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1

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems  

SciTech Connect

In natural photosynthesis, organisms optimize solar energy conversion through organized assemblies of photofunctional chromophores and catalysts within proteins that provide specifically tailored environments for chemical reactions. As with their natural counterparts, artificial photosynthetic systems for practical solar fuels production must collect light energy, separate charge, and transport charge to catalytic sites where multielectron redox processes will occur. While encouraging progress has been made on each aspect of this complex problem, researchers have not yet developed self-ordering and self-assembling components and the tailored environments necessary to realize a fully-functional artificial system. Previously researchers have used complex, covalent molecular systems comprised of chromophores, electron donors, and electron acceptors to mimic both the light-harvesting and the charge separation functions of photosynthetic proteins. These systems allow for study of the dependencies of electron transfer rate constants on donor?acceptor distance and orientation, electronic interaction, and the free energy of the reaction. The most useful and informative systems are those in which structural constraints control both the distance and the orientation between the electron donors and acceptors. Self-assembly provides a facile means for organizing large numbers of molecules into supramolecular structures that can bridge length scales from nanometers to macroscopic dimensions. The resulting structures must provide pathways for migration of light excitation energy among antenna chromophores, and from antennas to reaction centers. They also must incorporate charge conduits, that is, molecular 'wires' that can efficiently move electrons and holes between reaction centers and catalytic sites. The central scientific challenge is to develop small, functional building blocks with a minimum number of covalent linkages, which also have the appropriate molecular recognition properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving ?-stacking can be used to integrate light harvesting with charge separation and transport.

Wasielewski, Michael R. (NWU)

2011-09-28

2

Self-assembled nanoscale DNA-porphyrin complex for artificial light harvesting.  

PubMed

Mimicking green plants' and bacteria's extraordinary ability to absorb a vast number of photons and harness their energy is a longstanding goal in artificial photosynthesis. Resonance energy transfer among donor dyes has been shown to play a crucial role on the overall transfer of energy in the natural systems. Here, we present artificial, self-assembled, light-harvesting complexes consisting of DNA scaffolds, intercalated YO-PRO-1 (YO) donor dyes and a porphyrin acceptor anchored to a lipid bilayer, conceptually mimicking the natural light-harvesting systems. A model system consisting of 39-mer duplex DNA in a linear wire configuration with the porphyrin attached in the middle of the wire is primarily investigated. Utilizing intercalated donor fluorophores to sensitize the excitation of the porphyrin acceptor, we obtain an effective absorption coefficient 12 times larger than for direct excitation of the porphyrin. On the basis of steady-state and time-resolved emission measurements and Markov chain simulations, we show that YO-to-YO resonance energy transfer substantially contributes to the overall flow of energy to the porphyrin. This increase is explained through energy migration along the wire allowing the excited state energy to transfer to positions closer to the porphyrin. The versatility of DNA as a structural material is demonstrated through the construction of a more complex, hexagonal, light-harvesting scaffold yielding further increase in the effective absorption coefficient. Our results show that, by using DNA as a scaffold, we are able to arrange chromophores on a nanometer scale and in this way facilitate the assembly of efficient light-harvesting systems. PMID:23350631

Woller, Jakob G; Hannestad, Jonas K; Albinsson, Bo

2013-02-20

3

Self-assembly strategies for integrating light harvesting and charge separation in artificial photosynthetic systems.  

PubMed

In natural photosynthesis, organisms optimize solar energy conversion through organized assemblies of photofunctional chromophores and catalysts within proteins that provide specifically tailored environments for chemical reactions. As with their natural counterparts, artificial photosynthetic systems for practical solar fuels production must collect light energy, separate charge, and transport charge to catalytic sites where multielectron redox processes will occur. While encouraging progress has been made on each aspect of this complex problem, researchers have not yet developed self-ordering and self-assembling components and the tailored environments necessary to realize a fully-functional artificial system. Previously researchers have used complex, covalent molecular systems comprised of chromophores, electron donors, and electron acceptors to mimic both the light-harvesting and the charge separation functions of photosynthetic proteins. These systems allow for study of the dependencies of electron transfer rate constants on donor-acceptor distance and orientation, electronic interaction, and the free energy of the reaction. The most useful and informative systems are those in which structural constraints control both the distance and the orientation between the electron donors and acceptors. Self-assembly provides a facile means for organizing large numbers of molecules into supramolecular structures that can bridge length scales from nanometers to macroscopic dimensions. The resulting structures must provide pathways for migration of light excitation energy among antenna chromophores, and from antennas to reaction centers. They also must incorporate charge conduits, that is, molecular "wires" that can efficiently move electrons and holes between reaction centers and catalytic sites. The central scientific challenge is to develop small, functional building blocks with a minimum number of covalent linkages, which also have the appropriate molecular recognition properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving pi-stacking can be used to integrate light harvesting with charge separation and transport. Our current strategy uses covalent building blocks based on chemically robust arylene imide and diimide dyes, biomimetic porphyrins, and chlorophylls. We take advantage of the shapes, sizes, and intermolecular interactions--such as pi-pi and/or metal-ligand interactions--of these molecules to direct the formation of supramolecular structures having enhanced energy capture and charge-transport properties. We use small- and wide-angle X-ray scattering (SAXS/WAXS) from a synchrotron source to elucidate the solution phase structures of these monodisperse noncovalent aggregates. We expect that a greater understanding of self-assembly using pi-stacking and molecular designs that combine those features with hydrogen bonding and metal-ligand bonding could simplify the structure of the building blocks for artificial photosynthetic complexes, while retaining their ability to assemble complex, photofunctional structures. PMID:19803479

Wasielewski, Michael R

2009-12-21

4

Zinc chlorins for artificial light-harvesting self-assemble into antiparallel stacks forming a microcrystalline solid-state material  

PubMed Central

We introduce a concept to solve the structure of a microcrystalline material in the solid-state at natural abundance without access to distance constraints, using magic angle spinning (MAS) NMR spectroscopy in conjunction with X-ray powder diffraction and DFT calculations. The method is applied to a novel class of materials that form (semi)conductive 1D wires for supramolecular electronics and artificial light-harvesting. The zinc chlorins 3-devinyl-31-hydroxymethyl-132-demethoxycarbonylpheophorbide a (3?,5?-bis-dodecyloxy)benzyl ester zinc complex 1 and 3-devinyl-31-methoxymethyl-132-demethoxycarbonylpheophorbide a (3?,5?-bis-dodecyloxy)benzyl ester zinc complex 2, self-assemble into extended excitonically coupled chromophore stacks. 1H-13C heteronuclear dipolar correlation MAS NMR experiments provided the 1H resonance assignment of the chlorin rings that allowed accurate probing of ring currents related to the stacking of macrocycles. DFT ring-current shift calculations revealed that both chlorins self-assemble in antiparallel ?-stacks in planar layers in the solid-state. Concomitantly, X-ray powder diffraction measurements for chlorin 2 at 80 °C revealed a 3D lattice for the mesoscale packing that matches molecular mechanics optimized aggregate models. For chlorin 2 the stacks alternate with a periodicity of 0.68 nm and a 3D unit cell with an approximate volume of 6.28 nm3 containing 4 molecules, which is consistent with space group P21221. PMID:19587237

Ganapathy, Swapna; Sengupta, Sanchita; Wawrzyniak, Piotr K.; Huber, Valerie; Buda, Francesco; Baumeister, Ute; Wurthner, Frank; de Groot, Huub J. M.

2009-01-01

5

Quantum-dot-induced self-assembly of cricoid protein for light harvesting.  

PubMed

Stable protein one (SP1) has been demonstrated as an appealing building block to design highly ordered architectures, despite the hybrid assembly with other nano-objects still being a challenge. Herein, we developed a strategy to construct high-ordered protein nanostructures by electrostatic self-assembly of cricoid protein nanorings and globular quantum dots (QDs). Using multielectrostatic interactions between 12mer protein nanoring SP1 and oppositely charged CdTe QDs, highly ordered nanowires with sandwich structure were achieved by hybridized self-assembly. QDs with different sizes (QD1, 3-4 nm; QD2, 5-6 nm; QD3, ?10 nm) would induce the self-assembly protein rings into various nanowires, subsequent bundles, and irregular networks in aqueous solution. Atomic force microscopy, transmission electron microscopy, and dynamic light scattering characterizations confirmed that the size of QDs and the structural topology of the nanoring play critical functions in the formation of the superstructures. Furthermore, an ordered arrangement of QDs provides an ideal scaffold for designing the light-harvesting antenna. Most importantly, when different sized QDs (e.g., QD1 and QD3) self-assembled with SP1, an extremely efficient Förster resonance energy transfer was observed on these protein nanowires. The self-assembled protein nanostructures were demonstrated as a promising scaffold for the development of an artificial light-harvesting system. PMID:24601558

Miao, Lu; Han, Jishu; Zhang, Hao; Zhao, Linlu; Si, Chengye; Zhang, Xiyu; Hou, Chunxi; Luo, Quan; Xu, Jiayun; Liu, Junqiu

2014-04-22

6

Self-assembled photosynthesis-inspired light harvesting material and solar cells containing the same  

DOEpatents

A solar cell is described that comprises: (a) a semiconductor charge separation material; (b) at least one electrode connected to the charge separation material; and (c) a light-harvesting film on the charge separation material, the light-harvesting film comprising non-covalently coupled, self-assembled units of porphyrinic macrocycles. The porphyrinic macrocycles preferably comprise: (i) an intramolecularly coordinated metal; (ii) a first coordinating substituent; and (iii) a second coordinating substituent opposite the first coordinating substituent. The porphyrinic macrocycles can be assembled by repeating intermolecular coordination complexes of the metal, the first coordinating substituent and the second coordinating substituent.

Lindsey, Jonathan S. (Raleigh, NC); Chinnasamy, Muthiah (Raleigh, NC); Fan, Dazhong (Raleigh, NC)

2009-12-15

7

DNA-directed artificial light-harvesting antenna.  

PubMed

Designing and constructing multichromophoric, artificial light-harvesting antennas with controlled interchromophore distances, orientations, and defined donor-acceptor ratios to facilitate efficient unidirectional energy transfer is extremely challenging. Here, we demonstrate the assembly of a series of structurally well-defined artificial light-harvesting triads based on the principles of structural DNA nanotechnology. DNA nanotechnology offers addressable scaffolds for the organization of various functional molecules with nanometer scale spatial resolution. The triads are organized by a self-assembled seven-helix DNA bundle (7HB) into cyclic arrays of three distinct chromophores, reminiscent of natural photosynthetic systems. The scaffold accommodates a primary donor array (Py), secondary donor array (Cy3) and an acceptor (AF) with defined interchromophore distances. Steady-state fluorescence analyses of the triads revealed an efficient, stepwise funneling of the excitation energy from the primary donor array to the acceptor core through the intermediate donor. The efficiency of excitation energy transfer and the light-harvesting ability (antenna effect) of the triads was greatly affected by the relative ratio of the primary to the intermediate donors, as well as on the interchromophore distance. Time-resolved fluorescence analyses by time-correlated single-photon counting (TCSPC) and streak camera techniques further confirmed the cascading energy transfer processes on the picosecond time scale. Our results clearly show that DNA nanoscaffolds are promising templates for the design of artificial photonic antennas with structural characteristics that are ideal for the efficient harvesting and transport of energy. PMID:21714548

Dutta, Palash K; Varghese, Reji; Nangreave, Jeanette; Lin, Su; Yan, Hao; Liu, Yan

2011-08-10

8

Optimal Efficiency of Self-Assembling Light-Harvesting Arrays Ji-Hyun Kim and Jianshu Cao*  

E-print Network

Optimal Efficiency of Self-Assembling Light-Harvesting Arrays Ji-Hyun Kim and Jianshu Cao equation that describes energy transfer over a given lattice, we explore how energy transfer efficiency (derived in Appendix A) for efficiency shows a steep increase with a D-to-A transfer rate when

Cao, Jianshu

9

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates.  

PubMed

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ?120 nm in a 60 ?m length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates. PMID:24909123

Ocakoglu, Kasim; Joya, Khurram S; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T

2014-08-21

10

Self-assembled artificial cilia  

PubMed Central

Due to their small dimensions, microfluidic devices operate in the low Reynolds number regime. In this case, the hydrodynamics is governed by the viscosity rather than inertia and special elements have to be introduced into the system for mixing and pumping of fluids. Here we report on the realization of an effective pumping device that mimics a ciliated surface and imitates its motion to generate fluid flow. The artificial biomimetic cilia are constructed as long chains of spherical superparamagnetic particles, which self-assemble in an external magnetic field. Magnetic field is also used to actuate the cilia in a simple nonreciprocal manner, resulting in a fluid flow. We prove the concept by measuring the velocity of a cilia-pumped fluid as a function of height above the ciliated surface and investigate the influence of the beating asymmetry on the pumping performance. A numerical simulation was carried out that successfully reproduced the experimentally obtained data. PMID:19934055

Vilfan, Mojca; Poto?nik, Anton; Kav?i?, Blaž; Osterman, Natan; Poberaj, Igor; Vilfan, Andrej; Babi?, Dušan

2010-01-01

11

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates  

NASA Astrophysics Data System (ADS)

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ~120 nm in a 60 ?m length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ~120 nm in a 60 ?m length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01661k

Ocakoglu, Kasim; Joya, Khurram S.; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T.

2014-07-01

12

Influence of phospholipid composition on self-assembly and energy-transfer efficiency in networks of light-harvesting 2 complexes.  

PubMed

In the photosynthetic membrane of purple bacteria networks of light-harvesting 2 (LH2) complexes capture the sunlight and transfer the excitation energy. In order to investigate the mutual relationship between the supramolecular organization of the pigment-protein complexes and their biological function, the LH2 complexes were reconstituted into three types of phospholipid membranes, consisting of L-?-phosphatidylglycerol (PG), L-?-phosphatidylcholine (PC), and L-?-phosphatidylethanolamine (PE)/PG/cardiolipin (CL). Atomic force microscopy (AFM) revealed that the type of phospholipids had a crucial influence on the clustering tendency of the LH2 complexes increased from PG over PC to PE/PG/CL, where the LH2 complexes formed large, densely packed clusters. Time-resolved spectroscopy uncovered a strong quenching of the LH2 fluorescence that is ascribed to singlet-singlet and singlet-triplet annihilation by an efficient energy transfer between the LH2 complexes in the artificial membrane systems. Quantitative analysis reveals that the intercomplex energy transfer efficiency varies strongly as a function of the morphology of the nanostructure, namely in the order PE/PG/CL > PC > PG, which is in line with the clustering tendency of LH2 observed by AFM. These results suggest a strong influence of the phospholipids on the self-assembly of LH2 complexes into networks and concomitantly on the intercomplex energy transfer efficiency. PMID:23919556

Sumino, Ayumi; Dewa, Takehisa; Noji, Tomoyasu; Nakano, Yuki; Watanabe, Natsuko; Hildner, Richard; Bösch, Nils; Köhler, Jürgen; Nango, Mamoru

2013-09-12

13

Hybrid artificial photosynthetic systems comprising semiconductors as light harvesters and biomimetic complexes as molecular cocatalysts.  

PubMed

Solar fuel production through artificial photosynthesis may be a key to generating abundant and clean energy, thus addressing the high energy needs of the world's expanding population. As the crucial components of photosynthesis, the artificial photosynthetic system should be composed of a light harvester (e.g., semiconductor or molecular dye), a reduction cocatalyst (e.g., hydrogenase mimic, noble metal), and an oxidation cocatalyst (e.g., photosystem II mimic for oxygen evolution from water oxidation). Solar fuel production catalyzed by an artificial photosynthetic system starts from the absorption of sunlight by the light harvester, where charge separation takes place, followed by a charge transfer to the reduction and oxidation cocatalysts, where redox reaction processes occur. One of the most challenging problems is to develop an artificial photosynthetic solar fuel production system that is both highly efficient and stable. The assembly of cocatalysts on the semiconductor (light harvester) not only can facilitate the charge separation, but also can lower the activation energy or overpotential for the reactions. An efficient light harvester loaded with suitable reduction and oxidation cocatalysts is the key for high efficiency of artificial photosynthetic systems. In this Account, we describe our strategy of hybrid photocatalysts using semiconductors as light harvesters with biomimetic complexes as molecular cocatalysts to construct efficient and stable artificial photosynthetic systems. We chose semiconductor nanoparticles as light harvesters because of their broad spectral absorption and relatively robust properties compared with a natural photosynthesis system. Using biomimetic complexes as cocatalysts can significantly facilitate charge separation via fast charge transfer from the semiconductor to the molecular cocatalysts and also catalyze the chemical reactions of solar fuel production. The hybrid photocatalysts supply us with a platform to study the photocatalytic mechanisms of H2/O2 evolution and CO2 reduction at the molecular level and to bridge natural and artificial photosynthesis. We demonstrate the feasibility of the hybrid photocatalyst, biomimetic molecular cocatalysts, and semiconductor light harvester for artificial photosynthesis and therefore provide a promising approach for rational design and construction of highly efficient and stable artificial photosynthetic systems. PMID:23730891

Wen, Fuyu; Li, Can

2013-11-19

14

Ultrahigh-density storage media prepared by artificially assisted self-assembling methods  

Microsoft Academic Search

Two types of recording media possessing nanodot structures were investigated. The media were prepared by an artificially assisted self-assembling (AASA) method, which includes simple nanopatterning using a nanoimprint and fine nanopatterning using self-assembling organic molecules. One type of recording media is circumferential magnetic patterned media prepared on a 2.5-in.-diam glass plate. A Ni master disk possessing spiral patterns with 60-250

Katsuyuki Naito; Komukai Toshiba-cho

2005-01-01

15

Design and self-assembly of simple coat proteins for artificial viruses  

NASA Astrophysics Data System (ADS)

Viruses are among the simplest biological systems and are highly effective vehicles for the delivery of genetic material into susceptible host cells. Artificial viruses can be used as model systems for providing insights into natural viruses and can be considered a testing ground for developing artificial life. Moreover, they are used in biomedical and biotechnological applications, such as targeted delivery of nucleic acids for gene therapy and as scaffolds in material science. In a natural setting, survival of viruses requires that a significant fraction of the replicated genomes be completely protected by coat proteins. Complete protection of the genome is ensured by a highly cooperative supramolecular process between the coat proteins and the nucleic acids, which is based on reversible, weak and allosteric interactions only. However, incorporating this type of supramolecular cooperativity into artificial viruses remains challenging. Here, we report a rational design for a self-assembling minimal viral coat protein based on simple polypeptide domains. Our coat protein features precise control over the cooperativity of its self-assembly with single DNA molecules to finally form rod-shaped virus-like particles. We confirm the validity of our design principles by showing that the kinetics of self-assembly of our virus-like particles follows a previous model developed for tobacco mosaic virus. We show that our virus-like particles protect DNA against enzymatic degradation and transfect cells with considerable efficiency, making them promising delivery vehicles.

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

2014-09-01

16

Quantum coherence controls the charge separation in a prototypical artificial light-harvesting system  

PubMed Central

The efficient conversion of light into electricity or chemical fuels is a fundamental challenge. In artificial photosynthetic and photovoltaic devices, this conversion is generally thought to happen on ultrafast, femto-to-picosecond timescales and to involve an incoherent electron transfer process. In some biological systems, however, there is growing evidence that the coherent motion of electronic wavepackets is an essential primary step, raising questions about the role of quantum coherence in artificial devices. Here we investigate the primary charge-transfer process in a supramolecular triad, a prototypical artificial reaction centre. Combining high time-resolution femtosecond spectroscopy and time-dependent density functional theory, we provide compelling evidence that the driving mechanism of the photoinduced current generation cycle is a correlated wavelike motion of electrons and nuclei on a timescale of few tens of femtoseconds. We highlight the fundamental role of the interface between chromophore and charge acceptor in triggering the coherent wavelike electron-hole splitting. PMID:23511467

Andrea Rozzi, Carlo; Maria Falke, Sarah; Spallanzani, Nicola; Rubio, Angel; Molinari, Elisa; Brida, Daniele; Maiuri, Margherita; Cerullo, Giulio; Schramm, Heiko; Christoffers, Jens; Lienau, Christoph

2013-01-01

17

Light-harvesting nanorods based on pheophorbide-appending cellulose.  

PubMed

In contrast to the success in artificial DNA- and peptide-based nanostructures, the ability of polysaccharides to self-assemble into one-, two-, and three-dimensional nanostructures are limited. Here, we describe a strategy for designing and fabricating nanorods using a regioselectively functionalized cellulose derivative at the air-water interface in a stepwise manner. A semisynthetic chlorophyll derivative, pyro-pheophorbide a, was partially introduced into the C-6 position of the cellulose backbone for the design of materials with specific optical properties. Remarkably, controlled formation of cellulose nanorods can be achieved, producing light-harvesting nanorods that display a larger bathochromic shift than their solution counterparts. The results presented here demonstrate that the self-assembly of functionalized polysaccharides on surfaces could lead the nanostructures mimicking the naturally occurring chloroplasts. PMID:23865684

Sakakibara, Keita; Granström, Mari; Kilpeläinen, Ilkka; Helaja, Juho; Heinilehto, Santtu; Inoue, Rintaro; Kanaya, Toshiji; Hill, Jonathan P; Nakatsubo, Fumiaki; Tsujii, Yoshinobu; Ariga, Katsuhiko

2013-09-01

18

Stigmergic Self-Assembly of Prespecified Artificial Struct ures in a Constrained and Continuous Environment  

Microsoft Academic Search

The distributed control of self-assembly processes requir es local behaviors that will cause ini- tially unorganized components to form a desired goal structure. While important strides have been made in designing methods for self-assembling various geometric structures under ideal- ized simulated conditions, many unaddressed issues remain in extending these methods to more complex environments. In this work, we discuss the

Alexander Grushin; James A. Reggia

19

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

NASA Astrophysics Data System (ADS)

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.

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

2011-01-01

20

Photosynthetic Light-Harvesting  

NASA Astrophysics Data System (ADS)

Photosynthetic organisms utilize (bacterio) chlorophylls and carotenoids as main light-harvesting pigments. In this chapter, we review bacteriochlorophyll light-harvesting in photosynthetic purple bacteria; we discuss intra- and intercomplex energy transfer processes as well as energy trapping by reaction centers. From the viewpoint of light-harvesting, in most organisms carotenoids are accessory pigments absorbing in the blue-green region of the solar spectrum, where chlorophylls and bacteriochlorophylls have weak absorption. Here, we discuss carotenoid light-harvesting in a pigment-protein complex having carotenoids as main lightharvesting pigment, the peridinin chlorophyll protein (PCP).

Pullerits, T.; Polivka, T.; Sundström, V.

21

Question 9: Quantum Self-Assembly and Photoinduced Electron Tunneling in Photosynthetic Systems of Artificial Minimal Living Cells  

NASA Astrophysics Data System (ADS)

Natural and artificial living cells and their substructures are self-assembling, due to electron correlation interactions among biological and water molecules, which lead to attractive dispersion forces and hydrogen bonds. Dispersion forces are weak intermolecular forces that arise from the attractive force between quantum multipoles. A hydrogen bond is a special type of quantum attractive interaction that exists between an electronegative atom and a hydrogen atom bonded to another electronegative atom; and this hydrogen atom exist in two quantum states. The best method to simulate these dispersion forces and hydrogen bonds is to perform quantum mechanical non-local density functional potential calculations of artificial minimal living cells consisting of around 1,000 atoms. The cell systems studied are based on peptide nucleic acid and are 3.0-4.2 nm in diameter. The electron tunneling and associated light absorption of the most intense transitions, as calculated by the time dependent density functional theory method, differs from spectroscopic experiments by only 0.2-0.3 nm, which is within the value of experiment errors. This agreement implies that the quantum mechanically self-assembled structures of artificial minimal living cells very closely approximate realistic ones.

Tamulis, Arvydas; Tamulis, Vykintas

2007-10-01

22

Light harvesting arrays  

DOEpatents

A light harvesting array useful for the manufacture of devices such as solar cells comprises: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to the first electrode, each of the light harvesting rods comprising a polymer of Formula I: X.sup.1.paren open-st.X.sup.m+1).sub.m (I) wherein m is at least 1, and may be from two, three or four to 20 or more; X.sup.1 is a charge separation group (and preferably a porphyrinic macrocycle, which may be one ligand of a double-decker sandwich compound) having an excited-state of energy equal to or lower than that of X.sup.2, and X.sup.2 through X.sup.m+1 are chromophores (and again are preferably porphyrinic macrocycles).

Lindsey, Jonathan S. (Raleigh, NC)

2002-01-01

23

Self-assembled artificial pinning centres in thick YBCO superconducting films  

Microsoft Academic Search

Strong, artificial pinning centres are required in superconducting films of large thickness for power applications in high magnetic fields. One of the methods for the introduction of pinning centres in such films is substrate decoration, i.e., growing nanoscale islands of certain materials on the substrate prior to the deposition of the superconducting film. Two other methods are building up a

P. Mikheenko; J. S. Abell; A. Sarkar; V. S. Dang; M. M. Awang Kechik; J. L. Tanner; P. Paturi; H. Huhtinen; N. Hari Babu; D. A. Cardwell; A. Crisan

2010-01-01

24

Natural strategies for photosynthetic light harvesting.  

PubMed

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 to the spectral composition of light in their habitat, they acclimate to slowly varying light intensities and they rapidly respond to fast changes in light quality and quantity. This is particularly important for oxygen-producing organisms because an overdose of light in combination with oxygen can be lethal. Rapid progress is being made in understanding how different organisms maximize light harvesting and minimize deleterious effects. Here we summarize the latest findings and explain the main design principles used in nature. The available knowledge can be used for optimizing light harvesting in both natural and artificial photosynthesis to improve light-driven production processes. PMID:24937067

Croce, Roberta; van Amerongen, Herbert

2014-07-01

25

Core-like Particles of an Enveloped Animal Virus Can Self-Assemble Efficiently on Artificial Templates  

Microsoft Academic Search

Alphaviruses are animal viruses holding great promise for biomedical applications as drug delivery vectors, functional imaging probes, and nanoparticle delivery vesicles because of their efficient in vitro self-assembly properties. However, due to their complex structure, with a protein capsid encapsulating the genome and an outer membrane composed of lipids and glycoproteins, the in-vitro self-assembly of virus- like particles, which have

Nancy L. Goicochea; Mrinmoy de; Vincent M. Rotello; Suchetana Mukhopadhyay; Bogdan Dragnea

2007-01-01

26

Efficient light harvesting through carotenoids  

Microsoft Academic Search

We review the factors that control the efficiency of carotenoid-chlorophyll excitation transfer in photosynthetic light harvesting.\\u000a For this we summarize first the recently developed theory that describes electronic couplings between carotenoids and chlorophylls\\u000a and we outline in particular the influence of length of conjugated system and of symmetry breaking on the couplings. We focus\\u000a hereby on the structurally solved lycopene-BChl

Thorsten Ritz; Ana Damjanovi?; Klaus Schulten; Jian-Ping Zhang; Yasushi Koyama

2000-01-01

27

Inorganic self-assembly  

Microsoft Academic Search

Self-assembly processes provide an effective and environmentally benign method for synthesising novel ceramic and composite materials. The development of self-assembly methodology, which is the archetypal bioinspired synthesis route, has greatly expanded the methods of producing nanostructures. In the design of complex materials such as electrical devices, we currently rely on our ability to create designed patterns lithographically. New ways of

Laura E Depero; M Lucia Curri

2004-01-01

28

Self-assembled monolayers of A? peptides on Au electrodes: an artificial platform for probing the reactivity of redox active metals and cofactors relevant to Alzheimer's disease.  

PubMed

The water-soluble hydrophilic part of human A? peptide has been extended to include a C-terminal cysteine residue. Utilizing the thiol functionality of this cysteine residue, self-assembled monolayers (SAM) of these peptides are formed on Au electrodes. Atomic force microscopy imaging confirms formation of small A? aggregates on the surface of the electrode. These aggregates bind redox active metals like Cu and cofactors like heme, both of which are proposed to generate toxic partially reduced oxygen species (PROS) and play a vital role in Alzheimer's disease. The spectroscopic and electrochemical properties of these Cu and heme bound A? SAM are similar to those reported for the soluble Cu and heme bound A? peptide. Experiments performed on these A?-SAM electrodes clearly demonstrate that (1) heme bound A? is kinetically more competent in reducing O(2) than Cu bound A?, (2) under physiological conditions the reduced Cu site produces twice as much PROS (measured in situ) than the reduced heme site, and (3) chelators like clioquinol remove Cu from these aggregates, while drugs like methylene blue inhibit O(2) reactivity of the heme cofactor. This artificial construct provides a very easy platform for investigating potential drugs affecting aggregation of human A? peptides and PROS generation by its complexes with redox active metals and cofactors. PMID:22709431

Pramanik, Debajyoti; Sengupta, Kushal; Mukherjee, Soumya; Dey, Somdatta Ghosh; Dey, Abhishek

2012-07-25

29

Quantum mechanical modeling of self-assembly and photoinduced electron transfer in PNA-based artificial living organisms.  

PubMed

In order to support the creation of both artificial living organisms in the USA LANL "Protocell Assembly" project and programmable nano-biorobots in the EU "Programmable Artificial Cell Evolution" project, we used quantum mechanical (QM), density functional theory (DFT), the semiempirical PM3 method, and molecular mechanics (MM) software to investigate various complex photosynthetic systems based on peptide nucleic acid (PNA) in a water environment. Quantum mechanical DFT PBEPBE simulations, including electron correlations, confirm that water molecules that surround all the photosynthetic complex of the LANL protoorganism are main constructing factors and stabilize this system consisting of: PNA fragment attached by covalent bond sensitizer 1,4-bis(N,N-dimethylamino)naphthalene molecule, lipid precursor molecule and fragment of lipid molecules mono layer. The absorption spectrum shift to the red wavelengths in the complex artificial protocell photosynthetic center might be used as the measure of the complexity of this system. The electron pi-pi* transitions in the first and third excited states are from HOMO and HOMO-1 located on the conjugated water molecules and sensitizer 1,4-bis(N,N-dimethylamino)naphthalene molecule to the LUMO of the lipid precursor molecule as calculated using the time dependent (TD) PBEPBE/6-31G model. Electron charge tunneling in the first and third excited states should induce metabolic photodissociation of the lipid precursor molecule because of localization of the transferred electron cloud on the head (waste) of the lipid precursor molecule. TD electron correlation PBEPBE/6-31G calculations show that in the different energies of excitation, the charge transfer tunneling is from sensitizer to lipid precursor and cytosine molecules. One should note that in a water solvent, the electron charge transfer pi-pi* transition in the fifth and sixth excited state is from the HOMO and HOMO-1 located on the sensitizer 1,4-bis(N,N-dimethylamino)naphthalene molecule to the LUMO+2 located on the cytosine-PNA fragment molecule. Investigation results indicate that strong back electron tunneling from the sensitizer 1,4-bis(N,N-dimethylamino)naphthalene molecule to the cytosine molecule in the LANL artificial photosynthetic system exists. PMID:16736752

Tamulis, A; Tamulis, V; Graja, A

2006-04-01

30

Natural Light Harvesting Systems: Unraveling the quantum puzzles  

E-print Network

In natural light harvesting systems, the sequential quantum events of photon absorption by specialized biological antenna complexes, charge separation, exciton formation and energy transfer to localized reaction centers culminates in the conversion of solar to chemical energy. A notable feature in these processes is the exceptionally high efficiencies (> 95 %) at which excitation is transferred from the illuminated protein complex site to the reaction centers. Such high exciton propagation rates within a system of interwoven biomolecular network structures, is yet to be replicated in artificial light harvesting complexes. A clue to unraveling the quantum puzzles of nature may lie in the observation of long lived coherences lasting several picoseconds in the electronic spectra of photosynthetic complexes, even in noisy environmental baths. A number of experimental and theoretical studies have been devoted to unlocking the links between quantum processes and information protocols, in the hope of finding answers to nature's puzzling mode of energy propagation. This review presents developments in quantum theories, and links information-theoretic aspects with photosynthetic light-harvesting processes in biomolecular systems. There is examination of various attempts to pinpoint the processes that underpin coherence features arising from the light harvesting activities of biomolecular systems, with particular emphasis on the effects that factors such non-Markovianity, zeno mechanisms, teleportation, quantum predictability and the role of multipartite states have on the quantum dynamics of biomolecular systems. A discussion of how quantum thermodynamical principles and agent-based modeling and simulation approaches can improve our understanding of natural photosynthetic systems is included.

A. Thilagam

2013-10-29

31

Modeling Self Assembly  

NSDL National Science Digital Library

This lesson, presented by the National Nanotechnology Infrastructure Network, covers self-assembly of molecules. Two activity are contained in this lesson. The first is "a hands-on modeling activity designed to introduce students to the area of nanotechnology and give them a basic understanding of how researchers build very small devices by the self-assembly of molecules." The second activity follows up on the first and gives "the students a chance to practice and demonstrate what they have learned." Two Teacher Preparation Guides and Two Student Guides are included. 

2014-08-26

32

Modeling Protein Self Assembly  

ERIC Educational Resources Information Center

Understanding the structure and function of proteins is an important part of the standards-based science curriculum. Proteins serve vital roles within the cell and malfunctions in protein self assembly are implicated in degenerative diseases. Experience indicates that this topic is a difficult one for many students. We have found that the concept…

Baker, William P.; Jones, Carleton Buck; Hull, Elizabeth

2004-01-01

33

Self-assembling cytotoxins.  

PubMed

Decanal and N-amino-N'-1-octylguanidine (AOG), combined at 28 microM each, mediated erythrocyte lysis within 80 minutes under physiological conditions. By contrast, no lysis was observed after 20 hours with either decanal (56 microM) or AOG (100 microM) alone. The pronounced synergism observed for these chemicals and similar reactive pairs of chemicals is due to the self-assembly of more cytotoxic hydrazones in situ. Decanal and AOG also exhibit synergistic activity against cultured human cells (HeLa) and bacteria (Escherichia coli J96). This synergism may be useful in the design of cytotoxins that would self-assemble selectively from nontoxic precursors within tumors, while sparing normal tissue. PMID:3523757

Rideout, D

1986-08-01

34

Energy, Charge, and Spin Transport in Molecules and Self-Assembled Nanostructures Inspired by Photosynthesis  

SciTech Connect

Electron transfer in biological molecules provides both insight and inspiration for developing chemical systems having similar functionality. Photosynthesis is an example of an integrated system in which light harvesting, photoinduced charge separation, and catalysis combine to carry out two thermodynamically demanding processes, the oxidation of water and the reduction of carbon dioxide. The development of artificial photosynthetic systems for solar energy conversion requires a fundamental understanding of electron-transfer reactions between organic molecules. Since these reactions most often involve single-electron transfers, the spin dynamics of photogenerated radical ion pairs provide important information on how the rates and efficiencies of these reactions depend on molecular structure. Given this knowledge, the design and synthesis of large integrated structures to carry out artificial photosynthesis is moving forward. An important approach to achieving this goal is the development of small, functional building blocks, having a minimum number of covalent bonds, which also have the appropriate molecular recognition sites to facilitate self-assembly into a complete, functional artificial photosynthetic system.

Wasielewski, Michael R. (NWU)

2008-10-03

35

Self-Assembling Cytotoxins  

Microsoft Academic Search

Decanal and N-amino-N'-1-octylguanidine (AOG), combined at 28 mu M each, mediated erythrocyte lysis within 80 minutes under physiological conditions. By contrast, no lysis was observed after 20 hours with either decanal (56 mu M) or AOG (100 mu M) alone. The pronounced synergism observed for these chemicals and similar reactive pairs of chemicals is due to the self-assembly of more

Darryl Rideout

1986-01-01

36

Toward a molecular programming language for algorithmic self-assembly  

NASA Astrophysics Data System (ADS)

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 attainable. These tools provide a solid foundation for future work in both the Tile Assembly Model and explorations into more advanced models.

Patitz, Matthew John

37

Nanopropulsion by biocatalytic self-assembly.  

PubMed

A number of organisms and organelles are capable of self-propulsion at the micro- and nanoscales. Production of simple man-made mimics of biological transportation systems may prove relevant to achieving movement in artificial cells and nano/micronscale robotics that may be of biological and nanotechnological importance. We demonstrate the propulsion of particles based on catalytically controlled molecular self-assembly and fiber formation at the particle surface. Specifically, phosphatase enzymes (acting as the engine) are conjugated to a quantum dot (the vehicle), and are subsequently exposed to micellar aggregates (fuel) that upon biocatalytic dephosphorylation undergo fibrillar self-assembly, which in turn causes propulsion. The motion of individual enzyme/quantum dot conjugates is followed directly using fluorescence microscopy. While overall movement remains random, the enzyme-conjugates exhibit significantly faster transport in the presence of the fiber forming system, compared to controls without fuel, a non-self-assembling substrate, or a substrate which assembles into spherical, rather than fibrous structures upon enzymatic dephosphorylation. When increasing the concentration of the fiber-forming fuel, the speed of the conjugates increases compared to non-self-assembling substrate, although directionality remains random. PMID:25162764

Leckie, Joy; Hope, Alexander; Hughes, Meghan; Debnath, Sisir; Fleming, Scott; Wark, Alastair W; Ulijn, Rein V; Haw, Mark D

2014-09-23

38

Efficient energy transfer in light-harvesting systems, I: optimal temperature, reorganization energy and spatial–temporal correlations  

E-print Network

Understanding the mechanisms of efficient and robust energy transfer in light-harvesting systems provides new insights for the optimal design of artificial systems. In this paper, we use the Fenna–Matthews–Olson (FMO) ...

Wu, Jianlan

39

Solar cells incorporating light harvesting arrays  

DOEpatents

A solar cell incorporates a light harvesting array that comprises: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to the first electrode, each of the light harvesting rods comprising a polymer of Formula I: X.sup.1.paren open-st.X.sup.m+1).sub.m (I) wherein m is at least 1, and may be from two, three or four to 20 or more; X.sup.1 is a charge separation group (and preferably a porphyrinic macrocycle, which may be one ligand of a double-decker sandwich compound) having an excited-state of energy equal to or lower than that of X.sup.2 ; and X.sup.2 through X.sup.m+1 are chromophores (and again are preferably porphyrinic macrocycles).

Lindsey, Jonathan S. (Raleigh, NC); Meyer, Gerald J. (Baltimore, MD)

2002-01-01

40

Functionalized Nanoparticles and Surfaces for Controlled Chemical Catalysis and Effective Light Harvesting  

SciTech Connect

We have prepared a range of such arrays as key components for biotechnology and photonic applications. These involve self-assembled arrays of increasing complexity with three-dimensionally disposed multilayer interactions. These arrays also include dendrimers as the distinguishing structural building blocks. These photoactive integrated systems have a regular, highly-branched, three-dimensional architecture. Structural modifications of these units include variation of the core, bridging layers, and terminal groups. These modifications result in a large array of dendritic molecules with potential applications for light harvesting.

Marye Anne Fox, James K. Whitesell

2012-11-02

41

Lessons from nature about solar light harvesting  

NASA Astrophysics Data System (ADS)

Solar fuel production often starts with the energy from light being absorbed by an assembly of molecules; this electronic excitation is subsequently transferred to a suitable acceptor. For example, in photosynthesis, antenna complexes capture sunlight and direct the energy to reaction centres that then carry out the associated chemistry. In this Review, we describe the principles learned from studies of various natural antenna complexes and suggest how to elucidate strategies for designing light-harvesting systems. We envisage that such systems will be used for solar fuel production, to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control, or to transfer excitons over long distances. Also described are the notable properties of light-harvesting chromophores, spatial-energetic landscapes, the roles of excitonic states and quantum coherence, as well as how antennas are regulated and photoprotected.

Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra; van Grondelle, Rienk

2011-10-01

42

Exciton dynamics in light harvesting systems  

Microsoft Academic Search

The optical line shape of molecular ring aggregates with 18 molecular units, modeling bacteria photo-synthetic light harvesting systems, is investigated theoretically. The molecular units are described by two-level systems with an average excitation energy ? and interacting with each other through nearest-neighbor interaction. Furthermore, quasi-static and dynamic fluctuations of the local excitation energies are taken into account simulating slow motions

P. Reineker; Ch. Warns; Ch. Supritz; I. Barv??k

2003-01-01

43

Photosynthetic light harvesting: excitons and coherence  

PubMed Central

Photosynthesis begins with light harvesting, where specialized pigment–protein complexes transform sunlight into electronic excitations delivered to reaction centres to initiate charge separation. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications. We begin by examining the concept of an exciton, an excited electronic state delocalized over several spatially separated molecules, which is the most widely available signature of quantum coherence in light harvesting. We then discuss recent results concerning the possibility that quantum coherence between electronically excited states of donors and acceptors may give rise to a quantum coherent evolution of excitations, modifying the traditional incoherent picture of energy transfer. Key to this (partially) coherent energy transfer appears to be the structure of the environment, in particular the participation of non-equilibrium vibrational modes. We discuss the open questions and controversies regarding quantum coherent energy transfer and how these can be addressed using new experimental techniques. PMID:24352671

Fassioli, Francesca; Dinshaw, Rayomond; Arpin, Paul C.; Scholes, Gregory D.

2014-01-01

44

Nanotechnology and Quasicrystals: From self assembly to photonic applications  

E-print Network

After providing a concise overview on quasicrystals and their discovery more than a quarter of a century ago, I consider the unexpected interplay between nanotechnology and quasiperiodic crystals. Of particular relevance are efforts to fabricate artificial functional micro- or nanostructures, as well as efforts to control the self-assembly of nanostructures, where current knowledge about the possibility of having long-range order without periodicity can provide significant advantages. I discuss examples of systems ranging from artificial metamaterials for photonic applications, through self-assembled soft matter, to surface waves and optically-induced nonlinear photonic quasicrystals.

Ron Lifshitz

2008-10-28

45

Accessing exciton transport in light-harvesting structures with plasmonic nanotip  

NASA Astrophysics Data System (ADS)

Natural light-harvesting complexes, such as that of plant cells or photosynthetic bacteria, are considered as possible prototypes for artificially designed solar cell materials. In these structures the energy of light absorbed by a peripheral antenna is transmitted very efficiently in a form of excitons to a reaction center. Usually, information about the exciton transport is obtained from time-resolved nonlinear optical experiments where the frequencies of a pump and a probe fields select particular electronic transitions in the light-harvesting complex. We explore a complimentary setup utilizing a plasmonic nanotip as a local sub-wavelength probe of excitation dynamics. As specific examples we consider an LHII complex involved in the light-harvesting process of purple bacteria and a Fenna-Matthews-Olson pigment-protein complex of green-sulphur bacteria.

Saikin, Semion K.; Feist, Johannes; Homer Reid, M. T.; Lukin, Mikhail D.; Aspuru-Guzik, Alan

2012-02-01

46

Quantum mechanical light harvesting mechanisms in photosynthesis  

NASA Astrophysics Data System (ADS)

More than 10 million billion photons of light strike a leaf each second. Incredibly, almost every red-coloured photon is captured by chlorophyll pigments and initiates steps to plant growth. Last year we reported that marine algae use quantum mechanics in order to optimize photosynthesis [1], a process essential to its survival. These and other insights from the natural world promise to revolutionize our ability to harness the power of the sun. In a recent review [2] we described the principles learned from studies of various natural antenna complexes and suggested how to utilize that knowledge to shape future technologies. We forecast the need to develop ways to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control--not easy given that the energy is only stored for a billionth of a second. In this presentation I will describe new results that explain the observation and meaning of quantum-coherent energy transfer. [4pt] [1] Elisabetta Collini, Cathy Y. Wong, Krystyna E. Wilk, Paul M. G. Curmi, Paul Brumer, and Gregory D. Scholes, ``Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature'' Nature 463, 644-648 (2010).[0pt] [2] Gregory D. Scholes, Graham R. Fleming, Alexandra Olaya-Castro and Rienk van Grondelle, ``Lessons from nature about solar light harvesting'' Nature Chem. 3, 763-774 (2011).

Scholes, Gregory

2012-02-01

47

Solder self-assembly for MEMS fabrication  

E-print Network

This thesis examines and demonstrates self-assembly of MEMS components on the 25 micron scale onto substrates using the capillary force of solder. This is an order of magnitude smaller than current solder self-assembly in ...

Au, Hin Meng, 1977-

2004-01-01

48

Xanthophylls in light-harvesting complex II of higher plants: light harvesting and triplet quenching  

Microsoft Academic Search

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 that violaxanthin is not present in monomeric preparations, that it has most likely a red-most absorption maximum at 510 nm

Erwin J. G. Peterman; Claudiu C. Gradinaru; Florentine Calkoen; Jeroen C. Borst; Rienk van Grondelle; Herbert van Amerongen

1997-01-01

49

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

SciTech Connect

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.

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

2012-05-07

50

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

PubMed

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. PMID:22583207

Harel, Elad

2012-05-01

51

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

NASA Astrophysics Data System (ADS)

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.

Harel, Elad

2012-05-01

52

Patchy particles by self assembly  

NASA Astrophysics Data System (ADS)

Patchy particles offer novel means for colloidal assembly or clustering of functional groups but are generally made by batch processes rather than self-assembly. Selective binding of multivalent ligands within a mixture of polyvalent amphiphiles provides, in principle, a mechanism for driving domain formation in self-assemblies. Divalent cations are shown here to crossbridge polyanionic amphiphiles, which thereby demix from neutral amphiphiles and form spots or rafts within vesicles as well as stripes within cylindrical micelles. Calcium- and copper-crossbridged domains of synthetic block copolymers or natural lipid (phosphatidylinositol-4,5-bisphosphate) possess tunable sizes, shapes and/or spacings that can last for years. Lateral segregation in these `responsive Janus assemblies' couples weakly to curvature and proves to be restricted within phase diagrams to narrow regimes of pH and cation concentration that are centred near the characteristic binding constants for polyacid interactions. Remixing at high pH is surprising, but a theory for strong lateral segregation shows that counterion entropy dominates electrostatic crossbridges, thus illustrating the insights gained into ligand-induced pattern formation within self-assemblies. REFERENCES - [1] D.A. Christian, A. Tian, W.G. Ellenbroek, I. Levental, P.A. Janmey, A.J. Liu, T. Baumgart, D.E. Discher. Spotted vesicles, striped micelles, and Janus assemblies induced by ligand binding. Nature Materials 8: 843--849 (2009).

Discher, Dennis; Christian, David

2010-03-01

53

Efficiency enhancement in GaAs solar cells using self-assembled microspheres.  

PubMed

In this study we develop an efficient light harvesting scheme that can enhance the efficiency of GaAs solar cells using self-assembled microspheres. Based on the scattering of the microspheres and the theory of photonic crystals, the path length can be increased. In addition, the self-assembly of microspheres is one of the simplest and the fastest methods with which to build a 2D periodic structure. The experimental results are confirmed by the use of a simulation in which a finite-difference time-domain (FDTD) method is used to analyze the absorption and electric field of the 2D periodic structure. Both the results of the numerical simulations and the experimental results show an increase in the conversion power efficiency of GaAs solar cell of about 25% when 1 microm microspheres were assembled on the surface of GaAs solar cells. PMID:19365476

Chang, Te-Hung; Wu, Pei-Hsuan; Chen, Sheng-Hui; Chan, Chia-Hua; Lee, Cheng-Chung; Chen, Chii-Chang; Su, Yan-Kuin

2009-04-13

54

Nanotechnology and Quasicrystals: From Self-Assembly to Photonic Applications  

Microsoft Academic Search

After providing a concise overview on quasicrystals and their discovery more than a quarter of a century ago, I consider the\\u000a unexpected interplay between nano-technology and quasiperiodic crystals. Of particular relevance are efforts to fabricate\\u000a artificial functional micro- or nanostructures, as well as efforts to control the self-assembly of nanostructures, where current\\u000a knowledge about the possibility of having long-range order

Ron Lifshitz; Beverly Sackler

2009-01-01

55

Spectroscopic Investigations of the Photophysics of Cryptophyte Light-Harvesting  

NASA Astrophysics Data System (ADS)

The biological significance of photosynthesis is indisputable as it is necessary for nearly all life on earth. Photosynthesis provides chemical energy for plants, algae, and bacteria, while heterotrophic organisms rely on these species as their ultimate food source. The initial step in photosynthesis requires the absorption of sunlight to create electronic excitations. Light-harvesting proteins play the functional role of capturing solar radiation and transferring the resulting excitation to the reaction centers where it is used to carry out the chemical reactions of photosynthesis. Despite the wide variety of light-harvesting protein structures and arrangements, most light-harvesting proteins are able to utilize the captured solar energy for charge separation with near perfect quantum efficiency.1 This thesis will focus on understanding the energy transfer dynamics and photophysics of a specific subset of light-harvesting antennae known as phycobiliproteins. These proteins are extracted from cryptophyte algae and are investigated using steady-state and ultrafast spectroscopic techniques.

Dinshaw, Rayomond

56

Biogeography of Photosynthetic Light-Harvesting Genes in Marine Phytoplankton  

PubMed Central

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 in the iron-limited, high-nutrient low-chlorophyll region of the equatorial Pacific. This observation demonstrates the ecological importance of isiA genes in enabling marine Synechococcus to acclimate to iron limitation and suggests that the presence of this gene can be a natural biomarker for iron limitation in oceanic environments. PMID:19240807

Bibby, Thomas S.; Zhang, Yinan; Chen, Min

2009-01-01

57

Synergistic Two-Photon Absorption Enhancement in Photosynthetic Light Harvesting  

NASA Astrophysics Data System (ADS)

The grand scale fixation of solar energies into chemical substances by photosynthetic reactions of light-harvesting organisms provides Earth's other life forms a thriving environment. Scientific explorations in the past decades have unraveled the fundamental photophysical and photochemical processes in photosynthesis. Higher plants, green algae, and light-harvesting bacteria utilize organized pigment-protein complexes to harvest solar power efficiently and the resultant electronic excitations are funneled into a reaction center, where the first charge separation process takes place. Here we show experimental evidences that green algae (Chlorella vulgaris) in vivo display a synergistic two-photon absorption enhancement in their photosynthetic light harvesting. Their absorption coefficients at various wavelengths display dramatic dependence on the photon flux. This newly found phenomenon is attributed to a coherence-electronic-energy-transfer-mediated (CEETRAM) photon absorption process of light-harvesting pigment-protein complexes of green algae. Under the ambient light level, algae and higher plants can utilize this quantum mechanical mechanism to create two entangled electronic excitations adjacently in their light-harvesting networks. Concerted multiple electron transfer reactions in the reaction centers and oxygen evolving complexes can be implemented efficiently by the coherent motion of two entangled excitons from antennae to the charge separation reaction sites. To fabricate nanostructured, synthetic light-harvesting apparatus, the paramount role of the CEETRAM photon absorption mechanism should be seriously considered in the strategic guidelines.

Chen, Kuo-Mei; Chen, Yu-Wei; Gao, Ting-Fong

2012-06-01

58

Self-assembled granular walkers  

E-print Network

Mechanisms of locomotion in microscopic systems are of great interest not only for technological applications, but also for the sake of understanding, and potentially harnessing, processes far from thermal equilibrium. Down-scaling is a particular challenge, and has led to a number of interesting concepts including thermal ratchet systems and asymmetric swimmers. Here we present a system which is particularly intriguing, as it is self-assembling and uses a robust mechanism which can be implemented in various settings. It consists of small spheres of different size which adhere to each other, and are subject to an oscillating (zero average) external force eld. An inherent nonlinearity in the mutual force network leads to force rectication and hence to locomotion. We present a model that accounts for the observed behaviour and demonstrates the wide applicability and potential scalability of the concept.

Z. S. Khan; A. Steinberger; R. Seemann; and S. Herminghaus

2010-03-08

59

Nanopatterned self-assembled monolayers.  

PubMed

We report on the fabrication of chemically nanopatterned gold surfaces by combining electron-beam lithography with gas and liquid phase thiolization. The line-edge roughness of the patterns is ?4 nm, corresponding to a limiting feature size in the range of 15 nm. Indications for a lower packing density of the self-assembled monolayers grown in the nanofeatures are given, and evidences for the bleeding of thiols along the grain boundaries of the gold substrate are displayed. A comparison is provided between nanopatterned thiol and silane monolayers on gold and on silicon wafers, respectively. The line-edge roughnesses are shown to be close to each other for these two systems, indicating that the limiting step is currently the lithography step, suggesting possible improvement of the resolution. The advantages and drawbacks of thiol versus silane monolayers are finally discussed with respect to the formation of chemically nanopatterned surfaces. PMID:21727398

Baralia, Gabriel G; Pallandre, Antoine; Nysten, Bernard; Jonas, Alain M

2006-02-28

60

Nanopatterned self-assembled monolayers  

NASA Astrophysics Data System (ADS)

We report on the fabrication of chemically nanopatterned gold surfaces by combining electron-beam lithography with gas and liquid phase thiolization. The line-edge roughness of the patterns is ~4 nm, corresponding to a limiting feature size in the range of 15 nm. Indications for a lower packing density of the self-assembled monolayers grown in the nanofeatures are given, and evidences for the bleeding of thiols along the grain boundaries of the gold substrate are displayed. A comparison is provided between nanopatterned thiol and silane monolayers on gold and on silicon wafers, respectively. The line-edge roughnesses are shown to be close to each other for these two systems, indicating that the limiting step is currently the lithography step, suggesting possible improvement of the resolution. The advantages and drawbacks of thiol versus silane monolayers are finally discussed with respect to the formation of chemically nanopatterned surfaces.

Baralia, Gabriel G.; Pallandre, Antoine; Nysten, Bernard; Jonas, Alain M.

2006-02-01

61

Surface Modification with Self-Assembled Monolayer &  

E-print Network

, Absorption - Surface (Gold & Glass (Silicon Wafer), Plastics) of the substrate - Silane (Glass) - Amine (Gold1 1 / 40 Surface Modification with Self-Assembled Monolayer & Polymer Brush for Biotechnology Surface Modification with Self-Assembled Monolayer & Polymer Brush for Biotechnology 2 / 40 linear star

Hong, Deog Ki

62

Self-Assembly: How Nature Builds  

ERIC Educational Resources Information Center

Self-assembly or spontaneous assembly is a process in which materials build themselves without assistance. This process plays a central role in the construction of biological structures and materials such as cells, viruses, and bone, and also in abiotic processes like phase transitions and crystal formation. The principles of self-assembly help…

Jones, M. Gail; Falvo, Michael R.; Broadwell, Bethany; Dotger, Sharon

2006-01-01

63

Self-assembly: Served on a nanoplate  

NASA Astrophysics Data System (ADS)

Self-assembled cylinders can generally be extended only from their ends -- growth that is considered to be 'one-dimensional'. Now, platelet-like structures with controlled size and composition have been constructed by growth in two dimensions of self-assembled structures, starting from crystallite seed micelles.

Cai, Chunhua; Lin, Jiaping

2014-10-01

64

Bottom-Up Nanomanufacturing: Self Assembly  

NSDL National Science Digital Library

This overview of nanotechnology is presented by the NaMCATE project. "The process of self assembly is defined as the spontaneous association of numerous individual units of material into well organized, well defined structures without external instruction." An understanding of self assembly requires background knowledge in physics, chemistry, and biology and this module focuses on these fields. This lesson introduces these concepts by providing two learning activities on self assembly as well as a pre-test and performance assessment. Additionally, a powerpoint presentation is included.Users must create a free login in order to access the materials.

2011-09-22

65

Self-Assembly Behavior of Pullulan Abietate  

NASA Astrophysics Data System (ADS)

Wood is one of nature's most fascinating biological composites due to its toughness and resistance to fracture properties. These properties stem from the self-assembly of cellulose microfibrils in an amorphous matrix of hemicellulose and lignin. In recent years, science has looked to nature for guidance in preparing synthetic materials with desirable physical properties. In order to study the self-assembly process in wood, a model system composed of a polysaccharide, pullulan abietate, and a biomimetic cellulose substrate prepared by the Langmuir-Blodgett technique has been developed. Interfacial tension and surface plasmon resonance measurements used to study the self-assembly process will be discussed for different pullulan derivatives.

Gradwell, Sheila; Esker, Alan; Glasser, Wolgang; Heinze, Thomas

2003-03-01

66

Self-assembly of biomolecular soft matter.  

PubMed

Self-assembly programmed by molecular structure and guided dynamically by energy dissipation is a ubiquitous phenomenon in biological systems that build functional structures from the nanoscale to macroscopic dimensions. This paper describes examples of one-dimensional self-assembly of peptide amphiphiles and the consequent biological functions that emerge in these systems. We also discuss here hierarchical self-assembly of supramolecular peptide nanostructures and polysaccharides, and some new results are reported on supramolecular crystals formed by highly charged peptide amphiphiles. Reflecting on presentations at this Faraday Discussion, the paper ends with a discussion of some of the future opportunities and challenges of the field. PMID:24611266

Stupp, Samuel I; Zha, R Helen; Palmer, Liam C; Cui, Honggang; Bitton, Ronit

2013-01-01

67

Self-Assembly of Biomolecular Soft Matter  

PubMed Central

Self-assembly programmed by molecular structure and guided dynamically by energy dissipation is a ubiquitous phenomenon in biological systems that build functional structures from the nanoscale to macroscopic dimensions. This paper describes examples of one-dimensional self-assembly of peptide amphiphiles and the consequent biological functions that emerge in these systems. We also discuss here hierarchical self-assembly of supramolecular peptide nanostructures and polysaccharides, and some new results are reported on supramolecular crystals formed by highly charged peptide amphiphiles. Reflecting on presentations at this Faraday Discussion, the paper ends with a discussion of some of the future opportunities and challenges of the field. PMID:24611266

Zha, R. Helen; Palmer, Liam C.; Cui, Honggang; Bitton, Ronit

2014-01-01

68

Defects in Self Assembled Colloidal Crystals  

E-print Network

Colloidal self assembly is an efficient method for making 3-D ordered nanostructures suitable for materials such as photonic crystals and macroscopic solids for catalysis and sensor applications. Colloidal crystals grown ...

Koh, Yaw Koon

69

Self-assembled Materials for Catalysis  

SciTech Connect

The purpose of this review is to highlight developments on self-assembled nanostructured materials (i.e. mesoporous and nanoparticle based materials) and their catalytic applications. Since there are some reviews available for metal-based nanoparticles as catalysts, this review will mainly focus on self-assembled oxide-based catalytic materials. The content includes: (1) Design and synthetic strategy toward self-assembled mesoporous catalysts; (2) Polyoxometalates (POMs) based nanocatalysts; (3) Dendrimers based nanocatalysts; (4) Shaped nanomaterials and catalytic applications. We show that self-assemblies of molecules, crystalline seeds, nano-building blocks into organized mesoscopic structures paved new roads for tailoring porosities of heterogeneous catalysts and catalytic active sites.

Zhu, Kake; Wang, Donghai; Liu, Jun

2009-01-01

70

Light-harvesting materials: Soft support for energy conversion  

NASA Astrophysics Data System (ADS)

To convert solar energy into viable fuels, coupling light-harvesting materials to catalysts is a crucial challenge. Now, the combination of an organic supramolecular hydrogel and a non-precious metal catalyst has been demonstrated to be effective for photocatalytic H2 production.

Stolley, Ryan M.; Helm, Monte L.

2014-11-01

71

Light-harvesting photocatalysis for water oxidation using mesoporous organosilica.  

PubMed

An organic-based photocatalysis system for water oxidation, with visible-light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd-PMO), a visible-light harvesting antenna, was supported with [Ru(II)(bpy)3(2+)] complex (bpy = 2,2'-bipyridyl) coupled with iridium oxide (IrO(x)) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd-PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na2S2O8) to form Ru(3+) species. The Ru(3+) species extracts an electron from IrO(x) to oxidize water for oxygen production. The reaction quantum yield was 0.34?%, which was improved to 0.68 or 1.2?% by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem?II, 1)?light-harvesting, 2)?charge separation, and 3)?oxygen generation, were realized for the first time by using the light-harvesting PMO. PMID:24890840

Takeda, Hiroyuki; Ohashi, Masataka; Goto, Yasutomo; Ohsuna, Tetsu; Tani, Takao; Inagaki, Shinji

2014-07-14

72

Directed Self-Assembly of Nanodispersions  

SciTech Connect

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 directed self-assembly of anisotropic nanoparticles and their unique physical properties.

Furst, Eric M [University of Delaware] [University of Delaware

2013-11-15

73

Indicators of quantum coherence in light-harvesting dynamics  

NASA Astrophysics Data System (ADS)

Characterizing quantum dynamics of electronic excitations in a variety of light-harvesting systems is currently of much interest [1]. In particular, it is important to identify measures that appropriately quantify the strength of coherent dynamics and its impact on different time scales of the light-harvesting process. In this talk I will discuss quantum transport performance measures that are defined based on the probability for the dynamics to successfully distinguish different initial photo-excitation conditions. I will also discuss how initial state distinguisability can provide information on spatially correlated phonon fluctuations as well as on the non-markovian character of the quantum dynamics. The prototype systems considered here are cryptophyte light-harvesting antennae isolated from marine algae [2, 3]. Experimental quantification of state distinguishability can be realized by monitoring the evolution of selected off-diagonal density matrix elements and therefore it could be achieved with current two-dimensional spectroscopy techniques. [4pt] [1] A. Olaya-Castro and G. D. Scholes, "Energy transfer from F"orster-Dexter theory to quantum coherent light-harvesting", to appear in Int. Rev. Phys. Chem. (2010) [0pt] [2] E. Collini, C.Y. Wong, K.E. Wilk, P.M.G. Curmi, P. Brumer and G.D. Scholes, "Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature" Nature, 463, 644-647 (2010) [0pt] [3] A. Kolli, A Nazir, F. Fassioli, R. Dinshaw, G D Scholes, and A Olaya-Castro, "Energy transfer dynamics in cryptophyte antennae proteins", submitted for publication (2010)

Olaya-Castro, Alexandra

2011-03-01

74

Self-Assembling Behavior and Inhibition Effect of Dodecanethiol Self-Assembled Monolayers on Copper Surface  

NASA Astrophysics Data System (ADS)

The self-assembling behavior and inhibition effect of dodecanethiol self-assembled monolayers (SAMs) on copper surface were investigated by atomic force microscopy (AFM) and electrochemical methods. The assembling process was monitored by AFM phase images. The assembling time influences the corrosion protection efficiency of dodecanethiol SAMs. Surface friction significantly decreases when the copper surface is covered by SAMs.

Zhang, Xiulan; Zhang, Heng; Yang, Yihong; Chen, Zhenyu

2013-08-01

75

Molecular self-assembly on graphene.  

PubMed

The formation of ordered arrays of molecules via self-assembly is a rapid, scalable route towards the realization of nanoscale architectures with tailored properties. In recent years, graphene has emerged as an appealing substrate for molecular self-assembly in two dimensions. Here, the first five years of progress in supramolecular organization on graphene are reviewed. The self-assembly process can vary depending on the type of graphene employed: epitaxial graphene, grown in situ on a metal surface, and non-epitaxial graphene, transferred onto an arbitrary substrate, can have different effects on the final structure. On epitaxial graphene, the process is sensitive to the interaction between the graphene and the substrate on which it is grown. In the case of graphene that strongly interacts with its substrate, such as graphene/Ru(0001), the inhomogeneous adsorption landscape of the graphene moiré superlattice provides a unique opportunity for guiding molecular organization, since molecules experience spatially constrained diffusion and adsorption. On weaker-interacting epitaxial graphene films, and on non-epitaxial graphene transferred onto a host substrate, self-assembly leads to films similar to those obtained on graphite surfaces. The efficacy of a graphene layer for facilitating planar adsorption of aromatic molecules has been repeatedly demonstrated, indicating that it can be used to direct molecular adsorption, and therefore carrier transport, in a certain orientation, and suggesting that the use of transferred graphene may allow for predictible molecular self-assembly on a wide range of surfaces. PMID:24155272

MacLeod, J M; Rosei, F

2014-03-26

76

Evolution of photosynthetic reaction centers and light harvesting chlorophyll proteins.  

PubMed

It is proposed that there is a single evolutionary origin for photosynthetic reaction centers and also for most light-harvesting chlorophyll proteins. It is generally accepted that the purple bacterial reaction center (quinone-reducing photosystem) and the plant and cyanobacterial PSII (oxygen-evolving photosystem) are homologous. It is also apparent that the green sulfur bacterial reaction center is homologous to cyanobacterial PSI (the pyridine nucleotide reducing photosystem). However, it is less obvious that PSI is related to the purple bacterial reaction center. It is herein proposed that PSI represents a gene fusion of the precursors of small light harvesting bacteriochlorophyll proteins from purple bacteria and purple bacterial reaction centers. Furthermore, it is proposed that reaction centers evolved from the membrane-spanning cytochrome b of the cytochrome bc1 complex and that most membrane-spanning cytochromes may have a common origin. PMID:7888608

Meyer, T E

1994-01-01

77

Regulation and dynamics of the light-harvesting system.  

PubMed

Photosynthetic organisms are continuously subjected to changes in light quantity and quality, and must adjust their photosynthetic machinery so that it maintains optimal performance under limiting light and minimizes photodamage under excess light. To achieve this goal, these organisms use two main strategies in which light-harvesting complex II (LHCII), the light-harvesting system of photosystem II (PSII), plays a key role both for the collection of light energy and for photoprotection. The first is energy-dependent nonphotochemical quenching, whereby the high-light-induced proton gradient across the thylakoid membrane triggers a process in which excess excitation energy is harmlessly dissipated as heat. The second involves a redistribution of the mobile LHCII between the two photosystems in response to changes in the redox poise of the electron transport chain sensed through a signaling chain. These two processes strongly diminish the production of damaging reactive oxygen species, but photodamage of PSII is unavoidable, and it is repaired efficiently. PMID:24471838

Rochaix, Jean-David

2014-01-01

78

Fluctuating Two-State Light Harvesting in a Photosynthetic Membrane  

SciTech Connect

How light is converted into chemical energy in a natural photosynthetic system is of great interest in energy sciences. Using single-molecule and single-vesicle fluorescence spectroscopy and imaging, we have observed fluctuating inter-molecular protein energy transfers in the photosynthetic membranes of R. sphaeroides. Our results suggest that there are dynamic coupled and non-coupled states in the light-harvesting protein assembly.

Pan, Duohai; Hu, Dehong; Liu, Ruchuan; Zeng, Xiaohua; Kaplan, Samuel; Lu, H. Peter

2007-06-28

79

Amphipols and photosynthetic light-harvesting pigment-protein complexes.  

PubMed

The trimeric light-harvesting complexes II (LHCII) of plants and green algae are pigment-protein complexes involved in light harvesting and photoprotection. Different conformational states have been proposed to be responsible for their different functions. At present, detergent-solubilized LHCII is used as a model for the "light-harvesting conformation", whereas the "quenched conformation" is mimicked by LHCII aggregates. However, none of these conditions seem to perfectly reproduce the properties of LHCII in vivo. In addition, several monomeric LHC complexes are not fully stable in detergent. There is thus a need to find conditions that allow analyzing LHCs in vitro in stable and, hopefully, more native-like conformations. Here, we report a study of LHCII, the major antenna complex of plants, in complex with amphipols. We have trapped trimeric LHCII and monomeric Lhcb1 with either polyanionic or non-ionic amphipols and studied the effect of these polymers on the properties of the complexes. We show that, as compared to detergent solutions, amphipols have a stabilizing effect on LHCII. We also show that the average fluorescence lifetime of LHCII trapped in an anionic amphipol is ~30 % shorter than in ?-dodecylmaltoside, due to the presence of a conformation with 230-ps lifetime that is not present in detergent solutions. PMID:25107304

Opa?i?, Milena; Durand, Grégory; Bosco, Michael; Polidori, Ange; Popot, Jean-Luc

2014-10-01

80

Efficient energy transfer in light-harvesting systems, I: optimal temperature, reorganization energy, and spatial-  

E-print Network

Efficient energy transfer in light-harvesting systems, I: optimal temperature, reorganization of efficient and robust energy transfer in light-harvesting systems provides new insights for the optimal dynamics in light harvesting systems and energy transfer efficiency 2. Optimization in the Haken

Cao, Jianshu

81

S-Layer Protein Self-Assembly  

PubMed Central

Crystalline S(urface)-layers are the most commonly observed cell surface structures in prokaryotic organisms (bacteria and archaea). S-layers are highly porous protein meshworks with unit cell sizes in the range of 3 to 30 nm, and thicknesses of ~10 nm. One of the key features of S-layer proteins is their intrinsic capability to form self-assembled mono- or double layers in solution, and at interfaces. Basic research on S-layer proteins laid foundation to make use of the unique self-assembly properties of native and, in particular, genetically functionalized S-layer protein lattices, in a broad range of applications in the life and non-life sciences. This contribution briefly summarizes the knowledge about structure, genetics, chemistry, morphogenesis, and function of S-layer proteins and pays particular attention to the self-assembly in solution, and at differently functionalized solid supports. PMID:23354479

Pum, Dietmar; Toca-Herrera, Jose Luis; Sleytr, Uwe B.

2013-01-01

82

Thermodynamics of Phospholipid Self-Assembly  

PubMed Central

Negatively charged phospholipids are an important component of biological membranes. The thermodynamic parameters governing self-assembly of anionic phospholipids are deduced here from isothermal titration calorimetry. Heats of demicellization were determined for dioctanoyl phosphatidylglycerol (PG) and phosphatidylserine (PS) at different ionic strengths, and for dioctanoyl phosphatidic acid at different pH values. The large heat capacity (?CoP ? ?400 J.mol?1 K?1 for PG and PS), and zero enthalpy at a characteristic temperature near the physiological range (T? ? 300 K for PG and PS), demonstrate that the driving force for self-assembly is the hydrophobic effect. The pH and ionic-strength dependences indicate that the principal electrostatic contribution to self-assembly comes from the entropy associated with the electrostatic double layer, in agreement with theoretical predictions. These measurements help define the thermodynamic effects of anionic lipids on biomembrane stability. PMID:22404930

Marsh, Derek

2012-01-01

83

SELF-ASSEMBLED DNA NANOSTRUCTURES AND DNA-TEMPLATED SILVER NANOWIRES  

E-print Network

available to date by any method. The wires have been contacted by leads formed by electron beam lithography for fabricating nanostructures for the last two decades. Artificially designed, self-assembled DNA nanostructures with designed structures. We have also presented fabrication of size-controllable, fully addressable

Reif, John H.

84

Incremental Construction of Neighborhood Graphs Using the Ants Self-Assembly Behavior  

Microsoft Academic Search

In this paper we present a new incremental algorithm for building neighborhood graphs between data. It is inspired from the self-assembly behavior observed in real ants where ants progressively become attached to an existing support and then successively to other attached ants. Each artificial ant represents one data. The way ants move and build a graph depends on the similarity

Julien Lavergne; Hanane Azzag; Christiane Guinot; Gilles Venturini

2007-01-01

85

Early events in the biosynthesis and assembly of the cyanobacterial light-harvesting system  

NASA Astrophysics Data System (ADS)

The cyanobacteria are photosynthetic procaryotes that employ a mechanism of photosynthesis which is essentially identical to the systems found in plant chloroplasts and the eukaryotic green algae. Cyanobacteria can drive photosynthesis with light energy from a broad region of the visible spectrum (500 - 650 nm wavelength) that is not available to plants and green algae, which are limited to the narrow band of light energy that is absorbed by chlorophyll (660-680 nm). The light-harvesting capacity of the cyanobacteria is a function of a complex protein structure that resides on the surface of the photosynthetic membrane in contact with the PSII chlorophyll reaction centers. This light-harvesting complex is called a phycobilisome and functions as a protein scaffold for a rigid array of chromophores that absorbs light energy and transfers it to chlorophyll. The chromophores are linear tetrapyrroles (the bilins) that are covalently attached to the biliproteins, which comprise 80 - 85% of the total phycobilisome mass. There are three major classes of spectrally distinct biliproteins [phycoerythrin (PE), (lambda) max equals 565 nm; phycocyanin (PC), (lambda) max equals 617 nm; and allophycocyanin (AP), (lambda) max equals 650 nm] and their spatial organization within the phycobilisome creates an array of donor and acceptor chromophores that is optimized for resonance energy transfer to chlorophyll on a picosecond timescale and at close to 100% efficiency. The cyanobacteria can exert control over the biliprotein composition of the phycobilisomes in response to both light quality and light quantity, and they do so primarily by light-responsive transcription control mechanisms. The biosynthesis and assembly of a phycobilisome is an interesting example of self-assembly in a complex protein system. A phycobilisome from Synechocystis sp. strain 6701 can contain 400 proteins derived from a repertoire of 16 different polypeptides that includes the (alpha) and (beta) subunits for each major biliprotein and the achromic linker proteins that mediate assembly throughout the structure. The biliprotein subunit structures all show an identical motif that is reflected by significant amino acid sequence similarities across the different classes. Since phycobilisomes can comprise up to 40% of the cyanobacterial dry mass, assembly of these complexes must occur in the presence of high localized concentrations of components that are very similar in structure. That phycobilisome assembly is an efficient process with no evidence of significant misassembly suggests that effective molecular recognition during phycobilisome biosynthesis is based upon the subtle differences between subunits of different class biliproteins. We are using a protein engineering approach to examine structural features that mediate molecular recognition in two of the earliest steps of phycobilisome assembly, the docking of (alpha) and (beta) subunits and the selective attachment of chromophores.

Anderson, Lamont

1996-02-01

86

Separating annihilation and excitation energy transfer dynamics in light harvesting systems.  

PubMed

The dependence of excitation energy transfer kinetics on the electronic state of the acceptor (ground vs excited) has been resolved with a novel multipulse prePump-Pump-Probe spectroscopy. The primary energy transfer and annihilation dynamics in two model light-harvesting systems were explored: an artificially synthesized carotenoid-zinc-phthalocyanine dyad and a naturally occurring light-harvesting peridinin-chlorophyll protein complex from Amphidinium carterae. Both systems use carotenoid as the primary excitation energy donor with porphyrin chromophores as the acceptor molecules. The prePump-Pump-Probe transient signals were analyzed with Monte Carlo modeling to explicitly address the underlying step-by-step kinetics involved in both excitation migration and annihilation processes. Both energy transfer and annihilation dynamics were demonstrated to occur with approximately the same rate in both systems, regardless of the excitation status of the acceptor pigments. The possible reasons for these observations are discussed in the framework of the Förster energy transfer model. PMID:23662680

Vengris, Mikas; Larsen, Delmar S; Valkunas, Leonas; Kodis, Gerdenis; Herrero, Christian; Gust, Devens; Moore, Thomas; Moore, Ana; van Grondelle, Rienk

2013-09-26

87

Noise-assisted energy transfer in quantum networks and light-harvesting complexes  

E-print Network

We provide physically intuitive mechanisms for the effect of noise on excitation energy transfer (EET) in networks. Using these mechanisms of dephasing-assisted transport (DAT) in a hybrid basis of both excitons and sites, we develop a detailed picture of how noise enables energy transfer with efficiencies well above $90%$ across the Fenna-Matthew-Olson (FMO) complex, a type of light harvesting molecule. We demonstrate explicitly how noise alters the pathways of energy transfer across the complex, suppressing ineffective pathways and facilitating direct ones to the reaction centre. We explain that the fundamental mechanisms underpinning DAT are expected to be robust with respect to the considered noise model but show that the specific details of the exciton-phonon coupling, which remain largely unknown in these type of complexes, and in particular the impact of non-Markovian effects, results in variations of dynamical features that should be amenable to experimental verification within current or planned technology. A detailed understanding of DAT in natural compounds should open up a new paradigm of `noise-engineering' by which EET can be optimized in artificial light-harvesting structures.

Alex W. Chin; Animesh Datta; Filippo Caruso; Susana F. Huelga; Martin B. Plenio

2009-10-21

88

Computing by molecular self-assembly  

PubMed Central

The paper reviews two computing models by DNA self-assembly whose proof of principal have recently been experimentally confirmed. The first model incorporates DNA nano-devices and triple crossover DNA molecules to algorithmically arrange non-DNA species. This is achieved by simulating a finite-state automaton with output where golden nanoparticles are assembled to read-out the result. In the second model, a complex DNA molecule representing a graph emerges as a solution of a computational problem. This supports the idea that in molecular self-assembly computing, it may be necessary to develop the notion of shape processing besides the classical approach through symbol processing. PMID:23919130

Jonoska, Natasa; Seeman, Nadrian C.

2012-01-01

89

Computing by molecular self-assembly.  

PubMed

The paper reviews two computing models by DNA self-assembly whose proof of principal have recently been experimentally confirmed. The first model incorporates DNA nano-devices and triple crossover DNA molecules to algorithmically arrange non-DNA species. This is achieved by simulating a finite-state automaton with output where golden nanoparticles are assembled to read-out the result. In the second model, a complex DNA molecule representing a graph emerges as a solution of a computational problem. This supports the idea that in molecular self-assembly computing, it may be necessary to develop the notion of shape processing besides the classical approach through symbol processing. PMID:23919130

Jonoska, Nataša; Seeman, Nadrian C

2012-08-01

90

From Self-Assembled Vesicles to Protocells  

PubMed Central

Self-assembled vesicles are essential components of primitive cells. We review the importance of vesicles during the origins of life, fundamental thermodynamics and kinetics of self-assembly, and experimental models of simple vesicles, focusing on prebiotically plausible fatty acids and their derivatives. We review recent work on interactions of simple vesicles with RNA and other studies of the transition from vesicles to protocells. Finally we discuss current challenges in understanding the biophysics of protocells, as well as conceptual questions in information transmission and self-replication. PMID:20519344

Chen, Irene A.; Walde, Peter

2010-01-01

91

Binding polynomial in molecular self-assembly  

NASA Astrophysics Data System (ADS)

In the present work the concept of a binding polynomial is revisited for the most widely used case of self-assembly of identical molecular units and results in the re-construction of a link to the grand partition function of such a system. It is found that if the self-assembly process is not pronounced (i.e., the product of the equilibrium constant and the monomer concentration is close to zero), the binding polynomial has the meaning of a molecular partition function that is given by the summation over energy levels of any molecule in the system. In other cases the concept of a binding polynomial may be misleading.

Mosunov, Andrew A.; Rybakova, Kristina A.; Rogova, Olga V.; Evstigneev, Maxim P.

2014-06-01

92

?-Carotene to bacteriochlorophyll c energy transfer in self-assembled aggregates mimicking chlorosomes  

NASA Astrophysics Data System (ADS)

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 ?-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, ˜100-fs energy transfer from the S 2 state of ?-carotene to bacteriochlorophyll c was revealed, while no evidence for significant energy transfer from the S 1 state was found. Picosecond formation of the carotenoid triplet state (T 1) was observed, which was likely generated by singlet homo-fission from the S 1 state of ?-carotene.

Alster, J.; Polívka, T.; Arellano, J. B.; Chábera, P.; Vácha, F.; Pšen?ík, J.

2010-07-01

93

Fluidic self-assembly of silicon microstructures  

Microsoft Academic Search

Fluidic self-assembly is a new technique which makes possible the integration of devices fabricated using dissimilar materials and processes. The integration is accomplished by fluidically transporting trapezoidally shaped blocks made of one material into similarly shaped holes in a receptor substrate. In this paper, a systematic study of the FSA integration efficiency is presented. Blocks and holes were formed from

Ashish K. Verma; Mark A. Hadley; Hsi-Jen J. Yeh; J. S. Smith

1995-01-01

94

CONTRIBUTED Self-Assembly at the  

E-print Network

themselves, based on information coded in their components. By Roderich GroQ, Member IEEE, and Marco Dorigo motion; formation; growth; macro- scopic; modular robotics; self-assembly; self-propelled; self disband from, each other (e.g., based on shape recognition). Note that processes that occur within

Libre de Bruxelles, Université

95

Self-Assembly at the Macroscopic Scale  

Microsoft Academic Search

In this paper, we review half a century of research on the design of systems displaying (physical) self-assembly of macroscopic components. We report on the experience gained in the design of 21 such systems, exhibiting components ranging from passive mechanical parts to mobile robots. We present a taxonomy of the systems and discuss design principles and functions. Finally, we summarize

R. Gross; M. Dorigo

2008-01-01

96

Autonomous Self-assembly in Mobile Robotics  

Microsoft Academic Search

Abstract— In this paper, we present a comprehensive study on autonomous self-assembly. In particular, we discuss the selfassembling capabilities of the swarm-bot, a distributed robotics concept that lies at the intersection between collective an d selfreconfigurable robotics. A swarm-bot comprises autonomous

Michael Bonani; Francesco Mondada; Marco Dorigo

2005-01-01

97

Orthogonally self-assembled multifunctional block copolymers.  

PubMed

We report the synthesis of telechelic poly(norbornene) and poly(cyclooctene) homopolymers by ring-opening metathesis polymerization (ROMP) and their subsequent functionalization and block copolymer formation based on noncovalent interactions. Whereas all the poly(norbornene)s contain either a metal complex or a hydrogen-bonding moiety along the polymer side-chains, together with a single hydrogen-bonding-based molecular recognition moiety at one terminal end of the polymer chain. These homopolymers allow for the formation of side-chain-functionalized AB and ABA block copolymers through self-assembly. The orthogonal natures of all side- and main-chain self-assembly events were demonstrated by (1)H NMR spectroscopy and isothermal titration calorimetry. The resulting fully functionalized block copolymers are the first copolymers combining both side- and main-chain self-assembly, thereby providing a high degree of control over copolymer functionalization and architecture and bringing synthetic materials one step closer to the dynamic self-assembly structures found in nature. PMID:19774560

Ambade, Ashootosh V; Burd, Caroline; Higley, Mary Nell; Nair, Kamlesh P; Weck, Marcus

2009-11-01

98

Self-assembled thin film chemical sensors  

SciTech Connect

This is the final report of a one-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Current chemical sensors suffer from poor molecular specificity, sensitivity, and stability and seldom have the recovery properties needed for real-time monitoring applications. We have employed self-assembly techniques to covalently bond species- selective reagents directly to the surface of the transducer so that analyte/reagent chemistry occurs at the interface between the transducer and the media to be monitored. The use of self-assembling monolayer and -multilayer (SAM) techniques results in stable sensing elements with optimal specificity built in through the use of reagents that have been designed for molecular recognition. Moreover, self-assembly chemistry applied to oxide surfaces allows flexible means of transduction spanning optical, electrochemical, mass-loading, and conduction methods. The work conducted on this project focused on demonstration of the methodology and the application to selected organic vapors (aromatic compounds and halogenated hydrocarbons). We have been able to develop a series of surface acoustic wave (SAW) sensors that are specific for aromatic compounds and halogenated hydrocarbons based on self-assembled thin films of cyclodextrins and calixarenes. Monolayers of seven different cyclodextrins and clixarenes have been attached to SAW transducers and their response to several organic molecules in the vapor phase have been measured. This preliminary data confirms the efficacy of this approach for real- time monitoring of hydrocarbons.

Swanson, B.; Li, DeQuan

1996-11-01

99

Self-assembly micro optical filter  

NASA Astrophysics Data System (ADS)

Optical communication and sensor industry face critical challenges in manufacturing for system integration. Due to the assembly complexity and integration platform variety, micro optical components require costly alignment and assembly procedures, in which many required manual efforts. Consequently, self-assembly device architectures have become a great interest and could provide major advantages over the conventional optical devices. In this paper, we discussed a self-assembly integration platform for micro optical components. To demonstrate the adaptability and flexibility of the proposed optical device architectures, we chose a commercially available MEMS fabrication foundry service - MUMPs (Multi-User MEMS Process). In this work, polysilicon layers of MUMPS are used as the 3-D structural material for construction of micro component framework and actuators. However, because the polysilicon has high absorption in the visible and near infrared wavelength ranges, it is not suitable for optical interaction. To demonstrate the required optical performance, hybrid integration of materials was proposed and implemented. Organic compound materials were applied on the silicon-based framework to form the required optical interfaces. Organic compounds provide good optical transparency, flexibility to form filters or lens and inexpensive manufacturing procedures. In this paper, we have demonstrated a micro optical filter integrated with self-assembly structures. We will discuss the self-assembly mechanism, optical filter designs, fabrication issues and results.

Zhang, Ping (Cerina); Le, Kevin; Malalur-Nagaraja-Rao, Smitha; Hsu, Lun-Chen; Chiao, J.-C.

2006-01-01

100

Amphiphilic, hydrophilic, or hydrophobic synthetic bacteriochlorins in biohybrid light-harvesting architectures: consideration of molecular designs.  

PubMed

Biohybrid light-harvesting architectures can be constructed that employ native-like bacterial photosynthetic antenna peptides as a scaffold to which synthetic chromophores are attached to augment overall spectral coverage. Synthetic bacteriochlorins are attractive to enhance capture of solar radiation in the photon-rich near-infrared spectral region. The effect of the polarity of the bacteriochlorin substituents on the antenna self-assembly process was explored by the preparation of a bacteriochlorin-peptide conjugate using a synthetic amphiphilic bacteriochlorin (B1) to complement prior studies using hydrophilic (B2, four carboxylic acids) or hydrophobic (B3) bacteriochlorins. The amphiphilic bioconjugatable bacteriochlorin B1 with a polar ammonium-terminated tail was synthesized by sequential Pd-mediated reactions of a 3,13-dibromo-5-methoxybacteriochlorin. Each bacteriochlorin bears a maleimido-terminated tether for attachment to a cysteine-containing analog of the Rhodobacter sphaeroides antenna ?-peptide to give conjugates ?-B1, ?-B2, and ?-B3. Given the hydrophobic nature of the ?-peptide, the polarity of B1 and B2 facilitated purification of the respective conjugate compared to the hydrophobic B3. Bacteriochlorophyll a (BChl a) associates with each conjugate in aqueous micellar media to form a dyad containing two ?-peptides, two covalently attached synthetic bacteriochlorins, and a datively bonded BChl-a pair, albeit to a limited extent for ?-B2. The reversible assembly/disassembly of dyad (?-B2/BChl)2 was examined in aqueous detergent (octyl glucoside) solution by temperature variation (15-35 °C). The energy-transfer efficiency from the synthetic bacteriochlorin to the BChl-a dimer was found to be 0.85 for (?-B1/BChl)2, 0.40 for (?-B2/BChl)2, and 0.85 for (?-B3/BChl)2. Thus, in terms of handling, assembly and energy-transfer efficiency taken together, the amphiphilic design examined herein is more attractive than the prior hydrophilic or hydrophobic designs. PMID:24997120

Jiang, Jianbing; Reddy, Kanumuri Ramesh; Pavan, M Phani; Lubian, Elisa; Harris, Michelle A; Jiao, Jieying; Niedzwiedzki, Dariusz M; Kirmaier, Christine; Parkes-Loach, Pamela S; Loach, Paul A; Bocian, David F; Holten, Dewey; Lindsey, Jonathan S

2014-11-01

101

Solvation Effects in Self-Assembled Systems  

SciTech Connect

Many types of self-assembly can be found in nature. They include crystallization, the formation of micelles, and the folding of proteins. Recently there has been much interest in pursuing nano-to-microscopically engineered materials by way of self-assembly on imprinted or templated surfaces. In all of these diverse cases, wetting plays a critical role in the assembly process. Wetting involves the interactions of the substrate or amphiphilic molecule or macromolecule with a solvent. In many self-assembled systems we find that the critical feature of the system is a substrate! or macromolecule with a both hydrophilic and hydrophobic nature. In this paper we discuss the wetting properties of a striped surface where the stripes represent alternating chemical characteristics. We show how the chemical heterogeneity affects the wetting properties of the surface (e.g. the static contact angle), and discuss the length limitations on the soft lithography approach. In this paper, the wetting of a chemically heterogeneous surface is studied using a nonlocal Density Functional Theory (DFT). The results for the heterogeneous surface model we discuss have immediate implications for soft-lithography by self-assembly. It also lends fundamental insight into the mechanisms controlling self-assembly of macromolecules. We present the results of nonlocal 2D DFT calculations on the wetting properties of chemically heterogeneous surfaces. These calculations showed complex density distributions and phase behavior as a result of the heterogeneity. The location of the wetting transition are found to be strongly dependent on the extent and strength of the heterogeneity, and complete wetting was suppressed altogether if the hydrophobic parts of the surface were large enough. In these cases, the condensed nanophase may crystallize if the hydrophilic surface-fluid interactions are strong enough. By exploring the phase space including strength of hydrophilic interactions and extent of chemical heterogeneity, an operational phase diagram was established that could be used for designing nanoscopically tailored devices and materials.

Frink, L.J.D.

1998-11-10

102

A design for self-assembling robots in a system  

E-print Network

This thesis presents the design, construction, control, and application for a novel concept of self-assembling robots in a system. The system is composed of multiple cooperative robots that are designed to self-assemble ...

Kim, Myunghee, Ph. D. Massachusetts Institute of Technology

2006-01-01

103

Self-Assembling Nano-Electronics Turn a Corner  

NSF Publications Database

... Release 05-092Self-Assembling Nano-Electronics Turn a Corner The directed self-assembly process ... themselves into nanoscale patterns that turn corners and exhibit other complex geometries. Their ...

104

Templated self-assembly of sub-10 nm quantum dots  

E-print Network

Patterned templates can guide the self-assembly of nanoparticles into ordered arrays. Our motivation in pursuing templated self-assembly is to develop a robust method for the creation of ordered structures at length scales ...

Leu, Joshua C. (Joshua Chung)

2008-01-01

105

New polythiophene block copolymers for potential light harvesting applications  

NASA Astrophysics Data System (ADS)

This paper presents preliminary synthetic and physical study of a new polythiophene block copolymer. These are conjugated donor (D) block poly(hexylenedithiathiophene) copolymerized with an acceptor (A) block of fluorinated ester derivatized polythiophene via an aliphatic bridge (B) unit. Experimental results show that when -DBAB- type of block copolymer forms, there is strong photoluminescence (PL) quenching in -DBAB- relative to D/A blend or the pristine D or A blocks. PL quenching is attributed to both intra and inter chain photo induced electron transfer or charge separation. Since block copolymer can be easily tailored, this system appears attractive for light harvesting applications including photovoltaic applications.

Maaref, Shahin; Thomas, Shanneth; Wang, Meina; Sun, Sam-Shajing

2004-09-01

106

Light harvesting complex II B850 excitation dynamics  

NASA Astrophysics Data System (ADS)

The dynamics of excitation energy transfer within the B850 ring of light harvesting complex 2 from Rhodobacter sphaeroides and between neighboring B850 rings is investigated by means of dissipative quantum mechanics. The assumption of Boltzmann populated donor states for the calculation of intercomplex excitation transfer rates by generalized Förster theory is shown to give accurate results since intracomplex exciton relaxation to near-Boltzmann population exciton states occurs within a few picoseconds. The primary channels of exciton transfer between B850 rings are found to be the five lowest-lying exciton states, with non-850 nm exciton states making significant contributions to the total transfer rate.

Strümpfer, Johan; Schulten, Klaus

2009-12-01

107

Molecular factors controlling photosynthetic light harvesting by carotenoids.  

PubMed

Carotenoids are naturally occurring pigments that absorb light in the spectral region in which the sun irradiates maximally. These molecules transfer this energy to chlorophylls, initiating the primary photochemical events of photosynthesis. Carotenoids also regulate the flow of energy within the photosynthetic apparatus and protect it from photoinduced damage caused by excess light absorption. To carry out these functions in nature, carotenoids are bound in discrete pigment-protein complexes in the proximity of chlorophylls. A few three-dimensional structures of these carotenoid complexes have been determined by X-ray crystallography. Thus, the stage is set for attempting to correlate the structural information with the spectroscopic properties of carotenoids to understand the molecular mechanism(s) of their function in photosynthetic systems. In this Account, we summarize current spectroscopic data describing the excited state energies and ultrafast dynamics of purified carotenoids in solution and bound in light-harvesting complexes from purple bacteria, marine algae, and green plants. Many of these complexes can be modified using mutagenesis or pigment exchange which facilitates the elucidation of correlations between structure and function. We describe the structural and electronic factors controlling the function of carotenoids as energy donors. We also discuss unresolved issues related to the nature of spectroscopically dark excited states, which could play a role in light harvesting. To illustrate the interplay between structural determinations and spectroscopic investigations that exemplifies work in the field, we describe the spectroscopic properties of four light-harvesting complexes whose structures have been determined to atomic resolution. The first, the LH2 complex from the purple bacterium Rhodopseudomonas acidophila, contains the carotenoid rhodopin glucoside. The second is the LHCII trimeric complex from higher plants which uses the carotenoids lutein, neoxanthin, and violaxanthin to transfer energy to chlorophyll. The third, the peridinin-chlorophyll-protein (PCP) from the dinoflagellate Amphidinium carterae, is the only known complex in which the bound carotenoid (peridinin) pigments outnumber the chlorophylls. The last is xanthorhodopsin from the eubacterium Salinibacter ruber. This complex contains the carotenoid salinixanthin, which transfers energy to a retinal chromophore. The carotenoids in these pigment-protein complexes transfer energy with high efficiency by optimizing both the distance and orientation of the carotenoid donor and chlorophyll acceptor molecules. Importantly, the versatility and robustness of carotenoids in these light-harvesting pigment-protein complexes have led to their incorporation in the design and synthesis of nanoscale antenna systems. In these bioinspired systems, researchers are seeking to improve the light capture and use of energy from the solar emission spectrum. PMID:20446691

Polívka, Tomás; Frank, Harry A

2010-08-17

108

Optimal design for active self-assembly system  

Microsoft Academic Search

Two key issues in stochastic self-assembly are whether the system will converge to the desirable global equi- librium and how quickly it converges. In this paper an optimal self assembly design approach, which guarantees the unique desirable convergence and provides the fastest convergence rate, is proposed for active self-assembly systems. We adopt a Markov chain to model the self-assembly system.

Yuzhen Xue; Martha A. Grover

2011-01-01

109

Constructing biomaterials using self-assembling peptide building blocks  

Microsoft Academic Search

Molecular self-assembly is ubiquitous in nature and has recently emerged as a new bottom-up approach in constructing biomaterials.\\u000a Synthetic peptides assemble through specific molecular recognition and form diverse nanostructures. The resulting versatile\\u000a peptide self-assemblies may be used in a wide range of biological and medical applications. Examples of two self-assembling\\u000a peptide systems are presented and techniques for self-assembly control are

Sheng Lu; P. Chen

2010-01-01

110

Phase Transitions and Control in Self Assembly Yuliy Baryshnikov1  

E-print Network

Phase Transitions and Control in Self Assembly Yuliy Baryshnikov1 , Ed Coffman2 , and Petar Abstract. We introduce a general mathematical model of processes by which self-assembled objects are built of dynamical systems theory, thus representing the self assembly process by a system of ODEs. Our primary

Coffman Jr., E. G.

111

Self-assembling membranes and related methods thereof  

DOEpatents

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).

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

2013-08-20

112

Green grasses as light harvesters in dye sensitized solar cells.  

PubMed

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). PMID:25168231

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

2015-01-25

113

Broadband enhancement of light harvesting in luminescent solar concentrator  

E-print Network

Luminescent solar concentrator (LSC) can absorb large-area incident sunlight, then emit luminescence with high quantum efficiency, which finally be collected by a small photovoltaic (PV) system. The light-harvesting area of the PV system is much smaller than that of the LSC system, potentially improving the efficiency and reducing the cost of solar cells. Here, based on Fermi-golden rule, we present a theoretical description of the luminescent process in nanoscale LSCs where the conventional ray-optics model is no longer applicable. As an example calculated with this new model, we demonstrate that a slot waveguide consisting of a nanometer-sized low-index slot region sandwiched by two high-index regions provides a broadband enhancement of light harvesting by the luminescent centers in the slot region. This is because the slot waveguide can (1) greatly enhance the spontaneous emission due to the Purcell effect, (2) dramatically increase the effective absorption cross-section of luminescent centers, and (3) str...

Xiao, Yun-Feng; Xiao, Lixin; Sun, Fang-Wen; Gong, Qihuang

2010-01-01

114

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

PubMed

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. PMID:24422474

Shah, Vivek B; Biswas, Pratim

2014-02-25

115

Self-assembled nanoparticle drumhead resonators.  

PubMed

The self-assembly of nanoscale structures from functional nanoparticles has provided a powerful path to developing devices with emergent properties from the bottom-up. Here we demonstrate that freestanding sheets self-assembled from various nanoparticles form versatile nanomechanical resonators in the megahertz frequency range. Using spatially resolved laser-interferometry to measure thermal vibrational spectra and image vibration modes, we show that their dynamic behavior is in excellent agreement with linear elastic response for prestressed drumheads of negligible bending stiffness. Fabricated in a simple one-step drying-mediated process, these resonators are highly robust and their inorganic-organic hybrid nature offers an extremely low mass, low stiffness, and the potential to couple the intrinsic functionality of the nanoparticle building blocks to nanomechanical motion. PMID:23614346

Kanjanaboos, Pongsakorn; Lin, Xiao-Min; Sader, John E; Rupich, Sara M; Jaeger, Heinrich M; Guest, Jeffrey R

2013-05-01

116

Self-assembly of Janus Ellipsoids  

NASA Astrophysics Data System (ADS)

The self-assembly of particles into a desired mesoscopic structure and function are considered as a bottom-up strategy to obtain new bulk materials that have potential applications in broad fields including drug delivery, photonic crystals, biomaterials and electronics. We propose a primitive model of Janus ellipsoids that represent particles with an ellipsoidal core and two semi-surfaces coded with dissimilar properties, for example, hydrophobicity and hydrophilicity, respectively. We investigate the effects of the aspect ratio on the self-assembly morphology and dynamical aggregation processes using Monte Carlo simulations. We find that the size and structure of the aggregates can be controlled by the aspect ratio, which should be an interesting result from a design viewpoint.

Liu, Ya; Li, Wei; Perez, Toni; Brett, Genevieve; Gunton, James

2012-02-01

117

Programming protein self assembly with coiled coils  

NASA Astrophysics Data System (ADS)

The controlled assembly of protein domains into supramolecular structures will be an important prerequisite for the use of functional proteins in future nanotechnology applications. Coiled coils are multimerization motifs whose dimerization properties can be programmed by amino acid sequence. Here, we report programmed supramolecular self-assembly of protein molecules using coiled coils and directly demonstrate its potential on the single molecule level by AFM force spectroscopy. We flanked two different model proteins, Ig27 from human cardiac titin and green fluorescent protein (GFP), by coiled coil binding partners and studied the capability of these elementary building blocks to self-assemble into linear chains. Simple sterical constraints are shown to control the assembly process, providing evidence that many proteins can be assembled with this method. An application for this technique is the design of polyproteins for single molecule force spectroscopy with an integrated force-calibration standard.

Dietz, Hendrik; Bornschlögl, Thomas; Heym, Roland; König, Frauke; Rief, Matthias

2007-11-01

118

Engineering building blocks for self-assembling protein nanoparticles  

PubMed Central

Like natural viruses, manmade protein cages for drug delivery are to be ideally formed by repetitive subunits with self-assembling properties, mimicking viral functions and molecular organization. Naturally formed nanostructures (such as viruses, flagella or simpler protein oligomers) can be engineered to acquire specific traits of interest in biomedicine, for instance through the addition of cell targeting agents for desired biodistribution and specific delivery of associated drugs. However, fully artificial constructs would be highly desirable regarding finest tuning and adaptation to precise therapeutic purposes. Although engineering of protein assembling is still in its infancy, arising principles and promising strategies of protein manipulation point out the rational construction of nanoscale protein cages as a feasible concept, reachable through conventional recombinant DNA technologies and microbial protein production. PMID:21192790

2010-01-01

119

Self-assembly of Fmoc-diphenylalanine inside liquid marbles.  

PubMed

Liquid marbles made from Lycopodium clavatum spores are used to encapsulate aqueous solutions of 9-fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF). Acidification of the Fmoc-FF solution at the liquid/air interface of the liquid marble triggers the self-assembly of ribbon-like peptide fibrils into an ultrathin peptide membrane (50-500 nm). The membrane incorporates the lycopodium microparticles and as a result stabilizes the liquid marble against collapse, that could otherwise occur through particle disintegration at the floating interphase. Ultrathin nanostructured peptide membrane formation at the liquid/air interface is also observed within artificial microstructured floating objects. Thus, peptide membranes formed were inspected by SEM and TEM. Electron diffraction data reveal information about the molecular organization inside the oligopeptide membranes. PMID:22584262

Braun, Hans-Georg; Cardoso, André Zamith

2012-09-01

120

Self-assembled tunable photonic hyper-crystals  

NASA Astrophysics Data System (ADS)

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.

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

2014-09-01

121

Self-assembled tunable photonic hyper-crystals.  

PubMed

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. PMID:25027947

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

2014-01-01

122

Self-assembly of tubular fullerenes  

Microsoft Academic Search

Carbon nanotubes in the form of multiwalled fullerenes are shown here to self-assemble under homogeneous gas-phase conditions of carbon condensation in an inert atmosphere heated to 1200$DGR@C-conditions previously thought to be optimal only for the annealing and growth of Cââ and other spheroidal shells. Tubular fullerenes are known to be less stable than their spheroidal counterparts and have thus far

Ting Guo; P. Nikolaev; A. G. Rinzler; Daniel T. Colbert; Richard E. Smalley; D. Tomanek

1995-01-01

123

Templated Self Assemble of Nano-Structures  

SciTech Connect

This project will identify and model mechanisms that template the self-assembly of nanostructures. We focus on a class of systems involving a two-phase monolayer of molecules adsorbed on a solid surface. At a suitably elevated temperature, the molecules diffuse on the surface to reduce the combined free energy of mixing, phase boundary, elastic field, and electrostatic field. With no template, the phases may form a pattern of stripes or disks. The feature size is on the order of 1-100 nm, selected to compromise the phase boundary energy and the long-range elastic or electrostatic interaction. Both experimental observations and our theoretical simulations have shown that the pattern resembles a periodic lattice, but has abundant imperfections. To form a perfect periodic pattern, or a designed aperiodic pattern, one must introduce a template to guide the assembly. For example, a coarse-scale pattern, lithographically defined on the substrate, will guide the assembly of the nanoscale pattern. As another example, if the molecules on the substrate surface carry strong electric dipoles, a charged object, placed in the space above the monolayer, will guide the assembly of the molecular dipoles. In particular, the charged object can be a mask with a designed nanoscale topographic pattern. A serial process (e.g., e-beam lithography) is necessary to make the mask, but the pattern transfer to the molecules on the substrate is a parallel process. The technique is potentially a high throughput, low cost process to pattern a monolayer. The monolayer pattern itself may serve as a template to fabricate a functional structure. This project will model fundamental aspects of these processes, including thermodynamics and kinetics of self-assembly, templated self-assembly, and self-assembly on unconventional substrates. It is envisioned that the theory will not only explain the available experimental observations, but also motivate new experiments.

Suo, Zhigang [Harvard University

2013-04-29

124

Modeling coherent excitation energy transfer in photosynthetic light harvesting systems  

NASA Astrophysics Data System (ADS)

Recent non-linear spectroscopy experiments suggest the excitation energy transfer in some biological light harvesting systems initially occurs coherently. Treating such processes brings significant challenge for conventional theoretical tools that usually involve different approximations. In this dissertation, the recently developed Iterative Linearized Density Matrix (ILDM) propagation scheme, which is non-perturbative and non-Markovian is extended to study coherent excitation energy transfer in various light harvesting complexes. It is demonstrated that the ILDM approach can successfully describe the coherent beating of the site populations on model systems and gives quantitative agreement with both experimental results and the results of other theoretical methods have been developed recently to going beyond the usual approximations, thus providing a new reliable theoretical tool to study this phenomenon. This approach is used to investigate the excited energy transfer dynamics in various experimentally studied bacteria light harvesting complexes, such as Fenna-Matthews-Olsen (FMO) complex, Phycocyanin 645 (PC645). In these model calculations, quantitative agreement is found between computed de-coherence times and quantum beating pattens observed in the non-linear spectroscopy. As a result of these studies, it is concluded that the stochastic resonance behavior is important in determining the optimal throughput. To begin addressing possible mechanics for observed long de-coherence time, various models which include correlation between site energy fluctuations as well as correlation between site energy and inter-site coupling are developed. The influence of both types of correlation on the coherence and transfer rate is explored using with a two state system-bath hamiltonian parametrized to model the reaction center of Rhodobacter sphaeroides bacteria. To overcome the disadvantages of a fully reduced approach or a full propagation method, a brownian dynamics method is developed that only treats those degrees of freedom which directly couple to quantum systems and hence maintain the non-Markovian nature of the dynamics in contrast to the fully reduced master equation. This brownian dynamics approach has a significant reduced computational cost compared with ILDM propagation. The algorithm is tested with a spin-boson-global bath model, and shows potential for capturing non-markovian features that will be lost with a fully reduced master equation description of the excitation energy transfer.

Huo, Pengfei

125

Organization of the Bacterial Light-Harvesting Apparatus Rationalized by Exciton Transport Optimization  

Microsoft Academic Search

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 (RC-LH1-PufX) core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy (AFM)1. Here, we report that the structure of LH2 and

Elad Harel

2011-01-01

126

Phycobilisome: architecture of a light-harvesting supercomplex.  

PubMed

The phycobilisome (PBS) is an extra-membrane supramolecular complex composed of many chromophore (bilin)-binding proteins (phycobiliproteins) and linker proteins, which generally are colorless. PBS collects light energy of a wide range of wavelengths, funnels it to the central core, and then transfers it to photosystems. Although phycobiliproteins are evolutionarily related to each other, the binding of different bilin pigments ensures the ability to collect energy over a wide range of wavelengths. Spatial arrangement and functional tuning of the different phycobiliproteins, which are mediated primarily by linker proteins, yield PBS that is efficient and versatile light-harvesting systems. In this review, we discuss the functional and spatial tuning of phycobiliproteins with a focus on linker proteins. PMID:24081814

Watanabe, Mai; Ikeuchi, Masahiko

2013-10-01

127

Perspective: Detecting and measuring exciton delocalization in photosynthetic light harvesting.  

PubMed

Photosynthetic units perform energy transfer remarkably well under a diverse range of demanding conditions. However, the mechanism of energy transfer, from excitation to conversion, is still not fully understood. Of particular interest is the possible role that coherence plays in this process. In this perspective, we overview photosynthetic light harvesting and discuss consequences of excitons for energy transfer and how delocalization can be assessed. We focus on challenges such as decoherence and nuclear-coordinate dependent delocalization. These approaches complement conventional spectroscopy and delocalization measurement techniques. New broadband transient absorption data may help uncover the difference between electronic and vibrational coherences present in two-dimensional electronic spectroscopy data. We describe how multipartite entanglement from quantum information theory allows us to formulate measures that elucidate the delocalization length of excitation and the details of that delocalization even from highly averaged information such as the density matrix. PMID:24655162

Scholes, Gregory D; Smyth, Cathal

2014-03-21

128

Dimerization-assisted energy transport in light-harvesting complexes  

NASA Astrophysics Data System (ADS)

We study the role of the dimer structure of light-harvesting complex II (LH2) in excitation transfer from the LH2 [without a reaction center (RC)] to the LH1 (surrounding the RC) or from the LH2 to another LH2. The excited and unexcited states of a bacteriochlorophyll (BChl) are modeled by a quasispin. In the framework of quantum open system theory, we represent the excitation transfer as the total leakage of the LH2 system and then calculate the transfer efficiency and average transfer time. For different initial states with various quantum superposition properties, we study how the dimerization of the B850 BChl ring can enhance the transfer efficiency and shorten the average transfer time.

Yang, S.; Xu, D. Z.; Song, Z.; Sun, C. P.

2010-06-01

129

Communication: Tailoring the optical gap in light-harvesting molecules.  

PubMed

Systematically varying the optical gap that is associated with charge-transfer excitations is an important step in the design of light-harvesting molecules. So far the guidance that time-dependent density functional theory could give in this process was limited by the traditional functionals' inability to describe charge-transfer excitations. We show that a nonempirical range-separated hybrid approach allows to reliably predict charge-transfer excitations for molecules of practically relevant complexity. Calculated absorption energies agree with measured ones. We predict from theory that by varying the number of thiophenes in donor-acceptor-donor molecules, the energy of the lowest optical absorption can be tuned to the lower end of the visible spectrum. Saturation sets in at about five thiophene rings. PMID:21513368

Karolewski, A; Stein, T; Baer, R; Kümmel, S

2011-04-21

130

Self-assembly of Chiral Tubules  

E-print Network

The efficient and controlled assembly of complex structures from macromolecular building blocks is a critical open question in both biological systems and nanoscience. Using molecular dynamics simulations we study the self-assembly of tubular structures from model macromolecular monomers with multiple binding sites on their surfaces [Cheng et al., Soft Matter 8, 5666-5678 (2012)]. In this work we add chirality to the model monomer and a lock-and-key interaction. The self-assembly of free monomers into tubules yields a pitch value that often does not match the chirality of the monomer (including achiral monomers). We show that this mismatch occurs because of a twist deformation that brings the lateral interaction sites into alignment when the tubule pitch differs from the monomer chirality. The energy cost for this deformation is small as the energy distributions substantially overlap for small differences in the pitch and chirality. In order to control the tubule pitch by preventing the twist deformation, the interaction between the vertical surfaces must be increased without resulting in kinetically trapped structures. For this purpose, we employ the lock-and-key interactions and obtain good control of the self-assembled tubule pitch. These results explain some fundamental features of microtubules. The vertical interaction strength is larger than the lateral in microtubules because this yields a controlled assembly of tubules with the proper pitch. We also generally find that the control of the assembly into tubules is difficult, which explains the wide range of pitch and protofilament number observed in microtubule assembly.

Shengfeng Cheng; Mark J. Stevens

2013-11-19

131

Characterization of circular differential selective scattering in randomly and magnetically oriented chloroplasts and light harvesting chlorophyll a/b aggregates  

SciTech Connect

Comparative circular dichroism studies were carried out in chloroplasts and the aggregated chlorophyll a/b light harvesting pigment protein complex (LHC). Much of the intense circular dichroism (CD) signal of chloroplasts and that of aggregated, isolated LHC were found to originate in circular differential light scattering (CDS). The difference spectra obtained between the CD spectra of randomly and magnetically oriented thylakoids resembled the selective light scattering spectra of chloroplasts. Furthermore, orientation-dependent changes in the CDS signal outside the principal absorbance bands were correlated with changes in the non-selective forward light scattering. These results provide evidence of a significant contribution by CDS to the CD spectrum of chloroplasts. A comparison between the CD signals of chloroplasts and aggregated LHC revealed that both preparations exhibit ''anomalous'' CD bands. The spectral shape and amplitude of these bands are changed dramatically upon magnetic alignment of the particles. These similarities are suggestive of the existence of similar helical domains in chloroplasts and the isolated LHC aggregate; hence our experimental results support the hypothesis of Faludi-Daniel and Mustardy that the LHC in the thylakoid membrane is aggregated in a liquid crystal-like structure resembling that which self-assembles in vitro. 17 refs., 4 figs.

Garab, G.; Faludi-Daniel, A.; Sutherland, J.C.; Hind, G.

1986-01-01

132

Self-assembling triblock proteins for biofunctional surface modification  

NASA Astrophysics Data System (ADS)

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 of the triblock protein hydrogels, and the ease of introducing multiple functionalities to a substrate surface, a surface coating is tailored for neural stem cell culture in order to improve proliferation on the scaffold, while maintaining the stem cell phenotype. These studies demonstrate the unique advantages of genetic engineering over traditional techniques for surface modification. In addition to their unmatched sequence fidelity, recombinant proteins can easily be modified with bioactive ligands and their organization into coherent, supramolecular structures mimics natural self-assembly processes.

Fischer, Stephen E.

133

Self-assembly of colloidal surfactants  

NASA Astrophysics Data System (ADS)

We developed colloidal dumbbells with a rough and a smooth part, based on a method reported in Ref. [1]. Specific attraction between the smooth parts occurs upon addition of non-adsorbing polymers of appropriate size. We present the first results in terms of the assemblies that emerge in these systems. [4pt] [1] D.J. Kraft, W.S. Vlug, C.M. van Kats, A. van Blaaderen, A. Imhof and W.K. Kegel, Self-assembly of colloids with liquid protrusions, J. Am. Chem. Soc. 131, 1182, (2009)

Kegel, Willem

2012-02-01

134

Magnetically-responsive self assembled composites.  

PubMed

This tutorial review summarizes the recent advances on the self assembly of magnetic nanoparticles into one-, two-, and three-dimensional architectures using synthetic polymers and biopolymers. The materials have unique stimuli-responsive behavior that emerge in response to internal and external magnetic fields. For example, magnetic fields can be used to elicit a magnetic response from the materials, whether the material rearranges in response to the external field, or provides information regarding the local environment of the nanoparticles. These materials hold great promise for applications ranging from data storage to nanomedicine. PMID:20603662

Dai, Qiu; Nelson, Alshakim

2010-11-01

135

A Clustering Algorithm Based on the Ants Self-Assembly Behavior  

Microsoft Academic Search

\\u000a We have presented in this paper an ants based clustering algorithm which is inspired from the self-assembling behavior observed\\u000a in real ants. These ants progressively become connected to an initial point called the support and then successively to other\\u000a connected ants. The artificial ants that we have defined similarly build a tree where each ant represents a node\\/data. Ants\\u000a use

Hanene Azzag; Nicolas Monmarché; Mohamed Slimane; Christiane Guinot; Gilles Venturini

2003-01-01

136

On-chip self-assembly of cell embedded microstructures to vascular-like microtubes.  

PubMed

Currently, research on the construction of vascular-like tubular structures is a hot area of tissue engineering, since it has potential applications in the building of artificial blood vessels. In this paper, we report a fluidic self-assembly method using cell embedded microstructures to construct vascular-like microtubes. A novel 4-layer microfluidic device was fabricated using polydimethylsiloxane (PDMS), which contains fabrication, self-assembly and extraction areas inside one channel. Cell embedded microstructures were directly fabricated using poly(ethylene glycol) diacrylate (PEGDA) in the fabrication area, namely on-chip fabrication. Self-assembly of the fabricated microstructures was performed in the assembly area which has a micro well. Assembled tubular structures (microtubes) were extracted outside the channel into culture dishes using a normally closed (NC) micro valve in the extraction area. The self-assembly mechanism was experimentally demonstrated. The performance of the NC micro valve and embedded cell concentration were both evaluated. Fibroblast (NIH/3T3) embedded vascular-like microtubes were constructed inside this reusable microfluidic device. PMID:24472895

Yue, Tao; Nakajima, Masahiro; Takeuchi, Masaru; Hu, Chengzhi; Huang, Qiang; Fukuda, Toshio

2014-03-21

137

Discrete Redox Signaling Pathways Regulate Photosynthetic Light-Harvesting and Chloroplast Gene  

E-print Network

of absorbed light energy distribution by phosphorylation of light-harvesting complex II (LHC II). ChloroplastDiscrete Redox Signaling Pathways Regulate Photosynthetic Light-Harvesting and Chloroplast Gene Biofisica, Consiglio Nazionale delle Ricerche, Milano, Italy Abstract In photosynthesis in chloroplasts, two

Allen, John F.

138

Distance-Engineered Plasmon-Enhanced Light Harvesting in CdSe Quantum Dots  

E-print Network

Distance-Engineered Plasmon-Enhanced Light Harvesting in CdSe Quantum Dots Shengye Jin,,§, Erica De Supporting Information ABSTRACT: Improvement of light harvesting in semiconductor quantum dots (QDs. SECTION: Plasmonics, Optical Materials, and Hard Matter Semiconductor quantum dots (QDs) have received

139

Efficient light harvesting in multiple-device stacked structure for polymer solar cells  

E-print Network

Efficient light harvesting in multiple-device stacked structure for polymer solar cells Vishal structure of polymer solar cells for efficient light harvesting. Two polymer photovoltaic cells are stacked together and connected in series or in parallel to achieve a tandem structure. In this two-cell structure

140

Circuits and programmable self-assembling DNA structures  

Microsoft Academic Search

Self-assembly is beginning to be seen as a practical vehicle for computation. We investigate how basic ideas on tiling can be applied to the assembly and evaluation of circuits. We suggest that these procedures can be realized on the molecular scale through the medium of self-assembled DNA tiles. One layer of self-assembled DNA tiles will be used as the program

Alessandra Carbone; Nadrian C. Seeman

2002-01-01

141

Micropatterning of bioactive self-assembling gels†  

PubMed Central

Microscale topographical features have been known to affect cell behavior. An important target in this area is to integrate top down techniques with bottom up self-assembly to create three-dimensional (3D) patterned bioactive mimics of extracellular matrices. We report a novel approach toward this goal and demonstrate its use to study the behavior of human mesenchymal stem cells (hMSCs). By incorporating polymerizable acetylene groups in the hydrophobic segment of peptide amphiphiles (PAs), we were able to micro-pattern nanofiber gels of these bioactive materials. PAs containing the cell adhesive epitope arginine–glycine–aspartic acid–serine (RGDS) were allowed to self-assemble within microfabricated molds to create networks of either randomly oriented or aligned ~30 nm diameter nanofiber bundles that were shaped into topographical patterns containing holes, posts, or channels up to 8 ?m in height and down to 5 ?m in lateral dimensions. When topographical patterns contained nanofibers aligned through flow prior to gelation, the majority of hMSCs aligned in the direction of the nanofibers even in the presence of hole microtextures and more than a third of them maintained this alignment when encountering perpendicular channel microtextures. Interestingly, in topographical patterns with randomly oriented nanofibers, osteoblastic differentiation was enhanced on hole microtextures compared to all other surfaces. PMID:20047022

Mata, Alvaro; Hsu, Lorraine; Capito, Ramille; Aparicio, Conrado; Henrikson, Karl

2009-01-01

142

Beyond CMOS Electronics: Self-Assembled Nanostructures  

NASA Astrophysics Data System (ADS)

Self-assembled nanostructures offer a potential route to mitigate the physical and economic limits of conventional "top-down" fabrication. Strain-induced nanostructures and metal-catalyzed nanowires are two classes of nanostructures formed by self assembly. The stress in lattice mismatched heteroepitaxial layers can be relieved by expanding into the third dimension to form small islands or "quantum dots," which may take well-defined, characteristic, low-energy shapes. When the strain is anisotropic, the islands form long, narrow "quantum wires" on the substrate surface. Metal-catalyzed nanowires extending away from the substrate surface are grown when a catalytically active nanoparticle is exposed to a precursor containing the nanowire material. Selecting a suitable catalyst and forming appropriate-size nanoparticles is critical because the nanowire diameter is usually related to that of the nanoparticle. Nanowires can be grown epitaxially on a substrate. Because of the small contact area, the nanowire material can have a different lattice parameter than that of the substrate without generating significant defects near the interface. Connecting nanowires to form a useful system remains a challenge. Growing nanowires between pre-formed electrodes is a useful technique for connecting both ends of a nanowire. p-n junction diodes have been fabricated in nanowires, and field-effect transistors and sensors have been formed by inducing charge in nanowires to modulate their conductance.

Kamins, T. I.

143

Self-assembled software and method of overriding software execution  

DOEpatents

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.

Bouchard, Ann M.; Osbourn, Gordon C.

2013-01-08

144

Bio-inspired supramolecular self-assembly towards soft nanomaterials  

PubMed Central

Supramolecular self-assembly has proven to be a reliable approach towards versatile nanomaterials based on multiple weak intermolecular forces. In this review, the development of bio-inspired supramolecular self-assembly into soft materials and their applications are summarized. Molecular systems used in bio-inspired “bottom-up self-assembly” involve small organic molecules, peptides or proteins, nucleic acids, and viruses. Self-assembled soft nanomaterials have been exploited in various applications such as inorganic nanomaterial synthesis, drug or gene delivery, tissue engineering, and so on. PMID:21980594

LIN, Yiyang; MAO, Chuanbin

2011-01-01

145

Bio-inspired supramolecular self-assembly towards soft nanomaterials  

NASA Astrophysics Data System (ADS)

Supramolecular self-assembly has proven to be a reliable approach towards versatile nanomaterials based on multiple weak intermolecular forces. In this review, the development of bio-inspired supramolecular self-assembly into soft materials and their applications are summarized. Molecular systems used in bio-inspired "bottom-up self-assembly" involve small organic molecules, peptides or proteins, nucleic acids, and viruses. Self-assembled soft nanomaterials have been exploited in various applications such as inorganic nanomaterial synthesis, drug or gene delivery, tissue engineering, and so on.

Lin, Yiyang; Mao, Chuanbin

2011-09-01

146

Nanotechnology Applications in Self-Assembly and DNA Computing.  

E-print Network

??Nanotechnology spans and merges very diverse areas from device physics to molecular self-assembly, from development of new materials with nanoscale dimensions to manipulating existing materials… (more)

Akin, Hayri Engin

2011-01-01

147

Electron transport and light-harvesting switches in cyanobacteria  

PubMed Central

Cyanobacteria possess multiple mechanisms for regulating the pathways of photosynthetic and respiratory electron transport. Electron transport may be regulated indirectly by controlling the transfer of excitation energy from the light-harvesting complexes, or it may be more directly regulated by controlling the stoichiometry, localization, and interactions of photosynthetic and respiratory electron transport complexes. Regulation of the extent of linear vs. cyclic electron transport is particularly important for controlling the redox balance of the cell. This review discusses what is known of the regulatory mechanisms and the timescales on which they occur, with particular regard to the structural reorganization needed and the constraints imposed by the limited mobility of membrane-integral proteins in the crowded thylakoid membrane. Switching mechanisms requiring substantial movement of integral thylakoid membrane proteins occur on slower timescales than those that require the movement only of cytoplasmic or extrinsic membrane proteins. This difference is probably due to the restricted diffusion of membrane-integral proteins. Multiple switching mechanisms may be needed to regulate electron transport on different timescales. PMID:24478787

Mullineaux, Conrad W.

2014-01-01

148

Quantum control of energy flow in light harvesting.  

PubMed

Coherent light sources have been widely used in control schemes that exploit quantum interference effects to direct the outcome of photochemical processes. The adaptive shaping of laser pulses is a particularly powerful tool in this context: experimental output as feedback in an iterative learning loop refines the applied laser field to render it best suited to constraints set by the experimenter. This approach has been experimentally implemented to control a variety of processes, but the extent to which coherent excitation can also be used to direct the dynamics of complex molecular systems in a condensed-phase environment remains unclear. Here we report feedback-optimized coherent control over the energy-flow pathways in the light-harvesting antenna complex LH2 from Rhodopseudomonas acidophila, a photosynthetic purple bacterium. We show that phases imprinted by the light field mediate the branching ratio of energy transfer between intra- and intermolecular channels in the complex's donor acceptor system. This result illustrates that molecular complexity need not prevent coherent control, which can thus be extended to probe and affect biological functions. PMID:12037563

Herek, Jennifer L; Wohlleben, Wendel; Cogdell, Richard J; Zeidler, Dirk; Motzkus, Marcus

2002-05-30

149

Ultrafast light harvesting dynamics in the cryptophyte phycocyanin 645.  

PubMed

Steady-state and femtosecond time-resolved optical methods have been used to study spectroscopic features and energy transfer dynamics in the soluble antenna protein phycocyanin 645 (PC645), isolated from a unicellular cryptophyte Chroomonas CCMP270. Absorption, emission and polarization measurements as well as one-colour pump-probe traces are reported in combination with complementary quantum chemical calculations of electronic transitions of the bilins. Estimation of bilin spectral positions and energy transfer rates aids in the development of a model for light harvesting by PC645. At higher photon energies light is absorbed by the centrally located dimer (DBV, beta50/beta61) and the excitation is subsequently funneled through a complex interference of pathways to four peripheral pigments (MBV alpha19, PCB beta158). Those chromophores transfer the excitation energy to the red-most bilins (PCB beta82). We suggest that the final resonance energy transfer step occurs between the PCB 82 bilins on a timescale estimated to be approximately 15 ps. Such a rapid final energy transfer step cannot be rationalized by calculations that combine experimental parameters and quantum chemical calculations, which predict the energy transfer time to be 40 ps. PMID:17721595

Mirkovic, Tihana; Doust, Alexander B; Kim, Jeongho; Wilk, Krystyna E; Curutchet, Carles; Mennucci, Benedetta; Cammi, Roberto; Curmi, Paul M G; Scholes, Gregory D

2007-09-01

150

Self-assembling multimeric nucleic acid constructs  

DOEpatents

The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products.

Cantor, Charles R. (Boston, MA); Niemeyer, Christof M. (Bremen, DE); Smith, Cassandra L. (Boston, MA); Sano, Takeshi (Boston, MA); Hnatowich, Donald J. (Brookline, MA); Rusckowski, Mary (Southborough, MA)

1996-01-01

151

Self-assembling multimeric nucleic acid constructs  

DOEpatents

The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products.

Cantor, Charles R. (Boston, MA); Niemeyer, Christof M. (Bremen, DE); Smith, Cassandra L. (Boston, MA); Sano, Takeshi (Boston, MA); Hnatowich, Donald J. (Brookline, MA); Rusckowski, Mary (Southborough, MA)

1999-10-12

152

Self-assembling multimeric nucleic acid constructs  

DOEpatents

The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products. 5 figs.

Cantor, C.R.; Niemeyer, C.M.; Smith, C.L.; Sano, Takeshi; Hnatowich, D.J.; Rusckowski, M.

1996-10-01

153

Self-assembled magnetic surface swimmers.  

PubMed

We report studies of novel self-assembled magnetic surface swimmers (magnetic snakes) formed from a dispersion of magnetic microparticles at a liquid-air interface and energized by an alternating magnetic field. We show that under certain conditions the snakes spontaneously break the symmetry of surface flows and turn into self-propelled objects. Parameters of the driving magnetic field tune the propulsion velocity of these snakelike swimmers. We find that the symmetry of the surface flows can also be broken in a controlled fashion by attaching a large bead to a magnetic snake (bead-snake hybrid), transforming it into a self-locomoting entity. The observed phenomena have been successfully described by a phenomenological model based on the amplitude equation for surface waves coupled to a large-scale hydrodynamic mean flow equation. PMID:19392241

Snezhko, A; Belkin, M; Aranson, I S; Kwok, W-K

2009-03-20

154

Capillary Forces in Micro-Fluidic Self-Assembly  

Microsoft Academic Search

Parallel self-assembly in the fluidic phase is a promising al- ternative technique to conventional pick-and-place assembly. In this work the hydrophobic-hydrophilic material system between binding sites for microparts is simulated with re- spect to alignment precision. The results are compared with experimental findings and allow predictions for the optimiza- tion of the fluidic self assembly technique.

Andreas Greiner; Jan Lienemann; Jan G. Korvink; Xiaorong Xiong; Yael Hanein; Karl F. Böhringer

2002-01-01

155

Molecular rectifying diodes from self-assembly on silicon  

E-print Network

Molecular rectifying diodes from self-assembly on silicon Stéphane Lenfant , Christophe Krzeminski a molecular rectifying junction made from a sequential self-assembly on silicon. The device structure consists calculations and internal photoemission spectroscopy. This approach allows us to fabricate molecular rectifying

Paris-Sud XI, Université de

156

Light harvesting proteins for solar fuel generation in bioengineered photoelectrochemical cells.  

PubMed

The sun is the primary energy source of our planet and potentially can supply all societies with more than just their basic energy needs. Demand of electric energy can be satisfied with photovoltaics, however the global demand for fuels is even higher. The direct way to produce the solar fuel hydrogen is by water splitting in photoelectrochemical (PEC) cells, an artificial mimic of photosynthesis. There is currently strong resurging interest for solar fuels produced by PEC cells, but some fundamental technological problems need to be solved to make PEC water splitting an economic, competitive alternative. One of the problems is to provide a low cost, high performing water oxidizing and oxygen evolving photoanode in an environmentally benign setting. Hematite, ?-Fe2O3, satisfies many requirements for a good PEC photoanode, but its efficiency is insufficient in its pristine form. A promising strategy for enhancing photocurrent density takes advantage of photosynthetic proteins. In this paper we give an overview of how electrode surfaces in general and hematite photoanodes in particular can be functionalized with light harvesting proteins. Specifically, we demonstrate how low-cost biomaterials such as cyanobacterial phycocyanin and enzymatically produced melanin increase the overall performance of virtually no-cost metal oxide photoanodes in a PEC system. The implementation of biomaterials changes the overall nature of the photoanode assembly in a way that aggressive alkaline electrolytes such as concentrated KOH are not required anymore. Rather, a more environmentally benign and pH neutral electrolyte can be used. PMID:24678669

Ihssen, Julian; Braun, Artur; Faccio, Greta; Gajda-Schrantz, Krisztina; Thöny-Meyer, Linda

2014-01-01

157

Light Harvesting Proteins for Solar Fuel Generation in Bioengineered Photoelectrochemical Cells  

PubMed Central

The sun is the primary energy source of our planet and potentially can supply all societies with more than just their basic energy needs. Demand of electric energy can be satisfied with photovoltaics, however the global demand for fuels is even higher. The direct way to produce the solar fuel hydrogen is by water splitting in photoelectrochemical (PEC) cells, an artificial mimic of photosynthesis. There is currently strong resurging interest for solar fuels produced by PEC cells, but some fundamental technological problems need to be solved to make PEC water splitting an economic, competitive alternative. One of the problems is to provide a low cost, high performing water oxidizing and oxygen evolving photoanode in an environmentally benign setting. Hematite, ?-Fe2O3, satisfies many requirements for a good PEC photoanode, but its efficiency is insufficient in its pristine form. A promising strategy for enhancing photocurrent density takes advantage of photosynthetic proteins. In this paper we give an overview of how electrode surfaces in general and hematite photoanodes in particular can be functionalized with light harvesting proteins. Specifically, we demonstrate how low-cost biomaterials such as cyanobacterial phycocyanin and enzymatically produced melanin increase the overall performance of virtually no-cost metal oxide photoanodes in a PEC system. The implementation of biomaterials changes the overall nature of the photoanode assembly in a way that aggressive alkaline electrolytes such as concentrated KOH are not required anymore. Rather, a more environmentally benign and pH neutral electrolyte can be used. PMID:24678669

Ihssen, Julian; Braun, Artur; Faccio, Greta; Gajda-Schrantz, Krisztina; Thony-Meyer, Linda

2014-01-01

158

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

NASA Astrophysics Data System (ADS)

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 demonstrate an over 500-fold fluorescence enhancement of light-harvesting complex 2 (LH2) at the single-molecule level by coupling to a gold nanoantenna. The resonant antenna produces an excitation enhancement of circa 100 times and a fluorescence lifetime shortening to ~\

Wientjes, Emilie; Renger, Jan; Curto, Alberto G.; Cogdell, Richard; van Hulst, Niek F.

2014-06-01

159

Excitonic energy transfer in light-harvesting complexes in purple bacteria  

E-print Network

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. ...

Ye, Jun

160

IRON-INDUCED CHANGES IN LIGHT HARVESTING AND PHOTOCHEMICAL ENERGY CONVERSION IN EUKARYOTIC MARINE ALGAE  

EPA Science Inventory

The role of iron in regulating light harvesting and photochemical energy conversion process was examined in the marine unicellular chlorophyte Dunaliella tertiolecta and the marine diatom Phaeodactylum tricornutum. In both species, iron limitation led to a reduction in cellular c...

161

Solvent mediated self-assembly of solids  

SciTech Connect

Solvent-mediated crystallization represents a robust approach to self-assembly of nanostructures and microstructures. In organic systems, the relative ease with which the structure of hydrogen- bonded molecules can be manipulated allows for generation of a wide variety of nanoscale crystal structures. In living organisms, control over the micron-to-millimeter form of inorganic crystals is achieved through introduction of bio-organic molecules. The purpose of this proposal is to understand the interplay between solution chemistry, molecular structure, surface chemistry, and the processes of nucleation and crystal growth in solvent-mediated systems, with the goal of developing the atomic and molecular basis of a solvent-mediated self-assembly technology. We will achieve this purpose by: (1) utilizing an atomic force microscopy (AFM) approach that provides in situ, real time imaging during growth from solutions, (2) by modifying kinetic Monte Carlo (KMC) models to include solution-surface kinetics, (3) by introducing quantum chemistry (QC) calculations of the potentials of the relevant chemical species and the near-surface structure of the solution, and (4) by utilizing molecular dynamics (MD) simulations to identify the minimum energy pathways to the solid state. Our work will focus on two systems chosen to address both the manometer and micron-to-millimeter length scales of assembly, the family of 2,5- diketopiperazines (X-DKPs) and the system of CaCO{sub 3} with amino acids. Using AFM, we will record the evolution of surface morphology, critical lengths, step speeds, and step-step interactions as a function of supersaturation and temperature. In the case of the X-DKPs, these measurements will be repeated as the molecular structure of the growth unit is varied. In the case of CaCO{sub 3}, they will be performed as a function of solution chemistry including pH, ionic strength, and amino acid content. In addition, we will measure nucleation rates and orientations of CaCO{sub 3} on polyamino acid templates. From these measurements, we will extract fundamental growth parameters for input into KMC simulations whose predictions will in turn be compared to the experimental observations. The KMC simulations will incorporate atomic processes representing the minimum energy pathways as determined from the MD calculations. The interaction potentials of the relevant chemical species as well as the hydrated surface, including the electrochemical double layer, used in the MD simulations will be determined using coupled solutions to the Schrodinger and Poisson-Boltzmann equations which take account of electronic relaxation effects.

De Yoreo, J.; Wilson, W.D.; Palmore, T.

1997-12-12

162

RNA self-assembly and RNA nanotechnology.  

PubMed

CONSPECTUS: Nanotechnology's central goal involves the direct control of matter at the molecular nanometer scale to build nanofactories, nanomachines, and other devices for potential applications including electronics, alternative fuels, and medicine. In this regard, the nascent use of nucleic acids as a material to coordinate the precise arrangements of specific molecules marked an important milestone in the relatively recent history of nanotechnology. While DNA served as the pioneer building material in nucleic acid nanotechnology, RNA continues to emerge as viable alternative material with its own distinct advantages for nanoconstruction. Several complementary assembly strategies have been used to build a diverse set of RNA nanostructures having unique structural attributes and the ability to self-assemble in a highly programmable and controlled manner. Of the different strategies, the architectonics approach uniquely endeavors to understand integrated structural RNA architectures through the arrangement of their characteristic structural building blocks. Viewed through this lens, it becomes apparent that nature routinely uses thermodynamically stable, recurrent modular motifs from natural RNA molecules to generate unique and more complex programmable structures. With the design principles found in natural structures, a number of synthetic RNAs have been constructed. The synthetic nanostructures constructed to date have provided, in addition to affording essential insights into RNA design, important platforms to characterize and validate the structural self-folding and assembly properties of RNA modules or building blocks. Furthermore, RNA nanoparticles have shown great promise for applications in nanomedicine and RNA-based therapeutics. Nevertheless, the synthetic RNA architectures achieved thus far consist largely of static, rigid particles that are still far from matching the structural and functional complexity of natural responsive structural elements such as the ribosome, large ribozymes, and riboswitches. Thus, the next step in synthetic RNA design will involve new ways to implement these same types of dynamic and responsive architectures into nanostructures functioning as real nanomachines in and outside the cell. RNA nanotechnology will likely garner broader utility and influence with a greater focus on the interplay between thermodynamic and kinetic influences on RNA self-assembly and using natural RNAs as guiding principles. PMID:24856178

Grabow, Wade W; Jaeger, Luc

2014-06-17

163

Self-assembled nanostructures in oxide ceramics  

NASA Astrophysics Data System (ADS)

Self-assembled nanoislands in the gadolinia-doped ceria (GDC)/ yttria-stabilized zirconia (YSZ) system have recently been discovered. This dissertation is an attempt to study the mechanism by which these nanoislands form. Nanoislands in the GDC/YSZ system form via a strain based mechanism whereby the stress accumulated in the GDC-doped surface layer on the YSZ substrate is relieved by creation of self-assembled nanoislands by a mechanism similar to the ATG instability. Unlike what was previously believed, a modified surface layer is not required prior to annealing, that is, this modification can occur during annealing by surface diffusion of dopants from the GDC sources (distributed on the YSZ surface in either lithographically defined patch or powder form) with simultaneous breakup, which occurs at the hold temperature independent of the subsequent cooling. Additionally, we have developed a simple powder based process of producing nanoislands which bypasses lithography and thin film deposition setups. The versatility of the process is apparent in the fact that it allows us to study the effect of experimental parameters such as soak time, temperature, cooling rate and the effect of powder composition on nanoisland properties in a facile way. With the help of this process, we have shown that nanoislands are not peculiar to Gd containing oxide source materials on YSZ substrates and can also be produced with other source materials such as La2O3, Nd2O3, Sm 2O3, Eu2O3, Tb2O3 and even Y2O3, which is already present in the substrate and hence simplifies the system further. We have extended our work to include YSZ substrates of the (110) surface orientation and have found that instead of nanoisland arrays, we obtain an array of parallel nanobars which have their long axes oriented along the [1-10] direction on the YSZ-(110) surface. STEM EDS performed on both the bars and the nanoislands has revealed that they are solid YSZ-rich solid solutions with the dopant species and are heterogeneous in composition with dopant enrichment at the top of the islands (bars) while their bases are pure YSZ. Finally, we discuss some of the future work directions and possible applications of these nanostructures that are being explored in collaboration with our colleagues Kunal Parikh and Prof. Jessica O. Winter in the Dept. of Chemical and Biomolecular Engineering and Michael Susner and Prof. Michael Sumption in the Dept. of Materials Science and Engineering.

Ansari, Haris Masood

164

Independent evolution of the prochlorophyte and green plant chlorophyll ayb light-harvesting proteins  

Microsoft Academic Search

Theprochlorophytesareoxygenicprokaryotes differing from other cyanobacteria by the presence of a light- harvesting system containing both chlorophylls (Chls) aand b andbytheabsenceofphycobilins.Wedemonstrateherethatthe Chlaybbinding proteins from all three known prochlorophyte generaarecloselyrelatedtoIsiA,acyanobacterialChla-binding proteininducedbyironstarvation,andtoCP43,aconstitutively expressed Chl a antenna protein of photosystem II. The pro- chlorophyte Chl ayb protein (pcb) genes do not belong to the extended gene family encoding eukaryotic Chlayband Chlayc light-harvesting proteins. Although

J. LAROCHE; G. W. M. VAN; F. PARTENSKY; A. DUCRET; R. AEBERSOLD; R. G. HILLER; P. M. WRENCH; A. W. D. LARKUM; ANDB. R. GREEN

165

Phosphorylation Controls the Three-dimensional Structure of Plant Light Harvesting Complex II  

Microsoft Academic Search

The most abundant chlorophyll-binding complex in plants is the intrinsic membrane protein light-harvest- ing complex II (LHC II). LHC II acts as a light-harvesting antenna and has an important role in the distribution of absorbed energy between the two photosystems of pho- tosynthesis. We used spectroscopic techniques to study a synthetic peptide with identical sequence to the LHC IIb N

Anders Nilsson; Dalibor Stys; Torbjorn Drakenberg; Michael D. Spangfort; Sture Forsen; John F. Allen

1997-01-01

166

Optical Spectroscopy of Individual Light-Harvesting Complexes from Purple Bacteria  

Microsoft Academic Search

The primary reactions of purple bacterial photosynthesis take place within two well characterized pigment-protein complexes,\\u000a the core reaction center-light-harvesting 1 (RC-LH1) complex and the more peripheral light-harvesting 2 (LH2) complexes. These\\u000a antenna complexes serve to absorb incident solar radiation and to transfer it to the RCs, where it is used to ‘power’ the\\u000a photosynthetic redox reaction. This review describes how

Jürgen Köhler

167

Self-assembly and interactions of biomimetic thin films  

NASA Astrophysics Data System (ADS)

Bilayer lipid membranes create the natural environment for the immobilization of functional proteins and have been used as a model for understanding structure and properties of cell membranes. The development of biomimetic surfaces requires in depth knowledge of surface science, self-assembly, immobilization techniques, nanofabrication, biomolecular interactions and analytical techniques. This research is focused on synthesizing and characterizing biomimetic artificial surfaces for fundamental studies in membrane structure and better understanding of specific and non-specific interactions. The other main focus is on surface engineering of self-assembled, nanostructured interfaces that mimic cell membranes. These structures provide a powerful bottom-up approach to the studies of the structure and functionality of cell membranes and their interactions with other molecules. One of the advantages of this approach is that the complexity of the system can be controlled and gradually increased to add functionalities. This dissertation provides a first single molecule force measurement of the specific interactions between Salmonella typhimurium and P22 bacteriophage. This dissertation also provides a novel model system for the confined crystallization of drug molecules such as aspirin using the concept of phospholipid bilayer assembly at surfaces. The results will impact the development of biosensors and drug delivery. The defense will focus on the preparation and bio-recognition interactions between a monolayer of bacteriophage P22, covalently bound to glass substrates through a bifunctional cross linker 3-aminopropyltrimethoxysilane, and the outer membrane of Salmonella, lipopolysaccharides (LPS). The LPS bilayer was deposited on poly (ethylenimine)-modified mica from their sonicated unilamellar vesicle solution. The specific binding of Salmonella typhimurium to the phage monolayer was studied by enzyme-linked immunosorbent assay (ELISA) and atomic force microscopy (AFM). Using AFM force measurements discrete unbinding forces between surface attached P22 and LPS were obtained. Both whole P22 and tailspike proteins separated from the P22 capsid were used. The unbinding force histograms point to discrete forces between substrate-supported P22 and LPS. The unit unbinding force was found to decrease with decreasing force loading rate and increasing temperature. By fitting the force data with the Bell model, an energy barrier of approximately 55 KJ/mol was obtained. The resilience of phage binding to pH variation and hydration/dehydration cycles argues for the robustness of potential phage-based devices.

Handa, Hitesh

168

Stochastic self-assembly of incommensurate clusters  

NASA Astrophysics Data System (ADS)

Nucleation and molecular aggregation are important processes in numerous physical and biological systems. In many applications, these processes often take place in confined spaces, involving a finite number of particles. Analogous to treatments of stochastic chemical reactions, we examine the classic problem of homogeneous nucleation and self-assembly by deriving and analyzing a fully discrete stochastic master equation. We enumerate the highest probability steady states, and derive exact analytical formulae for quenched and equilibrium mean cluster size distributions. Upon comparison with results obtained from the associated mass-action Becker-Döring equations, we find striking differences between the two corresponding equilibrium mean cluster concentrations. These differences depend primarily on the divisibility of the total available mass by the maximum allowed cluster size, and the remainder. When such mass "incommensurability" arises, a single remainder particle can "emulsify" the system by significantly broadening the equilibrium mean cluster size distribution. This discreteness-induced broadening effect is periodic in the total mass of the system but arises even when the system size is asymptotically large, provided the ratio of the total mass to the maximum cluster size is finite. Ironically, classic mass-action equations are fairly accurate in the coarsening regime, before equilibrium is reached, despite the presence of large stochastic fluctuations found via kinetic Monte-Carlo simulations. Our findings define a new scaling regime in which results from classic mass-action theories are qualitatively inaccurate, even in the limit of large total system size.

D'Orsogna, M. R.; Lakatos, G.; Chou, T.

2012-02-01

169

Self-assembled nanostructures via electrospraying  

NASA Astrophysics Data System (ADS)

A concentrated nanoparticulate-based ethylene glycol suspension was prepared and electrosprayed at optimum and stable cone-jet mode conditions. Using laser spectroscopy, the droplets were measured and found to range within ?0.23-3.8 ?m. In parallel to spectroscopy-assisted sizing, a volume equivalence route for estimating droplet sizes was carried out by measuring contact angles and diameters of the deposits. The electrosprayed nanosuspension relics were examined using optical and transmission electron microscopy. These deposits were further characterized using energy-dispersive X-rays and selected area electron diffraction. Simultaneously deposits were formed by a controlled route through needle deposition without the presence of an electric field. The structures formed in this non-electric field driven route are compared with those formed with electric fields. Thus, elucidating electrosprays as a competing nanofabrication route for forming self-assemblies with a wide range of nanomaterials in the nanoscale for top-down based bottom-up assembly of structures.

Jayasinghe, S. N.

2006-07-01

170

Self Assembly of Tethered Nanoparticle Telechelics  

NASA Astrophysics Data System (ADS)

Simulations, theory, and experiement predict that aggregating nanoparticles functionalized with polymer tethers can self-assemble to form phases seen in block copolymer and surfactant systems, but with additional nanoparticle ordering and mesophase complexity. Here we consider a novel class of ``telechelic'' tethered nanoparticle building blocks, where two nanoparticles are connected together by a polymer tether. The architecture is similar to a triblock copolymer, but with additional geometric constraints imposed by the rigid particle end groups. Using Brownian dynamics simulations, we explore the phase diagrams of several examples of this class of nano-building-block, and present predictions of novel phases and their dependence on particle size, tether length, and thermodynamic parameters. We compare our results with recent simulations of di-tethered nanospheres [1, 2] and mono-tethered nanospheres [2, 3]. *Iacovella, C. R.; Glotzer, S. C.; Soft Matter 2009, 5, 4492-4498. *Iacovella, C. R.; Keys, A.S..; Glotzer, S. C. PNAS, in press. arXiv:1102.5589. *Phillips, C. L.; Iacovella, C. R.; Glotzer, S. C.; Soft Matter 2010, 6, 1693-1703.

Marson, Ryan; Phillips, Carolyn; Anderson, Joshua; Glotzer, Sharon

2012-02-01

171

Self-assembling holographic biosensors and biocomputers.  

SciTech Connect

We present concepts for self-assembly of diffractive optics with potential uses in biosensors and biocomputers. The simplest such optics, diffraction gratings, can potentially be made from chemically-stabilized microtubules migrating on nanopatterned tracks of the motor protein kinesin. We discuss the fabrication challenges involved in patterning sub-micron-scale structures with proteins that must be maintained in aqueous buffers to preserve their activity. A novel strategy is presented that employs dry contact printing onto glass-supported amino-silane monolayers of heterobifunctional crosslinkers, followed by solid-state reactions of these cross-linkers, to graft patterns of reactive groups onto the surface. Successive solution-phase addition of cysteine-mutant proteins and amine-reactive polyethylene glycol allows assembly of features onto the printed patterns. We present data from initial experiments showing successful micro- and nanopatterning of lines of single-cysteine mutants of kinesin interleaved with lines of polyethylene, indicating that this strategy can be employed to arrays of features with resolutions suitable for gratings.

Light, Yooli Kim; Bachand, George David (Sandia National Laboratories, Albuquerque, NM); Schoeniger, Joseph S.; Trent, Amanda M. (Sandia National Laboratories, Albuquerque, NM)

2006-05-01

172

Polymer blends for directed self-assembly  

NASA Astrophysics Data System (ADS)

The advantage of blend DSA (Directed Self Assembly) is milder anneal condition than PS-b-PMMA BCP DSA materials and availability of conventional instruments. In this paper, blend type DSA was applied for hole patterning. Target patterns were contact hole and oval hole. Polymer phase separation behavior has been studied from the point of ?N. In the case of polymer blend, ?N needs to be more than 2 to give phase separation. At first the effect of polymer size was studied. When the polymer weight was low, the shrunk hole was not clean because of low ?N. Furthermore, the correlation of shrink amount and ?N was studied. Higher ?N polymer blend system gave higher shrink amount. High ?N polymer systems give clear interface, then the intermixing area would be reduced, then the attached polymer blend part became larger. The polymer blend ratio effect was also investigated. The blend ratio was varied for polymer A/ polymer B=70/30-50/50. The shrink amount of oval hole was reduced with increasing the ratio of polymer B. However, the shrink amount ratio of CDY/CDX was almost constant (~3).

Namie, Yuuji; Anno, Yusuke; Naruoka, Takehiko; Minegishi, Shinya; Nagai, Tomoki; Hishiro, Yoshi; Yamaguchi, Yoshikazu

2013-03-01

173

Structural and Chemical Control of Supramolecular Coordination Self-Assembly Confined on Metal Surfaces  

NASA Astrophysics Data System (ADS)

This thesis is concerned with the structural and chemical control of two-dimensional (2D) supramolecular self-assemblies through judiciously manipulating bonding motifs at various intrinsic and external conditions. The self-selection and the self-recognition of the noncovalent interactions among organic and/or metallic building blocks govern the structural and chemical properties of the resultant self-assembled two-dimensional nanostructures, accompanying with the thermodynamic and kinetic process as well. In this thesis, we have investigated the supramolecular self-assembly achieved via coordination bonds assisted by transition metals and functional ligands on metal surfaces. The self-assembled nanostructures were studied by ultra-high vacuum scanning tunneling microscopy working at room temperatures. The structural transition processes were also inspected via the low energy electron diffraction. Further, artificial "quantum dots" represented by the cavities of the self-assembled networks were investigated. The modulation of surface electrons by these "quantum dots" was characterized by the local density of states detected by low-temperature scanning tunneling spectroscopy. The major contributions of this thesis are outlined as below: (1) Through modifying the chemical states of organic ligands, a unique coordination Kagome network structure was obtained for the first time by two distinct methods. TPyP (5, 10, 15, 20-tetra(4-pyridyl)porphyrin) species on Au(111) surfaces form the TPyP-Au coordination Kagome network achieved by a novel treatment that was suggested to modify the chemical state of the TPyP. In a condition that the TPyP coexists with Cu on a Au(111), Cu adatoms play two roles in the self-assembly---the coordination with pyridyl end-groups and the reaction with TPyP macrocycles, which control the chemical and structural phase of the self-assembly. Following a high temperature annealing, the same Kagome structure emerged from a precursor rhombus network structure. We proposed a new mechanism which provides a consistent explanation to both assembly methods. ZnTPyP (zinc 5, 10, 15, 20-tetra(4- pyridyl)porphyrin) molecules show chemical stability at high annealing temperature, which allows for preparing chemically pure ZnTPyP-Cu bimetallic networks. Furthermore, a reversible structural transformation between a hydrogen-bonded network and a coordination network was realized by either adding Cu atoms or annealing samples at certain temperatures. (2) The influence of the thermodynamic and kinetic effects on the selection of binding modes was studied by a combined STM and LEED investigation which offered spatial as well as temporal insights. The molecules of TPyB (1,3,5-trispyridylbenzene) coordinate with Cu or Fe respectively, forming two distinct polymorphism network structures. Two coordination binding modes show different binding energies. By the kinetic and thermodynamic control, either of binding modes was selected. LEED patterns revealed the dynamic process of structural transition from that of low binding-energy mode to that of high binding-energy mode. In the latter section the structural phase transition induced by two-dimensional compression is introduced. Pyridyl-Cu coordination bond is of certain liability, allowing for the alternation of bonds under various environments. Through increasing the coverage of molecules, distinctive polygraphic networks presented via different pyridyl-Cu binding modes. (3) The self-assembly of multiple components represent a much more complicated assembly system, where the elaborate balance of interactions among all components and substrates comprises greater challenging. To study such a system, the third part deals with the multiple-ligand self-assembly. Achieved by TPyP and PBTP 4',4"-(1,4- phenylene)bis(2,2':6',2"-terpyridine)) molecules and Fe, two types of network structure formed on Au(111) surfaces. Both networks coexisted due to similar bonding configurations and free energies. However, the entropy is presumably suggested to promote the

Shi, Ziliang

174

Organization of Inorganic Nanomaterials via Programmable DNA Self-Assembly and Peptide Molecular Recognition  

PubMed Central

An interesting alternative to top-down nanofabrication is to imitate biology, where nanoscale materials frequently integrate organic molecules for self-assembly and molecular recognition with ordered, inorganic minerals to achieve mechanical, sensory, or other advantageous functions. Using biological systems as inspiration, researchers have sought to mimic the nanoscale composite materials produced in nature. Here, we describe a combination of self-assembly, molecular recognition, and templating, relying on an oligonucleotide covalently conjugated to a high-affinity gold-binding peptide. After integration of the peptide-coupled DNA into a self-assembling superstructure, the templated peptides recognize and bind gold nanoparticles. In addition to providing new ways of building functional multi-nanoparticle systems, this work provides experimental proof that a single peptide molecule is sufficient for immobilization of a nanoparticle. This molecular construction strategy, combining DNA assembly and peptide recognition, can be thought of as programmable, granular, artificial biomineralization. We also describe the important observation that the addition of 1–2% Tween 20 surfactant to the solution during gold particle binding allows the gold nanoparticles to remain soluble within the magnesium containing DNA assembly buffer under conditions that usually lead to the aggregation and precipitation of the nanoparticles. PMID:21314176

Carter, Joshua D.; LaBean, Thomas H.

2011-01-01

175

Self-assembly of helical ribbons from chiral amphiphiles  

E-print Network

The study of the self-assembly of helical structures has been motivated by their newly found biological and technological importance. In many systems, helical ribbons are precursors to the formation of tubules, which may ...

Zastavker, Yevgeniya Vladimirovna, 1971-

2001-01-01

176

Colloidal Manipulation of Nanostructures: Stable Dispersion and Self-assembly  

E-print Network

This dissertation work addresses two important aspects of nanotechnology - stable dispersion and self-assembly of colloidal nanostructures. Three distinctly different types of nano-scaled materials have been studied: 0-dimensional ZnO quantum dots...

Sun, Dazhi

2013-12-16

177

Plasmonic Mode Engineering with Templated Self-Assembled Nanoclusters  

E-print Network

30%. The assembly of plasmonic nanoclusters on an elastomer paves the way for new classes nanostructures. Self- assembled clusters of metal-dielectric nanoparticles provide a foundation for the latter

Capasso, Federico

178

Self-assembly of globular protein-polymer diblock copolymers  

E-print Network

Self-assembly of protein-polymer block copolymers provides a simple bottom-up approach towards protein nanopatteming for the fabrication of more effective and efficient bioelectronic and biocatalytic devices. Changes in ...

Thomas, Carla S. (Carla Stephanie)

2014-01-01

179

Mechanical behavior and microstructure of self-assembling oligopeptide gels  

E-print Network

Hydrogels have become widely used in the fields of tissue engineering and drug delivery. One class of hydrogel is formed from synthetic oligopeptides that self-assemble into a solution of beta-sheet filaments. These filaments ...

Hammond, Nathan Allen

2010-01-01

180

Host-Guest Self-assembly in Block Copolymer Blends  

E-print Network

Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their ...

Park, Woon Ik

181

Differentially photo-crosslinked polymers enable self-assembling microfluidics  

PubMed Central

An important feature of naturally self-assembled systems such as leaves and tissues is that they are curved and have embedded fluidic channels that enable the transport of nutrients to, or removal of waste from, specific three-dimensional (3D) regions. Here, we report the self-assembly of photopatterned polymers, and consequently microfluidic devices, into curved geometries. We discovered that differentially photo-crosslinked SU-8 films spontaneously and reversibly curved upon film de-solvation and re-solvation. Photolithographic patterning of the SU-8 films enabled the self-assembly of cylinders, cubes, and bidirectionally folded sheets. We integrated polydimethylsiloxane (PDMS) microfluidic channels with these SU-8 films to self-assemble curved microfluidic networks. PMID:22068594

Jamal, Mustapha; Zarafshar, Aasiyeh M.; Gracias, David H.

2012-01-01

182

Ordering Control of Self-Assembled Colloidal Crystals  

E-print Network

Colloidal crystals are 3D nanostructures formed by self assembly of nanoparticles in suspension. The interaction forces between the colloid particles are expected to affect the ordering and the defect density in the resultant ...

Koh, Yaw Koon

183

Assessment of colloidal self-assembly for photonic crystal  

E-print Network

A suspension of monodisperse colloids has an interesting property of self-assembling into a three-dimensional ordered structure. This crystalline material has attracted significant interest on the implementation of photonic ...

Yip, Chan Hoe

2006-01-01

184

Plasmon-enhanced light harvesting of chlorophylls on near-percolating silver films via one-photon anti-Stokes upconversion.  

PubMed

There exists a wealth of means of efficient utilization of solar energy in nature, with photosynthesis of chlorophylls as a prime example. Separately, artificially structured plasmonic materials are versatile in light harvesting and energy conversion. Using a simple and scalable design of near-percolating silver nanostructures, we demonstrate that the light-harvesting efficiency of chlorophylls can be drastically enhanced by tuning the plasmon frequency of the constituent silver nanoparticles to coincide with the maximal photon flux of sunlight. In particular, we show that the photon upconversion efficiency can be readily enhanced by over 20 folds, with the room-temperature fluorescence quantum yield increased by a factor of 2.63. The underlying mechanism for the upconversion enhancement is attributed to a one-electron-per-photon anti-Stokes process, involving absorption of a characteristic phonon mode of the chlorophylls. These findings suggest that chlorophylls can serve as molecular building blocks for high-efficiency light harvesting and solar energy conversion. PMID:23689426

Wang, Ya-Lan; Nan, Fan; Liu, Xiao-Li; Zhou, Li; Peng, Xiao-Niu; Zhou, Zhang-Kai; Yu, Ying; Hao, Zhong-Hua; Wu, Yan; Zhang, Wei; Wang, Qu-Quan; Zhang, Zhenyu

2013-01-01

185

Plasmon-Enhanced Light Harvesting of Chlorophylls on Near-Percolating Silver Films via One-Photon Anti-Stokes Upconversion  

PubMed Central

There exists a wealth of means of efficient utilization of solar energy in nature, with photosynthesis of chlorophylls as a prime example. Separately, artificially structured plasmonic materials are versatile in light harvesting and energy conversion. Using a simple and scalable design of near-percolating silver nanostructures, we demonstrate that the light-harvesting efficiency of chlorophylls can be drastically enhanced by tuning the plasmon frequency of the constituent silver nanoparticles to coincide with the maximal photon flux of sunlight. In particular, we show that the photon upconversion efficiency can be readily enhanced by over 20 folds, with the room-temperature fluorescence quantum yield increased by a factor of 2.63. The underlying mechanism for the upconversion enhancement is attributed to a one-electron-per-photon anti-Stokes process, involving absorption of a characteristic phonon mode of the chlorophylls. These findings suggest that chlorophylls can serve as molecular building blocks for high-efficiency light harvesting and solar energy conversion. PMID:23689426

Wang, Ya-Lan; Nan, Fan; Liu, Xiao-Li; Zhou, Li; Peng, Xiao-Niu; Zhou, Zhang-Kai; Yu, Ying; Hao, Zhong-Hua; Wu, Yan; Zhang, Wei; Wang, Qu-Quan; Zhang, Zhenyu

2013-01-01

186

Inspection of directed self-assembly defects  

NASA Astrophysics Data System (ADS)

Directed Self-Assembly (DSA) is considered as a potential patterning solution for future generation devices. One of the most critical challenges for translating DSA into high volume manufacturing is to achieve low defect density in the DSA patterning process. The defect inspection capability is fundamental to defect reduction in any process, particularly the DSA process, as it provides engineers with information on the numbers and types of defects. While the challenges of other candidates of new generation lithography are well known (for example, smaller size, noise level due to LER etc.), the DSA process causes certain defects that are unique. These defects are nearly planar and in a material which produces very little defect scattering signal. These defects, termed as "dislocation" and "disclination" have unique shapes and have very little material contrast. While large clusters of these unique defects are easy to detect, single dislocation and disclination defects offer considerable challenge during inspection. In this investigation, etching the DSA pattern into a silicon (Si) substrate structure to enhance defect signal and Signal-to-Noise Ratio (SNR) is studied. We used a Rigorous Coupled-Wave Analysis (RCWA) method for solving Maxwell's equations to simulate the DSA unique defects and calculate inspection parameters. Controllable inspection parameters include various illumination and collection apertures, wavelength band, polarization, noise filtering, focus, pixel size, and signal processing. From the RCWA simulation, we compared SNR between "Post-SiN etch" and "Post-SiN+Si-substrate etch" steps. The study is also extended to investigate wafer-level data at post etch inspection. Both the simulations and inspection tool results showed dramatic signal and SNR improvements when the pattern was etched into the SiN+Si substrate allowing capture of DSA unique defect types.

Ito, Chikashi; Durant, Stephane; Lange, Steve; Harukawa, Ryota; Miyagi, Takemasa; Nagaswami, Venkat; Rincon Delgadillo, Paulina; Gronheid, Roel; Nealey, Paul

2014-03-01

187

Self assembly: An approach to terascale integration  

SciTech Connect

Surely one of the most remarkable accomplishments of modern times has been the miniaturization of electronic components, starting with discrete transistors and leading to Very Large Scale Integrated (VLSI) Circuits which will soon contain almost 100 million components in a few square centimeters. It led to an information processing industry that fuels almost every aspect of industrial societies and that has brought manifold benefits to their citizens. Although continuation of the miniaturization process is likely to produce even greater benefits, many experts are concerned that extrapolation of traditional silicon VLSI techniques will meet with increasingly severe difficulties. Some of these are fundamental in nature, e. g., granularity and fluctuations in semiconductors and interconnects and proximity effects such as tunneling. The first major difficulty to be encountered will be a rising cost of products due to increased complexity and difficulty of manufacturing and assembly. Such difficulties are likely to be seen in about 10 years when minimum component sizes are expected to decrease below 0.15--0.2 {mu}m. If alternatives to present VLSI techniques are to be available when needed, work on them must start now. At Los Alamos, we are exploring the feasibility of ultrasmall wires and switches that self-assemble themselves into computing elements and circuits. Their operation is based on the quantum properties of nanometer scale molecular clusters. This paper will describe our efforts in the development of these components and will summarize our work in four areas: (1) the development of conducting molecular wires, (2) conducting nanoparticle wires and switches based on the Coulomb Blockade principle, (3) the development of advanced architectures that benefit from the use of such components and that significantly advance the art of high performance computing, and (4) the development of novel methods for attaining sub-Angstrom 3-D non-destructive imaging.

Singer, S.

1993-09-01

188

Predicting the self-assembly of a model colloidal crystal  

Microsoft Academic Search

We investigate the self-assembly (crystallisation) of particles with hard cores and isotropic, square-well interactions, using a Monte Carlo scheme to simulate overdamped Langevin dynamics. We measure correlation and response functions during the early stages of assembly, and we analyse the results using fluctuation-dissipation theorems, aiming to predict which systems will self-assemble successfully and which will get stuck in disordered states.

Daphne Klotsa; Robert L. Jack

2011-01-01

189

Self-assembly drugs: from micelles to nanomedicine.  

PubMed

Self-assembly has fascinated many scientists over the past few decades. Rapid advances and widespread interest in the study of this subject has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nano- and mesoscopic dimensions. Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries for scientists seeking to design novel molecular materials exhibiting unusual properties, and for researchers investigating the structure and function of biomolecules. Consequently, self-assembly transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field including nanotechnology and nanomedicine. Basically, self-assembly focuses on a wide range of discrete molecules or molecular assemblies and uses physical transformations to achieve its goals. In this Review, we present a comprehensive overview of the advances in the field of drug self-assembly and discuss in detail the synthesis, self-assembly behavior, and physical properties as well as applications. We refer the reader to past reviews dealing with colloidal molecules and colloidal self-assembly. In the first part, we will discuss, compare, and link the various bioinformatic procedures: Molecular Dynamics and Quantitative Structure Activity Relationship. The second section deals with the self-assembly behavior in more detail, in which we focus on several experimental techniques, selected according to the depth of knowledge obtained. The last part will review the advances in drug-protein assembly. Nature provides many examples of proteins that form their substrate binding sites by bringing together the component pieces in a process of self-assembly. We will focus in the understanding of physical properties and applications developing thereof. PMID:24444168

Messina, Paula V; Besada-Porto, Jose Miguel; Ruso, Juan M

2014-03-01

190

Self-assembly of amphiphilic peanut-shaped nanoparticles  

E-print Network

We use computer simulation to investigate the self-assembly of Janus-like amphiphilic peanut-shaped nanoparticles, finding phases of clusters, bilayers and micelles in accord with ideas of packing familiar from the study of molecular surfactants. However, packing arguments do not explain the hierarchical self-assembly dynamics that we observe, nor the coexistence of bilayers and faceted polyhedra. This coexistence suggests that experimental realizations of our model can achieve multipotent assembly of either of two competing ordered structures.

Stephen Whitelam; Stefan A. F. Bon

2009-07-18

191

Various Aspects of the Interfacial Self-Assembly of Nanoparticles  

Microsoft Academic Search

\\u000a We describe the interfacial self-assembly of nanoparticles at liquid–liquid interfaces and in block copolymers. At the interface\\u000a of two immiscible liquids, the particles assemble into disordered but densely packed monolayers. This self-assembly process\\u000a was investigated ex situ with scanning force microscopy (SFM) and transmission electron microscopy (TEM), and laser scanning\\u000a confocal microscopy (LCSM) methods. Adsorbed particles can be crosslinked at

Nicole Popp; Sergej Kutuzov; Alexander Böker

2010-01-01

192

Evolving tiles for automated self-assembly design  

Microsoft Academic Search

Self-assembly is a distributed, asynchronous mech- anism that is pervasive across natural systems where hierarchi- cal complex structures are built from the bottom-up. The lack of a centralised master plan, no external intervention, and pre- programmed interactions among entities are within its most relevant and technologically appealing properties. This paper tackles the self-assembly Wang tiles designability problem by means of

Germán Terrazas; Marian Gheorghe; Graham Kendall; Natalio Krasnogor

2007-01-01

193

Templated self-assembly of functional oxide nanocomposites.  

PubMed

In perovskite/spinel self-assembled oxide nanocomposites, the substrate surface plays a dominant role in determining the final morphology. Topgraphic features, such as pits and trenches, are written in the substrate using either Focused Ion Beam or wet etching through a block co-polymer mask. These features are effective at templating the self-assembly, resulting in a wide range of attainable nano-assemblies. PMID:24677515

Aimon, Nicolas M; Choi, Hong Kyoon; Sun, Xue Yin; Kim, Dong Hun; Ross, Caroline A

2014-05-21

194

Biodegradable nanospheres self-assembled from complementary hydrophilic dextran macromers  

Microsoft Academic Search

Supramolecular self-assemblies are predominately driven by noncovalent molecular forces, and electrostatic interactions are the major force for charged molecules. In this paper, we demonstrate the self-assembly of hollow nanospheres from oppositely charged dextran-based hydrophilic macromers. Charged dextran derivatives were obtained by incorporating 2-bromoethylamine (Dex–BH) and chloroacetic acid (Dex–CA) into dextran. In a pH 5.0 buffer solution, Dex–BH and Dex–CA became

Guoming Sun; Chih-Chang Chu

2011-01-01

195

Electric Field Controlled Self-Assembly of Hierarchically Ordered Membranes  

PubMed Central

Self-assembly in the presence of external forces is an adaptive, directed organization of molecular components under nonequilibrium conditions. While forces may be generated as a result of spontaneous interactions among components of a system, intervention with external forces can significantly alter the final outcome of self-assembly. Superimposing these intrinsic and extrinsic forces provides greater degrees of freedom to control the structure and function of self-assembling materials. In this work we investigate the role of electric fields during the dynamic self-assembly of a negatively charged polyelectrolyte and a positively charged peptide amphiphile in water leading to the formation of an ordered membrane. In the absence of electric fields, contact between the two solutions of oppositely charged molecules triggers the growth of closed membranes with vertically oriented fibrils that encapsulate the polyelectrolyte solution. This process of self-assembly is intrinsically driven by excess osmotic pressure of counterions, and the electric field is found to modify the kinetics of membrane formation, and also its morphology and properties. Depending on the strength and orientation of the field we observe a significant increase or decrease of up to nearly 100% in membrane thickness, as well as the controlled rotation of nanofiber growth direction by 90 degrees, resulting in a significant increase in mechanical stiffness. These results suggest the possibility of using electric fields to control structure in self-assembly processes involving diffusion of oppositely charged molecules. PMID:23166533

Velichko, Yuri S.; Mantei, Jason R.; Bitton, Ronit; Carvajal, Daniel; Shull, Kenneth R.; Stupp, Samuel I.

2012-01-01

196

Impregnation of tubular self-assemblies into dextran hydrogels.  

PubMed

Amine groups are the building units of proteins. The incorporation of amine groups into polyethylene glycol diacrylate (PEGDA) hydrogel through dextran-allyl isocyanate-ethylamine (Dex-AE) enhances sustained protein release by introducing effective interactions. To investigate such an interaction effect and to improve protein release, we impregnated self-assembled tubular structures from dextran-bromoethylamine (Dex-BH) and dextran-chloroacetic acid (Dex-CA) into Dex-AE/PEGDA hydrogel. The morphology data obtained from scanning electron microscopy (SEM) reveal that pure PEGDA hydrogel had no effect on the distribution of the self-assembled tubules; the introduction of Dex-AE brought about the dispersion of these tubules, and an increase in Dex-AE content led to more evenly distributed structures. Moreover, the implantation of the self-assembled tubules had no distinct effect on the swelling capacity of the hybrid self-assembly embedded hydrogels. The in vitro albumin release study was carried out in a pH 7.4 buffer solution; the results show that the implantation of the self-assembly into the hydrogels reduced the burst release and prolonged the protein release time. These findings demonstrate that the impregnation of tubular self-assembly into hydrogel makes the hybrid hydrogel an excellent protein delivery system. PMID:20141216

Sun, Guoming; Chu, Chih-Chang

2010-02-16

197

Insights into the Photoprotective Switch of the Major Light-harvesting Complex II (LHCII)  

PubMed Central

Light-harvesting antennae of the LHC family form transmembrane three-helix bundles of which two helices are interlocked by conserved arginine-glutamate (Arg-Glu) ion pairs that form ligation sites for chlorophylls. The antenna proteins of photosystem II have an intriguing dual function. In excess light, they can switch their conformation from a light-harvesting into a photoprotective state, in which the excess and harmful excitation energies are safely dissipated as heat. Here we applied magic angle spinning NMR and selective Arg isotope enrichment as a noninvasive method to analyze the Arg structures of the major light-harvesting complex II (LHCII). The conformations of the Arg residues that interlock helix A and B appear to be preserved in the light-harvesting and photoprotective state. Several Arg residues have very downfield-shifted proton NMR responses, indicating that they stabilize the complex by strong hydrogen bonds. For the Arg C? chemical shifts, differences are observed between LHCII in the active, light-harvesting and in the photoprotective, quenched state. These differences are attributed to a conformational change of the Arg residue in the stromal loop region. We conclude that the interlocked helices of LHCII form a rigid core. Consequently, the LHCII conformational switch does not involve changes in A/B helix tilting but likely involves rearrangements of the loops and helical segments close to the stromal and lumenal ends. PMID:23629658

Sunku, Kiran; de Groot, Huub. J. M.; Pandit, Anjali

2013-01-01

198

The Self-Assembly of Nanogold for Optical Metamaterials  

NASA Astrophysics Data System (ADS)

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 nanoparticles and larger poly(styrene) ligands resulted in larger and smaller assemblies, respectively. Stirring the solution resulted in a wider size distribution of microbead assemblies due to the stirring's shear forces. Two undeveloped methods to self-assemble nanogold were investigated. One method used block-copolymer thin films as chemical templates to direct the electrostatic self-assembly of nanogold. Another method used gold nanorods that are passivated with different ligands on different faces. The stability of an alkanethiol ligand in different acids and bases was investigated to determine which materials could be used to produce Janus nanorods.

Nidetz, Robert A.

199

Structure-based model for light-harvesting properties of nucleic acid nanostructures  

E-print Network

Programmed self-assembly of DNA enables the rational design of megadalton-scale macromolecular assemblies with sub-nanometer scale precision. These assemblies can be programmed to serve as structural scaffolds for secondary ...

Pan, Keyao

200

Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting  

NASA Astrophysics Data System (ADS)

The effective absorption cross-section of a molecule (acceptor) can be greatly increased by associating it with a cluster of molecules that absorb light and transfer the excitation energy to the acceptor molecule. The basic mechanism of such light harvesting by Förster resonance energy transfer (FRET) is well established, but recent experiments have revealed a new feature whereby excitation is coherently shared among donor and acceptor molecules during FRET. In the present study, two-dimensional electronic spectroscopy was used to examine energy transfer at ambient temperature in a naturally occurring light-harvesting protein (PE545 of the marine cryptophyte alga Rhodomonas sp. strain CS24). Quantum beating was observed across a range of excitation frequencies. The shapes of those features in the two-dimensional spectra were examined. Through simulations, we show that two-dimensional electronic spectroscopy provides a probe of the adiabaticity of the free energy landscape underlying light harvesting.

Wong, Cathy Y.; Alvey, Richard M.; Turner, Daniel B.; Wilk, Krystyna E.; Bryant, Donald A.; Curmi, Paul M. G.; Silbey, Robert J.; Scholes, Gregory D.

2012-05-01

201

Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting.  

PubMed

The effective absorption cross-section of a molecule (acceptor) can be greatly increased by associating it with a cluster of molecules that absorb light and transfer the excitation energy to the acceptor molecule. The basic mechanism of such light harvesting by Förster resonance energy transfer (FRET) is well established, but recent experiments have revealed a new feature whereby excitation is coherently shared among donor and acceptor molecules during FRET. In the present study, two-dimensional electronic spectroscopy was used to examine energy transfer at ambient temperature in a naturally occurring light-harvesting protein (PE545 of the marine cryptophyte alga Rhodomonas sp. strain CS24). Quantum beating was observed across a range of excitation frequencies. The shapes of those features in the two-dimensional spectra were examined. Through simulations, we show that two-dimensional electronic spectroscopy provides a probe of the adiabaticity of the free energy landscape underlying light harvesting. PMID:22522260

Wong, Cathy Y; Alvey, Richard M; Turner, Daniel B; Wilk, Krystyna E; Bryant, Donald A; Curmi, Paul M G; Silbey, Robert J; Scholes, Gregory D

2012-05-01

202

Electronic Structure of Covalently Linked Zinc Bacteriochlorin Molecular Arrays: Insights into Molecular Design for NIR Light Harvesting.  

PubMed

Pigment-based molecular arrays, especially those based on porphyrins, have been extensively studied as viable components of artificial light harvesting devices. Unlike porphyrins, bacteriochlorins absorb strongly in the NIR, yet little is known of the applicability of covalently linked bacteriochlorin-based arrays in this arena. To lay the foundation for future studies of excited state properties of such arrays, we present a systematic study of the ground state electronic structure of zinc bacteriochlorin (ZnBC) molecular arrays with various linkers and linker attachment sites (meso vs ?) employing density functional theory in combination with the energy-based fragmentation (EBF) method, and the EBF with molecular orbitals (EBF-MO) method. We find that the level of steric hindrance between the ZnBC and the linker is directly correlated with the amount of ground sate electronic interactions between the ZnBCs. Low steric hindrance between the ZnBC and the linker found in alkyne-linked arrays results in strongly interacting arrays that are characterized by a decrease in the HOMO-LUMO energy gaps, large orbital energy dispersion in the frontier region, and low ZnBC-linker rotational barriers. In contrast, sterically hindered linkers, such as aryl-based linkers, result in weakly interacting arrays characterized by increased orbital energy degeneracy in the frontier region and high ZnBC-linker rotational barriers. For all linkers studied, the level of steric hindrance decreases when the ZnBCs are linked at the ? position. Hence, ZnBC arrays that exhibit strong, weak, or intermediate ground-state electronic interactions can be realized by adjusting the level of steric hindrance with a judicious choice of the linker type and linker attachment site. Such tuning may be essential for design of light harvesting arrays with desired spectral properties. PMID:25237715

Shrestha, Kushal; González-Delgado, Jessica M; Blew, James H; Jakubikova, Elena

2014-10-23

203

Bioinspired self-assembled peptide nanofibers with thermostable multivalent ?-helices.  

PubMed

The stabilization of peptide's active conformation is a critical determinant of its target binding efficiency. Here we present a structure-based self-assembly strategy for the design of nanostructures with multiple and thermostable ?-helices using bioinspired peptide amphiphiles. The design principle was inspired by the oligomerization of the human immunodeficiency virus type-1 (HIV-1) Rev protein. Our goal was to find a strategy to modify the Rev protein into a chemically manageable self-assembling peptide while stabilizing its ?-helical structure. Instead of using cyclic peptides for structure stabilization, this strategy utilizes the pseudocyclization for helix stabilization. The self-assembly induced stabilization of ?-helical conformation could be observed, and the ?-helices were found to be stable even at high temperature (at least up to 74 °C). Conjugation of a hydrophobic alkyl chain to the Rev peptide was crucial for forming the self-assembled nanostructures, and no nanostructures could be obtained without this modification. Because chemical modifications to the ?-helical peptide domain can be avoided, potentially any ?-helical peptide fragment can be grafted into this self-assembling peptide scaffold. PMID:23550841

Han, So-hee; Lee, Mun-kyung; Lim, Yong-beom

2013-05-13

204

Self-Assembly for the Synthesis of Functional Biomaterials  

PubMed Central

The use of self-assembly for the construction of functional biomaterials is a highly promising and exciting area of research, with great potential for the treatment of injury or disease. By using multiple noncovalent interactions, coded into the molecular design of the constituent components, self-assembly allows for the construction of complex, adaptable, and highly tunable materials with potent biological effects. This review describes some of the seminal advances in the use of self-assembly to make novel systems for regenerative medicine and biology. Materials based on peptides, proteins, DNA, or hybrids thereof have found application in the treatment of a wide range of injuries and diseases, and this review outlines the design principles and practical applications of these systems. Most of the examples covered focus on the synthesis of hydrogels for the scaffolding or transplantation of cells, with an emphasis on the biological, mechanical, and structural properties of the resulting materials. In addition, we will discuss the distinct advantages conferred by self-assembly (compared with traditional covalent materials), and present some of the challenges and opportunities for the next generation of self-assembled biomaterials. PMID:23457423

Stephanopoulos, Nicholas; Ortony, Julia H.; Stupp, Samuel I.

2012-01-01

205

Comparing open and closed molecular self-assembly  

E-print Network

We study theoretically in the present work the self-assembly of molecules in an open system, which is fed by monomers and depleted in partial or complete clusters. Such a scenario is likely to occur for example in the context of viral self-assembly. We provide a general formula for the mean-field size distribution which is valid both at equilibrium in a closed system, and in the stationary state in an open system. This allows us to explore in a simple way out-of-equilibrium features for self-assembly and compare them to equilibrium properties. In particular, we identify a region of parameter space for which the out-of-equilibrium size distribution in the presence of external fluxes is equal to the equilibrium size distribution in the absence of external fluxes, up to a constant renormalization factor. The range of validity of this result and its consequences are discussed.

Martin Castelnovo; Timothée Verdier; Lionel Foret

2014-02-17

206

Manipulating the self assembly of colloids in electric fields  

NASA Astrophysics Data System (ADS)

During the last decade the focus in colloid science on self-assembly has moved from mostly spherical particles and interaction potentials to more and more complex particle shapes, interactions and conditions. In this minireview we focus on how external electric fields, which in almost all cases can be replaced by magnetic particles and fields for similar effects, are used to manipulate the self-assembly process of ever more complex colloids. We will illustrate typical results from literature next to examples of our own work on how electric fields are used to achieve a broad range of different effects guiding the self-assembly of colloidal dispersions. In addition, preliminary measurements and calculations on how electric fields can be used to induce lock-and-key interactions will be presented as well.

van Blaaderen, A.; Dijkstra, M.; van Roij, R.; Imhof, A.; Kamp, M.; Kwaadgras, B. W.; Vissers, T.; Liu, B.

2013-11-01

207

Advances in self-assembled chitosan nanomaterials for drug delivery.  

PubMed

Nanomaterials based on chitosan have emerged as promising carriers of therapeutic agents for drug delivery due to good biocompatibility, biodegradability, and low toxicity. Chitosan originated nanocarriers have been prepared by mini-emulsion, chemical or ionic gelation, coacervation/precipitation, and spray-drying methods. As alternatives to these traditional fabrication methods, self-assembled chitosan nanomaterials show significant advantages and have received growing scientific attention in recent years. Self-assembly is a spontaneous process by which organized structures with particular functions and properties could be obtained without additional complicated processing or modification steps. In this review, we focus on recent progress in the design, fabrication and physicochemical aspects of chitosan-based self-assembled nanomaterials. Their applications in drug delivery of different therapeutic agents are also discussed in details. PMID:25109677

Yang, Yu; Wang, Shengpeng; Wang, Yitao; Wang, Xiaohui; Wang, Qun; Chen, Meiwan

2014-11-15

208

Guided and magnetic self-assembly of tunable magnetoceptive gels  

NASA Astrophysics Data System (ADS)

Self-assembly of components into complex functional patterns at microscale is common in nature, and used increasingly in numerous disciplines such as optoelectronics, microfabrication, sensors, tissue engineering and computation. Here, we describe the use of stable radicals to guide the self-assembly of magnetically tunable gels, which we call ‘magnetoceptive’ materials at the scale of hundreds of microns to a millimeter, each can be programmed by shape and composition, into heterogeneous complex structures. Using paramagnetism of free radicals as a driving mechanism, complex heterogeneous structures are built in the magnetic field generated by permanent magnets. The overall magnetic signature of final structure is erased via an antioxidant vitamin E, subsequent to guided self-assembly. We demonstrate unique capabilities of radicals and antioxidants in fabrication of soft systems with heterogeneity in material properties, such as porosity, elastic modulus and mass density; then in bottom-up tissue engineering and finally, levitational and selective assembly of microcomponents.

Tasoglu, S.; Yu, C. H.; Gungordu, H. I.; Guven, S.; Vural, T.; Demirci, U.

2014-09-01

209

Production of self-assembling biomaterials for tissue engineering  

PubMed Central

Self-assembling peptide-based biomaterials are being developed for use as 3D tissue engineering scaffolds and for therapeutic drug-release applications. Chemical synthesis provides custom-made peptides in small quantities, but production approaches based upon transgenic organisms might be more cost-effective for large-scale peptide production. Long lead times for developing appropriate animal clones or plant lines and potential negative public opinion are obstacles to these routes. Microbes, particularly safe organisms used in the food industry, offer a more rapid route to the large-scale production of recombinant self-assembling biomaterials. In this review, recent advances and challenges in the recombinant production of collagen, elastin and de novo designed self-assembling peptides are discussed. PMID:19497631

Kyle, Stuart; Aggeli, Amalia; Ingham, Eileen; McPherson, Michael J.

2009-01-01

210

Guided and magnetic self-assembly of tunable magnetoceptive gels  

PubMed Central

Self-assembly of components into complex functional patterns at microscale is common in nature, and used increasingly in numerous disciplines such as optoelectronics, microfabrication, sensors, tissue engineering and computation. Here, we describe the use of stable radicals to guide the self-assembly of magnetically tunable gels, which we call ‘magnetoceptive’ materials at the scale of hundreds of microns to a millimeter, each can be programmed by shape and composition, into heterogeneous complex structures. Using paramagnetism of free radicals as a driving mechanism, complex heterogeneous structures are built in the magnetic field generated by permanent magnets. The overall magnetic signature of final structure is erased via an antioxidant vitamin E, subsequent to guided self-assembly. We demonstrate unique capabilities of radicals and antioxidants in fabrication of soft systems with heterogeneity in material properties, such as porosity, elastic modulus and mass density; then in bottom-up tissue engineering and finally, levitational and selective assembly of microcomponents. PMID:25175148

Tasoglu, S.; Yu, C.H.; Gungordu, H.I.; Guven, S.; Vural, T.; Demirci, U.

2014-01-01

211

Hierarchical self-assembly of chiral fibres from achiral particles  

PubMed Central

We investigate, by molecular dynamics simulation, the behaviour of discotic particles in a solvent of Lennard-Jones spheres. When chromonic disc–sphere interactions are imposed on these systems, three regimes of self-assembly are observed. At moderate temperatures, numerous short threads of discs develop, but these threads remain isolated from one another. Quenching to low temperatures, alternatively, causes all of the discs to floc into a single extended aggregate which typically comprises several distinct sections and contains numerous packing defects. For a narrow temperature range between these regimes, however, defect-free chiral fibres are found to freely self-assemble. The spontaneous chirality of these fibres results from frustration between the hexagonal packing and interdigitation of neighbouring threads, the pitch being set by the particle shape. This demonstration of aggregate-wide chirality emerging owing to packing alone is pertinent to many biological and synthetic hierarchically self-assembling systems. PMID:24098850

Prybytak, P.; Frith, W. J.; Cleaver, D. J.

2012-01-01

212

Dynamic self-assembly of coordination polymers in aqueous solution.  

PubMed

The construction of supramolecular polymers has been intensively pursued because the nanostructures formed through weak non-covalent interactions can be triggered by external stimuli leading to smart materials and sensors. Self-assemblies of coordination polymers consisting of metal ions and organic ligands in aqueous solution also provide particular contributions in this area. The main motivation for developing those coordination polymers originates from the value-added combination between metal ions and ligands. This review highlights the recent progress of the dynamic self-assembly of coordination polymers that result from the sophisticated molecular design, towards fabricating stimuli-responsive systems and bio-related materials. Dynamic structural changes and switchable physical properties triggered by various stimuli are summarized. Finally, the outlook for aqueous nanostructures originated from the dynamic self-assembly of coordination polymers is also presented. PMID:24955807

Li, Wen; Kim, Yongju; Li, Jingfang; Lee, Myongsoo

2014-08-01

213

Guided and magnetic self-assembly of tunable magnetoceptive gels.  

PubMed

Self-assembly of components into complex functional patterns at microscale is common in nature, and used increasingly in numerous disciplines such as optoelectronics, microfabrication, sensors, tissue engineering and computation. Here, we describe the use of stable radicals to guide the self-assembly of magnetically tunable gels, which we call 'magnetoceptive' materials at the scale of hundreds of microns to a millimeter, each can be programmed by shape and composition, into heterogeneous complex structures. Using paramagnetism of free radicals as a driving mechanism, complex heterogeneous structures are built in the magnetic field generated by permanent magnets. The overall magnetic signature of final structure is erased via an antioxidant vitamin E, subsequent to guided self-assembly. We demonstrate unique capabilities of radicals and antioxidants in fabrication of soft systems with heterogeneity in material properties, such as porosity, elastic modulus and mass density; then in bottom-up tissue engineering and finally, levitational and selective assembly of microcomponents. PMID:25175148

Tasoglu, S; Yu, C H; Gungordu, H I; Guven, S; Vural, T; Demirci, U

2014-01-01

214

Self-assembly of colloidal one-dimensional nanocrystals.  

PubMed

The ability of nanoscopic materials to self-organize into large-scale assembly structures that exhibit unique collective properties has opened up new and exciting opportunities in the field of nanotechnology. Although earlier work on nanoscale self-assembly has focused on colloidal spherical nanocrystals as building blocks, there has been significant interest in recent years in the self-assembly of colloidal nanocrystals having well-defined facets or anisotropic shapes. In this review, particular attention is drawn to anisotropic one-dimensional (1D) nanocrystals, notably nanorods and nanowires, which can be arranged into a multitude of higher-order assembly structures. Different strategies have been developed to realize self-assembly of colloidal 1D nanocrystals and these are highlighted in the first part of this review. Self-assembly can take place (1) on substrates through evaporation control, external field facilitation and template use; (2) at interfaces, such as the liquid-liquid and the gas-liquid interface; and (3) in solutions via chemical bonding, depletion attraction forces and linker-mediated interactions. The choice of a self-assembly approach is pivotal to achieving the desired assembly configuration with properties that can be exploited for functional device applications. In the subsequent sections, the various assembly structures that have been created through 1D nanocrystal self-assembly are presented. These organized structures are broadly categorized into non-close-packed and close-packed configurations, and are further classified based on the different types of 1D nanocrystal alignment (side-by-side and end-to-end), orientation (horizontal and vertical) and ordering (nematic and smectic), and depending on the dimensionality of the structure (2D and 3D). The conditions under which different types of arrangements are achieved are also discussed. PMID:24413386

Zhang, Shuang-Yuan; Regulacio, Michelle D; Han, Ming-Yong

2014-04-01

215

Hydrazine-mediated construction of nanocrystal self-assembly materials.  

PubMed

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, CdSexTe1-x, and CdyHg1-yTe. 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. PMID:25296278

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

2014-10-28

216

Controlled self-assembly of periodic and aperiodic cluster crystals  

E-print Network

Soft particles are known to overlap and form stable clusters that self-assemble into periodic crystalline phases with density-independent lattice constants. We use molecular dynamics simulations in two dimensions to demonstrate that, through a judicious design of an isotropic pair potential, one can control the ordering of the clusters and generate a variety of phases, including decagonal and dodecagonal quasicrystals. Our results confirm analytical predictions based on a mean-field approximation, providing insight into the stabilization of quasicrystals in soft macromolecular systems, and suggesting a practical approach for their controlled self-assembly in laboratory realizations using synthesized soft-matter particles.

Kobi Barkan; Michael Engel; Ron Lifshitz

2014-01-17

217

Self-assembly of graphene nanoribbon ring on metallic nanowires  

NASA Astrophysics Data System (ADS)

Molecular dynamics simulations demonstrate that metallic nanowires (NWs) can activate and guide the self-assembly of graphene nanoribbon rings (GNR), allowing them to adopt a bilayered helical configuration on NWs. This unique technology attributes to the combined effects of the van der Waals force and the ?-? stacking interaction. The size and chirality effects of GNR on the self-assembly of GNR-NW system are calculated. Diverse NWs, acting as an external force, can initiate the conformational change of the GNRs to form bilayered helical structures. The stability of the formed nanosystems is further analyzed for numerous possible applications.

Li, Yunfang

2014-02-01

218

Self-assembly at a nonequilibrium critical point.  

PubMed

We use analytic theory and computer simulation to study patterns formed during the growth of two-component assemblies in two and three dimensions. We show that these patterns undergo a nonequilibrium phase transition, at a particular growth rate, between mixed and demixed arrangements of component types. This finding suggests that principles of nonequilibrium statistical mechanics can be used to predict the outcome of multicomponent self-assembly, and suggests an experimental route to the self-assembly of multicomponent structures of a qualitatively defined nature. PMID:24785052

Whitelam, Stephen; Hedges, Lester O; Schmit, Jeremy D

2014-04-18

219

Controlled self-assembly of periodic and aperiodic cluster crystals.  

PubMed

Soft particles are known to overlap and form stable clusters that self-assemble into periodic crystalline phases with density-independent lattice constants. We use molecular dynamics simulations in two dimensions to demonstrate that, through a judicious design of an isotropic pair potential, one can control the ordering of the clusters and generate a variety of phases, including decagonal and dodecagonal quasicrystals. Our results confirm analytical predictions based on a mean-field approximation, providing insight into the stabilization of quasicrystals in soft macromolecular systems, and suggesting a practical approach for their controlled self-assembly in laboratory realizations using synthesized soft-matter particles. PMID:25216013

Barkan, Kobi; Engel, Michael; Lifshitz, Ron

2014-08-29

220

Nano-engineering by optically directed self-assembly.  

SciTech Connect

Lack of robust manufacturing capabilities have limited our ability to make tailored materials with useful optical and thermal properties. For example, traditional methods such as spontaneous self-assembly of spheres cannot generate the complex structures required to produce a full bandgap photonic crystals. The goal of this work was to develop and demonstrate novel methods of directed self-assembly of nanomaterials using optical and electric fields. To achieve this aim, our work employed laser tweezers, a technology that enables non-invasive optical manipulation of particles, from glass microspheres to gold nanoparticles. Laser tweezers were used to create ordered materials with either complex crystal structures or using aspherical building blocks.

Furst, Eric (University of Delaware, Newark, DE); Dunn, Elissa (Yale University, New Haven, CT); Park, Jin-Gyu (Yale University, New Haven, CT); Brinker, C. Jeffrey; Sainis, Sunil (Yale University, New Haven, CT); Merrill, Jason (Yale University, New Haven, CT); Dufresne, Eric (Yale University, New Haven, CT); Reichert, Matthew D.; Brotherton, Christopher M.; Bogart, Katherine Huderle Andersen; Molecke, Ryan A.; Koehler, Timothy P.; Bell, Nelson Simmons; Grillet, Anne Mary; Gorby, Allen D.; Singh, John (University of Delaware, Newark, DE); Lele, Pushkar (University of Delaware, Newark, DE); Mittal, Manish (University of Delaware, Newark, DE)

2009-09-01

221

Structural simulations of nanomaterials self-assembled from ionic macrocycles.  

SciTech Connect

Recent research at Sandia has discovered a new class of organic binary ionic solids with tunable optical, electronic, and photochemical properties. These nanomaterials, consisting of a novel class of organic binary ionic solids, are currently being developed at Sandia for applications in batteries, supercapacitors, and solar energy technologies. They are composed of self-assembled oligomeric arrays of very large anions and large cations, but their crucial internal arrangement is thus far unknown. This report describes (a) the development of a relevant model of nonconvex particles decorated with ions interacting through short-ranged Yukawa potentials, and (b) the results of initial Monte Carlo simulations of the self-assembly binary ionic solids.

van Swol, Frank B.; Medforth, Craig John (University of New Mexico, Albuquerque, NM)

2010-10-01

222

Self-Assembly at a Nonequilibrium Critical Point  

NASA Astrophysics Data System (ADS)

We use analytic theory and computer simulation to study patterns formed during the growth of two-component assemblies in two and three dimensions. We show that these patterns undergo a nonequilibrium phase transition, at a particular growth rate, between mixed and demixed arrangements of component types. This finding suggests that principles of nonequilibrium statistical mechanics can be used to predict the outcome of multicomponent self-assembly, and suggests an experimental route to the self-assembly of multicomponent structures of a qualitatively defined nature.

Whitelam, Stephen; Hedges, Lester O.; Schmit, Jeremy D.

2014-04-01

223

Single-Molecule Electron Tunneling Spectroscopy of the Higher Plant Light-Harvesting Complex LHC II  

Microsoft Academic Search

Electronic spectroscopy of a single biological molecule is demonstrated with ?4 Å spatial resolution. The light-harvesting complex II (LHC II), in the ground and photo-excited states, was studied using scanning tunneling microscopy and spectroscopy of intact Photosystem II complexes. Analysis of the spectra indicates that the main mechanisms of tunneling between the STM tip and the surface involve delocalized electronic

Philip B. Lukins

1999-01-01

224

Ris-PhD-26(EN) Light Harvesting by Dye Linked  

E-print Network

Risø-PhD-26(EN) Light Harvesting by Dye Linked Conducting Polymers Kim Troensegaard Nielsen Risø by Dye Linked Conducting Polymers Department: The Danish Polymer Centre Risø-PhD-26(EN) June 2006 silicon solar cells are very costly to produce. In an attempt to produce cheap and flexible solar cells

225

Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria  

Microsoft Academic Search

The crystal structure of the light-harvesting antenna complex (LH2) from Rhodopseudomonas acidophila strain 10050 shows that the active assembly consists of two concentric cylinders of helical protein subunits which enclose the pigment molecules. Eighteen bacteriochlorophyll a molecules sandwiched between the helices form a continuous overlapping ring, and a further nine are positioned between the outer helices with the bacteriochlorin rings

G. McDermott; S. M. Prince; A. A. Freer; A. M. Hawthornthwaite-Lawless; M. Z. Papiz; R. J. Cogdell; N. W. Isaacs

1995-01-01

226

Structure, Dynamics, and Function in the Major Light-Harvesting Complex of Photosystem II  

E-print Network

-protein complexes (PPC) convert sunlight to chemical energy with near unity quantum efficiency. PPCs exhibit of Photosystem II (LHCII), the most abundant PPC in green plants. Studies using two-dimensional electronic, with the primary antenna PPC, the major light- harvesting complex of Photosystem II (LHCII), shown in Fig. 1b.[3

Fleming, Graham R.

227

Genomic analysis of mutants affecting xanthophyll biosynthesis and regulation of photosynthetic light harvesting in Chlamydomonas reinhardtii  

Microsoft Academic Search

When the absorption of light energy exceeds the capacity for its utilization in photosynthesis, regulation of light harvesting is critical in order for photosynthetic organisms to minimize photo-oxidative damage. Thermal dissipation of excess absorbed light energy, measured as non-photochemical quenching (NPQ) of chlorophyll fluorescence, is induced rapidly in response to excess light conditions, and it is known that xanthophylls such

M. Anwaruzzaman; Brian L. Chin; Xiao-Ping Li; Martin Lohr; Diego A. Martinez; Krishna K. Niyogi

2004-01-01

228

Optimization of light harvesting and photoprotection: molecular mechanisms and physiological consequences  

PubMed Central

The distinctive lateral organization of the protein complexes in the thylakoid membrane investigated by Jan Anderson and co-workers is dependent on the balance of various attractive and repulsive forces. Modulation of these forces allows critical physiological regulation of photosynthesis that provides efficient light-harvesting in limiting light but dissipation of excess potentially damaging radiation in saturating light. The light-harvesting complexes (LHCII) are central to this regulation, which is achieved by phosphorylation of stromal residues, protonation on the lumen surface and de-epoxidation of bound violaxanthin. The functional flexibility of LHCII derives from a remarkable pigment composition and configuration that not only allow efficient absorption of light and efficient energy transfer either to photosystem II or photosystem I core complexes, but through subtle configurational changes can also exhibit highly efficient dissipative reactions involving chlorophyll–xanthophyll and/or chlorophyll–chlorophyll interactions. These changes in function are determined at a macroscopic level by alterations in protein–protein interactions in the thylakoid membrane. The capacity and dynamics of this regulation are tuned to different physiological scenarios by the exact protein and pigment content of the light-harvesting system. Here, the molecular mechanisms involved will be reviewed, and the optimization of the light-harvesting system in different environmental conditions described. PMID:23148272

Horton, Peter

2012-01-01

229

The importance of PS I chlorophyll red forms in light-harvesting by leaves  

Microsoft Academic Search

We have investigated the importance of the long wavelength absorbing spectral forms (red forms) of Photosystem I in photosynthetic light harvesting by leaves. To this end leaf spectra were simulated by using a linear combination of absorption (OD) spectra of purified Photosystem I, Photosystem II and LHC II, multiplied by an empirical multiple scattering chloroplast\\/leaf conversion function. In this way

Andrea Rivadossi; Giuseppe Zucchelli; Flavio M. Garlaschi; Robert C. Jennings

1999-01-01

230

Bio serves nano: biological light-harvesting complex as energy donor for semiconductor quantum dots.  

PubMed

Light-harvesting complex (LHCII) of the photosynthetic apparatus in plants is attached to type-II core-shell CdTe/CdSe/ZnS nanocrystals (quantum dots, QD) exhibiting an absorption band at 710 nm and carrying a dihydrolipoic acid coating for water solubility. LHCII stays functional upon binding to the QD surface and enhances the light utilization of the QDs significantly, similar to its light-harvesting function in photosynthesis. Electronic excitation energy transfer of about 50% efficiency is shown by donor (LHCII) fluorescence quenching as well as sensitized acceptor (QD) emission and corroborated by time-resolved fluorescence measurements. The energy transfer efficiency is commensurable with the expected efficiency calculated according to Förster theory on the basis of the estimated donor-acceptor separation. Light harvesting is particularly efficient in the red spectral domain where QD absorption is relatively low. Excitation over the entire visible spectrum is further improved by complementing the biological pigments in LHCII with a dye attached to the apoprotein; the dye has been chosen to absorb in the "green gap" of the LHCII absorption spectrum and transfers its excitation energy ultimately to QD. This is the first report of a biological light-harvesting complex serving an inorganic semiconductor nanocrystal. Due to the charge separation between the core and the shell in type-II QDs the presented LHCII-QD hybrid complexes are potentially interesting for sensitized charge-transfer and photovoltaic applications. PMID:22401299

Werwie, Mara; Xu, Xiangxing; Haase, Mathias; Basché, Thomas; Paulsen, Harald

2012-04-01

231

DNA oligonucleotide templated nanohybrids using electronic type sorted carbon nanotubes for light harvesting.  

PubMed

Light harvesting nanostructure hybrids have been designed and demonstrated using single-wall carbon nanotubes (SWCNTs) and porphyrin chromophores. DNA oligonucleotides are used to conjugate SWCNTs with light-absorbing chromophores for transparent films which generate photocurrents. High-purity semiconducting SWCNTs demonstrate significant enhancement in the photocurrent compared to metallic or unsorted tubes. PMID:22887359

Zhang, Hanyu; Baker, Benjamin A; Cha, Tae-Gon; Sauffer, M Dane; Wu, Yujun; Hinkson, Nhigel; Bork, Matthew A; McShane, Colleen M; Choi, Kyoung-Shin; McMillin, David R; Choi, Jong Hyun

2012-10-23

232

Resonant cavity enhanced light harvesting in flexible thin-film organic solar cells  

E-print Network

Resonant cavity enhanced light harvesting in flexible thin-film organic solar cells Nicholas P and photocurrent in flexible organic solar cells. We demonstrate that this enhancement is attributed to a broadband://dx.doi.org/10.1364/OL.38.001431 Organic solar cells (OSCs) are promising candidates for large-scale deployment

Fan, Shanhui

233

Highly efficient nonradiative energy transfer mediated light harvesting in water using aqueous  

E-print Network

Highly efficient nonradiative energy transfer mediated light harvesting in water using aqueous Cd. Demir, "Highly efficient nonradiative energy transfer using charged CdSe/ZnS nanocrystals for light their excitonic excitation energy efficiently to dye molecules in water, without requiring ligand exchange

Demir, Hilmi Volkan

234

Excitation-Energy Transfer Dynamics of Higher Plant Photosystem I Light-Harvesting Complexes  

E-print Network

reactions of photosynthesis. In higher plants, PSI is composed of a core complex and four outer antennas. INTRODUCTION The driving force of photosynthesis is light, which is har- vested by membrane and a peripheral light-harvesting system. The core complex of PSI harbors the reaction center, the electron

van Stokkum, Ivo

235

Optimization of light harvesting and photoprotection: molecular mechanisms and physiological consequences.  

PubMed

The distinctive lateral organization of the protein complexes in the thylakoid membrane investigated by Jan Anderson and co-workers is dependent on the balance of various attractive and repulsive forces. Modulation of these forces allows critical physiological regulation of photosynthesis that provides efficient light-harvesting in limiting light but dissipation of excess potentially damaging radiation in saturating light. The light-harvesting complexes (LHCII) are central to this regulation, which is achieved by phosphorylation of stromal residues, protonation on the lumen surface and de-epoxidation of bound violaxanthin. The functional flexibility of LHCII derives from a remarkable pigment composition and configuration that not only allow efficient absorption of light and efficient energy transfer either to photosystem II or photosystem I core complexes, but through subtle configurational changes can also exhibit highly efficient dissipative reactions involving chlorophyll-xanthophyll and/or chlorophyll-chlorophyll interactions. These changes in function are determined at a macroscopic level by alterations in protein-protein interactions in the thylakoid membrane. The capacity and dynamics of this regulation are tuned to different physiological scenarios by the exact protein and pigment content of the light-harvesting system. Here, the molecular mechanisms involved will be reviewed, and the optimization of the light-harvesting system in different environmental conditions described. PMID:23148272

Horton, Peter

2012-12-19

236

Interaction of a small heat shock protein with light-harvesting cyanobacterial phycocyanins under stress conditions  

Microsoft Academic Search

Phycobiliproteins such as phycocyanins are the most abundant proteins found in cyanobacteria which are assembled to form the phycobilisome. Here, we showed that a small heat shock protein, HspA, interacts directly with phycocyanins from the cyanobacterium Synechococcus sp. strain PCC 7942 in vitro and suppresses inactivation of their light-harvesting functions due to heat denaturation in the presence of hydrogen peroxide.

Hitoshi Nakamoto; Daisuke Honma

2006-01-01

237

Enhanced light harvesting in photovoltaics with ZnO nanorod arrays  

NASA Astrophysics Data System (ADS)

The optical properties of ZnO NRA films deposited by CBD have been investigated. NRA having cavities between nanorods have high absorptance in solar region due to optical trapping. The use of ZnO NRA in enhancing the light harvesting properties of CdS and PbS thin films have been demonstrated.

Kothari, Anjana J.; Chaudhuri, T. K.

2012-06-01

238

Organization of the Bacterial Light-Harvesting Apparatus Rationalized by Exciton Transport Optimization  

E-print Network

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 (RC-LH1-PufX) core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy (AFM)1. Here, we report that the structure of LH2 and its organization within the membrane can be largely rationalized by a simple physical model that relies primarily on exciton transfer optimization. The process through which the light-harvesting complexes transfer excitation energy has been recognized to incorporate both coherent and incoherent processes mediated by the surrounding protein environment. Using the Haken-Strobl model, we show that the organization of the complexes in the membrane can be almost entirely explained by simple electrostatic considerations and that quantum effects act primarily to enforce robust...

Harel, Elad

2011-01-01

239

Organization of the Bacterial Light-Harvesting Apparatus Rationalized by Exciton Transport Optimization  

E-print Network

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 (RC-LH1-PufX) core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy (AFM)1. Here, we report that the structure of LH2 and its organization within the membrane can be largely rationalized by a simple physical model that relies primarily on exciton transfer optimization. The process through which the light-harvesting complexes transfer excitation energy has been recognized to incorporate both coherent and incoherent processes mediated by the surrounding protein environment. Using the Haken-Strobl model, we show that the organization of the complexes in the membrane can be almost entirely explained by simple electrostatic considerations and that quantum effects act primarily to enforce robustness with respect to spatial disorder between 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

Elad Harel

2011-10-31

240

Strigolactones are positive regulators of light-harvesting genes in tomato  

PubMed Central

Strigolactones are newly identified plant hormones, shown to participate in the regulation of lateral shoot branching and root development. However, little is known about their effects on biological processes, genes, and proteins. Transcription profiling of roots treated with GR24, a synthetic strigolactone with proven biological activity, and/or indole acetic acid (IAA) was combined with physiological and transcriptional analysis of a tomato mutant (Sl-ORT1) deficient in strigolactone production. GR24 treatment led to markedly induced expression of genes putatively involved in light harvesting. This was apparent in both the presence and absence of exogenously applied IAA, but not with IAA treatment alone. Following validation of the microarray results, transcriptional induction by light of the GR24-induced genes was demonstrated in leaves exposed to high or low light intensities. Sl-ORT1 contained less chlorophyll and showed reduced expression of light harvesting-associated genes than the wild type (WT). Moreover, perfusion of GR24 into WT and Sl-ORT1 leaves led to induction of most of the examined light harvesting-associated genes. Results suggest that GR24 treatment interferes with the root's response to IAA treatment and that strigolactones are potentially positive regulators of light harvesting in plants. PMID:20501744

Mayzlish-Gati, Einav; LekKala, Sivarama P.; Resnick, Nathalie; Wininger, Smadar; Bhattacharya, Chaitali; Lemcoff, J. Hugo; Kapulnik, Yoram; Koltai, Hinanit

2010-01-01

241

Studying the Effect of Light Quality on the Size of the Photosystem II Light Harvesting Complex  

ERIC Educational Resources Information Center

In this article the effect of light quality on the size of the photosystem II (PSII) light harvesting complex (LHCII) is studied by measuring the chlorophyll fluorescence emitted by leaf sections of oat ("Avena sativa," var. Prevision) plants previously treated with either white light or with light filtered through blue, green, red or farred…

Muhoz, Romualdo; Quiles, Maria J.

2003-01-01

242

Higher plants light harvesting proteins. Structure and function as revealed by mutation analysis of either protein or chromophore moieties  

Microsoft Academic Search

Mutation analysis of higher plants light harvesting proteins has been prevented for a long time by the lack of a suitable expression system providing chromophores essential for the folding of these membrane-intrinsic pigment-protein complexes. Early work on in vitro reconstitution of the major light harvesting complex of photosystem II (LHCII) indicated an alternative way to mutation analysis of these proteins.

Dorianna Sandonà; Roberta Croce; Aldo Pagano; Massimo Crimi; Roberto Bassi

1998-01-01

243

Excitons in a photosynthetic light-harvesting system: A combined molecular dynamics, quantum chemistry, and polaron model study  

E-print Network

electronic excitation to the photo- synthetic reaction center 1­4 . In the case of purple bacte- ria, lightExcitons in a photosynthetic light-harvesting system: A combined molecular dynamics, quantum. The molecular dynamics simulation of light-harvesting LH complexes was per- formed on an 87 055 atom system

Kosztin, Ioan

244

Functional analysis of light-harvesting-like protein 3 (LIL3) and its light-harvesting chlorophyll-binding motif in Arabidopsis.  

PubMed

The light-harvesting complex (LHC) constitutes the major light-harvesting antenna of photosynthetic eukaryotes. LHC contains a characteristic sequence motif, termed LHC motif, consisting of 25-30 mostly hydrophobic amino acids. This motif is shared by a number of transmembrane proteins from oxygenic photoautotrophs that are termed light-harvesting-like (LIL) proteins. To gain insights into the functions of LIL proteins and their LHC motifs, we functionally characterized a plant LIL protein, LIL3. This protein has been shown previously to stabilize geranylgeranyl reductase (GGR), a key enzyme in phytol biosynthesis. It is hypothesized that LIL3 functions to anchor GGR to membranes. First, we conjugated the transmembrane domain of LIL3 or that of ascorbate peroxidase to GGR and expressed these chimeric proteins in an Arabidopsis mutant lacking LIL3 protein. As a result, the transgenic plants restored phytol-synthesizing activity. These results indicate that GGR is active as long as it is anchored to membranes, even in the absence of LIL3. Subsequently, we addressed the question why the LHC motif is conserved in the LIL3 sequences. We modified the transmembrane domain of LIL3, which contains the LHC motif, by substituting its conserved amino acids (Glu-171, Asn-174, and Asp-189) with alanine. As a result, the Arabidopsis transgenic plants partly recovered the phytol-biosynthesizing activity. However, in these transgenic plants, the LIL3-GGR complexes were partially dissociated. Collectively, these results indicate that the LHC motif of LIL3 is involved in the complex formation of LIL3 and GGR, which might contribute to the GGR reaction. PMID:24275650

Takahashi, Kaori; Takabayashi, Atsushi; Tanaka, Ayumi; Tanaka, Ryouichi

2014-01-10

245

Fluidic self-assembly of micromirrors onto surface micromachined actuators  

Microsoft Academic Search

We describe the fluidic self-assembly of ultra-flat, single-crystal silicon micromirrors onto a surface micromachined actuator array. Sub-micron precision self-alignment of the mirrors onto the actuator platforms is achieved by pattern matching hydrophobic binding sites on the underside of the mirror and on the platform

Uthara Srinivasan; Michael Helmbrecht; Christian Rembe; Richard S. Muller; Roger T. Howe

2000-01-01

246

Multistep hierarchical self-assembly of chiral nanopore arrays.  

PubMed

A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements. PMID:25246585

Kim, Hanim; Lee, Sunhee; Shin, Tae Joo; Korblova, Eva; Walba, David M; Clark, Noel A; Lee, Sang Bok; Yoon, Dong Ki

2014-10-01

247

Basic parameters affecting nanoparticle self-assembly: An experimental approach  

NASA Astrophysics Data System (ADS)

Understanding the basic parameters that govern the nanoparticle self-assembly process is important for high-quality monolayer formation and technological advances. A complete theory that explains nanoparticle self assembly, in the bulk and at the liquid-air interface, is lacking. In this paper, dodecanethiolated gold nanoparticles were used as a model system for studying the forces that govern self assembly. These nanoparticles are known to make compact and highly-ordered monolayers at the liquid-air interface via a mechanism that is analogous to epitaxial growth of atomic layers. Epitaxial theory was used as a starting point to study the nanoparticle self-assembly at the liquid-air interface. Experimental measurements were successfully interpreted using an epitaxy-based analysis, including flux of nanoparticles onto the liquid air-interface, decay rate of the island density, and the dependence of critical nucleus size on nanoparticle diameter. Furthermore, anomalous diffusion was observed as was a remarkable ordering of islands at the liquid-air interface. This ordering was determined to be due to a long-range repulsive force between islands.

Joshi, Chakra; Kryukov, Yevgen; Amar, Jacques; Bigioni, Terry

2012-02-01

248

Polymer Adsorption-Driven Self-Assembly of Nanostructures  

Microsoft Academic Search

Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that

Arup K. Chakraborty; Aaron J. Golumbfskie

2001-01-01

249

Penn State Chemical Engineering Self-Assembly, Nanoscience, Colloids,  

E-print Network

Multiscale Theory and Simulation #12;Polymers and soft materials: organic solar cells, organic thin-film photovoltaics2 Self-assembled block copolymer solar cells1 Organic thin film transistors 100 µm Group approaches #12;#12;Structure-Property Relations: Synthesis, Small-Angle Scattering, Dielectric Spectroscopy

Giles, C. Lee

250

Self-assembly of anisotropic tethered nanoparticle shape amphiphiles  

Microsoft Academic Search

The varied and exotic shapes of new nanoscale organic and inorganic building blocks provide new opportunities to engineer materials possessing specific functionality and physical properties dictated by the unique packings of these particles. We briefly review some of the current strategies for inducing the self-assembly of these building blocks focusing on one strategy in particular—the attachment of tethers to the

Sharon C. Glotzer; Mark A. Horsch; Christopher R. Iacovella; Zhenli Zhang; Elaine R. Chan; Xi Zhang

2005-01-01

251

Structural Modifications to Polystyrene via Self-Assembling Molecules**  

E-print Network

Structural Modifications to Polystyrene via Self-Assembling Molecules** By John C. Stendahl, Eugene The use of glassy polymers such as polystyrene (PS) has tra- ditionally been limited by their tendency rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS

Zubarev, Eugene

252

Conformational flexibility facilitates self-assembly of complex DNA nanostructures  

E-print Network

, out of DNA three-point star motifs. In the current study, we have integrated tensegrity principle, but others do not. Ac- cording to tensegrity principle, triangular faces will lead to rigid structures (11, 12, 17­20). This fact prompts us to integrate the tensegrity principle into DNA self-assembly when

Jiang, Wen

253

SYNTHESIS AND CHARACTERIZATION OF SELF-ASSEMBLING BLOCK COPOLYMERS CONTAINING  

E-print Network

in nature. For example, it is known that marine mussels secrete unique adhesive proteins (mussel adhesiveSYNTHESIS AND CHARACTERIZATION OF SELF- ASSEMBLING BLOCK COPOLYMERS CONTAINING ADHESIVE MOIETIES characteristics of polymers is to introduce biological moieties that are known to possess adhesive properties

254

An imidazolium-functionalized self-assembling calix[4]pyrrole.  

PubMed

A calixpyrrole bearing a tethered imidazolium functional group was prepared in the form of its bromide salt. This compound was found to undergo self-assembly to produce supramolecular polymers, wherein both the bromide anion and the imidazolium cation are bound to the calixpyrrole core. PMID:25248079

Aydogan, Abdullah; Sessler, Jonathan L

2014-10-01

255

Self-assembly in additive manufacturing: opportunities and obstacles  

Microsoft Academic Search

Purpose – Additive manufacturing (AM) offers substantial flexibility in shape, but much less flexibility in materials and functionality – particularly at small size scales. A system for automatically incorporating microscale components would enable the fabrication of objects with more functionality. The purpose of this paper is to consider the potential of self-assembly to serve as an automated programmable integration method.

N. B. Crane; J. Tuckerman; G. N. Nielson

2011-01-01

256

Templated self-assembly for complex pattern fabrication  

E-print Network

The long-term goal of my Ph.D. study has been controlling the self-assembly of various materials using state-of-the-art nanofabrication techniques. Electron-beam lithography has been used for decades to generate nanoscale ...

Chang, Jae-Byum

2014-01-01

257

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

PubMed

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. PMID:20209016

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

2009-07-01

258

Patterned self-assembled beads in silicon channels.  

PubMed

A novel technique enabling selective bead trapping in microfluidic devices without the use of physical barriers is presented in this paper. It is a fast, convenient and simple method, involving microcontact printing and self-assembly, that can be applied to silicon, quartz or plastic substrates. In the first step, channels are etched in the substrate. The surface chemistry of the internal walls of the channels is then modified by microcontact printing. The chip is submerged in a bead slurry where beads self-assemble based on surface chemistry and immobilize on the internal walls of the channels. Silicon channels (100 microm wide and 50 microm deep) have been covered with monolayers of streptavidin-, amino- and hydroxy-functionalized microspheres and resulted in good surface coverage of beads on the channel walls. A high-resolution pattern of lines of self-assembled streptavidin beads, as narrow as 5 microm, has also been generated on the bottom of a 500 microm wide and 50 microm deep channel. Flow tests were performed in sealed channels with the different immobilized beads to confirm that the immobilized beads could withstand the forces generated by water flowing in the channels. The presented results indicate that single beads can be precisely positioned within microfluidic devices based on self-assembly which is useful as screening and analysis tools within the field of biochemistry and organic chemistry. PMID:11700716

Andersson, H; Jönsson, C; Moberg, C; Stemme, G

2001-10-01

259

Bicontinuous Surfaces in Self-assembling Amphiphilic Systems  

E-print Network

Bicontinuous Surfaces in Self-assembling Amphiphilic Systems Ulrich Schwarz1 and Gerhard Gompper2 1¨orperforschung, Forschungszentrum J¨ulich, D-52425 J¨ulich Abstract. Amphiphiles are molecules which have both hydrophilic due to the hydrophobic effect. The free energy of an amphiphilic system can be written as a functional

Schwarz, Ulrich

260

Nanostructures from the self-assembly of ?-helical peptide amphiphiles.  

PubMed

Self-assembly of PAs composed of palmitic acid and several repeated heptad peptide sequences, C??H??CO-(IEEYTKK)(n)-NH? (n?=?1-4, represented by PA1-PA4), was investigated systematically. The secondary structures of the PAs were characterized by CD. PA3 and PA4 (n?=?3 and 4, respectively) showed an ?-helical structure, whereas PA1 and PA2 (n?=?1 and 2, respectively) did not display an ?-helical conformations under the tested conditions. The morphology of the self-assembled peptides in aqueous medium was studied by transmission electron microscopy. As the number of heptad repeats in the PAs increased, the nanostructure of the self-assembled peptides changed from nanofibers to nanovesicles. Changes of the secondary structures and the self-assembly morphologies of PA3 and PA4 in aqueous medium with various cations were also studied. The critical micelle concentrations were determined using a pyrene fluorescence probe. In conclusion, this method may be used to design new peptide nanomaterials. PMID:24478261

Meng, Qingbin; Kou, Yingying; Ma, Xin; Guo, Lei; Liu, Keliang

2014-03-01

261

Cooperative self-assembly of peptide gelators and proteins.  

PubMed

Molecular self-assembly provides a versatile route for the production of nanoscale materials for medical and technological applications. Herein, we demonstrate that the cooperative self-assembly of amphiphilic small molecules and proteins can have drastic effects on supramolecular nanostructuring of resulting materials. We report that mesoscale, fractal-like clusters of proteins form at concentrations that are orders of magnitude lower compared to those usually associated with molecular crowding at room temperature. These protein clusters have pronounced effects on the molecular self-assembly of aromatic peptide amphiphiles (fluorenylmethoxycarbonyl- dipeptides), resulting in a reversal of chiral organization and enhanced order through templating and binding. Moreover, the morphological and mechanical properties of the resultant nanostructured gels can be controlled by the cooperative self-assembly of peptides and protein fractal clusters, having implications for biomedical applications where proteins and peptides are both present. In addition, fundamental insights into cooperative interplay of molecular interactions and confinement by clusters of chiral macromolecules is relevant to gaining understanding of the molecular mechanisms of relevance to the origin of life and development of synthetic mimics of living systems. PMID:24256076

Javid, Nadeem; Roy, Sangita; Zelzer, Mischa; Yang, Zhimou; Sefcik, Jan; Ulijn, Rein V

2013-12-01

262

Electrochemical impedance sensing of DNA at PNA self assembled monolayer  

E-print Network

2007 Elsevier B.V. All rights reserved. Keywords: Peptide nucleic acid; Self assembled monolayers; DNA­3]. Recently, there has been an increasing interest for DNA sensors based on the SAMs of peptide nucleic acid September 2007 Available online 14 September 2007 Abstract Monolayers of cysteine linked peptide nucleic

Kwak, Juhyoun

263

Electrochemically assisted self-assembly of mesoporous silica thin films  

Microsoft Academic Search

Supported mesostructured thin films are of major importance for applications in optical, electrochemical and sensing devices. However, good performance is restricted to mesostructured phases ensuring good accessibility from the film surface, which would be straightforward with cylindrical pores oriented normal to the underlying support, but this remains challenging. Here, we demonstrate that electrochemistry is likely to induce self-assembly of surfactant-templated

E. Sibottier; M. Etienne; J. Ghanbaja; A. Walcarius

2007-01-01

264

Developmental self-assembly of a DNA tetrahedron.  

PubMed

Kinetically controlled isothermal growth is fundamental to biological development, yet it remains challenging to rationally design molecular systems that self-assemble isothermally into complex geometries via prescribed assembly and disassembly pathways. By exploiting the programmable chemistry of base pairing, sophisticated spatial and temporal control have been demonstrated in DNA self-assembly, but largely as separate pursuits. By integrating temporal with spatial control, here we demonstrate the "developmental" self-assembly of a DNA tetrahedron, where a prescriptive molecular program orchestrates the kinetic pathways by which DNA molecules isothermally self-assemble into a well-defined three-dimensional wireframe geometry. In this reaction, nine DNA reactants initially coexist metastably, but upon catalysis by a DNA initiator molecule, navigate 24 individually characterizable intermediate states via prescribed assembly pathways, organized both in series and in parallel, to arrive at the tetrahedral final product. In contrast to previous work on dynamic DNA nanotechnology, this developmental program coordinates growth of ringed substructures into a three-dimensional wireframe superstructure, taking a step toward the goal of kinetically controlled isothermal growth of complex three-dimensional geometries. PMID:24720462

Sadowski, John P; Calvert, Colby R; Zhang, David Yu; Pierce, Niles A; Yin, Peng

2014-04-22

265

Self-assembled monolayer growth on chemically modified polymer surfaces  

E-print Network

plasma treatment, and N2 plasma treatment. X-ray photoelectron spectroscopy (XPS) spectra show rights reserved. Keywords: SiLK; Self-assembled monolayer; Plasma treatment; AFM; XPS; Contact angle 1 adopted to improve metal adhesion to the polymer surfaces, such as ion bombardment, plasma treatment, www

Wang, Gwo-Ching

266

Casting Metal Nanowires Within Discrete Self-Assembled Peptide Nanotubes  

Microsoft Academic Search

Tubular nanostructures are suggested to have a wide range of applications in nanotechnology. We report our observation of the self-assembly of a very short peptide, the Alzheimer's beta-amyloid diphenylalanine structural motif, into discrete and stiff nanotubes. Reduction of ionic silver within the nanotubes, followed by enzymatic degradation of the peptide backbone, resulted in the production of discrete nanowires with a

Meital Reches; Ehud Gazit

2003-01-01

267

Self-Assembly of Globular Protein-Polymer Diblock Copolymers  

NASA Astrophysics Data System (ADS)

The self-assembly of globular protein-polymer diblock copolymers into nanostructured phases is demonstrated as an elegant and simple method for structural control in biocatalysis or bioelectronics. In order to fundamentally investigate self-assembly in these complex block copolymer systems, a red fluorescent protein was expressed in E. coli and site-specifically conjugated to a low polydispersity poly(N-isopropyl acrylamide) (PNIPAM) block using thiol-maleimide coupling to form a well-defined model globular protein-polymer diblock. Functional protein materials are obtained by solvent evaporation and solvent annealing above and below the lower critical solution temperature of PNIPAM in order to access different pathways toward self-assembly. Small angle x-ray scattering and microscopy are used to show that the diblock forms lamellar nanostructures and to explore dependence of nanostructure formation on processing conditions. Circular dichroism and UV-vis show that a large fraction of the protein remains in its folded state after conjugation, and wide angle x-ray scattering demonstrates that diblock copolymer self-assembly changes the protein packing symmetry.

Thomas, C. S.; Olsen, B. D.

2011-03-01

268

Building polyhedra by self-assembly: theory and experiment.  

PubMed

Abstract 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 ?m. 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. PMID:25148546

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

2014-01-01

269

Hierarchical growth of curved organic nanowires upon evaporation induced self-assembly.  

PubMed

Self-assembly of a TTF derivative capable of forming self-assembled monolayers at the surface of graphite displays hierarchical growth of multilayers and concentric nanorings upon evaporation of the solvent as observed by AFM. PMID:25027031

Li, Bing; Puigmartí-Luis, Jiosep; Jonas, Alain M; Amabilino, David B; De Feyter, Steven

2014-11-11

270

Nanostructured gene and drug delivery systems based on molecular self-assembly  

E-print Network

Molecular self-assembly describes the assembly of molecular components into complex, supramolecular structures governed by weak, non-covalent interactions. In recent years, molecular self-assembly has been used extensively ...

Wood, Kris Cameron

2007-01-01

271

Development of self-assembling nanowires containing electronically active oligothiophenes  

NASA Astrophysics Data System (ADS)

This dissertation discusses the development of conductive one-dimensional nanowires from self-assembling oligothiophene molecules. Self-assembly has been demonstrated to be a promising alternative approach towards high performance, solution processable, and low-cost organic electronics. One of the many challenges in this field is the control of supramolecular morphologies of ordered structures containing pi-conjugated moieties. This research demonstrated several successful strategies to achieve self assembly of conductive nanowires using synergistic interactions combining pi stacking and hydrogen bonding. The first approach used was to develop a hairpin-shaped sexithiophene molecule, which features two arms of the conjugated structure. The diamidocyclohexyl headgroup of this molecule successfully directs the self-assembly from hydrogen bonding among the amides, forming high-aspect-ratio one-dimensional nanowires with well-defined diameters of 3.0 +/- 0.3 nm. The molecular orientation in the nanostructures promotes formation of sexithiophene H and J aggregates that facilitate efficient charge transport. Organic field-effect transistors were fabricated to reveal improved intrinsic hole mobility from films of the nanostructures, 3.46 x 10-6 cm2V-1s-1, which is one order of magnitude higher than films cast from unassembled molecules. Bulk heterojunction solar cells were developed from this molecule and fullerenes utilizing solution-phase fabrication methods. Intimate mix of the molecule and phenyl-C61-butyric acid methyl ester creates structured interfaces for efficient exciton splitting. The charge carrier mobilities of each material are improved by self-assembly in solution and thermal-energy assisted phase separation.The photovoltaic devices achieved the highest open-circuit voltage of 0.62 V, short-circuit current of 1.79 mA/cm2, fill factor of 35%, and power conversion efficiency of 0.48%. Another strategy to one-dimensional nanowires studied here involved the modification of a class of peptide lipids. The tripeptide segments in the molecular structure promote beta-sheet formation in nonpolar organic solvents, which is the main driving force for their self-assembly into 1D nanowires. Left-handed helical nanowires were formed with diameters of 8.9 nm and pitches between 50--150 nm. Substitutions of oligothiophenes lead to unprecedented supercoiling phenomena manifested as the transformation from helical to coiled or curved nanowires. We proposed that the curving of the nanowires is the consequence of relaxation from torsionally strained nanohelices, a process similar to supercoiling of strained DNA double helix. This process is governed by the mismatch in intermolecular distances required for peptide beta-sheets vs. pi-pi interactions of the conjugated segments decorating the periphery of the nanowires. Circular dichroism revealed helical arrangements of the conjugated moieties in these peptide lipids manifesting supercoiling phenomena. Peptide lipids without helical arrangement of the conjugated segments only exhibit helical morphologies. The self-assembly process of peptide lipids also leads to hierarchical assemblies of energetically favored single, double, and triple-helical nanostructures with well-defined dimensions. Self-assembled nanowires from oligothiophene-substituted peptide lipids revealed increased conductivity of 1.39--1.41 x 10-5 S/cm, two orders of magnitude higher than unassembled films and one order of magnitude higher than unsubstituted peptide lipids. The role of the primary beta-helix in controlling supramolecular organization was investigated by varying the chirality of the tripeptide segments, GAA. Four diastereomers of a peptide lipid substituted with p-toluene carboxylates were compared using L or D-alanines. Molecules with all L residues self-assemble into left-handed helical nanofibers with a pitch of 160 +/- 30 nm. Substitution of one or two D-alanines leads to assemblies of cylindrical nanofibers without any twisting, left-handed helices with smaller pitches (40 +/- 6 nm), or aggregates with

Tsai, Wei-Wen

272

Self-assembled photosystem-I biophotovoltaics on nanostructured TiO(2 )and ZnO.  

PubMed

The abundant pigment-protein membrane complex photosystem-I (PS-I) is at the heart of the Earth's energy cycle. It is the central molecule in the "Z-scheme" of photosynthesis, converting sunlight into the chemical energy of life. Commandeering this intricately organized photosynthetic nanocircuitry and re-wiring it to produce electricity carries the promise of inexpensive and environmentally friendly solar power. We here report that dry PS-I stabilized by surfactant peptides functioned as both the light-harvester and charge separator in solar cells self-assembled on nanostructured semiconductors. Contrary to previous attempts at biophotovoltaics requiring elaborate surface chemistries, thin film deposition, and illumination concentrated into narrow wavelength ranges the devices described here are straightforward and inexpensive to fabricate and perform well under standard sunlight yielding open circuit photovoltage of 0.5?V, fill factor of 71%, electrical power density of 81?µW/cm(2) and photocurrent density of 362?µA/cm(2), over four orders of magnitude higher than any photosystem-based biophotovoltaic to date. PMID:22355747

Mershin, Andreas; Matsumoto, Kazuya; Kaiser, Liselotte; Yu, Daoyong; Vaughn, Michael; Nazeeruddin, Md K; Bruce, Barry D; Graetzel, Michael; Zhang, Shuguang

2012-01-01

273

Self-assembled photosystem-I biophotovoltaics on nanostructured TiO2 and ZnO  

NASA Astrophysics Data System (ADS)

The abundant pigment-protein membrane complex photosystem-I (PS-I) is at the heart of the Earth's energy cycle. It is the central molecule in the ``Z-scheme'' of photosynthesis, converting sunlight into the chemical energy of life. Commandeering this intricately organized photosynthetic nanocircuitry and re-wiring it to produce electricity carries the promise of inexpensive and environmentally friendly solar power. We here report that dry PS-I stabilized by surfactant peptides functioned as both the light-harvester and charge separator in solar cells self-assembled on nanostructured semiconductors. Contrary to previous attempts at biophotovoltaics requiring elaborate surface chemistries, thin film deposition, and illumination concentrated into narrow wavelength ranges the devices described here are straightforward and inexpensive to fabricate and perform well under standard sunlight yielding open circuit photovoltage of 0.5 V, fill factor of 71%, electrical power density of 81 µW/cm2 and photocurrent density of 362 µA/cm2, over four orders of magnitude higher than any photosystem-based biophotovoltaic to date.

Mershin, Andreas; Matsumoto, Kazuya; Kaiser, Liselotte; Yu, Daoyong; Vaughn, Michael; Nazeeruddin, Md. K.; Bruce, Barry D.; Graetzel, Michael; Zhang, Shuguang

2012-02-01

274

Exciton annihilation and energy transfer in self-assembled peptide-porphyrin complexes depends on peptide secondary structure.  

PubMed

We used picosecond transient absorption and fluorescence lifetime spectroscopy to study singlet exciton annihilation and depolarization in self-assembled aggregates of meso-tetra(4-sulfonatophenyl)porphine (TPPS(4)) and a synthetic 22-residue polypeptide. The polypeptide was designed and previously shown to bind three TPPS(4) monomers via electrostatic interactions between the sulfonate groups and cationic lysine residues. Additionally, the peptide induces formation of TPPS(4) J-aggregates in acidic solutions when the peptide secondary structure is disordered. In neutral solutions, the peptide adopts an ?-helical secondary structure that can bind TPPS(4) with high affinity but J-aggregate formation is inhibited. Detailed analysis of excitation-power dependent transient absorption kinetics was used to obtain rate constants describing the energy transfer between TPPS(4) molecules in an aggregate under acidic and neutral conditions. Independently, such analysis was confirmed by picosecond fluorescence emission depolarization measurements. We find that energy transfer between TPPS(4) monomers in a peptide-TPPS(4) complex is more than 30 times faster in acidic aqueous solution than in neutral solutions (9 vs 279 ps). This result was attributed to a conformational change of the peptide backbone from disordered at low pH to ?-helical at neutral pH and suggests a new approach to control intermolecular energy transfer with possible applications in fluorescent sensors or biomimetic light harvesting antennas. PMID:21069973

Kuciauskas, Darius; Kiskis, Juris; Caputo, Gregory A; Gulbinas, Vidmantas

2010-12-01

275

Automated Self-Assembly Programming Paradigm: Initial Investigations Lin Li, Natalio Krasnogor, Jon Garibaldi  

E-print Network

Automated Self-Assembly Programming Paradigm: Initial Investigations Lin Li, Natalio Krasnogor, Jon This paper presents a model that simulates a self- assembly process for software components. Initial inves- tigations on the Automated Self-Assembly Programming Paradigm (ASAP2 ) is presented whereby software compo

Aickelin, Uwe

276

Self-assembly of long chain alkanes and their derivatives on graphite Teng Yang,1  

E-print Network

Self-assembly of long chain alkanes and their derivatives on graphite Teng Yang,1 Savas Berber,1 initio calculations to study the self-assembly of long chain alkanes and related alcohol and carboxylic the ordering of long chain alkanes in self-assembled monolayers and ways to modify it using alcohol and acid

277

Structurally Defined Nanoscale Sheets from Self-Assembly of Collagen-Mimetic Peptides  

E-print Network

Structurally Defined Nanoscale Sheets from Self-Assembly of Collagen-Mimetic Peptides Tao Jiang of two collagen-mimetic peptide sequences, NSI and NSII, that self-assemble into structurally defined. The molecularly programmed self- assembly of peptides NSI and NSII into nanosheets suggests that sequence

Salaita, Khalid

278

Pictures worth a thousand tiles, a geometrical programming language for self-assembly  

E-print Network

actually makes sense in terms of self-assembly. With this new formalism, we are able to give threePictures worth a thousand tiles, a geometrical programming language for self-assembly Florent.becker@ens-lyon.fr February 14, 2008 Abstract We present a novel way to design self-assembling systems using a notion

Paris-Sud XI, Université de

279

Monitored Dynamics of the Self-Assembled Peptide RADA16I Nanofiber Scaffold  

E-print Network

is applied2. The actual dynamics on how this self-assembly, or "self-healing", occurs is not actuallyMonitored Dynamics of the Self-Assembled Peptide RADA16I Nanofiber Scaffold Alicia Calero of proteins known as the self-assembling peptide nanofiber scaffolds. These kinds of proteins are known

Weston, Ken

280

An information-bearing seed for nucleating algorithmic self-assembly  

E-print Network

, as demonstrated by the algorithmic self-assembly of DNA tiles. How- ever, the lack of effective seeds has limitedAn information-bearing seed for nucleating algorithmic self-assembly Robert D. Barish1 , Rebecca for review September 4, 2008) Self-assembly creates natural mineral, chemical, and biological structures

Winfree, Erik

281

Two-dimensional electronic spectroscopy and photosynthesis: Fundamentals and applications to photosynthetic light-harvesting  

NASA Astrophysics Data System (ADS)

In natural light harvesting systems, pigment-protein complexes are able to harvest sunlight with near unity quantum efficiency. These complexes exhibit emergent properties that cannot be simply extrapolated from knowledge of their component parts. In this perspective, we focus on how two-dimensional electronic spectroscopy (2DES) can provide an incisive tool to probe the electronic, energetic, and spatial landscapes that must be understood to describe photosynthetic light-harvesting. We review the theoretical and experimental principles of 2DES, and demonstrate its application to the study of the Photosystem II supercomplex of green plants. We illustrate several capabilities of 2DES, including monitoring energy transfer pathways, observing excitonic coherence, determining excitonic geometry, and informing on the atomic structure.

Schlau-Cohen, Gabriela S.; Ishizaki, Akihito; Fleming, Graham R.

2011-07-01

282

A new form of chlorophyll C involved in light-harvesting.  

PubMed

A new form of chlorophyll c has been isolated from the pyrmnesiophyte Pavlova gyrans Butcher. This pigment is spectrally similar to chlorophyll c(2), but all the absorption maxima (454, 583, and 630 nm in diethyl ether) are shifted 4 to 6 nanometers to longer wavelengths. The new pigment can be separated from other chlorophyll c-type pigments by reversed-phase high performance liquid chromatography and thin layer chromatography. Both chlorophylls c(1) and c(2) are found with the new chlorophyll c pigment in P. gyrans, and it has also been detected in the chrysophyte Synura petersenii Korsh. The light-harvesting function of the new chlorophyll c pigment is indicated by its presence along with chlorophyll c(1) and c(2) in a light-harvesting pigment-protein complex isolated from P. gyrans in which chlorophyll c pigments efficiently transfer absorbed light energy to chlorophyll a. PMID:16667093

Fawley, M W

1989-10-01

283

A New Form of Chlorophyll c Involved in Light-Harvesting 1  

PubMed Central

A new form of chlorophyll c has been isolated from the pyrmnesiophyte Pavlova gyrans Butcher. This pigment is spectrally similar to chlorophyll c2, but all the absorption maxima (454, 583, and 630 nm in diethyl ether) are shifted 4 to 6 nanometers to longer wavelengths. The new pigment can be separated from other chlorophyll c-type pigments by reversed-phase high performance liquid chromatography and thin layer chromatography. Both chlorophylls c1 and c2 are found with the new chlorophyll c pigment in P. gyrans, and it has also been detected in the chrysophyte Synura petersenii Korsh. The light-harvesting function of the new chlorophyll c pigment is indicated by its presence along with chlorophyll c1 and c2 in a light-harvesting pigment-protein complex isolated from P. gyrans in which chlorophyll c pigments efficiently transfer absorbed light energy to chlorophyll a. PMID:16667093

Fawley, Marvin W.

1989-01-01

284

Quantitative investigations of quantum coherence for a light-harvesting protein at conditions simulating photosynthesis.  

PubMed

Recent measurements using two-dimensional electronic spectroscopy (2D ES) have shown that the initial dynamic response of photosynthetic proteins can involve quantum coherence. We show how electronic coherence can be differentiated from vibrational coherence in 2D ES. On that basis we conclude that both electronic and vibrational coherences are observed in the phycobiliprotein light-harvesting complex PC645 from Chroomonas sp. CCMP270 at ambient temperature. These light-harvesting antenna proteins of the cryptophyte algae are suspended in the lumen, where the pH drops significantly under sustained illumination by sunlight. Here we measured 2D ES of PC645 at increasing levels of acidity to determine if the change in pH affects the quantum coherence; quantitative analysis reveals that the dynamics are insensitive to the pH change. PMID:22374579

Turner, Daniel B; Dinshaw, Rayomond; Lee, Kyung-Koo; Belsley, Michael S; Wilk, Krystyna E; Curmi, Paul M G; Scholes, Gregory D

2012-04-14

285

Hyperdiversity of genes encoding integral light-harvesting proteins in the dinoflagellate Symbiodinium sp.  

PubMed

The superfamily of light-harvesting complex (LHC) proteins is comprised of proteins with diverse functions in light-harvesting and photoprotection. LHC proteins bind chlorophyll (Chl) and carotenoids and include a family of LHCs that bind Chl a and c. Dinophytes (dinoflagellates) are predominantly Chl c binding algal taxa, bind peridinin or fucoxanthin as the primary carotenoid, and can possess a number of LHC subfamilies. Here we report 11 LHC sequences for the chlorophyll a-chlorophyll c(2)-peridinin protein complex (acpPC) subfamily isolated from Symbiodinium sp. C3, an ecologically important peridinin binding dinoflagellate taxa. Phylogenetic analysis of these proteins suggests the acpPC subfamily forms at least three clades within the Chl a/c binding LHC family; Clade 1 clusters with rhodophyte, cryptophyte and peridinin binding dinoflagellate sequences, Clade 2 with peridinin binding dinoflagellate sequences only and Clades 3 with heterokontophytes, fucoxanthin and peridinin binding dinoflagellate sequences. PMID:23112815

Boldt, Lynda; Yellowlees, David; Leggat, William

2012-01-01

286

Nature-inspired light-harvesting liquid crystalline porphyrins for organic photovoltaics  

SciTech Connect

A new class of nanoscale light-harvesting discotic liquid crystalline porphyrins, with the same basic structure of the best photoreceptor in nature (chlorophyll), was synthesized. These materials can be exceptionally aligned into a highly ordered architecture in which the columns formed by intermolecular {pi}-{pi} stacking are spontaneously perpendicular to the substrate. The homeotropic alignment, well confirmed by synchrotron X-ray diffraction, could not only provide the most efficient pathway for hole conduction along the columnar axis crossing the device thickness, but also offer the largest area to the incident light for optimized light harvesting. Their preliminary photocurrent generation and photovoltaic performances were also demonstrated. The results provide new and efficient pathways to the development of organic photovoltaics by using homeotropically aligned liquid crystal thin films.

Li, Lanfang; Kang, Shin-Woong; Harden, John; Sun, Qingjiang; Zhou, Xiaoli; Dai, Liming; Jakli, Antal; Kumar, Satyendra; Li, Quan (NSF); (Kent); (Dayton)

2008-12-22

287

Dynamic supramolecular complexes constructed by orthogonal self-assembly.  

PubMed

CONSPECTUS: Supramolecular complexes, including various low-molecular-mass structures and large molecular aggregates that are assembled by reversible and highly directional noncovalent interactions, have attracted more and more attention due to their fascinating and unconventional chemical and physical properties that are different from those of traditional architectures encountered by covalently linked backbones. Supramolecular complexes are by nature dynamic architectures considering the reversibility of noncovalent interactions by which small molecular monomers can assemble into specific architectures that are able to be repeatably reorganized through the assembly/disassembly processes under certain environmental factors such as temperature, concentration, and solvent conditions. The construction of supramolecular complexes by orthogonal self-assembly with different types of highly specific, noninterfering interactions is currently attracting considerable interest since they not only can dynamically self-assemble, but also can be tuned by various external stimuli through addressing each type of noncovalent interaction separately. Therefore, these dynamic supramolecular complexes, especially with external responsiveness, represent the most outstanding candidates for the future development of functional and smart materials, and even mimic the assembling process of natural systems. In this Account, we will summarize the recent advances of dynamic supramolecular complexes constructed by orthogonal self-assembly in soluiton in two sections: (1) Construction strategies for supramolecular complexes based on orthogonal self-assembly, whose dynamic behaviors with external responsiveness were not experimentally investigated but potentially existed due to the intrinsic reversibility of noncovalent bonds; (2) dynamic behaviors of multiresponsive supramolecular complexes, which were experimentally reported to exhibit reversible multi-responsiveness to external stimuli. Dynamic nature is one of intrinsic properties of supramolecular complexes constructed by self-assembly. Therefore, in the first section, we will describe the dynamic self-assembly in the construction of supramolecular complexes, but will focus on their external responsive dynamic behaviors in the second section. In addition, considering that an increasing number of supramolecular complexes constructed by biological building blocks through bio-orthogonal assembly as mimics of biological systems have been reported in recent years, in the second section we will also present some typical examples on such special dynamic biological supramolecular complexes. The final part of this Account is devoted to foreseeing the rapid development of dynamic supramolecular complexes toward applications in functional and smart materials and fundamental questions facing dynamic supramolecular complexes in the future. PMID:24873508

Hu, Xiao-Yu; Xiao, Tangxin; Lin, Chen; Huang, Feihe; Wang, Leyong

2014-07-15

288

Predicting supramolecular self-assembly on reconstructed metal surfaces  

NASA Astrophysics Data System (ADS)

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern.The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern. GA image adapted from refs: (a) Phys. Chem. Chem. Phys., 2001, 3, 3399-3404, with permission from the PCCP Owner Societies, and (b) J. Phys. Chem. C, 2008, 112 (18), 7168-7172, reprinted with permission from the American Chemical Society, copyright © 2008.

Roussel, Thomas J.; Barrena, Esther; Ocal, Carmen; Faraudo, Jordi

2014-06-01

289

Chlorophylls, ligands and assembly of light-harvesting complexes in chloroplasts  

Microsoft Academic Search

Chlorophyll (Chl) b serves an essential function in accumulation of light-harvesting complexes (LHCs) in plants. In this article, this role of\\u000a Chl b is explored by considering the properties of Chls and the ligands with which they interact in the complexes. The overall\\u000a properties of the Chls, not only their spectral features, are altered as consequences of chemical modifications on

J. Kenneth Hoober; Laura L. Eggink; Min Chen

2007-01-01

290

Structure, function and assembly of Photosystem II and its light-harvesting proteins  

Microsoft Academic Search

Photosystem II (PSII) is a multisubunit chlorophyll–protein complex that drives electron transfer from water to plastoquinone using energy derived from light. In green plants, the native form of PSII is surrounded by the light-harvesting complex (LHCII complex) and thus it is called the PSII–LHCII supercomplex. Over the past several years, understanding of the structure, function, and assembly of PSII and

Jun Minagawa; Yuichiro Takahashi

2004-01-01

291

Insight into the Structure of Light Harvesting Complex II and its Stabilization in Detergent Solution  

Microsoft Academic Search

The structure of spinach light-harvesting complex II (LHC II), stabilized in a solution of the detergent n-octyl--d-glucoside (BOG), was investigated by small-angle neutron scattering (SANS). Physicochemical characterization of the isolated complex indicated that it was pure (>95%) and also in its native trimeric state. SANS with contrast variation was used to investigate the properties of the protein-detergent complex at three

Mateus B. Cardoso; Dmitriy Smolensky; William T. Heller; Hugh Michael ONeill

2009-01-01

292

Dephosphorylation of the thylakoid membrane light-harvesting complex-II by a stromal protein phosphatase  

Microsoft Academic Search

Light-harvesting complex-II (LHC-II) phosphatase activity has generally been examined in the intact thylakoid membrane. A recent report of peptide-phosphatase activity associated with the chloroplast stromal fraction (Hammer, M.F. et al. (1995) Photosynth Res 44: 107–115) has led to the question of whether this activity is capable of dephosphorylating membrane-bound LHC-II. To this end, heat-treated thylakoid membranes were examined as a

Mark F. Hammer; Gautam Sarath; John Markwell

1995-01-01

293

Discrete Redox Signaling Pathways Regulate Photosynthetic Light-Harvesting and Chloroplast Gene Transcription  

Microsoft Academic Search

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

John F. Allen; Stefano Santabarbara; Carol A. Allen; Sujith Puthiyaveetil; Ross Frederick Waller

2011-01-01

294

Efficient energy transfer in light-harvesting systems, I: optimal temperature, reorganization energy, and spatial-temporal correlations  

E-print Network

Understanding the mechanisms of efficient and robust energy transfer in light-harvesting systems provides new insights for the optimal design of artificial systems. In this paper, we use the Fenna-Matthews-Olson (FMO) protein complex and phycocyanin 645 (PC 645) to explore the general dependence on physical parameters that help maximize the efficiency and maintain its stability. With the Haken-Strobl model, the maximal energy transfer efficiency (ETE) is achieved under an intermediate optimal value of dephasing rate. To avoid the infinite temperature assumption in the Haken-Strobl model and the failure of the Redfield equation in predicting the Forster rate behavior, we use the generalized Bloch-Redfield (GBR) equation approach to correctly describe dissipative exciton dynamics and find that maximal ETE can be achieved under various physical conditions, including temperature, reorganization energy, and spatial-temporal correlations in noise. We also identify regimes of reorganization energy where the ETE changes monotonically with temperature or spatial correlation and therefore cannot be optimized with respect to these two variables.

Jianlan Wu; Fan Liu; Young Shen; Jianshu Cao; Robert J. Silbey

2010-08-13

295

Direct evidence of quantum transport in photosynthetic light-harvesting complexes  

PubMed Central

The photosynthetic light-harvesting apparatus moves energy from absorbed photons to the reaction center with remarkable quantum efficiency. Recently, long-lived quantum coherence has been proposed to influence efficiency and robustness of photosynthetic energy transfer in light-harvesting antennae. The quantum aspect of these dynamics has generated great interest both because of the possibility for efficient long-range energy transfer and because biology is typically considered to operate entirely in the classical regime. Yet, experiments to date show only that coherence persists long enough that it can influence dynamics, but they have not directly shown that coherence does influence energy transfer. Here, we provide experimental evidence that interaction between the bacteriochlorophyll chromophores and the protein environment surrounding them not only prolongs quantum coherence, but also spawns reversible, oscillatory energy transfer among excited states. Using two-dimensional electronic spectroscopy, we observe oscillatory excited-state populations demonstrating that quantum transport of energy occurs in biological systems. The observed population oscillation suggests that these light-harvesting antennae trade energy reversibly between the protein and the chromophores. Resolving design principles evident in this biological antenna could provide inspiration for new solar energy applications. PMID:22167798

Panitchayangkoon, Gitt; Voronine, Dmitri V.; Abramavicius, Darius; Caram, Justin R.; Lewis, Nicholas H. C.; Mukamel, Shaul; Engel, Gregory S.

2011-01-01

296

Metal-Enhanced Fluorescence of Chlorophylls in Light-Harvesting Complexes Coupled to Silver Nanowires  

PubMed Central

We investigate metal-enhanced fluorescence of peridinin-chlorophyll protein coupled to silver nanowires using optical microscopy combined with spectrally and time-resolved fluorescence techniques. In particular we study two different sample geometries: first, in which the light-harvesting complexes are deposited onto silver nanowires, and second, where solution of both nanostructures are mixed prior deposition on a substrate. The results indicate that for the peridinin-chlorophyll complexes placed in the vicinity of the silver nanowires we observe higher intensities of fluorescence emission as compared to the reference sample, where no nanowires are present. Enhancement factors estimated for the sample where the light-harvesting complexes are mixed together with the silver nanowires prior deposition on a substrate are generally larger in comparison to the other geometry of a hybrid nanostructure. While fluorescence spectra are identical both in terms of overall shape and maximum wavelength for peridinin-chlorophyll-protein complexes both isolated and coupled to metallic nanostructures, we conclude that interaction with plasmon excitations in the latter remains neutral to the functionality of the biological system. Fluorescence transients measured for the PCP complexes coupled to the silver nanowires indicate shortening of the fluorescence lifetime pointing towards modifications of radiative rate due to plasmonic interactions. Our results can be applied for developing ways to plasmonically control the light-harvesting capability of photosynthetic complexes. PMID:23533354

Kowalska, Dorota; Krajnik, Bartosz; Olejnik, Maria; Czechowski, Nikodem; Mackowski, Sebastian

2013-01-01

297

Efficient light harvesting by photosystem II requires an optimized protein packing density in Grana thylakoids.  

PubMed

A recently developed technique for dilution of the naturally high protein packing density in isolated grana membranes was applied to study the dependence of the light harvesting efficiency of photosystem (PS) II on macromolecular crowding. Slight dilution of the protein packing from 80% area fraction to the value found in intact grana thylakoids (70%) leads to an improved functionality of PSII (increased antenna size, enhanced connectivity between reaction centers). Further dilution induces a functional disconnection of light-harvesting complex (LHC) II from PSII. It is concluded that efficient light harvesting by PSII requires an optimal protein packing density in grana membranes that is close to 70%. We hypothesize that the decreased efficiency in overcrowded isolated grana thylakoids is caused by excited state quenching in LHCII, which has previously been correlated with neoxanthin distortion. Resonance Raman spectroscopy confirms this increase in neoxanthin distortion in overcrowded grana as compared with intact thylakoids. Furthermore, analysis of the changes in the antenna size in highly diluted membranes indicates a lipid-induced dissociation of up to two trimeric LHCII from PSII, leaving one trimer connected. This observation supports a hierarchy of LHCII-binding sites on PSII. PMID:20360011

Haferkamp, Silvia; Haase, Winfried; Pascal, Andrew A; van Amerongen, Herbert; Kirchhoff, Helmut

2010-05-28

298

Clustered Geometries Exploiting Quantum Coherence Effects for Efficient Energy Transfer in Light Harvesting  

E-print Network

Elucidating quantum coherence effects and geometrical factors for efficient energy transfer in photosynthesis has the potential to uncover non-classical design principles for advanced organic materials. We study energy transfer in a linear light-harvesting model to reveal that dimerized geometries with strong electronic coherences within donor and acceptor pairs exhibit significantly improved efficiency, which is in marked contrast to predictions of the classical F\\"orster theory. We reveal that energy tuning due to coherent delocalization of photoexcitations is mainly responsible for the efficiency optimization. This coherence-assisted energy-tuning mechanism also explains the energetics and chlorophyll arrangements in the widely-studied Fenna-Matthews-Olson complex. We argue that a clustered network with rapid energy relaxation among donors and resonant energy transfer from donor to acceptor states provides a basic formula for constructing efficient light-harvesting systems, and the general principles revealed here can be generalized to larger systems and benefit future innovation of efficient molecular light-harvesting materials.

Qing Ai; Tzu-Chi Yen; Bih-Yaw Jin; Yuan-Chung Cheng

2013-07-22

299

Investigations of photosynthetic light harvesting by two-dimensional electronic spectroscopy  

NASA Astrophysics Data System (ADS)

Photosynthesis begins with the harvesting of sunlight by antenna pigments, organized in a network of pigment-protein complexes that rapidly funnel energy to photochemical reaction centers. The intricate design of these systems---the widely varying structural motifs of pigment organization within proteins and protein organization within a larger, cooperative network---underlies the remarkable speed and efficiency of light harvesting. Advances in femtosecond laser spectroscopy have enabled researchers to follow light energy on its course through the energetic levels of photosynthetic systems. Now, newly-developed femtosecond two-dimensional electronic spectroscopy reveals deeper insight into the fundamental molecular interactions and dynamics that emerge in these structures. The following chapters present investigations of a number of natural light-harvesting complexes using two-dimensional electronic spectroscopy. These studies demonstrate the various types of information contained in experimental two-dimensional spectra, and they show that the technique makes it possible to probe pigment-protein complexes on the length- and time-scales relevant to their functioning. New methods are described that further extend the capabilities of two-dimensional electronic spectroscopy, for example, by independently controlling the excitation laser pulse polarizations. The experiments, coupled with theoretical simulation, elucidate spatial pathways of energy flow, unravel molecular and electronic structures, and point to potential new quantum mechanical mechanisms of light harvesting.

Read, Elizabeth Louise

300

Directed assembly of hierarchical light-harvesting complexes using virus capsid scaffolds and DNA origami tiles  

NASA Astrophysics Data System (ADS)

Directed assembly of nanostructures with molecular precision is of great importance to develop an insightful understanding of assembly pathways and dynamics as well as to derive new functionalities. In this work, we explore the use of virus capsids and DNA origami tiles as 3D scaffolds and 2D templates for directed assembly of light-harvesting molecules and plasmonic gold nanoparticles to achieve tunable photoemission. Bacteriophage MS2 virus capsids with well-defined spherical macromolecular structures are genetically modified to provide predictable steric arrangements of light-harvesting molecules. DNA origami tiles act as programmable planar templates to provide higher-order organization of oligonucleotide-functionalized light-harvesting capsids and plasmonic gold nanoparticles. The direct observation of distance dependent photoluminescence emission is carried out by our correlative approach combining atomic force microscopy and confocal fluorescence microscopy, which is in good agreement with our numerical simulation and theoretical calculation. This work will facilitate the construction of multicomponent biological-metal hybrid plasmonic nanostructures for nanophotonics and biosensing applications.

Wang, Debin; Capehart, Stacy; Pal, Suchetan; Liu, Minghui; Lau, Jolene; Yan, Hao; Francis, Matthew; Deyoreo, Jim

2013-03-01

301

Design principles and fundamental trade-offs in biomimetic light harvesting  

E-print Network

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 also have the potential to reproduce their remarkable light harvesting performance.

Mohan Sarovar; K. Birgitta Whaley

2012-10-07

302

Self-Assembly: Nature's Way to Do It  

NSDL National Science Digital Library

Biology operates at two levels: the large scale which we can see and the underlying microscopic one. This video lecture describes how intermolecular forces cause protein arrays to self-assemble, enabling nature to fabricate the large scale components of living systems. The lecturer explains how scale, forces and information cooperate to form complex structures. There are demonstrations of gravity, surface tension and capillary forces assembling materials, as well as experiments producing thin films from a ferritin solution. The presenter introduces his Protein Array Project, which attempts to fabricate thin hexagonal lattice films by imitating the beauty and utility of nature. Links to resources on self-assembly and nanotechnology are provided. The lecture is 58 minutes in length.

2007-04-17

303

Programmed self-assembly of a quadruplex DNA nanowire.  

PubMed

The ability to produce, reproducibly and systematically, well-defined quadruplex DNA nanowires through controlled rational design is poorly understood despite potential utility in structural nanotechnology. The programmed hierarchical self-assembly of a long four-stranded DNA nanowire through cohesive self-assembly of GpC and CpG "sticky" ends is reported. The encoding of bases within the quadruplex stem allows for an uninterrupted ?-stacking system with rectilinear propagation for hundreds of nanometers in length. The wire is mechanically stable and features superior nuclease resistance to double-stranded DNA. The study indicates the feasibility for programmed assembly of uninterrupted quadruplex DNA nanowires. This is fundamental to the systematic investigation of well-defined DNA nanostructures for uses in optoelectronic and electronic devices as well as other structural nanotechnology applications. PMID:24615753

Hessari, Nason Ma'ani; Spindler, Lea; Troha, Tinkara; Lam, Wan-Chi; Drevenšek-Olenik, Irena; da Silva, Mateus Webba

2014-03-24

304

Self-assembly of hyperbranched polymers and its biomedical applications.  

PubMed

Hyperbranched polymers (HBPs) are highly branched macromolecules with a three-dimensional dendritic architecture. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. In this paper, the recent developments in HBP self-assembly and their biomedical applications have been comprehensively reviewed. Many delicate supramolecular structures from zero-dimension (0D) to three-dimension (3D), such as micelles, fibers, tubes, vesicles, membranes, large compound vesicles and physical gels, have been prepared through the solution or interfacial self-assembly of amphiphilic HBPs. In addition, these supramolecular structures have shown promising applications in the biomedical areas including drug delivery, protein purification/detection/delivery, gene transfection, antibacterial/antifouling materials and cytomimetic chemistry. Such developments promote the interdiscipline researches among surpramolecular chemistry, biomedical chemistry, nano-technology and functional materials. PMID:20853374

Zhou, Yongfeng; Huang, Wei; Liu, Jinyao; Zhu, Xinyuan; Yan, Deyue

2010-11-01

305

Stable doping of carbon nanotubes via molecular self assembly  

NASA Astrophysics Data System (ADS)

We report a novel method for stable doping of carbon nanotubes (CNT) based on methods of molecular self assembly. A conformal growth of a self-assembled monolayer of fluoroalkyl trichloro-silane (FTS) at CNT surfaces results in a strong increase of the sheet conductivity of CNT electrodes by 60-300%, depending on the CNT chirality and composition. The charge carrier mobility of undoped partially aligned CNT films was independently estimated in a field-effect transistor geometry (˜100 cm2V-1s-1). The hole density induced by the FTS monolayer in CNT sheets is estimated to be ˜1.8 × 1014 cm-2. We also show that FTS doping of CNT anodes greatly improves the performance of organic solar cells. This large and stable doping effect, easily achieved in large-area samples, makes this approach very attractive for applications of CNTs in transparent and flexible electronics.

Lee, B.; Chen, Y.; Cook, A.; Zakhidov, A.; Podzorov, V.

2014-10-01

306

Self-Assembled Combinatorial Encoding Nanoarrays for Multiplexed Biosensing  

PubMed Central

Multiplexed and sensitive detection of nucleic acids, proteins, or other molecules from a single solution and a small amount of sample is of great demand in biomarker profiling and disease diagnostics. Here we describe a new concept using combinatorial self-assembly of DNA nanotiles into micrometer-sized two-dimensional arrays that carry nucleic acid probes and barcoded fluorescent dyes to achieve multiplexed detection. We demonstrated the specificity and sensitivity of the arrays by detecting multiple DNA sequences and aptamer binding molecules. This DNA tile-array-based sensor platform can be constructed through DNA self-assembly. The attachment of different molecular probes can be achieved by simple DNA hybridization so bioconjugation is not necessary for the labeling. Accurate control of the interprobe distances and solution-based binding reactions ensures fast target binding kinetics. PMID:17298017

Lin, Chenxiang; Liu, Yan; Yan, Hao

2007-01-01

307

Calixarene-encapsulated nanoparticles: self-assembly into functional nanomaterials†  

PubMed Central

Calixarenes are excellent surfactants for enhancing the dispersion and self-assembly of metal nanoparticles into well-defined structures, particularly those with unit length scales in the 10–100 nm size range. Particles within these ensembles are strongly coupled, giving rise to unique collective optical or magnetic properties. The self-assembled nanostructures described in this feature article include 2D arrays of colloidal Au nanoparticles with size-dependent plasmonic responses, and sub-100 nm Co nanoparticle rings with chiral magnetic states. These nanoparticle assemblies may be further developed for applications in chemical sensing based on surface-enhanced Raman scattering (SERS) and as binary elements for nonvolatile memory, respectively. PMID:16582988

Wei, Alexander

2007-01-01

308

Self-assembled liquid-crystal microlasers, microresonators, and microfibres  

NASA Astrophysics Data System (ADS)

When liquid crystals are dispersed in an immiscible fluid, microdroplets of liquid crystal are spontaneously formed in a fraction of a second. They have optically anisotropic internal structure, which is determined by the ordering of liquid crystal molecules at the interface. Spherical droplets of a nematic liquid crystal can function as whispering-gallery-mode microresonators with an unprecedented width of wavelength tunability by an electric field. WGM pulsed lasing in dyedoped nematic microdroplets is sensitive to strain, temperature and presence of molecules that change molecular orientation at the interface. Omnidirectional 3D lasing was demonstrated in droplets of chiral nematic liquid crystals that form 3D Bragg-onion resonators. We present recent progress in this field, including electric tuning of 3D lasing from chiral nematic droplets and self-assembly of ferroelectric smectic-C* microdroplets with the onion-Bragg structure. We show that anisotropic fibres could be self-assembled from smectic liquid crystals.

Muševi?, I.; Peng, Huang; Nikkhou, M.; Humar, M.

2014-03-01

309

Chiral plasmonics of self-assembled nanorod dimers  

NASA Astrophysics Data System (ADS)

Chiral nanoscale photonic systems typically follow either tetrahedral or helical geometries that require four or more different constituent nanoparticles. Smaller number of particles and different chiral geometries taking advantage of the self-organization capabilities of nanomaterials will advance understanding of chiral plasmonic effects, facilitate development of their theory, and stimulate practical applications of chiroplasmonics. Here we show that gold nanorods self-assemble into side-by-side orientated pairs and ``ladders'' in which chiral properties originate from the small dihedral angle between them. Spontaneous twisting of one nanorod versus the other one breaks the centrosymmetric nature of the parallel assemblies. Two possible enantiomeric conformations with positive and negative dihedral angles were obtained with different assembly triggers. The chiral nature of the angled nanorod pairs was confirmed by 4? full space simulations and the first example of single-particle CD spectroscopy. Self-assembled nanorod pairs and ``ladders'' enable the development of chiral metamaterials, (bio)sensors, and new catalytic processes.

Ma, Wei; Kuang, Hua; Wang, Libing; Xu, Liguang; Chang, Wei-Shun; Zhang, Huanan; Sun, Maozhong; Zhu, Yinyue; Zhao, Yuan; Liu, Liqiang; Xu, Chuanlai; Link, Stephan; Kotov, Nicholas A.

2013-06-01

310

Nanocrystal-micelle: synthesis, self-assembly and application.  

PubMed

Nanocrystals (NCs) are one of the important building blocks for fabrication of nanostructured arrays for wide range of optical, electronic, magnetic, catalytic and biosensing applications. Here, our recent advances in the synthesis, self-assembly and application of NC-micelles are highlighted. The NCs are encapsulated inside the core of surfactant micelles in a rapid, interfacially driven micro-emulsion process. The flexible surface chemistry of the NC-micelles causes them to be water-soluble and allows further self-assembly into two- and three-dimensional ordered arrays. The NC-micelles are biocompatible, of interest for bio-labeling. Finally, integration of the ordered arrays and charge transport property are discussed. PMID:18338033

Fan, Hongyou

2008-03-28

311

Electrostatic control of structure in self-assembled membranes.  

PubMed

Self-assembling peptide amphiphiles (PAs) can form hierarchically ordered membranes when brought in contact with aqueous polyelectrolytes of the opposite charge by rapidly creating a diffusion barrier composed of filamentous nanostructures parallel to the plane of the incipient membrane. Following this event, osmotic forces and charge complexation template nanofiber growth perpendicular to the plane of the membrane in a dynamic self-assembly process. In this work, we show that this hierarchical structure requires massive interfacial aggregation of PA molecules, suggesting the importance of rapid diffusion barrier formation. Strong PA aggregation is induced here through the use of heparin-binding PAs with heparin and also with polyelectrolytes of varying charge density. Small angle X-ray scattering shows that in the case of weak PA-polyelectrolyte interaction, membranes formed display a cubic phase ordering on the nanoscale that likely results from clusters of PA nanostructures surrounded by polyelectrolyte chains. PMID:24022896

Bitton, Ronit; Chow, Lesley W; Zha, R Helen; Velichko, Yuri S; Pashuck, E Thomas; Stupp, Samuel I

2014-02-12

312

Self-assembling enzymes and the origins of the cytoskeleton.  

PubMed

The bacterial cytoskeleton is composed of a complex and diverse group of proteins that self-assemble into linear filaments. These filaments support and organize cellular architecture and provide a dynamic network controlling transport and localization within the cell. Here, we review recent discoveries related to a newly appreciated class of self-assembling proteins that expand our view of the bacterial cytoskeleton and provide potential explanations for its evolutionary origins. Specifically, several types of metabolic enzymes can form structures similar to established cytoskeletal filaments and, in some cases, these structures have been repurposed for structural uses independent of their normal roles. The behaviors of these enzymes suggest that some modern cytoskeletal proteins may have evolved from dual-role proteins with catalytic and structural functions. PMID:22014508

Barry, Rachael M; Gitai, Zemer

2011-12-01

313

A switch based on self-assembled thymine  

NASA Astrophysics Data System (ADS)

The DNA base thymine is deposited at 100 K on Cu(111) and investigated and manipulated by low-temperature scanning tunneling microscopy at 5 K. At submonolayer coverage paired rows are observed. At monolayer coverage a hexagonal commensurate self-assembled layer with the methyl group pointing away from the surface forms. A reversible local manipulation of molecules within the self-assembled layer is demonstrated. This manipulation is interpreted as an out-of-plane relaxation of molecules within the layer induced by the change of the adsorption geometry of individual molecules between two meta-stable orientations. A positive field of 2-4 V leads to this local change in the molecular arrangement, while a field larger than 4 V restores the original geometry.

Kalkan, Fatih; Mehlhorn, Michael; Morgenstern, Karina

2012-10-01

314

Nanoparticle self-assembly by a highly stable recombinant spider wrapping silk protein subunit.  

PubMed

Artificial spider silk proteins may form fibers with exceptional strength and elasticity. Wrapping silk, or aciniform silk, is the toughest of the spider silks, and has a very different protein composition than other spider silks. Here, we present the characterization of an aciniform protein (AcSp1) subunit named W1, consisting of one AcSp1 199 residue repeat unit from Argiope trifasciata. The structural integrity of recombinant W1 is demonstrated in a variety of buffer conditions and time points. Furthermore, we show that W1 has a high thermal stability with reversible denaturation at ?71°C and forms self-assembled nanoparticle in near-physiological conditions. W1 therefore represents a highly stable and structurally robust module for protein-based nanoparticle formation. PMID:23994530

Xu, Lingling; Tremblay, Marie-Laurence; Orrell, Kathleen E; Leclerc, Jérémie; Meng, Qing; Liu, Xiang-Qin; Rainey, Jan K

2013-10-01

315

Self-assembled carbon nanotube honeycomb networks using a butterfly wing template as a multifunctional nanobiohybrid.  

PubMed

Insect wings have many unique and complex nano/microstructures that are presently beyond the capabilities of any current technology to reproduce them artificially. In particular, Morpho butterflies are an attractive type of insect because their multifunctional wings are composed of nano/microstructures. In this paper, we show that carbon nanotube-containing composite adopts honeycomb-shaped networks when simply self-assembled on Morpho butterfly wings used as a template. The unique nano/microstructure of the composites exhibits multifunctionalities such as laser-triggered remote-heating, high electrical conductivity, and repetitive DNA amplification. Our present study highlights the important progress that has been made toward the development of smart nanobiomaterials for various applications such as digital diagnosis, soft wearable electronic devices, photosensors, and photovoltaic cells. PMID:23952240

Miyako, Eijiro; Sugino, Takushi; Okazaki, Toshiya; Bianco, Alberto; Yudasaka, Masako; Iijima, Sumio

2013-10-22

316

Self-assembled monolayers formed on AZ31 Mg alloy  

NASA Astrophysics Data System (ADS)

Self-assembled monolayer (SAM) was successfully adsorbed on the AZ31 Mg alloy surface using oleic acid and stearic acid with various organic solvents, such as acetone, ethanol, and hexane. The surface monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and anodic polarization test. It was shown that the higher contact angle and the best anti-corrosion property were obtained with treatment in oleic acid with ethanol solution.

Salman, S. A.; Okido, M.

2012-07-01

317

Electrostatically self-assembled electro-optic thin films  

Microsoft Academic Search

Thin film electro-optic materials have been synthesized by a novel electrostatic self-assembly (ESA) method. This wet chemistry synthesis method allows the molecular-level, layer-by-layer formation of multilayer thin and thick films of alternating anionic and cationic molecules and other materials. We have found that during the adsorption of dipolar molecules from solution to form a single molecular layer, the dipoles align

Kristie L. Cooper; Yanjing Liu; Richard O. Claus; Liangmin Zhang

2000-01-01

318

Self assembled monolayers of rigid thiols on Gold  

Microsoft Academic Search

Self assembled monolayers (SAM) of phi-functionalized mercaptobiphenyls (phi-MBP) are stable, molecularly engineered ultrathin organic films, which can be used for the design of model surfaces with well-defined chemical and physical properties. For example, the number and distribution of terminal hydroxyl groups can be tailored to study water-surface interactions or the chemisorption of organic molecules from solution. We have prepared and

Svetlana Stoycheva; Joerg Fick; Alexander Kornviakov; Avi Ulman; Michael Himmelhaus; Michael Grunze

2005-01-01

319

Controlling guest-host interactions in self-assembled materials  

NASA Astrophysics Data System (ADS)

Aqueous solutions of self-assembling macromolecules can be found in many industrial formulations, as well as in many living organisms. Regardless of the specific system, the self-assembling macromolecules are rarely found in the absence of other solutes or guest species. Such components may include fragrance molecules incorporated into block-copolymer micelles for use in detergents, dyes included in micellar precursor solutions for the synthesis of mesostructured silica-block copolymer composites, or specifically designed additives for controlling protein folding and activity. A detailed understanding of the structures and dynamic molecular interactions among the various species in solution and their influences on macromolecule aggregation and phase behaviors is of paramount importance for designing systems with improved properties and performance. Unambiguous measurements of the loci of interaction and solubilization of small molecule species (e.g., dyes or surfactants) within self-assembling block-copolymer species or proteins in aqueous solutions have been established. This has been achieved by exploiting powerful correlative multidimensional nuclear magnetic resonance (NMR) spectroscopy techniques, including pulsed-field-gradient diffusion measurements, which provide detailed molecular insights into a variety of heterogeneous self-assembled systems. Furthermore, these insights and measurements enable the solution conditions to be established that permit the control and release of such guest molecules from association with macromolecular carrier species into the surrounding solution. Specifically, the use of temperature to control the distribution of porphyrin guest-species in a block-copolymer host and the light-dependent folding and unfolding of bovine serum albumin through varying interactions with an azo-benzene functionalized surfactant are demonstrated. In the absence of long-range order in these complex systems, advanced NMR spectroscopy methods provide crucial and highly selective means for characterizing component structures, dynamics and interactions at a molecular level. The analytical approach and the resulting insights developed here are general and anticipated to be of broad applicability to systems of interest in medicine, biology, and industry.

Steinbeck, Christian Alexander

320

Novel Self-Assembling Silane for Abhesive and Adhesive Applications  

Microsoft Academic Search

The potential benefits from using a novel vinyl-terminated long alkyl-chain self-assembling silane (VTS) have been investigated. A relatively high water contact angle of 83° was found for water on the VTS-pretreated soda-lime glass surface. This revealed that the degree of hydrophobicity of this surface was far more pronounced than for the ultrasonically-cleaned glass surface or the ?-glycidoxypropyltrimethoxy silane (GPS)–pretreated glass

A. J. Kinloch; K. T. Tan; J. F. Watts

2006-01-01

321

Self-assembly of bimodal particles inside emulsion droplets  

Microsoft Academic Search

Colloidal dispersion of bimodal particles were self-organized inside water-in-oil emulsion droplets by evaporationdriven self-assembly method. After droplet shrinkage by heating the complex fluid system, small numbers of microspheres were packed into minimal second moment clusters, which are partially coated with silica nanospheres, resulting in the generation of patchy particles. The patchy particles in this study possess potential applications for selfassembly

Young-Sang Cho; Gi-Ra Yi; Seung-Man Yang; Young-Kuk Kim; Chul-Jin Choi

2010-01-01

322

Computation via dynamic self-assembly of idealized protein networks.  

SciTech Connect

We describe stochastic agent-based simulations of protein-emulating agents to perform computation via dynamic self-assembly. The binding and actuation properties of the types of agents required to construct a RAM machine (equivalent to a Turing machine) are described. We present an example computation and describe the molecular biology and non-equilibrium statistical mechanics, and information science properties of this system.

Bouchard, Ann Marie; Osbourn, Gordon Cecil

2003-08-01

323

Novel Piezoelectric DDVP Sensor Based on Self?Assembly Method  

Microsoft Academic Search

A novel piezoelectric sensor was fabricated by depositing the films of polyvinyl pyrrolindone (PVP) and PVP with butyl cholinesterase (BuChE) (BuChE?PVP), respectively, on the surface of quartz crystal microbalance (QCM) using self?assembly method. The sensitive films were characterized with online examination and XPS technique. The obtained sensors were applied to measure o,o?dimethyl?o?2,2?dichlorovinyl phosphate (DDVP) pesticide concentration. It shows that BuChE?PVP

Hongjuan Zeng; Yadong Jiang; Guangzhong Xie; Junsheng Yu

2007-01-01

324

Order of epitaxial self-assembled quantum dots: linear analysis  

Microsoft Academic Search

Epitaxial self-assembled quantum dots (SAQDs) are of interest for\\u000ananostructured optoelectronic and electronic devices such as lasers,\\u000aphotodetectors and nanoscale logic. Spatial order and size order of SAQDs are\\u000aimportant to the development of usable devices. It is likely that these two\\u000atypes of order are strongly linked; thus, a study of spatial order will also\\u000ahave strong implications for

Lawrence H. Friedman

2007-01-01

325

Bicontinuous Surfaces in Self-assembling Amphiphilic Systems  

Microsoft Academic Search

Amphiphiles are molecules which have both hydrophilic and hydrophobic parts. In water- and\\/or oil-like solvent, they self-assemble\\u000a into extended sheet-like structures due to the hydrophobic effect. The free energy of an amphiphilic system can be written\\u000a as a functional of its interfacial geometry, and phase diagrams can be calculated by comparing the free energies following\\u000a from different geometries. Here we

Ulrich Schwarz; Gerhard Gompper

2002-01-01

326

Lighting up cells with lanthanide self-assembled helicates  

PubMed Central

Lanthanide bioprobes and bioconjugates are ideal luminescent stains in view of their low propensity to photobleaching, sharp emission lines and long excited state lifetimes permitting time-resolved detection for enhanced sensitivity. We show here how the interplay between physical, chemical and biochemical properties allied to microfluidics engineering leads to self-assembled dinuclear lanthanide luminescent probes illuminating live cells and selectively detecting biomarkers expressed by cancerous human breast cells. PMID:24511387

Bunzli, Jean-Claude G.

2013-01-01

327

Intramolecular energy transfer with butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.  

SciTech Connect

The synthesis and photophysical properties of butadiyne-linked chlorophyll and porphyrin dimers in toluene solution and in several self-assembled prismatic structures are described. The butadiyne linkage between the 20-positions of the macrocycles results in new electronic transitions polarized along the long axes of the dimers. These transitions greatly increase the ability of these dimers to absorb the solar spectrum over a broad wavelength range. Femtosecond transient absorption spectroscopy reveals the relative rate of rotation of the macrocycles around the butadiyne bond joining them. Following addition of 3-fold symmetric, metal-coordinating ligands, both macrocyclic dimers self-assemble into prismatic structures in which the dimers comprise the faces of the prisms. These structures were confirmed by small-angle X-ray scattering experiments in solution using a synchrotron source. Photoexcitation of the prismatic assemblies reveals that efficient, through-space energy transfer occurs between the macrocyclic dimers within the prisms. The distance dependence of energy transfer between the faces of the prisms was observed by varying the size of the prismatic assemblies through the use of 3-fold symmetric ligands having arms with different lengths. These results show that self-assembly of discrete macrocyclic prisms provides a useful new strategy for controlling singlet exciton flow in antenna systems for artificial photosynthesis and solar cell applications.

Kelley, R. F.; Lee, S. J.; Wilson, T. M.; Nakamura, Y.; Tiede, D. M.; Osuka, A.; Hupp, J. T.; Wasielewski, M. R.; SUF-USR; Chemical Sciences and Engineering Division; Northwestern Univ.; Kyoto Univ.

2008-01-01

328

Controlling RNA self-assembly to form filaments  

PubMed Central

Fundamental control over supra-molecular self-assembly for organization of matter on the nano-scale is a major objective of nanoscience and nanotechnology. ‘RNA tectonics’ is the design of modular RNA units, called tectoRNAs, that can be programmed to self-assemble into novel nano- and meso-scopic architectures of desired size and shape. We report the three-dimensional design of tectoRNAs incorporating modular 4-way junction (4WJ) motifs, hairpin loops and their cognate loop–receptors to create extended, programmable interaction interfaces. Specific and directional RNA–RNA interactions at these interfaces enable conformational, topological and orientational control of tectoRNA self-assembly. The interacting motifs are precisely positioned within the helical arms of the 4WJ to program assembly from only one helical stacking conformation of the 4WJ. TectoRNAs programmed to assemble with orientational compensation produce micrometer-scale RNA filaments through supra-molecular equilibrium polymerization. As visualized by transmission electron microscopy, these RNA filaments resemble actin filaments from the protein world. This work emphasizes the potential of RNA as a scaffold for designing and engineering new controllable biomaterials mimicking modern cytoskeletal proteins. PMID:16522648

Nasalean, Lorena; Baudrey, Stephanie; Leontis, Neocles B.; Jaeger, Luc

2006-01-01

329

Model-driven optimization of multicomponent self-assembly processes  

PubMed Central

Here, we report an engineering approach toward multicomponent self-assembly processes by developing a methodology to circumvent spurious, metastable assemblies. The formation of metastable aggregates often hampers self-assembly of molecular building blocks into the desired nanostructures. Strategies are explored to master the pathway complexity and avoid off-pathway aggregates by optimizing the rate of assembly along the correct pathway. We study as a model system the coassembly of two monomers, the R- and S-chiral enantiomers of a ?-conjugated oligo(p-phenylene vinylene) derivative. Coassembly kinetics are analyzed by developing a kinetic model, which reveals the initial assembly of metastable structures buffering free monomers and thereby slows the formation of thermodynamically stable assemblies. These metastable assemblies exert greater influence on the thermodynamically favored self-assembly pathway if the ratio between both monomers approaches 1:1, in agreement with experimental results. Moreover, competition by metastable assemblies is highly temperature dependent and hampers the assembly of equilibrium nanostructures most effectively at intermediate temperatures. We demonstrate that the rate of the assembly process may be optimized by tuning the cooling rate. Finally, it is shown by simulation that increasing the driving force for assembly stepwise by changing the solvent composition may circumvent metastable pathways and thereby force the assembly process directly into the correct pathway. PMID:24101463

Korevaar, Peter A.; Grenier, Christophe; Markvoort, Albert J.; Schenning, Albertus P. H. J.; de Greef, Tom F. A.; Meijer, E. W.

2013-01-01

330

Model-driven optimization of multicomponent self-assembly processes.  

PubMed

Here, we report an engineering approach toward multicomponent self-assembly processes by developing a methodology to circumvent spurious, metastable assemblies. The formation of metastable aggregates often hampers self-assembly of molecular building blocks into the desired nanostructures. Strategies are explored to master the pathway complexity and avoid off-pathway aggregates by optimizing the rate of assembly along the correct pathway. We study as a model system the coassembly of two monomers, the R- and S-chiral enantiomers of a ?-conjugated oligo(p-phenylene vinylene) derivative. Coassembly kinetics are analyzed by developing a kinetic model, which reveals the initial assembly of metastable structures buffering free monomers and thereby slows the formation of thermodynamically stable assemblies. These metastable assemblies exert greater influence on the thermodynamically favored self-assembly pathway if the ratio between both monomers approaches 1:1, in agreement with experimental results. Moreover, competition by metastable assemblies is highly temperature dependent and hampers the assembly of equilibrium nanostructures most effectively at intermediate temperatures. We demonstrate that the rate of the assembly process may be optimized by tuning the cooling rate. Finally, it is shown by simulation that increasing the driving force for assembly stepwise by changing the solvent composition may circumvent metastable pathways and thereby force the assembly process directly into the correct pathway. PMID:24101463

Korevaar, Peter A; Grenier, Christophe; Markvoort, Albert J; Schenning, Albertus P H J; de Greef, Tom F A; Meijer, E W

2013-10-22

331

Polymer adsorption-driven self-assembly of nanostructures.  

PubMed

Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context. PMID:11326074

Chakraborty, A K; Golumbfskie, A J

2001-01-01

332

Polymer Adsorption-Driven Self-Assembly of Nanostructures  

NASA Astrophysics Data System (ADS)

Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context.

Chakraborty, Arup K.; Golumbfskie, Aaron J.

2001-10-01

333

DNA Assisted Self-Assembly of PAMAM Dendrimers.  

PubMed

We report DNA assisted self-assembly of polyamidoamine (PAMAM) dendrimers using all atom Molecular Dynamics (MD) simulations and present a molecular level picture of a DNA-linked PAMAM dendrimer nanocluster, which was first experimentally reported by Choi et al. (Nano Lett., 2004, 4, 391-397). We have used single stranded DNA (ssDNA) to direct the self-assembly process. To explore the effect of pH on this mechanism, we have used both the protonated (low pH) and nonprotonated (high pH) dendrimers. In all cases studied here, we observe that the DNA strand on one dendrimer unit drives self-assembly as it binds to the complementary DNA strand present on the other dendrimer unit, leading to the formation of a DNA-linked dendrimer dimeric complex. However, this binding process strongly depends on the charge of the dendrimer and length of the ssDNA. We observe that the complex with a nonprotonated dendrimer can maintain a DNA length dependent inter-dendrimer distance. In contrast, for complexes with a protonated dendrimer, the inter-dendrimer distance is independent of the DNA length. We attribute this observation to the electrostatic complexation of a negatively charged DNA strand with the positively charged protonated dendrimer. PMID:25205346

Mandal, Taraknath; Kumar, Mattaparthi Venkata Satish; Maiti, Prabal K

2014-10-01

334

Spectroscopic critical dimension technology (SCD) for directed self assembly  

NASA Astrophysics Data System (ADS)

Directed self-assembly (DSA) is being actively investigated as a potential patterning solution for future generation devices. While SEM based CD measurement is currently used in research and development, scatterometry-based techniques like spectroscopic CD (SCD) are preferred for high volume manufacturing. SCD can offer information about sub-surface features that are not available from CD-SEM measurement. Besides, SCD is a non-destructive, high throughput technique already adopted in HVM in several advanced nodes. The directed self assembly CD measurement can be challenging because of small dimensions and extremely thin layers in the DSA stack. In this study, the SCD technology was investigated for a 14 nm resolution PS-b-PMMA chemical epitaxy UW process optimized by imec. The DSA stack involves new materials such as cross-linkable polysterene (XPS) of thickness approximately 5 nm, ArF immersion resist (subsequently removed), -OH terminated neutral brush layer, and BCP material (Polystyrene-blockmethyl methacrylate of thickness roughly 20 to 30 nm). The mask contains a large CD and pitch matrix, for studying the quality of self-assembly as a function of the guide pattern dimensions. We report on the ability of SCD to characterize the dimensional variation in these targets and hence provide a viable process control solution.

Nishibe, Senichi; Dziura, Thaddeus; Nagaswami, Venkat; Gronheid, Roel

2014-04-01

335

Three dimensional self-assembly at the nanoscale  

NASA Astrophysics Data System (ADS)

At the nanoscale, three dimensional manipulation and assembly becomes extremely challenging and also cost prohibitive. Self-assembly provides an attractive and possibly the only highly parallel methodology to structure truly three dimensional patterned materials and devices at this size scale for applications in electronics, optics, robotics and medicine. This is a concise review along with a perspective of an important and exciting field in nanotechnology and is related to a Nanoengineering Pioneer Award that I received at this SPIE symposium for my contributions to the 3D selfassembly of nanostructures. I detail a historical account of 3D self-assembly and outline important developments in this area which is put into context with the larger research areas of 3D nanofabrication, assembly and nanomanufacturing. A focus in this review is on our work as it relates to the self-assembly with lithographically patterned units; this approach provides a means for heterogeneous integration of periodic, curved and angled nanostructures with precisely defined three dimensional patterns.

Gracias, D. H.

2013-05-01

336

Surface Effects Mediate Self-Assembly of Amyloid-? Peptides.  

PubMed

Here we present a label-free method for studying the mechanism of surface effects on amyloid aggregation. In this method, spin-coating is used to rapidly dry samples, in a homogeneous manner, after various incubation times. This technique allows the control of important parameters for self-assembly, such as the surface concentration. Atomic force microscopy is then used to obtain high-resolution images of the morphology. While imaging under dry conditions, we show that the morphologies of self-assembled aggregates of a model amyloid-? peptide, A?12-28, are strongly influenced by the local surface concentration. On mica surfaces, where the peptides can freely diffuse, homogeneous, self-assembled protofibrils formed spontaneously and grew longer with longer subsequent incubation. The surface fibrillization rate was much faster than the rates of fibril formation observed in solution, with initiation occurring at much lower concentrations. These data suggest an alternative pathway for amyloid formation on surfaces where the nucleation stage is either bypassed entirely or too fast to measure. This simple preparation procedure for high-resolution atomic force microscopy imaging of amyloid oligomers and protofibrils should be applicable to any amyloidogenic protein species. PMID:25229233

Lin, Yi-Chih; Petersson, E James; Fakhraai, Zahra

2014-10-28

337

Algorithmic Self-Assembly of DNA Sierpinski Triangles  

PubMed Central

Algorithms and information, fundamental to technological and biological organization, are also an essential aspect of many elementary physical phenomena, such as molecular self-assembly. Here we report the molecular realization, using two-dimensional self-assembly of DNA tiles, of a cellular automaton whose update rule computes the binary function XOR and thus fabricates a fractal pattern—a Sierpinski triangle—as it grows. To achieve this, abstract tiles were translated into DNA tiles based on double-crossover motifs. Serving as input for the computation, long single-stranded DNA molecules were used to nucleate growth of tiles into algorithmic crystals. For both of two independent molecular realizations, atomic force microscopy revealed recognizable Sierpinski triangles containing 100–200 correct tiles. Error rates during assembly appear to range from 1% to 10%. Although imperfect, the growth of Sierpinski triangles demonstrates all the necessary mechanisms for the molecular implementation of arbitrary cellular automata. This shows that engineered DNA self-assembly can be treated as a Turing-universal biomolecular system, capable of implementing any desired algorithm for computation or construction tasks. PMID:15583715

2004-01-01

338

Optimal thermal bath for robust excitation energy transfer in disordered light-harvesting complex 2 of purple bacteria  

E-print Network

The existence of an optimal thermal bath to facilitate robust energy transfer between the spectrally separated B800 and B850 rings in light-harvesting complex 2 (LH2) of purple bacteria is investigated via the multichromophoric ...

Cleary, Liam

339

Efficient Light Harvesting in a Dark, Hot, Acidic Environment: The Structure and Function of PSI-LHCI from Galdieria sulphuraria  

PubMed Central

Photosystem I-light harvesting complex I (PSI-LHCI) was isolated from the thermoacidophilic red alga Galdieria sulphuraria, and its structure, composition, and light-harvesting function were characterized by electron microscopy, mass spectrometry, and ultrafast optical spectroscopy. The results show that Galdieria PSI is a monomer with core features similar to those of PSI from green algae, but with significant differences in shape and size. A comparison with the crystal structure of higher plant (pea) PSI-LHCI indicates that Galdieria PSI binds seven to nine light-harvesting proteins. Results from ultrafast optical spectroscopy show that the functional coupling of the LHCI proteins to the PSI core is tighter than in other eukaryotic PSI-LHCI systems reported thus far. This tight coupling helps Galdieria perform efficient light harvesting under the low-light conditions present in its natural endolithic habitat. PMID:21190665

Thangaraj, Balakumar; Jolley, Craig C.; Sarrou, Iosifina; Bultema, Jelle B.; Greyslak, Jason; Whitelegge, Julian P.; Lin, Su; Kouril, Roman; Subramanyam, Rajagopal; Boekema, Egbert J.; Fromme, Petra

2011-01-01

340

Molecular Self-Assembly into One-Dimensional Nanostructures  

PubMed Central

CONSPECTUS Self-assembly of small molecules into one-dimensional nanostructures offers many potential applications in electronically and biologically active materials. The recent advances discussed in this Account demonstrate how researchers can use the fundamental principles of supramolecular chemistry to craft the size, shape, and internal structure of nanoscale objects. In each system described here, we used atomic force microscopy (AFM) and transmission electron microscopy (TEM) to study the assembly morphology. Circular dichroism, nuclear magnetic resonance, infrared, and optical spectroscopy provided additional information about the self-assembly behavior in solution at the molecular level. Dendron rod–coil molecules self-assemble into flat or helical ribbons. They can incorporate electronically conductive groups and can be mineralized with inorganic semiconductors. To understand the relative importance of each segment in forming the supramolecular structure, we synthetically modified the dendron, rod, and coil portions. The self-assembly depended on the generation number of the dendron, the number of hydrogen-bonding functions, and the length of the rod and coil segments. We formed chiral helices using a dendron–rod–coil molecule prepared from an enantiomerically enriched coil. Because helical nanostructures are important targets for use in biomaterials, nonlinear optics, and stereoselective catalysis, researchers would like to precisely control their shape and size. Tripeptide-containing peptide lipid molecules assemble into straight or twisted nanofibers in organic solvents. As seen by AFM, the sterics of bulky end groups can tune the helical pitch of these peptide lipid nanofibers in organic solvents. Furthermore, we demonstrated the potential for pitch control using trans-to-cis photoisomerization of a terminal azobenzene group. Other molecules called peptide amphiphiles (PAs) are known to assemble in water into cylindrical nanostructures that appear as nanofiber bundles. Surprisingly, TEM of a PA substituted by a nitrobenzyl group revealed assembly into quadruple helical fibers with a braided morphology. Upon photocleavage of this the nitrobenzyl group, the helices transform into single cylindrical nanofibers. Finally, inspired by the tobacco mosaic virus, we used a dumbbell-shaped, oligo(phenylene ethynylene) template to control the length of a PA nanofiber self-assembly (<10 nm). AFM showed complete disappearance of long nanofibers in the presence of this rigid-rod template. Results from quick-freeze/deep-etch TEM and dynamic light scattering demonstrated the templating behavior in aqueous solution. This strategy could provide a general method to control size the length of non-spherical supramolecular nanostructures. PMID:18754628

PALMER, LIAM C.; STUPP, SAMUEL I.

2008-01-01

341

Nanoscale templating and self-assembly of organic semiconductors  

NASA Astrophysics Data System (ADS)

Improvements in organic electronic materials could lead to novel device applications, ranging from large-area, flexible displays to light weight, plastic electronics. Progress on these applications would benefit from development of low-cost, aqueous, solution-based fabrication techniques for organic semiconductors. Supramolecular self-assembly enables molecules to organize in complex structures through non-covalent interactions. The nanoscale structure and aggregation of organic semiconductors influence conductivity, charge mobility and luminescence. We developed three approaches to enhance the performance of organic semiconductors through molecular self-assembly. The first uses a liquid crystalline (LC) template to mediate electrochemical polymerization of poly(3,4-ethyldioxythiophene) (PEDOT), a conducting polymer used for hole injection in organic light emitting diodes (OLED). Monomers were polymerized in the cylindrical, hydrophobic cores of a hexagonal, lyotropic LC formed by a non-ionic amphiphile in water, The templated, conducting polymer films exhibited anisotropic optical properties and increased conductivity as a direct result of the nanoscale, self-organized structure of the template. Another approach was used to control molecular order by preparing organic semiconductors that are themselves liquid crystalline. We developed a novel series of triblock oligo(phenylene vinylene) (OPV) amphiphiles that form thermotropic and lyotropic LC mesophases. The self-organized, layered structure of these mesophases influences aggregation of OPV, enhancing fluorescence in the liquid crystalline state compared with disordered films. These OPV-amphiphiles are the first example of a water-soluble oligo(phenylene vinylene) that can self-organize into aligned, well-ordered, highly fluorescent films. In a third system, a triblock, dendron rod-coil (DRC) molecule containing a quaterthiophene segment was prepared and its self-assembly and electronic properties investigated. In non-polar solvents, this molecule formed high aspect ratio, supramolecular nanowires containing stacked oligo(thiophene) segments. These self-assembled nanowires formed conductive films that were aligned by an electric field. Using these three systems, we demonstrate how nanoscale templating and self-assembly can enhance the performance of thiophene- and phenylene vinylene-based organic semiconductors.

Hulvat, James Francis

342

Translational regulation of light-harvesting complex expression during photoacclimation to high-light in  Chlamydomonas reinhardtii  

Microsoft Academic Search

When challenged with excess light, the green alga Chlamydomonas reinhardtii responds, in part, by down-regulating light harvesting capacity at Photosystem II while concomitantly reorganising cellular metabolism to increase sink capacity. We examined the role of translational control during different stages of photoacclimation by analysing polysome profiles of two different light-harvesting complex (LHC) genes encoding a major LHCII component (Lhcbm) and CP29

S. M. McKim; D. G. Durnford

2006-01-01

343

The genes encoding light-harvesting subunits of Cyclotella cryptica (Bacillariophyceae) constitute a complex and heterogeneous family  

Microsoft Academic Search

Total RNA was isolated from the diatom Cyclotella cryptica and separated into poly(A)+ and poly(A)? fractions. These fractions were subjected to in vitro translation\\/immunoprecipitation experiments using an antiserum directed\\u000a against the predominant light-harvesting complex of Cy. cryptica (ccry antiserum) and a heterologous antiserum raised against the light-harvesting complex of the cryptophyte Cryptomonas maculata (cmac antiserum). From translation reactions programmed with

M. Eppard; E. Rhiel

1998-01-01

344

Functional and mutational analysis of the light-harvesting chlorophyll a\\/b protein of thylakoid membranes  

Microsoft Academic Search

The precursor for a Lemna light-harvesting chlorophyll a\\/b protein (pLHCP) has been synthe- sized in vitro from a single member of the nuclear LHCP multigene family. We report the sequence of this gene. When incubated with Lemna chloroplasts, the pLHCP is imported and processed into several polypeptides, and the mature form is assembled into the light-harvesting complex of photosystem II

Bruce D. Kohorn; Eitan Hard; Parag R. Chitnis; J. Philip Thornber; Elaine M. Tobin

1986-01-01

345

Combustion and self-assembly of nanoenergetic materials  

NASA Astrophysics Data System (ADS)

The recent worldwide interest in nanotechnology spans a wide variety of scientific fields such as electronics, biology, materials science and medicine. Because of their extremely small dimensions, nanoparticles demonstrate properties different from matter at larger scales. Understanding these unusual properties and utilizing them for macroscale devices is an overall goal for nanotechnology. Moreover, manipulating these small particles into organized structures is crucial for taking full advantage of what nanotechnology has to offer, however it has proven to be a difficult task. Recent work utilizing electrostatic forces shows great potential for the self-assembly of nanoparticles into organized two-dimensional and three-dimensional structures. Overall, this work examines how nanotechnology and self-assembly can benefit the field of energetic materials. Because of aluminum's high energy density and low cost, it has been used in the field of energetic materials for several decades. In order to achieve sufficient energy release rates, aluminum is typically manufactured as a powder having spherical particles with diameters on the micron scale. It is well-known that decreasing the original particle diameter of a fuel particle will increase the burning time and, thus, energy release rate. Therefore, aluminum particles have recently been made to have diameters on the nanoscale, and shown to be advantageous for several applications. The combustion of nanoaluminum (nAl) in various systems is the primary focus of this study. A progression of experiments is used to analyze the combustion of nAl: (1) a fully heterogeneous flame spread system, (2) a semi-homogeneous sonicated thermite system and (3) a quasi-homogeneous self-assembled thermite system. The flame spread experiment physically separates the nAl from the gaseous oxidizer allowing for a well-understood convective, diffusive, reactive system to be analyzed. Because of the simplicity of the experimental setup, variables are easily changed and their effects on the flame spread rate are observed. Overall, spread rates are 2 to 3 orders of magnitude greater than what is demonstrated with typical solid fuels due to the high reactivity of the nAl. This large difference in spread rate brings about a fingering combustion instability in normal gravity conditions that has only been shown to occur in microgravity conditions. Moreover, a stability map is created based on the nondimensional Lewis and Damkohler numbers that predicts when a continuous flame front will transition to a fingering instability. This, along with the various other trends, is predicted using a simple scaling analysis. A nanoscale thermite is created via sonication of nAl and nanocopper-oxide (nCuO) particles. Although the mixture is unorganized and random, these materials boast extremely exothermic reactions with propagation rates on the order of 1 km/s. Experiments are performed to examine the effect of adding a diluent to the system. Two types of materials are added, a stable end product, aluminum-oxide, and long alkyl chain hydrocarbons. Both materials severely hinder the propagation rate, however, experiments suggest that hydrocarbon addition could help with the material's sensitivity to electrostatic discharge. Equilibrium calculations suggest that a dual temperature and gas production criteria must be met to allow for the convective propagation mechanism to take place and fast propagation rates to occur. Because of the hydrocarbons required for self-assembly, these experiments also give an indication of how the self-assembled material will react. To electrostatically self-assemble a nAl/nCuO thermite, the constituents are first coated with an o-functionalized alkyl chain ligand and suspended in a separate solutions. Upon mixing, the opposite electrostatic charges agglomerate the two constituents, which subsequently precipitate out of solution. Analyzing the material with Scanning Electron Microscopy shows that a portion has self-assembled into microspheres having diameters from 1-5mum. This is the first know

Malchi, Jonathan Yaniv

346

Self-assembly triggered by self-assembly: optically active, paramagnetic micelles encapsulated in protein cage nanoparticles.  

PubMed

In this contribution, optically active and paramagnetic micelles of the ligand 1,4,7,10-tetraaza-1-(1-carboxymethylundecane)-4,7,10-triacetic acid cyclododecane (DOTAC10) have been incorporated inside capsids of the cowpea chlorotic mottle virus (CCMV) protein through a hierarchical process of self-assembly triggered by self-assembly. The DOTAC10 ligand was used to complex Gd(III), in order to form paramagnetic micelles, as well as to encapsulate an amphiphilic Zn(II) phthalocyanine (ZnPc) dye that optically confirmed the encapsulation of the micelles. The incorporation of ZnPc molecules in the paramagnetic micelles led to high capsid loading of both Gd(III) and ZnPc, as the micelles were stabilized by the amphiphilic dye encapsulation. The resulting protein cage nanoparticles (PCNs) show an improved r1 relaxivity, suggesting the possible use of these nanostructures as contrast agents (CAs) for magnetic resonance imaging (MRI). Since the encapsulated ZnPc dye also has a potential therapeutic value, the present results represent a first step towards the consecution of fully self-assembled PCNs for multimodal imaging and therapy. PMID:24513535

Millán, Jealemy Galindo; Brasch, Melanie; Anaya-Plaza, Eduardo; de la Escosura, Andrés; Velders, Aldrik H; Reinhoudt, David N; Torres, Tomás; Koay, Melissa S T; Cornelissen, Jeroen J L M

2014-07-01

347

Towards in vivo mutation analysis: knock-out of specific chlorophylls bound to the light-harvesting complexes of Arabidopsis thaliana - the case of CP24 (Lhcb6).  

PubMed

In the last ten years, a large series of studies have targeted antenna complexes of plants (Lhc) with the aim of understanding the mechanisms of light harvesting and photoprotection. Combining spectroscopy, modeling and mutation analyses, the role of individual pigments in these processes has been highlighted in vitro. In plants, however, these proteins are associated with multiple complexes of the photosystems and function within this framework. In this work, we have envisaged a way to bridge the gap between in vitro and in vivo studies by knocking out in vivo pigments that have been proposed to play an important role in excitation energy transfer between the complexes or in photoprotection. We have complemented a CP24 knock-out mutant of Arabidopsis thaliana with the CP24 (Lhcb6) gene carrying a His-tag and with a mutated version lacking the ligand for chlorophyll 612, a specific pigment that in vitro experiments have indicated as the lowest energy site of the complex. Both complexes efficiently integrated into the thylakoid membrane and assembled into the PSII supercomplexes, indicating that the His-tag does not impair the organization in vivo. The presence of the His-tag allowed the purification of CP24-WT and of CP24-612 mutant in their native states. It is shown that CP24-WT coordinates 10 chlorophylls and 2 carotenoid molecules and has properties identical to those of the reconstituted complex, demonstrating that the complex self-assembled in vitro assumes the same folding as in the plant. The absence of the ligand for chlorophyll 612 leads to the loss of one Chl a and of lutein, again as in vitro, indicating the feasibility of the method. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. PMID:24561227

Passarini, Francesca; Xu, Pengqi; Caffarri, Stefano; Hille, Jacques; Croce, Roberta

2014-09-01

348

Iterative linearized density matrix propagation for modeling coherent excitation energy transfer in photosynthetic light harvesting.  

PubMed

Rather than incoherent hopping between chromophores, experimental evidence suggests that the excitation energy transfer in some biological light harvesting systems initially occurs coherently, and involves coherent superposition states in which excitation spreads over multiple chromophores separated by several nanometers. Treating such delocalized coherent superposition states in the presence of decoherence and dissipation arising from coupling to an environment is a significant challenge for conventional theoretical tools that either use a perturbative approach or make the Markovian approximation. In this paper, we extend the recently developed iterative linearized density matrix (ILDM) propagation scheme [E. R. Dunkel et al., J. Chem. Phys. 129, 114106 (2008)] to study coherent excitation energy transfer in a model of the Fenna-Matthews-Olsen light harvesting complex from green sulfur bacteria. This approach is nonperturbative and uses a discrete path integral description employing a short time approximation to the density matrix propagator that accounts for interference between forward and backward paths of the quantum excitonic system while linearizing the phase in the difference between the forward and backward paths of the environmental degrees of freedom resulting in a classical-like treatment of these variables. The approach avoids making the Markovian approximation and we demonstrate that it successfully describes the coherent beating of the site populations on different chromophores and gives good agreement with other methods that have been developed recently for going beyond the usual approximations, thus providing a new reliable theoretical tool to study coherent exciton transfer in light harvesting systems. We conclude with a discussion of decoherence in independent bilinearly coupled harmonic chromophore baths. The ILDM propagation approach in principle can be applied to more general descriptions of the environment. PMID:21073214

Huo, P; Coker, D F

2010-11-14

349

In Vitro Reconstitution of Light-harvesting Complexes of Plants and Green Algae.  

PubMed

In plants and green algae, light is captured by the light-harvesting complexes (LHCs), a family of integral membrane proteins that coordinate chlorophylls and carotenoids. In vivo, these proteins are folded with pigments to form complexes which are inserted in the thylakoid membrane of the chloroplast. The high similarity in the chemical and physical properties of the members of the family, together with the fact that they can easily lose pigments during isolation, makes their purification in a native state challenging. An alternative approach to obtain homogeneous preparations of LHCs was developed by Plumley and Schmidt in 1987(1), who showed that it was possible to reconstitute these complexes in vitro starting from purified pigments and unfolded apoproteins, resulting in complexes with properties very similar to that of native complexes. This opened the way to the use of bacterial expressed recombinant proteins for in vitro reconstitution. The reconstitution method is powerful for various reasons: (1) pure preparations of individual complexes can be obtained, (2) pigment composition can be controlled to assess their contribution to structure and function, (3) recombinant proteins can be mutated to study the functional role of the individual residues (e.g., pigment binding sites) or protein domain (e.g., protein-protein interaction, folding). This method has been optimized in several laboratories and applied to most of the light-harvesting complexes. The protocol described here details the method of reconstituting light-harvesting complexes in vitro currently used in our laboratory, and examples describing applications of the method are provided. PMID:25350712

Natali, Alberto; Roy, Laura M; Croce, Roberta

2014-01-01

350

Neutron and light scattering studies of light-harvesting photosynthetic antenna complexes.  

PubMed

Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) have been employed in studying the structural information of various biological systems, particularly in systems without high-resolution structural information available. In this report, we briefly present some principles and biological applications of neutron scattering and DLS, compare the differences in information that can be obtained with small-angle X-ray scattering (SAXS), and then report recent studies of SANS and DLS, together with other biophysical approaches, for light-harvesting antenna complexes and reaction centers of purple and green phototrophic bacteria. PMID:21710338

Tang, Kuo-Hsiang; Blankenship, Robert E

2012-03-01

351

Long-distance electronic energy transfer in light-harvesting supramolecular polymers.  

PubMed

The efficient collection of solar energy relies on the design and construction of well-organized light-harvesting systems. Herein we report that supramolecular phenanthrene polymers doped with pyrene are effective collectors of light energy. The linear polymers are formed through the assembly of short amphiphilic oligomers in water. Absorption of light by phenanthrene residues is followed by electronic energy transfer along the polymer over long distances (>100?nm) to the accepting pyrene molecules. The high efficiency of the energy transfer, which is documented by large fluorescence quantum yields, suggests a quantum coherent process. PMID:25345576

Winiger, Christian B; Li, Shaoguang; Kumar, Ganesh R; Langenegger, Simon M; Häner, Robert

2014-12-01

352

Path induced coherent energy transfer in light-harvesting complexes in purple bacteria  

NASA Astrophysics Data System (ADS)

Features of path dependent energy transfer in a dual-ring light-harvesting (LH2) complexes (B850) system have been examined in detail systematically. The Frenkel-Dirac time dependent variational method with the Davydov D1 Ansatz is employed with detailed evolution of polaron dynamics in real space readily obtained. It is found that the phase of the transmission amplitude through the LH2 complexes plays an important role in constructing the coherent excitonic energy transfer. It is also found that the symmetry breaking caused by the dimerization of bacteriochlorophylls and coherence or correlation between two rings will be conducive in enhancing the exciton transfer efficiency.

Sun, Kewei; Ye, Jun; Zhao, Yang

2014-09-01

353

Light-harvesting in bacteria exploits a critical interplay between transport and trapping dynamics  

E-print Network

Light-harvesting bacteria Rhodospirillum Photometricum were recently found to adopt strikingly different architectures depending on illumination conditions. We present analytic and numerical calculations which explain this observation by quantifying a dynamical interplay between excitation transfer kinetics and reaction center cycling. High light-intensity membranes (HLIM) exploit dissipation as a photo-protective mechanism, thereby safeguarding a steady supply of chemical energy, while low light-intensity membranes (LLIM) efficiently process unused illumination intensity by channelling it to open reaction centers. More generally, our analysis elucidates and quantifies the trade-offs in natural network design for solar energy conversion.

Felipe Caycedo-Soler; Ferney J. Rodriguez; Luis Quiroga; Neil F. Johnson

2010-03-11

354

Fluorescence enhancement of light-harvesting complex 2 from purple bacteria coupled to spherical gold nanoparticles  

NASA Astrophysics Data System (ADS)

The influence of plasmon excitations in spherical gold nanoparticles on the optical properties of a light-harvesting complex 2 (LH2) from the purple bacteria Rhodopseudomonas palustris has been studied. Systematic analysis is facilitated by controlling the thickness of a silica layer between Au nanoparticles and LH2 complexes. Fluorescence of LH2 complexes features substantial increase when these complexes are separated by 12 nm from the gold nanoparticles. At shorter distances, non-radiative quenching leads to a decrease of fluorescence emission. The enhancement of fluorescence originates predominantly from an increase of absorption of pigments comprising the LH2 complex.

Bujak, ?.; Czechowski, N.; Piatkowski, D.; Litvin, R.; Mackowski, S.; Brotosudarmo, T. H. P.; Cogdell, R. J.; Pichler, S.; Heiss, W.

2011-10-01

355

Coherence dynamics in light-harvesting complexes with two-colour spectroscopy  

NASA Astrophysics Data System (ADS)

We investigate coherent dynamics in the cryptophyte light-harvesting complex Phycocyanin-645 (PC-645). A two-colour four-wave mixing experiment allows us to isolate a coherence pathway and observe its evolution in the absence of other signals. We measured a decoherence time of 540fs for the coherence [1]. Additionally oscillations in the signal pathway give evidence for the coherent excitation of states outside the bandwidth of the laser pulse. This suggests strong coupling between the excited states and phonon modes [1].

Richards, Gethin H.; Curmi, Paul M. G.; Wilk, Krystyna E.; Quiney, Harry M.; Davis, Jeffrey A.

2013-03-01

356

Self-assembly of amphiphilic molecules in organic liquids  

NASA Astrophysics Data System (ADS)

Amphiphilic molecules are well-known for their ability to self-assemble in water to form structures such as micelles and vesicles. In comparison, much less is known about amphiphilic self-assembly in nonpolar organic liquids. Such "reverse" self assembly can produce many of the counterparts to structures found in water. In this dissertation, we focus on the formation and dynamics of such reverse structures. We seek to obtain fundamental insight into the driving forces for reverse self-assembly processes. Three specific types of reverse structures are studied: (a) reverse wormlike micelles, i.e., long, flexible micellar chains; (b) reverse vesicles, i.e., hollow containers enclosed by reverse bilayers; and (c) organogel networks. While our focus is on the fundamentals, we note that reverse structures can be useful in a variety of applications ranging from drug delivery, controlled release, hosts for enzymatic reactions, and templates for nanomaterials synthesis. In the first part of this study, we describe a new route for forming reverse wormlike micelles in nonpolar organic liquids. This route involves the addition of trace amounts of a bile salt to solutions of the phospholipid, lecithin. We show that bile salts, due to their unique "facially amphiphilic" structure, can promote the aggregation of lecithin molecules into these reverse micellar chains. The resulting samples are viscoelastic and show interesting rheological properties. Unusual trends are seen in the temperature dependence of their rheology, which indicates the importance of hydrogen-bonding interactions in the formation of these micelles. Another remarkable feature of their rheology is the presence of strain-stiffening, where the material becomes stiffer at high deformations. Strain-stiffening has been seen before for elastic gels of biopolymers; here, we demonstrate the same properties for viscoelastic micellar solutions. The second reverse aggregate we deal with is the reverse vesicle. We present a new route for forming stable unilamellar reverse vesicles, and this involves mixing short- and long-chain lipids (lecithins) with a trace of sodium chloride. The ratio of the short to long-chain lipid controls the type and size of self-assembled structure formed, and as this ratio is increased, a transition from reverse micelles to vesicles occurs. The structural changes can be explained in terms of molecular geometry, with the sodium chloride acting as a "glue" in binding lipid headgroups together through electrostatic interactions. The final part of this dissertation focuses on organogels. The two-tailed anionic surfactant, AOT, is well-known to form spherical reverse micelles in organic solvents. We have found that trace amounts (e.g., less than 1 mM) of the dihydroxy bile salt, sodium deoxycholate (SDC) can transform these dilute micellar solutions into self-supporting, transparent organogels. The structure and rheology of these organogels is reminiscent of the self-assembled networks formed by proteins such as actin in water. The organogels are based on networks of long, rigid, cylindrical filaments, with SDC molecules stacked together in the filament core.

Tung, Shih-Huang

357

Self-Assembly of Heterogeneously Charged Particles under Confinement  

PubMed Central

Self-assembly—the spontaneous organization of microscopic units into well-defined mesoscopic structures—is a fundamental mechanism for a broad variety of nanotechnology applications in material science. The central role played by the anisotropy resulting from asymmetric shapes of the units and/or well-defined bonding sites on the particle surface has been widely investigated, highlighting the importance of properly designing the constituent entities in order to control the resulting mesoscopic structures. Anisotropy driven self-assembly can also result from the multipolar interactions characterizing many naturally occurring systems, such as proteins and viral capsids, as well as experimentally synthesized colloidal particles. Heterogeneously charged particles represent a class of multipolar units that are characterized by a competitive interplay between anisotropic attractive and repulsive interactions, due to the repulsion/attraction between charged-like/oppositely charged regions on the particle surface. In the present work, axially symmetric quadrupolar colloids are considered in a confined planar geometry; the role of both the overall particle charge and the patch extension as well as the effect of the substrate charge are studied in thermodynamic conditions such that the formation of extended structures is favored. A general tendency to form quasi-two-dimensional aggregates where particles align their symmetry axes within the plane is observed; among these planar self-assembled scenarios, a clear distinction between the formation of microcrystalline gels—branched networks consisting of purely crystalline domains—as opposed to disordered aggregates can be observed based on the specific features of the particle–particle interaction. Additionally, the possible competition of interparticle and particle–substrate interactions affects the size and the internal structure of the aggregates and can possibly inhibit the aggregation process. PMID:23627740

2013-01-01

358

Bacterial expression of self-assembling peptide hydrogelators  

NASA Astrophysics Data System (ADS)

For tissue regeneration and drug delivery applications, various architectures are explored to serve as biomaterial tools. Via de novo design, functional peptide hydrogel materials have been developed as scaffolds for biomedical applications. The objective of this study is to investigate bacterial expression as an alternative method to chemical synthesis for the recombinant production of self-assembling peptides that can form rigid hydrogels under physiological conditions. The Schneider and Pochan Labs have designed and characterized a 20 amino acid beta-hairpin forming amphiphilic peptide containing a D-residue in its turn region (MAX1). As a result, this peptide must be prepared chemically. Peptide engineering, using the sequence of MAX1 as a template, afforded a small family of peptides for expression (EX peptides) that have different turn sequences consisting of natural amino acids and amenable to bacterial expression. Each sequence was initially chemically synthesized to quickly assess the material properties of its corresponding gel. One model peptide EX1, was chosen to start the bacterial expression studies. DNA constructs facilitating the expression of EX1 were designed in such that the peptide could be expressed with different fusion partners and subsequently cleaved by enzymatic or chemical means to afford the free peptide. Optimization studies were performed to increase the yield of pure peptide that ultimately allowed 50 mg of pure peptide to be harvested from one liter of culture, providing an alternate means to produce this hydrogel-forming peptide. Recombinant production of other self-assembling hairpins with different turn sequences was also successful using this optimized protocol. The studies demonstrate that new beta-hairpin self-assembling peptides that are amenable to bacterial production and form rigid hydrogels at physiological conditions can be designed and produced by fermentation in good yield at significantly reduced cost when compared to chemical synthesis.

Sonmez, Cem

359

Self-assembly of free-standing RNA membranes  

NASA Astrophysics Data System (ADS)

RNA has emerged as a promising material for nanostructure and microstructure engineering. Although rare, some macroscopic RNA structures have also been constructed using lipid or polymer materials. Here, we report the first example of an enzymatically generated RNA membrane. This robust and free-standing RNA membrane has a macroscopic structure and is generated without any polymer support or complexation. Our RNA membrane is fabricated following two sequential processes, complementary rolling circle transcription and evaporation-induced self-assembly, and its structural and functional properties are rationally controlled by adjusting RNA base pairing. In this study, three types of RNA membranes are fabricated and are used to demonstrate potential applications.

Han, Daehoon; Park, Yongkuk; Kim, Hyejin; Lee, Jong Bum

2014-07-01

360

Energy levels in self-assembled quantum arbitrarily shaped dots.  

PubMed

A model to determine the electronic structure of self-assembled quantum arbitrarily shaped dots is applied. This model is based principally on constant effective mass and constant potentials of the barrier and quantum dot material. An analysis of the different parameters of this model is done and compared with those which take into account the variation of confining potentials, bands, and effective masses due to strain. The results are compared with several spectra reported in literature. By considering the symmetry, the computational cost is reduced with respect to other methods in literature. In addition, this model is not limited by the geometry of the quantum dot. PMID:15740390

Tablero, C

2005-02-01

361

Optical Metamaterials by Block-Copolymer Self-Assembly  

E-print Network

properties of the gyroid metamaterial by altering the structural parameters and the surrounding medium. A further development in the gyroid fabrication has led to the so-called hollow gyroid, presented in Chapter 5. The gyroid morphology was produced... . The block copolymer were supplied as a powder in an amorphous state. After the annealing and the self-assembly the PI phase was selectively removed by UV radiation (at 254 nm for 2 hours) to break the carbon-carbon double bonds of the polyisoprene. The film...

Salvatore, Stefano

2014-05-27

362

Model for dynamic self-assembled magnetic surface structures.  

PubMed

We propose a first-principles model for the dynamic self-assembly of magnetic structures at a water-air interface reported in earlier experiments. The model is based on the Navier-Stokes equation for liquids in shallow water approximation coupled to Newton equations for interacting magnetic particles suspended at a water-air interface. The model reproduces most of the observed phenomenology, including spontaneous formation of magnetic snakelike structures, generation of large-scale vortex flows, complex ferromagnetic-antiferromagnetic ordering of the snake, and self-propulsion of bead-snake hybrids. PMID:20866678

Belkin, M; Glatz, A; Snezhko, A; Aranson, I S

2010-07-01

363

Self-assembled GaN hexagonal micropyramid and microdisk  

NASA Astrophysics Data System (ADS)

The self-assembled GaN hexagonal micropyramid and microdisk were grown on LiAlO2 by plasma-assisted molecular-beam epitaxy. It was found that the (0001¯) disk was established with the capture of N atoms by most-outside Ga atoms as the (1×1) surface was constructing, while the pyramid was obtained due to the missing of most-outside N atoms. The intensity of cathode luminescence excited from the microdisk was one order of amplitude greater than that from M-plane GaN.

Lo, Ikai; Hsieh, Chia-Ho; Hsu, Yu-Chi; Pang, Wen-Yuan; Chou, Ming-Chi

2009-02-01

364

Self-assembly of silk fibroin under osmotic stress  

NASA Astrophysics Data System (ADS)

The supramolecular self-assembly behavior of silk fibroin was investigated using osmotic stress technique. In Chapter 2, a ternary phase diagram of water-silk-LiBr was constructed based on X-ray results on the osmotically stressed regenerated silk fibroin of Bombyx mori silkworm. Microscopic data indicated that silk I is a hydrated structure and a rough estimate of the number of water molecules lost by the structure upon converting from silk I to silk II has been made, and found to be about 2.2 per [GAGAGS] hexapeptide. In Chapter 3, wet-spinning of osmotically stressed, regenerated silk fibroin was performed, based on the prediction that the enhanced control over structure and phase behavior using osmotic stress method helps improve the physical properties of wet-spun regenerated silk fibroin fibers. The osmotic stress was applied in order to pre-structure the regenerated silk fibroin molecule from its original random coil state to more oriented state, manipulating the phase of the silk solution in the phase diagram before the start of spinning. Monofilament fiber with a diameter of 20 microm was produced. In Chapter 4, we investigated if there is a noticeable synergistic osmotic pressure increase between co-existing polymeric osmolyte and salt when extremely highly concentrated salt molecules are present both at sample subphase and stressing subphase, as is the case of silk fibroin self-assembly. The equilibration method that measures osmotic pressure relative to a reference with known osmotic pressure was introduced. Osmotic pressure of aqueous LiBr solution up to 2.75M was measured and it was found that the synergistic effect was insignificant up to this salt concentration. Solution parameters of stressing solutions and Arrhenius kinetics based on time-temperature relationship for the equilibration process were derived as well. In Chapter 5, self-assembly behavior of natural silk fibroin within the gland of Bombyx mori silkworm was investigated using osmotic stress technique. Microscopic and thermodynamic details of this self-assembly process along the spinline have been assessed. Formation of a needle-shaped molecular lath under appropriate osmotic stress was found. Silk I degree of hydration of silk gland was quantitatively estimated by image analysis of optical micrographs and the numbers varied from 2.2 to 2.7 depending on the region in the gland. Osmotic pressure in the gland was also estimated by equilibration method.

Sohn, Sungkyun

365

Buckling instability of self-assembled colloidal columns.  

PubMed

Suspended, slender self-assembled domains of magnetically responsive colloids are observed to buckle in microgravity. Upon cessation of the magnetic field that drives their assembly, these columns expand axially and buckle laterally. This phenomenon resembles the buckling of long beams due to thermal expansion; however, linear stability analysis predicts that the colloidal columns are inherently susceptible to buckling because they are freely suspended in a Newtonian fluid. The dominant buckling wavelength increases linearly with column thickness and is quantitatively described using an elastohydrodynamic model and the suspension thermodynamic equation of state. PMID:25302919

Swan, James W; Vasquez, Paula A; Furst, Eric M

2014-09-26

366

Buckling Instability of Self-Assembled Colloidal Columns  

NASA Astrophysics Data System (ADS)

Suspended, slender self-assembled domains of magnetically responsive colloids are observed to buckle in microgravity. Upon cessation of the magnetic field that drives their assembly, these columns expand axially and buckle laterally. This phenomenon resembles the buckling of long beams due to thermal expansion; however, linear stability analysis predicts that the colloidal columns are inherently susceptible to buckling because they are freely suspended in a Newtonian fluid. The dominant buckling wavelength increases linearly with column thickness and is quantitatively described using an elastohydrodynamic model and the suspension thermodynamic equation of state.

Swan, James W.; Vasquez, Paula A.; Furst, Eric M.

2014-09-01

367

Customizing mesoscale self-assembly with 3D printing  

E-print Network

Self-assembly due to capillary forces is a common method for generating 2D mesoscale structures from identical floating particles at the liquid-air interface. Designing building blocks to obtain a desired mesoscopic structure is a scientific challenge. We show herein that it is possible to shape the particles with a low cost 3D printer, for composing specific mesoscopic structures. Our method is based on the creation of capillary multipoles inducing either attractive or repulsive forces. Since capillary interactions can be downscaled, our method opens new ways to low cost microfabrication.

M. Poty; G. Lumay; N. Vandewalle

2013-10-17

368

Redox control of GPx catalytic activity through mediating self-assembly of Fmoc-phenylalanine selenide into switchable supramolecular architectures.  

PubMed

Artificial enzymes capable of achieving tunable catalytic activity through stimuli control of enzymatic structure transition are of significance in biosensor and biomedicine research. Herein we report a novel smart glutathione peroxidise (GPx) mimic with modulatory catalytic activity based on redox-induced supramolecular self-assembly. First, an amphiphilic Fmoc-phenylalanine-based selenide was designed and synthesized, which can self-assemble into nanospheres (NSs) in aqueous solution. The NSs demonstrate extremely low GPx activity. Upon the oxidation of hydroperoxides (ROOH), the selenide can be quickly transformed into the selenoxide form. The change of the molecular structure induces complete morphology transition of the self-assemblies from NSs to nanotubes (NTs), resulting in great enhancement in the GPx catalytic activity. Under the reduction of GSH, the selenoxide can be further reversibly reduced back into the selenide; therefore the reversible switch between the NSs and NTs can be successfully accomplished. The relationship between the catalytic activity and enzymatic structure was also investigated. The dual response nature makes this mimic play roles of both a sensor and a GPx enzyme at the same time, which can auto-detect the signal of ROOH and then auto-change its activity to achieve quick or slow/no scavenging of ROOH. The dynamic balance of ROOH is vital in organisms, in which an appropriate amount of ROOH does benefit to the metabolism, whereas surplus ROOH can cause oxidative damage of the cell instead and this smart mimic is of remarkable significance. We expect that such a mimic can be developed into an effective antioxidant drug and provide a new platform for the construction of intelligent artificial enzymes with multiple desirable properties. PMID:25366375

Huang, Zupeng; Luo, Quan; Guan, Shuwen; Gao, Jianxiong; Wang, Yongguo; Zhang, Bo; Wang, Liang; Xu, Jiayun; Dong, Zeyuan; Liu, Junqiu

2014-11-19

369

Biocompatible or biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications.  

PubMed

Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes. The primary self-assemblies can be further assembled into more complex structures through hierachical self-assembly processes. Besides, the hyperbranched polymer vesicles have demonstrated great potential to be used as model membranes to mimic cellular behaviors, such as fusion, fission and cell aggregation. Other biomedical applications of HBPs as well as their self-assemblies are also briefly summarized. PMID:22797315

Jin, Haibao; Huang, Wei; Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue

2012-09-21

370

Molecular self-assembly routes to optically functional thin films: Electroluminescent multilayer structures  

SciTech Connect

This contribution describes the use of layer-by-layer self-limiting siloxane chemisorption processes to self-assemble structurally regular multilayer organic LED (OLED) devices. Topics discussed include: (1) the synthesis of silyl-functionalized precursor molecules for hole transport layer (HTL), emissive layer (EML), and electron transport layer (ETL) self-assembly, (2) the use of layer-by-layer self-assembly for ITO electrode modification/passivation/hole-electron balancing in a vapor-deposited device, (3) the microstructure/chemical characterization of HTL self-assembly using a prototype triarylamine precursor, (4) fabrication and properties of a hybrid self-assembled + vapor deposited two-layer LED, and (5) fabrication and properties of a fully self-assembled two-layer OLED.

Li, W.; Malinsky, J.E.; Chou, H. [and others

1998-07-01

371

Lutein epoxide cycle, light harvesting and photoprotection in species of the tropical tree genus Inga.  

PubMed

Dynamics and possible function of the lutein epoxide (Lx) cycle, that is, the reversible conversion of Lx to lutein (L) in the light-harvesting antennae, were investigated in leaves of tropical tree species. Photosynthetic pigments were quantified in nine Inga species and species from three other genera. In Inga, Lx levels were high in shade leaves (mostly above 20 mmol mol(-1) chlorophyll) and low in sun leaves. In Virola surinamensis, both sun and shade leaves exhibited very high Lx contents (about 60 mmol mol(-1) chlorophyll). In Inga marginata grown under high irradiance, Lx slowly accumulated within several days upon transfer to deep shade. When shade leaves of I. marginata were briefly exposed to the sunlight, both violaxanthin and Lx were quickly de-epoxidized. Subsequently, overnight recovery occurred only for violaxanthin, not for Lx. In such leaves, containing reduced levels of Lx and increased levels of L, chlorophyll fluorescence induction showed significantly slower reduction of the photosystem II electron acceptor, Q(A), and faster formation as well as a higher level of non-photochemical quenching. The results indicate that slow Lx accumulation in Inga leaves may improve light harvesting under limiting light, while quick de-epoxidation of Lx to L in response to excess light may enhance photoprotection. PMID:18208510

Matsubara, Shizue; Krause, G Heinrich; Seltmann, Martin; Virgo, Aurelio; Kursar, Thomas A; Jahns, Peter; Winter, Klaus

2008-04-01

372

Excited state dynamics in photosynthetic reaction center and light harvesting complex 1.  

PubMed

Key to efficient harvesting of sunlight in photosynthesis is the first energy conversion process in which electronic excitation establishes a trans-membrane charge gradient. This conversion is accomplished by the photosynthetic reaction center (RC) that is, in case of the purple photosynthetic bacterium Rhodobacter sphaeroides studied here, surrounded by light harvesting complex 1 (LH1). The RC employs six pigment molecules to initiate the conversion: four bacteriochlorophylls and two bacteriopheophytins. The excited states of these pigments interact very strongly and are simultaneously influenced by the surrounding thermal protein environment. Likewise, LH1 employs 32 bacteriochlorophylls influenced in their excited state dynamics by strong interaction between the pigments and by interaction with the protein environment. Modeling the excited state dynamics in the RC as well as in LH1 requires theoretical methods, which account for both pigment-pigment interaction and pigment-environment interaction. In the present study we describe the excitation dynamics within a RC and excitation transfer between light harvesting complex 1 (LH1) and RC, employing the hierarchical equation of motion method. For this purpose a set of model parameters that reproduce RC as well as LH1 spectra and observed oscillatory excitation dynamics in the RC is suggested. We find that the environment has a significant effect on LH1-RC excitation transfer and that excitation transfers incoherently between LH1 and RC. PMID:22897312

Strümpfer, Johan; Schulten, Klaus

2012-08-14

373

Characterization of nanoporous gold disks for photothermal light harvesting and light-gated molecular release  

NASA Astrophysics Data System (ADS)

Nanoporous gold disks (NPGDs) with 400 nm diameter, 75 nm thickness, and 13 nm pores exhibit large specific surface area and effective photothermal light harvesting capability with a conversion efficiency of 56%. A potential application is demonstrated by light-gated, multi-step molecular release of the pre-adsorbed R6G fluorescent dye on arrayed NPGDs.Nanoporous gold disks (NPGDs) with 400 nm diameter, 75 nm thickness, and 13 nm pores exhibit large specific surface area and effective photothermal light harvesting capability with a conversion efficiency of 56%. A potential application is demonstrated by light-gated, multi-step molecular release of the pre-adsorbed R6G fluorescent dye on arrayed NPGDs. Electronic supplementary information (ESI) available: Chemicals and materials used in NPGD fabrication, thermal imaging, SEM images and extinction spectra of NPGDs, calculated average mass of materials and power measurements for light absorption at different wavelengths. See DOI: 10.1039/c4nr01266f

Santos, Greggy M.; Zhao, Fusheng; Zeng, Jianbo; Shih, Wei-Chuan

2014-05-01

374

Excited state dynamics in photosynthetic reaction center and light harvesting complex 1  

PubMed Central

Key to efficient harvesting of sunlight in photosynthesis is the first energy conversion process in which electronic excitation establishes a trans-membrane charge gradient. This conversion is accomplished by the photosynthetic reaction center (RC) that is, in case of the purple photosynthetic bacterium Rhodobacter sphaeroides studied here, surrounded by light harvesting complex 1 (LH1). The RC employs six pigment molecules to initiate the conversion: four bacteriochlorophylls and two bacteriopheophytins. The excited states of these pigments interact very strongly and are simultaneously influenced by the surrounding thermal protein environment. Likewise, LH1 employs 32 bacteriochlorophylls influenced in their excited state dynamics by strong interaction between the pigments and by interaction with the protein environment. Modeling the excited state dynamics in the RC as well as in LH1 requires theoretical methods, which account for both pigment-pigment interaction and pigment-environment interaction. In the present study we describe the excitation dynamics within a RC and excitation transfer between light harvesting complex 1 (LH1) and RC, employing the hierarchical equation of motion method. For this purpose a set of model parameters that reproduce RC as well as LH1 spectra and observed oscillatory excitation dynamics in the RC is suggested. We find that the environment has a significant effect on LH1-RC excitation transfer and that excitation transfers incoherently between LH1 and RC. PMID:22897312

Strumpfer, Johan; Schulten, Klaus

2012-01-01

375

Assembly of the Major Light-Harvesting Complex II in Lipid Nanodiscs  

PubMed Central

Self-aggregation of isolated plant light-harvesting complexes (LHCs) upon detergent extraction is associated with fluorescence quenching and is used as an in vitro model to study the photophysical processes of nonphotochemical quenching (NPQ). In the NPQ state, in vivo induced under excess solar light conditions, harmful excitation energy is safely dissipated as heat. To prevent self-aggregation and probe the conformations of LHCs in a lipid environment devoid from detergent interactions, we assembled LHCII trimer complexes into lipid nanodiscs consisting of a bilayer lipid matrix surrounded by a membrane scaffold protein (MSP). The LHCII nanodiscs were characterized by fluorescence spectroscopy and found to be in an unquenched, fluorescent state. Remarkably, the absorbance spectra of LHCII in lipid nanodiscs show fine structure in the carotenoid and Qy region that is different from unquenched, detergent-solubilized LHCII but similar to that of self-aggregated, quenched LHCII in low-detergent buffer without magnesium ions. The nanodisc data presented here suggest that 1), LHCII pigment-protein complexes undergo conformational changes upon assembly in nanodiscs that are not correlated with downregulation of its light-harvesting function; and 2), these effects can be separated from quenching and aggregation-related phenomena. This will expand our present view of the conformational flexibility of LHCII in different microenvironments. PMID:22098750

Pandit, Anjali; Shirzad-Wasei, Nazhat; Wlodarczyk, Lucyna M.; van Roon, Henny; Boekema, Egbert J.; Dekker, Jan P.; de Grip, Willem J.

2011-01-01

376

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

NASA Astrophysics Data System (ADS)

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.

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

2013-06-01

377

Forces guiding assembly of light-harvesting complex 2 in native membranes  

PubMed Central

Interaction forces of membrane protein subunits are of importance in their structure, assembly, membrane insertion, and function. In biological membranes, and in the photosynthetic apparatus as a paradigm, membrane proteins fulfill their function by ensemble actions integrating a tight assembly of several proteins. In the bacterial photosynthetic apparatus light-harvesting complexes 2 (LH2) transfer light energy to neighboring tightly associated core complexes, constituted of light-harvesting complexes 1 (LH1) and reaction centers (RC). While the architecture of the photosynthetic unit has been described, the forces and energies assuring the structural and functional integrity of LH2, the assembly of LH2 complexes, and how LH2 interact with the other proteins in the supramolecular architecture are still unknown. Here we investigate the molecular forces of the bacterial LH2 within the native photosynthetic membrane using atomic force microscopy single-molecule imaging and force measurement in combination. The binding between LH2 subunits is fairly weak, of the order of kBT, indicating the importance of LH2 ring architecture. In contrast LH2 subunits are solid with a free energy difference of 90 kBT between folded and unfolded states. Subunit ?-helices unfold either in one-step, ?- and ?-polypeptides unfold together, or sequentially. The unfolding force of transmembrane helices is approximately 150 pN. In the two-step unfolding process, the ?-polypeptide is stabilized by the molecular environment in the membrane. Hence, intermolecular forces influence the structural and functional integrity of LH2. PMID:21606335

Liu, Lu-Ning; Duquesne, Katia; Oesterhelt, Filipp; Sturgis, James N.; Scheuring, Simon

2011-01-01

378

Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature.  

PubMed

Photosynthesis makes use of sunlight to convert carbon dioxide into useful biomass and is vital for life on Earth. Crucial components for the photosynthetic process are antenna proteins, which absorb light and transmit the resultant excitation energy between molecules to a reaction centre. The efficiency of these electronic energy transfers has inspired much work on antenna proteins isolated from photosynthetic organisms to uncover the basic mechanisms at play. Intriguingly, recent work has documented that light-absorbing molecules in some photosynthetic proteins capture and transfer energy according to quantum-mechanical probability laws instead of classical laws at temperatures up to 180 K. This contrasts with the long-held view that long-range quantum coherence between molecules cannot be sustained in complex biological systems, even at low temperatures. Here we present two-dimensional photon echo spectroscopy measurements on two evolutionarily related light-harvesting proteins isolated from marine cryptophyte algae, which reveal exceptionally long-lasting excitation oscillations with distinct correlations and anti-correlations even at ambient temperature. These observations provide compelling evidence for quantum-coherent sharing of electronic excitation across the 5-nm-wide proteins under biologically relevant conditions, suggesting that distant molecules within the photosynthetic proteins are 'wired' together by quantum coherence for more efficient light-harvesting in cryptophyte marine algae. PMID:20130647

Collini, Elisabetta; Wong, Cathy Y; Wilk, Krystyna E; Curmi, Paul M G; Brumer, Paul; Scholes, Gregory D

2010-02-01

379

Allosteric regulation of the light-harvesting system of photosystem II.  

PubMed

Non-photochemical quenching of chlorophyll fluorescence (NPQ) is symptomatic of the regulation of energy dissipation by the light-harvesting antenna of photosystem II (PS II). The kinetics of NPQ in both leaves and isolated chloroplasts are determined by the transthylakoid delta pH and the de-epoxidation state of the xanthophyll cycle. In order to understand the mechanism and regulation of NPQ we have adopted the approaches commonly used in the study of enzyme-catalysed reactions. Steady-state measurements suggest allosteric regulation of NPQ, involving control by the xanthophyll cycle carotenoids of a protonation-dependent conformational change that transforms the PS II antenna from an unquenched to a quenched state. The features of this model were confirmed using isolated light-harvesting proteins. Analysis of the rate of induction of quenching both in vitro and in vivo indicated a bimolecular second-order reaction; it is suggested that quenching arises from the reaction between two fluorescent domains, possibly within a single protein subunit. A universal model for this transition is presented based on simple thermodynamic principles governing reaction kinetics. PMID:11127991

Horton, P; Ruban, A V; Wentworth, M

2000-10-29

380

Excited state dynamics in photosynthetic reaction center and light harvesting complex 1  

NASA Astrophysics Data System (ADS)

Key to efficient harvesting of sunlight in photosynthesis is the first energy conversion process in which electronic excitation establishes a trans-membrane charge gradient. This conversion is accomplished by the photosynthetic reaction center (RC) that is, in case of the purple photosynthetic bacterium Rhodobacter sphaeroides studied here, surrounded by light harvesting complex 1 (LH1). The RC employs six pigment molecules to initiate the conversion: four bacteriochlorophylls and two bacteriopheophytins. The excited states of these pigments interact very strongly and are simultaneously influenced by the surrounding thermal protein environment. Likewise, LH1 employs 32 bacteriochlorophylls influenced in their excited state dynamics by strong interaction between the pigments and by interaction with the protein environment. Modeling the excited state dynamics in the RC as well as in LH1 requires theoretical methods, which account for both pigment-pigment interaction and pigment-environment interaction. In the present study we describe the excitation dynamics within a RC and excitation transfer between light harvesting complex 1 (LH1) and RC, employing the hierarchical equation of motion method. For this purpose a set of model parameters that reproduce RC as well as LH1 spectra and observed oscillatory excitation dynamics in the RC is suggested. We find that the environment has a significant effect on LH1-RC excitation transfer and that excitation transfers incoherently between LH1 and RC.

Strümpfer, Johan; Schulten, Klaus

2012-08-01

381

Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna  

SciTech Connect

Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

2008-01-31

382

Toluidine blue modified self-assembled silica gel coated gold electrode as biosensor for NADH  

Microsoft Academic Search

A toluidine blue modified gold electrode was constructed using self-assembled silica gel technique. Firstly, toluidine blue was encapsulated within 3D network of silica self-assembly monolayer on the surface of gold electrode. Secondly, another layer of silica sol was further assembled to protect from leaching of mediator or possible contamination. The electrochemical characteristics of toluidine blue immobilized within self-assembled silica gel

Faming Tian; Guoyi Zhu

2004-01-01

383

Ternary Self-Assembly of Ordered Metal Oxide-Graphene Nanocomposites for Electrochemical Energy Storage  

Microsoft Academic Search

Surfactant or polymer directed self-assembly has been widely investigated to prepare nanostructured metal oxides, semiconductors and polymers, but this approach is mostly limited to two-phase materials, organic\\/inorganic hybrids, and nanoparticle or polymer-based nanocomposites. Self-assembled nanostructures from more complex, multiscale and multiphase building blocks have been explored with limited success. Here, we demonstrate a ternary self-assembly approach using graphene as fundamental

Donghai Wang; Rong Kou; Daiwon Choi; Zhenguo Yang; Zimin Nie; Juan Li; Laxmikant V. Saraf; Dehong Hu; Jiguang Zhang; Gordon L. Graff; Jun Liu; Michael A. Pope; Ilhan A. Aksay

2010-01-01

384

Self-assembled Silicon Nanotubes: new 1D semiconductors  

NASA Astrophysics Data System (ADS)

Silicon nanotubes (SiNTs) have recently attracted attention because of the peculiar properties. SiNTs is also compatible to the present Si microelectronic technology. Theoretically, many research groups have investigated the possible existence of SiNTs. Experimentally, amorphous SiNTs have been synthesized by using template methods. Nevertheless, these SiNTs cannot form good crystal structure due to disordered aggregation of silicon atoms in the inner wall of the templates. Recently, self- assembled silicon nanotubes were reported, which have good crystal structure under supercritically hydrothermal conditions. Here we report self-assembled SiNTs via dual RF-plasma treatments. This technique is compatible to the present integrated circuit technology without involving excessive synthesis pressures and temperatures. Furthermore, our SiNTs are vertically aligned on substrates, which can be easily extracted for devices fabrication. Tunneling spectroscopy was used to characterize the local density of states of these SiNTs. Results indicate that these SiNTs are p-type semiconductors, a new 1D semiconductor for future nanoelectronic devices.

Xie, Ming; Wang, Jiesheng; Khin Yap, Yoke

2007-03-01

385

Self-assembly processes in the prebiotic environment  

PubMed Central

An important question guiding research on the origin of life concerns the environmental conditions where molecular systems with the properties of life first appeared on the early Earth. An appropriate site would require liquid water, a source of organic compounds, a source of energy to drive polymerization reactions and a process by which the compounds were sufficiently concentrated to undergo physical and chemical interactions. One such site is a geothermal setting, in which organic compounds interact with mineral surfaces to promote self-assembly and polymerization reactions. Here, we report an initial study of two geothermal sites where mixtures of representative organic solutes (amino acids, nucleobases, a fatty acid and glycerol) and phosphate were mixed with high-temperature water in clay-lined pools. Most of the added organics and phosphate were removed from solution with half-times measured in minutes to a few hours. Analysis of the clay, primarily smectite and kaolin, showed that the organics were adsorbed to the mineral surfaces at the acidic pH of the pools, but could subsequently be released in basic solutions. These results help to constrain the range of possible environments for the origin of life. A site conducive to self-assembly of organic solutes would be an aqueous environment relatively low in ionic solutes, at an intermediate temperature range and neutral pH ranges, in which cyclic concentration of the solutes can occur by transient dry intervals. PMID:17008220

Deamer, David; Singaram, Sara; Rajamani, Sudha; Kompanichenko, Vladimir; Guggenheim, Stephen

2006-01-01

386

Modeling the Self-assembly of the Cellulosome Enzyme Complex*  

PubMed Central

Most bacteria use free enzymes to degrade plant cell walls in nature. However, some bacteria have adopted a different strategy wherein enzymes can either be free or tethered on a protein scaffold forming a complex called a cellulosome. The study of the structure and mechanism of these large macromolecular complexes is an active and ongoing research topic, with the goal of finding ways to improve biomass conversion using cellulosomes. Several mechanisms involved in cellulosome formation remain unknown, including how cellulosomal enzymes assemble on the scaffoldin and what governs the population of cellulosomes created during self-assembly. Here, we present a coarse-grained model to study the self-assembly of cellulosomes. The model captures most of the physical characteristics of three cellulosomal enzymes (Cel5B, CelS, and CbhA) and the scaffoldin (CipA) from Clostridium thermocellum. The protein structures are represented by beads connected by restraints to mimic the flexibility and shapes of these proteins. From a large simulation set, the assembly of cellulosomal enzyme complexes is shown to be dominated by their shape and modularity. The multimodular enzyme, CbhA, binds statistically more frequently to the scaffoldin than CelS or Cel5B. The enhanced binding is attributed to the flexible nature and multimodularity of this enzyme, providing a longer residence time around the scaffoldin. The characterization of the factors influencing the cellulosome assembly process may enable new strategies to create designers cellulosomes. PMID:21098021

Bomble, Yannick J.; Beckham, Gregg T.; Matthews, James F.; Nimlos, Mark R.; Himmel, Michael E.; Crowley, Michael F.

2011-01-01

387

Noncovalent self-assembly of a heterotetrameric diiron protein  

PubMed Central

Diiron and dimanganese proteins catalyze a wide range of hydrolytic and oxygen-dependent reactions. To probe the mechanisms by which individual members of this class of proteins are able to catalyze such a wide range of reactions, we have prepared a model four-helix bundle with a diiron site located near the center of the bundle. The four-helix bundle is constructed by the noncovalent self-assembly of three different chains (Aa, Ab, and B) that self-assemble into the desired heterotetramer when mixed in a 1:1:2 molar ratio. On addition of ferrous ions and oxygen, the protein forms a complex with a UV-visible spectrum closely resembling that of peroxo-bridged diferric species in natural proteins and model compounds. By combining a small collection of n variants of these peptides, it should now be possible to prepare an n3 member library, which will allow systematic exploration of the features giving rise to the catalytic properties of this class of proteins. PMID:11959963

Marsh, E. Neil G.; DeGrado, William F.

2002-01-01

388

Conformational flexibility facilitates self-assembly of complex DNA nanostructures.  

PubMed

Molecular self-assembly is a promising approach to the preparation of nanostructures. DNA, in particular, shows great potential to be a superb molecular system. Synthetic DNA molecules have been programmed to assemble into a wide range of nanostructures. It is generally believed that rigidities of DNA nanomotifs (tiles) are essential for programmable self-assembly of well defined nanostructures. Recently, we have shown that adequate conformational flexibility could be exploited for assembling 3D objects, including tetrahedra, dodecahedra, and buckyballs, out of DNA three-point star motifs. In the current study, we have integrated tensegrity principle into this concept to assemble well defined, complex nanostructures in both 2D and 3D. A symmetric five-point-star motif (tile) has been designed to assemble into icosahedra or large nanocages depending on the concentration and flexibility of the DNA tiles. In both cases, the DNA tiles exhibit significant flexibilities and undergo substantial conformational changes, either symmetrically bending out of the plane or asymmetrically bending in the plane. In contrast to the complicated natures of the assembled structures, the approach presented here is simple and only requires three different component DNA strands. These results demonstrate that conformational flexibility could be explored to generate complex DNA nanostructures. The basic concept might be further extended to other biomacromolecular systems, such as RNA and proteins. PMID:18667705

Zhang, Chuan; Su, Min; He, Yu; Zhao, Xin; Fang, Ping-an; Ribbe, Alexander E; Jiang, Wen; Mao, Chengde

2008-08-01

389

Self-assembly of nanoparticle amphiphiles with adaptive surface chemistry.  

PubMed

We investigate the self-assembly of amphiphilic nanoparticles (NPs) functionalized with mixed monolayers of hydrophobic and hydrophilic ligands in water. Unlike typical amphiphilic particles with "fixed" surface chemistries, the ligands used here are not bound irreversibly but can rearrange dynamically on the particles' surface during their assembly from solution. Depending on the assembly conditions, these adaptive amphiphiles form compact micellar clusters or extended chain-like assemblies in aqueous solution. By controlling the amount of hydrophobic ligands on the particles' surface, the average number of nearest neighbors-that is, the preferred coordination number-can be varied systematically from ?1 (dimers) to ?2 (linear chains) to ?3 (extended clusters). To explain these experimental findings, we present an assembly mechanism in which hydrophobic ligands organize dynamically to form discrete patches between proximal NPs to minimize contact with their aqueous surroundings. Monte Carlo simulations incorporating these adaptive hydrophobic interactions reproduce the three-dimensional assemblies observed in experiment. These results suggest a general strategy based on reconfigurable "sticky" patches that may allow for tunable control over particle coordination number within self-assembled structures. PMID:25229312

Lee, Hee-Young; Shin, Sun Hae Ra; Drews, Aaron M; Chirsan, Aaron M; Lewis, Sean A; Bishop, Kyle J M

2014-10-28

390

Packing and self-assembly of truncated triangular bipyramids  

NASA Astrophysics Data System (ADS)

Motivated by breakthroughs in the synthesis of faceted nano- and colloidal particles, as well as theoretical and computational studies of their packings, we investigate a family of truncated triangular bipyramids. We report dense periodic packings with small unit cells that were obtained via numerical and analytical optimization. The maximal packing fraction ?max changes continuously with the truncation parameter t. Eight distinct packings are identified based on discontinuities in the first and second derivatives of ?max(t). These packings differ in the number of particles in the fundamental domain (unit cell) and the type of contacts between the particles. In particular, we report two packings with four particles in the unit cell for which both ?max(t) and ?max'(t) are continuous and the discontinuity occurs in the second derivative only. In the self-assembly simulations that we perform for larger boxes with 2048 particles, only one out of eight packings is found to assemble. In addition, the degenerate quasicrystal reported previously for triangular bipyramids without truncation [Haji-Akbari , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.107.215702 107, 215702 (2011)] assembles for truncations as high as 0.45. The self-assembly propensities for the structures formed in the thermodynamic limit are explained using the isoperimetric quotient of the particles and the coordination number in the disordered fluid and in the assembled structure.

Haji-Akbari, Amir; Chen, Elizabeth R.; Engel, Michael; Glotzer, Sharon C.

2013-07-01

391

Packing and self-assembly of truncated triangular bipyramids.  

PubMed

Motivated by breakthroughs in the synthesis of faceted nano- and colloidal particles, as well as theoretical and computational studies of their packings, we investigate a family of truncated triangular bipyramids. We report dense periodic packings with small unit cells that were obtained via numerical and analytical optimization. The maximal packing fraction ?(max) changes continuously with the truncation parameter t. Eight distinct packings are identified based on discontinuities in the first and second derivatives of ?(max)(t). These packings differ in the number of particles in the fundamental domain (unit cell) and the type of contacts between the particles. In particular, we report two packings with four particles in the unit cell for which both ?(max)(t) and ?(max)'(t) are continuous and the discontinuity occurs in the second derivative only. In the self-assembly simulations that we perform for larger boxes with 2048 particles, only one out of eight packings is found to assemble. In addition, the degenerate quasicrystal reported previously for triangular bipyramids without truncation [Haji-Akbari et al., Phys. Rev. Lett. 107, 215702 (2011)] assembles for truncations as high as 0.45. The self-assembly propensities for the structures formed in the thermodynamic limit are explained using the isoperimetric quotient of the particles and the coordination number in the disordered fluid and in the assembled structure. PMID:23944434

Haji-Akbari, Amir; Chen, Elizabeth R; Engel, Michael; Glotzer, Sharon C

2013-07-01

392

Self-Assembling Peptide Nanofiber Scaffolds Accelerate Wound Healing  

PubMed Central

Cutaneous wound repair regenerates skin integrity, but a chronic failure to heal results in compromised tissue function and increased morbidity. To address this, we have used an integrated approach, using nanobiotechnology to augment the rate of wound reepithelialization by combining self-assembling peptide (SAP) nanofiber scaffold and Epidermal Growth Factor (EGF). This SAP bioscaffold was tested in a bioengineered Human Skin Equivalent (HSE) tissue model that enabled wound reepithelialization to be monitored in a tissue that recapitulates molecular and cellular mechanisms of repair known to occur in human skin. We found that SAP underwent molecular self-assembly to form unique 3D structures that stably covered the surface of the wound, suggesting that this scaffold may serve as a viable wound dressing. We measured the rates of release of EGF from the SAP scaffold and determined that EGF was only released when the scaffold was in direct contact with the HSE. By measuring the length of the epithelial tongue during wound reepithelialization, we found that SAP scaffolds containing EGF accelerated the rate of wound coverage by 5 fold when compared to controls without scaffolds and by 3.5 fold when compared to the scaffold without EGF. In conclusion, our experiments demonstrated that biomaterials composed of a biofunctionalized peptidic scaffold have many properties that are well-suited for the treatment of cutaneous wounds including wound coverage, functionalization with bioactive molecules, localized growth factor release and activation of wound repair. PMID:18183291

Schneider, Aurore; Garlick, Jonathan A.; Egles, Christophe

2008-01-01

393

Amination of surfaces via self-assembly of dopamine.  

PubMed

Catechols can strongly bind to a variety of substrates so as to functionalize the target surfaces by forming self-assembled monolayer. However, catecholic amine might self-oxidize and polymerize at high pH since the amine is susceptible to nucleophilic addition reaction that results in polymerized oligomers on surfaces. Therefore, the availability of amines for further derivation reaction would be restricted to a large extent. Herein, by controlling pH values to avoid self-oxidative polymerization, dopamine (DA) forms thin and surface-adherent monolayers onto a wide range of inorganic and organic materials, including mica, silica, and Au surface, allowing amination of the surfaces that resemble commercially used aminosilanization. The self-assembly process was traced by surface topography and elemental composition analysis using atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical characterization (electrochemical impedance spectroscopy and cyclic voltammetry measurements). Then, the aminated surfaces were used for secondary derivation reactions to create a variety of ad-layers, including patterned streptavidin through specific binding interaction with biotin and ferrocene surface via amidation reaction. The surface and interface properties of the obtained surfaces were tested by electrochemical measurements. PMID:21733526

Liu, Ying; Yu, Bo; Hao, Jingcheng; Zhou, Feng

2011-10-01

394

Patterning of conducting polymers using charged self-assembled monolayers.  

PubMed

We introduce a new approach to pattern conducting polymers by combining oppositely charged conducting polymers on charged self-assembled monolayers (SAMs). The polymer resist pattern behaves as a physical barrier, preventing the formation of SAMs. The patterning processes were carried out using commercially available conducting polymers: a negatively charged PEDOT/PSS (poly(3,4-ethylene-dioxythiophene)/poly(4-stylenesulphonic acid)) and a positively charged polypyrrole (PPy). A bifunctional NH 2 (positively charged) or COOH (negatively charged) terminated alkane thiol or silane was directly self-assembled on a substrate (Au or SiO 2). A suspension of the conducting polymers (PEDOT/PSS and PPy) was then spin-coated on the top surface of the SAMs and allowed to adsorb on the oppositely charged SAMs via an electrostatic driving force. After lift-off of the polymer resist, i.e., poly(methyl methacrylate, PMMA), using acetone, the conducting polymers remained on the charged SAMs surface. Optical microscopy, Auger electron spectroscopy, and atomic force microscopy reveal that the prepared nanolines have low line edge roughness and high line width resolution. Thus, conducting polymer patterns with high resolution could be produced by simply employing charged bifunctional SAMs. It is anticipated that this versatile new method can be applied to device fabrication processes of various nano- and microelectronics. PMID:18661959

Jung, Mi-Hee; Lee, Hyoyoung

2008-09-01

395

Molecular Self-Assembly Driven by London Dispersion Forces  

SciTech Connect

The nature and strength of intermolecular interactions are crucial to a variety of kinetic and dynamic processes at surfaces. Whereas strong chemisorption bonds are known to facilitate molecular binding, the importance of the weaker yet ubiquitous van der Waals (vdW) interactions remains elusive in most cases. Here we use first-principles calculations combined with kinetic Monte Carlo simulations to unambiguously demonstrate the vital role that vdW interactions play in molecular self-assembly, using styrene nanowire growth on silicon as a prototypical example. We find that, only when the London dispersion forces are included, accounting for the attractive parts of vdW interactions, can the effective intermolecular interaction be reversed from being repulsive to attractive. Such attractive interactions, in turn, ensure the preferred growth of long wires under physically realistic conditions as observed experimentally. We further propose a cooperative scheme, invoking the application of an electric field and the selective creation of Si dangling bonds, to drastically improve the ordered arrangement of the molecular structures. The present study represents a significant step forward in the fundamental understanding and precise control of molecular self-assembly guided by London dispersion forces.

Li, Guo [The Institute of Physics, Chinese Academy of Sciences; Cooper, Valentino R [ORNL; Cho, Jun-Hyung [Hanyang University, Korea; Du, Shixuan [The Institute of Physics, Chinese Academy of Sciences; Gao, Hongjun [The Institute of Physics, Chinese Academy of Sciences; Zhang, Zhenyu [University of Science and Technology, Beijing, China

2011-01-01

396

Structure of self - assembled two-dimensional spherical crystals  

NASA Astrophysics Data System (ADS)

Dense spherical particles on a flat surface usually pack into a simple triangular lattice, similar to billiard balls at the start of a game. The minimum energy configuration for interacting particles on the curved surface of a sphere, however, presents special difficulties, as recognized already by J.J. Thomson. We describe experimental investigations of the structure of two-dimensional spherical crystals. The crystals, formed by beads self-assembled on water droplets in oil, serve as model systems for exploring very general theories about the minimum energy configurations of particles with arbitrary repulsive interactions on curved surfaces. Above a critical system size we find that crystals develop distinctive high-angle grain boundaries or "scars" not found in planar crystals. The number of excess defects in a scar is shown to grow linearly with the dimensionless system size. First experiments where the melting of the crystal structure was observable will be discussed. Dynamic triangulation methods allow the analysis of the dynamics of the defects. Possible modifications towards mechanically stabilized self assembly structures result in so called Colloidosomes, which are promising for many different encapsulation purposes.

Bausch, Andreas R.

2004-03-01

397

Using lateral capillary forces to compute by self-assembly  

PubMed Central

Investigations of DNA computing have highlighted a fundamental connection between self-assembly (SA) and computation: in principle, any computation can be performed by a suitable self-assembling system. In practice, exploration of this connection is limited by our ability to control the geometry and specificity of binding interactions. Recently, a system has been developed that uses surface tension to assemble plastic tiles according to shape complementarity and likeness of wetting [Bowden, N., Terfort, A., Carbeck, J. & Whitesides, G. M. (1997) Science 276, 233–235]. Here the capacity of this system to compute by SA is explored. Tiles were prepared to test the system's ability to generate three structures of increasing complexity: a periodic checkerboard tiling, an aperiodic Penrose tiling, and a computational tiling that simulates a one-dimensional cellular automaton. Matching rules for these tilings were enforced by coating tiles with patterns of hydrophobic and hydrophilic patches or wetting codes. Energetic, kinetic, and mechanistic details of SA explain differences between experimental structures and mathematically ideal ones. In particular, the growth mechanism observed appears incompatible with computations that make use of a chosen input. PMID:10655471

Rothemund, Paul W. K.

2000-01-01

398

Molecular and electronic structure of electroactive self-assembled monolayers  

NASA Astrophysics Data System (ADS)

Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30° tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 A? above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

Méndez De Leo, Lucila P.; de la Llave, Ezequiel; Scherlis, Damián; Williams, Federico J.

2013-03-01

399

Design of single peptides for self-assembled conduction channels  

NASA Astrophysics Data System (ADS)

Self-assembly of peptides provides the possibility of achieving relatively long range order on surfaces. These ordered peptides can also form channels that can be used as conduction channels. In the past, studies were focused on electron conduction through the secondary structure and amine bond of peptides and these restrict conduction of electrons over a short range (a few nanometers). In this work, we demonstrate the realization of electron conduction over a longer range of a few hundred nanometers via ?-? stacking of the phenyl groups in the tyrosine residue of a single peptide. The peptide used in this work was designed with a phenyl ring for ?-? stacking at one end and a carboxylic group at the other end for binding to aminopropyltriethoxysilane (APTES) treated silicon wafer. The distance between the peptides is controlled by a disulfide bond formed between neighboring cysteine residue and also by the amine groups of aminopropyltriethoxysilane. We demonstrate that the self-assembled peptide is conducting in the dry state over hundreds of nanometers, realizing the possibility of using peptide as a molecular wire.

Yew, Sok Yee; Shekhawat, Gajendra; Wangoo, Nishima; Mhaisalkar, Subodh; Raman Suri, C.; Dravid, Vinayak P.; Lam, Yeng Ming

2011-05-01

400

Self-Assembly of Natural Silk Fibroin under Osmotic Stress  

NASA Astrophysics Data System (ADS)

Osmotic stress method was applied to investigate the supramolecular self-assembly behavior of natural silk fibroin within the gland. As with the experiments on re-generated silk fibroin, poly(ethylene glycol) 8K was used to apply an osmotic stress of 0.2-7.6 MPa to the gland of Bombyx mori silkworm, in vitro. Fibroin samples were extracted from the fibroin-dominant, water-soluble posterior region, and from three different parts in the middle region of the gland. Calcium chloride of 0.01 M was added to each stressing solution to balance the physiological salt content of the sample. Microscopic and thermodynamic details of this self-assembly process along the spinline have been assessed by wide angle X- ray diffraction, optical microscopy, etc. It is apparent that as osmotic stress increases, isotropic silk fibroin molecules in the posterior region are assembled together to form a water-soluble crystalline mesophase known as silk-I. Further increases in osmotic stress induce an anti- parallel beta-sheet structure known as silk-II.

Sohn, Sungkyun; Hata, Tamako; Strey, Helmut H.

2005-03-01

401

Copper sulfide self-assembly architectures with improved photothermal performance.  

PubMed

Copper chalcogenide nanomaterials are promising photothermal materials for establishing novel diagnostic and therapeutic methods owing to the low cost but high photothermal transduction efficiency. Further progresses of the correlated technologies greatly depend on the efforts on design and construction of novel nanostructures. In this paper, we demonstrate a facile one-pot route for constructing CuS nanostructures in aqueous media via a spontaneous assembly process. In the presence of polyvinylpyrrolidone (PVP) as the capping agents, a decomposition of Cu(CH3COSH)x precursors is induced by ammonia, which produces hexagonal CuS nanoparticles (NPs) with the diameter around 22 nm. The primary CuS NPs greatly tend to self-assembly into one-dimensional structures, which are triggered by short-range anisotropic dipolar attraction and enforced by long-range isotropic electrostatic repulsion. The further fusion of the assembled NPs generates 480 × 50 nm(2) CuS nanorods. Because the formation of nanorods enhances the internanorod van der Waals attraction, the nanorods finally self-assembly into shuttle-like bundles in micrometer size. In comparison to isolated NPs, the regular CuS assembly structures exhibit improved molar extinction coefficient up to 9.7 × 10(16) cm(-1) M(-1) by shortening the distance of neighboring CuS NPs and therewith generating new electronic structures of the CuS indirect transition. Consequently, better photothermal performance is achieved. PMID:24446661

Bu, Xinyuan; Zhou, Ding; Li, Jing; Zhang, Xue; Zhang, Kai; Zhang, Hao; Yang, Bai

2014-02-11

402

Self-assembly of gemini surfactants: a computer simulation study.  

PubMed

The self-assembly behavior of gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. A united atom model is employed for the surfactants with fully atomistic counterions and water. This gemini architecture, in which two single tailed surfactants are joined through a flexible hydrophobic linker, has been shown to exhibit concentration-dependent aqueous self-assembly into lyotropic phases including hexagonal, gyroid, and lamellar morphologies. Our simulations reproduce the experimentally observed phases at similar amphiphile concentrations in water, including the unusual ability of these surfactants to form gyroid phases over unprecedentedly large amphiphile concentration windows. We demonstrate quantitative agreement between the predicted and experimentally observed domain spacings of these nanostructured materials. Through careful conformation analyses of the surfactant molecules, we show that the gyroid phase is electrostatically stabilized related to the lamellar phase. By starting with a lamellar phase, we show that use of a bulkier N(CH(3))(4)(+) counterion in place of Na(+) drives the formation of a gyroid phase. Decreasing the charge on the surfactant headgroups by carboxylate protonation decreases the degree of order in the lamellar phase. Using our models, we show that the translational diffusion of water and the Na(+) counterions is decreased by several orders of magnitude over the studied concentration range, and we attribute these effects to strong correlations between the mobile species and the surfactant headgroups. PMID:22967267

Mondal, Jagannath; Mahanthappa, Mahesh; Yethiraj, Arun

2013-04-25

403

Delivery of therapeutics and molecules using self-assembled peptides.  

PubMed

The use of nanobiotechnology in the formulation of drug carriers has been gaining popularity in recent years. Peptide self-assembly technology is a particularly attractive option due to its simplicity and programmability. Selfassembling peptide amphiphiles are surfactant-like molecules that are capable of spontaneous organization into a variety of nanostructures. The structural and functional features of these nanostructures can be designed through alterations to the peptide sequence. With a keen understanding of the supramolecular principles governing the non-covalent interactions involved, drug loading strategies can be customised. Hydrophobic drugs can be hidden within the core via aromatic interactions while gene-based therapeutics can be complexed with a cationic region of lysine residues. This review article focuses on the application of self-assembling peptide amphiphiles to drug delivery in the area of anti-cancer therapeutics, protein- and peptide-based therapeutics and nucleic acid-based therapeutics. Specific examples are used to discuss the various systems available and emphasis is given to the encapsulation and release mechanism. PMID:24358972

Sundar, S; Chen, Y; Tong, Y W

2014-01-01

404

Aerosol-Assisted Self-Assembly of Mesostructured Spherical Nanoparticles  

SciTech Connect

Nanostructured particles exhibiting well-defined pore sizes and pore connectivities (1-, 2-, or 3-dimensional) are of interest for catalysis, chromatography, controlled release, low dielectric constant fillers, and custom-designed pigments and optical hosts. During the last several years considerable progress has been made on controlling the macroscopic forms of mesoporous silicas prepared by surfactant and block copolymer liquid crystalline templating procedures. Typically interfacial phenomena are used to control the macroscopic form (particles, fibers, or films), while self-assembly of amphiphilic surfactants or polymers is used to control the mesostructure. To date, although a variety of spherical or nearly-spherical particles have been prepared, their extent of order is limited as is the range of attainable mesostructures. They report a rapid, aerosol process that results in solid, completely ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures. The process relies on evaporation-induced interfacial self-assembly (EISA) confined to a spherical aerosol droplet. The process is simple and generalizable to a variety of materials combinations. Additionally, it can be modified to provide the first aerosol route to the formation of ordered mesostructured films.

Brinker, C.J.; Fan,; H.; Lu, Y.; Rieker, T.; Stump, A.; Ward, T.L.

1999-03-23

405

Molecular Self-Assembly at Metal-Electrolyte Interfaces  

PubMed Central

The self-assembly of molecular layers has become an important strategy in modern design of functional materials. However, in particular, large organic molecules may no longer be sufficiently volatile to be deposited by vapor deposition. In this case, deposition from solution may be a promising route; in ionic form, these molecules may even be soluble in water. In this contribution, we present and discuss results on the electrochemical deposition of viologen- and porphyrin molecules as well as their co-adsorption on chloride modified Cu(100) and Cu(111) single crystal electrode surfaces from aqueous acidic solutions. Using in situ techniques like cyclic voltametry and high resolution scanning tunneling microscopy, as well as ex-situ photoelectron spectroscopy data the highly ordered self-assembled organic layers are characterized with respect to their electrochemical behavior, lateral order and inner conformation as well as phase transitions thereof as a function of their redox-state and the symmetry of the substrate. As a result, detailed structure models are derived and are discussed in terms of the prevailing interactions. PMID:23439555

Phan, Thanh Hai; Wandelt, Klaus

2013-01-01

406

Self-assembling and self-limiting monolayer deposition  

NASA Astrophysics Data System (ADS)

Effects of spatial ordering of molecules on surfaces are commonly utilized to deposit ultra-thin films with a thickness of a few nm. In this review paper, several methods are discussed, that are distinguished from other thin film deposition processes by exactly these effects that lead to self-assembling and self-limiting layer growth and eventually to coatings with unique and fascinating properties and applications in micro-electronics, optics, chemistry, or biology. Traditional methods for the formation of self-assembled films of ordered organic molecules, such as the Langmuir-Blodgett technique along with thermal atomic layer deposition (ALD) of inorganic molecules are evaluated. The overview is complemented by more recent developments for the deposition of organic or hybrid films by molecular layer deposition. Particular attention is given to plasma assisted techniques, either as a preparative, supplementary step or as inherent part of the deposition as in plasma enhanced ALD or plasma assisted, repeated grafting deposition. The different methods are compared and their film formation mechanisms along with their advantages are presented from the perspective of a plasma scientist. The paper contains lists of established film compounds and a collection of the relevant literature is provided for further reading.

Foest, Rüdiger; Schmidt, Martin; Gargouri, Hassan

2014-02-01

407

Liposomes self-assembled from electrosprayed composite microparticles  

NASA Astrophysics Data System (ADS)

Composite microparticles, consisting of polyvinylpyrrolidone (PVP), naproxen (NAP) and lecithin (PC), have been successfully prepared using an electrospraying process and exploited as templates to manipulate molecular self-assembly for the synthesis of liposomes in situ. Field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) observations demonstrate that the microparticles have an average diameter of 960 ± 140 nm and a homogeneous structure. X-ray diffraction (XRD) patterns, differential scanning calorimetry (DSC) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) results verify that the building blocks NAP and PC are scattered in the polymer matrix in a molecular way owing to the very fast drying of the electrospraying process and the favorable secondary interactions among the components. FESEM, scanning probe microscope (SPM) and TEM observations demonstrate that the liposomes can be achieved through molecular self-assembly in situ when the microparticles contact water thanks to ‘like prefers like’ and by means of the confinement effect of the microparticles. The liposomes have an encapsulation rate of 91.3%, and 80.7% of the drug in the liposomes can be freed into the dissolution medium in a sustained way and by a diffusion mechanism over a period of 24 h. The developed strategy not only provides a new, facile, and effective method to assemble and organize molecules of multiple components into liposomes with electrosprayed microparticles as templates, but also opens a new avenue for nanofabrication in a step-by-step and controllable way.

Yu, Deng-Guang; Yang, Jun-He; Wang, Xia; Tian, Feng

2012-03-01

408

Controlled nanometric fibers of self-assembled designed protein scaffolds  

NASA Astrophysics Data System (ADS)

The use of biological molecules as platforms for templating and nanofabrication is an emerging field. Here, we use designed protein building blocks based on small repetitive units (consensus tetratricopeptide repeat - CTPR) to generate fibrillar linear nanostructures by controlling the self-assembly properties of the units. We fully characterize the kinetics and thermodynamics of the assembly and describe the polymerization process by a simple model that captures the features of the structures formed under defined conditions. This work, together with previously established functionalization potential, sets up the basis for the application of these blocks in the fabrication and templating of complex hybrid nanostructures.The use of biological molecules as platforms for templating and nanofabrication is an emerging field. Here, we use designed protein building blocks based on small repetitive units (consensus tetratricopeptide repeat - CTPR) to generate fibrillar linear nanostructures by controlling the self-assembly properties of the units. We fully characterize the kinetics and thermodynamics of the assembly and describe the polymerization process by a simple model that captures the features of the structures formed under defined conditions. This work, together with previously established functionalization potential, sets up the basis for the application of these blocks in the fabrication and templating of complex hybrid nanostructures. Electronic supplementary information (ESI) available: Detailed Materials and methods section. See DOI: 10.1039/c4nr01210k

Mejías, Sara H.; Sot, Begoña; Guantes, Raul; Cortajarena, Aitziber L.

2014-09-01

409

Folding and self-assembly of aromatic and aliphatic urea oligomers: towards connecting structure and function.  

PubMed

Folding and self-assembly of biomacromolecules has inspired the development of discrete, non-natural oligomers that fold and/or self-assemble in a controlled manner. Though aromatic and aliphatic oligoamides remain unmatched for structural diversity and synthetic versatility, oligomers based on amide bond surrogates, such as urea backbones, also demonstrated a propensity for folding and self-assembly. In this Perspective, we review the advances in the design of oligomeric aromatic and aliphatic urea sequences (essentially N,N'-linked) that fold and/or self-assemble. Whenever applicable, the relationship between structure and function will be highlighted. PMID:20502838

Fischer, Lucile; Guichard, Gilles

2010-07-21

410

Developing novel polymer architectures for applications In magnetic resonance imaging and self-assembly  

E-print Network

Macromolecular scaffolds for drug delivery, self-assembly, and imaging applications have attracted significant attention over the last several decades. As polymerization techniques become more sophisticated, it becomes ...

McCombs, Jessica R. (Jessica Rose)

2013-01-01

411

Self Assembly of Nano Metric Metallic Particles for Realization of Photonic and Electronic Nano Transistors  

E-print Network

Abstract: In this paper, we present the self assembly procedure as well as experimental results of a novel method for constructing well defined arrangements of self assembly metallic nano particles into sophisticated nano structures. The self assembly concept is based on focused ion beam (FIB) technology, where metallic nano particles are self assembled due to implantation of positive gallium ions into the insulating material (e.g., silica as in silicon on insulator wafers) that acts as intermediary layer between the substrate and the negatively charge metallic nanoparticles.

unknown authors

2010-01-01

412

Green fluorescent organic nanoparticles by self-assembly induced enhanced emission of a naphthalene diimide bolaamphiphile  

NASA Astrophysics Data System (ADS)

Naphthalene diimide (NDI) bolaamphiphilic molecules (1) self-assemble in water to form organic nanoparticles, which exhibit self-assembly induced preassociated excimer formation and hence an enhanced green fluorescence.Naphthalene diimide (NDI) bolaamphiphilic molecules (1) self-assemble in water to form organic nanoparticles, which exhibit self-assembly induced preassociated excimer formation and hence an enhanced green fluorescence. Electronic supplementary information (ESI) available: Additional experimental data, supporting figures and synthetic schemes. See DOI: 10.1039/c1nr10151j

Kumar, Mohit; George, Subi J.

2011-05-01

413

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

NASA Astrophysics Data System (ADS)

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.

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

2008-01-01

414

Nanoencapsulating living biological cells using electrostatic layer-by-layer self-assembly: platelets as a model  

PubMed Central

In the literature, a few biological cells have been used as templates to form microcapsules of a variety of shapes and sizes. In this study, we proved the concept that living cells like platelets can be encapsulated with polyelectrolytes using electrostatic layer-by-layer self-assembly (LBL), and, most importantly, the encapsulation process did not induce activation of the platelets. Glycol-chitosan and poly-L-glutamic acid were electrostatically deposited onto platelets, and the encapsulation was confirmed using confocal laser scanning microscopy and scanning electron microscopy. Transmission electron microscopy observation further confirmed that the encapsulation process was mild and the activation of platelets was negligible. The encapsulation of living biological cells like platelets can serve as a model system in a wide range of biomedical applications including local and sustained drug delivery, immune protection of artificial tissues, and versatile artificial blood. PMID:21359101

Zhao, Qinghe; Li, Hongshuai; Li, Bingyun

2010-01-01

415

Charge conduction and breakdown mechanisms in self-assembled nanodielectrics.  

PubMed

Developing alternative high dielectric constant (k) materials for use as gate dielectrics is essential for continued advances in conventional inorganic CMOS and organic thin film transistors (OTFTs). Thicker films of high-k materials suppress tunneling leakage currents while providing effective capacitances comparable to those of thin films of lower-k materials. Self-assembled monolayers (SAMs) and multilayers offer attractive options for alternative OTFT gate dielectrics. One class of materials, organosilane-based self-assembled nanodielectrics (SANDs), has been shown to form robust films with excellent insulating and surface passivation properties, enhancing both organic and inorganic TFT performance and lowering device operating voltages. Since gate leakage current through the dielectric is one factor limiting continued TFT performance improvements, we investigate here the current (voltage, temperature) (I (V,T)) transport characteristics of SAND types II (pi-conjugated layer) and III (sigma-saturated + pi-conjugated layers) in Si/native SiO(2)/SAND/Au metal-insulator-metal (MIS) devices over the temperature range -60 to +100 degrees C. It is found that the location of the pi-conjugated layer with respect to the Si/SiO(2) substrate surface in combination with a saturated alkylsilane tunneling barrier is crucial in controlling the overall leakage current through the various SAND structures. For small applied voltages, hopping transport dominates at all temperatures for the pi-conjugated system (type II). However, for type III SANDs, the sigma- and pi-monolayers dominate the transport in two different transport regimes: hopping between +25 degrees C and +100 degrees C, and an apparent switch to tunneling for temperatures below 25 degrees C. The sigma-saturated alkylsilane tunneling barrier functions to reduce type III current leakage by blocking injected electrons, and by enabling bulk-dominated (Poole-Frenkel) transport vs electrode-dominated (Schottky) transport in type II SANDs. These observations provide insights for designing next-generation self-assembled gate dielectrics, since the bulk-dominated transport resulting from combining sigma- and pi-layers should enable realization of gate dielectrics with further enhanced performance. PMID:19408943

DiBenedetto, Sara A; Facchetti, Antonio; Ratner, Mark A; Marks, Tobin J

2009-05-27

416

Electrochemical Properties of Organosilane Self Assembled Monolayers on Aluminum 2024  

NASA Technical Reports Server (NTRS)

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

Hintze, Paul E.; Calle, Luz Marina

2004-01-01

417

Multiscale modeling of self-assembly in surfactant systems  

NASA Astrophysics Data System (ADS)

Dynamics of self-assembly and structural transitions in amphiphilic systems play an important role in numerous processes, ranging from production of nanostructured materials to transport in biological cells. Theoretical and computational modeling of these processes is extremely challenging due to the large span of length- and time-scales involved. This study is focused on developing multiscale models for self-assembly in surfactant systems, with the main emphasis on the development of a multi-scale model for formation and disintegration of nonionic and ionic spherical micelles. The study is performed under the assumption that the dominant mechanism of micelle formation (disintegration) is a stepwise addition (removal) of single monomers to (from) a surfactant aggregate. Different scales of these processes are investigated using a combination of coarse-grained molecular dynamics simulations, analytical and numerical solution of stochastic differential equations, and a numerical solution of kinetic equations. The removal of a surfactant from an aggregate is modeled by a Langevin equation for a single reaction coordinate, the distance between the centers of mass of the surfactant and the aggregate, with parameters obtained from a series of constrained molecular dynamics simulations. We demonstrate that the reverse process of addition of a surfactant molecule to an aggregate involves at least two additional degrees of freedom: orientation of the surfactant molecule and micellar microstructure. Formation of the ionic micelles involves one more degree of freedom which describes collective dynamics of the charges in the system. Time-scales of the additional degrees of freedom are comparable with the time-scale of the monomer addition to a micelle and hence these degrees of freedom play an active role in the monomer addition process. We demonstrate that neglecting their contribution leads to qualitative discrepancies in predicted surfactant addition rates and propose a stochastic model for the monomer addition which takes the additional degrees of freedom into account. The model parameters are extracted from molecular dynamics simulations and the surfactant addition rates are determined from Brownian dynamics simulations of this model. The obtained addition and removal rates are then incorporated into the kinetic model of micelle formation and disintegration. It is expected that insights gained in the course of development of the multi-scale model for this relatively simple self-assembly process will aid in the development of models for dynamics of more complex processes in amphiphilic systems such as collision of reverse micelles involved in formation of nanoparticles, rheology of worm-like micellar solutions, and fusion of lipid bilayers.

Mohan, Gunjan

418

Theory and simulation of polymer and polyelectrolyte self-assembly  

NASA Astrophysics Data System (ADS)

Polymers and polyelectrolytes are ideal tools for the development of novel self-assembled materials. The ability to control the length-scales of self-assembly, and thus the properties, for soft materials lies in the understanding and subsequent manipulation of competing intermolecular interactions, such as hydrophobicity, hydrogen bonding, van der Waals, electrostatics. In this thesis, computer simulation and theory describe two separate phenomena in soft condensed matter---polymer gelation, as well as pattern formation at interfaces by charged macromolecules. A mean field theory of thermoreversible gelation is outlined, that incorporates a chemical approach to intermolecular interactions. For example, gels that form due to hydrogen bonding between polymer chains. Using Monte Carlo, the processes of chemical interactions, as well as physical interactions are used to describe gelation. Physical interactions refer to hydrogels, or gels that are formed through hydrophobic interactions. It is found that the mean field theory can be extended to describe physical gelation, by incorporating a concentration dependent association constant. The self-assembly of oppositely charged, immiscible molecular components at interfaces is introduced. The theoretical behavior is outlined at low temperatures, by assuming the formation of finite, strongly segregated lamellar or hexagonal domains. At high temperatures, density fluctuations are examined to determine the transition from the disordered to microphase region. Molecular dynamics simulations are designed to explore the phase behavior of this model at intermediate temperatures. The formation of lamellar and hexagonal domains are characterized. It is shown that the strength of the electrostatic interactions in competition with short range interactions determines the degree of interfacial ordering between the domains, and the periodicity, illustrating the transition between low and high temperatures. In addition, it is shown that for asymmetrically charged molecular components, increased electrostatic interactions can decrease the fluctuations in the local inter-domain structure. Molecular dynamics results are then be used in complement to theory, to describe the possibility of phase coexistence of the previous phases with a low charge density gas phase. It is found that the periodicity of the structure at intermediate temperatures can be well described, by accounting for the solid phase swelling at low densities.

Loverde, Sharon

419

Applications of molecular self-assembly in tissue engineering  

NASA Astrophysics Data System (ADS)

This thesis studied the application of three self-assembling molecular systems, as potential biomaterials for tissue engineering applications. Cholesteryl-(L-lactic acid)n molecules form thermotropic liquid crystals, which could be coated onto the inner and outer pores of biodegradable PLLA scaffolds, while retaining the lamellar order of the neat material. Primary bovine chondrocytes were cultured on these structures, demonstrating improved attachment and extended retention of phenotype on the C-LA-coated scaffolds. No difference in fibronectin adsorption to C-LA and PLLA surfaces was observed, suggesting a strong role for cholesterol in influencing cell phenotype. A family of peptide-amphiphiles, bearing the "RGD" adhesion sequence from fibronectin, was also assessed in the contexts of cartilage and bladder repair. These molecules self-assemble into one-dimensional fibers, with diameters of 6--8 nm, and lengths of 500 nm or greater. Chondrocytes were seeded and cultured on covalently-crosslinked PA gels and embedded within calcium-triggered PA gels. Cells became dormant over time, but remained viable, suggesting an inappropriate display of the adhesion sequence to cells. A family of "branched" PA molecules with lysine dendron headgroups was designed, in an effort to increase the spatial separation between molecules in the assembled state, and to theoretically improve epitope accessibility. These molecules coated reliably onto PGA fiber scaffolds, and dramatically increased the attachment of human bladder smooth muscle cells, possibly through better epitope display or electrostatic attraction. They also formed strong gels with several negatively-charged biologically-relevant macromolecules. In a third system, amphiphilic segmented dendrimers based on phenylene vinylene and L-lysine entered cells through an endocytic pathway with no discernible toxic effect on cell proliferation or morphology. These amphiphiles formed complex aggregates in aqueous solution, likely an equilibrium state of micelles (5--10 nm) and vesicles (25--35 nm). A pyrene analogue was shown to lyse cells, which correlated with the molecule's reduced propensity to form strong aggregates in aqueous solution. Other amino acid segments were substituted for L-lysine, and only those amphiphiles with basic residues were efficiently taken in by cells. For all three self-assembling systems, their nanoscale organization and their interaction with biological systems were directly related to the chemical nature of their constituent building blocks.

Harrington, Daniel Anton

420

Molecular engineering and characterization of self-assembled biorecognition surfaces  

NASA Astrophysics Data System (ADS)

The development of molecular engineering techniques for the fabrication of biomaterial surfaces is of importance in the field of biomaterials. It offers opportunities for better understanding of biological processes on material surfaces and rational design of contemporary biomaterials. Our work in this area aims to develop novel engineering strategies to design biorecognition surfaces via self-assembly and surface derivatization. Fundamental issues regarding self-assembled monolayer (SAM) structure, formation kinetics, and chemical derivatization were investigated systematically using electron spectroscopy for chemical analysis (ESCA), time-of-flight secondary ion mass spectrometry (TOF-SIMS), infrared reflection absorption spectroscopy (IRAS), atomic force microscopy (AFM), and contact angle measurements. Novel engineering concepts based on multifunctionality and statistical pattern matching were introduced and applied to develop biomimetic surfaces. Our study illustrated that molecules underwent structural transition and orientation development during self-assembly formation, from a disordered, low-density, more liquid-like structure to a highly ordered, closed-packed crystalline-like structure. Surface properties, such as wettability and the reactivity of outermost functional groups can be related to film structure, packing density, as well as molecular orientation. Given the order and organization of SAMs, the accessibility and reactivity of the outermost functional groups, reaction kinetics, stoichiometry, and SAMs stability were studied systematically by surface derivatization of trifluoroacetic anhydride (TFAA). The TFAA derivatization reactions exhibited rapid kinetics on the hydroxyl-terminated SAMs. The data from complementary surface analytical techniques consistently indicated a nearly complete surface reaction. Biomimetic surfaces were made by random immobilization of amino acid of arginine (R), glycine (G), and aspartic acid (D) on well-defined SAMs. The surface reaction process was systematically characterized by ESCA. In vitro cell adhesion studies demonstrated that the designed surfaces had the capability to stimulate cell attachment and spreading, even in the absence of serum proteins. The biospecific recognition between the surface and the cell receptors was attributed to the appropriate chemical environment and statistical pattern matching between the randomly distributed R+G+D groups on the surface and cell receptors.

Pan, Sheng