioxide

Directory of Open Access Journals (Sweden)

Eri Yoshida

2012-01-01

Full Text Available The synthesis of spherical particles was attained by the direct self-assembly of poly[2-(perfluorooctylethyl acrylate-random-acrylic acid], P(POA-r-AA, and by the indirect self-assembly poly[POA-random-2-(dimethylaminoethyl acrylate], P(POA-r-DAA, with dicarboxylic acids in supercritical carbon dioxide (scCO2. The copolymers formed spherical particles with hundreds of nanometer diameters in a heterogeneous state at pressures lower than the cloud point pressure. The formation of spherical particles was also dependent on the temperature. The formation of spherical particles could be optimized through varying the solvent quality by the manipulation of the CO2 pressure and temperature for the different copolymer compositions. The dynamic light scattering and 1H NMR studies demonstrated that the nanospheres had the micellar structures consisting of the CO2-philic POA shells and the CO2-phobic AA or DAA cores including the main chain cores. The nanospheres produced the superhydrophobic surfaces based on the water-proof shells of the POA units.

Combing and self-assembly phenomena in dry films of Taxol-stabilized microtubules

Directory of Open Access Journals (Sweden)

Rose Franck

2007-01-01

Full Text Available AbstractMicrotubules are filamentous proteins that act as a substrate for the translocation of motor proteins. As such, they may be envisioned as a scaffold for the self-assembly of functional materials and devices. Physisorption, self-assembly and combing are here investigated as a potential prelude to microtubule-templated self-assembly. Dense films of self-assembled microtubules were successfully produced, as well as patterns of both dendritic and non-dendritic bundles of microtubules. They are presented in the present paper and the mechanism of their formation is discussed.

Self-assembly of subwavelength nanostructures with symmetry breaking in solution

Science.gov (United States)

Tian, Xiang-Dong; Chen, Shu; Zhang, Yue-Jiao; Dong, Jin-Chao; Panneerselvam, Rajapandiyan; Zhang, Yun; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2016-01-01

Nanostructures with symmetry breaking can allow the coupling between dark and bright plasmon modes to induce strong Fano resonance. However, it is still a daunting challenge to prepare bottom-up self-assembled subwavelength asymmetric nanostructures with appropriate gaps between the nanostructures especially below 5 nm in solution. Here we present a viable self-assembly method to prepare symmetry-breaking nanostructures consisting of Ag nanocubes and Au nanospheres both with tunable size (90-250 nm for Au nanospheres; 100-160 nm for Ag nanocubes) and meanwhile control the nanogaps through ultrathin silica shells of 1-5 nm thickness. The Raman tag of 4-mercaptobenzoic acid (MBA) assists the self-assembly process and endows the subwavelength asymmetric nanostructures with surface-enhanced Raman scattering (SERS) activity. Moreover, thick silica shells (above 50 nm thickness) can be coated on the self-assembled nanostructures in situ to stabilize the whole nanostructures, paving the way toward bioapplications. Single particle scattering spectroscopy with a 360° polarization resolution is performed on individual Ag nanocube and Au nanosphere dimers, correlated with high-resolution TEM characterization. The asymmetric dimers exhibit strong configuration and polarization dependence Fano resonance properties. Overall, the solution-based self-assembly method reported here is opening up new opportunities to prepare diverse multicomponent nanomaterials with optimal performance.Nanostructures with symmetry breaking can allow the coupling between dark and bright plasmon modes to induce strong Fano resonance. However, it is still a daunting challenge to prepare bottom-up self-assembled subwavelength asymmetric nanostructures with appropriate gaps between the nanostructures especially below 5 nm in solution. Here we present a viable self-assembly method to prepare symmetry-breaking nanostructures consisting of Ag nanocubes and Au nanospheres both with tunable size (90-250 nm

Sulfate Anion Delays the Self-Assembly of Human Insulin by Modifying the Aggregation Pathway

OpenAIRE

Owczarz, Marta; Arosio, Paolo

2014-01-01

The understanding of the molecular mechanisms underlying protein self-assembly and of their dependence on solvent composition has implications in a large number of biological and biotechnological systems. In this work, we characterize the aggregation process of human insulin at acidic pH in the presence of sulfate ions using a combination of Thioflavin T fluorescence, dynamic light scattering, size exclusion chromatography, Fourier transform infrared spectroscopy, and transmission electron mi...

ARCHITECTURE OF A CHARGE-TRANSFER STATE REGULATING LIGHT HARVESTING IN A PLANT ANTENNA PROTEIN

Energy Technology Data Exchange (ETDEWEB)

Fleming, Graham; Ahn, Tae Kyu; Avenson, Thomas J.; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K.; Bassi, Roberto; Fleming, Graham R.

2008-04-02

Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge-transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). In this work, we present evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a de-localized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can `tune? the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophylls-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

Science.gov (United States)

Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

2008-09-01

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Control of electro-chemical processes using energy harvesting materials and devices.

Science.gov (United States)

Zhang, Yan; Xie, Mengying; Adamaki, Vana; Khanbareh, Hamideh; Bowen, Chris R

2017-12-11

Energy harvesting is a topic of intense interest that aims to convert ambient forms of energy such as mechanical motion, light and heat, which are otherwise wasted, into useful energy. In many cases the energy harvester or nanogenerator converts motion, heat or light into electrical energy, which is subsequently rectified and stored within capacitors for applications such as wireless and self-powered sensors or low-power electronics. This review covers the new and emerging area that aims to directly couple energy harvesting materials and devices with electro-chemical systems. The harvesting approaches to be covered include pyroelectric, piezoelectric, triboelectric, flexoelectric, thermoelectric and photovoltaic effects. These are used to influence a variety of electro-chemical systems such as applications related to water splitting, catalysis, corrosion protection, degradation of pollutants, disinfection of bacteria and material synthesis. Comparisons are made between the range harvesting approaches and the modes of operation are described. Future directions for the development of electro-chemical harvesting systems are highlighted and the potential for new applications and hybrid approaches are discussed.

In(1-x)Ga(x)N@ZnO: a rationally designed and quantum dot integrated material for water splitting and solar harvesting applications.

Science.gov (United States)

Rajaambal, Sivaraman; Mapa, Maitri; Gopinath, Chinnakonda S

2014-09-07

The highly desirable combination of the visible light absorption properties of In1-xGaxN Quantum dots (QD) along with the multifunctionality of ZnO into a single integrated material was prepared for solar harvesting. This is the first report on InGaN QD integrated with ZnO (InGaN@ZnO), synthesized by a highly reproducible, simple combustion method in 15 min. Structural, microstructural and electronic integration of the nitride and oxide components of InGaN@ZnO was demonstrated by appropriate characterization methods. Self-assembly of InGaN QD is induced in growing nascent zinc oxo nanoclusters taking advantage of the common wurtzite structure and nitrogen incorporation at the expense of oxygen vacancies. Direct integration brings about a single phase structure exhibiting extensive visible light absorption and high photostability. InGaN@ZnO suggests synergistic operation of light harvesting and charge conducting components for solar H2 generation without using any co-catalyst or sacrificial agent, and a promising photocurrent generation at 0 V under visible light illumination. The present study suggests a direct integration of QD with the host matrix and is a potential method to realize the advantages of QDs.

Omnidirectional Harvesting of Weak Light Using a Graphene Quantum Dot-Modified Organic/Silicon Hybrid Device

KAUST Repository

Tsai, Meng-Lin

2017-04-21

Despite great improvements in traditional inorganic photodetectors and photovoltaics, more progress is needed in the detection/collection of light at low-level conditions. Traditional photodetectors tend to suffer from high noise when operated at room temperature; therefore, these devices require additional cooling systems to detect weak or dim light. Conventional solar cells also face the challenge of poor light-harvesting capabilities in hazy or cloudy weather. The real world features such varying levels of light, which makes it important to develop strategies that allow optical devices to function when conditions are less than optimal. In this work, we report an organic/inorganic hybrid device that consists of graphene quantum dot-modified poly(3,4-ethylenedioxythiophene) polystyrenesulfonate spin-coated on Si for the detection/harvest of weak light. The hybrid configuration provides the device with high responsivity and detectability, omnidirectional light trapping, and fast operation speed. To demonstrate the potential of this hybrid device in real world applications, we measured near-infrared light scattered through human tissue to demonstrate noninvasive oximetric photodetection as well as characterized the device\\'s photovoltaic properties in outdoor (i.e., weather-dependent) and indoor weak light conditions. This organic/inorganic device configuration demonstrates a promising strategy for developing future high-performance low-light compatible photodetectors and photovoltaics.

Precision polymers and 3D DNA nanostructures: emergent assemblies from new parameter space.

Science.gov (United States)

Serpell, Christopher J; Edwardson, Thomas G W; Chidchob, Pongphak; Carneiro, Karina M M; Sleiman, Hanadi F

2014-11-05

Polymer self-assembly and DNA nanotechnology have both proved to be powerful nanoscale techniques. To date, most attempts to merge the fields have been limited to placing linear DNA segments within a polydisperse block copolymer. Here we show that, by using hydrophobic polymers of a precisely predetermined length conjugated to DNA strands, and addressable 3D DNA prisms, we are able to effect the formation of unprecedented monodisperse quantized superstructures. The structure and properties of larger micelles-of-prisms were probed in depth, revealing their ability to participate in controlled release of their constituent nanostructures, and template light-harvesting energy transfer cascades, mediated through both the addressability of DNA and the controlled aggregation of the polymers.

Architecture of the light-harvesting apparatus of the eustigmatophyte alga Nannochloropsis oceanica

Czech Academy of Sciences Publication Activity Database

Litvín, Radek; Bína, David; Herbstová, Miroslava; Gardian, Zdenko

2016-01-01

Roč. 130, 1-3 (2016), s. 137-150 ISSN 0166-8595 R&D Projects: GA ČR(CZ) GP14-01377P Institutional support: RVO:60077344 Keywords : Light harvesting * Thylakoid membrane * Vaucheriaxanthin * Violaxanthin–chlorophyll protein Subject RIV: BO - Biophysics Impact factor: 3.864, year: 2016

Energy Harvesting from the Animal/Human Body for Self-Powered Electronics.

Science.gov (United States)

Dagdeviren, Canan; Li, Zhou; Wang, Zhong Lin

2017-06-21

Living subjects (i.e., humans and animals) have abundant sources of energy in chemical, thermal, and mechanical forms. The use of these energies presents a viable way to overcome the battery capacity limitation that constrains the long-term operation of wearable/implantable devices. The intersection of novel materials and fabrication techniques offers boundless possibilities for the benefit of human health and well-being via various types of energy harvesters. This review summarizes the existing approaches that have been demonstrated to harvest energy from the bodies of living subjects for self-powered electronics. We present material choices, device layouts, and operation principles of these energy harvesters with a focus on in vivo applications. We discuss a broad range of energy harvesters placed in or on various body parts of human and animal models. We conclude with an outlook of future research in which the integration of various energy harvesters with advanced electronics can provide a new platform for the development of novel technologies for disease diagnostics, treatment, and prevention.

Self-assembled peptide-based nanostructures: Smart nanomaterials toward targeted drug delivery.

Science.gov (United States)

Habibi, Neda; Kamaly, Nazila; Memic, Adnan; Shafiee, Hadi

2016-02-01

Self-assembly of peptides can yield an array of well-defined nanostructures that are highly attractive nanomaterials for many biomedical applications such as drug delivery. Some of the advantages of self-assembled peptide nanostructures over other delivery platforms include their chemical diversity, biocompatibility, high loading capacity for both hydrophobic and hydrophilic drugs, and their ability to target molecular recognition sites. Furthermore, these self-assembled nanostructures could be designed with novel peptide motifs, making them stimuli-responsive and achieving triggered drug delivery at disease sites. The goal of this work is to present a comprehensive review of the most recent studies on self-assembled peptides with a focus on their "smart" activity for formation of targeted and responsive drug-delivery carriers.

Different roles of alpha- and beta-branch xanthophylls in photosystem assembly and photoprotection.

Science.gov (United States)

Dall'Osto, Luca; Fiore, Alessia; Cazzaniga, Stefano; Giuliano, Giovanni; Bassi, Roberto

2007-11-30

Xanthophylls (oxygenated carotenoids) are essential components of the plant photosynthetic apparatus, where they act in photosystem assembly, light harvesting, and photoprotection. Nevertheless, the specific function of individual xanthophyll species awaits complete elucidation. In this work, we analyze the photosynthetic phenotypes of two newly isolated Arabidopsis mutants in carotenoid biosynthesis containing exclusively alpha-branch (chy1chy2lut5) or beta-branch (chy1chy2lut2) xanthophylls. Both mutants show complete lack of qE, the rapidly reversible component of nonphotochemical quenching, and high levels of photoinhibition and lipid peroxidation under photooxidative stress. Both mutants are much more photosensitive than npq1lut2, which contains high levels of viola- and neoxanthin and a higher stoichiometry of light-harvesting proteins with respect to photosystem II core complexes, suggesting that the content in light-harvesting complexes plays an important role in photoprotection. In addition, chy1chy2lut5, which has lutein as the only xanthophyll, shows unprecedented photosensitivity even in low light conditions, reduced electron transport rate, enhanced photobleaching of isolated LHCII complexes, and a selective loss of CP26 with respect to chy1chy2lut2, highlighting a specific role of beta-branch xanthophylls in photoprotection and in qE mechanism. The stronger photosystem II photoinhibition of both mutants correlates with the higher rate of singlet oxygen production from thylakoids and isolated light-harvesting complexes, whereas carotenoid composition of photosystem II core complex was not influential. In depth analysis of the mutant phenotypes suggests that alpha-branch (lutein) and beta-branch (zeaxanthin, violaxanthin, and neoxanthin) xanthophylls have distinct and complementary roles in antenna protein assembly and in the mechanisms of photoprotection.

Proteins evolve on the edge of supramolecular self-assembly

Science.gov (United States)

Garcia-Seisdedos, Hector; Empereur-Mot, Charly; Elad, Nadav; Levy, Emmanuel D.

2017-08-01

The self-association of proteins into symmetric complexes is ubiquitous in all kingdoms of life. Symmetric complexes possess unique geometric and functional properties, but their internal symmetry can pose a risk. In sickle-cell disease, the symmetry of haemoglobin exacerbates the effect of a mutation, triggering assembly into harmful fibrils. Here we examine the universality of this mechanism and its relation to protein structure geometry. We introduced point mutations solely designed to increase surface hydrophobicity among 12 distinct symmetric complexes from Escherichia coli. Notably, all responded by forming supramolecular assemblies in vitro, as well as in vivo upon heterologous expression in Saccharomyces cerevisiae. Remarkably, in four cases, micrometre-long fibrils formed in vivo in response to a single point mutation. Biophysical measurements and electron microscopy revealed that mutants self-assembled in their folded states and so were not amyloid-like. Structural examination of 73 mutants identified supramolecular assembly hot spots predictable by geometry. A subsequent structural analysis of 7,471 symmetric complexes showed that geometric hot spots were buffered chemically by hydrophilic residues, suggesting a mechanism preventing mis-assembly of these regions. Thus, point mutations can frequently trigger folded proteins to self-assemble into higher-order structures. This potential is counterbalanced by negative selection and can be exploited to design nanomaterials in living cells.

Dark states and delocalization: Competing effects of quantum coherence on the efficiency of light harvesting systems.

Science.gov (United States)

Hu, Zixuan; Engel, Gregory S; Alharbi, Fahhad H; Kais, Sabre

2018-02-14

Natural light harvesting systems exploit electronic coupling of identical chromophores to generate efficient and robust excitation transfer and conversion. Dark states created by strong coupling between chromophores in the antenna structure can significantly reduce radiative recombination and enhance energy conversion efficiency. Increasing the number of the chromophores increases the number of dark states and the associated enhanced energy conversion efficiency yet also delocalizes excitations away from the trapping center and reduces the energy conversion rate. Therefore, a competition between dark state protection and delocalization must be considered when designing the optimal size of a light harvesting system. In this study, we explore the two competing mechanisms in a chain-structured antenna and show that dark state protection is the dominant mechanism, with an intriguing dependence on the parity of the number of chromophores. This dependence is linked to the exciton distribution among eigenstates, which is strongly affected by the coupling strength between chromophores and the temperature. Combining these findings, we propose that increasing the coupling strength between the chromophores can significantly increase the power output of the light harvesting system.

Improving light harvesting in polymer photodetector devices through nanoindented metal mask films

NARCIS (Netherlands)

Macedo, A. G.; Zanetti, F.; Mikowski, A.; Hummelen, J. C.; Lepienski, C. M.; da Luz, M. G. E.; Roman, L. S.

2008-01-01

To enhance light harvesting in organic photovoltaic devices, we propose the incorporation of a metal (aluminum) mask film in the system's usual layout. We fabricate devices in a sandwich geometry, where the mask (nanoindented with a periodic array of holes of sizes d and spacing s) is added between

Water-soluble light-emitting nanoparticles prepared by non-covalent bond self-assembly of a hydroxyl group functionalized oligo(p-phenyleneethynylene) with different water-soluble polymers

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Water-soluble light-emitting nanoparticles were prepared from hydroxyl group functionalized oligos(p-phenyleneethynylene) (OHOPEL) and water-soluble polymers(PEG,PAA,and PG) by non-covalent bond self-assembly.Their structure and optoelectronic properties were investigated through dynamic light scattering(DLS) ,UV and PL spectroscopy.The optical properties of OHOPEL-based water-soluble nanoparticles exhibited the same properties as that found in OHOPEL films,indicating the existence of interchain-aggregation of OHOPELs in the nanoparticles.OHOPEL-based nanoparticles prepared from conjugated oligomers show smaller size and lower dispersity than nanoparticles from conjugated polymers,which means that the structures of water-soluble nanoparticles are linked to the conjugated length.Furthermore,the OHOPEL/PG and OHOPEL/PAA systems produced smaller particles and lower polydispersity than the OHOPEL/PEG system,indicating that there may exist influence of the strength of non-covalent bonds on the size and degree of dispersity of the nanoparticles.

Carbon dioxide fixation by artificial photosynthesis

Energy Technology Data Exchange (ETDEWEB)

Ibusuki, Takashi; Koike, Kazuhide; Ishitani, Osamu [National Inst. for Resources and Environment, AIST, MITI, Tsukuba, Ibaraki (Japan)

1993-12-31

Green plants can absorb atmospheric CO{sub 2} and transform it to sugars, carbohydrates through their photosynthetic systems, but they become the source of CO{sub 2} when they are dead. This is the reason why artificial leaves which can be alive forever should be developed to meet with global warming due to the increase of CO{sub 2} concentration. The goal of artificial photosynthesis is not to construct the same system as the photosynthetic one, but to mimic the ability of green plants to utilize solar energy to make high energy chemicals. Needless to say, the artificial photosynthetic system is desired to be as simple as possible and to be as efficient as possible. From the knowledge on photosynthesis and the results of previous investigations, the critical components of artificial photosynthetic system are understood as follows: (1) light harvesting chromophore, (2) a center for electron transfer and charge separation, (3) catalytic sites for converting small molecules like water and CO{sub 2} (mutilelectron reactions) which are schematically described.

A self-assembled monolayer-assisted surface microfabrication and release technique

NARCIS (Netherlands)

Kim, B.J.; Liebau, M.; Huskens, Jurriaan; Reinhoudt, David; Brugger, J.P.

2001-01-01

This paper describes a method of thin film and MEMS processing which uses self-assembled monolayers as ultra-thin organic surface coating to enable a simple removal of microfabricated devices off the surface without wet chemical etching. A 1.5-nm thick self-assembled monolayer of

Exposure of tropical ecosystems to artificial light at night: Brazil as a case study

Science.gov (United States)

Bennie, Jon; Mantovani, Waldir; Gaston, Kevin J.

2017-01-01

Artificial nighttime lighting from streetlights and other sources has a broad range of biological effects. Understanding the spatial and temporal levels and patterns of this lighting is a key step in determining the severity of adverse effects on different ecosystems, vegetation, and habitat types. Few such analyses have been conducted, particularly for regions with high biodiversity, including the tropics. We used an intercalibrated version of the Defense Meteorological Satellite Program’s Operational Linescan System (DMSP/OLS) images of stable nighttime lights to determine what proportion of original and current Brazilian vegetation types are experiencing measurable levels of artificial light and how this has changed in recent years. The percentage area affected by both detectable light and increases in brightness ranged between 0 and 35% for native vegetation types, and between 0 and 25% for current vegetation (i.e. including agriculture). The most heavily affected areas encompassed terrestrial coastal vegetation types (restingas and mangroves), Semideciduous Seasonal Forest, and Mixed Ombrophilous Forest. The existing small remnants of Lowland Deciduous and Semideciduous Seasonal Forests and of Campinarana had the lowest exposure levels to artificial light. Light pollution has not often been investigated in developing countries but our data show that it is an environmental concern. PMID:28178352

Exposure of tropical ecosystems to artificial light at night: Brazil as a case study.

Science.gov (United States)

Freitas, Juliana Ribeirão de; Bennie, Jon; Mantovani, Waldir; Gaston, Kevin J

2017-01-01

Artificial nighttime lighting from streetlights and other sources has a broad range of biological effects. Understanding the spatial and temporal levels and patterns of this lighting is a key step in determining the severity of adverse effects on different ecosystems, vegetation, and habitat types. Few such analyses have been conducted, particularly for regions with high biodiversity, including the tropics. We used an intercalibrated version of the Defense Meteorological Satellite Program's Operational Linescan System (DMSP/OLS) images of stable nighttime lights to determine what proportion of original and current Brazilian vegetation types are experiencing measurable levels of artificial light and how this has changed in recent years. The percentage area affected by both detectable light and increases in brightness ranged between 0 and 35% for native vegetation types, and between 0 and 25% for current vegetation (i.e. including agriculture). The most heavily affected areas encompassed terrestrial coastal vegetation types (restingas and mangroves), Semideciduous Seasonal Forest, and Mixed Ombrophilous Forest. The existing small remnants of Lowland Deciduous and Semideciduous Seasonal Forests and of Campinarana had the lowest exposure levels to artificial light. Light pollution has not often been investigated in developing countries but our data show that it is an environmental concern.

Effects of High Pressure on Internally Self-Assembled Lipid Nanoparticles

DEFF Research Database (Denmark)

Kulkarni, Chandrashekhar V; Yaghmur, Anan; Steinhart, Milos

2016-01-01

We present the first report on the effects of hydrostatic pressure on colloidally stabilized lipid nanoparticles enveloping inverse nonlamellar self-assemblies in their interiors. These internal self-assemblies were systematically tuned into bicontinuous cubic (Pn3m and Im3m), micellar cubic (Fd3...... the tolerance of lipid nanoparticles [cubosomes, hexosomes, micellar cubosomes, and emulsified microemulsions (EMEs)] for high pressures, confirming their robustness for various technological applications.......We present the first report on the effects of hydrostatic pressure on colloidally stabilized lipid nanoparticles enveloping inverse nonlamellar self-assemblies in their interiors. These internal self-assemblies were systematically tuned into bicontinuous cubic (Pn3m and Im3m), micellar cubic (Fd3m......), hexagonal (H2), and inverse micellar (L2) phases by regulating the lipid/oil ratio as the hydrostatic pressure was varied from atmospheric pressure to 1200 bar and back to atmospheric pressure. The effects of pressure on these lipid nanoparticles were compared with those on their equilibrium bulk...

Anisotropic Self-Assembly of Organic–Inorganic Hybrid Microtoroids

KAUST Repository

Al-Rehili, Safa’a

2016-10-24

Toroidal structures based on self-assembly of predesigned building blocks are well-established in the literature, but spontaneous self-organization to prepare such structures has not been reported to date. Here, organic–inorganic hybrid microtoroids synthesized by simultaneous coordination-driven assembly of amphiphilic molecules and hydrophilic polymers are reported. Mixing amphiphilic molecules with iron(III) chloride and hydrophilic polymers in water leads, within minutes, to the formation of starlike nanostructures. A spontaneous self-organization of these nanostructures is then triggered to form stable hybrid microtoroids. Interestingly, the toroids exhibit anisotropic hierarchical growth, giving rise to a layered toroidal framework. These microstructures are mechanically robust and can act as templates to host metallic nanoparticles such as gold and silver. Understanding the nature of spontaneous assembly driven by coordination multiple non-covalent interactions can help explain the well-ordered complexity of many biological organisms in addition to expanding the available tools to mimic such structures at a molecular level.

Long-range energy transfer in self-assembled quantum dot-DNA cascades

Science.gov (United States)

Goodman, Samuel M.; Siu, Albert; Singh, Vivek; Nagpal, Prashant

2015-11-01

The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient transport of energy across QD-DNA thin films.The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient

Self-assembly strategies for the synthesis of functional nanostructured materials

Science.gov (United States)

Perego, M.; Seguini, G.

2016-06-01

Self-assembly is the autonomous organization of components into patterns or structures without human intervention. This is the approach followed by nature to generate living cells and represents one of the practical strategies to fabricate ensembles of nanostructures. In static self-assembly the formation of ordered structures could require energy but once formed the structures are stable. The introduction of additional regular features in the environment could be used to template the self-assembly guiding the organization of the components and determining the final structure they form. In this regard self-assembly of block copolymers represents a potent platform for fundamental studies at the nanoscale and for application-driven investigation as a tool to fabricate functional nanostructured materials. Block copolymers can hierarchically assemble into chemically distinct domains with size and periodicity on the order of 10nm or below, offering a potentially inexpensive route to generate large-area nanostructured materials. The final structure characteristics of these materials are dictated by the properties of the elementary block copolymers, like chain length, volume fraction or degree of block incompatibility. Modern synthetic chemistry offers the possibility to design these macromolecules with very specific length scales and geometries, directly embodying in the block copolymers the code that drives their self- assembling process. The understanding of the kinetics and thermodynamics of the block copolymer self-assembly process in the bulk phase as well as in thin films represents a fundamental prerequisite toward the exploitation of these materials. Incorporating block copolymer into device fabrication procedures or directly into devices, as active elements, will lead to the development of a new generation of devices fabricated using the fundamental law of nature to our advantage in order to minimize cost and power consumption in the fabrication process

Efficiency Enhancement of InGaN-Based Solar Cells via Stacking Layers of Light-Harvesting Nanospheres

KAUST Repository

Alamri, Amal M.

2016-06-24

An effective light-harvesting scheme for InGaN-based multiple quantum well solar cells is demonstrated using stacking layers of polystyrene nanospheres. Light-harvesting efficiencies on the solar cells covered with varied stacks of nanospheres are evaluated through numerical and experimental methods. The numerical simulation reveals that nanospheres with 3 stacking layers exhibit the most improved optical absorption and haze ratio as compared to those obtained by monolayer nanospheres. The experimental demonstration, agreeing with the theoretical analyses, shows that the application of 3-layer nanospheres improves the conversion efficiency of the solar cell by ~31%.

Efficiency Enhancement of InGaN-Based Solar Cells via Stacking Layers of Light-Harvesting Nanospheres

KAUST Repository

Alamri, Amal M.; Fu, Po-Han; Lai, Kun-Yu; Wang, Hsin-Ping; Li, Lain-Jong; He, Jr-Hau

2016-01-01

An effective light-harvesting scheme for InGaN-based multiple quantum well solar cells is demonstrated using stacking layers of polystyrene nanospheres. Light-harvesting efficiencies on the solar cells covered with varied stacks of nanospheres are evaluated through numerical and experimental methods. The numerical simulation reveals that nanospheres with 3 stacking layers exhibit the most improved optical absorption and haze ratio as compared to those obtained by monolayer nanospheres. The experimental demonstration, agreeing with the theoretical analyses, shows that the application of 3-layer nanospheres improves the conversion efficiency of the solar cell by ~31%.

Non-uniform self-assembly: On the anisotropic architecture of α-synuclein supra-fibrillar aggregates.

Science.gov (United States)

Semerdzhiev, Slav A; Shvadchak, Volodymyr V; Subramaniam, Vinod; Claessens, Mireille M A E

2017-08-09

Although the function of biopolymer hydrogels in nature depends on structural anisotropy at mesoscopic length scales, the self-assembly of such anisotropic structures in vitro is challenging. Here we show that fibrils of the protein α-synuclein spontaneously self-assemble into structurally anisotropic hydrogel particles. While the fibrils in the interior of these supra-fibrillar aggregates (SFAs) are randomly oriented, the fibrils in the periphery prefer to cross neighboring fibrils at high angles. This difference in organization coincides with a significant difference in polarity of the environment in the central and peripheral parts of the SFA. We rationalize the structural anisotropy of SFAs in the light of the observation that αS fibrils bind a substantial amount of counterions. We propose that, with the progress of protein polymerization into fibrils, this binding of counterions changes the ionic environment which triggers a change in fibril organization resulting in anisotropy in the architecture of hydrogel particles.

Reflection of circularly polarized light and the effect of particle distribution on circular dichroism in evaporation induced self-assembled cellulose nanocrystal thin films

Directory of Open Access Journals (Sweden)

D. Hewson

2017-06-01

Full Text Available Evaporation induced self-assembled (EISA thin films of cellulose nanocrystals (CNCs have shown great potential for displaying structural colour across the visible spectrum. They are believed primarily to reflect left handed circularly polarised (LCP light due to their natural tendency to form structures comprising left handed chirality. Accordingly the fabrication of homogenously coloured CNC thin films is challenging. Deposition of solid material towards the edge of a dried droplet, via the coffee-stain effect, is one such difficulty in achieving homogenous colour across CNC films. These effects are most easily observed in films prepared from droplets where observable reflection of visible light is localised around the edge of the dry film. We report here, the observation of both left and right hand circularly polarised (LCP/RCP light in reflection from distinct separate regions of CNC EISA thin films and we elucidate how these reflections are dependent on the distribution of CNC material within the EISA thin film. Optical models of reflection are presented which are based on structures revealed using high resolution transmission electron microscopy (TEM images of film cross sections. We have also employed spectroscopic characterisation techniques to evaluate the distribution of solid CNC material within a selection of CNC EISA thin films and we have correlated this distribution with polarised light spectra collected from each film. We conclude that film regions from which RCP light was reflected were associated with lower CNC concentrations and thicker film regions.

The magneto-elastica: from self-buckling to self-assembly

KAUST Repository

Vella, D.; du Pontavice, E.; Hall, C. L.; Goriely, A.

2013-01-01

Spherical neodymium-iron-boron magnets are permanent magnets that can be assembled into a variety of structures owing to their high magnetic strength. A one-dimensional chain of these magnets responds to mechanical loadings in a manner reminiscent of an elastic rod. We investigate the macroscopic mechanical properties of assemblies of ferromagnetic spheres by considering chains, rings and chiral cylinders of magnets. Based on energy estimates and simple experiments, we introduce an effective magnetic bending stiffness for a chain of magnets and show that, used in conjunction with classic results for elastic rods, it provides excellent estimates for the buckling and vibration dynamics of magnetic chains. We then use this estimate to understand the dynamic self-assembly of a cylinder from an initially straight chain of magnets.

The magneto-elastica: from self-buckling to self-assembly

KAUST Repository

Vella, D.

2013-12-04

Spherical neodymium-iron-boron magnets are permanent magnets that can be assembled into a variety of structures owing to their high magnetic strength. A one-dimensional chain of these magnets responds to mechanical loadings in a manner reminiscent of an elastic rod. We investigate the macroscopic mechanical properties of assemblies of ferromagnetic spheres by considering chains, rings and chiral cylinders of magnets. Based on energy estimates and simple experiments, we introduce an effective magnetic bending stiffness for a chain of magnets and show that, used in conjunction with classic results for elastic rods, it provides excellent estimates for the buckling and vibration dynamics of magnetic chains. We then use this estimate to understand the dynamic self-assembly of a cylinder from an initially straight chain of magnets.

Defect- and dopant-controlled carbon nanotubes fabricated by self-assembly of graphene nanoribbons

Institute of Scientific and Technical Information of China (English)

Cun Zhang and Shaohua Chen

2015-01-01

Molecular dynamics simulations showed that a basal carbon nanotube can activate and guide the fabrication of single-walled carbon nanotubes （CNTs） on its internal surface by self-assembly of edge-unpassivated graphene nanoribbons with defects. Furthermore, the distribution of defects on self-assembled CNTs is controllable. The system temperature and defect fraction are two main factors that influence the success of self-assembly. Due to possible joint flaws formed at the boundaries under a relatively high constant temperature, a technique based on increasing the temperature is adopted. Self-assembly is always successful for graphene nanoribbons with relatively small defect fractions, while it will fail in cases with relatively large ones. Similar to the self-assembly of graphene nanoribbons with defects, graphene nanoribbons with different types of dopants can also be self-assembled into carbon nanotubes. The finding provides a possible fabrication technique not only for carbon nanotubes with metallic or semi-con- ductive properties but also for carbon nanotubes with electromagnetic induction characteristics.

Resource Allocation for Outdoor Visible Light Communications with Energy Harvesting Capabilities

KAUST Repository

Abdelhady, Amr Mohamed Abdelaziz

2018-01-25

Visible light communication (VLC) is a promising technology that can support high data rate services for outdoor mass gathering night events while permitting energy harvesting. In this paper, a VLC system is considered where a transmitter sends data to multiple users with energy harvesting capabilities. This multi-user VLC scenario can be supported using time division multiple access (TDMA). The achievable rates using TDMA are expressed in terms of the allocated resources per user, represented by average optical intensity and time slots. This allocation is to be optimized in order to maximize the average spectral efficiency while meeting power and quality-of-service (QoS) constraints. Herein, QoS is defined as a worst-case guaranteed rate and a minimum harvested energy. To solve this optimization, the optimality conditions are first derived. Then, an efficient algorithm is developed based on the derived conditions, and its near-optimality is verified through several numerical evaluations. The obtained performance is also compared to lower-complexity algorithms, thus reflecting the performance-complexity trade-off of these algorithms.

Light harvesting by dye linked conducting polymers

Energy Technology Data Exchange (ETDEWEB)

Troensegaard Nielsen, K.

2006-06-15

The fact that the fossil fuel is finite and that the detrimental long-term effects of letting CO2 into our atmosphere exist, have created an enormous interest in developing new, cheap, renewable and less polluting energy resources. One of the most obvious abundant sources of energy in the solar system is the sun. Unfortunately the well developed silicon solar cells are very costly to produce. In an attempt to produce cheap and flexible solar cells, plastic solar cells have received a lot of attention in the last decades. There are still a lot of parameters to optimize if the plastic solar cell shall be able to compete with the silicon solar cells. One of the parameters is to ensure a high degree of charge carrier separation. Charge carrier separation can only happen at heterojunctions, which cover for example the interfaces between the polymers and the electrodes or the interface between an n-conductor and a p-conductor. The facts that the charge carrier separation only happens at the heterojunctions limits the thickness of the active layer in solar cells and thereby the effectiveness of the solar cells. In this project the charge carrier separation is attempted optimized by making plastic solar cells with a molecular heterojunction. The molecular heterojunction has been obtained by synthesizing a three domain super molecular assembly termed NPN. NPN consists of two poly[1-(2,5-dioctyltolanyl)ethynylene] chains (N-domains) coupled to the [10,20-bis(3,5-bistert-butylphenyl]-5,15-dibromoporphinato]zinc(II) (P-domain). It is shown that the N domains in NPN work as effective light harvesting antennas for the P domain and effectively transfer electrically generated excitons in the N domain to the P domain. Unfortunately the P domain does not separate the charge carriers but instead works as a charge carrier trap. This results in a performance of solar cells made of NPN that is much lower than the performance of solar cells made of pure poly[1-(2,5-dioctyltolanyl

Self-assembled containers based on extended tetrathiafulvalene.

Science.gov (United States)

Bivaud, Sébastien; Goeb, Sébastien; Croué, Vincent; Dron, Paul I; Allain, Magali; Sallé, Marc

2013-07-10

Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule.

Self-Assembled Hydrogel Nanoparticles for Drug Delivery Applications

Directory of Open Access Journals (Sweden)

Miguel Gama

2010-02-01

Full Text Available Hydrogel nanoparticles—also referred to as polymeric nanogels or macromolecular micelles—are emerging as promising drug carriers for therapeutic applications. These nanostructures hold versatility and properties suitable for the delivery of bioactive molecules, namely of biopharmaceuticals. This article reviews the latest developments in the use of self-assembled polymeric nanogels for drug delivery applications, including small molecular weight drugs, proteins, peptides, oligosaccharides, vaccines and nucleic acids. The materials and techniques used in the development of self-assembling nanogels are also described.

The light-harvesting complexes of higher plant Photosystem I: Lhca1/4 and Lhca2/3 form two red-emitting heterodimers

NARCIS (Netherlands)

Wientjes, I.E.; Croce, R.

2011-01-01

The outer antenna of higher-plant PSI (Photosystem I) is composed of four complexes [Lhc (light-harvesting complex) a1-Lhca4] belonging to the light-harvesting protein family. Difficulties in their purification have so far prevented the determination of their properties and most of the knowledge

The light-harvesting complexes of higher-plant Photosystem I : Lhca1/4 and Lhca2/3 form two red-emitting heterodimers

NARCIS (Netherlands)

Wientjes, Emilie; Croce, Roberta

2011-01-01

The outer antenna of higher-plant PSI (Photosystem I) is composed of four complexes [Lhc (light-harvesting complex) al-Lhca4] belonging to the light-harvesting protein family. Difficulties in their purification have so far prevented the determination of their properties and most of the knowledge