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Sample records for artificial light-harvesting self-assemble

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

    SciTech Connect

    Wasielewski, Michael R.

    2011-09-28

    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

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

    PubMed

    Wasielewski, Michael R

    2009-12-21

    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

  3. Hierarchical self-assembly of a biomimetic light-harvesting antenna based on DNA G-quadruplexes.

    PubMed

    Sancho Oltra, Núria; Browne, Wesley R; Roelfes, Gerard

    2013-02-11

    A new modular approach to an artificial light-harvesting antenna system is presented. The approach involves the hierarchical self-assembly of porphyrin acceptor molecules to G-quadruplexes tethered to coumarin donor moieties.

  4. One-Dimensional Multichromophor Arrays Based on DNA: From Self-Assembly to Light-Harvesting.

    PubMed

    Ensslen, Philipp; Wagenknecht, Hans-Achim

    2015-10-20

    Light-harvesting complexes collect light energy and deliver it by a cascade of energy and electron transfer processes to the reaction center where charge separation leads to storage as chemical energy. The design of artificial light-harvesting assemblies faces enormous challenges because several antenna chromophores need to be kept in close proximity but self-quenching needs to be avoided. Double stranded DNA as a supramolecular scaffold plays a promising role due to its characteristic structural properties. Automated DNA synthesis allows incorporation of artificial chromophore-modified building blocks, and sequence design allows precise control of the distances and orientations between the chromophores. The helical twist between the chromophores, which is induced by the DNA framework, controls energy and electron transfer and thereby reduces the self-quenching that is typically observed in chromophore aggregates. This Account summarizes covalently multichromophore-modified DNA and describes how such multichromophore arrays were achieved by Watson-Crick-specific and DNA-templated self-assembly. The covalent DNA systems were prepared by incorporation of chromophores as DNA base substitutions (either as C-nucleosides or with acyclic linkers as substitutes for the 2'-deoxyribofuranoside) and as DNA base modifications. Studies with DNA base substitutions revealed that distances but more importantly relative orientations of the chromophores govern the energy transfer efficiencies and thereby the light-harvesting properties. With DNA base substitutions, duplex stabilization was faced and could be overcome, for instance, by zipper-like placement of the chromophores in both strands. For both principal structural approaches, DNA-based light-harvesting antenna could be realized. The major disadvantages, however, for covalent multichromophore DNA conjugates are the poor yields of synthesis and the solubility issues for oligonucleotides with more than 5-10 chromophore

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

    DOEpatents

    Lindsey, Jonathan S.; Chinnasamy, Muthiah; Fan, Dazhong

    2009-12-15

    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.

  6. Micelle-Induced Self-Assembling Protein Nanowires: Versatile Supramolecular Scaffolds for Designing the Light-Harvesting System.

    PubMed

    Sun, Hongcheng; Zhang, Xiyu; Miao, Lu; Zhao, Linlu; Luo, Quan; Xu, Jiayun; Liu, Junqiu

    2016-01-26

    Organic nanoparticle induced self-assembly of proteins with periodic nanostructures is a promising and burgeoning strategy to develop functional biomimetic nanomaterials. Cricoid proteins afford monodispersed and well-defined hollow centers, and can be used to multivalently interact with geometrically symmetric nanoparticles to form one-dimensional protein nanoarrays. Herein, we report that core-cross-linked micelles can direct cricoid stable protein one (SP1) to self-assembling nanowires through multiple electrostatic interactions. One micelle can act as an organic nanoparticle to interact with two central concaves of SP1 in an opposite orientation to form a sandwich structure, further controlling the assembly direction to supramolecular protein nanowires. The reported versatile supramolecular scaffolds can be optionally manipulated to develop multifunctional integrated or synergistic biomimetic nanomaterials. Artificial light-harvesting nanowires are further developed to mimic the energy transfer process of photosynthetic bacteria for their structural similarity, by means of labeling donor and acceptor chromophores to SP1 rings and spherical micelles, respectively. The absorbing energy can be transferred within the adjacent donors around the ring and shuttling the collected energy to the nearby acceptor chromophore. The artificial light-harvesting nanowires are designed by mimicking the structural characteristic of natural LH-2 complex, which are meaningful in exploring the photosynthesis process in vitro.

  7. Self-assembly of light-harvesting crystalline nanosheets in aqueous media.

    PubMed

    Shahar, Chen; Baram, Jonathan; Tidhar, Yaron; Weissman, Haim; Cohen, Sidney R; Pinkas, Iddo; Rybtchinski, Boris

    2013-04-23

    A methodology leading to facile self-assembly of crystalline aromatic arrays in dilute aqueous solutions would enable efficient fabrication and processing of organic photonic and electronic materials in water. In particular, soluble 2D crystalline nanosheets may mimic the properties of photoactive thin films and self-assembled monolayers, covering large areas with ordered nanometer-thick material. We designed such solution-phase arrays using hierarchical self-assembly of amphiphilic perylene diimides in aqueous media. The assemblies were characterized by cryogenic transmission electron microscopy (cryo-TEM), revealing crystalline order and 2D morphology (confirmed by AFM studies). The order and morphology are preserved upon drying as evidenced by TEM and AFM. The 2D crystalline-like structures exhibit broadening and red-shifted absorption bands in UV-vis spectra, typical for PDI crystals and liquid crystals. Photophysical studies including femtosecond transient absorption spectroscopy reveal that two of the assemblies are superior light-harvesters due to excellent solar spectrum coverage and fast exciton transfer, in one case showing exciton diffusion comparable to solid-state crystalline systems based on perylene tetracarboxylic dianhidride (PTCDA).

  8. Self-assembled artificial cilia

    PubMed Central

    Vilfan, Mojca; Potočnik, Anton; Kavčič, Blaž; Osterman, Natan; Poberaj, Igor; Vilfan, Andrej; Babič, Dušan

    2010-01-01

    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

  9. Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles.

    PubMed

    Sahin, Tuba; Harris, Michelle A; Vairaprakash, Pothiappan; Niedzwiedzki, Dariusz M; Subramanian, Vijaya; Shreve, Andrew P; Bocian, David F; Holten, Dewey; Lindsey, Jonathan S

    2015-08-13

    Lipid vesicles are used as the organizational structure of self-assembled light-harvesting systems. Following analysis of 17 chromophores, six were selected for inclusion in vesicle-based antennas. The complementary absorption features of the chromophores span the near-ultraviolet, visible, and near-infrared region. Although the overall concentration of the pigments is low (~1 μM for quantitative spectroscopic studies) in a cuvette, the lipid-vesicle system affords high concentration (≥10 mM) in the bilayer for efficient energy flow from donor to acceptor. Energy transfer was characterized in 13 representative binary mixtures using static techniques (fluorescence-excitation versus absorptance spectra, quenching of donor fluorescence, modeling emission spectra of a mixture versus components) and time-resolved spectroscopy (fluorescence, ultrafast absorption). Binary donor-acceptor systems that employ a boron-dipyrrin donor (S0 ↔ S1 absorption/emission in the blue-green) and a chlorin or bacteriochlorin acceptor (S0 ↔ S1 absorption/emission in the red or near-infrared) have an average excitation-energy-transfer efficiency (ΦEET) of ~50%. Binary systems with a chlorin donor and a chlorin or bacteriochlorin acceptor have ΦEET ∼ 85%. The differences in ΦEET generally track the donor-fluorescence/acceptor-absorption spectral overlap within a dipole-dipole coupling (Förster) mechanism. Substantial deviation from single-exponential decay of the excited donor (due to the dispersion of donor-acceptor distances) is expected and observed. The time profiles and resulting ΦEET are modeled on the basis of (Förster) energy transfer between chromophores relatively densely packed in a two-dimensional compartment. Initial studies of two ternary and one quaternary combination of chromophores show the enhanced spectral coverage and energy-transfer efficacy expected on the basis of the binary systems. Collectively, this approach may provide one of the simplest designs for

  10. Highly Efficient Photon Upconversion in Self-Assembled Light-Harvesting Molecular Systems

    PubMed Central

    Ogawa, Taku; Yanai, Nobuhiro; Monguzzi, Angelo; Kimizuka, Nobuo

    2015-01-01

    To meet the world’s demands on the development of sunlight-powered renewable energy production, triplet–triplet annihilation-based photon upconversion (TTA–UC) has raised great expectations. However, an ideal highly efficient, low-power, and in-air TTA–UC has not been achieved. Here, we report a novel self-assembly approach to achieve this, which enabled highly efficient TTA–UC even in the presence of oxygen. A newly developed lipophilic 9,10-diphenylanthracene-based emitter molecule functionalized with multiple hydrogen-bonding moieties spontaneously coassembled with a triplet sensitizer in organic media, showing efficient triplet sensitization and subsequent triplet energy migration among the preorganized chromophores. This supramolecular light-harvesting system shows a high UC quantum yield of 30% optimized at low excitation power in deaerated conditions. Significantly, the UC emission largely remains even in an air-saturated solution, and this approach is facilely applicable to organogel and solid-film systems. PMID:26057321

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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 μm 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

  12. Anisotropic organization and microscopic manipulation of self-assembling synthetic porphyrin microrods that mimic chlorosomes: bacterial light-harvesting systems.

    PubMed

    Chappaz-Gillot, Cyril; Marek, Peter L; Blaive, Bruno J; Canard, Gabriel; Bürck, Jochen; Garab, Gyozo; Hahn, Horst; Jávorfi, Tamás; Kelemen, Loránd; Krupke, Ralph; Mössinger, Dennis; Ormos, Pál; Reddy, Chilla Malla; Roussel, Christian; Steinbach, Gábor; Szabó, Milán; Ulrich, Anne S; Vanthuyne, Nicolas; Vijayaraghavan, Aravind; Zupcanova, Anita; Balaban, Teodor Silviu

    2012-01-18

    Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems. They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores-which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions-have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces. PMID:22148684

  13. Artificial photosynthetic reaction centers coupled to light-harvesting antennas.

    PubMed

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu; Nori, Franco

    2011-12-01

    We analyze a theoretical model for energy and electron transfer in an artificial photosynthetic system. The photosystem consists of a molecular triad (i.e., with a donor, a photosensitive unit, and an acceptor) coupled to four accessory light-harvesting-antenna pigments. The resonant energy transfer from the antennas to the artificial reaction center (the molecular triad) is described here by the Förster mechanism. We consider two different kinds of arrangements of the accessory light-harvesting pigments around the reaction center. The first arrangement allows direct excitation transfer to the reaction center from all the surrounding pigments. The second configuration transmits energy via a cascade mechanism along a chain of light-harvesting chromophores, where only one chromophore is connected to the reaction center. We show that the artificial photosynthetic system using the cascade energy transfer absorbs photons in a broader wavelength range and converts their energy into electricity with a higher efficiency than the system based on direct couplings between all the antenna chromophores and the reaction center.

  14. Artificial light-harvesting arrays for solar energy conversion.

    PubMed

    Harriman, Anthony

    2015-07-28

    Solar fuel production, the process whereby an energy-rich substance is produced using electrons provided by water under exposure to sunlight, requires the cooperative accumulation of multiple numbers of photons. Identifying the optimum reagents is a difficult challenge, even without imposing the restriction that these same materials must function as both sensitiser and catalyst. The blockade caused by an inadequate supply of photons at the catalytic sites might be resolved by making use of an artificial light-harvesting array whose sole purpose is to funnel photons of appropriate frequency to the active catalyst, which can now be a dark reagent. Here we consider several types of artificial photon collectors built from fluorescent modules interconnected via electronic energy transfer. Emphasis is placed on the materials aspects and on establishing the basic operating principles.

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

    PubMed

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

    2013-09-12

    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-α-phosphatidylglycerol (PG), L-α-phosphatidylcholine (PC), and L-α-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.

  16. Protein-Framed Multi-Porphyrin Micelles for a Hybrid Natural-Artificial Light-Harvesting Nanosystem.

    PubMed

    Liu, Yannan; Jin, Jiyang; Deng, Hongping; Li, Ke; Zheng, Yongli; Yu, Chunyang; Zhou, Yongfeng

    2016-07-01

    A micelle-like hybrid natural-artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer. The nanosystem has a special structure of pomegranate-like unimolecular micelle aggregate with one phycocyanin acceptor in the center and multiple porphyrin donors in the shell. It can inhibit donor self-quenching effectively and display efficient transfer of excitation energy (about 80.1 %) in water. Furthermore, the number of donors contributing to a single acceptor could reach as high as about 179 in this nanosystem. PMID:27187799

  17. Discrete cyclic porphyrin arrays as artificial light-harvesting antenna.

    PubMed

    Aratani, Naoki; Kim, Dongho; Osuka, Atsuhiro

    2009-12-21

    The importance of photosynthesis has driven researchers to seek ways to mimic its fundamental features in simplified systems. The absorption of a photon by light-harvesting (antenna) complexes made up of a large number of protein-embedded pigments initiates photosynthesis. Subsequently the many pigments within the antenna system shuttle that photon via an efficient excitation energy transfer (EET) until it encounters a reaction center. Since the 1995 discovery of the circularly arranged chromophoric assemblies in the crystal structure of light-harvesting antenna complex LH2 of purple bacteria Rps. Acidophila, many designs of light-harvesting antenna systems have focused on cyclic porphyrin wheels that allow for efficient EET. In this Account, we review recent research in our laboratories in the synthesis of covalently and noncovalently linked discrete cyclic porphyrin arrays as models of the photosynthetic light-harvesting antenna complexes. On the basis of the silver(I)-promoted oxidative coupling strategy, we have prepared a series of extremely long yet discrete meso-meso-linked porphyrin arrays and covalently linked large porphyrin rings. We examined the photophysical properties of these molecules using steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related to the EET processes within the porphyrin rings. Within these structures, the exciton-exciton annihilation time and the polarization anisotropy rise time are well-described in terms of the Forster-type incoherent energy hopping model. In noncoordinating solvents such as CHCl(3), meso-pyridine-appended zinc(II) porphyrins and their meso-meso-linked dimers spontaneously assemble to form tetrameric porphyrin squares and porphyrin boxes, respectively. In the latter case, we have demonstrated

  18. Molecular and mesoscale mechanism for hierarchical self-assembly of dipeptide and porphyrin light-harvesting system.

    PubMed

    Liu, Kai; Kang, Yu; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-06-22

    A multi-scale theoretical investigation of dipeptide-porphyrin co-assembly systems has been carried out to establish such understanding, where two different types of the dipeptides, dilysine (KK(3+)) and diphenylalanine (FF(+)) are compared on tuning the porphyrin organization. Density functional theory results reveal that the electrostatic attraction between different functional groups has significantly strengthened the hydrogen bonds between them, which are considered as the driving force of the self-assembly at the molecular level. All-atom molecular dynamics (MD) simulation further indicates that the formation of the core-shell nanorods is driven and stabilized by the hydrophobic interaction between dipeptides and negatively charged porphyrin (H2TPPS(2-)), where the packed porphyrins stay inside as the core of the nanorods and the hydrophilic groups (amino- and carboxyl-groups) as the shell. With stronger hydrophobicity, FF(+) is more likely to insert into the porphyrin aggregates and build crosslinks than KK(3+). Moreover, dissipative particle dynamics (DPD) simulation suggests equilibrium morphologies with different dipeptides, where KK(3+)-H2TPPS(2-) assembled in fiber bundles, whereas FF(+)-H2TPPS(2-) assembled as microspheres, corresponding to the different packing behavior in MD simulations. The consistency of these results at different scales is discussed. The method used in this work could be extended for studying similar issues in hierarchical self-assembly of building blocks such biomaterials. PMID:27270974

  19. Electron transfer reaction of light harvesting zinc naphthalocyanine-subphthalocyanine self-assembled dyad: spectroscopic, electrochemical, computational, and photochemical studies.

    PubMed

    El-Khouly, Mohamed E

    2010-10-21

    Electron transfer reaction of a self-assembled donor-acceptor dyad formed by axial coordination of zinc naphthalocyanine, ZnNc, and subphthalocyanine appended with pyridine coordinating ligand, SubPc(py), was investigated in the present study. The SubPc(Py) : ZnNc self-assembled dyad absorbs the light in a wide section of the UV/Vis/NIR spectra. The formation constant of SubPc(py) : ZnNc in o-dichlorobenzene was found to be 1.2 × 10(5) M(-1) from the steady-state absorption and emission measurements, suggesting stable complex formation. The geometric and electronic calculations by using ab initio B3LYP/6-311G methods showed the majority of the highest occupied frontier molecular orbital (HOMO) on the zinc naphthalocyanine entity, while the lowest unoccupied molecular orbital (LUMO) was on the subphthalocyanine entity, suggesting that the charge-separated state of the supramolecular complex is (SubPc(py))˙(-) : ZnNc˙(+). The electrochemical results suggest the exothermic charge-separation process via the singlet states of both SubPc(py) and ZnNc entities. Upon coordination the pyridine appended subphthalocyanine to ZnNc; the main quenching pathway involved charge separation via the singlet excited states of ZnNc and SubPc(py). A clear evidence of the intramolecular electron transfer from the singlet state of ZnNc to SubPc(py) was monitored by femtosecond laser photolysis in o-dichlorobenzene by observing the characteristic absorption band of the ZnNc radical cation in the NIR region at 960 nm. The rate of charge-separation process was found to be 1.3 × 10(10) s(-1), indicating fast and efficient charge separation. The rate of charge recombination and the lifetime of the charge-separated state were found to be 1.0 × 10(9) s(-1) and 1 ns, respectively. The absorption in a wide section of the solar spectrum and high charge-separation/charge-recombination ratio suggests the usefulness of self-assembled SubPc(Py) : ZnNc for being a photosynthetic

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

    PubMed

    Wen, Fuyu; Li, Can

    2013-11-19

    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

  1. Artificial leaf structures as a UV detector formed by the self-assembly of ZnO nanoparticles.

    PubMed

    Wang, Fei; Zhao, Dongxu; Guo, Zhen; Liu, Lei; Zhang, Zhenzhong; Shen, Dezhen

    2013-04-01

    Artificial leaf structures have been fabricated by the self-assembly of ZnO nanoparticles. A hydrothermal method was used to synthesize the nanoparticles. The self-assembly patterns showed asymmetric dendritic morphologies, larger surface-to-volume ratios, a broad absorption band and high resistance. A non-equilibrium two-stage-formation process included diffusion limited aggregation, and the phase-field model was introduced to explain the formation mechanism of the pattern. A high-performance ultraviolet detector was fabricated on the artificial leaf structures, which showed that the current under the irradiation of a UV lamp (1.21 mW cm(-2)) was about 10(4) times greater than in the dark. The various and functional properties of the pattern show us the vast prospects of potential applications for light harvesting systems and other optical-electric devices. PMID:23446434

  2. Artificial leaf structures as a UV detector formed by the self-assembly of ZnO nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Zhao, Dongxu; Guo, Zhen; Liu, Lei; Zhang, Zhenzhong; Shen, Dezhen

    2013-03-01

    Artificial leaf structures have been fabricated by the self-assembly of ZnO nanoparticles. A hydrothermal method was used to synthesize the nanoparticles. The self-assembly patterns showed asymmetric dendritic morphologies, larger surface-to-volume ratios, a broad absorption band and high resistance. A non-equilibrium two-stage-formation process included diffusion limited aggregation, and the phase-field model was introduced to explain the formation mechanism of the pattern. A high-performance ultraviolet detector was fabricated on the artificial leaf structures, which showed that the current under the irradiation of a UV lamp (1.21 mW cm-2) was about 104 times greater than in the dark. The various and functional properties of the pattern show us the vast prospects of potential applications for light harvesting systems and other optical-electric devices.Artificial leaf structures have been fabricated by the self-assembly of ZnO nanoparticles. A hydrothermal method was used to synthesize the nanoparticles. The self-assembly patterns showed asymmetric dendritic morphologies, larger surface-to-volume ratios, a broad absorption band and high resistance. A non-equilibrium two-stage-formation process included diffusion limited aggregation, and the phase-field model was introduced to explain the formation mechanism of the pattern. A high-performance ultraviolet detector was fabricated on the artificial leaf structures, which showed that the current under the irradiation of a UV lamp (1.21 mW cm-2) was about 104 times greater than in the dark. The various and functional properties of the pattern show us the vast prospects of potential applications for light harvesting systems and other optical-electric devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33748k

  3. Out of the cleanroom, self-assembled magnetic artificial cilia.

    PubMed

    Wang, Ye; Gao, Yang; Wyss, Hans; Anderson, Patrick; den Toonder, Jaap

    2013-09-01

    Micro-sized hair-like structures, such as cilia, are abundant in nature and have various functionalities. Many efforts have been made to mimic the fluid pumping function of cilia, but most of the fabrication processes for these "artificial cilia" are tedious and expensive, hindering their practical application. In this paper a cost-effective in situ fabrication technique for artificial cilia is demonstrated. The cilia are constructed by self-assembly of micron sized magnetic beads and encapsulated with soft polymer coatings. Actuation of the cilia induces an effective fluid flow, and the cilia lengths and distribution can be adjusted by varying the magnetic bead concentration and fabrication parameters.

  4. Vibronic origin of long-lived coherence in an artificial molecular light harvester

    NASA Astrophysics Data System (ADS)

    Lim, James; Paleček, David; Caycedo-Soler, Felipe; Lincoln, Craig N.; Prior, Javier; von Berlepsch, Hans; Huelga, Susana F.; Plenio, Martin B.; Zigmantas, Donatas; Hauer, Jürgen

    2015-07-01

    Natural and artificial light-harvesting processes have recently gained new interest. Signatures of long-lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically aligned tubular system, polarization-controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence.

  5. Vibronic origin of long-lived coherence in an artificial molecular light harvester

    PubMed Central

    Lim, James; Paleček, David; Caycedo-Soler, Felipe; Lincoln, Craig N.; Prior, Javier; von Berlepsch, Hans; Huelga, Susana F.; Plenio, Martin B.; Zigmantas, Donatas; Hauer, Jürgen

    2015-01-01

    Natural and artificial light-harvesting processes have recently gained new interest. Signatures of long-lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton–vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically aligned tubular system, polarization-controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence. PMID:26158602

  6. Vibronic origin of long-lived coherence in an artificial molecular light harvester.

    PubMed

    Lim, James; Paleček, David; Caycedo-Soler, Felipe; Lincoln, Craig N; Prior, Javier; von Berlepsch, Hans; Huelga, Susana F; Plenio, Martin B; Zigmantas, Donatas; Hauer, Jürgen

    2015-07-09

    Natural and artificial light-harvesting processes have recently gained new interest. Signatures of long-lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically aligned tubular system, polarization-controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence.

  7. Extension of Light-Harvesting Ability of Photosynthetic Light-Harvesting Complex 2 (LH2) through Ultrafast Energy Transfer from Covalently Attached Artificial Chromophores.

    PubMed

    Yoneda, Yusuke; Noji, Tomoyasu; Katayama, Tetsuro; Mizutani, Naoto; Komori, Daisuke; Nango, Mamoru; Miyasaka, Hiroshi; Itoh, Shigeru; Nagasawa, Yutaka; Dewa, Takehisa

    2015-10-14

    Introducing appropriate artificial components into natural biological systems could enrich the original functionality. To expand the available wavelength range of photosynthetic bacterial light-harvesting complex 2 (LH2 from Rhodopseudomonas acidophila 10050), artificial fluorescent dye (Alexa Fluor 647: A647) was covalently attached to N- and C-terminal Lys residues in LH2 α-polypeptides with a molar ratio of A647/LH2 ≃ 9/1. Fluorescence and transient absorption spectroscopies revealed that intracomplex energy transfer from A647 to intrinsic chromophores of LH2 (B850) occurs in a multiexponential manner, with time constants varying from 440 fs to 23 ps through direct and B800-mediated indirect pathways. Kinetic analyses suggested that B800 chromophores mediate faster energy transfer, and the mechanism was interpretable in terms of Förster theory. This study demonstrates that a simple attachment of external chromophores with a flexible linkage can enhance the light harvesting activity of LH2 without affecting inherent functions of energy transfer, and can achieve energy transfer in the subpicosecond range. Addition of external chromophores, thus, represents a useful methodology for construction of advanced hybrid light-harvesting systems that afford solar energy in the broad spectrum.

  8. Charge transfer and quantum coherence in solar cells and artificial light harvesting system

    NASA Astrophysics Data System (ADS)

    Lienau, Christoph

    2014-03-01

    In artificial light harvesting systems the conversion of light into electrical or chemical energy happens on the femtosecond time scale, and is thought to involve the incoherent jump of an electron from the optical absorber to an electron acceptor. Here we investigate the primary dynamics of the photoinduced electronic charge transfer process in two prototypical structures: (i) a carotene-porphyrin-fullerene triad, a prototypical elementary component for an artificial light harvesting system and (ii) a polymer:fullerene blend as a model system for an organic solar cell. Our approach combines coherent femtosecond spectroscopy and first-principles quantum dynamics simulations. Our experimental and theoretical results provide strong evidence that the driving mechanism of the primary step within the current generation cycle is a quantum-correlated wavelike motion of electrons and nuclei on a timescale of few tens of femtoseconds. We furthermore highlight the fundamental role played by the flexible interface between the light-absorbing chromophore and the charge acceptor in triggering the coherent wavelike electron-hole splitting.

  9. Exploiting Collective Effects to Direct Light Absorption in Natural and Artificial Light-Harvesters

    NASA Astrophysics Data System (ADS)

    Schroeder, Christopher

    Photosynthesis---the conversion of sunlight to chemical energy---is fundamental for supporting life on our planet. Despite its importance, the physical principles that underpin the primary steps of photosynthesis, from photon absorption to electronic charge separation, remain to be understood in full. Electronic coherence within tightly-packed light-harvesting (LH) units or within individual reaction centers (RCs) has been recognized as an important ingredient for a complete understanding of the excitation energy transfer (EET) dynamics. However, the electronic coherence across units---RC and LH or LH and LH---has been consistently neglected as it does not play a significant role during these relatively slow transfer processes. Here, we turn our attention to the absorption process, which, as we will show, has a much shorter built-in timescale. We demonstrate that the---often overlooked---spatially extended but short-lived excitonic delocalization plays a relevant role in general photosynthetic systems. Most strikingly, we find that absorption intensity is, quite generally, redistributed from LH units to the RC, increasing the number of excitations which can effect charge separation without further transfer steps. A biomemetic nano-system is proposed which is predicted to funnel excitation to the RC-analogue, and hence is the first step towards exploiting these new design principles for efficient artificial light-harvesting.

  10. Artificial light-harvesting antennae: electronic energy transfer by way of molecular funnels.

    PubMed

    Ziessel, Raymond; Harriman, Anthony

    2011-01-14

    Electronic energy transfer (EET) plays a critical role in many biological processes and is used by nature to direct energy to a site where chemical reactions need to be initiated. Such EET can occur over large distances and can involve many individual molecules of identical, similar or disparate chemical identity. Advances in spectroscopy and data processing have allowed the rates of EET to be measured on extremely fast timescales such that improved mechanistic insight becomes feasible. At the same time, highly sophisticated synthetic operations have been devised that facilitate the isolation and purification of elaborate multi-component molecular arrays. A key feature of these arrays concerns the logical positioning of individual units in a way that favours directed EET along the molecular axis or along some other preferred pathway. The availability of these novel molecular materials allows close examination of popular theoretical models and paves the way for the development of advanced molecular sensors, artificial light harvesters, fluorescent labels and sensitizers. Of particular interest is the spectacular growth in the application of boron dipyrromethene dyes as basic reagents in such artificial photon collectors and these compounds have dominated the market in recent years because of their synthetic versatility and valuable photophysical properties. In this article, recent developments in the field are highlighted in terms of synthesis and subsequent spectroscopic exploration. PMID:20957235

  11. Functionalized dye encapsulated polymer nanoparticles attached with a BSA scaffold as efficient antenna materials for artificial light harvesting.

    PubMed

    Jana, Bikash; Bhattacharyya, Santanu; Patra, Amitava

    2016-09-21

    A potential strategy for a new generation light harvesting system is multi-chromophoric donor-acceptor pairs where light energy is absorbed by an antenna complex and subsequently transfers its energy to the acceptor via energy transfer. Here, we design a system of a functionalized polymer nanoparticle-protein scaffold for efficient light harvesting and white light generation where a dye doped polymer nanoparticle acts as a donor and a dye encapsulated BSA protein acts as an acceptor. Analysis reveals that 91.3% energy transfer occurs from the dye doped polymer nanoparticle to the dye encapsulated BSA protein. The antenna effect of this light harvesting system is found to be 31 at a donor to acceptor ratio of 0.82 : 1 which is unprecedented. The enhanced effective molar extinction coefficient of the acceptor dye is potential for the light harvesting system. Bright white light emission with a quantum yield of 14% under single wavelength excitation is obtained by changing the ratio of donor to acceptor. Analysis reveals that the efficient energy transfer in this polymer-protein assembly may open up new possibilities in designing artificial light harvesting systems for future applications.

  12. Functionalized dye encapsulated polymer nanoparticles attached with a BSA scaffold as efficient antenna materials for artificial light harvesting.

    PubMed

    Jana, Bikash; Bhattacharyya, Santanu; Patra, Amitava

    2016-09-21

    A potential strategy for a new generation light harvesting system is multi-chromophoric donor-acceptor pairs where light energy is absorbed by an antenna complex and subsequently transfers its energy to the acceptor via energy transfer. Here, we design a system of a functionalized polymer nanoparticle-protein scaffold for efficient light harvesting and white light generation where a dye doped polymer nanoparticle acts as a donor and a dye encapsulated BSA protein acts as an acceptor. Analysis reveals that 91.3% energy transfer occurs from the dye doped polymer nanoparticle to the dye encapsulated BSA protein. The antenna effect of this light harvesting system is found to be 31 at a donor to acceptor ratio of 0.82 : 1 which is unprecedented. The enhanced effective molar extinction coefficient of the acceptor dye is potential for the light harvesting system. Bright white light emission with a quantum yield of 14% under single wavelength excitation is obtained by changing the ratio of donor to acceptor. Analysis reveals that the efficient energy transfer in this polymer-protein assembly may open up new possibilities in designing artificial light harvesting systems for future applications. PMID:27546792

  13. DNA-Mediated Self-Assembly of Artificial Vesicles

    PubMed Central

    Hadorn, Maik; Eggenberger Hotz, Peter

    2010-01-01

    Background Although multicompartment systems made of single unilamellar vesicles offer the potential to outperform single compartment systems widely used in analytic, synthetic, and medical applications, their use has remained marginal to date. On the one hand, this can be attributed to the binary character of the majority of the current tethering protocols that impedes the implementation of real multicomponent or multifunctional systems. On the other hand, the few tethering protocols theoretically providing multicompartment systems composed of several distinct vesicle populations suffer from the readjustment of the vesicle formation procedure as well as from the loss of specificity of the linking mechanism over time. Methodology/Principal Findings In previous studies, we presented implementations of multicompartment systems and resolved the readjustment of the vesicle formation procedure as well as the loss of specificity by using linkers consisting of biotinylated DNA single strands that were anchored to phospholipid-grafted biotinylated PEG tethers via streptavidin as a connector. The systematic analysis presented herein provides evidences for the incorporation of phospholipid-grafted biotinylated PEG tethers to the vesicle membrane during vesicle formation, providing specific anchoring sites for the streptavidin loading of the vesicle membrane. Furthermore, DNA-mediated vesicle-vesicle self-assembly was found to be sequence-dependent and to depend on the presence of monovalent salts. Conclusions/Significance This study provides a solid basis for the implementation of multi-vesicle assemblies that may affect at least three distinct domains. (i) Analysis. Starting with a minimal system, the complexity of a bottom-up system is increased gradually facilitating the understanding of the components and their interaction. (ii) Synthesis. Consecutive reactions may be implemented in networks of vesicles that outperform current single compartment bioreactors in

  14. Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity.

    PubMed

    Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

    2016-01-01

    Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen.

  15. Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity.

    PubMed

    Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

    2016-01-01

    Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen. PMID:27622274

  16. Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity

    PubMed Central

    Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

    2016-01-01

    Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen. PMID:27622274

  17. Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity

    NASA Astrophysics Data System (ADS)

    Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

    2016-09-01

    Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen.

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

    NASA Astrophysics Data System (ADS)

    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

    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.

  19. In vitro maturation of oocytes via the pre-fabricated self-assembled artificial human ovary

    PubMed Central

    Robins, Jared C.; Ferruccio, Toni-Marie; Moore, Richard; Steinhoff, Margaret M.; Morgan, Jeffrey R.; Carson, Sandra

    2010-01-01

    Purpose Create a 3-Dimensional artificial human ovary to mature human oocytes. Methods Theca and granulosa cells were isolated from antral follicles of reproductive-aged women, seeded into micro-molded gels and self-assembled into complex 3D microtissues. Immunohistochemistry and live-dead staining confirmed theca cell identity and cellular viability at one week respectively. Placement of granulosa cell spheroids or cumulus-oocyte complexes into theca cell honeycomb openings resulted in creation of an artificial human ovary. Oocytes from this construct were assessed for polar body extrusion. Results Theca and granulosa cells self-assembled into complex microtissues, remaining viable for one week. At 72 h after artificial human ovary construction, theca cells completely surrounded the granulosa spheroids or COCs without stromal invasion or disruption. Polar body extrusion occurred in one of three COCs assessed. Conclusions An artifical human ovary can be created with self-assembled human theca and granulosa cell microtissues, and used for IVM and future oocyte toxicology studies. PMID:20737203

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

    PubMed Central

    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

    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

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

    PubMed

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

    2015-06-01

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

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

    SciTech Connect

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

    2015-06-07

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

  3. Self-assembled artificial pinning centres in thick YBCO superconducting films

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

    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 layered distribution of a second phase and homogeneous incorporation of second phase inclusions from a compositional target. In this paper, we compare the effectiveness of these methods in terms of the type of the self-assembly of nanoparticles. The comparison is made over a large set of YBa2Cu3O7 films of thickness up to 6.6 μm deposited with Au, Ag, Pd, LaNiO3, PrBa2Cu3O7, YBCO, BaZrO3 and Gd2Ba4CuWOy nanoparticles. It is found that substrate-decoration self-assembly is able to provide higher critical current in low magnetic field than the incorporation of homogeneous second phase in the sample microstructure. By specific modification of substrate decoration we achieved the self-field critical current per centimetre of width of 896 A/cm at 77.3 K and 1620 A/cm at 65 K in a film of thickness of 4.8 μm.

  4. Triplet excitons in natural photosynthetic and artificial light harvesting systems: Measurement and modeling

    NASA Astrophysics Data System (ADS)

    Hartzler, Daniel Allen

    artificial (B)Chl and porphyrin dimers by experimental and computational methods. This data set obtained allowed for the development of an empirical model for prediction of the triplet state site energy from a given singlet site energy and for development and calibration of a T-T coupling model. Use of these models shows that triplet state lowering by pigment-protein interaction provides photoprotection to the FMO complex, while triplet state lowering by triplet exciton formation is insufficient to provide protection to the chlorosome antenna. Additionally, the T-T coupling model shows that in dimers and other aggregates, the coupling is highly sensitive to relative monomer orientation and position, contrary to what was previously assumed. The simple exponential models used to estimate T-T couplings miss this orientation sensitivity, thus in systems with significant contact between adjacent monomers a more accurate approach is required.

  5. Highly permeable artificial water channels that can self-assemble into two-dimensional arrays.

    PubMed

    Shen, Yue-Xiao; Si, Wen; Erbakan, Mustafa; Decker, Karl; De Zorzi, Rita; Saboe, Patrick O; Kang, You Jung; Majd, Sheereen; Butler, Peter J; Walz, Thomas; Aksimentiev, Aleksei; Hou, Jun-li; Kumar, Manish

    2015-08-11

    Bioinspired artificial water channels aim to combine the high permeability and selectivity of biological aquaporin (AQP) water channels with chemical stability. Here, we carefully characterized a class of artificial water channels, peptide-appended pillar[5]arenes (PAPs). The average single-channel osmotic water permeability for PAPs is 1.0(± 0.3) × 10(-14) cm(3)/s or 3.5(± 1.0) × 10(8) water molecules per s, which is in the range of AQPs (3.4 ∼ 40.3 × 10(8) water molecules per s) and their current synthetic analogs, carbon nanotubes (CNTs, 9.0 × 10(8) water molecules per s). This permeability is an order of magnitude higher than first-generation artificial water channels (20 to ∼ 10(7) water molecules per s). Furthermore, within lipid bilayers, PAP channels can self-assemble into 2D arrays. Relevant to permeable membrane design, the pore density of PAP channel arrays (∼ 2.6 × 10(5) pores per μm(2)) is two orders of magnitude higher than that of CNT membranes (0.1 ∼ 2.5 × 10(3) pores per μm(2)). PAP channels thus combine the advantages of biological channels and CNTs and improve upon them through their relatively simple synthesis, chemical stability, and propensity to form arrays. PMID:26216964

  6. Highly permeable artificial water channels that can self-assemble into two-dimensional arrays

    PubMed Central

    Shen, Yue-xiao; Si, Wen; Erbakan, Mustafa; Decker, Karl; De Zorzi, Rita; Saboe, Patrick O.; Kang, You Jung; Majd, Sheereen; Butler, Peter J.; Walz, Thomas; Aksimentiev, Aleksei; Hou, Jun-li; Kumar, Manish

    2015-01-01

    Bioinspired artificial water channels aim to combine the high permeability and selectivity of biological aquaporin (AQP) water channels with chemical stability. Here, we carefully characterized a class of artificial water channels, peptide-appended pillar[5]arenes (PAPs). The average single-channel osmotic water permeability for PAPs is 1.0(±0.3) × 10−14 cm3/s or 3.5(±1.0) × 108 water molecules per s, which is in the range of AQPs (3.4∼40.3 × 108 water molecules per s) and their current synthetic analogs, carbon nanotubes (CNTs, 9.0 × 108 water molecules per s). This permeability is an order of magnitude higher than first-generation artificial water channels (20 to ∼107 water molecules per s). Furthermore, within lipid bilayers, PAP channels can self-assemble into 2D arrays. Relevant to permeable membrane design, the pore density of PAP channel arrays (∼2.6 × 105 pores per μm2) is two orders of magnitude higher than that of CNT membranes (0.1∼2.5 × 103 pores per μm2). PAP channels thus combine the advantages of biological channels and CNTs and improve upon them through their relatively simple synthesis, chemical stability, and propensity to form arrays. PMID:26216964

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

    PubMed

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

    2011-01-01

    A novel delivery carrier was developed using artificial oil bodies (AOBs). Plant seed oil bodies (OBs) consist of a triacylglycerol matrix surrounded by a monolayer of phospholipids embedded with the storage protein oleosin (Ole). Ole consists of a central hydrophobic domain with two amphiphatic arms that extrude from the surface of OBs. In this study, a bivalent anti-HER2/neu affibody domain (ZH2) was fused with Ole at the C terminus. After overproduction in Escherichia coli, the fusion protein (Ole-ZH2) was recovered to assemble AOBs. The size of self-assembled AOBs was tailored by varying the oil/Ole-ZH2 ratio and pH to reach a nanoscale. Upon co-incubation with tumor cells, the nanoscale AOBs encapsulated with a hydrophobic fluorescence dye were selectively internalized by HER2/neu-overexpressing cells and displayed biocompatibility with the cells. In addition, the ZH2-mediated endosomal entry of AOBs occurred in a time- and AOB dose-dependent manner. The internalization efficiency was as high as 90%. The internalized AOBs disintegrated at the non-permissive pH (e.g. in acidic endosomes) and the cargo dye was released. Results of in vitro study revealed a sustained and prolonged release profile. Taken together, our findings indicate the potential of AOBs as a delivery carrier. PMID:21135463

  8. Structure of Light-Harvesting Aggregates in Individual Chlorosomes.

    PubMed

    Günther, Lisa M; Jendrny, Marc; Bloemsma, Erik A; Tank, Marcus; Oostergetel, Gert T; Bryant, Donald A; Knoester, Jasper; Köhler, Jürgen

    2016-06-23

    Among all photosynthetic organisms, green bacteria have evolved one of the most efficient light-harvesting antenna, the chlorosome, that contains hundreds of thousands of bacteriochlorophyll molecules, allowing these bacteria to grow photosynthetically by absorbing only a few photons per bacteriochlorophyll molecule per day. In contrast to other photosynthetic light-harvesting antenna systems, for which a protein scaffold imposes the proper positioning of the chromophores with respect to each other, in chlorosomes, this is accomplished solely by self-assembly. This has aroused enormous interest in the structure-function relations of these assemblies, as they can serve as blueprints for artificial light harvesting systems. In spite of these efforts, conclusive structural information is not available yet, reflecting the sample heterogeneity inherent to the natural system. Here we combine mutagenesis, polarization-resolved single-particle fluorescence-excitation spectroscopy, cryo-electron microscopy, and theoretical modeling to study the chlorosomes of the green sulfur bacterium Chlorobaculum tepidum. We demonstrate that only the combination of these techniques yields unambiguous information on the structure of the bacteriochlorophyll aggregates within the chlorosomes. Moreover, we provide a quantitative estimate of the curvature variation of these aggregates that explains ongoing debates concerning the chlorosome structure. PMID:27240572

  9. In vitro re-hardening of artificial enamel caries lesions using enamel matrix proteins or self-assembling peptides

    PubMed Central

    Schmidlin, Patrick; Zobrist, Katja; Attin, Thomas; Wegehaupt, Florian

    2016-01-01

    ABSTRACT Objectives To assess the re-hardening potential of enamel matrix derivatives (EMD) and self-assembling peptides in vitro, hypothesizing that these materials may increase the mineralization of artificial carious lesions and improve hardness profiles. Material and Methods Forty-eight enamel samples were prepared from extracted bovine lower central incisors. After embedding and polishing, nail varnish was applied, leaving a defined test area. One third of this area was covered with a flowable composite (non-demineralized control). The remaining area was demineralized in an acidic buffer solution for 18 d to simulate a carious lesion. Half the demineralized area was then covered with composite (demineralized control), while the last third was left open for three test and one control treatments: (A) Application of enamel-matrix proteins (EMD - lyophilized protein fractions dissolved in acetic acid, Straumann), (B) self-assembling peptides (SAP, Curodont), or (C) amine fluoride solution (Am-F, GABA) for 5 min each. Untreated samples (D) served as control. After treatment, samples were immersed in artificial saliva for four weeks (remineralization phase) and microhardness (Knoop) depth profiles (25-300 µm) were obtained at sections. Two-way ANOVA was calculated to determine differences between the areas (re-hardening or softening). Results Decalcification resulted in significant softening of the subsurface enamel in all groups (A-D). A significant re-hardening up to 125 µm was observed in the EMD and SAP groups. Conclusions This study showed that EMD and SAP were able to improve the hardness profiles when applied to deep demineralized artificial lesions. However, further research is needed to verify and improve this observed effect. PMID:27008255

  10. Programmable self-assembly of metal ions inside artificial DNA duplexes

    NASA Astrophysics Data System (ADS)

    Tanaka, Kentaro; Clever, Guido H.; Takezawa, Yusuke; Yamada, Yasuyuki; Kaul, Corinna; Shionoya, Mitsuhiko; Carell, Thomas

    2006-12-01

    The ultimate bottom-up approach for the construction of functional nanosystems requires the precise arrangement of atoms and molecules in three dimensions. DNA is currently one of the most prominent molecules able to self-assemble into complex networks and is therefore regarded as the `silicon of the nano-world'. Metals and metal ions, in contrast, are the atomic building-blocks needed in such materials to establish functions such as electrical conductivity or magnetism. Here we report a new concept, which efficiently combines metal ions and DNA. The DNA structure is used as a matrix to program robustly the complexation of different metal ions under precise control with regard to element, number and composition.

  11. Natural strategies for photosynthetic light harvesting.

    PubMed

    Croce, Roberta; van Amerongen, Herbert

    2014-07-01

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

  12. Towards self-assembled hybrid artificial cells: novel bottom-up approaches to functional synthetic membranes.

    PubMed

    Brea, Roberto J; Hardy, Michael D; Devaraj, Neal K

    2015-09-01

    There has been increasing interest in utilizing bottom-up approaches to develop synthetic cells. A popular methodology is the integration of functionalized synthetic membranes with biological systems, producing "hybrid" artificial cells. This Concept article covers recent advances and the current state-of-the-art of such hybrid systems. Specifically, we describe minimal supramolecular constructs that faithfully mimic the structure and/or function of living cells, often by controlling the assembly of highly ordered membrane architectures with defined functionality. These studies give us a deeper understanding of the nature of living systems, bring new insights into the origin of cellular life, and provide novel synthetic chassis for advancing synthetic biology.

  13. Towards Self-Assembled Hybrid Artificial Cells: Novel Bottom-Up Approaches to Functional Synthetic Membranes

    PubMed Central

    Brea, Roberto J.; Hardy, Michael D.; Devaraj, Neal K.

    2015-01-01

    There has been increasing interest in utilizing bottom-up approaches to develop synthetic cells. A popular methodology is the integration of functionalized synthetic membranes with biological systems, producing “hybrid” artificial cells. This Concept article covers recent advances and the current state-of-the-art of such hybrid systems. Specifically, we describe minimal supramolecular constructs that faithfully mimic the structure and/or function of living cells, often by controlling the assembly of highly ordered membrane architectures with defined functionality. These studies give us a deeper understanding of the nature of living systems, bring new insights into the origin of cellular life, and provide novel synthetic chassis for advancing synthetic biology. PMID:26149747

  14. Dynamic, self-assembled aggregates of magnetized, millimeter-sized objects rotating at the liquid-air interface: macroscopic, two-dimensional classical artificial atoms and molecules.

    PubMed

    Grzybowski, B A; Jiang, X; Stone, H A; Whitesides, G M

    2001-07-01

    This paper describes self-assembly of millimeter-sized, magnetized disks floating on a liquid-air interface, and rotating under the influence of a rotating external magnetic field. Spinning of the disks results in hydrodynamic repulsion between them, while the rotating magnetic field produces an average confining potential acting on all disks. The interplay between hydrodynamic and magnetic interactions leads to the formation of patterns. Theoretical analysis of hydrodynamic and magnetic forces indicates that the interactions in this system are similar to those acting in systems of finite numbers of particles behaving classically ("classical artificial atoms"). Macroscopic artificial atoms and molecules are described, and the rules governing their morphologies outlined.

  15. The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c, d, or e mimics.

    PubMed

    Jochum, Tobias; Reddy, Chilla Malla; Eichhöfer, Andreas; Buth, Gernot; Szmytkowski, Jedrzej; Kalt, Heinz; Moss, David; Balaban, Teodor Silviu

    2008-09-01

    Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3(1) hydroxyl group and the 13(1) carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by approximately 30 cm(-1) to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom.

  16. Towards a comprehensive insight into efficient hydrogen production by self-assembled Ru(bpy)3(2+)-polymer-Pt artificial photosystems.

    PubMed

    Lin, Huan; Liu, Dan; Long, Jinlin; Zhang, Zizhong; Zhuang, Huaqiang; Zheng, Yi; Wang, Xuxu

    2015-04-28

    The role of polymers in artificial photosystems has been studied in detail. The photosystems were composed of tris(2,2'-bipyridyl) ruthenium(II) chloride as a photosensitizer (PS), colloidal Pt stabilized by polymer as a hydrogen-evolving catalyst and sodium ascorbate as an electron donor, without the addition of a traditional molecular electron mediator. Comprehensive insights into the production of hydrogen on irradiation with visible light were achieved. Several polymers, including neutral polyvinyl pyrrolidone, anionic poly(sodium 4-styrene sulfonate) and poly(acrylic acid) not only stabilized the nanoparticles, but were also effective in the production of hydrogen. Under the optimum conditions, an outstanding apparent quantum efficiency of 12.8% for the evolution of hydrogen was achieved. The formation of self-assembled and spatially separated donor-acceptor complexes via the non-covalent intermolecular interaction between PS and the polymer-Pt was pivotal in the efficient conversion of solar energy to hydrogen fuel. Important details of the photo-induced electron and energy transfer processes in the self-assembled artificial photosystems were determined by nanosecond transient absorption spectrometry and time-resolved fluorescence spectrometry. The initial step in the photo-catalytic production of hydrogen was a reductive quenching of the triplet excited state of the PS by sodium ascorbate, leading to a reduced form of PS, which could then be quickly quenched by the polymer. The rate-determining step was the electron transfer from PS to the catalyst via the polymer bridge. PMID:25811660

  17. Towards a comprehensive insight into efficient hydrogen production by self-assembled Ru(bpy)3(2+)-polymer-Pt artificial photosystems.

    PubMed

    Lin, Huan; Liu, Dan; Long, Jinlin; Zhang, Zizhong; Zhuang, Huaqiang; Zheng, Yi; Wang, Xuxu

    2015-04-28

    The role of polymers in artificial photosystems has been studied in detail. The photosystems were composed of tris(2,2'-bipyridyl) ruthenium(II) chloride as a photosensitizer (PS), colloidal Pt stabilized by polymer as a hydrogen-evolving catalyst and sodium ascorbate as an electron donor, without the addition of a traditional molecular electron mediator. Comprehensive insights into the production of hydrogen on irradiation with visible light were achieved. Several polymers, including neutral polyvinyl pyrrolidone, anionic poly(sodium 4-styrene sulfonate) and poly(acrylic acid) not only stabilized the nanoparticles, but were also effective in the production of hydrogen. Under the optimum conditions, an outstanding apparent quantum efficiency of 12.8% for the evolution of hydrogen was achieved. The formation of self-assembled and spatially separated donor-acceptor complexes via the non-covalent intermolecular interaction between PS and the polymer-Pt was pivotal in the efficient conversion of solar energy to hydrogen fuel. Important details of the photo-induced electron and energy transfer processes in the self-assembled artificial photosystems were determined by nanosecond transient absorption spectrometry and time-resolved fluorescence spectrometry. The initial step in the photo-catalytic production of hydrogen was a reductive quenching of the triplet excited state of the PS by sodium ascorbate, leading to a reduced form of PS, which could then be quickly quenched by the polymer. The rate-determining step was the electron transfer from PS to the catalyst via the polymer bridge.

  18. Self-assembled lipid bilayer materials

    DOEpatents

    Sasaki, Darryl Y.; Waggoner, Tina A.; Last, Julie A.

    2005-11-08

    The present invention is a self-assembling material comprised of stacks of lipid bilayers formed in a columnar structure, where the assembly process is mediated and regulated by chemical recognition events. The material, through the chemical recognition interactions, has a self-regulating system that corrects the radial size of the assembly creating a uniform diameter throughout most of the structure. The materials form and are stable in aqueous solution. These materials are useful as structural elements for the architecture of materials and components in nanotechnology, efficient light harvesting systems for optical sensing, chemical processing centers, and drug delivery vehicles.

  19. Light harvesting in photosystem II.

    PubMed

    van Amerongen, Herbert; Croce, Roberta

    2013-10-01

    Water oxidation in photosynthesis takes place in photosystem II (PSII). This photosystem is built around a reaction center (RC) where sunlight-induced charge separation occurs. This RC consists of various polypeptides that bind only a few chromophores or pigments, next to several other cofactors. It can handle far more photons than the ones absorbed by its own pigments and therefore, additional excitations are provided by the surrounding light-harvesting complexes or antennae. The RC is located in the PSII core that also contains the inner light-harvesting complexes CP43 and CP47, harboring 13 and 16 chlorophyll pigments, respectively. The core is surrounded by outer light-harvesting complexes (Lhcs), together forming the so-called supercomplexes, at least in plants. These PSII supercomplexes are complemented by some "extra" Lhcs, but their exact location in the thylakoid membrane is unknown. The whole system consists of many subunits and appears to be modular, i.e., both its composition and organization depend on environmental conditions, especially on the quality and intensity of the light. In this review, we will provide a short overview of the relation between the structure and organization of pigment-protein complexes in PSII, ranging from individual complexes to entire membranes and experimental and theoretical results on excitation energy transfer and charge separation. It will become clear that time-resolved fluorescence data can provide invaluable information about the organization and functioning of thylakoid membranes. At the end, an overview will be given of unanswered questions that should be addressed in the near future.

  20. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine-phenylalanine motif.

    PubMed

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K; Anson, Christopher E; Powell, Annie K; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N; Coles, Simon J; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G; Balaban, Teodor Silviu

    2016-01-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence. PMID:27582363

  1. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine-phenylalanine motif

    NASA Astrophysics Data System (ADS)

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-09-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence.

  2. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif

    PubMed Central

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-01-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence. PMID:27582363

  3. Semiconducting nanowires from hairpin-shaped self-assembling sexithiophenes.

    PubMed

    Tsai, Wei-Wen; Tevis, Ian D; Tayi, Alok S; Cui, Honggang; Stupp, Samuel I

    2010-11-18

    Conjugated organic molecules can be designed to self-assemble from solution into nanostructures for functions such as charge transport, light emission, or light harvesting. We report here the design and synthesis of a novel hairpin-shaped self-assembling molecule containing electronically active sexithiophene moieties. In several nonpolar organic solvents, such as toluene or chlorocyclohexane, this compound was found to form organogels composed of nanofibers with uniform diameters of 3.0 (±0.3) nm. NMR analysis and spectroscopic measurements revealed that the self-assembly is driven by π-π interactions of the sexithiophene moieties and hydrogen bonding among the amide groups at the head of the hairpin. Field effect transistors built with this molecule revealed p-type semiconducting behavior and higher hole mobilities when films were cast from solvents that promote self-assembly. We propose that hydrogen bonding and π-π stacking act synergistically to create ordered stacking of sexithiophene moieties, thus providing an efficient pathway for charge carriers within the nanowires. The nanostructures formed exhibit unusually broad absorbance in their UV-vis spectrum, which we attribute to the coexistence of both H and J aggregates from face-to-face π-π stacking of sexithiophene moieties and hierarchical bundling of the nanowires. The large absorption range associated with self-assembly of the hairpin molecules makes them potentially useful in light harvesting for energy applications. PMID:20698523

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

    PubMed

    Tamulis, A; Tamulis, V; Graja, A

    2006-04-01

    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

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

    PubMed

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

    2012-07-25

    The water-soluble hydrophilic part of human Aβ 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 Aβ 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 Aβ SAM are similar to those reported for the soluble Cu and heme bound Aβ peptide. Experiments performed on these Aβ-SAM electrodes clearly demonstrate that (1) heme bound Aβ is kinetically more competent in reducing O(2) than Cu bound Aβ, (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 Aβ peptides and PROS generation by its complexes with redox active metals and cofactors.

  6. Biogenesis of light harvesting proteins.

    PubMed

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

    2015-09-01

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

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

    PubMed Central

    Bradley, Kevin M

    2014-01-01

    Summary Synthetic biologists wishing to self-assemble large DNA (L-DNA) constructs from small DNA fragments made by automated synthesis need fragments that hybridize predictably. Such predictability is difficult to obtain with nucleotides built from just the four standard nucleotides. Natural DNA's peculiar combination of strong and weak G:C and A:T pairs, the context-dependence of the strengths of those pairs, unimolecular strand folding that competes with desired interstrand hybridization, and non-Watson–Crick interactions available to standard DNA, all contribute to this unpredictability. In principle, adding extra nucleotides to the genetic alphabet can improve the predictability and reliability of autonomous DNA self-assembly, simply by increasing the information density of oligonucleotide sequences. These extra nucleotides are now available as parts of artificially expanded genetic information systems (AEGIS), and tools are now available to generate entirely standard DNA from AEGIS DNA during PCR amplification. Here, we describe the OligArch (for "oligonucleotide architecting") software, an application that permits synthetic biologists to engineer optimally self-assembling DNA constructs from both six- and eight-letter AEGIS alphabets. This software has been used to design oligonucleotides that self-assemble to form complete genes from 20 or more single-stranded synthetic oligonucleotides. OligArch is therefore a key element of a scalable and integrated infrastructure for the rapid and designed engineering of biology. PMID:25161743

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

    PubMed

    Bradley, Kevin M; Benner, Steven A

    2014-01-01

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

  9. Principles of light harvesting from single photosynthetic complexes

    PubMed Central

    Schlau-Cohen, G. S.

    2015-01-01

    Photosynthetic systems harness sunlight to power most life on Earth. In the initial steps of photosynthetic light harvesting, absorbed energy is converted to chemical energy with near-unity quantum efficiency. This is achieved by an efficient, directional and regulated flow of energy through a network of proteins. Here, we discuss the following three key principles of this flow and of photosynthetic light harvesting: thermal fluctuations of the protein structure; intrinsic conformational switches with defined functional consequences; and environmentally triggered conformational switches. Through these principles, photosynthetic systems balance two types of operational costs: metabolic costs, or the cost of maintaining and running the molecular machinery, and opportunity costs, or the cost of losing any operational time. Understanding how the molecular machinery and dynamics are designed to balance these costs may provide a blueprint for improved artificial light-harvesting devices. With a multi-disciplinary approach combining knowledge of biology, this blueprint could lead to low-cost and more effective solar energy conversion. Photosynthetic systems achieve widespread light harvesting across the Earth's surface; in the face of our growing energy needs, this is functionality we need to replicate, and perhaps emulate. PMID:26052423

  10. Principles of light harvesting from single photosynthetic complexes.

    PubMed

    Schlau-Cohen, G S

    2015-06-01

    Photosynthetic systems harness sunlight to power most life on Earth. In the initial steps of photosynthetic light harvesting, absorbed energy is converted to chemical energy with near-unity quantum efficiency. This is achieved by an efficient, directional and regulated flow of energy through a network of proteins. Here, we discuss the following three key principles of this flow and of photosynthetic light harvesting: thermal fluctuations of the protein structure; intrinsic conformational switches with defined functional consequences; and environmentally triggered conformational switches. Through these principles, photosynthetic systems balance two types of operational costs: metabolic costs, or the cost of maintaining and running the molecular machinery, and opportunity costs, or the cost of losing any operational time. Understanding how the molecular machinery and dynamics are designed to balance these costs may provide a blueprint for improved artificial light-harvesting devices. With a multi-disciplinary approach combining knowledge of biology, this blueprint could lead to low-cost and more effective solar energy conversion. Photosynthetic systems achieve widespread light harvesting across the Earth's surface; in the face of our growing energy needs, this is functionality we need to replicate, and perhaps emulate. PMID:26052423

  11. Controlling Light Harvesting with Light.

    PubMed

    Gwizdala, Michal; Berera, Rudi; Kirilovsky, Diana; van Grondelle, Rienk; Krüger, Tjaart P J

    2016-09-14

    When exposed to intense sunlight, all organisms performing oxygenic photosynthesis implement various photoprotective strategies to prevent potentially lethal photodamage. The rapidly responding photoprotective mechanisms, occurring in the light-harvesting pigment-protein antennae, take effect within tens of seconds, while the dramatic and potentially harmful light intensity fluctuations manifest also on shorter time scales. Here we show that, upon illumination, individual phycobilisomes from Synechocystis PCC 6803, which, in vivo under low-light conditions, harvest solar energy, and have the built-in capacity to switch rapidly and reversibly into light-activated energy-dissipating states. Simultaneously measured fluorescence intensity, lifetime, and spectra, compared with a multicompartmental kinetic model, revealed that essentially any subunit of a phycobilisome can be quenched, and that the core complexes were targeted most frequently. Our results provide the first evidence for fluorescence blinking from a biologically active system at physiological light intensities and suggest that the light-controlled switches to intrinsically available energy-dissipating states are responsible for a novel type of photoprotection in cyanobacteria. We anticipate other photosynthetic organisms to employ similar strategies to respond instantly to rapid solar light intensity fluctuations. A detailed understanding of the photophysics of photosynthetic antenna complexes is of great interest for bioinspired solar energy technologies. PMID:27546794

  12. Controlling Light Harvesting with Light.

    PubMed

    Gwizdala, Michal; Berera, Rudi; Kirilovsky, Diana; van Grondelle, Rienk; Krüger, Tjaart P J

    2016-09-14

    When exposed to intense sunlight, all organisms performing oxygenic photosynthesis implement various photoprotective strategies to prevent potentially lethal photodamage. The rapidly responding photoprotective mechanisms, occurring in the light-harvesting pigment-protein antennae, take effect within tens of seconds, while the dramatic and potentially harmful light intensity fluctuations manifest also on shorter time scales. Here we show that, upon illumination, individual phycobilisomes from Synechocystis PCC 6803, which, in vivo under low-light conditions, harvest solar energy, and have the built-in capacity to switch rapidly and reversibly into light-activated energy-dissipating states. Simultaneously measured fluorescence intensity, lifetime, and spectra, compared with a multicompartmental kinetic model, revealed that essentially any subunit of a phycobilisome can be quenched, and that the core complexes were targeted most frequently. Our results provide the first evidence for fluorescence blinking from a biologically active system at physiological light intensities and suggest that the light-controlled switches to intrinsically available energy-dissipating states are responsible for a novel type of photoprotection in cyanobacteria. We anticipate other photosynthetic organisms to employ similar strategies to respond instantly to rapid solar light intensity fluctuations. A detailed understanding of the photophysics of photosynthetic antenna complexes is of great interest for bioinspired solar energy technologies.

  13. Self-assembling RNA square

    SciTech Connect

    Dibrov, Sergey M.; McLean, Jaime; Parsons, Jerod; Hermann, Thomas

    2011-12-22

    The three-dimensional structures of noncoding RNA molecules reveal recurring architectural motifs that have been exploited for the design of artificial RNA nanomaterials. Programmed assembly of RNA nanoobjects from autonomously folding tetraloop-receptor complexes as well as junction motifs has been achieved previously through sequence-directed hybridization of complex sets of long oligonucleotides. Due to size and complexity, structural characterization of artificial RNA nanoobjects has been limited to low-resolution microscopy studies. Here we present the design, construction, and crystal structure determination at 2.2 {angstrom} of the smallest yet square-shaped nanoobject made entirely of double-stranded RNA. The RNA square is comprised of 100 residues and self-assembles from four copies each of two oligonucleotides of 10 and 15 bases length. Despite the high symmetry on the level of secondary structure, the three-dimensional architecture of the square is asymmetric, with all four corners adopting distinct folding patterns. We demonstrate the programmed self-assembly of RNA squares from complex mixtures of corner units and establish a concept to exploit the RNA square as a combinatorial nanoscale platform.

  14. Self assembling proteins

    DOEpatents

    Yeates, Todd O.; Padilla, Jennifer; Colovos, Chris

    2004-06-29

    Novel fusion proteins capable of self-assembling into regular structures, as well as nucleic acids encoding the same, are provided. The subject fusion proteins comprise at least two oligomerization domains rigidly linked together, e.g. through an alpha helical linking group. Also provided are regular structures comprising a plurality of self-assembled fusion proteins of the subject invention, and methods for producing the same. The subject fusion proteins find use in the preparation of a variety of nanostructures, where such structures include: cages, shells, double-layer rings, two-dimensional layers, three-dimensional crystals, filaments, and tubes.

  15. Optimal Energy Transfer in Light-Harvesting Systems.

    PubMed

    Chen, Lipeng; Shenai, Prathamesh; Zheng, Fulu; Somoza, Alejandro; Zhao, Yang

    2015-08-20

    Photosynthesis is one of the most essential biological processes in which specialized pigment-protein complexes absorb solar photons, and with a remarkably high efficiency, guide the photo-induced excitation energy toward the reaction center to subsequently trigger its conversion to chemical energy. In this work, we review the principles of optimal energy transfer in various natural and artificial light harvesting systems. We begin by presenting the guiding principles for optimizing the energy transfer efficiency in systems connected to dissipative environments, with particular attention paid to the potential role of quantum coherence in light harvesting systems. We will comment briefly on photo-protective mechanisms in natural systems that ensure optimal functionality under varying ambient conditions. For completeness, we will also present an overview of the charge separation and electron transfer pathways in reaction centers. Finally, recent theoretical and experimental progress on excitation energy transfer, charge separation, and charge transport in artificial light harvesting systems is delineated, with organic solar cells taken as prime examples.

  16. Optimal Energy Transfer in Light-Harvesting Systems.

    PubMed

    Chen, Lipeng; Shenai, Prathamesh; Zheng, Fulu; Somoza, Alejandro; Zhao, Yang

    2015-01-01

    Photosynthesis is one of the most essential biological processes in which specialized pigment-protein complexes absorb solar photons, and with a remarkably high efficiency, guide the photo-induced excitation energy toward the reaction center to subsequently trigger its conversion to chemical energy. In this work, we review the principles of optimal energy transfer in various natural and artificial light harvesting systems. We begin by presenting the guiding principles for optimizing the energy transfer efficiency in systems connected to dissipative environments, with particular attention paid to the potential role of quantum coherence in light harvesting systems. We will comment briefly on photo-protective mechanisms in natural systems that ensure optimal functionality under varying ambient conditions. For completeness, we will also present an overview of the charge separation and electron transfer pathways in reaction centers. Finally, recent theoretical and experimental progress on excitation energy transfer, charge separation, and charge transport in artificial light harvesting systems is delineated, with organic solar cells taken as prime examples. PMID:26307957

  17. Modeling Protein Self Assembly

    ERIC Educational Resources Information Center

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

    2004-01-01

    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…

  18. Photovoltaic self-assembly.

    SciTech Connect

    Lavin, Judith; Kemp, Richard Alan; Stewart, Constantine A.

    2010-10-01

    This late-start LDRD was focused on the application of chemical principles of self-assembly on the ordering and placement of photovoltaic cells in a module. The drive for this chemical-based self-assembly stems from the escalating prices in the 'pick-and-place' technology currently used in the MEMS industries as the size of chips decreases. The chemical self-assembly principles are well-known on a molecular scale in other material science systems but to date had not been applied to the assembly of cells in a photovoltaic array or module. We explored several types of chemical-based self-assembly techniques, including gold-thiol interactions, liquid polymer binding, and hydrophobic-hydrophilic interactions designed to array both Si and GaAs PV chips onto a substrate. Additional research was focused on the modification of PV cells in an effort to gain control over the facial directionality of the cells in a solvent-based environment. Despite being a small footprint research project worked on for only a short time, the technical results and scientific accomplishments were significant and could prove to be enabling technology in the disruptive advancement of the microelectronic photovoltaics industry.

  19. PS2013 Satellite Workshop on Photosynthetic Light-Harvesting Systems

    SciTech Connect

    Niederman, Robert A.; Blankenship, Robert E.; Frank, Harry A.

    2015-02-07

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

  20. Programming Light-Harvesting Efficiency Using DNA Origami.

    PubMed

    Hemmig, Elisa A; Creatore, Celestino; Wünsch, Bettina; Hecker, Lisa; Mair, Philip; Parker, M Andy; Emmott, Stephen; Tinnefeld, Philip; Keyser, Ulrich F; Chin, Alex W

    2016-04-13

    The remarkable performance and quantum efficiency of biological light-harvesting complexes has prompted a multidisciplinary interest in engineering biologically inspired antenna systems as a possible route to novel solar cell technologies. Key to the effectiveness of biological "nanomachines" in light capture and energy transport is their highly ordered nanoscale architecture of photoactive molecules. Recently, DNA origami has emerged as a powerful tool for organizing multiple chromophores with base-pair accuracy and full geometric freedom. Here, we present a programmable antenna array on a DNA origami platform that enables the implementation of rationally designed antenna structures. We systematically analyze the light-harvesting efficiency with respect to number of donors and interdye distances of a ring-like antenna using ensemble and single-molecule fluorescence spectroscopy and detailed Förster modeling. This comprehensive study demonstrates exquisite and reliable structural control over multichromophoric geometries and points to DNA origami as highly versatile platform for testing design concepts in artificial light-harvesting networks. PMID:26906456

  1. Programming Light-Harvesting Efficiency Using DNA Origami

    PubMed Central

    2016-01-01

    The remarkable performance and quantum efficiency of biological light-harvesting complexes has prompted a multidisciplinary interest in engineering biologically inspired antenna systems as a possible route to novel solar cell technologies. Key to the effectiveness of biological “nanomachines” in light capture and energy transport is their highly ordered nanoscale architecture of photoactive molecules. Recently, DNA origami has emerged as a powerful tool for organizing multiple chromophores with base-pair accuracy and full geometric freedom. Here, we present a programmable antenna array on a DNA origami platform that enables the implementation of rationally designed antenna structures. We systematically analyze the light-harvesting efficiency with respect to number of donors and interdye distances of a ring-like antenna using ensemble and single-molecule fluorescence spectroscopy and detailed Förster modeling. This comprehensive study demonstrates exquisite and reliable structural control over multichromophoric geometries and points to DNA origami as highly versatile platform for testing design concepts in artificial light-harvesting networks. PMID:26906456

  2. Microtubule Self- Assembly

    NASA Astrophysics Data System (ADS)

    Jho, Yongseok; Choi, M. C.; Farago, O.; Kim, Mahnwon; Pincus, P. A.

    2008-03-01

    Microtubules are important structural elements for neurons. Microtubles are cylindrical pipes that are self-assembled from tubulin dimers, These structures are intimately related to the neuron transport system. Abnormal microtubule disintegration contributes to neuro-disease. For several decades, experimentalists investigated the structure of the microtubules using TEM and Cryo-EM. However, the detailed structure at a molecular level remain incompletely understood. . In this presentation, we report numerically studies of the self-assembly process using a toy model for tubulin dimers. We investigate the nature of the interactions which are essential to stabilize such the cylindrical assembly of protofilaments. We use Monte Carlo simulations to suggest the pathways for assembly and disassembly of the microtubules.

  3. Solar cells incorporating light harvesting arrays

    DOEpatents

    Lindsey, Jonathan S.; Meyer, Gerald J.

    2002-01-01

    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).

  4. Solar cells incorporating light harvesting arrays

    DOEpatents

    Lindsey, Jonathan S.; Meyer, Gerald J.

    2003-07-22

    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: ##EQU1## 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).

  5. A srikaya-like light-harvesting antenna based on graphene quantum dots and porphyrin unimolecular micelles.

    PubMed

    Liu, Yannan; Li, Shanlong; Li, Ke; Zheng, Yongli; Zhang, Meng; Cai, Caiyun; Yu, Chunyang; Zhou, Yongfeng; Yan, Deyue

    2016-07-19

    A novel hybrid light-harvesting antenna with a srikaya-like structure of multi-graphene quantum dots (GQDs) as donors and one porphyrin unimolecular micelle as the acceptor was constructed through electrostatic self-assembly. The constructed antenna showed a high energy transfer efficiency of up to 93.6% and an antenna effect of 7.3 in an aqueous solution. PMID:27374891

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

    SciTech Connect

    Marye Anne Fox, James K. Whitesell

    2012-11-02

    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.

  7. Toward a molecular programming language for algorithmic self-assembly

    NASA Astrophysics Data System (ADS)

    Patitz, Matthew John

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

  8. [INVITED] Self-assembled optical metamaterials

    NASA Astrophysics Data System (ADS)

    Baron, Alexandre; Aradian, Ashod; Ponsinet, Virginie; Barois, Philippe

    2016-08-01

    Self-assembled metamaterials constitute a promising platform to achieving bulk and homogenous optical materials that exhibit unusual effective medium properties. For many years now, the research community has contemplated lithographically fabricated metasurfaces, with extraordinary optical features. However, achieving large volumes at low cost is still a challenge by top-down fabrication. Bottom-up fabrication, that relies both on nanochemistry and self-assembly, is capable of building such materials while greatly reducing the energy footprint in the formulation of the metamaterial. Self-assembled metamaterials have shown that they are capable of reaching unprecedented values of bulkiness and homogeneity figures of merit. This feat is achieved by synthesizing plasmonic nanoresonators (meta-atoms in the sense of artificial polarizable units) and assembling them into a fully three-dimensional matrix through a variety of methods. Furthermore it has been shown that a wide range of material parameters can be tailored by controlling the geometry and composition of the meta-atoms as well as the volume fraction of the nano-objects in the metamaterial. Here we conduct a non-comprehensive review of some of the recent trends in self-assembled optical metamaterials and illustrate these trends with our recent work.

  9. Controlling self assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wei, Yanhu

    2007-12-01

    In this thesis, we demonstrate novel methods of controlling the morphology of self-assembled monolayers at the solution-graphite interface. Scanning tunneling microscopy is used to evaluate the capacity of chain length and weak dipolar interactions to direct packing and neighboring chain selection within monolayers. We designed and synthesized a series of 1,5-substituted anthracene derivatives and investigated the relationship between side chain structure and monolayer morphology. We report that the morphology of monolayers formed on HOPG from symmetrically substituted anthracene derivatives switches from a 2D racemate to a 2D conglomerate by the addition of a single methylene unit to each side chain, i.e., by changing the side chain lengths from even to odd. We introduced ether groups into the side chains of anthracene derivatives in an attempt to use dipolar interactions to alter monolayer morphology. We report that the insertion of electronegative oxygen atoms into the side chains of anthracene derivatives can disturb the odd - even effect of chain length and influence monolayer morphology. By introducing a proper number of ether groups at specific side chain locations, we designed two self-repelling and complementary chains: COC12OC and C2OC10OC 2. COC12OC (or C2OC10OC2) chains repel themselves but select the other C2OC10OC 2 (or COC12OC) chains as their neighbors in self-assembled monolayers. Taking into account chain length matching and dipolar complementary as mechanisms for adjacent side chain selection, we designed and synthesized two symmetrical anthracenes 12 (COC12OC-An-COC 12OC), 13 (C2OC10OC2-An-C 2OC10OC2) and two unsymmetrical anthracenes 15 (C11OC-An-COC12OC) and 16 (C 18OC2-An-C2OC10OC2). Using a mixture solution of these molecules, we prepared a highly ordered AABB monolayer pattern in which paired rows of 15 alternate with paired rows of 16, and a highly ordered AAB monolayer pattern in which rows consisting of 12 are sandwiched between paired

  10. Self-Assembling Hydrogel Scaffolds for Photocatalytic Hydrogen Production

    PubMed Central

    Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; McClendon, Mark; Koltonow, Andrew R.; Samuel, Amanda P. S.; Kiebala, Derek J.; Wasielewski, Michael R.; Stupp, Samuel I.

    2015-01-01

    catalysts for water oxidation and proton reduction3-7. In other recent work, catalysts have been coupled to light absorbing CdSe quantum dots8, Si microrods9, and organic dyes10,11 to create artificial photosynthetic systems. Also functional devices capable of performing water-splitting and fuel-generating reactions using earth-abundant resources have been demonstrated12. The development of bionspired soft materials that can be shaped into forms and integrate light-harvesting, charge transport, and catalytic functions to produce solar fuels is an obvious gap. This gap can be addressed through self-assembly strategies for materials in which a bottom-up approach fine tunes all functional aspects of a catalytic system13. Organic systems may have shorter lifetimes than their inorganic counterparts, but could have their own niche in sustainable energy given their soft matter nature and low energy requirements for production. We report here on a strategy to create supramolecular hydrogels that integrate both light-absorbing chromophores and catalysts into a material for light-driven hydrogen (H2) production. Our work here is focused only on the supramolecular chemistry necessary to create a formable catalytic material and therefore does not explore its possible integration into a photocathode that would not require a sacrificial electron donor. We designed a charged amphiphilic chromophore with the capacity to self-assemble into supramolecular polymers via hydrophobic collapse. At sufficiently high concentrations and under electrostatic screening conditions, charged supramolecular polymers can easily produce a three-dimensional network that takes the form of a gel. These networks could be highly hydrated and host the soluble components necessary to produce the solar fuel. At the same time, much like natural photosynthetic antennae, supramolecular structures of conjugated molecules formed through π orbital overlap should have the capacity to absorb light, split excitons, and

  11. Photosynthetic light harvesting: excitons and coherence

    PubMed Central

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

    2014-01-01

    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

  12. Photosynthetic light harvesting: excitons and coherence.

    PubMed

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

    2014-03-01

    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.

  13. Solid-state NMR applied to photosynthetic light-harvesting complexes.

    PubMed

    Pandit, Anjali; de Groot, Huub J M

    2012-03-01

    This short review describes how solid-state NMR has provided a mechanistic and electronic picture of pigment-protein and pigment-pigment interactions in photosynthetic antenna complexes. NMR results on purple bacterial antenna complexes show how the packing of the protein and the pigments inside the light-harvesting oligomers induces mutual conformational stress. The protein scaffold produces deformation and electrostatic polarization of the BChl macrocycles and leads to a partial electronic charge transfer between the BChls and their coordinating histidines, which can tune the light-harvesting function. In chlorosome antennae assemblies, the NMR template structure reveals how the chromophores can direct their self-assembly into higher macrostructures which, in turn, tune the light-harvesting properties of the individual molecules by controlling their disorder, structural deformation, and electronic polarization without the need for a protein scaffold. These results pave the way for addressing the next challenge, which is to resolve the functional conformational dynamics of the lhc antennae of oxygenic species that allows them to switch between light-emitting and light-energy dissipating states.

  14. Self-assembly of peptide-porphyrin complexes leads to pH-dependent excitonic coupling.

    PubMed

    Kuciauskas, Darius; Caputo, Gregory A

    2009-10-29

    Using absorbance, fluorescence, resonance light scattering, and circular dichroism spectroscopy, we studied the self-assembly of the anionic meso-tetra(4-sulfonatophenyl)porphine (TPPS(4)(2-/4-)) and a cationic 22-residue polypeptide. We found that three TPPS(4)(2-/4-) molecules bind to the peptide, which contains nine lysine residues in the primary sequence. In acidic solutions, when the peptide is in the random-coil conformation, TPPS(4)(2-) bound to the peptide forms excitonically coupled J-aggregates. In pH 7.6 solutions, when the peptide secondary structure is partially alpha-helical, the porphyrin-to-peptide binding constants are approximately the same as in acidic solutions (approximately 3 x 10(6) M(-1)), but excitonic interactions between the porphyrins are insignificant. The binding of TPPS(4)(2-/4-) to lysine-containing peptides is cooperative and can be described by the Hill model. Our results show that porphyrin binding can be used to change the secondary structure of peptide-based biomaterials. In addition, binding to peptides could be used to optimize porphyrin intermolecular electronic interactions (exciton coupling), which is relevant for the design of light-harvesting antennas for artificial photosynthesis.

  15. Rod-like nano-light harvester.

    PubMed

    Ling, Jun; Zheng, Zhicheng; Köhler, Anna; Müller, Axel H E

    2014-01-01

    Imitating the natural "energy cascade" architecture, we present a single-molecular rod-like nano-light harvester (NLH) based on a cylindrical polymer brush. Block copolymer side chains carrying (9,9-diethylfluoren-2-yl)methyl methacrylate units as light absorbing antennae (energy donors) are tethered to a linear polymer backbone containing 9-anthracenemethyl methacrylate units as emitting groups (energy acceptors). These NLHs exhibit very efficient energy absorption and transfer. Moreover, we manipulate the energy transfer by tuning the donor-acceptor distance.

  16. Temperature and Ionic Strength Effects on the Chlorosome Light-Harvesting Antenna Complex

    SciTech Connect

    Tang, Kuo-Hsiang; Zhu, Liying; Urban, Volker S; Collins, Aaron M.; Biswas, Pratim; Blankenship, R. E.

    2011-03-15

    Chlorosomes, the peripheral light-harvesting antenna complex from green photosynthetic bacteria, are the largest and one of the most efficient light-harvesting antenna complexes found in nature. In contrast to other light-harvesting antennas, chlorosomes are constructed from more than 150,000 self-assembled bacteriochlorophylls (BChls) and contain relatively few proteins that play secondary roles. These unique properties have led to chlorosomes as an attractive candidate for developing biohybrid solar cell devices. In this article, we investigate the temperature and ionic strength effects on the viability of chlorosomes from the photosynthetic green bacterium Chloroflexus aurantiacus using small-angle neutron scattering and dynamic light scattering. Our studies indicate that chlorosomes remain intact up to 75 °C and that salt induces the formation of large aggregates of chlorosomes. No internal structural changes are observed for the aggregates. The salt-induced aggregation, which is a reversible process, is more efficient with divalent metal ions than with monovalent metal ions. Moreover, with treatment at 98 °C for 2 min, the bulk of the chlorosome pigments are undamaged, while the baseplate is destroyed. Chlorosomes without the baseplate remain rodlike in shape and are 30-40% smaller than with the baseplate attached. Further, chlorosomes are stable from pH 5.5 to 11.0. Together, this is the first time such a range of characterization tools have been used for chlorosomes, and this has enabled elucidation of properties that are not only important to understanding their functionality but also may be useful in biohybrid devices for effective light harvesting.

  17. Quantum mechanical light harvesting mechanisms in photosynthesis

    NASA Astrophysics Data System (ADS)

    Scholes, Gregory

    2012-02-01

    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).

  18. Design strategies for self-assembly of discrete targets

    SciTech Connect

    Madge, Jim; Miller, Mark A.

    2015-07-28

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

  19. Nanoparticle induced self-assembly.

    PubMed

    Helgesen, G; Svåsand, E; Skjeltorp, A T

    2008-05-21

    Self-assembly has for the large part focused on the assembly of molecules without guidance or management from an outside source. However, self-assembly is in principle by no means limited to molecules or the nanoscale. A particularly interesting method to the self-assembly of micro- to millimetre sized components is the use of the 'magnetic hole' effect. In this method, nonmagnetic particles can be manipulated by external magnetic fields by immersing them in a dispersion of colloidal, magnetic nanoparticles, denoted ferrofluids. Nonmagnetic particles in magnetized ferrofluids are in many ways ideal model systems to test various forms of particle self-assembly and dynamics. When microspheres are confined to a monolayer between two parallel plates and subjected to static or oscillating magnetic fields they show a variety of dynamical behaviours and assemblages, depending on the frequency and direction of the external fields. A single pair of magnetic holes oscillating in a ferrofluid layer may be used to measure the viscosity of tiny volumes of the fluid. We have also observed ordering of dilute dispersions of macromolecules and nanoparticles in magnetized ferrofluids. The self-assembly at this length scale results from structural correlations between these nanostructures and ferrofluid particles rather than from the macroscopic magnetostatic effect for the magnetic holes.

  20. Applications of textured surfaces for light harvesting

    NASA Astrophysics Data System (ADS)

    Cocilovo, Byron

    Surface textures add another dimension to optical design. They can be used to redirect light, isolate spectral bands, and enhance optical fields. They effectively take up no space, so can be applied to any optical surface -- from intermediary elements to substrates. Here I present three applications of textured surfaces for light harvesting. The first project places scattering textures inside a film that can be applied to windows to scatter infrared light towards solar cells at the edges. The collected energy is then used to power tinting films. The second project uses modular diffractive structures to increase the absorption in solar cells. Lastly, structured silver surfaces are used to enhance plasmonics fields and increase two-photon excitation fluorescence.

  1. The use of layer by layer self-assembled coatings of hyaluronic acid and cationized gelatin to improve the biocompatibility of poly(ethylene terephthalate) artificial ligaments for reconstruction of the anterior cruciate ligament.

    PubMed

    Li, Hong; Chen, Chen; Zhang, Shurong; Jiang, Jia; Tao, Hongyue; Xu, Jialing; Sun, Jianguo; Zhong, Wei; Chen, Shiyi

    2012-11-01

    In this study layer by layer (LBL) self-assembled coatings of hyaluronic acid (HA) and cationized gelatin (CG) were used to modify polyethylene terephthalate (PET) artificial ligament grafts. Changes in the surface properties were characterized by scanning electron microscopy, attenuated total reflection Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and contact angle and biomechanical measurements. The cell compatibility of this HA-CG coating was investigated in vitro on PET films seeded with human foreskin dermal fibroblasts over 7days. The results of our in vitro studies demonstrated that the HA-CG coating significantly enhanced cell adhesion, facilitated cell growth, and suppressed the expression of inflammation-related genes relative to a pure PET graft. Furthermore, rabbit and porcine anterior cruciate ligament reconstruction models were used to evaluate the effect of this LBL coating in vivo. The animal experiment results proved that this LBL coating significantly inhibited inflammatory cell infiltration and promoted new ligament tissue regeneration among the graft fibers. In addition, the formation of type I collagen in the HA-CG coating group was much higher than in the control group. Based on these results we conclude that PET grafts coated with HA-CG have considerable potential as substitutes for ligament reconstruction.

  2. Self-assembly via microfluidics.

    PubMed

    Wang, Lei; Sánchez, Samuel

    2015-12-01

    The self-assembly of amphiphilic building blocks has attracted extensive interest in myriad fields in recent years, due to their great potential in the nanoscale design of functional hybrid materials. Microfluidic techniques provide an intriguing method to control kinetic aspects of the self-assembly of molecular amphiphiles by the facile adjustment of the hydrodynamics of the fluids. Up to now, there have been several reports about one-step direct self-assembly of different building blocks with versatile and multi-shape products without templates, which demonstrated the advantages of microfluidics. These assemblies with different morphologies have great applications in various areas such as cancer therapy, micromotor fabrication, and controlled drug delivery.

  3. Onset of self-assembly

    SciTech Connect

    Chitanvis, S.M.

    1998-02-01

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

  4. Self-assembling amphiphilic peptides†

    PubMed Central

    Dehsorkhi, Ashkan; Castelletto, Valeria; Hamley, Ian W

    2014-01-01

    The self-assembly of several classes of amphiphilic peptides is reviewed, and selected applications are discussed. We discuss recent work on the self-assembly of lipopeptides, surfactant-like peptides and amyloid peptides derived from the amyloid-β peptide. The influence of environmental variables such as pH and temperature on aggregate nanostructure is discussed. Enzyme-induced remodelling due to peptide cleavage and nanostructure control through photocleavage or photo-cross-linking are also considered. Lastly, selected applications of amphiphilic peptides in biomedicine and materials science are outlined. © 2014 The Authors. Journal of Peptide Science published by European Peptide Society and John Wiley & Sons, Ltd. PMID:24729276

  5. Light-Harvesting Nanoparticle Core-Shell Clusters with Controllable Optical Output.

    PubMed

    Sun, Dazhi; Tian, Ye; Zhang, Yugang; Xu, Zhihua; Sfeir, Matthew Y; Cotlet, Mircea; Gang, Oleg

    2015-06-23

    We used DNA self-assembly methods to fabricate a series of core-shell gold nanoparticle-DNA-colloidal quantum dot (AuNP-DNA-Qdot) nanoclusters with satellite-like architecture to modulate optical (photoluminescence) response. By varying the intercomponent distance through the DNA linker length designs, we demonstrate precise tuning of the plasmon-exciton interaction and the optical behavior of the nanoclusters from regimes characterized by photoluminescence quenching to photoluminescence enhancement. The combination of detailed X-ray scattering probing with photoluminescence intensity and lifetime studies revealed the relation between the cluster structure and its optical output. Compared to conventional light-harvesting systems like conjugated polymers and multichromophoric dendrimers, the proposed nanoclusters bring enhanced flexibility in controlling the optical behavior toward a desired application, and they can be regarded as controllable optical switches via the optically pumped color.

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

    NASA Astrophysics Data System (ADS)

    Harel, Elad

    2012-05-01

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

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

    SciTech Connect

    Harel, Elad

    2012-05-07

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

  8. Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

    NASA Astrophysics Data System (ADS)

    Tian, Yongming; M. Beavers, Christine; Busani, Tito; Martin, Kathleen E.; Jacobsen, John L.; Mercado, Brandon Q.; Swartzentruber, Brian S.; van Swol, Frank; Medforth, Craig J.; Shelnutt, John A.

    2012-02-01

    Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS4- (an electron donor) and three half molecules of dihydroxy-SnTNMePyP4+ (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π-π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π-π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers.Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room

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

    PubMed Central

    Patole, Samson; Vasilev, Cvetelin; El-Zubir, Osama; Wang, Lin; Johnson, Matthew P.; Cadby, Ashley J.; Leggett, Graham J.; Hunter, C. Neil

    2015-01-01

    We describe a facile approach for nanopatterning of photosynthetic light-harvesting complexes over macroscopic areas, and use optical spectroscopy to demonstrate retention of native properties by both site-specifically and non-specifically attached photosynthetic membrane proteins. A Lloyd's mirror dual-beam interferometer was used to expose self-assembled monolayers of amine-terminated alkylthiolates on gold to laser irradiation. Following exposure, photo-oxidized adsorbates were replaced by oligo(ethylene glycol) terminated thiols, and the remaining intact amine-functionalized regions were used for attachment of the major light-harvesting chlorophyll–protein complex from plants, LHCII. These amine patterns could be derivatized with nitrilotriacetic acid (NTA), so that polyhistidine-tagged bacteriochlorophyll–protein complexes from phototrophic bacteria could be attached with a defined surface orientation. By varying parameters such as the angle between the interfering beams and the laser irradiation dose, it was possible to vary the period and widths of NTA and amine-functionalized lines on the surfaces; periods varied from 1200 to 240 nm and linewidths as small as 60 nm (λ/4) were achieved. This level of control over the surface chemistry was reflected in the surface topology of the protein nanostructures imaged by atomic force microscopy; fluorescence imaging and spectral measurements demonstrated that the surface-attached proteins had retained their native functionality. PMID:26464784

  10. Development of Scaffolds for Light Harvesting and Photocatalysis from the Coat Protein of Tobacco Mosaic Virus

    NASA Astrophysics Data System (ADS)

    Dedeo, Michel Toussaint

    The utility of a previously developed TMV-based light harvesting system has been dramatically expanded through the introduction of reactive handles for the site-specific modification of the interior and exterior surfaces. Further experiments to reengineer the coat protein have produced structures with unique, unexpected, and useful assembly properties that complement the newly available surface modifications. Energy transfer from chromophores in the RNA channel of self-assembled TMV structures to the exterior was made possible by conjugation of acceptor dyes and porphyrins to the N-terminus. By repositioning the N-terminus to the pore through circular permutation, this process was repeated to create structures that mimic the light harvesting 1 complex of photosynthetic bacteria. To study and improve upon natural photosynthesis, closely packed chromophore arrays and gold nanoparticles were tethered to the pore of stabilized TMV disks through introduction of a uniquely reactive lysine. Finally, a dimeric TMV coat protein was produced to control the distribution and arrangement of synthetic groups with synergistic activity.

  11. Polymer light harvesting composites for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Wang, Dan

    2015-09-01

    Polymer based optoelectronic composites and thin film devices exhibit great potential in space applications due to their lightweight, flexible shape, high photon absorption coefficients, and robust radiation tolerance in space environment. Polymer/dye composites appear promising for optoelectronics applications due to potential enhancements in both light harvesting and charge separation. In this study, the optoelectronic properties of a series of molecular dyes paired with a conjugated polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT) were investigated. Specifically, the solution PL quenching coefficients (Ksv) of dye/polymer follows a descending order from dyes of Chloro(protoporphyrinato)iron(III) (Hemin), Protoporphyrin, to meso-Tetra(4-carboxyphenyl)porphine (TCPP). In optoelectronic devices made of the P3HT/dye/PCBM composites, the short circuit current densities Jsc as well as the overall power conversion efficiencies (PCE) also follow a descending order from Hemin, Protoporphyrin, to TCPP, despite Hemin exhibits the intermediate polymer/dye LUMO (lowest unoccupied molecular orbital) offset and lowest absorption coefficient as compared to the other two dyes, i.e., the cell optoelectronic efficiency did not follow the LUMO offsets which are the key driving forces for the photo induced charge separations. This study reveals that too large LUMO offset or electron transfer driving force may result in smaller PL quenching and optoelectronic conversion efficiency, this could be another experimental evidence for the Marcus electron transfer model, particularly for the Marcus `inverted region'. It appears an optimum electron transfer driving force or strong PL quenching appears more critical than absorption coefficient for optoelectronic conversion devices.

  12. Multifunctional self-assembled monolayers

    SciTech Connect

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F.; Ferrais, J.

    1996-06-01

    This is the final report of at three year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The specific goals of this research project were threefold: to develop multifunctional self-assembled monolayers, to understand the role of monolayer structure on the functioning of such systems, and to apply this knowledge to the development of electrochemical enzyme sensors. An array of molecules that can be used to attach electrochemically active biomolecules to gold surfaces has been synthesized. Several members of a class of electroactive compounds have been characterized and the factors controlling surface modification are beginning to be characterized. Enzymes have been attached to self-assembled molecules arranged on the gold surface, a critical step toward the ultimate goal of this project. Several alternative enzyme attachment strategies to achieve robust enzyme- modified surfaces have been explored. Several means of juxtaposing enzymes and mediators, electroactive compounds through which the enzyme can exchange electrons with the electrode surface, have also been investigated. Finally, the development of sensitive biosensors based on films loaded with nanoscale-supported gold particles that have surface modified with the self-assembled enzyme and mediator have been explored.

  13. Self-assembled plasmonic metamaterials

    NASA Astrophysics Data System (ADS)

    Mühlig, Stefan; Cunningham, Alastair; Dintinger, José; Scharf, Toralf; Bürgi, Thomas; Lederer, Falk; Rockstuhl, Carsten

    2013-07-01

    Nowadays for the sake of convenience most plasmonic nanostructures are fabricated by top-down nanofabrication technologies. This offers great degrees of freedom to tailor the geometry with unprecedented precision. However, it often causes disadvantages as well. The structures available are usually planar and periodically arranged. Therefore, bulk plasmonic structures are difficult to fabricate and the periodic arrangement causes undesired effects, e.g., strong spatial dispersion is observed in metamaterials. These limitations can be mitigated by relying on bottom-up nanofabrication technologies. There, self-assembly methods and techniques from the field of colloidal nanochemistry are used to build complex functional unit cells in solution from an ensemble of simple building blocks, i.e., in most cases plasmonic nanoparticles. Achievable structures are characterized by a high degree of nominal order only on a short-range scale. The precise spatial arrangement across larger dimensions is not possible in most cases; leading essentially to amorphous structures. Such self-assembled nanostructures require novel analytical means to describe their properties, innovative designs of functional elements that possess a desired near- and far-field response, and entail genuine nanofabrication and characterization techniques. Eventually, novel applications have to be perceived that are adapted to the specifics of the self-assembled nanostructures. This review shall document recent progress in this field of research. Emphasis is put on bottom-up amorphous metamaterials. We document the state-of-the-art but also critically assess the problems that have to be overcome.

  14. Spectroscopic Investigations of the Photophysics of Cryptophyte Light-Harvesting

    NASA Astrophysics Data System (ADS)

    Dinshaw, Rayomond

    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.

  15. Biogeography of Photosynthetic Light-Harvesting Genes in Marine Phytoplankton

    PubMed Central

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

    2009-01-01

    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

  16. The structure and function of bacterial light-harvesting complexes.

    PubMed

    Law, Christopher J; Roszak, Aleksander W; Southall, June; Gardiner, Alastair T; Isaacs, Neil W; Cogdell, Richard J

    2004-01-01

    The harvesting of solar radiation by purple photosynthetic bacteria is achieved by circular, integral membrane pigment-protein complexes. There are two main types of light-harvesting complex, termed LH2 and LH1, that function to absorb light energy and to transfer that energy rapidly and efficiently to the photochemical reaction centres where it is trapped. This mini-review describes our present understanding of the structure and function of the purple bacterial light-harvesting complexes.

  17. Synergistic Two-Photon Absorption Enhancement in Photosynthetic Light Harvesting

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    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.

  18. A self-assembled ionophore

    NASA Astrophysics Data System (ADS)

    Tirumala, Sampath K.

    1997-11-01

    Ionophores are compounds that bind and transport ions. Ion binding and transport are fundamental to many biological and chemical processes. In this thesis we detail the structural characterization and cation binding properties of a self-assembled ionophore built from an isoguanosine (isoG) derivative, 5sp'-t-butyldimethylsilyl-2sp',3sp'-isopropylidene isoG 30. We begin with a summary of the themes that facilitate ionophore design and the definitions of "self-assembly" and "self-assembled ionophore" in Chapter 1. In Chapter 2, we describe the structural characterization of the isoG 30 self-assembly. IsoG possesses complementary hydrogen bond donor and acceptor sites suitable to form a Csb4-symmetric tetramer, (isoG)sb4 51, that is stable even in high dielectric organic solvents such as CDsb3CN and dsb6-acetone. The isoG tetramer 51 has been characterized by vapor phase osmometry, UV spectroscopy, and by 1D and 2D NMR spectroscopy. The isoG tetramer 51 organizes by hydrogen bonding between the Watson-Crick face of one isoG base and the complementary bottom edge of another purine. The tetramer 51 is stabilized by an inner and outer ring of hydrogen bonds. The inner ring forms between the imino NH1 proton of one monomer and the C2 carbonyl oxygen of an adjacent monomer, while the outer ring is made up of four NH6-N3 hydrogen bonds. The isoG tetramer 51 is thermodynamically stable, with an equilibrium constant (Ksba) of ca. 10sp9-10sp{10} Msp{-3} at room temperature, and a DeltaGsp° of tetramer formation of -12.5 kcal molsp{-1} in dsb6-acetone at 25sp°C. The van't Hoff plots indicated that the thermodynamic parameters for tetramer formation were DeltaHsp° = -18.2 ± 0.87 kcal molsp{-1} and DeltaSsp°sb{298} = -19.1 ± 5.45 eu. In Chapter 3, we describe the cation binding properties of isoG tetramer 51. The isoG tetramer 51 has a central cavity, containing four oxygen atoms, that is suitable for cation coordination. Depending on the cation, the resulting iso

  19. Self-assembling magnetic "snakes"

    SciTech Connect

    2010-01-01

    Nickel particles float peacefully in a liquid medium until a giant snake seems to swim by and snatch several particles up, adding to its own mass. The self-assembled "snakes" act like biological systems, but they are not alive and are driven by a magnetic field. The research may someday offer some insight into the organization of life itself. Read more at Wired: http://www.wired.com/wiredscience/2009/03/snakes/ Research and video by Alex Snezhko and Igor Aronson, Argonne National Laboratory.

  20. Self-assembled controllable microswimmers

    NASA Astrophysics Data System (ADS)

    Grosjean, Galien; Lagubeau, Guillaume; Darras, Alexis; Lumay, Geoffroy; Hubert, Maxime; Vandewalle, Nicolas

    2015-11-01

    Because they cause a deformation of the interface, floating particles interact. In particular, identical particles attract each other. To counter this attraction, particles possessing a large magnetic moment m-> are used. When m-> is perpendicular to the surface, dipole-dipole interaction is repulsive. This competition of forces can lead to the spontaneous formation of organized structures. By using submillimetric steel spheres for which m-> ~ B-> , interdistances in the system can be precisely tuned. Here, we deform these self-assemblies by adding a horizontal contribution m-> to the magnetic moment. Time reversal symmetry is broken in the system, leading to locomotion at low Reynolds number. Moreover, swimming direction depends on the orientation of field, meaning that swimming trajectories can be finely controlled. A model allows to understand the breaking of symmetry, while a study of the vibration modes gives further informations on the dynamics of this sytem. Because this system forms by self-assembly, it allows miniaturization with applications such as cargo transport or solvent flows. It is highly versatile, being composed of simple passive particles and controlled by magnetic fields.

  1. Chemical reactions directed Peptide self-assembly.

    PubMed

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-01-01

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

  2. Chemical Reactions Directed Peptide Self-Assembly

    PubMed Central

    Rasale, Dnyaneshwar B.; Das, Apurba K.

    2015-01-01

    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly. PMID:25984603

  3. Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces.

    PubMed

    Shi, Yanhui; Sánchez-Molina, Irene; Cao, Changsheng; Cook, Timothy R; Stang, Peter J

    2014-07-01

    Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP.

  4. Convergent synthesis of multiporphyrin light-harvesting rods

    DOEpatents

    Lindsey, Jonathan S.; Loewe, Robert S.

    2003-08-05

    The present invention provides a convergent method for the synthesis of light harvesting rods. The rods are oligomers of the formula A.sup.1 (A.sup.b+1).sub.b, wherein b is at least 1, A.sup.1 through A.sup.b+1 are covalently coupled rod segments, and each rod segment A.sup.1 through A.sup.1+b comprises a compound of the formula X.sup.1 (X.sup.m+1).sub.m wherein m is at least 1 and X.sup.1 through X.sup.m+1 are covalently coupled porphyrinic macrocycles. Light harvesting arrays and solar cells containing such light harvesting rods are also described, along with intermediates useful in such methods and rods produced by such methods.

  5. Self-assembled nanomaterials for photoacoustic imaging

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  6. Self-Assembly: How Nature Builds

    ERIC Educational Resources Information Center

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

    2006-01-01

    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…

  7. Transport and photodetection in self-assembled semiconductor quantum dots.

    PubMed

    Razeghi, M; Lim, H; Tsao, S; Szafraniec, J; Zhang, W; Mi, K; Movaghar, B

    2005-02-01

    A great step forward in science and technology was made when it was discovered that lattice mismatch can be used to grow highly ordered, artificial atom-like structures called self-assembled quantum dots. Several groups have in the meantime successfully demonstrated useful infrared photodetection devices which are based on this technology. The new physics is fascinating, and there is no doubt that many new applications will be found when we have developed a better understanding of the underlying physical processes, and in particular when we have learned how to integrate the exciting new developments made in nanoscopic addressing and molecular self-assembly methods with semiconducting dots. In this paper we examine the scientific and technical questions encountered in current state of the art infrared detector technology and suggest ways of overcoming these difficulties. Promoting simple physical pictures, we focus in particular on the problem of high temperature detector operation and discuss the origin of dark current, noise, and photoresponse.

  8. Light-harvesting photocatalysis for water oxidation using mesoporous organosilica.

    PubMed

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

    2014-07-14

    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.

  9. Design directed self-assembly of donor-acceptor polymers.

    PubMed

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements. PMID:27440174

  10. Protein self-assembly via supramolecular strategies.

    PubMed

    Bai, Yushi; Luo, Quan; Liu, Junqiu

    2016-05-21

    Proteins, as the elemental basis of living organisms, mostly execute their biological tasks in the form of supramolecular self-assemblies with subtle architectures, dynamic interactions and versatile functionalities. Inspired by the structural harmony and functional beauty of natural protein self-assemblies to fabricate sophisticated yet highly ordered protein superstructures represents an adventure in the pursuit of nature's supreme wisdom. In this review, we focus on building protein self-assembly systems based on supramolecular strategies and classify recent progress by the types of utilized supramolecular driving forces. Especially, the design strategy, structure control and the thermodynamic/kinetic regulation of the self-assemblies, which will in turn provide insights into the natural biological self-assembly mechanism, are highlighted. In addition, recently, this research field is starting to extend its interest beyond constructing complex morphologies towards the potential applications of the self-assembly systems; several attempts to design functional protein complexes are also discussed. As such, we hope that this review will provide a panoramic sketch of the field and draw a roadmap towards the ultimate construction of advanced protein self-assemblies that even can serve as analogues of their natural counterparts.

  11. Self-assembling nanoparticles into holographic nanopatterns

    NASA Astrophysics Data System (ADS)

    Lee, Seung-Heon; Diana, Frédéric S.; Badolato, Antonio; Petroff, Pierre M.; Kramer, Edward J.

    2004-05-01

    We demonstrate a method to self-assemble metal nanoparticles into two-dimensional lattices. Monodisperse cobalt nanoparticles were synthesized within inverse micelles of polystyrene-block-poly(2-vinylpyridine) copolymer in toluene. A periodic hole pattern of photoresist (PR) was fabricated on a GaAs substrate by holographic lithography. The nanoparticles as prepared above were self-assembled onto the PR nanopatterns by dip or spin casting. They were selectively positioned in the holes due to the capillary forces related to the pattern geometry. Our study reveals that self-assembled nanoparticles in two-dimensional lattices can be obtained with a controllable number of particles per lattice point.

  12. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome’s Facet

    DOE PAGESBeta

    Mahalik, J. P.; Brown, Kirsten A.; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-02-24

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome s function and how it can be modified tomore » create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we explain a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome s facets is driven by a nucleation growth process, which in turn could play an important role in the hierarchical self- assembly of BMC shells in general.« less

  13. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome's Facet.

    PubMed

    Mahalik, J P; Brown, Kirsten A; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-06-28

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome's function and how it can be modified to create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we describe a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome's facets is driven by a nucleation-growth process, which in turn could play an important role in the hierarchical self-assembly of BMC shells in general. PMID:26906087

  14. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome's Facet.

    PubMed

    Mahalik, J P; Brown, Kirsten A; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-06-28

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome's function and how it can be modified to create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we describe a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome's facets is driven by a nucleation-growth process, which in turn could play an important role in the hierarchical self-assembly of BMC shells in general.

  15. Adaptive soft molecular self-assemblies.

    PubMed

    Wang, Andong; Shi, Wenyue; Huang, Jianbin; Yan, Yun

    2016-01-14

    Adaptive molecular self-assemblies provide possibility of constructing smart and functional materials in a non-covalent bottom-up manner. Exploiting the intrinsic properties of responsiveness of non-covalent interactions, a great number of fancy self-assemblies have been achieved. In this review, we try to highlight the recent advances in this field. The following contents are focused: (1) environmental adaptiveness, including smart self-assemblies adaptive to pH, temperature, pressure, and moisture; (2) special chemical adaptiveness, including nanostructures adaptive to important chemicals, such as enzymes, CO2, metal ions, redox agents, explosives, biomolecules; (3) field adaptiveness, including self-assembled materials that are capable of adapting to external fields such as magnetic field, electric field, light irradiation, and shear forces. PMID:26509717

  16. Self-assembled chitin nanofibers and applications.

    PubMed

    Rolandi, Marco; Rolandi, Ranieri

    2014-05-01

    Self-assembled natural biomaterials offer a variety of ready-made nanostructures available for basic science research and technological applications. Most natural structural materials are made of self-assembled nanofibers with diameters in the nanometer range. Among these materials, chitin is the second most abundant polysaccharide after cellulose and is part of the exoskeleton or arthropods and mollusk shells. Chitin has several desirable properties as a biomaterial including mechanical strength, chemical and thermal stability, and biocompatibility. However, chitin insolubility in most organic solvents has somewhat limited its use. In this research highlight, we describe recent developments in producing biogenic chitin nanofibers using self-assembly from a solution of squid pen β-chitin in hexafluoroisopropanol. With this solution based assembly, we have demonstrated chitin-silk composite self-assembly, chitin nanofiber fabrication across length-scales, and manufacturing of chitin nanofiber substrates for tissue engineering. PMID:24556234

  17. Directed Self-Assembly of Nanodispersions

    SciTech Connect

    Furst, Eric M

    2013-11-15

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

  18. From Solvolysis to Self-Assembly*

    PubMed Central

    Stang, Peter J.

    2009-01-01

    My sojourn from classical physical-organic chemistry and solvolysis to self-assembly and supramolecular chemistry, over the last forty years, is described. My contributions to unsaturated reactive intermediates, namely vinyl cations and unsaturated carbenes, along with my decade long involvement with polyvalent iodine chemistry, especially alkynyliodonium salts, as well as my more recent research with metal-ligand, coordination driven and directed self-assembly of finite supramolecular ensembles are discussed. PMID:19111062

  19. Directed Self-Assembly of Colloidal Particles

    NASA Astrophysics Data System (ADS)

    Zeravcic, Zorana; Collins, Jesse; Manoharan, Vinothan; Brenner, Michael

    2011-03-01

    In nature, simple constituents like atoms, molecules and polymer chains, spontaneously organize into larger, higher order structures. Interactions involved in this self-assembly act on a local level. These facts inspire experimental and theoretical engineering of components able to organize into pre-designed complex systems. We perform numerical simulations of collections of DNA coated colloidal particles. We test different design rules for self-assembly with short-range interactions and explore the stability of equilibrium structures.

  20. Silk Reconstitution Disrupts Fibroin Self-Assembly.

    PubMed

    Koebley, Sean R; Thorpe, Daniel; Pang, Pei; Chrisochoides, Panos; Greving, Imke; Vollrath, Fritz; Schniepp, Hannes C

    2015-09-14

    Using atomic force microscopy, we present the first molecular-scale comparison of two of the most important silk dopes, native (NSF) and reconstituted (RSF) silkworm fibroin. We found that both systems depended on shear to show self-assembly. Significant differences in the nature of self-assembly between NSF and RSF were shown. In the highest studied concentration of 1000 mg/L, NSF exhibited assembly into 20-30 nm-wide nanofibrils closely resembling the surface structures found in natural silk fibers. RSF, in contrast, showed no self-assembly whatsoever at the same concentration, which suggests that the reconstitution process significantly disrupts silk's inherent self-assembly capability. At lower concentrations, both RSF and NSF formed fibrils under shear, apparently denatured by the substrate. Using image analysis, we quantified the properties of these self-assembled fibrils as a function of concentration and found low-concentration fibrils of NSF to form larger continuous structures than those of RSF, further supporting NSF's superior self-assembly capabilities. PMID:26284914

  1. Silk Reconstitution Disrupts Fibroin Self-Assembly.

    PubMed

    Koebley, Sean R; Thorpe, Daniel; Pang, Pei; Chrisochoides, Panos; Greving, Imke; Vollrath, Fritz; Schniepp, Hannes C

    2015-09-14

    Using atomic force microscopy, we present the first molecular-scale comparison of two of the most important silk dopes, native (NSF) and reconstituted (RSF) silkworm fibroin. We found that both systems depended on shear to show self-assembly. Significant differences in the nature of self-assembly between NSF and RSF were shown. In the highest studied concentration of 1000 mg/L, NSF exhibited assembly into 20-30 nm-wide nanofibrils closely resembling the surface structures found in natural silk fibers. RSF, in contrast, showed no self-assembly whatsoever at the same concentration, which suggests that the reconstitution process significantly disrupts silk's inherent self-assembly capability. At lower concentrations, both RSF and NSF formed fibrils under shear, apparently denatured by the substrate. Using image analysis, we quantified the properties of these self-assembled fibrils as a function of concentration and found low-concentration fibrils of NSF to form larger continuous structures than those of RSF, further supporting NSF's superior self-assembly capabilities.

  2. Replication of Leaf Surface Structures for Light Harvesting

    PubMed Central

    Huang, Zhongjia; Yang, Sai; Zhang, Hui; Zhang, Meng; Cao, Wei

    2015-01-01

    As one of the most important hosts of natural light harvesting, foliage normally has complicated surface structures to capture solar radiances. Bio-mimicking leaf surface structures can provide novel designs of covers in photovoltaic systems. In this article, we reported on replicating leaf surface structures on poly-(methyl methacrylate) polymers to prompt harvesting efficiencies. Prepared via a double transfer process, the polymers were found to have high optical transparencies and transmission hazes, with both values exceeding 80% in some species. Benefiting from optical properties and wrinkled surfaces, the biomimetic polymers brought up to 17% gains to photovoltaic efficiencies. Through Monte-Carlo simulations of light transport, ultrahigh haze values and low reflections were attributed to lightwave guidance schemes lead by the nano- and micro-morphologies which are inherited from master leaves. Thus, leaf surface bio-mimicking can be considered as a strategic direction to design covers of light harvesting systems. PMID:26381702

  3. Ultraviolet-B photodestruction of a light-harvesting complex.

    PubMed Central

    Lao, K; Glazer, A N

    1996-01-01

    Cyanobacteria are important contributors to global photosynthesis in both marine and terrestrial environments. Quantitative data are presented on UV-B-induced damage to the major cyanobacterial photosynthetic light harvesting complex, the phycobilisome, and to each of its constituent phycobiliproteins. The photodestruction quantum yield, phi295 nm, for the phycobiliproteins is high (approximately 10(-3), as compared with approximately 10(-7) for visible light). Energy transfer on a picosecond time scale does not compete with photodestruction. Photodamage to phycobilisomes in vitro and in living cells is amplified by causing dissociation and loss of function of the complex. In photosynthetic organisms, UV-B damage to light-harvesting complexes may significantly exceed that to DNA. Images Fig. 1 PMID:8643563

  4. Light-harvesting materials: Soft support for energy conversion

    SciTech Connect

    Stolley, Ryan M.; Helm, Monte L.

    2014-11-10

    To convert solar energy into viable fuel sources, coupling light-harvesting materials to catalysts is a critical challenge. Now, coupling between an organic supramolecular hydrogel and a non precious metal catalyst has been demonstrated to be effective for photocatalytic H2 production. Ryan M. Stolley and Monte L. Helm are at Pacific Northwest National Laboratory (PNNL), Richland, WA, USA 99352. PNNL is operated by Battelle for the US Department of Energy. e-mail: Monte.Helm@pnnl.gov

  5. Fluctuating Two-State Light Harvesting in a Photosynthetic Membrane

    SciTech Connect

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

    2007-06-28

    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.

  6. A light-harvesting array of synthetic porphyrins

    NASA Astrophysics Data System (ADS)

    Davila, Jorge; Harriman, Anthony; Milgrom, Lionel R.

    1987-05-01

    An array of five porphyrin molecules has been synthesized and used as a simple model of the light-harvesting complex found in natural photosynthesis. Efficient Förster energy transfer occurs from antenna zinc porphyrins to a central free-base porphyrin molecule. This central porphyrin retains long-lived singlet and triplet excited states that can be quenched by diffusional processes, Both electron and energy transfer quenching reactions can be observed.

  7. Electronic instabilities in self-assembled atom wires

    SciTech Connect

    Snijders, Paul C; Weitering, Harm H

    2010-01-01

    Low dimensional systems have fascinated physicists for a long time due to their unusual properties such as charge fractionalization, semionic statistics, and Luttinger liquid behavior among others. In nature, however, low dimensional systems often suffer from thermal fluctuations that can make these systems structurally unstable. Human beings, however, can trick nature by producing artificial structures which are not naturally produced. This Colloquium reviews the problem of self-assembled atomic wires on solid surfaces from an experimental and theoretical point of view. These materials represent a class of one-dimensional systems with very unusual properties that can open doors to the study of exotic physics that cannot be studied otherwise.

  8. Designing artificial photosynthetic devices using hybrid organic-inorganic modules based on polyoxometalates.

    PubMed

    Symes, Mark D; Cogdell, Richard J; Cronin, Leroy

    2013-08-13

    Artificial photosynthesis aims at capturing solar energy and using it to produce storable fuels. However, while there is reason to be optimistic that such approaches can deliver higher energy conversion efficiencies than natural photosynthetic systems, many serious challenges remain to be addressed. Perhaps chief among these is the issue of device stability. Almost all approaches to artificial photosynthesis employ easily oxidized organic molecules as light harvesters or in catalytic centres, frequently in solution with highly oxidizing species. The 'elephant in the room' in this regard is that oxidation of these organic moieties is likely to occur at least as rapidly as oxidation of water, meaning that current device performance is severely curtailed. Herein, we discuss one possible solution to this problem: using self-assembling organic-polyoxometalate hybrid structures to produce compartments inside which the individual component reactions of photosynthesis can occur without such a high incidence of deleterious side reactions.

  9. Recent Progress on Bioinspired Self-Propelled Micro/Nanomotors via Controlled Molecular Self-Assembly.

    PubMed

    Wu, Zhiguang; Lin, Xiankun; Si, Tieyan; He, Qiang

    2016-06-01

    The combination of bottom-up controllable self-assembly technique with bioinspired design has opened new horizons in the development of self-propelled synthetic micro/nanomotors. Over the past five years, a significant advances toward the construction of bioinspired self-propelled micro/nanomotors has been witnessed based on the controlled self-assembly technique. Such a strategy permits the realization of autonomously synthetic motors with engineering features, such as sizes, shapes, composition, propulsion mechanism, and function. The construction, propulsion mechanism, and movement control of synthetic micro/nanomotors in connection with controlled self-assembly in recent research activities are summarized. These assembled nanomotors are expected to have a tremendous impact on current artificial nanomachines in future and hold potential promise for biomedical applications including drug targeted delivery, photothermal cancer therapy, biodetoxification, treatment of atherosclerosis, artificial insemination, crushing kidney stones, cleaning wounds, and removing blood clots and parasites.

  10. Recent Progress on Bioinspired Self-Propelled Micro/Nanomotors via Controlled Molecular Self-Assembly.

    PubMed

    Wu, Zhiguang; Lin, Xiankun; Si, Tieyan; He, Qiang

    2016-06-01

    The combination of bottom-up controllable self-assembly technique with bioinspired design has opened new horizons in the development of self-propelled synthetic micro/nanomotors. Over the past five years, a significant advances toward the construction of bioinspired self-propelled micro/nanomotors has been witnessed based on the controlled self-assembly technique. Such a strategy permits the realization of autonomously synthetic motors with engineering features, such as sizes, shapes, composition, propulsion mechanism, and function. The construction, propulsion mechanism, and movement control of synthetic micro/nanomotors in connection with controlled self-assembly in recent research activities are summarized. These assembled nanomotors are expected to have a tremendous impact on current artificial nanomachines in future and hold potential promise for biomedical applications including drug targeted delivery, photothermal cancer therapy, biodetoxification, treatment of atherosclerosis, artificial insemination, crushing kidney stones, cleaning wounds, and removing blood clots and parasites. PMID:27073065

  11. Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

    PubMed Central

    Shi, Yanhui; Sánchez-Molina, Irene; Cao, Changsheng; Cook, Timothy R.; Stang, Peter J.

    2014-01-01

    Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by 31P and 1H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP. PMID:24979805

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

    NASA Astrophysics Data System (ADS)

    Yip, Hin-Lap

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

  13. Directed self-assembly of performance materials

    NASA Astrophysics Data System (ADS)

    Nealey, Paul

    Directed self-assembly (DSA) is a promising strategy for high-volume cost-effective manufacturing at the nanoscale. Over the past decades, manufacturing techniques have been developed with such remarkable efficiency that it is now possible to engineer complex systems of heterogeneous materials at the scale of a few tens of nanometers. Further evolution of these techniques, however, is faced with difficult challenges not only in feasibility of implementation at scales of 10 nm and below, but also in prohibitively high capital equipment costs. Materials that self-assemble, on the other hand, spontaneously form structures at the mesoscale, but the micrometer areas or volumes over which the materials self-assemble with adequate perfection in structure is incommensurate with the macroscopic dimensions of working devices and systems of devices of industrial relevance. Directed Self-Assembly (DSA) refers to the integration of self-assembling materials with traditional manufacturing processes. Here we will discuss DSA of block copolymers to revolutionize sub 10 nm lithography and the manufacture of integrated circuits and storage media, DSA of ex-situ synthesized nanoparticles for applications in nanophotonics, and DSA of liquid crystals for advanced optics.

  14. Self-assembly of nanocomposite materials

    DOEpatents

    Brinker, C. Jeffrey; Sellinger, Alan; Lu, Yunfeng

    2001-01-01

    A method of making a nanocomposite self-assembly is provided where at least one hydrophilic compound, at least one hydrophobic compound, and at least one amphiphilic surfactant are mixed in an aqueous solvent with the solvent subsequently evaporated to form a self-assembled liquid crystalline mesophase material. Upon polymerization of the hydrophilic and hydrophobic compounds, a robust nanocomposite self-assembled material is formed. Importantly, in the reaction mixture, the amphiphilic surfactant has an initial concentration below the critical micelle concentration to allow formation of the liquid-phase micellar mesophase material. A variety of nanocomposite structures can be formed, depending upon the solvent evaporazation process, including layered mesophases, tubular mesophases, and a hierarchical composite coating composed of an isotropic worm-like micellar overlayer bonded to an oriented, nanolaminated underlayer.

  15. Theory of Programmable Hierarchic Self-Assembly

    NASA Astrophysics Data System (ADS)

    Tkachenko, Alexei V.

    2011-06-01

    We present a theoretical analysis of the inverse problem in self-assembly. A particular scheme is proposed for building an arbitrary desired nanostructure out of self-assembled building blocks (“octopus” nanoparticles). The conditions for robust self-assembly of the target structure are identified. This includes the minimal number of “colors” needed to encode interparticle bonds, which are to be implemented as pairs of complementary DNA sequences. As a part of this analysis, it is demonstrated that a floppy network with thermal fluctuations, in a certain range of coordination numbers ⟨Z⟩, possesses entropic rigidity and can be described as a traditional elastic solid. The onset of the entropic rigidity, ⟨Z⟩=d+1, determines the minimal number of bond types per particle needed to encode the desired structure. Thermodynamic considerations give additional conditions for the implementation of this scheme.

  16. Self-Assembly of Peptides to Nanostructures

    PubMed Central

    Mandal, Dindyal; Shirazi, Amir Nasrolahi; Parang, Keykavous

    2014-01-01

    The formation of well-ordered nanostructures through self-assembly of diverse organic and inorganic building blocks has drawn much attention owing to their potential applications in biology and chemistry. Among all organic building blocks, peptides are one of the most promising platforms due to their biocompatibility, chemical diversity, and resemblance with proteins. Inspired from the protein assembly in biological systems, various self-assembled peptide structures have been constructed using several amino acids and sequences. This review focuses on this emerging area, the recent advances in peptide self-assembly, and formation of different nanostructures, such as tubular, fibers, vesicles, spherical, and rod coil structures. While different peptide nanostructures are discovered, potential applications will be explored in drug delivery, tissue engineering, wound healing, and surfactants. PMID:24756480

  17. Biomimetic Branched Hollow Fibers Templated by Self-assembled Fibrous Polyvinylpyrrolidone (PVP) Structures in Aqueous Solution

    PubMed Central

    Qiu, Penghe; Mao, Chuanbin

    2010-01-01

    Branched hollow fibers are common in nature, but to form artificial fibers with a similar branched hollow structure is still a challenge. We discovered that polyvinylpyrrolidone (PVP) could self-assemble into branched hollow fibers in an aqueous solution after aging the PVP solution for about two weeks. Based on this finding, we demonstrated two approaches by which the self-assembly of PVP into branched hollow fibers could be exploited to template the formation of branched hollow inorganic fibers. First, inorganic material such as silica with high affinity against the PVP could be deposited on the surface of the branched hollow PVP fibers to form branched hollow silica fibers. To extend the application of PVP self-assembly in templating the formation of hollow branched fibers, we then adopted a second approach where the PVP molecules bound to inorganic nanoparticles (using gold nanoparticles as a model) co-self-assemble with the free PVP molecules in an aqueous solution, resulting in the formation of the branched hollow fibers with the nanoparticles embedded in the PVP matrix constituting the walls of the fibers. Heating the resultant fibers above the glass transition temperature of PVP led to the formation of branched hollow gold fibers. Our work suggests that the self-assembly of the PVP molecules in the solution can serve as a general method for directing the formation of branched hollow inorganic fibers. The branched hollow fibers may find potential applications in microfluidics, artificial blood vessel generation, and tissue engineering. PMID:20158250

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

    PubMed

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

    2015-08-12

    Peptide self-assembly is an attractive route for the synthesis of intricate organic nanostructures that possess remarkable structural variety and biocompatibility. Recent studies on peptide-based, self-assembled materials have expanded beyond the construction of high-order architectures; they are now reporting new functional materials that have application in the emerging fields such as artificial photosynthesis and rechargeable batteries. Nevertheless, there have been few reviews particularly concentrating on such versatile, emerging applications. Herein, recent advances in the synthesis of self-assembled peptide nanomaterials (e.g., cross β-sheet-based amyloid nanostructures, peptide amphiphiles) are selectively reviewed and their new applications in diverse, interdisciplinary fields are described, ranging from optics and energy storage/conversion to healthcare. The applications of peptide-based self-assembled materials in unconventional fields are also highlighted, such as photoluminescent peptide nanostructures, artificial photosynthetic peptide nanomaterials, and lithium-ion battery components. The relation of such functional materials to the rapidly progressing biomedical applications of peptide self-assembly, which include biosensors/chips and regenerative medicine, are discussed. The combination of strategies shown in these applications would further promote the discovery of novel, functional, small materials. PMID:25929870

  19. Amyloid inspired self-assembled peptide nanofibers.

    PubMed

    Cinar, Goksu; Ceylan, Hakan; Urel, Mustafa; Erkal, Turan S; Deniz Tekin, E; Tekinay, Ayse B; Dâna, Aykutlu; Guler, Mustafa O

    2012-10-01

    Amyloid peptides are important components in many degenerative diseases as well as in maintaining cellular metabolism. Their unique stable structure provides new insights in developing new materials. Designing bioinspired self-assembling peptides is essential to generate new forms of hierarchical nanostructures. Here we present oppositely charged amyloid inspired peptides (AIPs), which rapidly self-assemble into nanofibers at pH 7 upon mixing in water caused by noncovalent interactions. Mechanical properties of the gels formed by self-assembled AIP nanofibers were analyzed with oscillatory rheology. AIP gels exhibited strong mechanical characteristics superior to gels formed by self-assembly of previously reported synthetic short peptides. Rheological studies of gels composed of oppositely charged mixed AIP molecules (AIP-1 + 2) revealed superior mechanical stability compared to individual peptide networks (AIP-1 and AIP-2) formed by neutralization of net charges through pH change. Adhesion and elasticity properties of AIP mixed nanofibers and charge neutralized AIP-1, AIP-2 nanofibers were analyzed by high resolution force-distance mapping using atomic force microscopy (AFM). Nanomechanical characterization of self-assembled AIP-1 + 2, AIP-1, and AIP-2 nanofibers also confirmed macroscopic rheology results, and mechanical stability of AIP mixed nanofibers was higher compared to individual AIP-1 and AIP-2 nanofibers self-assembled at acidic and basic pH, respectively. Experimental results were supported with molecular dynamics simulations by considering potential noncovalent interactions between the amino acid residues and possible aggregate forms. In addition, HUVEC cells were cultured on AIP mixed nanofibers at pH 7 and biocompatibility and collagen mimetic scaffold properties of the nanofibrous system were observed. Encapsulation of a zwitterionic dye (rhodamine B) within AIP nanofiber network was accomplished at physiological conditions to demonstrate that this

  20. 3D self-assembly of aluminium nanoparticles for plasmon-enhanced solar desalination

    NASA Astrophysics Data System (ADS)

    Zhou, Lin; Tan, Yingling; Wang, Jingyang; Xu, Weichao; Yuan, Ye; Cai, Wenshan; Zhu, Shining; Zhu, Jia

    2016-06-01

    Plasmonics has generated tremendous excitement because of its unique capability to focus light into subwavelength volumes, beneficial for various applications such as light harvesting, photodetection, sensing, catalysis and so on. Here we demonstrate a plasmon-enhanced solar desalination device, fabricated by the self-assembly of aluminium nanoparticles into a three-dimensional porous membrane. The formed porous plasmonic absorber can float naturally on water surface, efficiently absorb a broad solar spectrum (>96%) and focus the absorbed energy at the surface of the water to enable efficient (˜90%) and effective desalination (a decrease of four orders of magnitude). The durability of the devices has also been examined, indicating a stable performance over 25 cycles under various illumination conditions. The combination of the significant desalination effect, the abundance and low cost of the materials, and the scalable production processes suggest that this type of plasmon-enhanced solar desalination device could provide a portable desalination solution.

  1. Nondeterministic self-assembly with asymmetric interactions

    NASA Astrophysics Data System (ADS)

    Tesoro, S.; Göpfrich, K.; Kartanas, T.; Keyser, U. F.; Ahnert, S. E.

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  2. Self-assembling segmented coiled tubing

    DOEpatents

    Raymond, David W.

    2016-09-27

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

  3. Nondeterministic self-assembly with asymmetric interactions.

    PubMed

    Tesoro, S; Göpfrich, K; Kartanas, T; Keyser, U F; Ahnert, S E

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation. PMID:27627332

  4. Remote control of self-assembled microswimmers

    NASA Astrophysics Data System (ADS)

    Grosjean, G.; Lagubeau, G.; Darras, A.; Hubert, M.; Lumay, G.; Vandewalle, N.

    2015-11-01

    Physics governing the locomotion of microorganisms and other microsystems is dominated by viscous damping. An effective swimming strategy involves the non-reciprocal and periodic deformations of the considered body. Here, we show that a magnetocapillary-driven self-assembly, composed of three soft ferromagnetic beads, is able to swim along a liquid-air interface when powered by an external magnetic field. More importantly, we demonstrate that trajectories can be fully controlled, opening ways to explore low Reynolds number swimming. This magnetocapillary system spontaneously forms by self-assembly, allowing miniaturization and other possible applications such as cargo transport or solvent flows.

  5. Nondeterministic self-assembly with asymmetric interactions.

    PubMed

    Tesoro, S; Göpfrich, K; Kartanas, T; Keyser, U F; Ahnert, S E

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  6. Remote control of self-assembled microswimmers

    PubMed Central

    Grosjean, G.; Lagubeau, G.; Darras, A.; Hubert, M.; Lumay, G.; Vandewalle, N.

    2015-01-01

    Physics governing the locomotion of microorganisms and other microsystems is dominated by viscous damping. An effective swimming strategy involves the non-reciprocal and periodic deformations of the considered body. Here, we show that a magnetocapillary-driven self-assembly, composed of three soft ferromagnetic beads, is able to swim along a liquid-air interface when powered by an external magnetic field. More importantly, we demonstrate that trajectories can be fully controlled, opening ways to explore low Reynolds number swimming. This magnetocapillary system spontaneously forms by self-assembly, allowing miniaturization and other possible applications such as cargo transport or solvent flows. PMID:26538006

  7. Self-assembly of lithographically patterned nanoparticles

    PubMed Central

    Cho, Jeong-Hyun; Gracias, David H.

    2009-01-01

    The construction of three dimensional (3D) objects, with any desired surface patterns, is both critical to and easily achieved in macroscale, science and engineering. However, on the nanoscale, 3D fabrication is limited to particles with only very limited surface patterning. Here, we demonstrate a self-assembly strategy that harnesses the strengths of well established 2D nanoscale patterning techniques and additionally enables the construction of stable 3D polyhedral nanoparticles. As a proof of the concept, we self-assembled cubic particles with sizes as small as 100 nm and with specific and lithographically defined surface patterns. PMID:19681638

  8. Computer simulation of nanocube self-assemblies

    NASA Astrophysics Data System (ADS)

    Zhang, Xi

    Self-assembly of nanoscale building blocks and molecules into ordered nanostructures is a promising venue for bottom-up materials design. A wide variety of nanoparticles with unique shapes and uniform sizes have been successfully synthesized. However, organizing these nanoparticles into desired, predefined nanostructures is a formidable challenge now facing the materials community. For example, simple 2-D arrays and 3-D superlattices are the prevalent structures from most nanocube self-assemblies. Two practical strategies to impart anisotropy onto nanocubes, namely, attaching polymer tethers to nanoparticle surfaces and introducing directional dipolar interactions, can be applied to achieve more complex assembled structures. In this dissertation, we conduct computer simulations on nanocube self-assemblies induced by polymer tethers and directional dipole interactions, to examine the various parameters involved in such complicated self-assembly processes, including temperature, concentration, solvent condition, cube size, tether length, tether topology, tether placement, tether number, dipole direction, dipole strength and polydispersity, in order to understand how the packing geometry and interactions between nanocubes can be manipulated to confer precise control over the assembled structures and the phase behavior. First, we simulate monotethered nanocubes and find that the nanocubes favor face-to-face packing in poor solvents, stabilizing the lamellae phases. Next, we simulate different architectures of tethered nanocubes and demonstrate that the steric influence of tether beads can be manipulated to interfere with the face-to-face packing of nanocubes and alter the phase behaviors. We also study the self-assembly of nanocubes with dipoles. We find that the head-to-tail alignment of dipoles, coupled with the face-to-face close packing of nanocubes, dictates the assembled structures. The face-face attraction between nanocubes can also be utilized to control the

  9. Computing by molecular self-assembly

    PubMed Central

    Jonoska, Nataša; Seeman, Nadrian C.

    2012-01-01

    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

  10. The structural basis of light-harvesting in purple bacteria.

    PubMed

    Cogdell, Richard J; Isaacs, Neil W; Freer, Andrew A; Howard, Tina D; Gardiner, Alastair T; Prince, Steve M; Papiz, Miroslavr Z

    2003-11-27

    A typical purple bacterial photosynthetic unit consists of two types of light-harvesting complex (LH1 and LH2) together with a reaction centre. This short review presents a description of the structure of the LH2 complex from Rhodopseudomonas acidophila, which has recently been improved to a resolution of 2.0 A [Papiz et al., J. Mol. Biol. 326 (2003) 1523-1538]. We show how this structure has helped to reveal the details of the various excitation energy transfer events in which it is involved.

  11. Molecular Factors Controlling Photosynthetic Light-Harvesting by Carotenoids

    PubMed Central

    Polívka, Tomáš; Frank, Harry A.

    2010-01-01

    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 photo-induced damage caused by excess light absorption. To carry out these functions in nature, carotenoids are bound in discrete pigment-protein complexes in close proximity to chlorophylls. A few 3D 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 making the 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

  12. Ultrafast energy relaxation in single light-harvesting complexes

    PubMed Central

    Malý, Pavel; Gruber, J. Michael; Cogdell, Richard J.; Mančal, Tomáš; van Grondelle, Rienk

    2016-01-01

    Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations. PMID:26903650

  13. Green grasses as light harvesters in dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  14. Ultrafast energy relaxation in single light-harvesting complexes.

    PubMed

    Malý, Pavel; Gruber, J Michael; Cogdell, Richard J; Mančal, Tomáš; van Grondelle, Rienk

    2016-03-15

    Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub-100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump-probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations. PMID:26903650

  15. Regulation of photosystem I light harvesting by zeaxanthin.

    PubMed

    Ballottari, Matteo; Alcocer, Marcelo J P; D'Andrea, Cosimo; Viola, Daniele; Ahn, Tae Kyu; Petrozza, Annamaria; Polli, Dario; Fleming, Graham R; Cerullo, Giulio; Bassi, Roberto

    2014-06-10

    In oxygenic photosynthetic eukaryotes, the hydroxylated carotenoid zeaxanthin is produced from preexisting violaxanthin upon exposure to excess light conditions. Zeaxanthin binding to components of the photosystem II (PSII) antenna system has been investigated thoroughly and shown to help in the dissipation of excess chlorophyll-excited states and scavenging of oxygen radicals. However, the functional consequences of the accumulation of the light-harvesting complex I (LHCI) proteins in the photosystem I (PSI) antenna have remained unclarified so far. In this work we investigated the effect of zeaxanthin binding on photoprotection of PSI-LHCI by comparing preparations isolated from wild-type Arabidopsis thaliana (i.e., with violaxanthin) and those isolated from the A. thaliana nonphotochemical quenching 2 mutant, in which violaxanthin is replaced by zeaxanthin. Time-resolved fluorescence measurements showed that zeaxanthin binding leads to a previously unrecognized quenching effect on PSI-LHCI fluorescence. The efficiency of energy transfer from the LHCI moiety of the complex to the PSI reaction center was down-regulated, and an enhanced PSI resistance to photoinhibition was observed both in vitro and in vivo. Thus, zeaxanthin was shown to be effective in inducing dissipative states in PSI, similar to its well-known effect on PSII. We propose that, upon acclimation to high light, PSI-LHCI changes its light-harvesting efficiency by a zeaxanthin-dependent quenching of the absorbed excitation energy, whereas in PSII the stoichiometry of LHC antenna proteins per reaction center is reduced directly.

  16. Ultrafast energy relaxation in single light-harvesting complexes.

    PubMed

    Malý, Pavel; Gruber, J Michael; Cogdell, Richard J; Mančal, Tomáš; van Grondelle, Rienk

    2016-03-15

    Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub-100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump-probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.

  17. Triplet Energy Transport in Platinum-Acetylide Light Harvesting Arrays.

    PubMed

    Chen, Zhuo; Hsu, Hsien-Yi; Arca, Mert; Schanze, Kirk S

    2015-06-18

    Light harvesting and triplet energy transport is investigated in chromophore-functionalized polystyrene polymers featuring light harvesting and energy acceptor chromophores (traps) at varying loading. The series of precision polymers was constructed via reversible addition-fragmentation transfer polymerization and functionalized with platinum acetylide triplet chromophores by using an azide-alkyne "click" reaction. The polymers have narrow polydispersity and degree of polymerization ∼60. The chromophores have the general structure, trans-[-R-C6H4-C≡C-Pt(PBu3)2-C≡C-Ar], where R is the attachment point to the polystyrene backbone and Ar is either -C6H4-C≡C-Ph or -pyrenyl (PE2-Pt and Py-Pt, respectively, with triplet energies of 2.35 and 1.88 eV). The polychromophores contain mainly the high-energy PE2-Pt units (light absorber and energy donor), with randomly distributed Py-Pt units (3-20% loading, energy acceptor). Photophysical methods are used to study the dynamics and efficiency of energy transport from the PE2-Pt to Py-Pt units in the polychromophores. The energy transfer efficiency is >90% for copolymers that contain 5% of the Py-Pt acceptor units. Time-resolved phosphorescence measurements combined with Monte Carlo exciton dynamics simulations suggest that the mechanism of exciton transport is exchange energy transfer hopping between PE2-Pt units.

  18. Self-assembled supramolecular nanotube yarn.

    PubMed

    Liu, Yaqing; Wang, Tianyu; Huan, Yong; Li, Zhibo; He, Guowei; Liu, Minghua

    2013-11-01

    Metric length supramolecular nanotube yarns are fabricated though a spinning process from the diluted aqueous solution of self-assembled nanotubes, with bolaamphiphiles working as molecular building blocks. These non-covalent bonding based nanotube yarns show outstanding mechanical strength compared with some conventional polymers and could be operated under the macro conditions. PMID:23943418

  19. Self-assembly micro optical filter

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

    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.

  20. Self-assembling materials for therapeutic delivery✩

    PubMed Central

    Branco, Monica C.; Schneider, Joel P.

    2009-01-01

    A growing number of medications must be administered through parenteral delivery, i.e., intravenous, intramuscular, or subcutaneous injection, to ensure effectiveness of the therapeutic. For some therapeutics, the use of delivery vehicles in conjunction with this delivery mechanism can improve drug efficacy and patient compliance. Macromolecular self-assembly has been exploited recently to engineer materials for the encapsulation and controlled delivery of therapeutics. Self-assembled materials offer the advantages of conventional crosslinked materials normally used for release, but also provide the ability to tailor specific bulk material properties, such as release profiles, at the molecular level via monomer design. As a result, the design of materials from the “bottom up” approach has generated a variety of supramolecular devices for biomedical applications. This review provides an overview of self-assembling molecules, their resultant structures, and their use in therapeutic delivery. It highlights the current progress in the design of polymer- and peptide-based self-assembled materials. PMID:19010748

  1. Inverse Problem in Self-assembly

    NASA Astrophysics Data System (ADS)

    Tkachenko, Alexei

    2012-02-01

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

  2. Self-assembled nanolaminate coatings (SV)

    SciTech Connect

    Fan, H.

    2012-03-01

    Sandia National Laboratories (Sandia) and Lockheed Martin Aeronautics (LM Aero) are collaborating to develop affordable, self-assembled, nanocomposite coatings and associated fabrication processes that will be tailored to Lockheed Martin product requirements. The purpose of this project is to develop a family of self-assembled coatings with properties tailored to specific performance requirements, such as antireflective (AR) optics, using Sandia-developed self-assembled techniques. The project met its objectives by development of a simple and economic self-assembly processes to fabricate multifunctional coatings. Specifically, materials, functionalization methods, and associated coating processes for single layer and multiple layers coatings have been developed to accomplish high reflective coatings, hydrophobic coatings, and anti-reflective coatings. Associated modeling and simulations have been developed to guide the coating designs for optimum optical performance. The accomplishments result in significant advantages of reduced costs, increased manufacturing freedom/producibility, improved logistics, and the incorporation of new technology solutions not possible with conventional technologies. These self-assembled coatings with tailored properties will significantly address LMC's needs and give LMC a significant competitive lead in new engineered materials. This work complements SNL's LDRD and BES programs aimed at developing multifunctional nanomaterials for microelectronics and optics as well as structure/property investigations of self-assembled nanomaterials. In addition, this project will provide SNL with new opportunities to develop and apply self-assembled nanocomposite optical coatings for use in the wavelength ranges of 3-5 and 8-12 micrometers, ranges of vital importance to military-based sensors and weapons. The SANC technologies will be applied to multiple programs within the LM Company including the F-35, F-22, ADP (Future Strike Bomber, UAV, UCAV

  3. Self-assembly of azide containing dipeptides.

    PubMed

    Yuran, Sivan; Razvag, Yair; Das, Priyadip; Reches, Meital

    2014-07-01

    Functional structures and materials are formed spontaneously in nature through the process of self-assembly. Mimicking this process in vitro will lead to the formation of new substances that would impact many areas including energy production and storage, biomaterials and implants, and drug delivery. The considerable structural diversity of peptides makes them appealing building blocks for self-assembly in vitro. This paper describes the self-assembly of three aromatic dipeptides containing an azide moiety: H-Phe(4-azido)-Phe(4-azido)-OH, H-Phe(4-azido)-Phe-OH, and H-Phe-Phe(4-azido)-OH. The peptide H-Phe(4-azido)-Phe(4-azido)-OH self-assembled into porous spherical structures, whereas the peptides H-Phe(4-azido)-Phe-OH and H-Phe-Phe(4-azido)-OH did not form any ordered structures under the examined experimental conditions. The azido group of the peptide can serve as a photo cross-linking agent upon irradiation with UV light. To examine the effect of this group and its activity on the self-assembled structures, we irradiated the assemblies in solution for different time periods. Using electron microscopy, we determined that the porous spherical assemblies formed by the peptide H-Phe(4-azido)-Phe(4-azido)-OH underwent a structural change upon irradiation. In addition, using FT-IR, we detected the chemical change of the peptide azido group. Moreover, using indentation experiments with atomic force microscopy, we showed that the Young's modulus of the spherical assemblies increased after 20 min of irradiation with UV light. Overall, irradiating the solution of the peptide assemblies containing the azido group resulted in a change both in the morphology and mechanical properties of the peptide-based structures. These ordered assemblies or their peptide monomer building blocks can potentially be incorporated into other peptide assemblies to generate stiffer and more stable materials. PMID:24889029

  4. Nanoparticles Self-Assembly Driven by High Affinity Repeat Protein Pairing.

    PubMed

    Gurunatha, Kargal L; Fournier, Agathe C; Urvoas, Agathe; Valerio-Lepiniec, Marie; Marchi, Valérie; Minard, Philippe; Dujardin, Erik

    2016-03-22

    Proteins are the most specific yet versatile biological self-assembling agents with a rich chemistry. Nevertheless, the design of new proteins with recognition capacities is still in its infancy and has seldom been exploited for the self-assembly of functional inorganic nanoparticles. Here, we report on the protein-directed assembly of gold nanoparticles using purpose-designed artificial repeat proteins having a rigid but modular 3D architecture. αRep protein pairs are selected for their high mutual affinity from a library of 10(9) variants. Their conjugation onto gold nanoparticles drives the massive colloidal assembly of free-standing, one-particle thick films. When the average number of proteins per nanoparticle is lowered, the extent of self-assembly is limited to oligomeric particle clusters. Finally, we demonstrate that the aggregates are reversibly disassembled by an excess of one free protein. Our approach could be optimized for applications in biosensing, cell targeting, or functional nanomaterials engineering.

  5. Modeling coherent excitation energy transfer in photosynthetic light harvesting systems

    NASA Astrophysics Data System (ADS)

    Huo, Pengfei

    2011-12-01

    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

  6. Dynamic self-assembly of chemically-propelled nanoscale building blocks

    NASA Astrophysics Data System (ADS)

    Chen, Yanping; Shi, Yunfeng

    2011-03-01

    Self-assembly technique offers spontaneous, massively-parallel structure formation from bottom-up. So far, most research efforts have been focused on static self-assembly that is thermally driven towards a thermodynamic equilibrium. Less attention has been paid to dynamic self-assembly that evolves to a non-equilibrium steady state under a dissipative driving force. This project aims to investigate the non-equilibrium self-assembly behaviors of chemically-propelled nanoscale building blocks via molecular dynamics simulations. We utilize a catalytic building block, that has been shown, when isolated, to exhibit self-motile behavior when immersed in a fuel environment. Upon increasing the number density of the building blocks, interesting collective behaviors emerge due to direct interactions between the building blocks or indirect interactions via the fuel environment. The simulation system is also subjected to an artificial operation of converting products back to fuel molecules. The heat generated by the exothermic chemical reaction will also be removed. In this way, a steady-state, as well as the resulting dynamic self-assembly pattern, can be obtained.

  7. Self-assembly approaches to photonic structures

    NASA Astrophysics Data System (ADS)

    Yin, Yadong

    Self-assembly of spherical colloids has been demonstrated as a simple and effective strategy for fabricating a variety of photonic structures that include photonic crystals, arrayed microlenses, and waveguides. Unlike the top-down fabrication techniques, self-assembly approaches can produce functional structures under ambient conditions of pressure and temperature without the need for costly instruments. A confined self-assembly approach was developed to organize spherical colloids into highly ordered three-dimensional photonic crystals. Such colloidal photonic crystals can block the propagation of photons for a range of wavelengths along specific directions. The capability of this method has been demonstrated with monodispersed spherical colloids of various materials and a range of dimensions. The orientation of the crystals can be controlled by assembling the colloids against two-dimensional arrays of templates patterned in the surfaces of substrates. The colloidal crystals were further explored to fabricate inverse opals with complementary structures. Photonic bandgap properties of these crystals have been characterized by measuring their transmission and reflectance spectra. Self-assembly of nonspherical building blocks may lead to the formation of photonic crystals that can prohibit a band of optical frequencies in all directions of propagation. As the first step along this direction, a general approach based on physical confinement and attractive capillary force has been developed to produce nonspherical building blocks with well-defined structures and dimensions. Complex aggregates such as polygonal and polyhedral clusters, zigzag or helical chains have been fabricated using monodispersed polymer or silica colloids. Arrayed microlenses were fabricated by self-assembling monodispersed polymer colloids in two-dimensional arrays of cylindrical holes patterned on substrates. The spherical colloids were subsequently transformed into mushroom-shaped and then

  8. Dendrimer light-harvesting: intramolecular electrodynamics and mechanisms.

    PubMed

    Andrews, David L; Bradshaw, David S; Jenkins, Robert D; Rodríguez, Justo

    2009-12-01

    In the development of highly efficient materials for harvesting solar energy, there is an increasing focus on purpose-built dendrimers and allied multi-chromophore systems. A proliferation of antenna chromophores is not the only factor determining the sought light-harvesting efficiency; the internal geometry and photophysics of these molecules are also crucially important. In particular, the mechanisms by means of which radiant energy is ultimately trapped depends on an intricate interplay of electronic, structural, energetic and symmetry properties. To better understand these processes a sound theoretical representation of the intramolecular electrodynamics is required. A suitable formalism, based on quantum electrodynamics, readily delivers physical insights into the necessary excitation channelling processes, and it affords a rigorous basis for modelling the intramolecular flow of energy.

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

    SciTech Connect

    Scholes, Gregory D. Smyth, Cathal

    2014-03-21

    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.

  10. Phycobilisome: architecture of a light-harvesting supercomplex.

    PubMed

    Watanabe, Mai; Ikeuchi, Masahiko

    2013-10-01

    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.

  11. Designing dye-nanochannel antenna hybrid materials for light harvesting, transport and trapping.

    PubMed

    Calzaferri, Gion; Méallet-Renault, Rachel; Brühwiler, Dominik; Pansu, Robert; Dolamic, Igor; Dienel, Thomas; Adler, Pauline; Li, Huanrong; Kunzmann, Andreas

    2011-02-25

    We discuss artificial photonic antenna systems that are built by incorporating chromophores into one-dimensional nanochannel materials and by organizing the latter in specific ways. Zeolite L (ZL) is an excellent host for the supramolecular organization of different kinds of molecules and complexes. The range of possibilities for filling its one-dimensional channels with suitable guests has been shown to be much larger than one might expect. Geometrical constraints imposed by the host structure lead to supramolecular organization of the guests in the channels. The arrangement of dyes inside the ZL channels is what we call the first stage of organization. It allows light harvesting within the volume of a dye-loaded ZL crystal and also the radiationless transport of energy to either the channel ends or center. One-dimensional FRET transport can be realized in these guest-host materials. The second stage of organization is realized by coupling either an external acceptor or donor stopcock fluorophore at the ends of the ZL channels, which can then trap or inject electronic excitation energy. The third stage of organization is obtained by interfacing the material to an external device via a stopcock intermediate. A possibility to achieve higher levels of organization is by controlled assembly of the host into ordered structures and preparation of monodirectional materials. The usually strong light scattering of ZL can be suppressed by refractive-index matching and avoidance of microphase separation in hybrid polymer/dye-ZL materials. The concepts are illustrated and discussed in detail on a bidirectional dye antenna system. Experimental results of two materials with a donor-to-acceptor ratio of 33:1 and 52:1, respectively, and a three-dye system illustrate the validity and challenges of this approach for synthesizing dye-nanochannel hybrid materials for light harvesting, transport, and trapping.

  12. Self-assembling membranes and related methods thereof

    DOEpatents

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

    2013-08-20

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

  13. Controlling and imaging biomimetic self-assembly.

    PubMed

    Aliprandi, Alessandro; Mauro, Matteo; De Cola, Luisa

    2016-01-01

    The self-assembly of chemical entities represents a very attractive way to create a large variety of ordered functional structures and complex matter. Although much effort has been devoted to the preparation of supramolecular nanostructures based on different chemical building blocks, an understanding of the mechanisms at play and the ability to monitor assembly processes and, in turn, control them are often elusive, which precludes a deep and comprehensive control of the final structures. Here the complex supramolecular landscape of a platinum(II) compound is characterized fully and controlled successfully through a combination of supramolecular and photochemical approaches. The supramolecular assemblies comprise two kinetic assemblies and their thermodynamic counterpart. The monitoring of the different emission properties of the aggregates, used as a fingerprint for each species, allows the real-time visualization of the evolving self-assemblies. The control of multiple supramolecular pathways will help the design of complex systems in and out of their thermodynamic equilibrium.

  14. Self-Assembled Plasmonic Nanoparticle Clusters

    NASA Astrophysics Data System (ADS)

    Fan, Jonathan A.; Wu, Chihhui; Bao, Kui; Bao, Jiming; Bardhan, Rizia; Halas, Naomi J.; Manoharan, Vinothan N.; Nordlander, Peter; Shvets, Gennady; Capasso, Federico

    2010-05-01

    The self-assembly of colloids is an alternative to top-down processing that enables the fabrication of nanostructures. We show that self-assembled clusters of metal-dielectric spheres are the basis for nanophotonic structures. By tailoring the number and position of spheres in close-packed clusters, plasmon modes exhibiting strong magnetic and Fano-like resonances emerge. The use of identical spheres simplifies cluster assembly and facilitates the fabrication of highly symmetric structures. Dielectric spacers are used to tailor the interparticle spacing in these clusters to be approximately 2 nanometers. These types of chemically synthesized nanoparticle clusters can be generalized to other two- and three-dimensional structures and can serve as building blocks for new metamaterials.

  15. Dissipative self-assembly of vesicular nanoreactors.

    PubMed

    Maiti, Subhabrata; Fortunati, Ilaria; Ferrante, Camilla; Scrimin, Paolo; Prins, Leonard J

    2016-07-01

    Dissipative self-assembly is exploited by nature to control important biological functions, such as cell division, motility and signal transduction. The ability to construct synthetic supramolecular assemblies that require the continuous consumption of energy to remain in the functional state is an essential premise for the design of synthetic systems with lifelike properties. Here, we show a new strategy for the dissipative self-assembly of functional supramolecular structures with high structural complexity. It relies on the transient stabilization of vesicles through noncovalent interactions between the surfactants and adenosine triphosphate (ATP), which acts as the chemical fuel. It is shown that the lifetime of the vesicles can be regulated by controlling the hydrolysis rate of ATP. The vesicles sustain a chemical reaction but only as long as chemical fuel is present to keep the system in the out-of-equilibrium state. The lifetime of the vesicles determines the amount of reaction product produced by the system.

  16. Self-assembled microdevices driven by muscle.

    PubMed

    Xi, Jianzhong; Schmidt, Jacob J; Montemagno, Carlo D

    2005-02-01

    Current procedures for manual extraction of mature muscle tissue in micromechanical structures are time consuming and can damage the living components. To overcome these limitations, we have devised a new system for assembling muscle-powered microdevices based on judicious manipulations of materials phases and interfaces. In this system, individual cells grow and self-assemble into muscle bundles that are integrated with micromechanical structures and can be controllably released to enable free movement. Having realized such an assembly with cardiomyocytes we demonstrate two potential applications: a force transducer able to characterize in situ the mechanical properties of muscle and a self-assembled hybrid (biotic/abiotic) microdevice that moves as a consequence of collective cooperative contraction of muscle bundles. Because the fabrication of silicon microdevices is independent of the subsequent assembly of muscle cells, this system is highly versatile and may lead to the integration of cells and tissues with a variety of other microstructures.

  17. Self-assembled Oniontype Multiferroic Nanostructures

    NASA Astrophysics Data System (ADS)

    Ren, Shenqiang; Briber, Robert M.; Wuttig, Manfred

    2009-03-01

    Spontaneously self-assembled oniontype multiferroic nanostructures based on block copolymers as templating materials are reported. Diblock copolymer containing two different magnetoelectric precursors separately segregated to the two microdomains have been shown to form well-ordered templated lamellar structures. Onion-type multilamellar ordered multiferroic (PZT/CoFe2O4) nanostructures have been induced by room temperature solvent annealing in a magnetic field oriented perpendicular to the plane of the film. The evolution of the onion-like microstructure has been characterized by AFM, MFM, and TEM. The structure retains lamellar periodicity observed at zero field. The onion structure is superparamagnetic above and antiferromagnetic below the blocking temperature. This templating process opens a route for nanometer-scale patterning of magnetic toroids by means of self-assembly on length scales that are difficult to obtain by standard lithography techniques.

  18. Templated Self Assemble of Nano-Structures

    SciTech Connect

    Suo, Zhigang

    2013-04-29

    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.

  19. Meniscus height controlled convective self-assembly

    NASA Astrophysics Data System (ADS)

    Choudhary, Satyan; Crosby, Alfred

    Convective self-assembly techniques based on the 'coffee-ring effect' allow for the fabrication of materials with structural hierarchy and multi-functionality across a wide range of length scales. The coffee-ring effect describes deposition of non-volatiles at the edge of droplet due to capillary flow and pattern formations due to pinning and de-pinning of meniscus with the solvent evaporation. We demonstrate a novel convective self-assembly method which uses a piezo-actuated bending motion for driving the de-pinning step. In this method, a dilute solution of nanoparticles or polymers is trapped by capillary forces between a blade and substrate. As the blade oscillates with a fixed frequency and amplitude and the substrate translates at a fixed velocity, the height of the capillary meniscus oscillates. The meniscus height controls the contact angle of three phase contact line and at a critical angle de-pinning occurs. The combination of convective flux and continuously changing contact angle drives the assembly of the solute and subsequent de-pinning step, providing a direct means for producing linear assemblies. We demonstrate a new method for convective self-assembly at an accelerated rate when compared to other techniques, with control over deposit dimensions. Army Research Office (W911NF-14-1-0185).

  20. Self-Assembly of Nanoparticle Surfactants

    NASA Astrophysics Data System (ADS)

    Lombardo, Michael T.

    Self-assembly utilizes non-covalent forces to organize smaller building blocks into larger, organized structures. Nanoparticles are one type of building block and have gained interest recently due to their unique optical and electrical properties which have proved useful in fields such as energy, catalysis, and advanced materials. There are several techniques currently used to self-assemble nanoparticles, each with its own set of benefits and drawbacks. Here, we address the limited number of techniques in non-polar solvents by introducing a method utilizing amphiphilic gold nanoparticles. Grafted polymer chains provide steric stabilization while small hydrophilic molecules induce assembly through short range attractive forces. The properties of these self-assembled structures are found to be dependent on the polymer and small molecules surface concentrations and chemistries. These particles act as nanoparticle surfactants and can effectively stabilize oil-water interfaces, such as in an emulsion. In addition to the work in organic solvent, similar amphiphilic particles in aqueous media are shown to effectively stabilize oil-in-water emulsions that show promise as photoacoustic/ultrasound theranostic agents.

  1. Interparticle Forces Underlying Nanoparticle Self-Assemblies.

    PubMed

    Luo, Dan; Yan, Cong; Wang, Tie

    2015-12-01

    Studies on the self-assembly of nanoparticles have been a hot topic in nanotechnology for decades and still remain relevant for the present and future due to their tunable collective properties as well as their remarkable applications to a wide range of fields. The novel properties of nanoparticle assemblies arise from their internal interactions and assemblies with the desired architecture key to constructing novel nanodevices. Therefore, a comprehensive understanding of the interparticle forces of nanoparticle self-assemblies is a pre-requisite to the design and control of the assembly processes, so as to fabricate the ideal nanomaterial and nanoproducts. Here, different categories of interparticle forces are classified and discussed according to their origins, behaviors and functions during the assembly processes, and the induced collective properties of the corresponding nanoparticle assemblies. Common interparticle forces, such as van der Waals forces, electrostatic interactions, electromagnetic dipole-dipole interactions, hydrogen bonds, solvophonic interactions, and depletion interactions are discussed in detail. In addition, new categories of assembly principles are summarized and introduced. These are termed template-mediated interactions and shape-complementary interactions. A deep understanding of the interactions inside self-assembled nanoparticles, and a broader perspective for the future synthesis and fabrication of these promising nanomaterials is provided.

  2. Symmetry, Equivalence and Self-Assembly

    NASA Astrophysics Data System (ADS)

    Douglas, Jack

    2006-03-01

    Molecular self-assembly at equilibrium is central to the formation of many biological structures and the emulation of this process through the creation of synthetic counterparts offers great promise for nanofabrication. The central problems in this field are an understanding of how the symmetry of the interacting particles encodes the geometrical structure of the organized structure and the nature of the thermodynamic transitions involved. Our approach is inspired by the self-assembly of actin, tubulin and icosahedral structures of plant and animal viruses. We observe chain, membrane,`nanotube' and hollow icosahedron structures using `equivalent' particles exhibiting an interplay between directional (dipolar and multi-polar) interactions and short-range (van der Waals) interactions. Specifically, a dipolar potential (continuous rotational symmetry) gives rise to chain formation, while potentials having discrete rotational symmetries (e.g., square quadrupole or triangular ring of dipoles) led to the self-organization of nanotube and icosahedral structures with some resemblance to tubulin and icosahedral viruses. The simulations are compared to theoretical models of molecular self-assembly, especially in the case of dipolar fluids where the corresponding analytic theory of equilibrium polymerization is well developed. These computations give insights into the design elements required for the development of synthetic systems exhibiting this type of organization.

  3. Designer self-assembling peptide materials.

    PubMed

    Zhao, Xiaojun; Zhang, Shuguang

    2007-01-01

    Understanding of macromolecular materials at the molecular level is becoming increasingly important for a new generation of nanomaterials for nanobiotechnology and other disciplines, namely, the design, synthesis, and fabrication of nanodevices at the molecular scale from bottom up. Basic engineering principles for microfabrication can be learned through fully grasping the molecular self-assembly and programmed assembly phenomena. Self- and programmed-assembly phenomena are ubiquitous in nature. Two key elements in molecular macrobiological material productions are chemical complementarity and structural compatibility, both of which require weak and non-covalent interactions that bring building blocks together during self-assembly. Significant advances have been made during the 1990s at the interface of materials chemistry and biology. They include the design of helical ribbons, peptide nanofiber scaffolds for three-dimensional cell cultures and tissue engineering, peptide surfactants for solubilizing and stabilizing diverse types of membrane proteins and their complexes, and molecular ink peptides for arbitrary printing and coating surfaces as well as coiled-coil helical peptides for multi-length scale fractal structures. These designer self-assembling peptides have far reaching implications in a broad spectrum of applications in biology, medicine, nanobiotechnology, and nanobiomedical technology, some of which are beyond our current imaginations. [image: see text

  4. Polymer Self-assembly on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Giulianini, Michele; Motta, Nunzio

    This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV-Vis and Raman), we show how the polymer's higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT π-π stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

  5. Self-assembled tunable photonic hyper-crystals

    PubMed Central

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

    2014-01-01

    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

  6. Self-assembled tunable photonic hyper-crystals.

    PubMed

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

    2014-01-01

    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

  7. Self-assembled tunable photonic hyper-crystals

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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.

  8. Self-assembled tunable photonic hyper-crystals

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  9. Self-assembly of Fmoc-diphenylalanine inside liquid marbles.

    PubMed

    Braun, Hans-Georg; Cardoso, André Zamith

    2012-09-01

    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.

  10. Self-assembled tunable photonic hyper-crystals

    NASA Astrophysics Data System (ADS)

    Smolyaninov, Igor; Smolyaninova, Vera; Yost, Bradley; Lahneman, David; Gresock, Thomas; Narimanov, Evgenii

    2015-03-01

    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. This work was supported in part by NSF Grant DMR-1104676, NSF Center for Photonic and Multiscale Nanomaterials, ARO MURI and Gordon and Berry Moore Foundation.

  11. Self-assembled biomimetic nanoreactors I: Polymeric template

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  12. Differential self-assembly behaviors of cyclic and linear peptides.

    PubMed

    Choi, Sung-ju; Jeong, Woo-jin; Kang, Seong-Kyun; Lee, Myongsoo; Kim, Eunhye; Ryu, Du Yeol; Lim, Yong-beom

    2012-07-01

    Here we ask the fundamental questions about the effect of peptide topology on self-assembly. The study revealed that the self-assembling behaviors of cyclic and linear peptides are significantly different in several respects, in addition to sharing several similarities. Their clear differences included the morphological dissimilarities of the self-assembled nanostructures and their thermal stability. The similarities include their analogous critical aggregation concentration values and cytotoxicity profiles, which are in fact closely related. We believe that understanding topology-dependent self-assembly behavior of peptides is important for developing tailor-made self-assembled peptide nanostructures.

  13. Self-Assembled Quantum Dots of Indium

    NASA Astrophysics Data System (ADS)

    Leonard, Devin Blaine

    1995-01-01

    The deposition of InAs or In_ xGa_{1-x}As upon GaAs substrates by molecular beam epitaxy (MBE) generally proceeds via the mode first described by Stranski and von Krastanow (SK). After the deposition of a certain thickness of this material, small islands of the deposited material nucleate on the surface. The island formation is attributed not to a large epitaxial surface energies, but to an elastic (dislocation free) relaxation of the mismatch strain (a _{InAs}=1.07cdot a_{GaAs}). I present a detailed study of the nucleation and growth of these InAs islands using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The islands are found to be lens-shaped, coherently-strained and remarkably uniform in their size. Embedding these 4 nm tall, 25 nm diameter InAs islands in GaAs confines injected carriers in three dimensions. The islands thus formed fulfill the requirements of a quantum dot (or box), which behave as "artificial atoms" whose allowed energy eigenstates are discrete. Quantum dots have been the "holy grail" for many scientists because of the advantages these discrete energy levels provide in electronic and optical devices, such as semiconductor lasers. Self-assembled quantum dots (SAQD), presented in this dissertation, surmount the fabrication difficulties typical for quantum dots, reducing efforts to more fundamental problems of size uniformity and control. SAQDs have distinct advantages over quantum dots formed with other methods. For instance, no processing is required before or after growth. In addition, layers of SAQDs can be easily integrated into GaAs/AlGaAs devices. Contrary to quantum dots formed with other techniques, a strong light emission is observed from the SAQD at ~1.2 eV. Further photoluminescence (PL) experiments reveal emission linewidths less than.5 meV from individual SAQD, but a ~50 meV linewidth from larger arrays due to small SAQD thickness fluctuations. PL excitation (PLE) spectra reveal a large shift between

  14. Enhanced Conversion Efficiencies in Dye-Sensitized Solar Cells Achieved through Self-Assembled Platinum(II) Metallacages

    NASA Astrophysics Data System (ADS)

    He, Zuoli; Hou, Zhiqiang; Xing, Yonglei; Liu, Xiaobin; Yin, Xingtian; Que, Meidan; Shao, Jinyou; Que, Wenxiu; Stang, Peter J.

    2016-07-01

    Two-component self-assembly supramolecular coordination complexes with particular photo-physical property, wherein unique donors are combined with a single metal acceptor, can be utilized for many applications including in photo-devices. In this communication, we described the synthesis and characterization of two-component self-assembly supramolecular coordination complexes (SCCs) bearing triazine and porphyrin faces with promising light-harvesting properties. These complexes were obtained from the self-assembly of a 90° Pt(II) acceptor with 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPyT) or 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphine (TPyP). The greatly improved conversion efficiencies of the dye-sensitized TiO2 solar cells were 6.79 and 6.08 respectively, while these SCCs were introduced into the TiO2 nanoparticle film photoanodes. In addition, the open circuit voltage (Voc) of dye-sensitized solar cells was also increased to 0.769 and 0.768 V, which could be ascribed to the inhibited interfacial charge recombination due to the addition of SCCs.

  15. Enhanced Conversion Efficiencies in Dye-Sensitized Solar Cells Achieved through Self-Assembled Platinum(II) Metallacages

    PubMed Central

    He, Zuoli; Hou, Zhiqiang; Xing, Yonglei; Liu, Xiaobin; Yin, Xingtian; Que, Meidan; Shao, Jinyou; Que, Wenxiu; Stang, Peter J.

    2016-01-01

    Two-component self-assembly supramolecular coordination complexes with particular photo-physical property, wherein unique donors are combined with a single metal acceptor, can be utilized for many applications including in photo-devices. In this communication, we described the synthesis and characterization of two-component self-assembly supramolecular coordination complexes (SCCs) bearing triazine and porphyrin faces with promising light-harvesting properties. These complexes were obtained from the self-assembly of a 90° Pt(II) acceptor with 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPyT) or 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphine (TPyP). The greatly improved conversion efficiencies of the dye-sensitized TiO2 solar cells were 6.79 and 6.08 respectively, while these SCCs were introduced into the TiO2 nanoparticle film photoanodes. In addition, the open circuit voltage (Voc) of dye-sensitized solar cells was also increased to 0.769 and 0.768 V, which could be ascribed to the inhibited interfacial charge recombination due to the addition of SCCs. PMID:27404912

  16. Integrated Nanosystems Templated by Self-assembled Virus Capsids

    NASA Astrophysics Data System (ADS)

    Stephanopoulos, Nicholas

    This dissertation presents the synthesis and modeling of multicomponent nanosystems templated by self-assembled virus capsids. The design principles, synthesis, analysis, and future directions for these capsid-based materials are presented. Chapter 1 gives an overview of the literature on the application of virus capsids in constructing nanomaterials. The uses of capsids in three main areas are considered: (1) as templates for inorganic materials or nanoparticles; (2) as vehicles for biological applications like medical imaging and treatment; and (3) as scaffolds for catalytic materials. In light of this introduction, an overview of the material in this dissertation is described. Chapters 2-4 all describe integrated nanosystems templated by bacteriophage MS2, a spherical icosahedral virus capsid. MS2 possesses an interior and exterior surface that can be modified orthogonally using bioconjugation chemistry to create multivalent, multicomponent constructs with precise localization of components attached to the capsid proteins. Chapter 2 describes the use of MS2 to synthesize a photocatalytic construct by modifying the internal surface with sensitizing chromophores and the external surface with a photocatalytic porphyrin. The chromophores absorbed energy that the porphyrin could not, and transferred it to the porphyrin via FRET through the protein shell. The porphyrin was then able to utilize the energy to carry out photocatalysis at new wavelengths. In Chapter 3, porphyrins were installed on the interior surface of MS2 and DNA aptamers specific for Jurkat leukemia T cells on the exterior surface. The dual-modified capsids were able to bind to Jurkat cells, and upon illumination the porphyrins generated singlet oxygen to kill them selectively over non-targeted cells. Chapter 4 explores integrating MS2 with DNA origami in order to arrange the capsids at larger length scales. Capsids modified with fluorescent dyes inside and single-stranded DNA outside were able to

  17. Light-harvesting supramolecular porphyrin macrocycle accommodating a fullerene-tripodal ligand.

    PubMed

    Kuramochi, Yusuke; Satake, Akiharu; Itou, Mitsunari; Ogawa, Kazuya; Araki, Yasuyuki; Ito, Osamu; Kobuke, Yoshiaki

    2008-01-01

    Trisporphyrinatozinc(II) (1-Zn) with imidazolyl groups at both ends of the porphyrin self-assembles exclusively into a light-harvesting cyclic trimer (N-(1-Zn)(3)) through complementary coordination of imidazolyl to zinc(II). Because only the two terminal porphyrins in 1-Zn are employed in ring formation, macrocycle N-(1-Zn)(3) leaves three uncoordinated porphyrinatozinc(II) groups as a scaffold that can accommodate ligands into the central pore. A pyridyl tripodal ligand with an appended fullerene connected through an amide linkage (C(60)-Tripod) was synthesized by coupling tripodal ligand 3 with pyrrolidine-modified fullerene, and this ligand was incorporated into N-(1-Zn)(3). The binding constant for C(60)-Tripod in benzonitrile reached the order of 10(8) M(-1). This value is ten times larger than those of pyridyl tetrapodal ligand 2 and tripodal ligand 3. This behavior suggests that the fullerene moiety contributes to enhance the binding of C(60)-Tripod in N-(1-Zn)(3). The fluorescence of N-(1-Zn)(3) was almost completely quenched (approximately 97 %) by complexation with C(60)-Tripod, without any indication of the formation of charge-separated species or a triplet excited state of either porphyrin or fullerene in the transient absorption spectra. These observations are explained by the idea that the fullerene moiety of C(60)-Tripod is in direct contact with the porphyrin planes of N-(1-Zn)(3) through fullerene-porphyrin pi-pi interactions. Thus, C(60)-Tripod is accommodated in N-(1-Zn)(3) with a pi-pi interaction and two pyridyl coordinations. The cooperative interaction achieves a sufficiently high affinity for quantitative and specific introduction of one equivalent of tripodal guest into the antenna ring, even under dilute conditions ( approximately 10(-7) M) in polar solvents such as benzonitrile. Additionally, complete fluorescence quenching of N-(1-Zn)(3) when accommodating C(60)-Tripod demonstrates that all of the excitation energy collected by the nine

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

    PubMed

    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

    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 β-peptide to give conjugates β-B1, β-B2, and β-B3. Given the hydrophobic nature of the β-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 β-peptides, two covalently attached synthetic bacteriochlorins, and a datively bonded BChl-a pair, albeit to a limited extent for β-B2. The reversible assembly/disassembly of dyad (β-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 (β-B1/BChl)2, 0.40 for (β-B2/BChl)2, and 0.85 for (β-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

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

    PubMed

    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

    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 β-peptide to give conjugates β-B1, β-B2, and β-B3. Given the hydrophobic nature of the β-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 β-peptides, two covalently attached synthetic bacteriochlorins, and a datively bonded BChl-a pair, albeit to a limited extent for β-B2. The reversible assembly/disassembly of dyad (β-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 (β-B1/BChl)2, 0.40 for (β-B2/BChl)2, and 0.85 for (β-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

  20. Energizing the light harvesting antenna: Insight from CP29.

    PubMed

    Ioannidis, Nikolaos E; Papadatos, Sotiris; Daskalakis, Vangelis

    2016-10-01

    How do plants cope with excess light energy? Crop health and stress tolerance are governed by molecular photoprotective mechanisms. Protective exciton quenching in plants is activated by membrane energization, via unclear conformational changes in proteins called antennas. Here we show that pH and salt gradients stimulate the response of such an antenna under low and high energization by all-atom Molecular Dynamics Simulations. Novel insight establishes that helix-5 (H5) conformation in CP29 from spinach is regulated by chemiosmotic factors. This is selectively correlated with the chl-614 macrocycle deformation and interactions with nearby pigments, that could suggest a role in plant photoprotection. Adding to the significance of our findings, H5 domain is conserved among five antennas (LHCB1-5). These results suggest that light harvesting complexes of Photosystem II, one of the most abundant proteins on earth, can sense chemiosmotic gradients via their H5 domains in an upgraded role from a solar detector to also a chemiosmotic sensor. PMID:27438094

  1. 2-D Pigment Langmuir Monolayer Assemblies for Light Harvesting Applications.

    NASA Astrophysics Data System (ADS)

    Gregory, Brian W.; Vaknin, David; Cotton, Therese M.; Struve, Walter S.

    1996-03-01

    The use of Coulombic forces to isolate charged, water-soluble macrocycles at the air/water interface (through their interactions with the oppositely charged headgroups of a phospholipid Langmuir monolayer) is currently being exploited in this laboratory as a means to create two-dimensional arrays of pigments for light-harvesting purposes. Significant differences have been observed in the surface pressure-molecular area (π-A) isotherms of dihexadecyl phosphate on subphases containing either tetra-(N-methylaza)- phthalocyanine (i.e., tetra-(N-methyl)-2,3-pyridinoporphyrazine) or tetra- (N-methylpyridyl)-porphyrin, both of which are cationic. In situ x-ray specular reflectivity has been employed to determine interfacial organization in these systems and to elucidate the origin of their different phase behavior at the air/water interface. In addition, electronic absorption spectra and electronic linear dichroism have been utilized to determine average pigment orientation in transferred films. * Ames Laboratory is operated by Iowa State University for the U.S. Department of Energy under Cotract No. W-4705-Eng-82.

  2. Multiscale model of light harvesting by photosystem II in plants.

    PubMed

    Amarnath, Kapil; Bennett, Doran I G; Schneider, Anna R; Fleming, Graham R

    2016-02-01

    The first step of photosynthesis in plants is the absorption of sunlight by pigments in the antenna complexes of photosystem II (PSII), followed by transfer of the nascent excitation energy to the reaction centers, where long-term storage as chemical energy is initiated. Quantum mechanical mechanisms must be invoked to explain the transport of excitation within individual antenna. However, it is unclear how these mechanisms influence transfer across assemblies of antenna and thus the photochemical yield at reaction centers in the functional thylakoid membrane. Here, we model light harvesting at the several-hundred-nanometer scale of the PSII membrane, while preserving the dominant quantum effects previously observed in individual complexes. We show that excitation moves diffusively through the antenna with a diffusion length of 50 nm until it reaches a reaction center, where charge separation serves as an energetic trap. The diffusion length is a single parameter that incorporates the enhancing effect of excited state delocalization on individual rates of energy transfer as well as the complex kinetics that arise due to energy transfer and loss by decay to the ground state. The diffusion length determines PSII's high quantum efficiency in ideal conditions, as well as how it is altered by the membrane morphology and the closure of reaction centers. We anticipate that the model will be useful in resolving the nonphotochemical quenching mechanisms that PSII employs in conditions of high light stress.

  3. Multiscale model of light harvesting by photosystem II in plants

    PubMed Central

    Amarnath, Kapil; Bennett, Doran I. G.; Schneider, Anna R.; Fleming, Graham R.

    2016-01-01

    The first step of photosynthesis in plants is the absorption of sunlight by pigments in the antenna complexes of photosystem II (PSII), followed by transfer of the nascent excitation energy to the reaction centers, where long-term storage as chemical energy is initiated. Quantum mechanical mechanisms must be invoked to explain the transport of excitation within individual antenna. However, it is unclear how these mechanisms influence transfer across assemblies of antenna and thus the photochemical yield at reaction centers in the functional thylakoid membrane. Here, we model light harvesting at the several-hundred-nanometer scale of the PSII membrane, while preserving the dominant quantum effects previously observed in individual complexes. We show that excitation moves diffusively through the antenna with a diffusion length of 50 nm until it reaches a reaction center, where charge separation serves as an energetic trap. The diffusion length is a single parameter that incorporates the enhancing effect of excited state delocalization on individual rates of energy transfer as well as the complex kinetics that arise due to energy transfer and loss by decay to the ground state. The diffusion length determines PSII’s high quantum efficiency in ideal conditions, as well as how it is altered by the membrane morphology and the closure of reaction centers. We anticipate that the model will be useful in resolving the nonphotochemical quenching mechanisms that PSII employs in conditions of high light stress. PMID:26787911

  4. Energizing the light harvesting antenna: Insight from CP29.

    PubMed

    Ioannidis, Nikolaos E; Papadatos, Sotiris; Daskalakis, Vangelis

    2016-10-01

    How do plants cope with excess light energy? Crop health and stress tolerance are governed by molecular photoprotective mechanisms. Protective exciton quenching in plants is activated by membrane energization, via unclear conformational changes in proteins called antennas. Here we show that pH and salt gradients stimulate the response of such an antenna under low and high energization by all-atom Molecular Dynamics Simulations. Novel insight establishes that helix-5 (H5) conformation in CP29 from spinach is regulated by chemiosmotic factors. This is selectively correlated with the chl-614 macrocycle deformation and interactions with nearby pigments, that could suggest a role in plant photoprotection. Adding to the significance of our findings, H5 domain is conserved among five antennas (LHCB1-5). These results suggest that light harvesting complexes of Photosystem II, one of the most abundant proteins on earth, can sense chemiosmotic gradients via their H5 domains in an upgraded role from a solar detector to also a chemiosmotic sensor.

  5. Understanding photosynthetic light-harvesting: a bottom up theoretical approach.

    PubMed

    Renger, Thomas; Müh, Frank

    2013-03-14

    We discuss a bottom up approach for modeling photosynthetic light-harvesting. Methods are reviewed for a full structure-based parameterization of the Hamiltonian of pigment-protein complexes (PPCs). These parameters comprise (i) the local transition energies of the pigments in their binding sites in the protein, the site energies; (ii) the couplings between optical transitions of the pigments, the excitonic couplings; and (iii) the spectral density characterizing the dynamic modulation of pigment transition energies and excitonic couplings by protein vibrations. Starting with quantum mechanics perturbation theory, we provide a microscopic foundation for the standard PPC Hamiltonian and relate the expressions obtained for its matrix elements to quantities that can be calculated with classical molecular mechanics/electrostatics approaches including the whole PPC in atomic detail and using charge and transition densities obtained with quantum chemical calculations on the isolated building blocks of the PPC. In the second part of this perspective, the Hamiltonian is utilized to describe the quantum dynamics of excitons. Situations are discussed that differ in the relative strength of excitonic and exciton-vibrational coupling. The predictive power of the approaches is demonstrated in application to different PPCs, and challenges for future work are outlined.

  6. Self-assembly of magnetic biofunctional nanoparticles

    NASA Astrophysics Data System (ADS)

    Sun, Xiangcheng; Thode, C. J.; Mabry, J. K.; Harrell, J. W.; Nikles, D. E.; Sun, K.; Wang, L. M.

    2005-05-01

    Spherical, ferromagnetic FePt nanoparticles with a particle size of 3 nm were prepared by the simultaneous polyol reduction of Fe(acac)3 and Pt(acac)2 in phenyl ether in the presence of oleic acid and oleylamine. The oleic acid ligands can be replaced with 11-mercaptoundecanoic acid, giving particles that can be dispersed in water. Both x-ray diffraction and transmission electron microscopy indicated that FePt particles were not affected by ligands replacement. Dispersions of the FePt particles with 11-mercaptoundecanoic acid ligands and ammonium counter ions gave self-assembled films consisting of highly ordered hexagonal arrays of particles.

  7. Self-assembly of Random Copolymers

    PubMed Central

    Li, Longyu; Raghupathi, Kishore; Song, Cunfeng; Prasad, Priyaa; Thayumanavan, S.

    2014-01-01

    Self-assembly of random copolymers has attracted considerable attention recently. In this feature article, we highlight the use of random copolymers to prepare nanostructures with different morphologies and to prepare nanomaterials that are responsive to single or multiple stimuli. The synthesis of single-chain nanoparticles and their potential applications from random copolymers are also discussed in some detail. We aim to draw more attention to these easily accessible copolymers, which are likely to play an important role in translational polymer research. PMID:25036552

  8. Self-assembling triblock proteins for biofunctional surface modification

    NASA Astrophysics Data System (ADS)

    Fischer, Stephen E.

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

  9. Self-Assembly of Gemini Surfactants

    NASA Astrophysics Data System (ADS)

    Yethiraj, Arun; Mondal, Jagannath; Mahanthappa, Mahesh

    2013-03-01

    The self-assembly behavior of Gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. 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 quanitative 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 decreasing the charge on the surfactant headgroups by carboxylate protonation or use of a bulkier tetramethyl ammonium counterion in place of sodium drives the formation of a gyroid phase.

  10. Directed Self-Assembly: Expectations and Achievements

    PubMed Central

    2010-01-01

    Nanotechnology has been a revolutionary thrust in recent years of development of science and technology for its broad appeal for employing a novel idea for relevant technological applications in particular and for mass-scale production and marketing as common man commodity in general. An interesting aspect of this emergent technology is that it involves scientific research community and relevant industries alike. Top–down and bottom–up approaches are two broad division of production of nanoscale materials in general. However, both the approaches have their own limits as far as large-scale production and cost involved are concerned. Therefore, novel new techniques are desired to be developed to optimize production and cost. Directed self-assembly seems to be a promising technique in this regard; which can work as a bridge between the top–down and bottom–up approaches. This article reviews how directed self-assembly as a technique has grown up and outlines its future prospects. PMID:20730077

  11. Self-assembled virus-membrane complexes

    SciTech Connect

    Yang, Lihua; Liang, Hongjun; Angelini, Thomas; Butler, John; Coridan, Robert; Tang, Jay; Wong, Gerard

    2010-11-16

    Anionic polyelectrolytes and cationic lipid membranes can self-assemble into lamellar structures ranging from alternating layers of membranes and polyelectrolytes to 'missing layer' superlattice structures. We show that these structural differences can be understood in terms of the surface-charge-density mismatch between the polyelectrolyte and membrane components by examining complexes between cationic membranes and highly charged M13 viruses, a system that allowed us to vary the polyelectrolyte diameter independently of the charge density. Such virus-membrane complexes have pore sizes that are about ten times larger in area than DNA-membrane complexes, and can be used to package and organize large functional molecules; correlated arrays of Ru(bpy){sub 3}{sup 2+} macroionic dyes have been directly observed within the virus-membrane complexes using an electron-density reconstruction. These observations elucidate fundamental design rules for rational control of self-assembled polyelectrolyte-membrane structures, which have applications ranging from non-viral gene therapy to biomolecular templates for nanofabrication.

  12. Triggered self-assembly of magnetic nanoparticles

    PubMed Central

    Ye, L.; Pearson, T.; Cordeau, Y.; Mefford, O. T.; Crawford, T. M.

    2016-01-01

    Colloidal magnetic nanoparticles are candidates for application in biology, medicine and nanomanufac-turing. Understanding how these particles interact collectively in fluids, especially how they assemble and aggregate under external magnetic fields, is critical for high quality, safe, and reliable deployment of these particles. Here, by applying magnetic forces that vary strongly over the same length scale as the colloidal stabilizing force and then varying this colloidal repulsion, we can trigger self-assembly of these nanoparticles into parallel line patterns on the surface of a disk drive medium. Localized within nanometers of the medium surface, this effect is strongly dependent on the ionic properties of the colloidal fluid but at a level too small to cause bulk colloidal aggregation. We use real-time optical diffraction to monitor the dynamics of self-assembly, detecting local colloidal changes with greatly enhanced sensitivity compared with conventional light scattering. Simulations predict the triggering but not the dynamics, especially at short measurement times. Beyond using spatially-varying magnetic forces to balance interactions and drive assembly in magnetic nanoparticles, future measurements leveraging the sensitivity of this approach could identify novel colloidal effects that impact real-world applications of these nanoparticles. PMID:26975332

  13. Computational Modeling of Tissue Self-Assembly

    NASA Astrophysics Data System (ADS)

    Neagu, Adrian; Kosztin, Ioan; Jakab, Karoly; Barz, Bogdan; Neagu, Monica; Jamison, Richard; Forgacs, Gabor

    As a theoretical framework for understanding the self-assembly of living cells into tissues, Steinberg proposed the differential adhesion hypothesis (DAH) according to which a specific cell type possesses a specific adhesion apparatus that combined with cell motility leads to cell assemblies of various cell types in the lowest adhesive energy state. Experimental and theoretical efforts of four decades turned the DAH into a fundamental principle of developmental biology that has been validated both in vitro and in vivo. Based on computational models of cell sorting, we have developed a DAH-based lattice model for tissues in interaction with their environment and simulated biological self-assembly using the Monte Carlo method. The present brief review highlights results on specific morphogenetic processes with relevance to tissue engineering applications. Our own work is presented on the background of several decades of theoretical efforts aimed to model morphogenesis in living tissues. Simulations of systems involving about 105 cells have been performed on high-end personal computers with CPU times of the order of days. Studied processes include cell sorting, cell sheet formation, and the development of endothelialized tubes from rings made of spheroids of two randomly intermixed cell types, when the medium in the interior of the tube was different from the external one. We conclude by noting that computer simulations based on mathematical models of living tissues yield useful guidelines for laboratory work and can catalyze the emergence of innovative technologies in tissue engineering.

  14. Triggered self-assembly of magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Ye, L.; Pearson, T.; Cordeau, Y.; Mefford, O. T.; Crawford, T. M.

    2016-03-01

    Colloidal magnetic nanoparticles are candidates for application in biology, medicine and nanomanufac-turing. Understanding how these particles interact collectively in fluids, especially how they assemble and aggregate under external magnetic fields, is critical for high quality, safe, and reliable deployment of these particles. Here, by applying magnetic forces that vary strongly over the same length scale as the colloidal stabilizing force and then varying this colloidal repulsion, we can trigger self-assembly of these nanoparticles into parallel line patterns on the surface of a disk drive medium. Localized within nanometers of the medium surface, this effect is strongly dependent on the ionic properties of the colloidal fluid but at a level too small to cause bulk colloidal aggregation. We use real-time optical diffraction to monitor the dynamics of self-assembly, detecting local colloidal changes with greatly enhanced sensitivity compared with conventional light scattering. Simulations predict the triggering but not the dynamics, especially at short measurement times. Beyond using spatially-varying magnetic forces to balance interactions and drive assembly in magnetic nanoparticles, future measurements leveraging the sensitivity of this approach could identify novel colloidal effects that impact real-world applications of these nanoparticles.

  15. Transmetalation of self-assembled, supramolecular complexes.

    PubMed

    Carnes, Matthew E; Collins, Mary S; Johnson, Darren W

    2014-03-21

    Substituting one metal for another in inorganic and organometallic systems is a proven strategy for synthesizing complex molecules, and in some cases, provides the only route to a particular system. The multivalent nature of the coordination in metal-ligand assemblies lends itself more readily to some types of transmetalation. For instance, a binding site can open up for exchange without greatly effecting the many other interactions holding the structure together. In addition to exchanging the metal and altering the local binding environment, transmetalation in supramolecular systems can also lead to substantial changes in the nature of the secondary and tertiary structure of a larger assembly. In this tutorial review we will cover discrete supramolecular assemblies in which metals are exchanged. First we will address fully formed structures where direct substitution replaces one type of metal for another without changing the overall supramolecular assembly. We will then address systems where the disruptive exchange of one metal for another leads to a larger change in the supramolecular assembly. When possible we have tried to highlight systems that use supramolecular self-assembly in tandem with transmetalation to synthesize new structures not accessible through a more direct approach. At the end of this review, we highlight the use of transmetalation in self-assembled aqueous inorganic clusters and discuss the consequences for material science applications. PMID:24346298

  16. Self-assembled Nanofibrils for Immunomodulation

    NASA Astrophysics Data System (ADS)

    Zhao, Fan

    This thesis has been mainly focused on applying self-assembled nanofibrils as unique depots for controlled release to modulate immune system, with two major chapters on modulation of innate immunity in chapter 2 and adaptive immunity in chapter 3, respectively. There are 5 chapters in the thesis. Chapter 1 gives a detailed review on the discovery, synthesis and application of self-assembled nanofibrils of therapeutic agents (termed as "self-delivery drugs"), including bioactive molecules; Chapter 2 demonstrates the supramolecular hydrogel of chemotactic peptides as a prolonged inflammation model through proper molecular engineering; Chapter 3 reports a suppressive antibody response achieved by encapsulation of antigens by supramolecular hydrogel of glycopeptide; Chapter 4 illustrates an example of supramolecular hydrogel formation of molecules with extremely low solubility, based on the fact that many small organic drugs have poor solubility. Chapter 5 used beta-galatosidase as a model to study glycosidase-instructed supramolecular hydrogel formation, with potential to target cancer cells due to their distinct metabolic profile.

  17. Self-Assemblies of novel molecules, VECAR

    NASA Astrophysics Data System (ADS)

    Shrestha, Bijay; Kim, Hye-Young; Lee, Soojin; Novak, Brian; Moldovan, Dorel

    2015-03-01

    VECAR is a newly synthesized molecule, which is an amphiphilic antioxidant molecule that consists of two molecular groups, vitamin-E and Carnosine, linked by a hydrocarbon chain. The hydrocarbon chain is hydrophobic and both vitamin-E and Carnosine ends are hydrophilic. In the synthesis process, the length of the hydrophobic chain of VECAR molecules can vary from the shortest (n =0) to the longest (n =18), where n indicates the number of carbon atoms in the chain. We conducted MD simulation studies of self-assembly of VECAR molecules in water using GROMACS on LONI HPC resources. Our study shows that there is a strong correlation between the shape and atomistic structure of the self-assembled nano-structures (SANs) and the chain-length (n) of VECAR molecules. We will report the results of data analyses including the atomistic structure of each SANs and the dynamic and energetic mechanisms of their formation as function of time. In summary, both VECAR molecules of chain-length n =18 and 9 form worm-like micelles, which may be used as a drug delivery system. This research is supported by the Louisiana Board of Regents-RCS Grant (LEQSF(2012-15)-RD-A-19).

  18. A Diatom Light-Harvesting Pigment-Protein Complex 1

    PubMed Central

    Friedman, Alan L.; Alberte, Randall S.

    1984-01-01

    A light-harvesting pigment-protein complex was isolated from the diatom Phaeodactylum tricornutum using the zwitterionic detergent CHAPS (3-[3-cholamidopropyl)dimethylammonio]-1-propanesulfonate). Detergent-solubilized membranes were fractionated by sucrose density gradient centrifugation into three components. The medium density fraction contained chlorophyll a, chlorophyll c, and fucoxanthin. This fraction was purified by DEAE-ion exchange chromatography, and contained chlorophyll a, chlorophyll c, and fucoxanthin in a molar ratio of 2.4:1.0:4.8. Fluorescence emission and excitation spectra of the isolated complex demonstrated that light energy absorbed by chlorophyll c and fucoxanthin was coupled to chlorophyll a fluorescence. Upon denaturation, the apoprotein yielded a polypeptide doublet at 17.5 to 18.0 kilodaltons which accounted for 30 to 40% of the toal membrane protein. These findings indicate that this pigment-protein complex is a major component of the diatom photosynthetic lammellae. The quantitative amino acid composition of the apoprotein was very similar to those reported for other membrane-bound pigment-protein complexes. Based on the protein to chlorophyll a ratio of 7700 grams protein per mole chlorophyll a for the complex, each apoprotein molecule contains, to the nearest integer, two chlorophyll a, one chlorophyll c, and five fucoxanthin molecules. Polyclonal antibodies raised against the 17.5 to 18.0 kilodaltons apoprotein showed a monospecific reaction with only the 17.5 to 18.0 protein zone from denatured P. tricornutum membranes as well as to the nondenatured pigment-protein complex. It appears that this complex is common to other diatom species. Images Fig. 2 Fig. 3 PMID:16663869

  19. Construction of a smart microgel glutathione peroxidase mimic based on supramolecular self-assembly.

    PubMed

    Yin, Yanzhen; Jiao, Shufei; Zhang, Ruirui; Hu, Xiaoxi; Shi, Zhongfeng; Huang, Zuqiang

    2015-07-14

    In an effort to construct smart artificial glutathione peroxidase (GPx) featuring high catalytic activity in an efficient preparation process, an artificial microgel GPx (PPAM-ADA-Te) has been prepared using a supramolecular host-guest self-assembly technique. Herein, 6,6'-telluro-bis(6-deoxy-β-cyclodextrin) (CD-Te-CD) was selected as a tellurium-containing host molecule, which also served as the crosslinker for the scaffold of the supramolecular microgel. And an adamantane-containing block copolymer (PPAM-ADA) was designed and synthesized as a guest building block copolymer. Subsequently, PPAM-ADA-Te was constructed through the self-assembly of CD-Te-CD and PPAM-ADA. The formation of this self-assembled construct was confirmed by dynamic light scattering, NMR, SEM and TEM. Notably, PPAM-ADA-Te not only exhibits a significant temperature responsive catalytic activity, but also features the characteristic saturation kinetics behaviour similar to that of a natural enzyme catalyst. We demonstrate in this paper that both the hydrophobic microenvironment and the crosslinker in this supramolecular microgel network played significant roles in enhancing and altering the temperature responsive catalytic behaviour. The successful construction of PPAM-ADA-Te not only provides a novel method for the preparation of microgel artificial GPx with high catalytic activity but also provides properties suitable for the future development of intelligent antioxidant drugs. PMID:26053236

  20. Metal induced self-assembly of designed V-shape protein into 2D wavy supramolecular nanostructure

    NASA Astrophysics Data System (ADS)

    Qiao, S. P.; Lang, C.; Wang, R. D.; Li, X. M.; Yan, T. F.; Pan, T. Z.; Zhao, L. L.; Fan, X. T.; Zhang, X.; Hou, C. X.; Luo, Q.; Xu, J. Y.; Liu, J. Q.

    2015-12-01

    In order to understand and imitate the more complex bio-processes and fascinating functions in nature, protein self-assembly has been studied and has attracted more and more interest in recent years. Artificial self-assemblies of proteins have been constructed through many strategies. However, the design of complicated protein self-assemblies utilizing the special profile of building blocks remains a challenge. We herein report linear and 2D nanostructures constructed from a V shape SMAC protein and induced by metal coordination. Zigzag nanowires and wavy 2D nanostructures have been demonstrated by AFM and TEM. The zigzag nanowires can translate to a 2D nanostructure with an excess of metal ions, which reveals the step by step assembly process. Fluorescence and UV/Vis spectra have also been obtained to further study the mechanism and process of self-assembly. Upon the protein nanostructure, fluorescence resonance energy transfer (FRET) could also be detected using fluorescein modified proteins as building blocks. This article provides an approach for designing and controlling self-assembled protein nanostructures with a distinctive topological morphology.In order to understand and imitate the more complex bio-processes and fascinating functions in nature, protein self-assembly has been studied and has attracted more and more interest in recent years. Artificial self-assemblies of proteins have been constructed through many strategies. However, the design of complicated protein self-assemblies utilizing the special profile of building blocks remains a challenge. We herein report linear and 2D nanostructures constructed from a V shape SMAC protein and induced by metal coordination. Zigzag nanowires and wavy 2D nanostructures have been demonstrated by AFM and TEM. The zigzag nanowires can translate to a 2D nanostructure with an excess of metal ions, which reveals the step by step assembly process. Fluorescence and UV/Vis spectra have also been obtained to further

  1. Macromolecular self-assembly and nanotechnology in China.

    PubMed

    Xu, Huaping; Chen, Daoyong; Wang, Shu; Zhou, Yongfeng; Sun, Junqi; Zhang, Wenke; Zhang, Xi

    2013-10-13

    Macromolecular self-assembly refers to the assembly of synthetic polymers, biomacromolecules and supra-molecular polymers. Through macromolecular self-assembly, the fabrication of ordered structures at different scales, the control of the dynamic assembly process and the integrations of advanced functions can be realized. Macromolecular self-assembly and nanotechnology research in China has developed rapidly, from the early periods of follow-up at low to high level and progress into a stage of innovation and creation. This review selects some representative progresses achieved recently, aiming to reflect the current status of macromolecular self-assembly and nanotechnology research in China.

  2. Self-assembled software and method of overriding software execution

    SciTech Connect

    Bouchard, Ann M.; Osbourn, Gordon C.

    2013-01-08

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

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

    PubMed

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

    2014-01-01

    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, α-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

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

    PubMed

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

    2014-01-01

    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, α-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.

  5. Surface-Cross-Linked Micelles as Multifunctionalized Organic Nanoparticles for Controlled Release, Light Harvesting, and Catalysis

    PubMed Central

    2016-01-01

    Surfactant micelles are dynamic entities with a rapid exchange of monomers. By “clicking” tripropargylammonium-containing surfactants with diazide cross-linkers, we obtained surface-cross-linked micelles (SCMs) that could be multifunctionalized for different applications. They triggered membrane fusion through tunable electrostatic interactions with lipid bilayers. Antenna chromophores could be installed on them to create artificial light-harvesting complexes with efficient energy migration among tens to hundreds of chromophores. When cleavable cross-linkers were used, the SCMs could break apart in response to redox or pH signals, ejecting entrapped contents quickly as a result of built-in electrostatic stress. They served as caged surfactants whose surface activity was turned on by environmental stimuli. They crossed cell membranes readily. Encapsulated fluorophores showed enhanced photophysical properties including improved quantum yields and greatly expanded Stokes shifts. Catalytic groups could be installed on the surface or in the interior, covalently attached or physically entrapped. As enzyme mimics, the SCMs enabled rational engineering of the microenvironment around the catalysts to afford activity and selectivity not possible with conventional catalysts. PMID:27181610

  6. Light Harvesting Proteins for Solar Fuel Generation in Bioengineered Photoelectrochemical Cells

    PubMed Central

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

    2014-01-01

    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, α-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

  7. Surface-Cross-Linked Micelles as Multifunctionalized Organic Nanoparticles for Controlled Release, Light Harvesting, and Catalysis.

    PubMed

    Zhao, Yan

    2016-06-14

    Surfactant micelles are dynamic entities with a rapid exchange of monomers. By "clicking" tripropargylammonium-containing surfactants with diazide cross-linkers, we obtained surface-cross-linked micelles (SCMs) that could be multifunctionalized for different applications. They triggered membrane fusion through tunable electrostatic interactions with lipid bilayers. Antenna chromophores could be installed on them to create artificial light-harvesting complexes with efficient energy migration among tens to hundreds of chromophores. When cleavable cross-linkers were used, the SCMs could break apart in response to redox or pH signals, ejecting entrapped contents quickly as a result of built-in electrostatic stress. They served as caged surfactants whose surface activity was turned on by environmental stimuli. They crossed cell membranes readily. Encapsulated fluorophores showed enhanced photophysical properties including improved quantum yields and greatly expanded Stokes shifts. Catalytic groups could be installed on the surface or in the interior, covalently attached or physically entrapped. As enzyme mimics, the SCMs enabled rational engineering of the microenvironment around the catalysts to afford activity and selectivity not possible with conventional catalysts. PMID:27181610

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

    PubMed Central

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

    2014-01-01

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

  9. Supramolecular energy transfer from photoexcited chlorosomal zinc porphyrin self-aggregates to a chlorin or bacteriochlorin monomer as models of main light-harvesting antenna systems in green photosynthetic bacteria.

    PubMed

    Kataoka, Yumiko; Shibata, Yutaka; Tamiaki, Hitoshi

    2012-08-15

    Self-aggregates of a synthetic zinc porphyrin worked as a light absorber and photoexcited energy donor, transferred the collected energy to a small amount of 3-acetyl-(bacterio)chlorin monomer, and induced near-infrared fluorescence from the acceptors in aqueous micellar solution. These artificial supramolecular systems are novel models of the main light-harvesting antennas of green photosynthetic bacteria, chlorosomes.

  10. Magnetic self-assembly of small parts

    NASA Astrophysics Data System (ADS)

    Shetye, Sheetal B.

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

  11. Light Harvesting and White-Light Generation in a Composite of Carbon Dots and Dye-Encapsulated BSA-Protein-Capped Gold Nanoclusters.

    PubMed

    Barman, Monoj Kumar; Paramanik, Bipattaran; Bain, Dipankar; Patra, Amitava

    2016-08-01

    Several strategies have been adopted to design an artificial light-harvesting system in which light energy is captured by peripheral chromophores and it is subsequently transferred to the core via energy transfer. A composite of carbon dots and dye-encapsulated BSA-protein-capped gold nanoclusters (AuNCs) has been developed for efficient light harvesting and white light generation. Carbon dots (C-dots) act as donor and AuNCs capped with BSA protein act as acceptor. Analysis reveals that energy transfer increases from 63 % to 83 % in presence of coumarin dye (C153), which enhances the cascade energy transfer from carbon dots to AuNCs. Bright white light emission with a quantum yield of 19 % under the 375 nm excitation wavelength is achieved by changing the ratio of components. Interesting findings reveal that the efficient energy transfer in carbon-dot-metal-cluster nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications. PMID:27383453

  12. Cascade exciton-pumping engines with manipulated speed and efficiency in light-harvesting porous π-network films.

    PubMed

    Gu, Cheng; Huang, Ning; Xu, Fei; Gao, Jia; Jiang, Donglin

    2015-03-09

    Light-harvesting antennae are the machinery for exciton pumping in natural photosynthesis, whereas cascade energy transfer through chlorophyll is key to long-distance, efficient energy transduction. Numerous artificial antennae have been developed. However, they are limited in their cascade energy-transfer abilities because of a lack of control over complex chromophore aggregation processes, which has impeded their advancement. Here we report a viable approach for addressing this issue by using a light-harvesting porous polymer film in which a three-dimensional π-network serves as the antenna and micropores segregate multiple dyes to prevent aggregation. Cascade energy-transfer engines are integrated into the films; the rate and efficiency of the energy-funneling engines are precisely manipulated by tailoring the dye components and contents. The nanofilms allow accurate and versatile luminescence engineering, resulting in the production of thirty emission hues, including blue, green, red and white. This advance may open new pathways for realising photosynthesis and photoenergy conversion.

  13. Cascade exciton-pumping engines with manipulated speed and efficiency in light-harvesting porous π-network films

    NASA Astrophysics Data System (ADS)

    Gu, Cheng; Huang, Ning; Xu, Fei; Gao, Jia; Jiang, Donglin

    2015-03-01

    Light-harvesting antennae are the machinery for exciton pumping in natural photosynthesis, whereas cascade energy transfer through chlorophyll is key to long-distance, efficient energy transduction. Numerous artificial antennae have been developed. However, they are limited in their cascade energy-transfer abilities because of a lack of control over complex chromophore aggregation processes, which has impeded their advancement. Here we report a viable approach for addressing this issue by using a light-harvesting porous polymer film in which a three-dimensional π-network serves as the antenna and micropores segregate multiple dyes to prevent aggregation. Cascade energy-transfer engines are integrated into the films; the rate and efficiency of the energy-funneling engines are precisely manipulated by tailoring the dye components and contents. The nanofilms allow accurate and versatile luminescence engineering, resulting in the production of thirty emission hues, including blue, green, red and white. This advance may open new pathways for realising photosynthesis and photoenergy conversion.

  14. Fabrication of bioinspired nanostructured materials via colloidal self-assembly

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Han

    ultimate strains than nacre and pure GO paper (also synthesized by filtration). Specifically, it exhibits ˜30 times higher fracture energy than filtrated graphene paper and nacre, ˜100 times tougher than filtrated GO paper. Besides reinforced nanocomposites, we further explored the self-assembly of spherical colloids and the templating nanofabrication of moth-eye-inspired broadband antireflection coatings. Binary crystalline structures can be easily accomplished by spin-coating double-layer nonclose-packed colloidal crystals as templates, followed by colloidal templating. The polymer matrix between self-assembled colloidal crystal has been used as a sacrificial template to define the resulting periodic binary nanostructures, including intercalated arrays of silica spheres and polymer posts, gold nanohole arrays with binary sizes, and dimple-nipple antireflection coatings. The binary-structured antireflection coatings exhibit better antireflective properties than unitary coatings. Natural optical structures and nanocomposites teach us a great deal on how to create high performance artificial materials. The bottom-up technologies developed in this thesis are scalable and compatible with standard industrial processes, promising for manufacturing high-performance materials for the benefits of human beings.

  15. Ion current behaviors of mesoporous zeolite-polymer composite nanochannels prepared by water-assisted self-assembly.

    PubMed

    Zhang, Wenjuan; Meng, Zheyi; Zhai, Jin; Heng, Liping

    2014-04-01

    Inspired by the asymmetry of biological ion channels in structure and composition, we designed a novel type of artificial asymmetric nanochannels based on mesoporous zeolite (MCM-41) and polyimide (PI) by water-assisted self-assembly. Meanwhile, we studied ionic current behaviors and rectifying characteristics of the mesoporous zeolite-polymer composite nanochannels. PMID:24394328

  16. Controlling water evaporation through self-assembly.

    PubMed

    Roger, Kevin; Liebi, Marianne; Heimdal, Jimmy; Pham, Quoc Dat; Sparr, Emma

    2016-09-13

    Water evaporation concerns all land-living organisms, as ambient air is dryer than their corresponding equilibrium humidity. Contrarily to plants, mammals are covered with a skin that not only hinders evaporation but also maintains its rate at a nearly constant value, independently of air humidity. Here, we show that simple amphiphiles/water systems reproduce this behavior, which suggests a common underlying mechanism originating from responding self-assembly structures. The composition and structure gradients arising from the evaporation process were characterized using optical microscopy, infrared microscopy, and small-angle X-ray scattering. We observed a thin and dry outer phase that responds to changes in air humidity by increasing its thickness as the air becomes dryer, which decreases its permeability to water, thus counterbalancing the increase in the evaporation driving force. This thin and dry outer phase therefore shields the systems from humidity variations. Such a feedback loop achieves a homeostatic regulation of water evaporation. PMID:27573848

  17. Pseudotannins self-assembled into antioxidant complexes.

    PubMed

    Cheng, H A; Drinnan, C T; Pleshko, N; Fisher, O Z

    2015-10-21

    Natural tannins are attractive as building blocks for biomaterials due to their antioxidant properties and ability to form interpolymer complexes (IPCs) with other macromolecules. One of the major challenges to tannin usage in biomedical applications is their instability at physiological conditions and a lack of control over the purity and reactivity. Herein, we report the synthesis and characterization of tannin-like polymers with controlled architecture, reactivity, and size. These pseudotannins were synthesized by substituting linear dextran chains with gallic, resorcylic, and protocatechuic pendant groups to mimic the structure of natural hydrolysable tannins. We demonstrate that these novel materials can self-assemble to form reductive and colloidally stable nanoscale and microscale particles. Specifically, the synthesis, turbidity, particle size, antioxidant power, and cell uptake of IPCs derived from pseudotannins and poly(ethylene glycol) was evaluated. PMID:26313262

  18. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1996-10-01

    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.

  19. Self-assembling multimeric nucleic acid constructs

    DOEpatents

    Cantor, Charles R.; Niemeyer, Christof M.; Smith, Cassandra L.; Sano, Takeshi; Hnatowich, Donald J.; Rusckowski, Mary

    1996-01-01

    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.

  20. Self-assembling multimeric nucleic acid constructs

    DOEpatents

    Cantor, Charles R.; Niemeyer, Christof M.; Smith, Cassandra L.; Sano, Takeshi; Hnatowich, Donald J.; Rusckowski, Mary

    1999-10-12

    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.

  1. Molecular Dynamics in Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Bochinski, Jason; Stevens, Derrick; Scott, Mary; Guy, Laura; Dedeugd, Casey; Clarke, Laura

    2007-03-01

    Silane self-assembled monolayers (SAMs) are an important tool for both scientific research and technological applications. Despite their widespread use, few experimental investigations have addressed molecular motion within these films, which offer a unique and useful physical system for fundamental scientific studies, such as observing dipolar and other glass transitions in two-dimensions. In addition, relaxations such as ``rotator'' phases where molecular groups rotate in a plane parallel to the surface have been correlated with film conductivity, adhesive, and wetting properties. We utilize surface-sensitive, dielectric relaxation spectroscopy to probe molecular motion as a function of temperature within silane chemistry-based monolayers formed upon interdigitated electrodes. Our latest results exploring a previously published motion as well as comparisons to linear polymer films will be discussed.

  2. Self Assembly and Elasticity of Nuclear Pasta

    NASA Astrophysics Data System (ADS)

    Caplan, Matthew; Horowitz, Chuck; Berry, Don; da Silva Schneider, Andre

    2015-10-01

    While the outer crust of a neutron star is likely a solid ion lattice, the core consists of uniform nuclear matter at or above saturation density. In between, nuclei adopt exotic non-spherical geometries called ``nuclear pasta'' in order to minimize the nuclear attraction and Coulomb repulsion between protons. These structures have been well studied with both classical and quantum molecular dynamics, and their geometry can be predicted from the density, temperature, and proton fraction. Recent classical molecular dynamics simulations find evidence for a phase transition at T ~ 0 . 5 MeV, where simulations with low proton fractions undergo a solid-liquid phase transition, while simulations with high proton fractions under a glass-rubber phase transition. This is expected to have nontrivial consequences for the elastic properties of the pasta. Additionally, recent observations indicate that the structure of nuclear pasta may be related to structures observed in biophysics, specifically self assembling lipid membranes.

  3. Self-Assembled Magnetic Surface Swimmers

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

    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.

  4. Self-assembled magnetic surface swimmers.

    SciTech Connect

    Snezhko, A.; Belkin, M.; Aranson, I. S.; Kwok, W.-K.; Materials Science Division; Illinois Inst. of Tech.

    2009-03-20

    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.

  5. Smart self-assembled hybrid hydrogel biomaterials.

    PubMed

    Kopeček, Jindřich; Yang, Jiyuan

    2012-07-23

    Hybrid biomaterials are systems created from components of at least two distinct classes of molecules, for example, synthetic macromolecules and proteins or peptide domains. The synergistic combination of two types of structures may produce new materials that possess unprecedented levels of structural organization and novel properties. This Review focuses on biorecognition-driven self-assembly of hybrid macromolecules into functional hydrogel biomaterials. First, basic rules that govern the secondary structure of peptides are discussed, and then approaches to the specific design of hybrid systems with tailor-made properties are evaluated, followed by a discussion on the similarity of design principles of biomaterials and macromolecular therapeutics. Finally, the future of the field is briefly outlined.

  6. Self-assembled multilayers of nanocomponents.

    PubMed

    Krishnan, R S; Mackay, Michael E; Duxbury, Phillip M; Pastor, Alicia; Hawker, Craig J; Van Horn, Brooke; Asokan, Subashini; Wong, Michael S

    2007-02-01

    We show it is possible to assemble nanoparticle-polymer layers in a controllable manner dictated by the difference in nano-object morphology and dielectric properties. A thin (10-100 nm) layer of the two components is spin coated onto a solid substrate and the system thermally aged to activate a cross-linking process between polymer molecules. The nanoparticles segregate to the solid substrate prior to complete cross-linking if entropic forces are dominant or to the air interface if dielectric (surface energy) forces are properly tuned. Subsequent layers are then spin coated onto the layer below, and the process is repeated to create layered structures with nanometer accuracy useful for tandem solar cells, sensors, optical coatings, etc. Unlike other self-assembly techniques the layer thicknesses are dictated by the spin coating conditions and relative concentration of the two components. PMID:17261075

  7. Supramolecular self-assemblies as functional nanomaterials

    NASA Astrophysics Data System (ADS)

    Busseron, Eric; Ruff, Yves; Moulin, Emilie; Giuseppone, Nicolas

    2013-07-01

    In this review, we survey the diversity of structures and functions which are encountered in advanced self-assembled nanomaterials. We highlight their flourishing implementations in three active domains of applications: biomedical sciences, information technologies, and environmental sciences. Our main objective is to provide the reader with a concise and straightforward entry to this broad field by selecting the most recent and important research articles, supported by some more comprehensive reviews to introduce each topic. Overall, this compilation illustrates how, based on the rules of supramolecular chemistry, the bottom-up approach to design functional objects at the nanoscale is currently producing highly sophisticated materials oriented towards a growing number of applications with high societal impact.

  8. Controlling water evaporation through self-assembly.

    PubMed

    Roger, Kevin; Liebi, Marianne; Heimdal, Jimmy; Pham, Quoc Dat; Sparr, Emma

    2016-09-13

    Water evaporation concerns all land-living organisms, as ambient air is dryer than their corresponding equilibrium humidity. Contrarily to plants, mammals are covered with a skin that not only hinders evaporation but also maintains its rate at a nearly constant value, independently of air humidity. Here, we show that simple amphiphiles/water systems reproduce this behavior, which suggests a common underlying mechanism originating from responding self-assembly structures. The composition and structure gradients arising from the evaporation process were characterized using optical microscopy, infrared microscopy, and small-angle X-ray scattering. We observed a thin and dry outer phase that responds to changes in air humidity by increasing its thickness as the air becomes dryer, which decreases its permeability to water, thus counterbalancing the increase in the evaporation driving force. This thin and dry outer phase therefore shields the systems from humidity variations. Such a feedback loop achieves a homeostatic regulation of water evaporation.

  9. Self assembled structures for 3D integration

    NASA Astrophysics Data System (ADS)

    Rao, Madhav

    Three dimensional (3D) micro-scale structures attached to a silicon substrate have various applications in microelectronics. However, formation of 3D structures using conventional micro-fabrication techniques are not efficient and require precise control of processing parameters. Self assembly is a method for creating 3D structures that takes advantage of surface area minimization phenomena. Solder based self assembly (SBSA), the subject of this dissertation, uses solder as a facilitator in the formation of 3D structures from 2D patterns. Etching a sacrificial layer underneath a portion of the 2D pattern allows the solder reflow step to pull those areas out of the substrate plane resulting in a folded 3D structure. Initial studies using the SBSA method demonstrated low yields in the formation of five different polyhedra. The failures in folding were primarily attributed to nonuniform solder deposition on the underlying metal pads. The dip soldering method was analyzed and subsequently refined. A modified dip soldering process provided improved yield among the polyhedra. Solder bridging referred as joining of solder deposited on different metal patterns in an entity influenced the folding mechanism. In general, design parameters such as small gap-spacings and thick metal pads were found to favor solder bridging for all patterns studied. Two types of soldering: face and edge soldering were analyzed. Face soldering refers to the application of solder on the entire metal face. Edge soldering indicates application of solder only on the edges of the metal face. Mechanical grinding showed that face soldered SBSA structures were void free and robust in nature. In addition, the face soldered 3D structures provide a consistent heat resistant solder standoff height that serve as attachments in the integration of dissimilar electronic technologies. Face soldered 3D structures were developed on the underlying conducting channel to determine the thermo-electric reliability of

  10. Self assembly properties of primitive organic compounds

    NASA Technical Reports Server (NTRS)

    Deamer, D. W.

    1991-01-01

    A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic

  11. Enhancing light-harvesting power with coherent vibrational interactions: A quantum heat engine picture

    SciTech Connect

    Killoran, N.; Huelga, S. F.; Plenio, M. B.

    2015-10-21

    Recent evidence suggests that quantum effects may have functional importance in biological light-harvesting systems. Along with delocalized electronic excitations, it is now suspected that quantum coherent interactions with certain near-resonant vibrations may contribute to light-harvesting performance. However, the actual quantum advantage offered by such coherent vibrational interactions has not yet been established. We investigate a quantum design principle, whereby coherent exchange of single energy quanta between electronic and vibrational degrees of freedom can enhance a light-harvesting system’s power above what is possible by thermal mechanisms alone. We present a prototype quantum heat engine which cleanly illustrates this quantum design principle and quantifies its quantum advantage using thermodynamic measures of performance. We also demonstrate the principle’s relevance in parameter regimes connected to natural light-harvesting structures.

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

    SciTech Connect

    Patra, Astam K.; Dutta, Arghya; Bhaumik, Asim

    2014-07-01

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

  13. Tetrastyryl-BODIPY-based dendritic light harvester and estimation of energy transfer efficiency.

    PubMed

    Kostereli, Ziya; Ozdemir, Tugba; Buyukcakir, Onur; Akkaya, Engin U

    2012-07-20

    Versatile BODIPY dyes can be transformed into bright near-IR-emitting fluorophores by quadruple styryl substitutions. When clickable functionalities on the styryl moieties are inserted, an efficient synthesis of a light harvester is possible. In addition, clear spectral evidence is presented showing that, in dendritic light harvesters, calculations commonly based on quantum yield or emission lifetime changes of the donor are bound to yield large overestimations of energy transfer efficiency.

  14. Self-Assembly of Micromachining Systems Powered by Janus Micromotors.

    PubMed

    Maggi, Claudio; Simmchen, Juliane; Saglimbeni, Filippo; Katuri, Jaideep; Dipalo, Michele; De Angelis, Francesco; Sanchez, Samuel; Di Leonardo, Roberto

    2016-01-27

    Janus particles can self-assemble around microfabricated gears in reproducible configurations with a high degree of spatial and orientational order. The final configuration maximizes the torque applied on the rotor leading to a unidirectional and steady rotating motion. The interplay between geometry and dynamical behavior leads to the self-assembly of Janus micromotors starting from randomly distributed particles. PMID:26649462

  15. Molecular adaptation of photoprotection: triplet states in light-harvesting proteins.

    PubMed

    Gall, Andrew; Berera, Rudi; Alexandre, Maxime T A; Pascal, Andrew A; Bordes, Luc; Mendes-Pinto, Maria M; Andrianambinintsoa, Sandra; Stoitchkova, Katerina V; Marin, Alessandro; Valkunas, Leonas; Horton, Peter; Kennis, John T M; van Grondelle, Rienk; Ruban, Alexander; Robert, Bruno

    2011-08-17

    The photosynthetic light-harvesting systems of purple bacteria and plants both utilize specific carotenoids as quenchers of the harmful (bacterio)chlorophyll triplet states via triplet-triplet energy transfer. Here, we explore how the binding of carotenoids to the different types of light-harvesting proteins found in plants and purple bacteria provides adaptation in this vital photoprotective function. We show that the creation of the carotenoid triplet states in the light-harvesting complexes may occur without detectable conformational changes, in contrast to that found for carotenoids in solution. However, in plant light-harvesting complexes, the triplet wavefunction is shared between the carotenoids and their adjacent chlorophylls. This is not observed for the antenna proteins of purple bacteria, where the triplet is virtually fully located on the carotenoid molecule. These results explain the faster triplet-triplet transfer times in plant light-harvesting complexes. We show that this molecular mechanism, which spreads the location of the triplet wavefunction through the pigments of plant light-harvesting complexes, results in the absence of any detectable chlorophyll triplet in these complexes upon excitation, and we propose that it emerged as a photoprotective adaptation during the evolution of oxygenic photosynthesis.

  16. Anisotropic Packing of DNA-Mediated Colloidal Self-Assembly

    NASA Astrophysics Data System (ADS)

    Vo, Thi; Lu, Fang; Zhang, Yugang; Gang, Oleg; Kumar, Sanat

    The self-assembly of DNA-grafted nanoparticles has garnered considerable interest in recent years. However, many efforts focused on the usage of spherical nanoparticles, which limits us to the formation of only a handful of crystal lattices. Recent advances in the synthesis of non-spherical particles have directed attention towards the usage of these anisotropic particles for self-assembly. Here we combine experiments and theory on a series of DNA-grafted nanocubes. Our studies indicate that anisotropy not only directs where DNA linkers graft onto the particle but also affects how they pack and orient within a lattice, giving rise to both a preferential attachment effect and orientation-directed self-assembly. These results emphasize anisotropic self-assembly as a powerful new tool that allows for precise and directed control of nanoparticle self-assembly.

  17. Self-Assembly of Optical Molecules with Supramolecular Concepts

    PubMed Central

    Okamoto, Ken; Chithra, Parayalil; Richards, Gary J.; Hill, Jonathan P.; Ariga, Katsuhiko

    2009-01-01

    Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces. PMID:19564931

  18. Trifluoromethylated Nucleic Acid Analogues Capable of Self-Assembly through Hydrophobic Interactions

    PubMed Central

    Wang, RuoWen; Wang, Chunming; Cao, Yang; Zhu, Zhi; Yang, Chaoyong; Chen, Jianzhong

    2014-01-01

    An artificial nucleic acid analogue capable of self-assembly into duplex merely through hydrophobic interactions is presented. The replacement of Watson-Crick hydrogen bonding with strictly hydrophobic interactions has the potential to confer new properties and facilitate the construction of complex DNA nanodevices. To study how the hydrophobic effect works during the self-assembly of nucleic acid bases, we have designed and synthesized a series of fluorinated nucleic acids (FNA) containing 3,5-bis(trifluoromethyl) benzene (F) and nucleic acids incorporating 3,5-dimethylbenzene (M) as hydrophobic base surrogates. Our experiments illustrate that two single-stranded nucleic acid oligomers could spontaneously organize into a duplex entirely by hydrophobic base pairing if the bases were size-complementary and the intermolecular forces were sufficiently strong. PMID:25285193

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  20. Trifluoromethylated Nucleic Acid Analogues Capable of Self-Assembly through Hydrophobic Interactions.

    PubMed

    Wang, RuoWen; Wang, Chunming; Cao, Yang; Zhu, Zhi; Yang, Chaoyong; Chen, Jianzhong; Qing, Feng-Ling; Tan, Weihong

    2014-10-01

    An artificial nucleic acid analogue capable of self-assembly into duplex merely through hydrophobic interactions is presented. The replacement of Watson-Crick hydrogen bonding with strictly hydrophobic interactions has the potential to confer new properties and facilitate the construction of complex DNA nanodevices. To study how the hydrophobic effect works during the self-assembly of nucleic acid bases, we have designed and synthesized a series of fluorinated nucleic acids (FNA) containing 3,5-bis(trifluoromethyl) benzene (F) and nucleic acids incorporating 3,5-dimethylbenzene (M) as hydrophobic base surrogates. Our experiments illustrate that two single-stranded nucleic acid oligomers could spontaneously organize into a duplex entirely by hydrophobic base pairing if the bases were size-complementary and the intermolecular forces were sufficiently strong. PMID:25285193

  1. Robotics. Programmable self-assembly in a thousand-robot swarm.

    PubMed

    Rubenstein, Michael; Cornejo, Alejandro; Nagpal, Radhika

    2014-08-15

    Self-assembly enables nature to build complex forms, from multicellular organisms to complex animal structures such as flocks of birds, through the interaction of vast numbers of limited and unreliable individuals. Creating this ability in engineered systems poses challenges in the design of both algorithms and physical systems that can operate at such scales. We report a system that demonstrates programmable self-assembly of complex two-dimensional shapes with a thousand-robot swarm. This was enabled by creating autonomous robots designed to operate in large groups and to cooperate through local interactions and by developing a collective algorithm for shape formation that is highly robust to the variability and error characteristic of large-scale decentralized systems. This work advances the aim of creating artificial swarms with the capabilities of natural ones. PMID:25124435

  2. Synthesis of 1D Silica Nanostructures with Controllable Sizes Based on Short Anionic Peptide Self-Assembly.

    PubMed

    Wang, Shengjie; Cai, Qingwei; Du, Mingxuan; Xue, Junyi; Xu, Hai

    2015-09-10

    Artificial synthesis of silica under benign conditions is usually achieved by using cationic organic matrices as templates while the anionic analogues have not received enough consideration, albeit they are also functioning in biosilica formation. In this work, we report the design and self-assembly of an anionic peptide amphiphile (I3E) and the use of its self-assemblies as templates to synthesize 1D silica nanostructures with tunable sizes. We show that short I3E readily formed long nanofibrils in aqueous solution via a hierarchical self-assembly process. By using APTES and TEOS as silica precursors, we found that the I3E nanofibrils templated the production of silica nanotubes with a wide size distribution, in which the silica size regulation was achieved by tuning the interactions among the peptide template and silicon species. These results clearly illustrate a facile method for generating silica nanomaterials based on anionic matrices.

  3. Solvent mediated self-assembly of solids

    SciTech Connect

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

    1997-12-12

    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

  4. RNA self-assembly and RNA nanotechnology.

    PubMed

    Grabow, Wade W; Jaeger, Luc

    2014-06-17

    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

  5. β-Carotene to bacteriochlorophyll c energy transfer in self-assembled aggregates mimicking chlorosomes

    NASA Astrophysics Data System (ADS)

    Alster, J.; Polívka, T.; Arellano, J. B.; Chábera, P.; Vácha, F.; Pšenčík, J.

    2010-07-01

    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 β-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 β-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 β-carotene.

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

    NASA Astrophysics Data System (ADS)

    Patra, Astam K.; Dutta, Arghya; Bhaumik, Asim

    2014-07-01

    We demonstrate a facile chemical approach to produce self-assembled ultra-small mesoporous zinc oxide nanocrystals using sodium salicylate (SS) as a template under hydrothermal conditions. These ZnO nanomaterials have been successfully fabricated as a photoanode for the dye-sensitized solar cell (DSSC) in the presence of N719 dye and iodine-triiodide electrolyte. The structural features, crystallinity, purity, mesophase and morphology of the nanostructure ZnO are investigated by several characterization tools. N2 sorption analysis revealed high surface areas (203 m2 g-1) and narrow pore size distributions (5.1-5.4 nm) for different samples. The mesoporous structure and strong photoluminescence facilitates the high dye loading at the mesoscopic void spaces and light harvesting in DSSC. By utilizing this ultra-small ZnO photoelectrode with film thickness of about 7 μm in the DSSC with an open-circuit voltage (VOC) of 0.74 V, short-circuit current density (JSC) of 3.83 mA cm-2 and an overall power conversion efficiency of 1.12% has been achieved.

  7. Strongly Coupled Plasmonic Modes on Macroscopic Areas via Template-Assisted Colloidal Self-Assembly

    PubMed Central

    2014-01-01

    We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an interparticle spacing of 1–2 nm. We find evidence for well-defined plasmonic modes of quasi-infinite chains, such as resonance splitting and multiple radiant modes. Beyond elementary simulations on the individual chain level, we introduce an advanced model, which considers the chain length distribution as well as disorder. The step toward macroscopic sample areas not only opens perspectives for a range of applications in sensing, plasmonic light harvesting, surface enhanced spectroscopy, and information technology but also eases the investigation of hybridization and metamaterial effects fundamentally. PMID:25347293

  8. Nanoscale elongating control of the self-assembled protein filament with the cysteine-introduced building blocks

    PubMed Central

    Usui, Kengo; Maki, Tei; Ito, Fuyu; Suenaga, Atsushi; Kidoaki, Satoru; Itoh, Masayoshi; Taiji, Makoto; Matsuda, Takehisa; Hayashizaki, Yoshihide; Suzuki, Harukazu

    2009-01-01

    Self-assembly of artificially designed proteins is extremely desirable for nanomaterials. Here we show a novel strategy for the creation of self-assembling proteins, named “Nanolego.” Nanolego consists of “structural elements” of a structurally stable symmetrical homo-oligomeric protein and “binding elements,” which are multiple heterointeraction proteins with relatively weak affinity. We have established two key technologies for Nanolego, a stabilization method and a method for terminating the self-assembly process. The stabilization method is mediated by disulfide bonds between Cysteine-residues incorporated into the binding elements, and the termination method uses “capping Nanolegos,” in which some of the binding elements in the Nanolego are absent for the self-assembled ends. With these technologies, we successfully constructed timing-controlled and size-regulated filament-shape complexes via Nanolego self-assembly. The Nanolego concept and these technologies should pave the way for regulated nanoarchitecture using designed proteins. PMID:19384998

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

    NASA Astrophysics Data System (ADS)

    Yaghoubi, Houman

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

  10. Self-Assembly of Tetraphenylalanine Peptides.

    PubMed

    Mayans, Enric; Ballano, Gema; Casanovas, Jordi; Díaz, Angélica; Pérez-Madrigal, Maria M; Estrany, Francesc; Puiggalí, Jordi; Cativiela, Carlos; Alemán, Carlos

    2015-11-16

    Three different tetraphenylalanine (FFFF) based peptides that differ at the N- and C-termini have been synthesized by using standard procedures to study their ability to form different nanoassemblies under a variety of conditions. The FFFF peptide assembles into nanotubes that show more structural imperfections at the surface than those formed by the diphenylalanine (FF) peptide under the same conditions. Periodic DFT calculations (M06L functional) were used to propose a model that consists of three FFFF molecules defining a ring through head-to-tail NH3(+)⋅⋅⋅(-)OOC interactions, which in turn stack to produce deformed channels with internal diameters between 12 and 16 Å. Depending on the experimental conditions used for the peptide incubation, N-fluorenylmethoxycarbonyl (Fmoc) protected FFFF self-assembles into a variety of polymorphs: ultra-thin nanoplates, fibrils, and star-like submicrometric aggregates. DFT calculations indicate that Fmoc-FFFF prefers a parallel rather than an antiparallel β-sheet assembly. Finally, coexisting multiple assemblies (up to three) were observed for Fmoc-FFFF-OBzl (OBzl = benzyl ester), which incorporates aromatic protecting groups at the two peptide terminals. This unusual and noticeable feature is attributed to the fact that the assemblies obtained by combining the Fmoc and OBzl groups contained in the peptide are isoenergetic.

  11. Self-assembly of smallest magnetic particles

    PubMed Central

    Mehdizadeh Taheri, Sara; Michaelis, Maria; Friedrich, Thomas; Förster, Beate; Drechsler, Markus; Römer, Florian M.; Bösecke, Peter; Narayanan, Theyencheri; Weber, Birgit; Rehberg, Ingo; Rosenfeldt, Sabine; Förster, Stephan

    2015-01-01

    The assembly of tiny magnetic particles in external magnetic fields is important for many applications ranging from data storage to medical technologies. The development of ever smaller magnetic structures is restricted by a size limit, where the particles are just barely magnetic. For such particles we report the discovery of a kind of solution assembly hitherto unobserved, to our knowledge. The fact that the assembly occurs in solution is very relevant for applications, where magnetic nanoparticles are either solution-processed or are used in liquid biological environments. Induced by an external magnetic field, nanocubes spontaneously assemble into 1D chains, 2D monolayer sheets, and large 3D cuboids with almost perfect internal ordering. The self-assembly of the nanocubes can be elucidated considering the dipole–dipole interaction of small superparamagnetic particles. Complex 3D geometrical arrangements of the nanodipoles are obtained under the assumption that the orientation of magnetization is freely adjustable within the superlattice and tends to minimize the binding energy. On that basis the magnetic moment of the cuboids can be explained. PMID:26554000

  12. Dissipative adaptation in driven self-assembly

    NASA Astrophysics Data System (ADS)

    England, Jeremy L.

    2015-11-01

    In a collection of assembling particles that is allowed to reach thermal equilibrium, the energy of a given microscopic arrangement and the probability of observing the system in that arrangement obey a simple exponential relationship known as the Boltzmann distribution. Once the same thermally fluctuating particles are driven away from equilibrium by forces that do work on the system over time, however, it becomes significantly more challenging to relate the likelihood of a given outcome to familiar thermodynamic quantities. Nonetheless, it has long been appreciated that developing a sound and general understanding of the thermodynamics of such non-equilibrium scenarios could ultimately enable us to control and imitate the marvellous successes that living things achieve in driven self-assembly. Here, I suggest that such a theoretical understanding may at last be emerging, and trace its development from historic first steps to more recent discoveries. Focusing on these newer results, I propose that they imply a general thermodynamic mechanism for self-organization via dissipation of absorbed work that may be applicable in a broad class of driven many-body systems.

  13. Polymer blends for directed self-assembly

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    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 χN. In the case of polymer blend, χN 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 χN. Furthermore, the correlation of shrink amount and χN was studied. Higher χN polymer blend system gave higher shrink amount. High χN 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).

  14. Surfactant mediated polyelectrolyte self-assembly

    DOE PAGESBeta

    Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; Sumpter, Bobby G.

    2015-11-25

    Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain andmore » surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.« less

  15. What promotes derected self assembly (DSA)?

    NASA Astrophysics Data System (ADS)

    Nakagawa, S. T.

    2016-09-01

    A low-energy electron beam (EB) can create self-interstitial atoms (SIA) in a solid and can cause directed self-assembly (DSA), e.g. {3 1 1}SIA platelets in c-Si. The crystalline structure of this planar defect is known from experiment to be made up of SIAs that form well aligned <1 1 0> atomic rows on each (3 1 1) plane. To simulate the experiment we distributed Frenkel pairs (FP) randomly in bulk c-Si. Then making use of a molecular dynamic (MD) simulation, we have reproduced the experimental result, where SIAs are trapped at metastable sites in bulk. With increasing pre-doped FP concentration, the number of SIAs that participate in DSA tends to be increased but soon slightly supressed. On the other hand, when the FP concentration is less than 3%, a cooperative motion of target atoms was characterized from the long-range-order (LRO) parameter. Here we investigated the correlation between DSA and that cooperative motion, by adding a case of intrinsic c-Si. We confirmed that the cooperative motion slightly promote DSA by assisting migration of SIAs toward metastable sites as long as the FP concentration is less than 3%, however, it is essentially independent of DSA.

  16. Surfactant mediated polyelectrolyte self-assembly

    SciTech Connect

    Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; Sumpter, Bobby G.

    2015-11-25

    Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain and surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.

  17. Self-assembly programming of DNA polyominoes.

    PubMed

    Ong, Hui San; Syafiq-Rahim, Mohd; Kasim, Noor Hayaty Abu; Firdaus-Raih, Mohd; Ramlan, Effirul Ikhwan

    2016-10-20

    Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously. PMID:27569553

  18. Initial condition of stochastic self-assembly.

    PubMed

    Davis, Jason K; Sindi, Suzanne S

    2016-02-01

    The formation of a stable protein aggregate is regarded as the rate limiting step in the establishment of prion diseases. In these systems, once aggregates reach a critical size the growth process accelerates and thus the waiting time until the appearance of the first critically sized aggregate is a key determinant of disease onset. In addition to prion diseases, aggregation and nucleation is a central step of many physical, chemical, and biological process. Previous studies have examined the first-arrival time at a critical nucleus size during homogeneous self-assembly under the assumption that at time t=0 the system was in the all-monomer state. However, in order to compare to in vivo biological experiments where protein constituents inherited by a newly born cell likely contain intermediate aggregates, other possibilities must be considered. We consider one such possibility by conditioning the unique ergodic size distribution on subcritical aggregate sizes; this least-informed distribution is then used as an initial condition. We make the claim that this initial condition carries fewer assumptions than an all-monomer one and verify that it can yield significantly different averaged waiting times relative to the all-monomer condition under various models of assembly.

  19. Self-assembling holographic biosensors and biocomputers.

    SciTech Connect

    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

    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.

  20. Initial condition of stochastic self-assembly

    NASA Astrophysics Data System (ADS)

    Davis, Jason K.; Sindi, Suzanne S.

    2016-02-01

    The formation of a stable protein aggregate is regarded as the rate limiting step in the establishment of prion diseases. In these systems, once aggregates reach a critical size the growth process accelerates and thus the waiting time until the appearance of the first critically sized aggregate is a key determinant of disease onset. In addition to prion diseases, aggregation and nucleation is a central step of many physical, chemical, and biological process. Previous studies have examined the first-arrival time at a critical nucleus size during homogeneous self-assembly under the assumption that at time t =0 the system was in the all-monomer state. However, in order to compare to in vivo biological experiments where protein constituents inherited by a newly born cell likely contain intermediate aggregates, other possibilities must be considered. We consider one such possibility by conditioning the unique ergodic size distribution on subcritical aggregate sizes; this least-informed distribution is then used as an initial condition. We make the claim that this initial condition carries fewer assumptions than an all-monomer one and verify that it can yield significantly different averaged waiting times relative to the all-monomer condition under various models of assembly.

  1. Self-assembly programming of DNA polyominoes.

    PubMed

    Ong, Hui San; Syafiq-Rahim, Mohd; Kasim, Noor Hayaty Abu; Firdaus-Raih, Mohd; Ramlan, Effirul Ikhwan

    2016-10-20

    Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously.

  2. Self-assembly of smallest magnetic particles.

    PubMed

    Mehdizadeh Taheri, Sara; Michaelis, Maria; Friedrich, Thomas; Förster, Beate; Drechsler, Markus; Römer, Florian M; Bösecke, Peter; Narayanan, Theyencheri; Weber, Birgit; Rehberg, Ingo; Rosenfeldt, Sabine; Förster, Stephan

    2015-11-24

    The assembly of tiny magnetic particles in external magnetic fields is important for many applications ranging from data storage to medical technologies. The development of ever smaller magnetic structures is restricted by a size limit, where the particles are just barely magnetic. For such particles we report the discovery of a kind of solution assembly hitherto unobserved, to our knowledge. The fact that the assembly occurs in solution is very relevant for applications, where magnetic nanoparticles are either solution-processed or are used in liquid biological environments. Induced by an external magnetic field, nanocubes spontaneously assemble into 1D chains, 2D monolayer sheets, and large 3D cuboids with almost perfect internal ordering. The self-assembly of the nanocubes can be elucidated considering the dipole-dipole interaction of small superparamagnetic particles. Complex 3D geometrical arrangements of the nanodipoles are obtained under the assumption that the orientation of magnetization is freely adjustable within the superlattice and tends to minimize the binding energy. On that basis the magnetic moment of the cuboids can be explained.

  3. Stochastic self-assembly of incommensurate clusters

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    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.

  4. Self-assembly and interactions of biomimetic thin films

    NASA Astrophysics Data System (ADS)

    Handa, Hitesh

    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

  5. Enzyme-assisted self-assembly under thermodynamic control

    NASA Astrophysics Data System (ADS)

    Williams, Richard J.; Smith, Andrew M.; Collins, Richard; Hodson, Nigel; Das, Apurba K.; Ulijn, Rein V.

    2009-01-01

    The production of functional molecular architectures through self-assembly is commonplace in biology, but despite advances, it is still a major challenge to achieve similar complexity in the laboratory. Self-assembled structures that are reproducible and virtually defect free are of interest for applications in three-dimensional cell culture, templating, biosensing and supramolecular electronics. Here, we report the use of reversible enzyme-catalysed reactions to drive self-assembly. In this approach, the self-assembly of aromatic short peptide derivatives provides a driving force that enables a protease enzyme to produce building blocks in a reversible and spatially confined manner. We demonstrate that this system combines three features: (i) self-correction-fully reversible self-assembly under thermodynamic control; (ii) component-selection-the ability to amplify the most stable molecular self-assembly structures in dynamic combinatorial libraries; and (iii) spatiotemporal confinement of nucleation and structure growth. Enzyme-assisted self-assembly therefore provides control in bottom-up fabrication of nanomaterials that could ultimately lead to functional nanostructures with enhanced complexities and fewer defects.

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

    SciTech Connect

    Cardoso, Mateus B; Smolensky, Dmitriy; Heller, William T; O'Neill, Hugh Michael

    2009-01-01

    The structure of spinach light-harvesting complex II (LHC II), stabilized in a solution of the detergent n-octyl-{beta}-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 different H{sub 2}O/D{sub 2}O contrast match points, enabling the scattering properties of the protein and detergent to be investigated independently. The topological shape of LHC II, determined using ab initio shape restoration methods from the SANS data at the contrast match point of BOG, was consistent with the X-ray crystallographic structure of LHC II (Liu et al. Nature 2004 428, 287-292). The interactions of the protein and detergent were investigated at the contrast match point for the protein and also in 100% D{sub 2}O. The data suggested that BOG micelle structure was altered by its interaction with LHC II, but large aggregate structures were not formed. Indirect Fourier transform analysis of the LHC II/BOG scattering curves showed that the increase in the maximum dimension of the protein-detergent complex was consistent with the presence of a monolayer of detergent surrounding the protein. A model of the LHC II/BOG complex was generated to interpret the measurements made in 100% D{sub 2}O. This model adequately reproduced the overall size of the LHC II/BOG complex, but demonstrated that the detergent does not have a highly regular shape that surrounds the hydrophobic periphery of LHC II. In addition to demonstrating that natively structured LHC II can be produced for functional characterization and for use in artificial solar energy applications, the analysis and modeling approaches described here can be used for characterizing detergent-associated {alpha}-helical transmembrane proteins.

  7. Colloidosome like structures: self-assembly of silica microrods

    DOE PAGESBeta

    Datskos, P.; Polizos, G.; Bhandari, M.; Cullen, D. A.; Sharma, J.

    2016-03-07

    Self-assembly of one-dimensional structures is attracting a great deal of interest because assembled structures can provide better properties compared to individual building blocks. We demonstrate silica microrod self-assembly by exploiting Pickering emulsion based strategy. Micron-sized silica rods were synthesized employing previously reported methods based on polyvinylpyrrolidone/ pentanol emulsion droplets. Moreover, rods self-assembled to make structures in the range of z10 40 mm. Smooth rods assembled better than segmented rods. Finally, the assembled structures were bonded by weak van der Waals forces.

  8. Bio-inspired supramolecular self-assembly towards soft nanomaterials

    PubMed Central

    LIN, Yiyang; MAO, Chuanbin

    2011-01-01

    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

  9. Magnetic manipulation of self-assembled colloidal asters

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor S.

    2011-09-01

    Self-assembled materials must actively consume energy and remain out of equilibrium to support structural complexity and functional diversity. Here we show that a magnetic colloidal suspension confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters, which exhibit locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, we show that asters can capture, transport, and position target microparticles. The ability to manipulate colloidal structures is crucial for the further development of self-assembled microrobots.

  10. Magnetic manipulation of self-assembled colloidal asters.

    SciTech Connect

    Snezhko, A.; Aranson, I. S.

    2011-09-01

    Self-assembled materials must actively consume energy and remain out of equilibrium to support structural complexity and functional diversity. Here we show that a magnetic colloidal suspension confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters, which exhibit locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, we show that asters can capture, transport, and position target microparticles. The ability to manipulate colloidal structures is crucial for the further development of self-assembled microrobots

  11. Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.

    PubMed

    Coelho, João Paulo; Tardajos, Gloria; Stepanenko, Vladimir; Rödle, Alexander; Fernández, Gustavo; Guerrero-Martínez, Andrés

    2015-11-24

    The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs. PMID:26493583

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

    PubMed Central

    Carter, Joshua D.; LaBean, Thomas H.

    2011-01-01

    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

  13. Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.

    PubMed

    Coelho, João Paulo; Tardajos, Gloria; Stepanenko, Vladimir; Rödle, Alexander; Fernández, Gustavo; Guerrero-Martínez, Andrés

    2015-11-24

    The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs.

  14. Predicting self-assembled patterns on spheres with multicomponent coatings.

    PubMed

    Edlund, Erik; Lindgren, Oskar; Jacobi, Martin Nilsson

    2014-05-01

    Patchy colloids are promising candidates for building blocks in directed self-assembly, but large scale synthesis of colloids with controlled surface patterns remains challenging. One potential fabrication method is to self-assemble the surface patterns themselves, allowing complex morphologies to organize spontaneously. For this approach to be competitive, prediction and control of the pattern formation process are necessary. However, structure formation in many-body systems is fundamentally hard to understand, and new theoretical methods are needed. Here we present a theory for self-assembling pattern formation in multi-component systems on the surfaces of colloidal particles, formulated as an analytic technique that predicts morphologies directly from the interactions in an effective model. As a demonstration we formulate an isotropic model of alkanethiols on gold, a suggested system for directed self-assembly, and predict its morphologies and transitions as a function of the interaction parameters.

  15. Directed flexibility: self-assembly of a supramolecular tetrahedron.

    PubMed

    Ludlow, James M; Xie, Tingzheng; Guo, Zaihong; Guo, Kai; Saunders, Mary Jane; Moorefield, Charles N; Wesdemiotis, Chrys; Newkome, George R

    2015-03-01

    Self-assembly of a tribenzo-27-crown-9 ether functionalized with six terpyridines generated (85%) an expanded tetrahedral structure comprised of four independent triangular surfaces interlinked by crown ether vertices.

  16. Directed self-assembly of proteins into discrete radial patterns

    PubMed Central

    Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

    2013-01-01

    Unlike physical patterning of materials at nanometer scale, manipulating soft matter such as biomolecules into patterns is still in its infancy. Self-assembled monolayer (SAM) with surface density gradient has the capability to drive biomolecules in specific directions to create hierarchical and discrete structures. Here, we report on a two-step process of self-assembly of the human serum albumin (HSA) protein into discrete ring structures based on density gradient of SAM. The methodology involves first creating a 2-dimensional (2D) polyethylene glycol (PEG) islands with responsive carboxyl functionalities. Incubation of proteins on such pre-patterned surfaces results in direct self-assembly of protein molecules around PEG islands. Immobilization and adsorption of protein on such structures over time evolve into the self-assembled patterns. PMID:23719678

  17. Converting molecular information of redox coenzymes via self-assembly.

    PubMed

    Morikawa, Masa-aki; Kimizuka, Nobuo

    2012-11-21

    β-Nicotinamide adenine dinucleotide (NAD(+)) and its reduced form NADH specifically interact with a cyanine dye in aqueous media, giving distinct spectral and nanostructural characteristics to which molecular information of constituent coenzymes are converted via self-assembly.

  18. Enabling complex nanoscale pattern customization using directed self-assembly

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  19. Liquid crystal organization of self-assembling cyclic peptides.

    PubMed

    Amorín, Manuel; Pérez, Ana; Barberá, Joaquín; Ozores, Haxel Lionel; Serrano, José Luis; Granja, Juan R; Sierra, Teresa

    2014-01-21

    Self-assembling cyclic peptides decorated with mesogens form porous columnar mesophases in which, depending on the number of hydrocarbon chains, double or single channels are formed along each column. PMID:24281818

  20. Self-Assembly of Structures with Addressable Complexity.

    PubMed

    Jacobs, William M; Frenkel, Daan

    2016-03-01

    The self-assembly of structures with "addressable complexity", where every component is distinct and is programmed to occupy a specific location within a target structure, is a promising route to engineering materials with precisely defined morphologies. Because systems with many components are inherently complicated, one might assume that the chances of successful self-assembly are extraordinarily small. Yet recent advances suggest otherwise: addressable structures with hundreds of distinct building blocks have been designed and assembled with nanometer precision. Despite this remarkable success, it is often challenging to optimize a self-assembly reaction to ensure that the intended structure is kinetically accessible. In this Perspective, we focus on the prediction of kinetic pathways for self-assembly and implications for the design of robust experimental protocols. The development of general principles to predict these pathways will enable the engineering of complex materials using a much wider range of building blocks than is currently possible. PMID:26862684

  1. Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properities

    PubMed Central

    Sun, Xiang; Lai, Guoqiao; Li, Zhifang; Ma, Yuwen; Yuan, Xiao; Shen, Yongjia

    2015-01-01

    Summary This paper reports the self-assembly of two new tetrathiafulvalene (TTF) derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which showed that the self-assembly ability of T 1 was better than that of T 2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T 1 and T 2 films was tested by a four-probe method. PMID:26734083

  2. Activity-assisted self-assembly of colloidal particles.

    PubMed

    Mallory, S A; Cacciuto, A

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process.

  3. Modeling the Kinetics of Open Self-Assembly.

    PubMed

    Verdier, Timothée; Foret, Lionel; Castelnovo, Martin

    2016-07-01

    In this work, we explore theoretically the kinetics of molecular self-assembly in the presence of constant monomer flux as an input, and a maximal size. The proposed model is supposed to reproduce the dynamics of viral self-assembly for enveloped virus. It turns out that the kinetics of open self-assembly is rather quantitatively different from the kinetics of similar closed assembly. In particular, our results show that the convergence toward the stationary state is reached through assembly waves. Interestingly, we show that the production of complete clusters is much more efficient in the presence of a constant input flux, rather than providing all monomers at the beginning of the self-assembly.

  4. Activity-assisted self-assembly of colloidal particles

    NASA Astrophysics Data System (ADS)

    Mallory, S. A.; Cacciuto, A.

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process.

  5. Self-assembled peptide nanostructures for functional materials

    NASA Astrophysics Data System (ADS)

    Sardan Ekiz, Melis; Cinar, Goksu; Aref Khalily, Mohammad; Guler, Mustafa O.

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.

  6. Activity-assisted self-assembly of colloidal particles.

    PubMed

    Mallory, S A; Cacciuto, A

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process. PMID:27627360

  7. Differentially photo-crosslinked polymers enable self-assembling microfluidics

    PubMed Central

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

    2012-01-01

    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

  8. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    PubMed

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  9. Self-assembly drugs: from micelles to nanomedicine.

    PubMed

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

    2014-03-01

    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.

  10. Self-assembly drugs: from micelles to nanomedicine.

    PubMed

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

    2014-03-01

    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

  11. A hybrid photocatalytic system comprising ZnS as light harvester and an [Fe(2)S(2)] hydrogenase mimic as hydrogen evolution catalyst.

    PubMed

    Wen, Fuyu; Wang, Xiuli; Huang, Lei; Ma, Guijun; Yang, Jinhui; Li, Can

    2012-05-01

    Photo opportunity: A highly efficient and stable hybrid artificial photosynthetic H(2) evolution system is assembled by using a semiconductor (ZnS) as light-harvester and an [Fe(2)S(2)] hydrogenase mimic ([(μ-SPh-4-NH(2) )(2) Fe(2) (CO)(6)]) as catalyst for H(2) evolution. Photocatalytic H(2) production is achieved with more than 2607 turnovers (based on [Fe(2)S(2)]) and an initial turnover frequency of 100 h(-1) through the efficient transfer of photogenerated electrons from ZnS to the [Fe(2)S(2)] complex.

  12. Scaling up self-assembly: bottom-up approaches to macroscopic particle organization.

    PubMed

    Lash, M H; Fedorchak, M V; McCarthy, J J; Little, S R

    2015-07-28

    This review presents an overview of recent work in the field of non-Brownian particle self-assembly. Compared to nanoparticles that naturally self-assemble due to Brownian motion, larger, non-Brownian particles (d > 6 μm) are less prone to autonomously organize into crystalline arrays. The tendency for particle systems to experience immobilization and kinetic arrest grows with particle radius. In order to overcome this kinetic limitation, some type of external driver must be applied to act as an artificial "thermalizing force" upon non-Brownian particles, inducing particle motion and subsequent crystallization. Many groups have explored the use of various agitation methods to overcome the natural barriers preventing self-assembly to which non-Brownian particles are susceptible. The ability to create materials from a bottom-up approach with these characteristics would allow for precise control over their pore structure (size and distribution) and surface properties (topography, functionalization and area), resulting in improved regulation of key characteristics such as mechanical strength, diffusive properties, and possibly even photonic properties. This review will highlight these approaches, as well as discuss the potential impact of bottom-up macroscale particle assembly. The applications of such technology range from customizable and autonomously self-assembled niche microenvironments for drug delivery and tissue engineering to new acoustic dampening, battery, and filtration materials, among others. Additionally, crystals made from non-Brownian particles resemble naturally derived materials such as opals, zeolites, and biological tissue (i.e. bone, cartilage and lung), due to their high surface area, pore distribution, and tunable (multilevel) hierarchy. PMID:25947543

  13. Electric Field Controlled Self-Assembly of Hierarchically Ordered Membranes.

    PubMed

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

    2012-01-25

    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

  14. DNA-based self-assembly for functional nanomaterials.

    PubMed

    Wang, Zhen-Gang; Ding, Baoquan

    2013-07-26

    The unprecedented development of DNA nanotechnology has caused DNA self-assembly to attract close attention in many disciplines. In this research news article, the employment of DNA self-assembly in the fields of materials science and nanotechnology is described. DNA self-assembly can be used to prepare bulk-scale hydrogels and 3D macroscopic crystals with nanoscale internal structures, to induce the crystallization of nanoparticles, to template the fabrication of organic conductive nanomaterials, and to act as drug delivery vehicles for therapeutic agents. The properties and functions are fully tunable because of the designability and specificity of DNA assembly. Moreover, because of the intrinsic dynamics, DNA self-assembly can act as a program switch and can efficiently control stimuli responsiveness. We highlight the power of DNA self-assembly in the preparation and function regulation of materials, aiming to motivate future multidisciplinary and interdisciplinary research. Finally, we describe some of the challenges currently faced by DNA assembly that may affect the functional evolution of such materials, and we provide our insights into the future directions of several DNA self-assembly-based nanomaterials. PMID:24048977

  15. Electronic structure of covalently linked zinc bacteriochlorin molecular arrays: insights into molecular design for NIR light harvesting.

    PubMed

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

    2014-10-23

    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 β) 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 β 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.

  16. DNA-directed spatial assembly of photosynthetic light-harvesting proteins.

    PubMed

    Henry, Sarah L; Withers, Jamie M; Singh, Ishwar; Cooper, Jonathan M; Clark, Alasdair W; Burley, Glenn A; Cogdell, Richard J

    2016-01-28

    This manuscript describes the surface immobilization of a light-harvesting complex to prescribed locations directed by the sequence-selective recognition of duplex DNA. An engineered light-harvesting complex (RC-LH1) derived from Rhodopseudomonas (Rps.) palustris containing the zinc finger (ZF) domain zif268 was prepared. The zif268 domain directed the binding of zfRC-LH1 to target double-stranded DNA sequences both in solution and when immobilized on lithographically defined micro-patterns. Excitation energy transfer from the carotenoids to the bacteriochlorophyll pigments within zfRC-LH1 confirmed that the functional and structural integrity of the complex is retained after surface immobilization.

  17. Structures Self-Assembled Through Directional Solidification

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2005-01-01

    dry plasma etch. The wet chemical etches the silicon away, exposing the TiSi2 rods, whereas plasma etching preferentially etches the Si-TiSi2 interface to form a crater. The porous architectures are applicable to fabricating microdevices or creating templates for part fabrication. The porous rod structure can serve as a platform for fabricating microplasma devices for propulsion or microheat exchangers and for fabricating microfilters for miniatured chemical reactors. Although more work is required, self-assembly from DSE can have a role in microdevice fabrication.

  18. Lipid-like self-assembling peptides.

    PubMed

    Zhang, Shuguang

    2012-12-18

    One important question in prebiotic chemistry is the search for simple structures that might have enclosed biological molecules in a cell-like space. Phospholipids, the components of biological membranes, are highly complex. Instead, we looked for molecules that might have been available on prebiotic Earth. Simple peptides with hydrophobic tails and hydrophilic heads that are made up of merely a combination of these robust, abiotically synthesized amino acids and could self-assemble into nanotubes or nanovesicles fulfilled our initial requirements. These molecules could provide a primitive enclosure for the earliest enzymes based on either RNA or peptides and other molecular structures with a variety of functions. We discovered and designed a class of these simple lipid-like peptides, which we describe in this Account. These peptides consist of natural amino acids (glycine, alanine, valine, isoleucine, leucine, aspartic acid, glutamic acid, lysine, and arginine) and exhibit lipid-like dynamic behaviors. These structures further undergo spontaneous assembly to form ordered arrangements including micelles, nanovesicles, and nanotubes with visible openings. Because of their simplicity and stability in water, such assemblies could provide examples of prebiotic molecular evolution that may predate the RNA world. These short and simple peptides have the potential to self-organize to form simple enclosures that stabilize other fragile molecules, to bring low concentration molecules into a local environment, and to enhance higher local concentration. As a result, these structures plausibly could not only accelerate the dehydration process for new chemical bond formation but also facilitate further self-organization and prebiotic evolution in a dynamic manner. We also expect that this class of lipid-like peptides will likely find a wide range of uses in the real world. Because of their favorable interactions with lipids, these lipid-like peptides have been used to

  19. Self-assembly of DNA-polymer complexes using template polymerization.

    PubMed Central

    Trubetskoy, V S; Budker, V G; Hanson, L J; Slattum, P M; Wolff, J A; Hagstrom, J E

    1998-01-01

    The self-assembly of supramolecular complexes of nucleic acids and polymers is of relevance to several biological processes including viral and chromatin formation as well as gene therapy vector design. We now show that template polymerization facilitates condensation of DNA into particles that are <150 nm in diameter. Inclusion of a poly(ethylene glycol)-containing monomer prevents aggregation of these particles. The DNA within the particles remains biologically active and can express foreign genes in cells. The formation or breakage of covalent bonds has until now not been employed to compact DNA into artificial particles. PMID:9722638

  20. Self-assembly of DNA-polymer complexes using template polymerization.

    PubMed

    Trubetskoy, V S; Budker, V G; Hanson, L J; Slattum, P M; Wolff, J A; Hagstrom, J E

    1998-09-15

    The self-assembly of supramolecular complexes of nucleic acids and polymers is of relevance to several biological processes including viral and chromatin formation as well as gene therapy vector design. We now show that template polymerization facilitates condensation of DNA into particles that are <150 nm in diameter. Inclusion of a poly(ethylene glycol)-containing monomer prevents aggregation of these particles. The DNA within the particles remains biologically active and can express foreign genes in cells. The formation or breakage of covalent bonds has until now not been employed to compact DNA into artificial particles.

  1. Photoelectron transport tuning of self-assembled subbands

    NASA Astrophysics Data System (ADS)

    Xiong, Zhengwei; Wang, Xinmin; Wu, Weidong; Wang, Xuemin; Peng, Liping; Zhao, Yan; Yan, Dawei; Jiang, Tao; Shen, Changle; Zhan, Zhiqiang; Cao, Linhong; Li, Weihua

    2016-02-01

    Conventionally, electrical transport of quantum subbands occurs at very high electric fields, indicating that the medium is easy to break down. In the experiments and practical applications, the extreme condition is difficult to satisfy. For quantum information transmission, low power consumption and convenient implementation are what we expect. In this paper, we engineered a special quantum dot array (QDA) embedded in a single crystal matrix. By external optical field excitation, we found a series of subbands made of the self-assembled QDA discretely located in the matrix. Changing the spacing between the quantum dots leads to the variation of subband spacing. Artificially manipulating the microcosmic QDA system can bring interesting macroscopic effects, such as an enhanced absorption intensity in the ultraviolet range, a blue-shift of the surface plasmon resonance peak and nonlinear absorption changed from two-photon absorption to saturated absorption. The intrinsic mechanism of the subband optical response was revealed due to the strong quantum confinement effect and dominant intraband transitions. The weak surface plasmon resonance absorption of Ni QDA gave an excellent figure of merit of the order of 10-10. The composite films are expectation enough to become a prime candidate for nonlinear applications near 532 nm. Therefore with interplay of the weak optical field and subbands, we achieved a tunable photoelectron transport process.Conventionally, electrical transport of quantum subbands occurs at very high electric fields, indicating that the medium is easy to break down. In the experiments and practical applications, the extreme condition is difficult to satisfy. For quantum information transmission, low power consumption and convenient implementation are what we expect. In this paper, we engineered a special quantum dot array (QDA) embedded in a single crystal matrix. By external optical field excitation, we found a series of subbands made of the self-assembled

  2. The Self-Assembly of Nanogold for Optical Metamaterials

    NASA Astrophysics Data System (ADS)

    Nidetz, Robert A.

    2011-12-01

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

  3. Bright Fluorescence and Host-Guest Sensing with a Nanoscale M₄L₆ Tetrahedron Accessed by Self-Assembly of Zinc-Imine Chelate Vertices and Perylene Bisimide Edges.

    PubMed

    Frischmann, Peter D; Kunz, Valentin; Würthner, Frank

    2015-06-15

    A highly luminescent Zn4L6 tetrahedron is reported with 3.8 nm perylene bisimide edges and hexadentate Zn(II)-imine chelate vertices. Replacing Fe(II) and monoamines commonly utilized in subcomponent self-assembly with Zn(II) and tris(2-aminoethyl)amine provides access to a metallosupramolecular host with the rare combination of structural integrity at concentrations <10(-7) mol L(-1) and an exceptionally high fluorescence quantum yield of Φ(em) =0.67. Encapsulation of multiple perylene or coronene guest molecules is accompanied by strong luminescence quenching. We anticipate this self-assembly strategy may be generalized to improve access to brightly fluorescent coordination cages tailored for host-guest light-harvesting, photocatalysis, and sensing.

  4. Dynamic, Directed Self-Assembly of Nanoparticles via Toggled Interactions.

    PubMed

    Sherman, Zachary M; Swan, James W

    2016-05-24

    Crystals self-assembled from nanoparticles have useful properties such as optical activity and sensing capability. During fabrication, however, gelation and glassification often leave these materials arrested in defective or disordered metastable states. This is a key difficulty preventing adoption of self-assembled nanoparticle materials at scale. Processes which suppress kinetic arrest and defect formation while accelerating growth of ordered materials are essential for bottom-up approaches to creating nanomaterials. Dynamic, directed self-assembly processes in which the interactions between self-assembling components are actuated temporally offer one promising methodology for accelerating and controlling bottom-up growth of nanostructures. In this article, we show through simulation and theory how time-dependent, periodically toggled interparticle attractions can avoid kinetic barriers and yield well-ordered crystalline domains for a dispersion of nanoparticles interacting via a short-ranged, isotropic potential. The growth mechanism and terminal structure of the dispersion are controlled by parameters of the toggling protocol. This control allows for selection of processes that yield rapid self-assembled, low defect crystals. Although self-assembly via periodically toggled attractions is inherently unsteady and out-of-equilibrium, its outcome is predicted by a first-principles theory of nonequilibrium thermodynamics. The theory necessitates equality of the time average of pressure and chemical potential in coexisting phases of the dispersion. These quantities are evaluated using well known equations of state. The phase behavior predicted by this theory agrees well with measurements made in Brownian dynamics simulations of sedimentation equilibrium and homogeneous nucleation. The theory can easily be extended to model dynamic self-assembly directed by other toggled conservative force fields.

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

    PubMed

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

    2014-06-23

    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 ~20 ps. The radiative rate enhancement results in a 5.5-fold-improved fluorescence quantum efficiency. Exploiting the unique brightness, we have recorded the first photon antibunching of a single light-harvesting complex under ambient conditions, showing that the 27 bacteriochlorophylls coordinated by LH2 act as a non-classical single-photon emitter. The presented bright antenna-enhanced LH2 emission is a highly promising system to study energy transfer and the role of quantum coherence at the level of single complexes.

  6. Atomistic study of energy funneling in the light-harvesting complex of green sulfur bacteria.

    PubMed

    Huh, Joonsuk; Saikin, Semion K; Brookes, Jennifer C; Valleau, Stéphanie; Fujita, Takatoshi; Aspuru-Guzik, Alán

    2014-02-01

    Phototrophic organisms such as plants, photosynthetic bacteria, and algae use microscopic complexes of pigment molecules to absorb sunlight. Within the light-harvesting complexes, which frequently have several functional and structural subunits, the energy is transferred in the form of molecular excitations with very high efficiency. Green sulfur bacteria are considered to be among the most efficient light-harvesting organisms. Despite multiple experimental and theoretical studies of these bacteria, the physical origin of the efficient and robust energy transfer in their light-harvesting complexes is not well understood. To study excitation dynamics at the systems level, we introduce an atomistic model that mimics a complete light-harvesting apparatus of green sulfur bacteria. The model contains approximately 4000 pigment molecules and comprises a double wall roll for the chlorosome, a baseplate, and six Fenna-Matthews-Olson trimer complexes. We show that the fast relaxation within functional subunits combined with the transfer between collective excited states of pigments can result in robust energy funneling to the initial excitation conditions and temperature changes. Moreover, the same mechanism describes the coexistence of multiple time scales of excitation dynamics frequently observed in ultrafast optical experiments. While our findings support the hypothesis of supertransfer, the model reveals energy transport through multiple channels on different length scales.

  7. Plasmon enhanced light harvesting: multiscale modeling of the FMO protein coupled with gold nanoparticles.

    PubMed

    Andreussi, Oliviero; Caprasecca, Stefano; Cupellini, Lorenzo; Guarnetti-Prandi, Ingrid; Guido, Ciro A; Jurinovich, Sandro; Viani, Lucas; Mennucci, Benedetta

    2015-05-28

    Plasmonic systems, such as metal nanoparticles, are becoming increasingly important in spectroscopies and devices because of their ability to enhance, even by several orders of magnitude, the photophysical properties of neighboring systems. In particular, it has been shown both theoretically and experimentally that combining nanoplasmonic devices with natural light-harvesting proteins substantially increases the fluorescence and absorption properties of the system. This kind of biohybrid device can have important applications in the characterization and design of efficient light-harvesting systems. In the present work, the FMO light-harvesting protein was combined with gold nanoparticles of different sizes, and its photophysical properties were characterized using a multiscale quantum-mechanical classical-polarizable and continuum model (QM/MMPol/PCM). By optimal tuning of the plasmon resonance of the metal nanoparticles, fluorescence enhancements of up to 2 orders of magnitude were observed. Orientation effects were found to be crucial: amplifications by factors of up to 300 were observed for the absorption process, while the radiative decay of the emitting state increased at most by a factor of 10, mostly as a result of poor alignment of the emitting state with the considered metal aggregates. Despite being a limiting factor for high-fluorescence-enhancement devices, the strong orientation dependence may represent an important feature of the natural light-harvesting system that could allow selective enhancement of a specific excited state of the complex.

  8. Ab inito study on triplet excitation energy transfer in photosynthetic light-harvesting complexes.

    PubMed

    You, Zhi-Qiang; Hsu, Chao-Ping

    2011-04-28

    We have studied the triplet energy transfer (TET) for photosynthetic light-harvesting complexes, the bacterial light-harvesting complex II (LH2) of Rhodospirillum molischianum and Rhodopseudomonas acidophila, and the peridinin-chlorophyll a protein (PCP) from Amphidinium carterae. The electronic coupling factor was calculated with the recently developed fragment spin difference scheme (You and Hsu, J. Chem. Phys. 2010, 133, 074105), which is a general computational scheme that yields the overall coupling under the Hamiltonian employed. The TET rates were estimated based on the couplings obtained. For all light-harvesting complexes studied, there exist nanosecond triplet energy transfer from the chlorophylls to the carotenoids. This result supports a direct triplet quenching mechanism for the photoprotection function of carotenoids. The TET rates are similar for a broad range of carotenoid triplet state energy, which implies a general and robust TET quenching role for carotenoids in photosynthesis. This result is also consistent with the weak dependence of TET kinetics on the type or the number of π conjugation lengths in the carotenoids and their analogues reported in the literature. We have also explored the possibility of forming triplet excitons in these complexes. In B850 of LH2 or the peridinin cluster in PCP, it is unlikely to have triplet exciton since the energy differences of any two neighboring molecules are likely to be much larger than their TET couplings. Our results provide theoretical limits to the possible photophysics in the light-harvesting complexes.

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

    PubMed

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

    2012-04-01

    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.

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

    ERIC Educational Resources Information Center

    Muhoz, Romualdo; Quiles, Maria J.

    2003-01-01

    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…

  11. Hierarchical Self-Assembly of Discrete Organoplatinum(II) Metallacycles with Polysaccharide via Electrostatic Interactions and Their Application for Heparin Detection.

    PubMed

    Chen, Li-Jun; Ren, Yuan-Yuan; Wu, Nai-Wei; Sun, Bin; Ma, Jian-Qiu; Zhang, Li; Tan, Hongwei; Liu, Minghua; Li, Xiaopeng; Yang, Hai-Bo

    2015-09-16

    In recent past years, investigation of hierarchical self-assembly for constructing artificial functional materials has attracted considerable attention. Discrete metallacycles based on coordination bonds have proven to be valid scaffolds to fabricate various supramolecular polymers or smart soft matter through hierarchical self-assembly. Here, we present the first example of the hierarchical self-assembly of discrete metallacycles by taking advantage of the positive charges of the organoplatinum(II) metallacycle skeleton through multiple electrostatic interactions. Heparin, a sulfated glycosaminoglycan polymer that has been widely used as an anticoagulant drug, was selected to induce hierarchical self-assembly because of the existence of multiple negative charges. To investigate the hierarchical self-assembly process, an aggregation-induced emission (AIE) active moiety, tetra-phenylethylene (TPE), was introduced onto the metallacycle via coordination-driven self-assembly. Photophysical studies revealed that the addition of heparin to the tris-TPE metallacycles solution resulted in dramatic fluorescence enhancement, which supported the aggregation between metallacycle and heparin driven by multiple electrostatic interactions. Moreover, the entangled pearl-necklace networks were obtained through hierarchical self-assembly as detected by SEM, TEM, and LSCM experiments. In particular, single bead-like chains were observed in the AFM and TEM images, which provided direct, visual evidence for the aggregation of positively charged metallacycles and negatively charged heparin. More interestingly, further optical study demonstrated that this TPE-decorated metallacycle could function as a turn-on fluorescent probe for heparin detection with high sensitivity and selectivity. Thus, this research presents the first example of counter polyanion-induced hierarchical self-assembly of discrete metallacycles and provides a "proof-of-principle" method for heparin sensing and binding.

  12. Hierarchical Self-Assembly of Discrete Organoplatinum(II) Metallacycles with Polysaccharide via Electrostatic Interactions and Their Application for Heparin Detection.

    PubMed

    Chen, Li-Jun; Ren, Yuan-Yuan; Wu, Nai-Wei; Sun, Bin; Ma, Jian-Qiu; Zhang, Li; Tan, Hongwei; Liu, Minghua; Li, Xiaopeng; Yang, Hai-Bo

    2015-09-16

    In recent past years, investigation of hierarchical self-assembly for constructing artificial functional materials has attracted considerable attention. Discrete metallacycles based on coordination bonds have proven to be valid scaffolds to fabricate various supramolecular polymers or smart soft matter through hierarchical self-assembly. Here, we present the first example of the hierarchical self-assembly of discrete metallacycles by taking advantage of the positive charges of the organoplatinum(II) metallacycle skeleton through multiple electrostatic interactions. Heparin, a sulfated glycosaminoglycan polymer that has been widely used as an anticoagulant drug, was selected to induce hierarchical self-assembly because of the existence of multiple negative charges. To investigate the hierarchical self-assembly process, an aggregation-induced emission (AIE) active moiety, tetra-phenylethylene (TPE), was introduced onto the metallacycle via coordination-driven self-assembly. Photophysical studies revealed that the addition of heparin to the tris-TPE metallacycles solution resulted in dramatic fluorescence enhancement, which supported the aggregation between metallacycle and heparin driven by multiple electrostatic interactions. Moreover, the entangled pearl-necklace networks were obtained through hierarchical self-assembly as detected by SEM, TEM, and LSCM experiments. In particular, single bead-like chains were observed in the AFM and TEM images, which provided direct, visual evidence for the aggregation of positively charged metallacycles and negatively charged heparin. More interestingly, further optical study demonstrated that this TPE-decorated metallacycle could function as a turn-on fluorescent probe for heparin detection with high sensitivity and selectivity. Thus, this research presents the first example of counter polyanion-induced hierarchical self-assembly of discrete metallacycles and provides a "proof-of-principle" method for heparin sensing and binding

  13. Allelic variations of a light harvesting chlorophyll A/B protein gene (Lhcb1) associated with agronomic traits in Barley

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Light-harvesting chlorophyll a/b-binding protein (LHCP) is one of the most abundant chloroplast proteins in plants. Its main function is to collect and transfer light energy to photosynthetic reaction centers. However, the roles of different LHCPs in light-harvesting antenna systems remain obscure. ...

  14. Large Femtosecond Two-Photon Absorption Cross-Sections of Fullerosome Vesicle Nanostructures Derived from Highly Photoresponsive Amphiphilic C60-Light-Harvesting Fluorene Dyad

    PubMed Central

    Wang, Min; Nalla, Venkatram; Jeon, Seaho; Mamidala, Venkatesh; Ji, Wei; Tan, Loon-Seng; Cooper, Thomas; Chiang, Long Y.

    2011-01-01

    We demonstrated ultrafast femtosecond nonlinear optical (NLO) absorption characteristics of bilayered fullerosome vesicle nanostructures derived from molecular self-assembly of amphiphilic oligo(ethylene glycolated) C60-(light-harvesting diphenylaminofluorene antenna). Fullerene conjugates were designed to enhance photoresponse in a femtosecond time scale by applying an isomerizable periconjugation linker between the C60 cage and diphenylaminofluorene antenna subunit in an intramolecular contact distance of only < 3.0 Å. Morphology of C60(>DPAF-EG12C1)-based fullerosome nanovesicles in H2O was characterized to consist of a bilayered shell with a sphere diameter of 20–70 nm and a chromophore shell-width of 9.0–10 nm, fitting well with a head-to-head packing configuration of the molecular length. At the estimated effective nanovesicle concentration as low as 5.5 × 10−8 MV (molecular molar concentration of 5.0 × 10−4 M) in H2O, two-photon absorption (2PA) phenomena were found to be the dominating photophysical events showing a large molar concentration-insensitive 2PA cross-section value equivalent to 8500 GM in a form of nanovesicles, on average. The observed NLO characteristics led to a sharp trend of efficient light-transmittance intensity reduction at the input laser intensity above 100 GW/cm2. PMID:22022620

  15. Sequential programmable self-assembly: Role of cooperative interactions.

    PubMed

    Halverson, Jonathan D; Tkachenko, Alexei V

    2016-03-01

    We propose a general strategy of "sequential programmable self-assembly" that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenient platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call "DNA spider," that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a "GEOMAG" magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.

  16. Sequential programmable self-assembly: Role of cooperative interactions

    NASA Astrophysics Data System (ADS)

    Halverson, Jonathan D.; Tkachenko, Alexei V.

    2016-03-01

    We propose a general strategy of "sequential programmable self-assembly" that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenient platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call "DNA spider," that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a "GEOMAG" magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.

  17. Functional architectures based on self-assembly of bio-inspired dipeptides: Structure modulation and its photoelectronic applications.

    PubMed

    Chen, Chengjun; Liu, Kai; Li, Junbai; Yan, Xuehai

    2015-11-01

    Getting inspiration from nature and further developing functional architectures provides an effective way to design innovative materials and systems. Among bio-inspired materials, dipeptides and its self-assembled architectures with functionalities have recently been the subject of intensive studies. However, there is still a great challenge to explore its applications likely due to the lack of effective adaptation of their self-assembled structures as well as a lack of understanding of the self-assembly mechanisms. In this context, taking diphenylalanine (FF, a core recognition motif for molecular self-assembly of the Alzheimer's β-amyloid polypeptides) as a model of bio-inspired dipeptides, recent strategies on modulation of dipeptide-based architectures were introduced with regard to both covalent (architectures modulation by coupling functional groups) and non-covalent ways (controlled architectures by different assembly pathways). Then, applications are highlighted in some newly emerging fields of innovative photoelectronic devices and materials, such as artificial photosynthetic systems for renewable solar energy storage and renewable optical waveguiding materials for optoelectronic devices. At last, the challenges and future perspectives of these bio-inspired dipeptides are also addressed.

  18. Functional architectures based on self-assembly of bio-inspired dipeptides: Structure modulation and its photoelectronic applications.

    PubMed

    Chen, Chengjun; Liu, Kai; Li, Junbai; Yan, Xuehai

    2015-11-01

    Getting inspiration from nature and further developing functional architectures provides an effective way to design innovative materials and systems. Among bio-inspired materials, dipeptides and its self-assembled architectures with functionalities have recently been the subject of intensive studies. However, there is still a great challenge to explore its applications likely due to the lack of effective adaptation of their self-assembled structures as well as a lack of understanding of the self-assembly mechanisms. In this context, taking diphenylalanine (FF, a core recognition motif for molecular self-assembly of the Alzheimer's β-amyloid polypeptides) as a model of bio-inspired dipeptides, recent strategies on modulation of dipeptide-based architectures were introduced with regard to both covalent (architectures modulation by coupling functional groups) and non-covalent ways (controlled architectures by different assembly pathways). Then, applications are highlighted in some newly emerging fields of innovative photoelectronic devices and materials, such as artificial photosynthetic systems for renewable solar energy storage and renewable optical waveguiding materials for optoelectronic devices. At last, the challenges and future perspectives of these bio-inspired dipeptides are also addressed. PMID:26365127

  19. Self-assembly of size-controlled liposomes on DNA nanotemplates

    PubMed Central

    Yang, Yang; Wang, Jing; Shigematsu, Hideki; Xu, Weiming; Shih, William M; Rothman, James E; Lin, Chenxiang

    2016-01-01

    Artificial lipid-bilayer membranes are valuable tools for the study of membrane structure and dynamics. For applications such as studying vesicular transport and drug delivery, there is a pressing need for artificial vesicles with controlled size. However, controlling vesicle size and shape with nanometer precision is challenging and approaches to achieve this can be heavily affected by lipid composition. Here we present a bio-inspired templating method to generate highly monodispersed sub-100nm unilamellar vesicles, where liposome self-assembly was nucleated and confined inside rigid DNA nanotemplates. Using this method we produced homogenous liposomes with four distinct pre-defined sizes. We also show that the method can be used with a variety of lipid compositions and probed the mechanism of the templated liposome formation by capturing key intermediates during membrane self-assembly. The DNA nanotemplating strategy represents a conceptually novel way to guide the lipid bilayer formation, and could be generalized to engineer complex membrane/protein structures with nanoscale precision. PMID:27102682

  20. Self-assembly of size-controlled liposomes on DNA nanotemplates

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Wang, Jing; Shigematsu, Hideki; Xu, Weiming; Shih, William M.; Rothman, James E.; Lin, Chenxiang

    2016-05-01

    Artificial lipid-bilayer membranes are valuable tools for the study of membrane structure and dynamics. For applications such as the study of vesicular transport and drug delivery, there is a pressing need for artificial vesicles with controlled size. However, controlling vesicle size and shape with nanometre precision is challenging, and approaches to achieve this can be heavily affected by lipid composition. Here, we present a bio-inspired templating method to generate highly monodispersed sub-100-nm unilamellar vesicles, where liposome self-assembly was nucleated and confined inside rigid DNA nanotemplates. Using this method, we produce homogeneous liposomes with four distinct predefined sizes. We also show that the method can be used with a variety of lipid compositions and probe the mechanism of templated liposome formation by capturing key intermediates during membrane self-assembly. The DNA nanotemplating strategy represents a conceptually novel way to guide lipid bilayer formation and could be generalized to engineer complex membrane/protein structures with nanoscale precision.

  1. Guided and magnetic self-assembly of tunable magnetoceptive gels

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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.

  2. Cell Environment-Differentiated Self-Assembly of Nanofibers.

    PubMed

    Zheng, Zhen; Chen, Peiyao; Xie, Maolin; Wu, Chengfan; Luo, Yufeng; Wang, Wentao; Jiang, Jun; Liang, Gaolin

    2016-09-01

    Employing cellular environment for the self-assembly of supramolecular nanofibers for biological applications has been widely explored. But using one precursor to differentiate the extra- and intracellular environments to self-assemble into two different nanofibers remains challenging. With the knowledge that the extracellualr environment of some cancer cells contains large amounts of alkaline phosphatase (ALP) while their intracellular environment is glutathione (GSH)-abundant in mind, we rationally designed a precursor Cys(SEt)-Glu-Tyr(H2PO3)-Phe-Phe-Gly-CBT (1) that can efficiently yield amphiphilic 2 and 2-D to self-assemble into two different nanofibers in hydrogels under the sequential treatment of ALP and GSH. We envision that, by employing a click condensation reaction, this work offers a platform for facilely postmodulation of supramolecular nanofibers, and the versatile precursor 1 could be used to kill two birds with one stone. PMID:27532322

  3. Self-Assembly of DNA-coated colloids

    NASA Astrophysics Data System (ADS)

    Pine, David

    DNA-coated particles have emerged as a powerful tool for programming the self-assembly of colloids and nanoparticles. The power of this approach lies in the highly specific molecular recognition properties of DNA and in the thermal reversibility of the interactions between DNA strands attached to different particles. These two properties taken together can, in principle, direct the bottom-up self-assembly of different materials into almost any desired structure. Here we discuss the self-assembly of single and multi-component crystals of DNA-coated colloids. This work is supported by the Army Research Office under MURI Grant Award Number W911NF-10-1-0518 and the MRSEC Program of the NSF under Award Number DMR-1420073.

  4. Guided and magnetic self-assembly of tunable magnetoceptive gels

    PubMed Central

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

    2014-01-01

    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

  5. Self-assembly: mastering photonic processes at nanoscale

    NASA Astrophysics Data System (ADS)

    Fiorini, C.; Charra, F.

    2010-12-01

    Supramolecular ordering happens as an important parameter for the control of light emission processes. In this review paper, we discuss several examples of application of self-assembly to the realization of nano-structures designed in view of mastering specific photonic processes. This comprises the formation of highly localized plasmon modes in self-organized 2D assemblies of metal nanoparticles, the immobilization of dyes inside highly homogeneous 2D alveolar self-assembled molecular matrices and molecular 3D building blocks designed to combine in-plane periodicity and off-plane π-conjugated protrusions. Finally, we will discuss 3D self-assembly in solution with the example of fluorescent labelling of DNA.

  6. Functional self-assembled lipidic systems derived from renewable resources

    PubMed Central

    Silverman, Julian R.; Samateh, Malick; John, George

    2015-01-01

    Self-assembled lipidic amphiphile systems can create a variety of multi-functional soft materials with value-added properties. When employing natural reagents and following biocatalytic syntheses, self-assembling monomers may be inherently designed for degradation, making them potential alternatives to conventional and persistent polymers. By using non-covalent forces, self-assembled amphiphiles can form nanotubes, fibers, and other stimuli responsive architectures prime for further applied research and incorporation into commercial products. By viewing these lipid derivatives under a lens of green principles, there is the hope that in developing a structure–function relationship and functional smart materials that research may remain safe, economic, and efficient. PMID:26766923

  7. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  8. Multivalent Protein Assembly Using Monovalent Self-Assembling Building Blocks

    PubMed Central

    Petkau-Milroy, Katja; Sonntag, Michael H.; Colditz, Alexander; Brunsveld, Luc

    2013-01-01

    Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard to streptavidin. Next to tetravalent streptavidin, monovalent streptavidin was used to study the protein assembly along the supramolecular polymer in detail without the interference of cross-linking. Upon self-assembly of the monovalent biotinylated discotics, multivalent proteins can be assembled along the supramolecular polymer. The concentration of discotics, which influences the length of the final polymers at the same time dictates the amount of assembled proteins. PMID:24152447

  9. Self-assembled tunable networks of sticky colloidal particles

    NASA Astrophysics Data System (ADS)

    Demortière, Arnaud; Snezhko, Alexey; Sapozhnikov, Maksim V.; Becker, Nicholas; Proslier, Thomas; Aranson, Igor S.

    2014-01-01

    Surfaces decorated with dense arrays of microscopic fibres exhibit unique materials properties, including superhydrophobicity and low friction. Nature relies on ‘hairy’ surfaces to protect blood capillaries from wear and infection (endothelial glycocalyx). Here we report on the discovery of self-assembled tunable networks of microscopic polymer fibres ranging from wavy colloidal ‘fur’ to highly interconnected networks. The networks emerge via dynamic self-assembly in an alternating electric field from a non-aqueous suspension of ‘sticky’ polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles. We demonstrate, using atomic layer deposition, that the networks can serve as a template for a transparent conductor. These self-assembled tunable materials are promising candidates for large surface area electrodes in batteries and organic photovoltaic cells, as well as for microfluidic sensors and filters.

  10. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented. PMID:15787373

  11. Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents, whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. Details addressing the design, synthesis and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental clean-up necessary after 40 years of weapons grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  12. Self-assembly and structural-functional flexibility of oxygenic photosynthetic machineries: personal perspectives.

    PubMed

    Garab, Győző

    2016-01-01

    This short review, with a bit of historical aspect and a strong personal bias and emphases on open questions, is focusing on the (macro-)organization and structural-functional flexibilities of the photosynthetic apparatus of oxygenic photosynthetic organisms at different levels of the structural complexity-selected problems that have attracted most my attention in the past years and decades. These include (i) the anisotropic organization of the pigment-protein complexes and photosynthetic membranes-a basic organizing principle of living matter, which can, and probably should be adopted to intelligent materials; (ii) the organization of protein complexes into chiral macrodomains, large self-assembling highly organized but structurally flexible entities with unique spectroscopic fingerprints-structures, where, important, high-level regulatory functions appear to 'reside'; (iii) a novel, dissipation-assisted mechanism of structural changes, based on a thermo-optic effect: ultrafast thermal transients in the close vicinity of dissipation of unused excitation energy, which is capable of inducing elementary structural changes; it makes plants capable of responding to excess excitation with reaction rates proportional to the overexcitation above the light-saturation of photosynthesis; (iv) the 3D ultrastructure of the granum-stroma thylakoid membrane assembly and other multilamellar membrane systems, and their remodelings-associated with regulatory mechanisms; (v) the molecular organization and structural-functional plasticity of the main light-harvesting complex of plants, in relation to their crystal structure and different in vivo and in vitro states; and (vi) the enigmatic role of non-bilayer lipids and lipid phases in the bilayer thylakoid membrane-warranting its high protein content and contributing to its structural flexibility. PMID:26494196

  13. Interfacial and mechanical properties of self-assembling systems

    NASA Astrophysics Data System (ADS)

    Carvajal, Daniel

    Self-assembly is a fascinating phenomena where interactions between small subunits allow them to aggregate and form complex structures that can span many length scales. These self-assembled structures are especially important in biology where they are necessary for life as we know it. This dissertation is a study of three very different self-assembling systems, all of which have important connections to biology and biological systems. Drop shape analysis was used to study the interfacial assembly of amphiphilic block copolymers at the oil/water interface. When biologically functionalyzed copolymers are used, this system can serve as a model for receptor-ligand interactions that are used by cells to perform many activities, such as interact with their surroundings. The physical properties of a self-assembling membrane system were quantified using membrane inflation and swelling experiments. These types of membranes may have important applications in medicine such as drug eluting (growth factor eluting) scaffolds to aid in wound healing. The factors affecting the properties of bis(leucine) oxalamide gels were also explored. We believe that this particular system will serve as an appropriate model for biological gels that are made up of fiber-like and/or rod-like structures. During the course of the research presented in this dissertation, many new techniques were developed specifically to allow/aid the study of these distinct self-assembling systems. For example, numerical methods were used to predict drop stability for drop shape analysis experiments and the methods used to create reproducibly create self-assembling membranes were developed specifically for this purpose. The development of these new techniques is an integral part of the thesis and should aid future students who work on these projects. A number ongoing projects and interesting research directions for each one of the projects is also presented.

  14. Self-Assembled DNA Templated Nano-wires and Circuits

    NASA Astrophysics Data System (ADS)

    Braun, Erez

    2000-03-01

    The realization that conventional microelectronics is approaching its miniaturization limits has motivated the search for an alternative route based on self-assembled nanometer-scale electronics. We have recently proposed a new approach based on the hybridization of biological and electronic materials (Braun E., Eichen Y., Sivan U. and Ben-Yoseph G., Nature 391, 775 (1998)). The concept relies on a two-step self-assembly process. The inherent molecular recognition capabilities of DNA molecules are first utilized to construct a network that serves as a template for the subsequent assembly of electronic materials into a circuit. The utilization of DNA and its associated enzymatic machinery enables: (a) self-assembly of complex substrates, (b) specific molecular addresses for the localization of electronic materials (e.g., gold colloids) by standard molecular biology techniques, (c) interdevice wiring and (d) bridging the microscopic structures to the macroscopic world. The self-assembly of nanometer scale electronics relies on two complementary developments. First, the ability to convert DNA molecules into thin conductive wires and second, the self-assembly of complex extended DNA templates. Our progress in these two directions will be presented. Regarding the first issue, a physical process resulting in condensation of gold colloids onto DNA molecules enables the assembly of thin gold wires (around 100-200 A wide) having, in principle, unlimited extensions. The second issue is developed in the context of recombinant DNA which allows the self-assembly of precise molecular junctions and networks. Specifically, we use RecA protein, which is the main protein responsible for genetic recombination in E. Coli bacteria, to construct DNA junctions at pre-designed addresses (sequences) on the molecules. The integration of these processes allows advancing nanometer-scale electronics. A realistic fabrication scheme for a room-temperature single-electron transistor

  15. Hydrazine-mediated construction of nanocrystal self-assembly materials.

    PubMed

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

    2014-10-28

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

  16. Nanofibers Self-assembled from Structural Complementary Borono-decapeptides.

    PubMed

    Chen, Chang-Sheng; Ji, Tian-Jiao; Xu, Xiao-Ding; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2010-11-01

    A series of structural complementary decapeptides with phenyl boronic acid tails or borono-decapeptides (BPs) were designed and synthesized for supramolecular self-assembly. After dissolving these borono-decapeptides in deionized (DI) water, well-defined nanofibers were formed in BP1 (B(OH)(2) VEKELVKEKL-OH) and BP3 (B(OH)(2) AELELARARL-OH). It was found that the self-assembled borono-decapeptide BP1 and BP3 have a parallel β-sheet conformation in the formed nanofibers. The strategy demonstrated here shows a great prospect in preparation of well-ordered nanofibers via rationally designing the molecular structures of peptides.

  17. Self-Assembled Organic Nanocrystals with Strong Nonlinear Optical Response.

    PubMed

    Rosenne, Shaked; Grinvald, Eran; Shirman, Elijah; Neeman, Lior; Dutta, Sounak; Bar-Elli, Omri; Ben-Zvi, Regev; Oksenberg, Eitan; Milko, Petr; Kalchenko, Vyacheslav; Weissman, Haim; Oron, Dan; Rybtchinski, Boris

    2015-11-11

    Facile molecular self-assembly affords a new family of organic nanocrystals that, unintuitively, exhibit a significant nonlinear optical response (second harmonic generation, SHG) despite the relatively small molecular dipole moment of the constituent molecules. The nanocrystals are self-assembled in aqueous media from simple monosubstituted perylenediimide (PDI) molecular building blocks. Control over the crystal dimensions can be achieved via modification of the assembly conditions. The combination of a simple fabrication process with the ability to generate soluble SHG nanocrystals with tunable sizes may open new avenues in the area of organic SHG materials.

  18. Structural simulations of nanomaterials self-assembled from ionic macrocycles.

    SciTech Connect

    van Swol, Frank B.; Medforth, Craig John

    2010-10-01

    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.

  19. Molecular beam epitaxy grown indium self-assembled plasmonic nanostructures

    NASA Astrophysics Data System (ADS)

    Gibson, Ricky; Gehl, Michael; Sears, Jasmine; Zandbergen, Sander; Nader, Nima; Keiffer, Patrick; Hendrickson, Joshua; Arnoult, Alexandre; Khitrova, Galina

    2015-09-01

    We describe molecular beam epitaxy (MBE) growth conditions for self-assembled indium nanostructures, or islands, which allow for the tuning of the density and size of the indium nanostructures. How the plasmonic resonance of indium nanostructures is affected by the island density, size, distribution in sizes, and indium purity of the nanostructures is explored. These self-assembled nanostructures provide a platform for integration of resonant and non-resonant plasmonic structures within a few nm of quantum wells (QWs) or quantum dots (QDs) in a single process. A 4× increase in peak photoluminescence intensity is demonstrated for near-surface QDs resonantly coupled to indium nanostructures.

  20. Nano-engineering by optically directed self-assembly.

    SciTech Connect

    Furst, Eric; Dunn, Elissa; Park, Jin-Gyu; Brinker, C. Jeffrey; Sainis, Sunil; Merrill, Jason; Dufresne, Eric; 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; Lele, Pushkar; Mittal, Manish

    2009-09-01

    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.

  1. Scanning tunneling microscopy of self-assembled viral nanostructures

    NASA Astrophysics Data System (ADS)

    Anacleto, Benjamin; Steinsultz, Nat; Sharma, Prashant

    2010-03-01

    We use scanning tunneling microscopy to investigate self-assembled monolayers of M13 bacteriophages on graphite surface. The bacteriophages we use have gold binding peptide motifs on their outer protein coat (˜1μm long, ˜10 nm diameter) allowing us to self-assemble gold nanoparticles on graphite. Using scanning tunneling microscopy we are able to resolve sub-molecular structure of the protein coat of M13 bacteriophage. Scanning tunneling spectroscopy allows us to study the binding of gold nanoparticles to the peptide motif on the bacteriophage.

  2. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles.

  3. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles. PMID:25112916

  4. Light-harvesting chlorophyll a/b-binding protein inserted into isolated thylakoids binds pigments and is assembled into trimeric light-harvesting complex.

    PubMed Central

    Kuttkat, A; Grimm, R; Paulsen, H

    1995-01-01

    The light-harvesting chlorophyll a/b-binding protein (LHCP) is largely protected against protease (except for about 1 kD on the N terminus) in the thylakoid membrane; this protease resistance is often used to assay successful insertion of LHCP into isolated thylakoids in vitro. In this paper we show that this protease resistance is exhibited by trimeric light-harvesting complex of photosystem II (LHCII) but not by monomeric LHCII in which about 5 kD on the N terminus of LHCP are cleaved off by protease. When a mutant version of LHCP that is unable to trimerize in an in vitro reconstitution assay is inserted into isolated thylakoids, it gives rise to only the shorter protease digestion product indicative of monomeric LHCII. We conclude that more of the N-terminal domain of LHCP is shielded in trimeric than in monomeric LHCII and that this difference in protease sensitivity can be used to distinguish between LHCP assembled in LHCII monomers or trimers. The data presented prove that upon insertion of LHCP into isolated thylakoids at least part of the protein spontaneously binds pigments to form LHCII, which then is assembled in trimers. The dependence of the protease sensitivity of thylakoid-inserted LHCP on the oligomerization state of the newly formed LHCII justifies caution when using a protease assay to verify successful insertion of LHCP into the membrane. PMID:8539291

  5. Differential Self-Assembly of Novel Redox Crown Ethers

    NASA Astrophysics Data System (ADS)

    Merithew, Andrew William

    Retinal prosthesis relies on the stimulation of living nerve tissue behind the rods and cones of the eye. The current state of the art relies on electrodes controlled by cameras which directly stimulate the nerve tissue to elicit a response to an image. These types of retinal implants have allowed for short-term crude vision in patients but have had limited long term success due to external battery packs and electroplating of the implanted electrodes. Ionic stimulation is one of the principle mechanisms that sensory neurons utilize in the generation of an action potential. In a complex transduction pathway, ionic gradients are constantly altered inside the neuron by voltage sensors or mechanically controlled gates embedded in the neuronal cell membrane; responsible for the open and close state of these ion channels. It has been demonstrated that local concentration increases of K + by direct injection proximal to the nerve can elicit nerve firing at a concentration of 15-20 mM (3-4X normal concentration) increase in K + concentration. As part of a larger concept of integrating biotechnology with nanofabrication, the materials for the development of potassium selective sequestration/storage and delivery were developed in the form of a redox-gated K+ selective crown ether. The structure of the anthraquinone-based crown was deduced by computational simulation and stoichiometry of the complex confirmed by mass spec. along with 2D diffusion NMR techniques. In this instance, the stoichiometry could be controlled by the addition of different salts to give a 1:1 complex with large, aromatic anions and a 2:1 complex with smaller anions such as triflate. The synthesis of the molecule was optimized by computational modeling and simulations of transport through an artificial membrane. The selectivity of the architecture developed was specific for K+ over Na+, the other major ionic species present in the blood. The mechanism influencing the self-assembly of this class of

  6. Light Harvesting as a Simple and Versatile Way to Enhance Brightness of Luminescent Sensors

    PubMed Central

    2009-01-01

    The emissive output of indicator dyes in luminescent sensors can be amplified by the addition of antenna dyes with a higher brightness. The highly concentrated antenna dye molecules absorb the excitation light and transfer the energy to an indicator dye. This harvesting of light makes thin sensor layers (thickness <500 nm) and nanometer sized sensor particles with exceptionally high brightness and compatible with the most powerful LEDs available. The performance of sensor layers of ∼250 nm thickness employing light harvesting was investigated and compared with established sensors. The principle is demonstrated for oxygen and ammonia sensors. An overview of possible application of light harvesting to various reagent mediated optical sensing schemes is given.

  7. Anti-Correlated Pigment Fluctuations of Allophycocyanin for Highly Efficient Photosynthetic Light Harvesting in Cyanobacteria

    NASA Astrophysics Data System (ADS)

    Moran, Andrew; Nome, Rene; Scherer, Norbert

    2008-03-01

    The phycobiliprotein, allophycocyanin (APC), is an excellent model system for the study of light harvesting pigment interactions with a protein bath. This work investigates the relaxation of electronic excitations in APC with electric field-resolved transient grating and photon echo spectroscopies. Transient grating experiments observe a 35 fs internal conversion process between single exciton levels. Most importantly, our analysis shows that anti-correlated phycocyanobilin pigment energy level fluctuations cause the anti-diagonal orientation of the node in the measured dispersive photon echo spectrum. We believe this novel observation to reflect concerted protein bath fluctuations over the 2 nm length scale that separates the pigments. Consideration of the Forster energy transfer rate theory suggests that APC has evolved with this property to enhance its photosynthetic light harvesting efficiency.

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

    SciTech Connect

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

    2008-12-22

    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.

  9. Quantum coherent energy transfer over varying pathways in single light-harvesting complexes.

    PubMed

    Hildner, Richard; Brinks, Daan; Nieder, Jana B; Cogdell, Richard J; van Hulst, Niek F

    2013-06-21

    The initial steps of photosynthesis comprise the absorption of sunlight by pigment-protein antenna complexes followed by rapid and highly efficient funneling of excitation energy to a reaction center. In these transport processes, signatures of unexpectedly long-lived coherences have emerged in two-dimensional ensemble spectra of various light-harvesting complexes. Here, we demonstrate ultrafast quantum coherent energy transfer within individual antenna complexes of a purple bacterium under physiological conditions. We find that quantum coherences between electronically coupled energy eigenstates persist at least 400 femtoseconds and that distinct energy-transfer pathways that change with time can be identified in each complex. Our data suggest that long-lived quantum coherence renders energy transfer in photosynthetic systems robust in the presence of disorder, which is a prerequisite for efficient light harvesting.

  10. Plasmon-controlled light-harvesting: design rules for biohybrid devices via multiscale modeling.

    PubMed

    Andreussi, Oliviero; Biancardi, Alessandro; Corni, Stefano; Mennucci, Benedetta

    2013-09-11

    Photosynthesis is triggered by the absorption of light by light-harvesting (LH) pigment-protein complexes followed by excitation energy transfer to the reaction center(s). A promising strategy to achieve control on and to improve light harvesting is to complement the LH complexes with plasmonic particles. Here a recently developed QM/MM/continuum approach is used to investigate the LH process of the peridinin-chlorophyll-protein (PCP) complex on a silver island film. The simulations not only reproduce and interpret the experiments but they also suggest general rules to design novel biohybrid devices; hot-spot configurations in which the LH complex is sandwiched between couples of metal aggregates are found to produce the largest amplifications. Indications about the best distances and orientations are also reported together with illumination and emission geometries of the PCP-NP system necessary to achieve the maximum enhancement.

  11. ARCHITECTURE OF A CHARGE-TRANSFER STATE REGULATING LIGHT HARVESTING IN A PLANT ANTENNA PROTEIN

    SciTech Connect

    Fleming, Graham; Ahn, Tae Kyu; Avenson, Thomas J.; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K.; Bassi, Roberto; Fleming, Graham R.

    2008-04-02

    Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge-transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). In this work, we present evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a de-localized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can `tune? the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophylls-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

  12. Silica entrapment for significantly stabilized, energy-conducting light-harvesting complex (LHCII).

    PubMed

    Roeder, Sebastian; Hobe, Stephan; Paulsen, Harald

    2014-12-01

    The major light-harvesting chlorophyll a/b complex (LHCII) of the photosynthetic apparatus in green plants consists of a membrane protein and numerous noncovalently bound pigments that make up about one-third of the molecular mass of the pigment-protein complex. Due to this high pigment density, LHCII is potentially interesting as a light-harvesting component in synthetic constructs. However, for such applications its stability needs to be significantly improved. In this work, LHCII was dramatically stabilized by enclosing it within polymerizing colloidal silica. The entrapped LHCII stayed functional at 50 °C for up to 24 h instead of a few minutes in detergent solution and clearly showed energy transfer between complexes. Entrapment yield was enhanced by a polycationic peptide attached to the N terminus. Both the extent of stabilization and the yield of entrapment strongly increased with decreasing diameters of the silica particles.

  13. Molecular design of the photosystem II light-harvesting antenna: photosynthesis and photoprotection.

    PubMed

    Horton, Peter; Ruban, Alexander

    2005-01-01

    The photosystem II (PSII) light-harvesting system carries out two essential functions, the efficient collection of light energy for photosynthesis, and the regulated dissipation of excitation energy in excess of that which can be used. This dual function requires structural and functional flexibility, in which light-harvesting proteins respond to an external signal, the thylakoid DeltapH, to induce feedback control. This process, referred to as non-photochemical quenching (NPQ) depends upon the xanthophyll cycle and the PsbS protein. In nature, NPQ is heterogeneous in terms of kinetics and capacity, and this adapts photosynthetic systems to the specific dynamic features of the light environment. The molecular features of the thylakoid membrane which may enable this flexibility and plasticity are discussed.

  14. Architecture of a charge-transfer state regulating light harvesting in a plant antenna protein.

    PubMed

    Ahn, Tae Kyu; Avenson, Thomas J; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K; Bassi, Roberto; Fleming, Graham R

    2008-05-01

    Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). We found evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a delocalized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can "tune" the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophyll-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  16. Revealing Linear Aggregates of Light Harvesting Antenna Proteins in Photosynthetic Membranes

    PubMed Central

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

    2010-01-01

    How light energy is harvested in a natural photosynthetic membrane through energy transfer is closely related to the stoichiometry and arrangement of light harvesting antenna proteins in the membrane. The specific photosynthetic architecture facilitates a rapid and efficient energy transfer among the light harvesting proteins (LH2 and LH1) and to the reaction center. Here we report the identification of linear aggregates of light harvesting proteins, LH2, in the photosynthetic membranes under ambient conditions by using atomic force microscopy (AFM) imaging and spectroscopic analysis. Our results suggest that the light harvesting protein, LH2, can exist as linear aggregates of 4±2 proteins in the photosynthetic membranes and that the protein distributions are highly heterogeneous. In the photosynthetic membranes examined in our measurements, the ratio of the aggregated to the non-aggregated LH2 proteins is about 3:1 to 5:1 depending on the intensity of the illumination used during sample incubation and on the bacterial species. AFM images further identify that the LH2 proteins in the linear aggregates are monotonically tilted at an angle 4°±2° from the plane of the photosynthetic membranes. The aggregates result in red-shifted absorption and emission spectra that are measured using various mutant membranes, including an LH2 knock-out, LH1 knock-out, and LH2 at different population densities. Measuring the fluorescence lifetimes of purified LH2 and LH2 in membranes, we have observed that the LH2 proteins in membranes exhibit biexponential lifetime decays whereas the purified LH2 proteins gave single exponential lifetime decays. We attribute that the two lifetime components originate from the existence of both aggregated and non-aggregated LH2 proteins in the photosynthetic membranes. PMID:19572507

  17. Light-Harvesting Nanotubes Formed by Supramolecular Assembly of Aromatic Oligophosphates.

    PubMed

    Bösch, Caroline D; Langenegger, Simon M; Häner, Robert

    2016-08-16

    A 2,7-disubstituted phosphodiester-linked phenanthrene trimer forms tubular structures in aqueous media. Chromophores are arranged in H-aggregates. Incorporation of small quantities of pyrene results in the development of light-harvesting nanotubes in which phenanthrenes act as antenna chromophores and pyrenes as energy acceptors. Energy collection is most efficient after excitation at the phenanthrene H-band. Fluorescence quantum yields up to 23 % are reached in pyrene doped, supramolecular nanotubes. PMID:27375116

  18. Intrinsically unstructured phosphoprotein TSP9 regulates light harvesting in Arabidopsis thaliana.

    PubMed

    Fristedt, Rikard; Carlberg, Inger; Zygadlo, Agnieszka; Piippo, Mirva; Nurmi, Markus; Aro, Eva-Mari; Scheller, Henrik Vibe; Vener, Alexander V

    2009-01-20

    Thylakoid-soluble phosphoprotein of 9 kDa, TSP9, is an intrinsically unstructured plant-specific protein [Song, J., et al. (2006) Biochemistry 45, 15633-15643] with unknown function but established associations with light-harvesting proteins and peripheries of both photosystems [Hansson, M., et al. (2007) J. Biol. Chem. 282, 16214-16222]. To investigate the function of this protein, we used a combination of reverse genetics and biochemical and fluorescence measurement methods in Arabidopsis thaliana. Differential gene expression analysis of plants with a T-DNA insertion in the TSP9 gene using an array of 24000 Arabidopsis genes revealed disappearance of high light-dependent induction of a specific set of mostly signaling and unknown proteins. TSP9-deficient plants had reduced levels of in vivo phosphorylation of light-harvesting complex II polypeptides. Recombinant TSP9 was phosphorylated in light by thylakoid membranes isolated from the wild-type and mutant plants lacking STN8 protein kinase but not by the thylakoids deficient in STN7 kinase, essential for photosynthetic state transitions. TSP9-lacking mutant and RNAi plants with downregulation of TSP9 showed reduced ability to perform state transitions. The nonphotochemical quenching of chlorophyll fluorescence at high light intensities was also less efficient in the mutant compared to wild-type plants. Blue native electrophoresis of thylakoid membrane protein complexes revealed that TSP9 deficiency increased relative stability of photosystem II dimers and supercomplexes. It is concluded that TSP9 regulates plant light harvesting acting as a membrane-binding protein facilitating dissociation of light-harvesting proteins from photosystem II. PMID:19113838

  19. A thioredoxin-like/β-propeller protein maintains the efficiency of light harvesting in Arabidopsis.

    PubMed

    Brooks, Matthew D; Sylak-Glassman, Emily J; Fleming, Graham R; Niyogi, Krishna K

    2013-07-16

    The light-harvesting complexes of plants have evolved the ability to switch between efficient light harvesting and quenching forms to optimize photosynthesis in response to the environment. Several distinct mechanisms, collectively termed "nonphotochemical quenching" (NPQ), provide flexibility in this response. Here we report the isolation and characterization of a mutant, suppressor of quenching 1 (soq1), that has high NPQ even in the absence of photosystem II subunit S (PsbS), a protein that is necessary for the rapidly reversible component of NPQ. The formation of NPQ in soq1 was light intensity-dependent, and it exhibited slow relaxation kinetics and other characteristics that distinguish it from known NPQ components. Treatment with chemical inhibitors or an uncoupler, as well as crosses to mutants known to affect other NPQ components, showed that the NPQ in soq1 does not require a transthylakoid pH gradient, zeaxanthin formation, or the phosphorylation of light-harvesting complexes, and it appears to be unrelated to the photosystem II damage-and-repair cycle. Measurements of pigments and chlorophyll fluorescence lifetimes indicated that the additional NPQ in soq1 is the result of a decrease in chlorophyll excited-state lifetime and not pigment bleaching. The SOQ1 gene was isolated by map-based cloning, and it encodes a previously uncharacterized thylakoid membrane protein with thioredoxin-like and β-propeller domains located in the lumen and a haloacid-dehalogenase domain exposed to the chloroplast stroma. We propose that the role of SOQ1 is to prevent formation of a slowly reversible form of antenna quenching, thereby maintaining the efficiency of light harvesting.

  20. Atomistic mechanisms of rapid energy transport in light-harvesting molecules

    NASA Astrophysics Data System (ADS)

    Ohmura, Satoshi; Koga, Shiro; Akai, Ichiro; Shimojo, Fuyuki; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

    2011-03-01

    Synthetic supermolecules such as π-conjugated light-harvesting dendrimers efficiently harvest energy from sunlight, which is of significant importance for the global energy problem. Key to their success is rapid transport of electronic excitation energy from peripheral antennas to photochemical reaction cores, the atomistic mechanisms of which remains elusive. Here, quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals the key molecular motion that significantly accelerates the energy transport based on the Dexter mechanism.

  1. Developmental self-assembly of a DNA tetrahedron.

    PubMed

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

    2014-04-22

    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.

  2. Cooperative Self-Assembly of Peptide Gelators and Proteins

    PubMed Central

    2014-01-01

    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

  3. Self-assembling multidomain peptide fibers with aromatic cores

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Self-assembling multidomain peptides have been shown to have desirable properties, such as the ability to form hydrogels that rapidly recover following shear-thinning and the potential to be tailored by amino acid selection to vary their elasticity and encapsulate and deliver proteins and cells. Her...

  4. Nano-imaging enabled via self-assembly

    PubMed Central

    McLeod, Euan; Ozcan, Aydogan

    2014-01-01

    SUMMARY Imaging object details with length scales below approximately 200 nm has been historically difficult for conventional microscope objective lenses because of their inability to resolve features smaller than one-half the optical wavelength. Here we review some of the recent approaches to surpass this limit by harnessing self-assembly as a fabrication mechanism. Self-assembly can be used to form individual nano- and micro-lenses, as well as to form extended arrays of such lenses. These lenses have been shown to enable imaging with resolutions as small as 50 nm half-pitch using visible light, which is well below the Abbe diffraction limit. Furthermore, self-assembled nano-lenses can be used to boost contrast and signal levels from small nano-particles, enabling them to be detected relative to background noise. Finally, alternative nano-imaging applications of self-assembly are discussed, including three-dimensional imaging, enhanced coupling from light-emitting diodes, and the fabrication of contrast agents such as quantum dots and nanoparticles. PMID:25506387

  5. Self-assembling biomolecular catalysts for hydrogen production

    NASA Astrophysics Data System (ADS)

    Jordan, Paul C.; Patterson, Dustin P.; Saboda, Kendall N.; Edwards, Ethan J.; Miettinen, Heini M.; Basu, Gautam; Thielges, Megan C.; Douglas, Trevor

    2016-02-01

    The chemistry of highly evolved protein-based compartments has inspired the design of new catalytically active materials that self-assemble from biological components. A frontier of this biodesign is the potential to contribute new catalytic systems for the production of sustainable fuels, such as hydrogen. Here, we show the encapsulation and protection of an active hydrogen-producing and oxygen-tolerant [NiFe]-hydrogenase, sequestered within the capsid of the bacteriophage P22 through directed self-assembly. We co-opted Escherichia coli for biomolecular synthesis and assembly of this nanomaterial by expressing and maturing the EcHyd-1 hydrogenase prior to expression of the P22 coat protein, which subsequently self assembles. By probing the infrared spectroscopic signatures and catalytic activity of the engineered material, we demonstrate that the capsid provides stability and protection to the hydrogenase cargo. These results illustrate how combining biological function with directed supramolecular self-assembly can be used to create new materials for sustainable catalysis.

  6. Photoresponsive self-assemblies based on fatty acids.

    PubMed

    Fameau, A-L; Arnould, A; Lehmann, M; von Klitzing, R

    2015-02-18

    Photoresponsive surfactant system based on fatty acids has been developed by the introduction in aqueous solution of a photoacid generator (PAG). Self-assembly transitions are triggered by UV irradiation due to a pH change induced by the presence of PAG.

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

    PubMed Central

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

    2009-01-01

    The design and fabrication techniques for microelectromechanical systems (MEMS) and nanodevices are progressing rapidly. However, due to material and process flow incompatibilities in the fabrication of sensors, actuators and electronic circuitry, a final packaging step is often necessary to integrate all components of a heterogeneous microsystem on a common substrate. Robotic pick-and-place, although accurate and reliable at larger scales, is a serial process that downscales unfavorably due to stiction problems, fragility and sheer number of components. Self-assembly, on the other hand, is parallel and can be used for device sizes ranging from millimeters to nanometers. In this review, the state-of-the-art in methods and applications for self-assembly is reviewed. Methods for assembling three-dimensional (3D) MEMS structures out of two-dimensional (2D) ones are described. The use of capillary forces for folding 2D plates into 3D structures, as well as assembling parts onto a common substrate or aggregating parts to each other into 2D or 3D structures, is discussed. Shape matching and guided assembly by magnetic forces and electric fields are also reviewed. Finally, colloidal self-assembly and DNA-based self-assembly, mainly used at the nanoscale, are surveyed, and aspects of theoretical modeling of stochastic assembly processes are discussed. PMID:20209016

  8. Directed intermixing in multi-component self-assembling biomaterials

    PubMed Central

    Gasiorowski, Joshua Z.; Collier, Joel H.

    2011-01-01

    The non-covalent co-assembly of multiple different peptides can be a useful route for producing multifunctional biomaterials. However, to date such materials have almost exclusively been investigated as homogeneous self-assemblies, having functional components uniformly distributed throughout their supramolecular structures. Here we illustrate control over the intermixing of multiple different self-assembling peptides, in turn providing a simple but powerful means for modulating these materials’ mechanical and biological properties. In beta-sheet fibrillizing hydrogels, significant increases in stiffening could be achieved using heterobifunctional cross-linkers by sequestering peptides bearing different reactive groups into distinct populations of fibrils, thus favoring inter-fibril cross-linking. Further, by specifying the intermixing of RGD-bearing peptides in 2-D and 3-D self-assemblies, the growth of HUVECs and NIH 3T3 cells could be significantly modulated. This approach may be immediately applicable towards a wide variety of self-assembling systems that form stable supramolecular structures. PMID:21863894

  9. Soft self-assembled nanoparticles with temperature-dependent properties

    NASA Astrophysics Data System (ADS)

    Rovigatti, Lorenzo; Capone, Barbara; Likos, Christos N.

    2016-02-01

    The fabrication of versatile building blocks that reliably self-assemble into desired ordered and disordered phases is amongst the hottest topics in contemporary materials science. To this end, microscopic units of varying complexity, aimed at assembling the target phases, have been thought, designed, investigated and built. Such a path usually requires laborious fabrication techniques, especially when specific functionalisation of the building blocks is required. Telechelic star polymers, i.e., star polymers made of a number of f di-block copolymers consisting of solvophobic and solvophilic monomers grafted on a central anchoring point, spontaneously self-assemble into soft patchy particles featuring attractive spots (patches) on the surface. Here we show that the tunability of such a system can be widely extended by controlling the physical and chemical parameters of the solution. Indeed, under fixed external conditions the self-assembly behaviour depends only on the number of arms and on the ratio of solvophobic to solvophilic monomers. However, changes in temperature and/or solvent quality make it possible to reliably change the number and size of the attractive patches. This allows the steering of the mesoscopic self-assembly behaviour without modifying the microscopic constituents. Interestingly, we also demonstrate that diverse combinations of the parameters can generate stars with the same number of patches but different radial and angular stiffness. This mechanism could provide a neat way of further fine-tuning the elastic properties of the supramolecular network without changing its topology.

  10. Self-assembled peptide nanostructures for functional materials.

    PubMed

    Ekiz, Melis Sardan; Cinar, Goksu; Khalily, Mohammad Aref; Guler, Mustafa O

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies. PMID:27578525

  11. An exactly solvable model of hierarchical self-assembly.

    PubMed

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

    2009-06-14

    Many living and nonliving structures in the natural world form by hierarchical organization, but physical theories that describe this type of organization are scarce. To address this problem, a model of equilibrium self-assembly is formulated in which dynamically associating species organize into hierarchical structures that preserve their shape at each stage of assembly. In particular, we consider symmetric m-gons that associate at their vertices into Sierpinski gasket structures involving the hierarchical association of triangles, squares, hexagons, etc., at their corner vertices, thereby leading to fractal structures after many generations of assembly. This rather idealized model of hierarchical assembly yields an infinite sequence of self-assembly transitions as the morphology progressively organizes to higher levels of the hierarchy, and these structures coexists at dynamic equilibrium, as found in real hierarchically self-assembling systems such as amyloid fiber forming proteins. Moreover, the transition sharpness progressively grows with increasing m, corresponding to larger and larger loops in the assembled structures. Calculations are provided for several basic thermodynamic properties (including the order parameters for assembly for each stage of the hierarchy, average mass of clusters, specific heat, transition sharpness, etc.) that are required for characterizing the interaction parameters governing this type of self-assembly and for elucidating other basic qualitative aspects of these systems. Our idealized model of hierarchical assembly gives many insights into this ubiquitous type of self-organization process. PMID:19530788

  12. An exactly solvable model of hierarchical self-assembly

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

    Many living and nonliving structures in the natural world form by hierarchical organization, but physical theories that describe this type of organization are scarce. To address this problem, a model of equilibrium self-assembly is formulated in which dynamically associating species organize into hierarchical structures that preserve their shape at each stage of assembly. In particular, we consider symmetric m-gons that associate at their vertices into Sierpinski gasket structures involving the hierarchical association of triangles, squares, hexagons, etc., at their corner vertices, thereby leading to fractal structures after many generations of assembly. This rather idealized model of hierarchical assembly yields an infinite sequence of self-assembly transitions as the morphology progressively organizes to higher levels of the hierarchy, and these structures coexists at dynamic equilibrium, as found in real hierarchically self-assembling systems such as amyloid fiber forming proteins. Moreover, the transition sharpness progressively grows with increasing m, corresponding to larger and larger loops in the assembled structures. Calculations are provided for several basic thermodynamic properties (including the order parameters for assembly for each stage of the hierarchy, average mass of clusters, specific heat, transition sharpness, etc.) that are required for characterizing the interaction parameters governing this type of self-assembly and for elucidating other basic qualitative aspects of these systems. Our idealized model of hierarchical assembly gives many insights into this ubiquitous type of self-organization process.

  13. Amphiphilic self-assembly of alkanols in protic ionic liquids.

    PubMed

    Jiang, Haihui Joy; FitzGerald, Paul A; Dolan, Andrew; Atkin, Rob; Warr, Gregory G

    2014-08-21

    Strong cohesive forces in protic ionic liquids (PILs) can induce a liquid nanostructure consisting of segregated polar and apolar domains. Small-angle X-ray scattering has shown that these forces can also induce medium chain length n-alkanols to self-assemble into micelle- and microemulsion-like structures in ethylammonium (EA(+)) and propylammonium (PA(+)) PILs, in contrast to their immiscibility with both water and ethanolammonium (EtA(+)) PILs. These binary mixtures are structured on two distinct length scales: one associated with the self-assembled n-alkanol aggregates and the other with the underlying liquid nanostructure. This suggests that EA(+) and PA(+) enable n-alkanol aggregation by acting as cosurfactants, which EtA(+) cannot do because its terminating hydroxyl renders the cation nonamphiphilic. The primary determining factor for miscibility and self-assembly is the ratio of alkyl chain lengths of the alkanol and PIL cation, modulated by the anion type. These results show how ILs can support the self-assembly of nontraditional amphiphiles and enable the creation of new forms of soft matter. PMID:25068766

  14. Self-assembled peptide nanostructures for functional materials.

    PubMed

    Ekiz, Melis Sardan; Cinar, Goksu; Khalily, Mohammad Aref; Guler, Mustafa O

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.

  15. A Precise Packing Sequence for Self-Assembled Convex Structures

    NASA Astrophysics Data System (ADS)

    Chen, Ting; Zhang, Zhenli; Glotzer, Sharon

    2007-03-01

    We present molecular simulations of the self-assembly of cone-shaped particles with patchy, attractive interactions[1,2]. Upon cooling from random initial conditions, we find that the cones self assemble into clusters and that clusters comprised of particular numbers of cones have a unique and precisely packed structure that is robust over a range of cone angles. These precise clusters form precise packing sequence that for small sizes is identical to that observed in evaporation-driven assembly of colloidal spheres. This sequence is reproduced and extended in simulations of two simple models of spheres self-assembling from random initial conditions subject to convexity constraints, and contains six of the most common virus capsid structures obtained in vivo including large chiral clusters, and a cluster that may correspond to several non- icosahedral, spherical virus capsid structures obtained in vivo. For prolate spheroidal convexity conditions, we demonstrate the formation of several prolate virus structures from self-assembling hard spheres[3]. [1] Chen T, Zhang ZL, Glotzer SC, PNAS, in press (http://xxx.lanl.gov/pdf/cond-mat/ 0608592) [2] Chen T, Zhang ZL, Glotzer SC, http://xxx.lanl.gov/pdf/cond-mat/0608613 [3] Chen T, Glotzer SC http://xxx.lanl.gov/pdf/q-bio.BM/0608040

  16. Multistep hierarchical self-assembly of chiral nanopore arrays

    PubMed Central

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

    2014-01-01

    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

  17. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; Southall, June; Cogdell, Richard J.; Novoderezhkin, Vladimir I.; Scholes, Gregory D.; van Grondelle, Rienk

    2016-02-01

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.

  18. Light harvesting in photonic crystals revisited: why do slow photons at the blue edge enhance absorption?

    PubMed

    Deparis, O; Mouchet, S R; Su, B-L

    2015-11-11

    Light harvesting enhancement by slow photons in photonic crystal catalysts or dye-sensitized solar cells is a promising approach for increasing the efficiency of photoreactions. This structural effect is exploited in inverse opal TiO2 photocatalysts by tuning the red edge of the photonic band gap to the TiO2 electronic excitation band edge. In spite of many experimental demonstrations, the slow photon effect is not fully understood yet. In particular, observed enhancement by tuning the blue edge has remained unexplained. Based on rigorous couple wave analysis simulations, we quantify light harvesting enhancement in terms of absorption increase at a specific wavelength (monochromatic UV illumination) or photocurrent increase (solar light illumination), with respect to homogeneous flat slab of equivalent material thickness. We show that the commonly accepted explanation relying on light intensity confinement in high (low) dielectric constant regions at the red (blue) edge is challenged in the case of TiO2 inverse opals because of the sub-wavelength size of the material skeleton. The reason why slow photons at the blue edge are also able to enhance light harvesting is the loose confinement of the field, which leads to significant resonantly enhanced field intensity overlap with the skeleton in both red and blue edge tuning cases, yet with different intensity patterns. PMID:26517229

  19. Molecular basis of photoprotection and control of photosynthetic light-harvesting.

    PubMed

    Pascal, Andrew A; Liu, Zhenfeng; Broess, Koen; van Oort, Bart; van Amerongen, Herbert; Wang, Chao; Horton, Peter; Robert, Bruno; Chang, Wenrui; Ruban, Alexander

    2005-07-01

    In order to maximize their use of light energy in photosynthesis, plants have molecules that act as light-harvesting antennae, which collect light quanta and deliver them to the reaction centres, where energy conversion into a chemical form takes place. The functioning of the antenna responds to the extreme changes in the intensity of sunlight encountered in nature. In shade, light is efficiently harvested in photosynthesis. However, in full sunlight, much of the energy absorbed is not needed and there are vitally important switches to specific antenna states, which safely dissipate the excess energy as heat. This is essential for plant survival, because it provides protection against the potential photo-damage of the photosynthetic membrane. But whereas the features that establish high photosynthetic efficiency have been highlighted, almost nothing is known about the molecular nature of the dissipative states. Recently, the atomic structure of the major plant light-harvesting antenna protein, LHCII, has been determined by X-ray crystallography. Here we demonstrate that this is the structure of a dissipative state of LHCII. We present a spectroscopic analysis of this crystal form, and identify the specific changes in configuration of its pigment population that give LHCII the intrinsic capability to regulate energy flow. This provides a molecular basis for understanding the control of photosynthetic light-harvesting.

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

    PubMed Central

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

    2013-01-01

    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

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

    NASA Astrophysics Data System (ADS)

    Krüger, T. P. J.; van Grondelle, R.

    2016-01-01

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

  2. Two Cyanobacterial Photoreceptors Regulate Photosynthetic Light Harvesting by Sensing Teal, Green, Yellow, and Red Light

    PubMed Central

    Wiltbank, Lisa B.

    2016-01-01

    ABSTRACT The genomes of many photosynthetic and nonphotosynthetic bacteria encode numerous phytochrome superfamily photoreceptors whose functions and interactions are largely unknown. Cyanobacterial genomes encode particularly large numbers of phytochrome superfamily members called cyanobacteriochromes. These have diverse light color-sensing abilities, and their functions and interactions are just beginning to be understood. One of the best characterized of these functions is the regulation of photosynthetic light-harvesting antenna composition in the cyanobacterium Fremyella diplosiphon by the cyanobacteriochrome RcaE in response to red and green light, a process known as chromatic acclimation. We have identified a new cyanobacteriochrome named DpxA that maximally senses teal (absorption maximum, 494 nm) and yellow (absorption maximum, 568 nm) light and represses the accumulation of a key light-harvesting protein called phycoerythrin, which is also regulated by RcaE during chromatic acclimation. Like RcaE, DpxA is a two-component system kinase, although these two photoreceptors can influence phycoerythrin expression through different signaling pathways. The peak responsiveness of DpxA to teal and yellow light provides highly refined color discrimination in the green spectral region, which provides important wavelengths for photosynthetic light harvesting in cyanobacteria. These results redefine chromatic acclimation in cyanobacteria and demonstrate that cyanobacteriochromes can coordinately impart sophisticated light color sensing across the visible spectrum to regulate important photosynthetic acclimation processes. PMID:26861023

  3. Metal-enhanced fluorescence of chlorophylls in light-harvesting complexes coupled to silver nanowires.

    PubMed

    Kowalska, Dorota; Krajnik, Bartosz; Olejnik, Maria; Twardowska, Magdalena; Czechowski, Nikodem; Hofmann, Eckhard; Mackowski, Sebastian

    2013-01-01

    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.

  4. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy.

    PubMed

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; Southall, June; Cogdell, Richard J; Novoderezhkin, Vladimir I; Scholes, Gregory D; van Grondelle, Rienk

    2016-02-09

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.

  5. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

    PubMed Central

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; Southall, June; Cogdell, Richard J.; Novoderezhkin, Vladimir I.; Scholes, Gregory D.; van Grondelle, Rienk

    2016-01-01

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy. PMID:26857477

  6. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

    DOE PAGESBeta

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; Southall, June; Cogdell, Richard J.; Novoderezhkin, Vladimir I.; Scholes, Gregory D.; van Grondelle, Rienk

    2016-02-09

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines themore » selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. In conclusion, we suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.« less

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    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.

  8. Light harvesting in photonic crystals revisited: why do slow photons at the blue edge enhance absorption?

    PubMed

    Deparis, O; Mouchet, S R; Su, B-L

    2015-11-11

    Light harvesting enhancement by slow photons in photonic crystal catalysts or dye-sensitized solar cells is a promising approach for increasing the efficiency of photoreactions. This structural effect is exploited in inverse opal TiO2 photocatalysts by tuning the red edge of the photonic band gap to the TiO2 electronic excitation band edge. In spite of many experimental demonstrations, the slow photon effect is not fully understood yet. In particular, observed enhancement by tuning the blue edge has remained unexplained. Based on rigorous couple wave analysis simulations, we quantify light harvesting enhancement in terms of absorption increase at a specific wavelength (monochromatic UV illumination) or photocurrent increase (solar light illumination), with respect to homogeneous flat slab of equivalent material thickness. We show that the commonly accepted explanation relying on light intensity confinement in high (low) dielectric constant regions at the red (blue) edge is challenged in the case of TiO2 inverse opals because of the sub-wavelength size of the material skeleton. The reason why slow photons at the blue edge are also able to enhance light harvesting is the loose confinement of the field, which leads to significant resonantly enhanced field intensity overlap with the skeleton in both red and blue edge tuning cases, yet with different intensity patterns.

  9. Cell differentiation on disk- and string-shaped hydrogels fabricated from Ca(2+) -responsive self-assembling peptides.

    PubMed

    Fukunaga, Kazuto; Tsutsumi, Hiroshi; Mihara, Hisakazu

    2016-11-01

    We recently developed a self-assembling peptide, E1Y9, that self-assembles into nanofibers and forms a hydrogel in the presence of Ca(2+) . E1Y9 derivatives conjugated with functional peptide sequences derived from extracellular matrices (ECMs) reportedly self-assemble into peptide nanofibers that enhance cell adhesion and differentiation. In this study, E1Y9/E1Y9-IKVAV-mixed hydrogels were constructed to serve as artificial ECMs that promote cell differentiation. E1Y9 and E1Y9-IKVAV co-assembled into networked nanofibers, and hydrogels with disk and string shapes were formed in response to Ca(2+) treatment. The neuronal differentiation of PC12 cells was facilitated on hydrogels of both shapes that contained the IKVAV motifs. Moreover, long neurites extended along the long axis of the string-shaped gel, suggesting that the structure of hydrogels of this shape can affect cellular orientation. Thus, E1Y9 hydrogels can potentially be used as artificial ECMs with desirable bioactivities and shapes that could be useful in tissue engineering applications. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 476-483, 2016.

  10. Clustering and self-assembly in colloidal systems

    NASA Astrophysics Data System (ADS)

    Smallenburg, F.

    2012-01-01

    A colloidal dispersion consists of small particles called colloids, typically tens of nanometers to a few micrometers in size, suspended in a solvent. Due to collisions with the much smaller particles in the solvent, colloids perform Brownian motion: randomly directed movements that cause the particles to diffuse through the system. In principle, this motion allow the system of particles to explore all configurations available to them, sampling all of phase space according to the Boltzmann distribution. Analogous to molecular and atomic systems, colloidal systems can form disordered gas and liquid phases, as well as more ordered phases such as crystals, liquid crystals, or finite-sized aggregates. Since the particles form these phases based purely on their interactions and the Brownian motion that results from thermal fluctuations in their solvent, the process of forming these ordered structures is called self-assembly. In this thesis, we study the self-assembly of a variety of colloidal systems. We attempt to determine what structures can be expected to form, investigate the order and stability of these phases, and examine the nucleation of self-assembled crystals. To do this, we make use of computers to simulate the behavior of colloidal particles in suspension. Depending on the system under consideration, we perform either Monte Carlo simulations or event-driven molecular dynamics. In particular, we study the self-assembly of particles of several shapes in external electric or magnetic fields, the phase behavior of hard colloidal cubes, and the phase diagrams of charged colloidal spheres with a constant surface potential. Furthermore, we investigate the nucleation of binary hard sphere mixtures, the self-assembly of colloidal particles in evaporating emulsion droplets, and the formation of colloidal micelles. Where possible, we compare our results with experimental findings in similar systems.

  11. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly.

    PubMed

    Moore, Tyler G; Garzon, Max H; Deaton, Russell J

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are "strong" assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly systems

  12. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly

    PubMed Central

    Moore, Tyler G.; Garzon, Max H.; Deaton, Russell J.

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are “strong” assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly

  13. Flexible Fabrication of Shape-Controlled Collagen Building Blocks for Self-Assembly of 3D Microtissues.

    PubMed

    Zhang, Xu; Meng, Zhaoxu; Ma, Jingyun; Shi, Yang; Xu, Hui; Lykkemark, Simon; Qin, Jianhua

    2015-08-12

    Creating artificial tissue-like structures that possess the functionality, specificity, and architecture of native tissues remains a big challenge. A new and straightforward strategy for generating shape-controlled collagen building blocks with a well-defined architecture is presented, which can be used for self-assembly of complex 3D microtissues. Collagen blocks with tunable geometries are controllably produced and released via a membrane-templated microdevice. The formation of functional microtissues by embedding tissue-specific cells into collagen blocks with expression of specific proteins is described. The spontaneous self-assembly of cell-laden collagen blocks into organized tissue constructs with predetermined configurations is demonstrated, which are largely driven by the synergistic effects of cell-cell and cell-matrix interactions. This new strategy would open up new avenues for the study of tissue/organ morphogenesis, and tissue engineering applications.

  14. Flexible Fabrication of Shape-Controlled Collagen Building Blocks for Self-Assembly of 3D Microtissues.

    PubMed

    Zhang, Xu; Meng, Zhaoxu; Ma, Jingyun; Shi, Yang; Xu, Hui; Lykkemark, Simon; Qin, Jianhua

    2015-08-12

    Creating artificial tissue-like structures that possess the functionality, specificity, and architecture of native tissues remains a big challenge. A new and straightforward strategy for generating shape-controlled collagen building blocks with a well-defined architecture is presented, which can be used for self-assembly of complex 3D microtissues. Collagen blocks with tunable geometries are controllably produced and released via a membrane-templated microdevice. The formation of functional microtissues by embedding tissue-specific cells into collagen blocks with expression of specific proteins is described. The spontaneous self-assembly of cell-laden collagen blocks into organized tissue constructs with predetermined configurations is demonstrated, which are largely driven by the synergistic effects of cell-cell and cell-matrix interactions. This new strategy would open up new avenues for the study of tissue/organ morphogenesis, and tissue engineering applications. PMID:25920010

  15. Self-assembling organic nanotubes with precisely defined, sub-nanometer pores: formation and mass transport characteristics.

    PubMed

    Gong, Bing; Shao, Zhifeng

    2013-12-17

    The transport of molecules and ions across nanometer-scaled pores, created by natural or artificial molecules, is a phenomenon of both fundamental and practical significance. Biological channels are the most remarkable examples of mass transport across membranes and demonstrate nearly exclusive selectivity and high efficiency with a diverse collection of molecules. These channels are critical for many basic biological functions, such as membrane potential, signal transduction, and osmotic homeostasis. If such highly specific and efficient mass transport or separation could be achieved with artificial nanostructures under controlled conditions, they could create revolutionary technologies in a variety of areas. For this reason, investigators from diverse disciplines have vigorously studied small nondeformable nanopores. The most exciting studies have focused on carbon nanotubes (CNTs), which have exhibited fast mass transport and high ion selectivity despite their very simple structure. However, the limitations of CNTs and the dearth of other small (≤2 nm) nanopores have severely hampered the systematic investigation of nanopore-mediated mass transport, which will be essential for designing artificial nanopores with desired functions en masse. Researchers can overcome the difficulties associated with CNT and other artificial pores by stacking macrocyclic building blocks with persistent shapes to construct tunable, self-assembling organic pores. This effort started when we discovered a highly efficient, one-pot macrocyclization process to efficiently prepare several classes of macrocycles with rigid backbones containing nondeformable cavities. Such macrocycles, if stacked atop one another, should lead to nanotubular assemblies with defined inner pores determined by their constituent macrocycles. One class of macrocycles with aromatic oligoamide backbones had a very high propensity for directional assembly, forming nanotubular structures containing nanometer and sub

  16. Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains

    NASA Astrophysics Data System (ADS)

    Mubeena, Shaikh; Chatterji, Apratim

    2015-03-01

    We report many different nanostructures which are formed when model nanoparticles of different sizes (diameter σn) are allowed to aggregate in a background matrix of semiflexible self-assembled polymeric wormlike micellar chains. The different nanostructures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nanoparticles. The different morphologies obtained are the result of an interplay of the available free volume, the elastic energy of deformation of polymers, the density (chemical potential) of the nanoparticles in the polymer matrix, and, of course, the ratio of the size of self-assembling nanoparticles and self-avoidance diameter of polymeric chains. We have used a hybrid semi-grand-canonical Monte Carlo simulation scheme to obtain the (nonequilibrium) phase diagram of the self-assembled nanostructures. We observe rodlike structures of nanoparticles which get self-assembled in the gaps between the nematically ordered chains, as well as percolating gel-like network of conjoined nanotubes. We also find a totally unexpected interlocked crystalline phase of nanoparticles and monomers, in which each crystal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the condition which leads to such interlocked crystal structure. We suggest experimental possibilities of how the results presented in this paper could be used to obtain different nanostructures in the laboratory.

  17. The Self-Made Puzzle: Integrating Self-Assembly and Pattern Formation Under Non-Random Genetic Regulation

    NASA Astrophysics Data System (ADS)

    Doursat, René

    On the one hand, research in self-assembling systems, whether natural or artificial, has traditionally focused on pre-existing components endowed with fixed shapes. Biological development, by contrast, dynamically creates new cells that acquire selective adhesion properties through differentiation induced by their neighborhood. On the other hand, pattern formation phenomena are generally construed as orderly states of activity on top of a continuous 2-D or 3-D substrate. Yet, again, the spontaneous patterning of an organism into domains of gene expression arises within a multicellular medium in perpetual expansion and reshaping. Finally, both phenomena are often thought in terms of stochastic events, whether mixed components that randomly collide in self-assembly, or spots and stripes that occur unpredictably from instabilities in pattern formation. Here too, these notions need significant revision if they are to be extended and applied to embryogenesis. Cells are not randomly mixed but pre-positioned where cell division occurs. Genetic identity domains are not randomly distributed but highly regulated in number and position. In this work, I present a computational model of program-mable and reproducible artificial morphogenesis that integrates self-assembly and pattern formation under the control of a nonrandom gene regulatory network. The specialized properties of cells (division, adhesion, migration) are determined by the gene expression domains to which they belong, while at the same time these domains further expand and segment into subdomains due to the self-assembly of specialized cells. Through this model, I also promote a new discipline, embryomorphic engineering to solve the paradox of "meta-designing" decentralized, autonomous systems.

  18. A Case Study of the Likes and Dislikes of DNA and RNA in Self-Assembly.

    PubMed

    Zuo, Hua; Wu, Siyu; Li, Mo; Li, Yulin; Jiang, Wen; Mao, Chengde

    2015-12-01

    Programmed self-assembly of nucleic acids (DNA and RNA) is an active research area as it promises a general approach for nanoconstruction. Whereas DNA self-assembly has been extensively studied, RNA self-assembly lags much behind. One strategy to boost RNA self-assembly is to adapt the methods of DNA self-assembly for RNA self-assembly because of the chemical and structural similarities of DNA and RNA. However, these two types of molecules are still significantly different. To enable the rational design of RNA self-assembly, a thorough examination of their likes and dislikes in programmed self-assembly is needed. The current work begins to address this task. It was found that similar, two-stranded motifs of RNA and DNA lead to similar, but clearly different nanostructures.

  19. Self-Assembled Epitaxial Au-Oxide Vertically Aligned Nanocomposites for Nanoscale Metamaterials.

    PubMed

    Li, Leigang; Sun, Liuyang; Gomez-Diaz, Juan Sebastian; Hogan, Nicki L; Lu, Ping; Khatkhatay, Fauzia; Zhang, Wenrui; Jian, Jie; Huang, Jijie; Su, Qing; Fan, Meng; Jacob, Clement; Li, Jin; Zhang, Xinghang; Jia, Quanxi; Sheldon, Matthew; Alù, Andrea; Li, Xiaoqin; Wang, Haiyan

    2016-06-01

    Metamaterials made of nanoscale inclusions or artificial unit cells exhibit exotic optical properties that do not exist in natural materials. Promising applications, such as super-resolution imaging, cloaking, hyperbolic propagation, and ultrafast phase velocities have been demonstrated based on mostly micrometer-scale metamaterials and few nanoscale metamaterials. To date, most metamaterials are created using costly and tedious fabrication techniques with limited paths toward reliable large-scale fabrication. In this work, we demonstrate the one-step direct growth of self-assembled epitaxial metal-oxide nanocomposites as a drastically different approach to fabricating large-area nanostructured metamaterials. Using pulsed laser deposition, we fabricated nanocomposite films with vertically aligned gold (Au) nanopillars (∼20 nm in diameter) embedded in various oxide matrices with high epitaxial quality. Strong, broad absorption features in the measured absorbance spectrum are clear signatures of plasmon resonances of Au nanopillars. By tuning their densities on selected substrates, anisotropic optical properties are demonstrated via angular dependent and polarization resolved reflectivity measurements and reproduced by full-wave simulations and effective medium theory. Our model predicts exotic properties, such as zero permittivity responses and topological transitions. Our studies suggest that these self-assembled metal-oxide nanostructures provide an exciting new material platform to control and enhance optical response at nanometer scales.

  20. Smart gating membranes with in situ self-assembled responsive nanogels as functional gates

    PubMed Central

    Luo, Feng; Xie, Rui; Liu, Zhuang; Ju, Xiao-Jie; Wang, Wei; Lin, Shuo; Chu, Liang-Yin

    2015-01-01

    Smart gating membranes, inspired by the gating function of ion channels across cell membranes, are artificial membranes composed of non-responsive porous membrane substrates and responsive gates in the membrane pores that are able to dramatically regulate the trans-membrane transport of substances in response to environmental stimuli. Easy fabrication, high flux, significant response and strong mechanical strength are critical for the versatility of such smart gating membranes. Here we show a novel and simple strategy for one-step fabrication of smart gating membranes with three-dimensionally interconnected networks of functional gates, by self-assembling responsive nanogels on membrane pore surfaces in situ during a vapor-induced phase separation process for membrane formation. The smart gating membranes with in situ self-assembled responsive nanogels as functional gates show large flux, significant response and excellent mechanical property simultaneously. Because of the easy fabrication method as well as the concurrent enhancement of flux, response and mechanical property, the proposed smart gating membranes will expand the scope of membrane applications, and provide ever better performances in their applications. PMID:26434387

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

    PubMed Central

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

    2013-01-01

    Biofabrication of living structures with desired topology and functionality requires the interdisciplinary effort of practitioners of the physical, life, medical and engineering sciences. Such efforts are being undertaken in many laboratories around the world. Numerous approaches are being pursued, such as those based on the use of natural or artificial scaffolds, decellularized cadaveric extracellular matrices and lately bioprinting. To be successful in this endeavor it is crucial to provide in vitro micro-environmental clues for the cells resembling those in the organism. Therefore scaffolds populated with differentiated cells or stem cells of increasing complexity and sophistication are being fabricated. However, scaffolds, no matter how sophisticated they are, can cause problems stemming from their degradation, eliciting immunogenic reactions and other a priori unforeseen complications. It is also being realized that ultimately the best approach is to rely on the self-assembly and self-organizing properties of cells and tissues and the innate regenerative capability of the organism itself, not just simply prepare tissue and organ structures in vitro followed by their implantation. Here we briefly review the different strategies for the fabrication of three-dimensional biological structures, in particular bioprinting. We detail a fully biological, scaffoldless, print-based engineering approach that uses self-assembling multicellular units as bioink particles and employs early developmental morphogenetic principles, such as cell sorting and tissue fusion. PMID:20811127

  2. Self-Assembled Epitaxial Au-Oxide Vertically Aligned Nanocomposites for Nanoscale Metamaterials.

    PubMed

    Li, Leigang; Sun, Liuyang; Gomez-Diaz, Juan Sebastian; Hogan, Nicki L; Lu, Ping; Khatkhatay, Fauzia; Zhang, Wenrui; Jian, Jie; Huang, Jijie; Su, Qing; Fan, Meng; Jacob, Clement; Li, Jin; Zhang, Xinghang; Jia, Quanxi; Sheldon, Matthew; Alù, Andrea; Li, Xiaoqin; Wang, Haiyan

    2016-06-01

    Metamaterials made of nanoscale inclusions or artificial unit cells exhibit exotic optical properties that do not exist in natural materials. Promising applications, such as super-resolution imaging, cloaking, hyperbolic propagation, and ultrafast phase velocities have been demonstrated based on mostly micrometer-scale metamaterials and few nanoscale metamaterials. To date, most metamaterials are created using costly and tedious fabrication techniques with limited paths toward reliable large-scale fabrication. In this work, we demonstrate the one-step direct growth of self-assembled epitaxial metal-oxide nanocomposites as a drastically different approach to fabricating large-area nanostructured metamaterials. Using pulsed laser deposition, we fabricated nanocomposite films with vertically aligned gold (Au) nanopillars (∼20 nm in diameter) embedded in various oxide matrices with high epitaxial quality. Strong, broad absorption features in the measured absorbance spectrum are clear signatures of plasmon resonances of Au nanopillars. By tuning their densities on selected substrates, anisotropic optical properties are demonstrated via angular dependent and polarization resolved reflectivity measurements and reproduced by full-wave simulations and effective medium theory. Our model predicts exotic properties, such as zero permittivity responses and topological transitions. Our studies suggest that these self-assembled metal-oxide nanostructures provide an exciting new material platform to control and enhance optical response at nanometer scales. PMID:27186652

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

    PubMed Central

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

    2012-01-01

    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. PMID:22355747

  4. Water-dispersible nanospheres of hydrogen-bonded supramolecular polymers and their application for mimicking light-harvesting systems.

    PubMed

    Peng, Hui-Qing; Xu, Jiang-Fei; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

    2014-02-01

    Water-dispersible nanospheres of hydrogen-bonded supramolecular polymers have been prepared for the first time by using the miniemulsion method. Nanospheres containing chromophores with high fluorescence quantum yields were fabricated to mimic the natural light-harvesting system.

  5. Self-assembly of hybrid structures on nano templates

    NASA Astrophysics Data System (ADS)

    Wang, Ruomiao

    This dissertation describes the investigation on the synthesis of hybrid structures on nano-templates. Fabrication of molecular nano-patterns of organic amphiphiles (e.g. fatty acids) by self-assembly has been discussed here, and their application as templates for two-dimensional in situ synthesis of metal soap molecular pattern has been demonstrated. The synthesis of nanoparticle---nanorod hybrid structure represents another effort to achieve hybrid materials. Therefore, methods to create complex inorganic---organic nano---hybrid are provided by this work. AFM disclosed the pattern structures of the self-assembled monolayers as designed nanoscaled patterns. It is observed two pattern periodicities reflecting the head-to-head and head-to-tail molecular assembly tendencies of the fatty acids and their dependence on the molecular structure and chain length, which exhibits a linear increase in the periodicity with an increasing molecular chain length. The investigation on molecular patterns of self-assembled monolayers of metal arachidates on graphite by AFM and FTIR is described. Metal arachidate self-assemblies show similar stripe pattern and periodicities as those of arachidic acid. The monolayer structure is mainly dictated by graphite, while the type of metal ions mainly affects the domain size, shape and regularity. The results of AFM and FTIR are correlated to the Irving-Williams Series, which predicts bond strength of the metal ions to ligands. The spin coated films from binary solutions of nanoparticles and fatty acids with different chain lengths (Even number of carbon, C18--C26), have been used to study the effect of nanoparticles on self-assemble pattern of fatty acids. C18--C22 acids formed uniform nanorods attached and induced by nanoparticles, while the self-assembled stripe patterns of C24 and C26 were unaffected by the presence of nanoparticles. The nanoparticles were aligned on C26 monolayer. The seeded nucleation mechanism has been studied by AFM

  6. Self assembled nanoparticle aggregates from line focused femtosecond laser ablation.

    PubMed

    Zuhlke, Craig A; Alexander, Dennis R; Bruce, John C; Ianno, Natale J; Kamler, Chad A; Yang, Weiqing

    2010-03-01

    In this paper we present the use of a line focused femtosecond laser beam that is rastered across a 2024 T3 aluminum surface to produce nanoparticles that self assemble into 5-60 micron diameter domed and in some cases sphere-shaped aggregate structures. Each time the laser is rastered over initial aggregates their diameter increases as new layers of nanoparticles self assemble on the surface. The aggregates are thus composed of layers of particles forming discrete layered shells inside of them. When micron size aggregates are removed, using an ultrasonic bath, rings are revealed that have been permanently formed in the sample surface. These rings appear underneath, and extend beyond the physical boundary of the aggregates. The surface is blackened by the formation of these structures and exhibits high light absorption. PMID:20389444

  7. Self Assembled Structures by Directional Solidification of Eutectics

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2004-01-01

    Interest in ordered porous structures has grown because of there unique properties such as photonic bandgaps, high backing packing density and high surface to volume ratio. Inspired by nature, biometric strategies using self assembled organic molecules dominate the development of hierarchical inorganic structures. Directional solidification of eutectics (DSE) also exhibit self assembly characteristics to form hierarchical metallic and inorganic structures. Crystallization of diphasic materials by DSE can produce two dimensional ordered structures consisting of rods or lamella. By selective removal of phases, DSE is capable to fabricate ordered pore arrays or ordered pin arrays. Criteria and limitations to fabricate hierarchical structures will be presented. Porous structures in silicon base alloys and ceramic systems will be reported.

  8. Stable doping of carbon nanotubes via molecular self assembly

    SciTech Connect

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

    2014-10-14

    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 ×10¹⁴cm⁻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.

  9. Protein-directed self-assembly of a fullerene crystal.

    PubMed

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B; Acharya, Rudresh; DeGrado, William F; Kim, Yong Ho; Grigoryan, Gevorg

    2016-04-26

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design.

  10. Directed self-assembly of nanoparticles for nanomotors.

    PubMed

    Dong, Bin; Zhou, Tian; Zhang, Hui; Li, Christopher Y

    2013-06-25

    We report, for the first time, the design and fabrication of a nanoparticle-based nanomotor system by directly self-assembling nanoparticles onto functional, nanometer-thin lamellae, such as polymer single crystals. Tens of thousands of judiciously selected nanoparticles (gold, iron oxide, and platinum nanoparticles) with sizes ranging from <5 to a few tens of nanometers have been introduced into a single nanomotor via directed self-assembly. The resulting nanomotor realizes functions such as autonomous movement, remote control, and cargo transportation by utilizing the advantages offered by nanoparticles, such as the small size, surface plasmon resonance, catalytic and magnetic properties. Because of the structural and functional versatility of nanoparticles, the facile fabricating procedure, and the potential for mass production, our strategy shows a key step toward the development of next generation multifunctional nanomotors.

  11. Self-assembly of amorphous calcium carbonate microlens arrays

    PubMed Central

    Lee, Kyubock; Wagermaier, Wolfgang; Masic, Admir; Kommareddy, Krishna P.; Bennet, Mathieu; Manjubala, Inderchand; Lee, Seung-Woo; Park, Seung B.; Cölfen, Helmut; Fratzl, Peter

    2012-01-01

    Biological materials are often based on simple constituents and grown by the principle of self-assembly under ambient conditions. In particular, biomineralization approaches exploit efficient pathways of inorganic material synthesis. There is still a large gap between the complexity of natural systems and the practical utilization of bioinspired formation mechanisms. Here we describe a simple self-assembly route leading to a CaCO3 microlens array, somewhat reminiscent of the brittlestars' microlenses, with uniform size and focal length, by using a minimum number of components and equipment at ambient conditions. The formation mechanism of the amorphous CaCO3 microlens arrays was elucidated by confocal Raman spectroscopic imaging to be a two-step growth process mediated by the organic surfactant. CaCO3 microlens arrays are easy to fabricate, biocompatible and functional in amorphous or more stable crystalline forms. This shows that advanced optical materials can be generated by a simple mineral precipitation. PMID:22395616

  12. Environmental and Sensing Applications of Molecular Self-Assembly

    SciTech Connect

    Fryxell, Glen E.; Addleman, Raymond S.; Mattigod, Shas V.; Lin, Yuehe; Zemanian, Thomas S.; Wu, Hong; Birnbaum, Jerome C.; Liu, J.; Feng, X.

    2004-03-31

    In the last decade we have witnessed many exciting new discoveries in the ability to manipulate and measure matter at the nanometer scale. Honeycombed pores structures, spheres, icosahedra, nanotubes and nanorods, self-assembled structural hierarchies; the esthetics of the nanometer regime offers Nature’s elegance in its purest form. Understanding the driving forces behind these shapes and the self-assembly processes provides key understanding for this chemistry to be exploited for positive impact on our daily lives. For this to take place, we must not only understand how the nanoscopic structures impact the structural and chemical properties of these novel new materials, but we must also understand the critical problems that we face today and how these nanoscopic properties can be tailored to address these specific needs and critical problems.

  13. Amphipathicity and self-assembly behavior of amphiphilic alginate esters.

    PubMed

    Yang, Ji Sheng; Zhou, Qi Quan; He, Wen

    2013-01-30

    Amphiphilic alginate esters (Alg-C(n)) with different degree of substitution (DS) and hydrophobic alkyl length were synthesized by the reaction between partially protonated sodium alginate and aliphatic alcohols (octanol, dodecanol or hexadecanol) and characterized by conventional methods. The critical micelles concentration (CMC) of Alg-C(n) was determined by measuring the fluorescence intensity of pyrene as a fluorescent probe, conductance and surface tension (SFT). Formation and characteristics of the self-assembly micelles of Alg-C(n) were studied by transmission electron microscopy (TEM) and Zetasizer Nano Series method. The results indicate that CMC value and the self-assembled micelle size decreased with the increasing of the hydrophobic alkyl chain length, as the DS of Alg-C(n) is similar.

  14. Self-Assembly of Graphene on Carbon Nanotube Surfaces

    PubMed Central

    Li, Kaiyuan; Eres, Gyula; Howe, Jane; Chuang, Yen-Jun; Li, Xufan; Gu, Zhanjun; Zhang, Litong; Xie, Sishen; Pan, Zhengwei

    2013-01-01

    The rolling up of a graphene sheet into a tube is a standard visualization tool for illustrating carbon nanotube (CNT) formation. However, the actual processes of rolling up graphene sheets into CNTs in laboratory syntheses have never been demonstrated. Here we report conformal growth of graphene by carbon self-assembly on single-wall and multi-wall CNTs using chemical vapor deposition (CVD) of methane without the presence of metal catalysts. The new graphene layers roll up into seamless coaxial cylinders encapsulating the existing CNTs, but their adhesion to the primary CNTs is weak due to the existence of lattice misorientation. Our study shows that graphene nucleation and growth by self-assembly of carbon on the inactive carbon basal plane of CNTs occurs by a new mechanism that is markedly different from epitaxial growth on metal surfaces, opening up the possibility of graphene growth on many other non-metal substrates by simple methane CVD. PMID:23912638

  15. Self-assembled and nanostructured siRNA delivery systems.

    PubMed

    Jeong, Ji Hoon; Park, Tae Gwan; Kim, Sun Hwa

    2011-09-01

    A wide range of organic and inorganic materials have been used in the development of nano-scale self-assembling gene delivery systems to improve the therapeutic efficacy of nucleic acid drugs. Small interfering RNA (siRNA) has recently been recognized as a promising and potent nucleic acid medicine for the treatment of incurable genetic disorders including cancer; however, siRNA-based therapeutics suffer from the same delivery problems as conventional nucleic acid drugs such as plasmid DNA and antisense oligonucleotides. Many of the delivery strategies developed for nucleic acid drugs have been applied to siRNA therapeutics, but they have not produced satisfactory in vivo gene silencing efficiencies to warrant clinical trials. This review discusses recent progress in the development of self-assembled and nanostructured delivery systems for efficient siRNA-induced gene silencing and their potential application in clinical settings. PMID:21424157

  16. Self-Assembled Magnetic Surface Swimmers: Theoretical Model

    NASA Astrophysics Data System (ADS)

    Aranson, Igor; Belkin, Maxim; Snezhko, Alexey

    2009-03-01

    The mechanisms of self-propulsion of living microorganisms are a fascinating phenomenon attracting enormous attention in the physics community. A new type of self-assembled micro-swimmers, magnetic snakes, is an excellent tool to model locomotion in a simple table-top experiment. The snakes self-assemble from a dispersion of magnetic microparticles suspended on the liquid-air interface and subjected to an alternating magnetic field. Formation and dynamics of these swimmers are captured in the framework of theoretical model coupling paradigm equation for the amplitude of surface waves, conservation law for the density of particles, and the Navier-Stokes equation for hydrodynamic flows. The results of continuum modeling are supported by hybrid molecular dynamics simulations of magnetic particles floating on the surface of fluid.

  17. Protein-directed self-assembly of a fullerene crystal

    NASA Astrophysics Data System (ADS)

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B.; Acharya, Rudresh; Degrado, William F.; Kim, Yong Ho; Grigoryan, Gevorg

    2016-04-01

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design.

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

    PubMed Central

    Wei, Alexander

    2007-01-01

    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

  19. Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules

    PubMed Central

    Parker, Richard M; Zhang, Jing; Zheng, Yu; Coulston, Roger J; Smith, Clive A; Salmon, Andrew R; Yu, Ziyi; Scherman, Oren A; Abell, Chris

    2015-01-01

    Supramolecular self-assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule-forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet interface by a complementary charged surfactant for subsequent supramolecular cross-linking via cucurbit[8]uril. This dynamic assembly process is employed to selectively form both hollow, ultrathin microcapsules and solid microparticles from a single solution. The ability to dictate the distribution of a mixture of charged copolymers within the microdroplet, as demonstrated by the single-step fabrication of distinct core–shell microcapsules, gives access to a new generation of innovative self-assembled constructs. PMID:26213532

  20. Self-Assembled Silicon Nanotubes under Supercritically Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Tang, Y. H.; Pei, L. Z.; Chen, Y. W.; Guo, C.

    2005-09-01

    Self-assembled silicon nanotubes with one-dimensional structure have been synthesized from silicon monoxide powder under supercritically hydrothermal conditions with a temperature of 470 °C and a pressure of 6.8 MPa. The silicon nanotubes were identified by transmission electron microscopy and high-resolution transmission electron microscopy. The results show that the silicon nanotubes (SiNT) have closed caps. The structures of the silicon nanotubes are hollow inner pore, crystalline silicon wall layers with a 0.31 nm interplanar spacing and 2-3 nm amorphous silica outer layers. Pure crystalline silicon nanotubes survive after etching the silicon nanotubes with 5% HF acid for enough time to imply that the self-assembled silicon nanotubes are stable. A possible theoretical reason for the growth of SiNTs from SiO under supercritically hydrothermal conditions was also proposed.

  1. Linker-Mediated Self-Assembly Dynamics of Charged Nanoparticles.

    PubMed

    Lin, Guanhua; Chee, See Wee; Raj, Sanoj; Král, Petr; Mirsaidov, Utkur

    2016-08-23

    Using in situ liquid cell transmission electron microscopy (TEM), we visualized a stepwise self-assembly of surfactant-coated and hydrated gold nanoparticles (NPs) into linear chains or branched networks. The NP binding is facilitated by linker molecules, ethylenediammonium, which form hydrogen bonds with surfactant molecules of neighboring NPs. The observed spacing between bound neighboring NPs, ∼15 Å, matches the combined length of two surfactants and one linker molecule. Molecular dynamics simulations reveal that for lower concentrations of linkers, NPs with charged surfactants cannot be fully neutralized by strongly binding divalent linkers, so that NPs carry higher effective charges and tend to form chains, due to poor screening. The highly polar NP surfaces polarize and partly immobilize nearby water molecules, which promotes NPs binding. The presented experimental and theoretical approach allows for detail observation and explanation of self-assembly processes in colloidal nanosystems. PMID:27494560

  2. Self-assembled photonic crystals for a chemical sensing

    NASA Astrophysics Data System (ADS)

    Bourdillon, C.; Gam Derouich, S.; Daney de Marcillac, W.; Coolen, L.; Maître, A.; Mangeney, C.; Schwob, C.

    2016-03-01

    As they allow the control of light propagation, photonic crystals find many fields of application. Among them, self-assembled 3D-photonic crystals are ordered at the nanometric scale over centrimetric areas. Furthermore, self-assembly allows the design of complexes structures leading, for example, to the controlled disruption of the crystal periodicity (called defect) and the appearance of permitted optical frequency bands within the photonic bandgap. Light frequencies included in the corresponding passband are then localized in the defect allowing manipulation of nano-emitters fluorescence. We present the fabrication and the optical characterization of a heterostructure composed of a sputtered silica layer sandwiched between two silica opals. We show by photoluminescence measurements than this structure strongly modifies the transmitted fluorescence of nanocrystals.

  3. Biomolecular decision-making process for self assembly.

    SciTech Connect

    Osbourn, Gordon Cecil

    2005-01-01

    The brain is often identified with decision-making processes in the biological world. In fact, single cells, single macromolecules (proteins) and populations of molecules also make simple decisions. These decision processes are essential to survival and to the biological self-assembly and self-repair processes that we seek to emulate. How do these tiny systems make effective decisions? How do they make decisions in concert with a cooperative network of other molecules or cells? How can we emulate the decision-making behaviors of small-scale biological systems to program and self-assemble microsystems? This LDRD supported research to answer these questions. Our work included modeling and simulation of protein populations to help us understand, mimic, and categorize molecular decision-making mechanisms that nonequilibrium systems can exhibit. This work is an early step towards mimicking such nanoscale and microscale biomolecular decision-making processes in inorganic systems.

  4. Self-assembly of nanomaterials at fluid interfaces.

    PubMed

    Toor, Anju; Feng, Tao; Russell, Thomas P

    2016-05-01

    Recent developments in the field of the self-assembly of nanoscale materials such as nanoparticles, nanorods and nanosheets at liquid/liquid interfaces are reviewed. Self-assembly behavior of both biological and synthetic particles is discussed. For biological nanoparticles, the nanoparticle assembly at fluid interfaces provides a simple route for directing nanoparticles into 2D or 3D constructs with hierarchical ordering. The interfacial assembly of single-walled carbon nanotubes (SWCNTs) at liquid interfaces would play a key role in applications such as nanotube fractionation, flexible electronic thin-film fabrication and synthesis of porous SWCNT/polymer composites foams. Liquids can be structured by the jamming of nanoparticle surfactants at fluid interfaces. By controlling the interfacial packing of nanoparticle surfactants using external triggers, a new class of materials can be generated that combines the desirable characteristics of fluids such as rapid transport of energy carriers with the structural stability of a solid. PMID:27233643

  5. Self-assembly of graphene on carbon nanotube surfaces.

    PubMed

    Li, Kaiyuan; Eres, Gyula; Howe, Jane; Chuang, Yen-Jun; Li, Xufan; Gu, Zhanjun; Zhang, Litong; Xie, Sishen; Pan, Zhengwei

    2013-01-01

    The rolling up of a graphene sheet into a tube is a standard visualization tool for illustrating carbon nanotube (CNT) formation. However, the actual processes of rolling up graphene sheets into CNTs in laboratory syntheses have never been demonstrated. Here we report conformal growth of graphene by carbon self-assembly on single-wall and multi-wall CNTs using chemical vapor deposition (CVD) of methane without the presence of metal catalysts. The new graphene layers roll up into seamless coaxial cylinders encapsulating the existing CNTs, but their adhesion to the primary CNTs is weak due to the existence of lattice misorientation. Our study shows that graphene nucleation and growth by self-assembly of carbon on the inactive carbon basal plane of CNTs occurs by a new mechanism that is markedly different from epitaxial growth on metal surfaces, opening up the possibility of graphene growth on many other non-metal substrates by simple methane CVD. PMID:23912638

  6. Intrinsic universality and the computational power of self-assembly.

    PubMed

    Woods, Damien

    2015-07-28

    Molecular self-assembly, the formation of large structures by small pieces of matter sticking together according to simple local interactions, is a ubiquitous phenomenon. A challenging engineering goal is to design a few molecules so that large numbers of them can self-assemble into desired complicated target objects. Indeed, we would like to understand the ultimate capabilities and limitations of this bottom-up fabrication process. We look to theoretical models of algorithmic self-assembly, where small square tiles stick together according to simple local rules in order to carry out a crystal growth process. In this survey, we focus on the use of simulation between such models to classify and separate their computational and expressive powers. Roughly speaking, one model simulates another if they grow the same structures, via the same dynamical growth processes. Our journey begins with the result that there is a single intrinsically universal tile set that, with appropriate initialization and spatial scaling, simulates any instance of Winfree's abstract Tile Assembly Model. This universal tile set exhibits something stronger than Turing universality: it captures the geometry and dynamics of any simulated system in a very direct way. From there we find that there is no such tile set in the more restrictive non-cooperative model, proving it weaker than the full Tile Assembly Model. In the two-handed model, where large structures can bind together in one step, we encounter an infinite set of infinite hierarchies of strictly increasing simulation power. Towards the end of our trip, we find one tile to rule them all: a single rotatable flipable polygonal tile that simulates any tile assembly system. We find another tile that aperiodically tiles the plane (but with small gaps). These and other recent results show that simulation is giving rise to a kind of computational complexity theory for self-assembly. It seems this could be the beginning of a much longer journey

  7. Lighting up cells with lanthanide self-assembled helicates

    PubMed Central

    Bünzli, Jean-Claude G.

    2013-01-01

    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

  8. Sequential programmable self-assembly: Role of cooperative interactions

    DOE PAGESBeta

    Jonathan D. Halverson; Tkachenko, Alexei V.

    2016-03-04

    Here, we propose a general strategy of “sequential programmable self-assembly” that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenientmore » platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call “DNA spider,” that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a “GEOMAG” magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.« less

  9. Design of Controllable Bio-Inspired Chiroptic Self-Assemblies.

    PubMed

    Tao, Kai; Jacoby, Guy; Burlaka, Luba; Beck, Roy; Gazit, Ehud

    2016-09-12

    Modulation of chiroptics, chiral phenomena of the optical properties, is pivotal in a variety of advanced applications, including chirality-specific biosensing and photonic switches. One of the most effective methods for achieving this control is assembly of the optical moieties into chiral nanostructures. Lipopeptide self-assemblies have been extensively employed as soft templates to organize composites into low-dimensional superstructures due to their rigidity and ease of functionalization. Therefore, an appealing approach is to provide chiroptical control by using lipopeptide self-assemblies as templates to assemble chromophores. Herein, two lipopeptidic molecules, namely, C14-FFK and C14-FK, composed of phenylalanine and lysine residues conjugated to a myristic acid chain, were custom-designed. Spectroscopic and microscopic characterizations indicated that C14-FFK self-assembled to wide, slightly left-handed nanoribbons, while C14-FK formed narrow, intensely right-handed nanofibers. The different chirality was derived from the distinct self-assembly driving forces, especially the molecular bending dimensions. These superstructures presented an ideal capability to serve as soft templates to assemble porphyrin (ZnTPyP) through noncovalent electrostatic attractive interactions, or assemble the phenolic groups through covalent conjugation to peptide backbones. The distinct exciton coupling of the chromophores allowed their achiral optics to become chiral, showing negative Cotton effect when templated by nanoribbons and positive Cotton effect with nanofibers as templates. Following replacement of the lipopeptides with their d-type enantiomers, the handedness of the superstructures and the associated chiroptics were reversed and presented "mirror" symmetric CD signals to their l-type counterparts. These findings may pave the way to the formation of morphologically and chioptically controllable nanomaterials. PMID:27461453

  10. Recent progress on patchy colloids and their self-assembly

    NASA Astrophysics Data System (ADS)

    Yi, Gi-Ra; Pine, David J.; Sacanna, Stefano

    2013-05-01

    ‘Patchy colloids’ is a term that has been recently introduced to indicate specially engineered particles with directional interactions. Based on this concept, a ‘bottom-up’ process for fabricating functional materials and devices has been envisioned, which employs colloidal building blocks and mimics molecular bonding. This article reviews recent progress which has been made in the synthesis and self-assembly of patchy colloids and discusses future directions as well as unresolved challenges.

  11. Controlling guest-host interactions in self-assembled materials

    NASA Astrophysics Data System (ADS)

    Steinbeck, Christian Alexander

    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

  12. The position of hydrophobic residues tunes peptide self-assembly.

    PubMed

    Bortolini, Christian; Liu, Lei; Gronewold, Thomas M A; Wang, Chen; Besenbacher, Flemming; Dong, Mingdong

    2014-08-21

    The final structure and properties of synthetic peptides mainly depend on their sequence composition and experimental conditions. This work demonstrates that a variation in the positions of hydrophobic residues within a peptide sequence can tune the self-assembly. Techniques employed are atomic force microscopy, transmission electron microscopy and an innovative method based on surface acoustic waves. In addition, a systematic investigation on pH dependence was carried out by utilizing constant experimental parameters. PMID:24995505

  13. Self-assembly of double helical nanostructures inside carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Lv, Cheng; Xue, Qingzhong; Shan, Meixia; Jing, Nuannuan; Ling, Cuicui; Zhou, Xiaoyan; Jiao, Zhiyong; Xing, Wei; Yan, Zifeng

    2013-05-01

    We use molecular dynamics (MD) simulations to show that a DNA-like double helix of two poly(acetylene) (PA) chains can form inside single-walled carbon nanotubes (SWNTs). The computational results indicate that SWNTs can activate and guide the self-assembly of polymer chains, allowing them to adopt a helical configuration in a SWNT through the combined action of the van der Waals potential well and the π-π stacking interaction between the polymer and the inner surface of SWNTs. Meanwhile both the SWNT size and polymer chain stiffness determine the outcome of the nanostructure. Furthermore, we also found that water clusters encourage the self-assembly of PA helical structures in the tube. This molecular model may lead to a better understanding of the formation of a double helix biological molecule inside SWNTs. Alternatively, it could form the basis of a novel nanoscale material by utilizing the `empty' spaces of SWNTs.We use molecular dynamics (MD) simulations to show that a DNA-like double helix of two poly(acetylene) (PA) chains can form inside single-walled carbon nanotubes (SWNTs). The computational results indicate that SWNTs can activate and guide the self-assembly of polymer chains, allowing them to adopt a helical configuration in a SWNT through the combined action of the van der Waals potential well and the π-π stacking interaction between the polymer and the inner surface of SWNTs. Meanwhile both the SWNT size and polymer chain stiffness determine the outcome of the nanostructure. Furthermore, we also found that water clusters encourage the self-assembly of PA helical structures in the tube. This molecular model may lead to a better understanding of the formation of a double helix biological molecule inside SWNTs. Alternatively, it could form the basis of a novel nanoscale material by utilizing the `empty' spaces of SWNTs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33157h

  14. Ultrathin efficient perovskite solar cells employing a periodic structure of a composite hole conductor for elevated plasmonic light harvesting and hole collection

    NASA Astrophysics Data System (ADS)

    Long, Mingzhu; Chen, Zefeng; Zhang, Tiankai; Xiao, Yubin; Zeng, Xiaoliang; Chen, Jian; Yan, Keyou; Xu, Jianbin

    2016-03-01

    We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure composite (PMC) HTM in combination with the conformal Au electrode could promote the absorption through the enhanced cavity effects, leading to comparable absorption even using much thinner perovskite (240 nm). We identified that the cavity was the combination of Fabry-Pérot interferometer and surface plasmonic resonance, with light harvesting enhancement through surface plasmon polariton or waveguide modes that propagate in the plane of the perovskite layer. On the other hand, the PMC HTM increased hole conductivity by one order of magnitude with respect to standard spiro-OMeTAD HTM due to molecular packing and self-assembly, embodying traceable hole mobility and density elevation up to 3 times, and thus the hysteresis was greatly avoided. Owing to dual optical and electronic enhancement, the PMC PSC afforded high efficiency PSC using as thin as 240 nm perovskite layer, delivering a Voc of 1.05 V, Jsc of 22.9 mA cm-2, FF of 0.736, and efficiency amounting to 17.7% PCE, the highest efficiency with ultrathin perovskite layer.We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure

  15. Self-assembled amyloid fibrils with controllable conformational heterogeneity

    PubMed Central

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  16. Self-assembled amyloid fibrils with controllable conformational heterogeneity.

    PubMed

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  17. Self-assembled magnetic filter for highly efficient immunomagnetic separation.

    PubMed

    Issadore, David; Shao, Huilin; Chung, Jaehoon; Newton, Andita; Pittet, Mikael; Weissleder, Ralph; Lee, Hakho

    2011-01-01

    We have developed a compact and inexpensive microfluidic chip, the self-assembled magnetic filter, to efficiently remove magnetically tagged cells from suspension. The self-assembled magnetic filter consists of a microfluidic channel built directly above a self-assembled NdFeB magnet. Micrometre-sized grains of NdFeB assemble to form alternating magnetic dipoles, creating a magnetic field with a very strong magnitude B (from the material) and field gradient ▽B (from the configuration) in the microfluidic channel. The magnetic force imparted on magnetic beads is measured to be comparable to state-of-the-art microfabricated magnets, allowing for efficient separations to be performed in a compact, simple device. The efficiency of the magnetic filter is characterized by sorting non-magnetic (polystyrene) beads from magnetic beads (iron oxide). The filter enriches the population of non-magnetic beads to magnetic beads by a factor of >10(5) with a recovery rate of 90% at 1 mL h(-1). The utility of the magnetic filter is demonstrated with a microfluidic device that sorts tumor cells from leukocytes using negative immunomagnetic selection, and concentrates the tumor cells on an integrated membrane filter for optical detection. PMID:20949198

  18. Self-assembled polymer nanocomposites and their networks

    NASA Astrophysics Data System (ADS)

    Patil, Nitin Vikas

    This dissertation describes new routes to synthesize polymer nanocomposite networks via self-assembly. Polymerizable structure directing agents (referred to as surfmers) obtained by end-group functionalization preserves the structure-directing capabilities of the surfactant for templating ordered mesoporous silica particle growth, while simultaneously generating a reactive matrix for polymer network formation through reactive end groups in the presence of intimately mixed mesoporous silicates. A combination of small angle X-ray scattering, surface area, and microscopy experiments on mesoporous silica indicated the structure directing capabilities of surfmers. Free-radical polymerization of the surfmer leads to novel crosslinked nanocomposites networks. Multiple experiments, including gel permeation chromatography, swelling, and solid state NMR experiments on polymer nanocomposites gave evidence of the polymerization of surfmer leading to formation of crosslink networks. Polymer nanocomposites with varied silica content were prepared. Effects of silica content on polymer nanocomposites were studied on rheometer. Results obtained from rheological experiments indicate that the storage (G') and loss modulus (G") increases with increase in the content of mesoporous silica. In this way, the nanocomposites networks obtained via self-assembly shows independent behavior with respect to frequency in rheological experiments. Additionally, this self-assembled route was extended to synthesize biodegradable and biocompatible polymer nanocomposites networks. The nanocomposite networks obtained with 15% of silica content showed the increase in storage modulus by two orders of magnitude in rheological experiments.

  19. Engineering hierarchical nanostructures by elastocapillary self-assembly.

    PubMed

    De Volder, Michaël; Hart, A John

    2013-02-25

    Surfaces coated with nanoscale filaments such as silicon nanowires and carbon nanotubes are potentially compelling for high-performance battery and capacitor electrodes, photovoltaics, electrical interconnects, substrates for engineered cell growth, dry adhesives, and other smart materials. However, many of these applications require a wet environment or involve wet processing during their synthesis. The capillary forces introduced by these wet environments can lead to undesirable aggregation of nanoscale filaments, but control of capillary forces can enable manipulation of the filaments into discrete aggregates and novel hierarchical structures. Recent studies suggest that the elastocapillary self-assembly of nanofilaments can be a versatile and scalable means to build complex and robust surface architectures. To enable a wider understanding and use of elastocapillary self-assembly as a fabrication technology, we give an overview of the underlying fundamentals and classify typical implementations and surface designs for nanowires, nanotubes, and nanopillars made from a wide variety of materials. Finally, we discuss exemplary applications and future opportunities to realize new engineered surfaces by the elastocapillary self-assembly of nanofilaments. PMID:23339106

  20. Evolutionary dynamics in a simple model of self-assembly

    NASA Astrophysics Data System (ADS)

    Johnston, Iain G.; Ahnert, Sebastian E.; Doye, Jonathan P. K.; Louis, Ard A.

    2011-06-01

    We investigate the evolutionary dynamics of an idealized model for the robust self-assembly of two-dimensional structures called polyominoes. The model includes rules that encode interactions between sets of square tiles that drive the self-assembly process. The relationship between the model’s rule set and its resulting self-assembled structure can be viewed as a genotype-phenotype map and incorporated into a genetic algorithm. The rule sets evolve under selection for specified target structures. The corresponding complex fitness landscape generates rich evolutionary dynamics as a function of parameters such as the population size, search space size, mutation rate, and method of recombination. Furthermore, these systems are simple enough that in some cases the associated model genome space can be completely characterized, shedding light on how the evolutionary dynamics depends on the detailed structure of the fitness landscape. Finally, we apply the model to study the emergence of the preference for dihedral over cyclic symmetry observed for homomeric protein tetramers.

  1. Size-controlled self-assembly of superparamagnetic polymersomes.

    PubMed

    Hickey, Robert J; Koski, Jason; Meng, Xin; Riggleman, Robert A; Zhang, Peijun; Park, So-Jung

    2014-01-28

    We report the size-controlled self-assembly of polymersomes through the cooperative self-assembly of nanoparticles and amphiphilic polymers. Polymersomes densely packed with magnetic nanoparticles in the polymersome membrane (magneto-polymersome) were fabricated with a series of different sized iron oxide nanoparticles. The distribution of nanoparticles in a polymersome membrane was size-dependent; while small nanoparticles were dispersed in a polymer bilayer, large particles formed a well-ordered superstructure at the interface between the inner and outer layer of a bilayer membrane. The yield of magneto-polymersomes increased with increasing the diameter of incorporated nanoparticles. Moreover, the size of the polymersomes was effectively controlled by varying the size of incorporated nanoparticles. This size-dependent self-assembly was attributed to the polymer chain entropy effect and the size-dependent localization of nanoparticles in polymersome bilayers. The transverse relaxation rates (r2) of magneto-polymersomes increased with increasing the nanoparticle diameter and decreasing the size of polymersomes, reaching 555 ± 24 s(-1) mM(-1) for 241 ± 16 nm polymersomes, which is the highest value reported to date for superparamagnetic iron oxide nanoparticles.

  2. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    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.

  3. Patterning self-assembled FePt nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Min; Nikles, David E.; Yin, Huaqin; Wang, Shoutao; Harrell, J. W.; Majetich, Sara A.

    2003-10-01

    We describe a potential way to extend the ordered domain of self-assembled FePt nanoparticles. The FePt particles, with an average diameter of 3 nm, were prepared by simultaneous thermal decomposition of Fe(CO) 5 and chemical reduction of Pt(acac) 2 and then were dispersed in a mixture of hexane and octane. When self-assembling on a plain silicon wafer, FePt nanoparticles formed ordered hexagonal arrays in a range of tens to a few hundred nanometers. A silicon wafer with patterned holes of a photoresist film, made using UV-lithographing technique, was used as a template to direct the stacking direction of the FePt nanoparticles. The FePt dispersion was dropped on the patterned holes of the photoresist film. After being heat-treated at 100°C for 30 min under vacuum condition, the photoresist was stripped out by dipping the sample in acetone. The patterned disks, with an average diameter of 2.0 μm and a height of 250 nm, of self-assembled FePt nanoparticles were examined using SEM and Auger mapping. Their magnetic properties were measured using AGM. The Auger electrons of neither Fe LMM nor Pt MNN could be detected from the sample, which indicated the adsorption of oleic acid and oleylamine on the surface of FePt nanoparticles. The coercivity of patterned FePt significantly increased with the annealing temperature above 600°C.

  4. Dynamic self-assembly and control of microfluidic particle crystals

    PubMed Central

    Lee, Wonhee; Amini, Hamed; Stone, Howard A.; Di Carlo, Dino

    2010-01-01

    Engineered two-phase microfluidic systems have recently shown promise for computation, encryption, and biological processing. For many of these systems, complex control of dispersed-phase frequency and switching is enabled by nonlinearities associated with interfacial stresses. Introducing nonlinearity associated with fluid inertia has recently been identified as an easy to implement strategy to control two-phase (solid-liquid) microscale flows. By taking advantage of inertial effects we demonstrate controllable self-assembling particle systems, uncover dynamics suggesting a unique mechanism of dynamic self-assembly, and establish a framework for engineering microfluidic structures with the possibility of spatial frequency filtering. Focusing on the dynamics of the particle–particle interactions reveals a mechanism for the dynamic self-assembly process; inertial lift forces and a parabolic flow field act together to stabilize interparticle spacings that otherwise would diverge to infinity due to viscous disturbance flows. The interplay of the repulsive viscous interaction and inertial lift also allow us to design and implement microfluidic structures that irreversibly change interparticle spacing, similar to a low-pass filter. Although often not considered at the microscale, nonlinearity due to inertia can provide a platform for high-throughput passive control of particle positions in all directions, which will be useful for applications in flow cytometry, tissue engineering, and metamaterial synthesis. PMID:21149674

  5. Molecular pathways for defect annihilation in directed self-assembly.

    PubMed

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A; Li, Weihua; Müller, Marcus; Nealey, Paul F; de Pablo, Juan J

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm(2). In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales-a handful of nanometers-and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  6. Equilibrium self-assembly of small RNA viruses

    NASA Astrophysics Data System (ADS)

    Bruinsma, R. F.; Comas-Garcia, M.; Garmann, R. F.; Grosberg, A. Y.

    2016-03-01

    We propose a description for the quasiequilibrium self-assembly of small, single-stranded (ss) RNA viruses whose capsid proteins (CPs) have flexible, positively charged, disordered tails that associate with the negatively charged RNA genome molecules. We describe the assembly of such viruses as the interplay between two coupled phase-transition-like events: the formation of the protein shell (the capsid) by CPs and the condensation of a large ss viral RNA molecule. Electrostatic repulsion between the CPs competes with attractive hydrophobic interactions and attractive interaction between neutralized RNA segments mediated by the tail groups. An assembly diagram is derived in terms of the strength of attractive interactions between CPs and between CPs and the RNA molecules. It is compared with the results of recent studies of viral assembly. We demonstrate that the conventional theory of self-assembly, which does describe the assembly of empty capsids, is in general not applicable to the self-assembly of RNA-encapsidating virions.

  7. Equilibrium self-assembly of small RNA viruses.

    PubMed

    Bruinsma, R F; Comas-Garcia, M; Garmann, R F; Grosberg, A Y

    2016-03-01

    We propose a description for the quasiequilibrium self-assembly of small, single-stranded (ss) RNA viruses whose capsid proteins (CPs) have flexible, positively charged, disordered tails that associate with the negatively charged RNA genome molecules. We describe the assembly of such viruses as the interplay between two coupled phase-transition-like events: the formation of the protein shell (the capsid) by CPs and the condensation of a large ss viral RNA molecule. Electrostatic repulsion between the CPs competes with attractive hydrophobic interactions and attractive interaction between neutralized RNA segments mediated by the tail groups. An assembly diagram is derived in terms of the strength of attractive interactions between CPs and between CPs and the RNA molecules. It is compared with the results of recent studies of viral assembly. We demonstrate that the conventional theory of self-assembly, which does describe the assembly of empty capsids, is in general not applicable to the self-assembly of RNA-encapsidating virions.

  8. Self-assembly of lipopolysaccharide layers on allantoin crystals.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Jiang, Qiu Zhen; Gagnon, Pete

    2014-08-01

    Self-assembly of lipopolysaccharides (LPS) on solid surfaces is important for the study of bacterial membranes, but has not been possible due to technical difficulties and the lack of suitable solid supports. Recently we found that crystals of the natural compound allantoin selectively bind pure LPS with sub-nanomolar affinity. The physicochemical origins of this selectivity and the adsorption mode of LPS on allantoin crystals remain, however, unknown. In this study we present evidence that LPS adsorption on allantoin crystals is initiated through hydrogen-bond attachment of hydrophilic LPS regions. Hydrophobic interactions between alkyl chains of adjacently adsorbed LPS molecules subsequently promote self-assembly of LPS layers. The essential role of hydrogen-bond interactions is corroborated by our finding that allantoin crystals bind to practically any hydrophilic surface chemistry. Binding contributions of hydrophobic interactions between LPS alkyl chains are evidenced by the endothermic nature of the adsorption process and explain why the binding affinity for LPS is several orders of magnitude higher than for proteins (lysozyme, BSA and IgG) and polysaccharides. Self-assembly of LPS layers via hydrogen-bond attachment on allantoin crystals emerges as a novel binding mechanism and could be considered as a practical method for preparing biomimetic membranes on a solid support.

  9. Molecular pathways for defect annihilation in directed self-assembly.

    DOE PAGESBeta

    Hur, Su-Mi; Thapar, Vikram; Ramirez-Hernandez, Abelardo; Khaira, Gurdaman S.; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Muller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free-energymore » barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers, how they depend on material characteristics, and we propose strategies designed to over-come them. The validity of our conclusions for industrially-relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales - a handful of nanometers -, and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail.« less

  10. Molecular pathways for defect annihilation in directed self-assembly.

    SciTech Connect

    Hur, Su-Mi; Thapar, Vikram; Ramirez-Hernandez, Abelardo; Khaira, Gurdaman S.; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Muller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free-energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers, how they depend on material characteristics, and we propose strategies designed to over-come them. The validity of our conclusions for industrially-relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales - a handful of nanometers -, and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail.

  11. Directed self-assembly of a colloidal kagome lattice.

    PubMed

    Chen, Qian; Bae, Sung Chul; Granick, Steve

    2011-01-20

    A challenging goal in materials chemistry and physics is spontaneously to form intended superstructures from designed building blocks. In fields such as crystal engineering and the design of porous materials, this typically involves building blocks of organic molecules, sometimes operating together with metallic ions or clusters. The translation of such ideas to nanoparticles and colloidal-sized building blocks would potentially open doors to new materials and new properties, but the pathways to achieve this goal are still undetermined. Here we show how colloidal spheres can be induced to self-assemble into a complex predetermined colloidal crystal-in this case a colloidal kagome lattice-through decoration of their surfaces with a simple pattern of hydrophobic domains. The building blocks are simple micrometre-sized spheres with interactions (electrostatic repulsion in the middle, hydrophobic attraction at the poles, which we call 'triblock Janus') that are also simple, but the self-assembly of the spheres into an open kagome structure contrasts with previously known close-packed periodic arrangements of spheres. This open network is of interest for several theoretical reasons. With a view to possible enhanced functionality, the resulting lattice structure possesses two families of pores, one that is hydrophobic on the rims of the pores and another that is hydrophilic. This strategy of 'convergent' self-assembly from easily fabricated colloidal building blocks encodes the target supracolloidal architecture, not in localized attractive spots but instead in large redundantly attractive regions, and can be extended to form other supracolloidal networks.

  12. Spectroscopic critical dimension technology (SCD) for directed self assembly

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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.

  13. Molecular pathways for defect annihilation in directed self-assembly

    PubMed Central

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Müller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-01-01

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales—a handful of nanometers—and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  14. Chiral Perylene Materials by Ionic Self-Assembly.

    PubMed

    Echue, Geraldine; Hamley, Ian; Lloyd Jones, Guy C; Faul, Charl F J

    2016-09-01

    Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV-vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure-function relationship is easily explored here due to the wide selection and easy availability of common surfactants. PMID:27486788

  15. Self-assembly of strongly dipolar molecules on metal surfaces

    NASA Astrophysics Data System (ADS)

    Kunkel, Donna A.; Hooper, James; Simpson, Scott; Miller, Daniel P.; Routaboul, Lucie; Braunstein, Pierre; Doudin, Bernard; Beniwal, Sumit; Dowben, Peter; Skomski, Ralph; Zurek, Eva; Enders, Axel

    2015-03-01

    The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(⋯ NHR)2(⋯ O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings.

  16. Enhanced photoluminescence by tyrosine-containing bolaamphiphile self-assembly.

    PubMed

    Kwak, Jinyoung; Lee, Sang-Yup

    2013-04-01

    Photoluminescent spherical nanostructures were prepared through the self-assembly of a tyrosine-containing bolaamphiphilic molecule, and their antenna effect was examined. The photoluminescent spherical nanostructures were simply prepared by self-assembly of bolaamphiphile molecules in an aqueous solution in which water-soluble photosensitizers and lanthanide ions were dissolved. The photosensitizers and lanthanide cations were incorporated with the phenol group and the carboxyl end of the tyrosine moiety, respectively. Through fluorescence microscopy and photoluminescence spectroscopy analyses, the various combinations of two lanthanide ions (Eu and Tb) and four photosensitizers were screened for synergetic photoluminescence with bolaamphiphile self-assembly. The bolaamphiphile assembly enhanced the photoluminescence intensity by a factor of around 2 when it was associated with Tb and salicylic acid. This enhancement is driven by the phosphorescence enhancement of the photosensitizer induced by the π-π interactions with the phenol group in tyrosine. These results indicate that the tyrosine-containing bolaamphiphile is a promising molecule that can easily produce a soft nanoscaled host matrix with an antenna effect for photoluminescence.

  17. Three dimensional self-assembly at the nanoscale

    NASA Astrophysics Data System (ADS)

    Gracias, D. H.

    2013-05-01

    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.

  18. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    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

  19. Multilayer block copolymer meshes by orthogonal self-assembly

    PubMed Central

    Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

    2016-01-01

    Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders. PMID:26796218

  20. Algorithmic Self-Assembly of DNA Sierpinski Triangles

    PubMed Central

    2004-01-01

    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