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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 properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving ?-stacking can be used to integrate light harvesting with charge separation and transport.

  2. 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 modifications in a row. A logical alternative approach is to leave out the phosphodiester bridges between the chromophores and let chromophore-nucleoside conjugates self-assemble specifically along single stranded DNA as template. The self-organization of chromophores along the DNA template based on canonical base pairing would be advantageous because sequence selective base pairing could provide a structural basis for programmed complexity within the chromophore assembly. The self-assembly is governed by two interactions. The chromophore-nucleoside conjugates as guest molecules are recognized via hydrogen bonds to the corresponding counter bases in the single stranded DNA template. Moreover, the ?-? interactions between the stacked chromophores stabilize these self-assembled constructs with increasing length. Longer DNA templates are more attractive for self-assembled antenna. The helicity in the stack of porphyrins as guest molecules assembled on the DNA template can be switched by environmental changes, such as pH variations. DNA-templated stacks of ethynyl pyrene and nile red exhibit left-handed chirality, which stands in contrast to similar covalent multichromophore-DNA conjugates with enforced right-handed helicity. With ethynyl nile red, it is possible to occupy every available binding site on the templates. Mixed assemblies of ethynyl pyrene and nile red show energy transfer and thereby provide a proof-of-principle that simple light-harvesting antennae can be obtained in a noncovalent and self-assembled fashion. With respect to the next important step, chemical storage of the absorbed light energy, future research has to focus on the coupling of sophisticated DNA-based light-harvesting antenna to reaction centers. PMID:26411920

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

    DOEpatents

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

    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.

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

    E-print Network

    Cao, Jianshu

    Optimal Efficiency of Self-Assembling Light-Harvesting Arrays Ji-Hyun Kim and Jianshu Cao be optimized for efficient light-harvesting energy transfer. I. Introduction Photosynthesis, an essential ecological process, efficiently converts light energy into chemical energy through various membrane complexes

  5. 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 ?M 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 (?EET) of ~50%. Binary systems with a chlorin donor and a chlorin or bacteriochlorin acceptor have ?EET ? 85%. The differences in ?EET 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 ?EET 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 self-assembled light-harvesting systems that afford broad solar collection and efficient energy transfer. PMID:26230425

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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.

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

    PubMed

    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

  8. 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

  9. Self-assembly of artificial microtubules

    E-print Network

    Shengfeng Cheng; Ankush Aggarwal; Mark J. Stevens

    2012-01-10

    Understanding the complex self-assembly of biomacromolecules is a major outstanding question. Microtubules are one example of a biopolymer that possesses characteristics quite distinct from standard synthetic polymers that are derived from its hierarchical structure. In order to understand how to design and build artificial polymers that possess features similar to those of microtubules, we have initially studied the self-assembly of model monomers into a tubule geometry. Our model monomer has a wedge shape with lateral and vertical binding sites that are designed to form tubules. We used molecular dynamics simulations to study the assembly process for a range of binding site interaction strengths. In addition to determining the optimal regime for obtaining tubules, we have calculated a diagram of the structures that form over a wide range of interaction strengths. Unexpectedly, we find that the helical tubules form, even though the monomer geometry is designed for nonhelical tubules. We present the detailed dynamics of the tubule self-assembly process and show that the interaction strengths must be in a limited range to allow rearrangement within clusters. We extended previous theoretical methods to treat our system and to calculate the boundaries between different structures in the diagram.

  10. Self-assembled artificial cilia Mojca Vilfana,1

    E-print Network

    Osterman, Natan

    Self-assembled artificial cilia Mojca Vilfana,1 , Anton Potoc v nika , Blaz Kavc v ic v b , Natan to generate fluid flow. The artificial biomimetic cilia are constructed as long chains of spherical pumping mechanism leads to the idea of using the same principle for designing artificial cilia that act

  11. Photocurrent generation in a light-harvesting system with multifunctional artificial nanochannels.

    PubMed

    Zhang, Qianqian; Liu, Zhaoyue; Zhai, Jin

    2015-08-01

    We develop an artificial light-harvesting system for photocurrent generation. Platinized TiO2 nanochannels are used as ultraviolet-light-harvesting antennae, which generate a transmembrane electrochemical gradient by asymmetric work function driven photochemical reactions. As a result, a potential difference is formed across the nanochannels, producing a photocurrent flowing through the external circuit. PMID:26139227

  12. Photochemical Bleaching of an Elaborate Artificial Light-Harvesting Antenna.

    PubMed

    Alamiry, Mohammed A H; Harriman, Anthony; Haefele, Alexandre; Ziessel, Raymond

    2015-06-22

    The target artificial light-harvesting antenna, comprising 21 discrete chromophores arranged in a logical order, undergoes photochemical bleaching when dispersed in a thin plastic film. The lowest-energy component, which has an absorption maximum at 660 nm, bleaches through first-order kinetics at a relatively fast rate. The other components bleach more slowly, in part, because their excited-state lifetimes are rendered relatively short by virtue of fast intramolecular electronic energy transfer to the terminal acceptor. Two of the dyes, these being close to the terminal acceptor but interconnected through a reversible energy-transfer step, bleach by way of an autocatalytic step. Loss of the terminal acceptor, thereby switching off the energy-transfer route, escalates the rate of bleaching of these ancillary dyes. The opposite terminal, formed by a series of eight pyrene-based chromophores, does not bleach to any significant degree. Confirmation of the various bleaching steps is obtained by examination of an antenna lacking the terminal acceptor, where the autocatalytic route does not exist and bleaching is very slow. PMID:25900879

  13. 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 model. PMID:20820580

  14. 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 photocatalytic mechanisms of H2/O2 evolution and CO2 reduction at the molecular level and to bridge natural and artificial photosynthesis. We demonstrate the feasibility of the hybrid photocatalyst, biomimetic molecular cocatalysts, and semiconductor light harvester for artificial photosynthesis and therefore provide a promising approach for rational design and construction of highly efficient and stable artificial photosynthetic systems. PMID:23730891

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

    NASA Astrophysics Data System (ADS)

    Lim, James; Pale?ek, 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.

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

    PubMed Central

    Lim, James; Pale?ek, 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

  17. 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 ?-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. PMID:26403467

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

    E-print Network

    Perlík, Václav; Cranston, Laura J; Cogdell, Richard J; Lincoln, Craig N; Savolainen, Janne; Šanda, František; Man?al, Tomáš; Hauer, Jürgen

    2015-01-01

    The initial energy transfer in photosynthesis occurs between the light-harvesting pigments and 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 F\\"orster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which leads 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 state 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 el...

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

    PubMed

    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. PMID:25150720

  20. 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.

  1. 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 ?m(2)) is two orders of magnitude higher than that of CNT membranes (0.1 ? 2.5 × 10(3) pores per ?m(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

  2. 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

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

    NASA Astrophysics Data System (ADS)

    Perlík, Václav; Seibt, Joachim; Cranston, Laura J.; Cogdell, Richard J.; Lincoln, Craig N.; Savolainen, Janne; Šanda, František; Man?al, 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.

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

    SciTech Connect

    Perlík, Václav; Seibt, Joachim; Šanda, František; Man?al, 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.

  5. 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

  6. 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.

  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

    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. PMID:25161743

  8. Self-assembling RNA square

    PubMed Central

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

    2011-01-01

    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 ? 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. PMID:21464284

  9. 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.

  10. 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.

  11. Trifluoromethylated nucleic acid analogues capable of self-assembly through hydrophobic

    E-print Network

    Tan, Weihong

    Trifluoromethylated nucleic acid analogues capable of self-assembly through hydrophobic*d and Weihong Tan*a An artificial nucleic acid analogue capable of self-assembly into a duplex merely through DNA nanodevices. To study how the hydrophobic effect works during the self-assembly of nucleic acid

  12. Self-assembly concepts for multicompartment nanostructures

    NASA Astrophysics Data System (ADS)

    Gröschel, André H.; Müller, Axel H. E.

    2015-07-01

    Compartmentalization is ubiquitous to many biological and artificial systems, be it for the separate storage of incompatible matter or to isolate transport processes. Advancements in the synthesis of sequential block copolymers offer a variety of tools to replicate natural design principles with tailor-made soft matter for the precise spatial separation of functionalities on multiple length scales. Here, we review recent trends in the self-assembly of amphiphilic block copolymers to multicompartment nanostructures (MCNs) under (semi-)dilute conditions, with special emphasis on ABC triblock terpolymers. The intrinsic immiscibility of connected blocks induces short-range repulsion into discrete nano-domains stabilized by a third, soluble block or molecular additive. Polymer blocks can be synthesized from an arsenal of functional monomers directing self-assembly through packing frustration or response to various fields. The mobility in solution further allows the manipulation of self-assembly processes into specific directions by clever choice of environmental conditions. This review focuses on practical concepts that direct self-assembly into predictable nanostructures, while narrowing particle dispersity with respect to size, shape and internal morphology. The growing understanding of underlying self-assembly mechanisms expands the number of experimental concepts providing the means to target and manipulate progressively complex superstructures.

  13. 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…

  14. 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.

  15. 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

  16. 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. PMID:25687893

  17. A novel artificial nerve graft for repairing long-distance sciatic nerve defects: a self-assembling peptide nanofiber scaffold-containing poly(lactic-co-glycolic acid) conduit.

    PubMed

    Wang, Xianghai; Pan, Mengjie; Wen, Jinkun; Tang, Yinjuan; Hamilton, Audra D; Li, Yuanyuan; Qian, Changhui; Liu, Zhongying; Wu, Wutian; Guo, Jiasong

    2014-12-15

    In this study, we developed a novel artificial nerve graft termed self-assembling peptide nanofiber scaffold (SAPNS)-containing poly(lactic-co-glycolic acid) (PLGA) conduit (SPC) and used it to bridge a 10-mm-long sciatic nerve defect in the rat. Retrograde tracing, behavioral testing and histomorphometric analyses showed that compared with the empty PLGA conduit implantation group, the SPC implantation group had a larger number of growing and extending axons, a markedly increased diameter of regenerated axons and a greater thickness of the myelin sheath in the conduit. Furthermore, there was an increase in the size of the neuromuscular junction and myofiber diameter in the target muscle. These findings suggest that the novel artificial SPC nerve graft can promote axonal regeneration and remyelination in the transected peripheral nerve and can be used for repairing peripheral nerve injury. PMID:25657734

  18. A novel artificial nerve graft for repairing long-distance sciatic nerve defects: a self-assembling peptide nanofiber scaffold-containing poly(lactic-co-glycolic acid) conduit

    PubMed Central

    Wang, Xianghai; Pan, Mengjie; Wen, Jinkun; Tang, Yinjuan; Hamilton, Audra D.; Li, Yuanyuan; Qian, Changhui; Liu, Zhongying; Wu, Wutian; Guo, Jiasong

    2014-01-01

    In this study, we developed a novel artificial nerve graft termed self-assembling peptide nanofiber scaffold (SAPNS)-containing poly(lactic-co-glycolic acid) (PLGA) conduit (SPC) and used it to bridge a 10-mm-long sciatic nerve defect in the rat. Retrograde tracing, behavioral testing and histomorphometric analyses showed that compared with the empty PLGA conduit implantation group, the SPC implantation group had a larger number of growing and extending axons, a markedly increased diameter of regenerated axons and a greater thickness of the myelin sheath in the conduit. Furthermore, there was an increase in the size of the neuromuscular junction and myofiber diameter in the target muscle. These findings suggest that the novel artificial SPC nerve graft can promote axonal regeneration and remyelination in the transected peripheral nerve and can be used for repairing peripheral nerve injury. PMID:25657734

  19. 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

  20. Nanopropulsion by biocatalytic self-assembly.

    PubMed

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

    2014-09-23

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

  1. Optical Metamaterials by Block-Copolymer Self-Assembly

    E-print Network

    Salvatore, Stefano

    2014-05-27

    COPOLYMER SELF-ASSEMBLY Stefano Salvatore Department of Physics University of Cambridge A thesis submitted for the degree of Philosophiae Doctor November 2013 i This work was supported by the EPSRC Cambridge NanoDTC, EP/G037221/1 i This dissertation... and a more ordinary experience without her friendship. Abstract This thesis explores the fabrication processes and the optical charac- terization of a metamaterials made by block copolymer self-assembly. Optical metamaterials are artificial systems...

  2. 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 ?-? 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 ?-? 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 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 ?-? 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 ?-? 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. Electronic supplementary information (ESI) available: Details of the crystallographic refinement, tables of refinement parameters and bond distances and NSD analysis, and figures showing SEM images of Zn/Sn nanosheets and clovers, the solid grown at different porphyrin concentrations, SEM images of nanosheets at high and low magnification, an ORTEP image showing the five crystallographically distinct porphyrin molecules and the water molecules, and a view of the crystal structure down the b axis are given in the ESI. CCDC reference number 833006. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr11826b

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

    PubMed

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

    2012-03-01

    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-ZnTPPS(4-) (an electron donor) and three half molecules of dihydroxy-SnTNMePyP(4+) (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 ?-? 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 ?-? 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. PMID:22310932

  4. 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

    Integration in a soft material of all molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles such as plant chloroplasts which co-localize molecules involved in light absorption, charge transport, and catalysis to create chemical bonds with light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports. The development of soft materials that integrate all necessary molecular components to generate storable fuels in the presence of sunlight is an unexplored area of chemistry with potential impact in renewable energy. Such systems could have advantages over the use of large volumes of liquids, dispersions of expensive or toxic inorganic particles, or complex devices. The use of such soft materials with integrated functions and high water content is bioinspired by the internal structure of chloroplasts in plants. These photosynthetic organelles have evolved to co-localize within stacked lipid bilayers in their stroma the protein machinery which integrates light-absorption, charge transport, and the catalytic functions necessary to convert light energy into chemical bonds1,2. Efforts to emulate natural photosynthetic systems over the past several decades have concentrated on the development of efficient 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 ? orbital overlap should have the capacity to absorb light, split excitons, and transport the charges to catalytic reaction centers. Despite the large body of work on th

  5. 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 represented a diverse international and multidisciplinary group, with over 160 individuals attending from a total of 17 different countries. Attendees came from a wide range of fields assuring that the widest possible interdisciplinary exchanges. They included prominent biochemists, biophysicists, plant physiologists, chemical physicists, as well as theoretical and computational physical chemists, who presented their research findings or to hear the latest advances in this very dynamic field. In the choice of speakers, a balance was created between established scientists and young, emerging researchers, given this opportunity to showcase their results. Sessions were held on electronic and vibrational coherence including coherent sharing of excitations among donor and acceptor molecules during excitation energy transfer, nonphotochemical quenching, acclimation to light environments, evolution, adaptation and biodiversity of light-harvesting pigment-protein complexes, their structure and membrane organization, spectroscopy and dynamics, as well as artificial antenna systems. A joint session was also held with the participants from the Cyanobacterial Satellite Conference. A special issue of Photosynthesis Research devoted to light harvesting (Volume 121, Issue No. 1, July 2014) has recently appeared which contains peer-reviewed original research contributions arising from talks and posters presented at the PS2013 Satellite Workshop on Photosynthetic Light-Harvesting Systems. Edited by the Organizers of the Workshop, Robert E. Blankenship, Harry A. Frank and Robert A. Niederman, it includes topics ranging from the isolation of new bacteriochlorophyll species from green bacteria, temperature effects on the excited states of the newly discovered chlorophyll (Chl) ƒ, new architectures for enhancing energy capture by biohybrid light-harvesting complexes, forces governing the formation of light-harvesting rings, spectroscopy of carotenoids of algae and diatoms and the supramolecular organization of caroteno-Chl proteins in diatoms, the molecular basis for urea dissociation o

  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. Nanotechnology and Quasicrystals: From self assembly to photonic applications

    E-print Network

    Ron Lifshitz

    2008-10-28

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

  8. Solar cells incorporating light harvesting arrays

    DOEpatents

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

    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).

  9. Design strategies for self-assembly of discrete targets

    NASA Astrophysics Data System (ADS)

    Madge, Jim; Miller, Mark A.

    2015-07-01

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

  10. Design Strategies for Self-Assembly of Discrete Targets

    E-print Network

    Jim Madge; Mark A. Miller

    2015-08-11

    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.

  11. A Geometrical Approach to the Incompatible Substructure Problem in Parallel Self-Assembly

    E-print Network

    Libre de Bruxelles, Université

    . An experiment using millimeter-scale, 3D printed components is used to provide physical evidence to support our geometrical approach. Keywords: Self-assembly, parallelism, yield, mesoscale, 3D printing. 1 Introduction Self of artificial systems [12]. Self- assembly is the autonomous organization of a set of components, in an environ

  12. 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. PMID:26486277

  13. 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-? 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

  14. 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

  15. Evolution and function of light harvesting proteins.

    PubMed

    Büchel, Claudia

    2015-01-01

    Photosynthetic eukaryotes exhibit very different light-harvesting proteins, but all contain membrane-intrinsic light-harvesting complexes (Lhcs), either as additional or sole antennae. Lhcs non-covalently bind chlorophyll a and in most cases another Chl, as well as very different carotenoids, depending on the taxon. The proteins fall into two major groups: The well-defined Lhca/b group of proteins binds typically Chl b and lutein, and the group is present in the 'green lineage'. The other group consists of Lhcr/Lhcf, Lhcz and Lhcx/LhcSR proteins. The former are found in the so-called Chromalveolates, where they mostly bind Chl c and carotenoids very efficient in excitation energy transfer, and in their red algae ancestors. Lhcx/LhcSR are present in most Chromalveolates and in some members of the green lineage as well. Lhcs function in light harvesting, but also in photoprotection, and they influence the organisation of the thylakoid membrane. The different functions of the Lhc subfamilies are discussed in the light of their evolution. PMID:25240794

  16. Nanostructured films from hierarchical self-assembly of amyloidogenic proteins

    NASA Astrophysics Data System (ADS)

    Knowles, Tuomas P. J.; Oppenheim, Tomas W.; Buell, Alexander K.; Chirgadze, Dimitri Y.; Welland, Mark E.

    2010-03-01

    In nature, sophisticated functional materials are created through hierarchical self-assembly of simple nanoscale motifs. In the laboratory, much progress has been made in the controlled assembly of molecules into one-, two- and three-dimensional artificial nanostructures, but bridging from the nanoscale to the macroscale to create useful macroscopic materials remains a challenge. Here we show a scalable self-assembly approach to making free-standing films from amyloid protein fibrils. The films were well ordered and highly rigid, with a Young's modulus of up to 5-7 GPa, which is comparable to the highest values for proteinaceous materials found in nature. We show that the self-organizing protein scaffolds can align otherwise unstructured components (such as fluorophores) within the macroscopic films. Multiscale self-assembly that relies on highly specific biomolecular interactions is an attractive path for realizing new multifunctional materials built from the bottom up.

  17. Solder self-assembly for MEMS fabrication

    E-print Network

    Au, Hin Meng, 1977-

    2004-01-01

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

  18. Ordering self-assembled nanostructures

    NASA Astrophysics Data System (ADS)

    Shi, Feng

    Many innovative applications of nanosciences, such as semiconductor lasers, quantum computing, information storage, quantum cryptography, and semiconductor transistors largely rely on the ability to fabricate long-range ordered nanostructures. However, conventional top-down techniques have mostly reached a bottleneck that thwarts the progress toward future miniaturization needed for the next generation of nanodevices. This constraint imposes the need to develop new manufacturing methods to engineering nanodevices on the single-digit-nanometer scale. Self-assembly, the spontaneous formation of regular arrays, is emerging as one of the most promising avenues for both miniaturization and fabrication. While self-assembly can bring us the direct large scale fabrication of nanostructures, the stochastic nature stemming from symmetry breaking bifurcation inhibits the full realization of ordered nano-arrays. Since the quality of electronic, optical, magnetic and photonic properties of nanodevices depends substantially on the uniformity of their arrangement, avoiding imperfections in self-assembly is important; thus forms the central subject of this dissertation. We propose a method for ordering self-assembled nanostructures by imposing control on the deposition using an opaque mask placed a finite distance above the substrate. This choice is motivated by studies of symmetry breaking, which suggest that boundary conditions provide a means to select among all possible broken symmetry states. We have conducted both linear and nonlinear stability analyses to derive optimal control parameters that support specific pattern formation. Numerical integrations of two morphological self-assembly models (2D biphasic surface islands in a monolayer and 3D epitaxial quantum dot growth in Stranski-Krastanow mode) show that the proposed method can indeed give large scale, well organized nanostructures.

  19. 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. PMID:25933097

  20. Self-assembled magnetocapillary swimmers

    NASA Astrophysics Data System (ADS)

    Hubert, Maxime; Lumay, Geoffroy; Weyer, Floriane; Obara, Noriko; Vandewalle, Nicolas

    2013-11-01

    Capillary driven self-assembly consists of suspending small objects at a water-air interface. Due to the effects of wetting, gravity and surface tension, the interface is slightly deformed, inducing a net force between the particles. In the experiments we present, we consider the presence of a vertical magnetic field acting on soft-ferromagnetic particles. Dipole-dipole repulsion competes with capillary attraction such that 2d ordered structures are self-assembling. By adding a secondary horizontal and oscillating magnetic field, periodic deformations of the assembly are induced. Pulsating particle arrangements start to swim, either translating or rotating. The physical mechanisms and geometrical ingredients behind this cooperative locomotion are identified. Furthermore, strategies to control the swimming dynamics are proposed.

  1. Patchy particles by self assembly

    NASA Astrophysics Data System (ADS)

    Discher, Dennis; Christian, David

    2010-03-01

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

  2. 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.

  3. 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 (?/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

  4. 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.

  5. 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

  6. 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.

  7. Mechanisms of light harvesting by photosystem II in plants

    E-print Network

    Amarnath, Kapil; Schneider, Anna R; Fleming, Graham R

    2015-01-01

    Light harvesting by photosystem II (PSII) in plants is highly efficient and acclimates to rapid changes in the intensity of sunlight. However, the mechanisms of PSII light harvesting have remained experimentally inaccessible. Using a structure-based model of excitation energy flow in 200 nanometer (nm) x 200 nm patches of the grana membrane, where PSII is located, we accurately simulated chlorophyll fluorescence decay data with no free parameters. Excitation movement through the light harvesting antenna is diffusive, but becomes subdiffusive in the presence of charge separation at reaction centers. The influence of membrane morphology on light harvesting efficiency is determined by the excitation diffusion length of 50 nm in the antenna. Our model provides the basis for understanding how nonphotochemical quenching mechanisms affect PSII light harvesting in grana membranes.

  8. Dynamic self-assembly of microscale rotors and swimmers

    E-print Network

    Megan S. Davies Wykes; Jeremie Palacci; Takuji Adachi; Leif Ristroph; Xiao Zhong; Michael D. Ward; Jun Zhang; Michael J. Shelley

    2015-12-02

    Biological systems often involve the self-assembly of basic components into complex and function- ing structures. Artificial systems that mimic such processes can provide a well-controlled setting to explore the principles involved and also synthesize useful micromachines. Our experiments show that immotile, but active, components self-assemble into two types of structure that exhibit the fundamental forms of motility: translation and rotation. Specifically, micron-scale metallic rods are designed to induce extensile surface flows in the presence of a chemical fuel; these rods interact with each other and pair up to form either a swimmer or a rotor. Such pairs can transition reversibly be- tween these two configurations, leading to kinetics reminiscent of bacterial run-and-tumble motion.

  9. 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…

  10. ULTRAFAST STUDIES OF EXCITON DYNAMICS IN LIGHT HARVESTING DIMERS

    E-print Network

    Scherer, Norbert F.

    " anisotropy and coherent anisotropy. A variety of excitation and detection conditions provide the first room of a photon by an array of light harvesting antenna pigment-protein complexes, energy (excitation) transfer

  11. Light Harvesting and Its Regulation in Photosynthetic Grana Membranes

    E-print Network

    Amarnath, Kapil

    2013-01-01

    spectroscopy has enabled the visualization of energy transfer in pigment-pigment-protein complexes. Measuring light harvesting Ultrafast spectroscopypigment-protein complex is calculated using a combination of x-ray crystallography data and ultrafast spectroscopy

  12. 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.

  13. Optical properties, light-harvesting, and energy transfer in hybrid nanomaterials

    NASA Astrophysics Data System (ADS)

    Govorov, Alexander

    2011-10-01

    Modern nanotechnology involves both nanocrystals (metal and semiconductor) and biomaterials. Using biomolecules as linkers, solid-state nanocrystals with modified surfaces can be assembled into hybrid (i.e. assembled from different materials) superstructures with unique optical properties. In a superstructure, individual building blocks (nanocrystals and biomolecules) strongly interact and these interactions bring new properties. In particular, Coulomb and electromagnetic interactions in a hybrid nanostructure cause several interesting effects: Energy transfer between nanoparticles (NPs), plasmon enhancement, modified exciton diffusion in nanowires, Fano interference effect, non-linear phenomena, etc. In our studies, we also look at the properties of artificial light- harvesting complexes composed of chlorophylls, photosynthetic bacterial reaction centers, and NPs. Using superior optical properties of metal and semiconductor NPs, it is possible to strongly enhance an efficiency of light harvesting in such complexes. In conclusion, our theory explains current experimental results and also provides rationale for future experiments and applications. Potential applications of dynamic hybrid nanostructures include sensors, nonlinear optical media, and light-harvesting systems.

  14. 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

  15. Adaptive soft molecular self-assemblies.

    PubMed

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

    2015-12-23

    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. Defects in Self Assembled Colloidal Crystals

    E-print Network

    Koh, Yaw Koon

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

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

  18. Supramolecular Coordination Polymer Formed from Artificial Light-Harvesting Dendrimer.

    PubMed

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

    2015-09-30

    We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 ?M) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased due to the efficient energy transfer from PZn wings in PZnPCu to PyPFB. PMID:26349620

  19. 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.

  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. Two-dimensional patterning of bacterial light-harvesting 2 complexes on lipid-modified gold surface

    NASA Astrophysics Data System (ADS)

    Yajima, Shunsuke; Furukawa, Rei A.; Nagata, Morio; Sakai, Shunsuke; Kondo, Masaharu; Iida, Kouji; Dewa, Takehisa; Nango, Mamoru

    2012-06-01

    In a photosynthetic membrane, nano-scale patterns of light-harvesting (LH) pigment-protein complexes play an essential role in capturing photons and ensuring efficient excitation energy transfer. LH complexes 1 and 2 have drawn attention as building blocks of a nano-scale photoelectric device. For obtaining a device with efficiency comparable to that of the natural photosynthesis, a method has to be established for forming a two-dimensional assembly of LH complexes around a metal electrode. In this study, LH2 complexes isolated from Rb. sphaeroides were immobilized on a patterned gold surface. Quenching of photo-excitation energy by gold was prevented through the placement of a self-assembled phospholipid monolayer between the LH2 complexes and the gold surface.

  2. 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 ?-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

  3. Limits of quantum speedup in photosynthetic light harvesting

    E-print Network

    Stephan Hoyer; Mohan Sarovar; K. Birgitta Whaley

    2010-05-07

    It has been suggested that excitation transport in photosynthetic light harvesting complexes features speedups analogous to those found in quantum algorithms. Here we compare the dynamics in these light harvesting systems to the dynamics of quantum walks, in order to elucidate the limits of such quantum speedups. For the Fenna-Matthews-Olson (FMO) complex of green sulfur bacteria, we show that while there is indeed speedup at short times, this is short lived (70 fs) despite longer lived (ps) quantum coherence. Remarkably, this time scale is independent of the details of the decoherence model. More generally, we show that the distinguishing features of light-harvesting complexes not only limit the extent of quantum speedup but also reduce rates of diffusive transport. These results suggest that quantum coherent effects in biological systems are optimized for efficiency or robustness rather than the more elusive goal of quantum speedup.

  4. Light-harvesting chlorophyll c-like pigment in Prochloron.

    PubMed Central

    Larkum, A W; Scaramuzzi, C; Cox, G C; Hiller, R G; Turner, A G

    1994-01-01

    A chlorophyll c-like pigment, similar to magnesium-3,8-divinyl pheoporphyrin a5 monomethyl ester, has been isolated from Prochloron sp. obtained from five species of didemnid ascidians from the Great Barrier Reef, Australia, and from Palau, Micronesia. The pigment represents 4-15% of the total chlorophyll content and is shown to function in a light-harvesting pigment protein complex of Prochloron. The observation that all of the major chlorophylls (a+b+c) function in a light-harvesting role in Prochloron and possibly in other prochlorophytes is discussed in terms of the phylogeny of the prochlorophytes. PMID:11607451

  5. 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

  6. Self-assembly of nanocomposite materials

    DOEpatents

    Brinker, C. Jeffrey (Albuquerque, NM); Sellinger, Alan (Palo Alto, CA); Lu, Yunfeng (New Orleans, LA)

    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.

  7. Handedness and self assembly of chiral rods

    NASA Astrophysics Data System (ADS)

    Efrati, Efi

    2014-03-01

    When handed building blocks, such as twisted fusilli, self-assemble the resulting assembled object is typically also handed (as are its physical response properties). This phenomenon plays a central role in fields raging from biological self-assembly to optimizing the design of optical meta-materials. Despite the importance of this problem, predicting the relation between the handedness of the constituents of an assembled object and its overall handedness has remained an elusive goal even for the simplest of cases. At the heart of this problem lies the difficulty of quantifying the handedness of even a single building block. In this talk I will show how a recent orientation-dependent interpretation of handedness as a relation between directions and rotations sidesteps most of the difficulties associated with the quantification of handedness and resolves an existing puzzle regarding the self-assembly of handed colloidal rods.

  8. 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

  9. Remote control of self-assembled microswimmers.

    PubMed

    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

  10. 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.

  11. Self-assembly of chlorophenols in water

    PubMed Central

    Rogalska, Ewa; Rogalski, Marek; Gulik-Krzywicki, Tadeusz; Gulik, Annette; Chipot, Christophe

    1999-01-01

    In saturated solutions of some di- and trichlorophenols, structures with complex morphologies, consisting of thin, transparent sheets often coiling into helices and ultimately twisting into filaments, were observed under the optical microscope. Freeze-fracture electron microscopy, x-ray diffraction, phase diagrams, and molecular modeling were performed to elucidate the observed phenomena. Here, we present evidence that the chlorophenols studied, when interacting with water, self-assemble into bilayers. The fact that some chlorophenols form the same supramolecular structures as those described previously for structurally nonrelated surfactants sheds light on the mechanisms of self-assembly. PMID:10359753

  12. Remote control of self-assembled microswimmers

    E-print Network

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

    2015-07-03

    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.

  13. Insights from Placing Photosynthetic Light Harvesting into Context.

    PubMed

    Demmig-Adams, Barbara; Stewart, Jared J; Burch, Tyson A; Adams, William W

    2014-08-21

    Solar-energy conversion through natural photosynthesis forms the base of virtually all food chains on Earth and provides fiber, materials, and fuels, as well as inspiration for the design of biomimetic energy-conversion systems. We summarize well-known as well as recently discovered feedback loops between natural light-harvesting systems and whole-organism function in natural settings. We propose that the low effective quantum yield of natural light-harvesting systems in high light is caused by downstream limitations rather than unavoidable intrinsic vulnerabilities. We evaluate potential avenues, and their costs and benefits, for increasing the maximal rate and photon yield of photosynthesis in high light in plants and photosynthetic microbes. By summarizing mechanisms observable only in complex systems (whole plants, algae, or, in some cases, intact leaves), we aim to stimulate future research efforts on reciprocal feedback loops between light harvesting and downstream processes in whole organisms and to provide additional arguments for the significance of research on photosynthetic light harvesting. PMID:26278094

  14. Light harvesting: Strike while the iron is cold

    NASA Astrophysics Data System (ADS)

    Galoppini, Elena

    2015-11-01

    For many years, chemists have tried and failed to find efficient light-harvesting molecules based on Earth-abundant, environmentally friendly iron. Now, an iron complex has been developed with photoluminescent properties that are tuned to efficiently convert light to electrons.

  15. Research article Translational regulation of light-harvesting complex expression

    E-print Network

    Durnford, Dion G.

    examined are loaded back onto polysomes. Disassembly of polysomes was mimicked by hydrogen peroxide application to non-shifted cultures suggesting that production of hydrogen peroxide due to HL-stress may,1-dimethylurea; H2O2, hydrogen peroxide; HL, High-Light; LHC, Light harvesting complex; LL, Low-Light; PSII

  16. Block copolymer self-assembly for the responsive reinforcement of injectable protein hydrogels

    NASA Astrophysics Data System (ADS)

    Glassman, M. J.; Li, S.; Chan, J.; Olsen, B. D.

    2012-02-01

    Shear-thinning injectable protein hydrogels are emerging as important biomaterials for the minimally-invasive implantation of scaffolds for tissue engineering and drug delivery. In this work, responsive block copolymer self-assembly is employed to trigger nanostructure formation in hydrogels made from artificial associative proteins, producing hydrogels with resistance to shear-thinning post injection, reduced erosion rate, higher toughness, and dramatically reduced creep compliance. Polymer-protein-polymer triblock copolymers have been synthesized by conjugating poly(N-isopropylacrylamide) to either end of a protein midblock decorated with self-associating pentavalent sticker domains. Self-assembly at elevated temperatures introduces a second physical network into the protein hydrogel with an independent and tunable relaxation time. The phase behavior of these dual-network hydrogels has been explored, revealing the ability to access nanostructured morphologies, and the effect of self-assembled polymer domains on the linear mechanics and toughness of injectable hydrogels has been investigated.

  17. Self-assembled DNA Structures for Nanoconstruction

    E-print Network

    Yin, Peng

    -patterned materials. We have prototyped a new DNA nanostructure known as a cross structure. This nanostructure has a 4 advantages of DNA as a nanoconstruction material explain the rapid and exciting progress in DNA basedSelf-assembled DNA Structures for Nanoconstruction Hao Yan, Peng Yin, Sung Ha Park, Hanying Li

  18. Communications Self-Assembled Nanocomposite Polymer Light-

    E-print Network

    Carter, Sue

    emission.[6] In this paper, we show that nanopar- ticles assembled at a semiconducting polymer/electrode inCommunications Self-Assembled Nanocomposite Polymer Light- Emitting Diodes with Improved Efficiency- tronics applications because they combine the advantages of organic polymers with those of inorganic

  19. Self-assembled thin film chemical sensors

    SciTech Connect

    Swanson, B.; Li, DeQuan

    1996-11-01

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

  20. 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.

  1. Communications Self-assembly of Tiled Perovskite

    E-print Network

    Communications Self-assembly of Tiled Perovskite Monolayer and Multilayer Thin Films Raymond E optical2 and electronic3 properties. One of the outstanding challenges in this area is to devise synthetic with specific electronic, magnetic, optical, catalytic, and other properties. Toward this goal, perovskite

  2. A design for self-assembling robots in a system

    E-print Network

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

    2006-01-01

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

  3. Templated self-assembly of sub-10 nm quantum dots

    E-print Network

    Leu, Joshua C. (Joshua Chung)

    2008-01-01

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

  4. 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, etc.). The SANC technologies will establish LMA and related US manufacturing capability for commercial and military applications therefore reducing reliance on off-shore development and production of related critical technologies. If these technologies are successfully licensed, production of these coatings in manufactory will create significant technical employment opportunities.

  5. 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).

  6. Hydrophobically-Driven Self-Assembly: A Geometric Packing Analysis

    E-print Network

    resulting from the self-assembly of amphiphile nanoparticles possessing a hydrophobic "tail by self-assembly of peptide amphiphiles into cylindrical fibers. Subsequently, these cylindrical of the cylindrical fibers based on existing knowledge of amphiphile self- assembly, according to which an amphiphile

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

    NASA Astrophysics Data System (ADS)

    Anderson, Lamont

    1996-02-01

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

  8. Cascade exciton-pumping engines with manipulated speed and efficiency in light-harvesting porous ?-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 ?-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.

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

    E-print Network

    Cao, Jianshu

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

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

    E-print Network

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

    2010-06-23

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

  11. 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

  12. Replication of Leaf Surface Structures for Light Harvesting.

    PubMed

    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

  13. Functional Subsystems and Quantum Redundancy in Photosynthetic Light Harvesting

    E-print Network

    Nolan Skochdopole; David A. Mazziotti

    2011-12-07

    The Fenna-Matthews-Olson (FMO) antennae complex, responsible for light harvesting in green sulfur bacteria, consists of three monomers, each with seven chromophores. Here we show that multiple subsystems of the seven chromophores can transfer energy from either chromophore 1 or 6 to the reaction center with an efficiency matching or in many cases exceeding that of the full seven chromophore system. In the FMO complex these functional subsystems support multiple quantum pathways for efficient energy transfer that provide a built-in quantum redundancy. There are many instances of redundancy in nature, providing reliability and protection, and in photosynthetic light harvesting this quantum redundancy provides protection against the temporary or permanent loss of one or more chromophores. The complete characterization of functional subsystems within the FMO complex offers a detailed map of the energy flow within the FMO complex, which has potential applications to the design of more efficient photovoltaic devices.

  14. 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

  15. 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

  16. 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.

  17. Self-assembly of Janus Ellipsoids

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  18. 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. PMID:26673259

  19. Self-assembled microdevices driven by muscle

    NASA Astrophysics Data System (ADS)

    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.

  20. The dynamics of nacre self-assembly

    PubMed Central

    Cartwright, Julyan H.E; Checa, Antonio G

    2006-01-01

    We show how nacre and pearl construction in bivalve and gastropod molluscs can be understood in terms of successive processes of controlled self-assembly from the molecular- to the macro-scale. This dynamics involves the physics of the formation of both solid and liquid crystals and of membranes and fluids to produce a nanostructured hierarchically constructed biological composite of polysaccharides, proteins and mineral, whose mechanical properties far surpass those of its component parts. PMID:17251136

  1. 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.

  2. 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 ?-peptide to give conjugates ?-B1, ?-B2, and ?-B3. Given the hydrophobic nature of the ?-peptide, the polarity of B1 and B2 facilitated purification of the respective conjugate compared to the hydrophobic B3. Bacteriochlorophyll a (BChl a) associates with each conjugate in aqueous micellar media to form a dyad containing two ?-peptides, two covalently attached synthetic bacteriochlorins, and a datively bonded BChl-a pair, albeit to a limited extent for ?-B2. The reversible assembly/disassembly of dyad (?-B2/BChl)2 was examined in aqueous detergent (octyl glucoside) solution by temperature variation (15-35 °C). The energy-transfer efficiency from the synthetic bacteriochlorin to the BChl-a dimer was found to be 0.85 for (?-B1/BChl)2, 0.40 for (?-B2/BChl)2, and 0.85 for (?-B3/BChl)2. Thus, in terms of handling, assembly and energy-transfer efficiency taken together, the amphiphilic design examined herein is more attractive than the prior hydrophilic or hydrophobic designs. PMID:24997120

  3. 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. PMID:26436692

  4. Trioctylphosphine as self-assembly inducer.

    PubMed

    Okram, Gunadhor S; Singh, Jaiveer; Kaurav, Netram; Lalla, Niranjan P

    2015-01-01

    Nickel nanoparticles (NPs) of different shapes and sizes in polydispersed as well as monodispersed forms were synthesized using trioctylphosphine (TOP), triphenylphosphine (TPP), oleylamine (OA) and their combinations as surfactants to study their self-assembly inducing capabilities. Randomly agglomerated polydispersed NPs were found for TPP and OA, and TPP or OA separately. However, in consolidation with the earlier report of Singh et al., J. Mater. Chem. C, 2014, 2, 8918, NPs formed using TOP only and a combination of TOP with OA naturally exhibited monodispersed NPs associated with natural nanolattice formation without any other external force or surfactants, demonstrating clearly the self-inducing capacity of TOP into monodispersed NPs and their self-assembled nanolattices. Fourier-transformed infra-red (FTIR) data clearly indicated the capping of these surfactants along with acetylacetonate ligands from nickel acetylacetonate precursor on the surface of the NPs. Remarkably, the narrowest zeta potential (?) base-widths were observed for samples possessing a self-assembled nanolattice, compared to the broader ones for randomly agglomerated particles. PMID:25917190

  5. Manipulating Excited-State Dynamics of Individual Light-Harvesting Chromophores through Restricted Motions in a Hydrated Nanoscale Protein Cavity.

    PubMed

    Noriega, Rodrigo; Finley, Daniel T; Haberstroh, John; Geissler, Phillip L; Francis, Matthew B; Ginsberg, Naomi S

    2015-06-11

    Manipulating the photophysical properties of light-absorbing units is a crucial element in the design of biomimetic light-harvesting systems. Using a highly tunable synthetic platform combined with transient absorption and time-resolved fluorescence measurements and molecular dynamics simulations, we interrogate isolated chromophores covalently linked to different positions in the interior of the hydrated nanoscale cavity of a supramolecular protein assembly. We find that, following photoexcitation, the time scales over which these chromophores are solvated, undergo conformational rearrangements, and return to the ground state are highly sensitive to their position within this cavity and are significantly slower than in a bulk aqueous solution. Molecular dynamics simulations reveal the hindered translations and rotations of water molecules within the protein cavity with spatial specificity. The results presented herein show that fully hydrated nanoscale protein cavities are a promising way to mimic the tight protein pockets found in natural light-harvesting complexes. We also show that the interplay between protein, solvent, and chromophores can be used to substantially tune the relaxation processes within artificial light-harvesting assemblies in order to significantly improve the yield of interchromophore energy transfer and extend the range of excitation transport. Our observations have implications for other important, similarly sized bioinspired materials, such as nanoreactors and biocompatible targeted delivery agents. PMID:26035585

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

    PubMed

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

    2014-03-21

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

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

  8. 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-?-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

  9. Functional membranes via nanoparticle self-assembly.

    PubMed

    Green, Erica; Fullwood, Emily; Selden, Julieann; Zharov, Ilya

    2015-05-01

    This article summarizes a recently developed approach for the preparation of membrane materials by the self-assembly of inorganic, polymeric or hybrid nanoparticles, with the focus on functional membranes possessing permselectivity. Two types of such membranes are discussed, those possessing size and charge selectivity suitable for ultra- and nanofiltration and chemoselective separation, and those possessing proton or lithium transport properties suitable for fuel cell and lithium battery applications, respectively. This article describes the preparation methods of nanoparticle membranes, as well as their mechanical, molecular, and ionic transport properties. PMID:25873312

  10. 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

  11. Self-assembly of magnetic biofunctional nanoparticles

    SciTech Connect

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

    2005-05-15

    Spherical, ferromagnetic FePt nanoparticles with a particle size of 3 nm were prepared by the simultaneous polyol reduction of Fe(acac){sub 3} and Pt(acac){sub 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.

  12. Diblock copolymer based self-assembled nanomagnetoelectric

    E-print Network

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

    2008-10-31

    . The ?fast? Fourier transforms shown as ?a? inserts confirm the hexagonal order of the self-assembled gel thin film, and ?b? crystallized CFO cylinders. APPLIED PHYSICS LETTERS 93, 173507 ?2008? 0003-6951/2008/93?17?/173507/3/$23.00 © 2008 American Institute... that it is well sintered and, according to the orien- tation of the adjacent local grains, not epitaxial. Since the average MI response of the MEC can be accounted for using macroscopic CFO and PZT parameters and the dimensions of the MEC, the interface enables...

  13. Ultrafast Energy Relaxation in Single Light-Harvesting Complexes

    E-print Network

    Malý, Pavel; Cogdell, Richard J; Man?al, Tomáš; van Grondelle, Rienk

    2015-01-01

    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 employ 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 behaviour 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 repe...

  14. 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).

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

    PubMed

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

    2015-01-25

    Chlorophylls, the major pigments presented in plants are responsible for the process of photosynthesis. The working principle of dye sensitized solar cell (DSSC) is analogous to natural photosynthesis in light-harvesting and charge separation. In a similar way, natural dyes extracted from three types of grasses viz. Hierochloe Odorata (HO), Torulinium Odoratum (TO) and Dactyloctenium Aegyptium (DA) were used as light harvesters in dye sensitized solar cells (DSSCs). The UV-Vis absorption spectroscopy, Fourier transform infrared (FT-IR), and liquid chromatography-mass spectrometry (LC-MS) were used to characterize the dyes. The electron transport mechanism and internal resistance of the DSSCs were investigated by the electrochemical impedance spectroscopy (EIS). The performance of the cells fabricated with the grass extract shows comparable efficiencies with the reported natural dyes. Among the three types of grasses, the DSSC fabricated with the dye extracted from Hierochloe Odorata (HO) exhibited the maximum efficiency. LC-MS investigations indicated that the dominant pigment present in HO dye was pheophytin a (Pheo a). PMID:25168231

  16. Light-Harvesting Function in the Diatom Phaeodactylum tricornutum1

    PubMed Central

    Owens, Thomas G.; Wold, Evarina R.

    1986-01-01

    Three pigment-protein complexes were isolated from the marine diatom Phaeodactylum tricornutum (Bohlin) by treatment of thylakoid membrane fragments with 1% Triton X-100 at 4°C followed by centrifugation on sucrose density gradients. The major complex contains chlorophyll a, c1, c2, and the carotenoid fucoxanthin (chlorophyll a: c1: c2: fucoxanthin = 1.0: 0.09: 0.28: 2.22) bound to an apoprotein doublet of 16.4 and 16.9 kilodaltons. This complex accounts for >70% of the total pigment and 20 to 40% of the protein in the thylakoid membranes. Efficient coupling of chlorophyll c and fucoxanthin absorption to chlorophyll a fluorescence supports a light-harvesting function for the complex. A minor light-harvesting complex containing chlorophyll a, c1, and c2 but no fucoxanthin (chlorophyll a: c1: c2 = 1.0: 0.23: 0.26) was also isolated at Triton: chlorophyll a ratios between 20 and 40. These pigments are bound to a similar molecular weight apoprotein doublet. The third complex isolated was the P700-chlorophyll a protein, the reaction center of photosystem I, which showed characteristics similar to those isolated from other plant sources. The yield of the chlorophyll a/c-fucoxanthin complex was shown to respond strongly to changes in light intensity during growth, accounting for most of the changes in cellular pigmentation. Images Fig. 1 Fig. 5 PMID:16664694

  17. 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

  18. Self-assembled palladium nanowires by electroless deposition

    NASA Astrophysics Data System (ADS)

    Shi, Zhongliang; Wu, Shanqiang; Szpunar, Jerzy A.

    2006-05-01

    A simple approach to the self-assembly production of palladium nanowires by electroless deposition on a porous stainless steel template is reported. Various arrays of self-assembled palladium nanowires in the form of single wire, parallel and curved wires, intersections and network structures are illustrated. This experimental result demonstrates that metal nanowires can be built in a self-assembled manner by the assembly of nanoparticles generated in the initial stages of the deposition without any external field except the chemical reaction. Such self-assembled nanowires may attract engineering applications because the electroless deposition process and the preparation of the substrate are simple and inexpensive.

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

    DOEpatents

    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.

  20. 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.

  1. Chiral Self-Assembly of Helical Particles

    E-print Network

    Hima Bindu Kolli; Giorgio Cinacchi; Alberta Ferrarini; Achille Giacometti

    2015-10-21

    The shape of the building blocks plays a crucial role in directing self-assembly towards desired architectures. Out of the many different shapes, helix has a unique position. Helical structures are ubiquitous in nature and a helical shape is exhibited by the most important biopolymers like polynucleotides, polypeptides and polysaccharides as well as by cellular organelles like flagella. Helical particles can self-assemble into chiral superstructures, which may have a variety of applications, e.g. as photonic (meta)materials. However,a clear and definite understanding of these structures has not been entirely achieved yet. We have recently undertaken an extensive investigation on the phase behaviour of hard helical particles, using numerical simulations and classical density functional theory. Here we present a detailed study of the phase diagram of hard helices as a function of their morphology. This includes a variety of liquid-crystal phases, with different degrees of orientational and positional ordering. We show how, by tuning the helix parameters, it is possible to control the organization of the system. Starting from slender helices, whose phase behaviour is similar to that of rodlike particles, the increase in curliness leads to the onset of azimuthal correlations between the particles and the formation of phases specific to helices. These phases feature a new kind of screw order, of which there is experimental evidence in colloidal suspensions of helical flagella.

  2. Micropatterning of bioactive self-assembling gels†

    PubMed Central

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

    2009-01-01

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

  3. 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.

  4. 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).

  5. 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.

  6. Pigment interactions in light-harvesting complex II in different molecular environments.

    PubMed

    Akhtar, Parveen; Dorogi, Márta; Pawlak, Krzysztof; Kovács, László; Bóta, Attila; Kiss, Teréz; Garab, Gy?z?; Lambrev, Petar H

    2015-02-20

    Extraction of plant light-harvesting complex II (LHCII) from the native thylakoid membrane or from aggregates by the use of surfactants brings about significant changes in the excitonic circular dichroism (CD) spectrum and fluorescence quantum yield. To elucidate the cause of these changes, e.g. trimer-trimer contacts or surfactant-induced structural perturbations, we compared the CD spectra and fluorescence kinetics of LHCII aggregates, artificial and native LHCII-lipid membranes, and LHCII solubilized in different detergents or trapped in polymer gel. By this means we were able to identify CD spectral changes specific to LHCII-LHCII interactions, at (-)-437 and (+)-484 nm, and changes specific to the interaction with the detergent n-dodecyl-?-maltoside (?-DM) or membrane lipids, at (+)-447 and (-)-494 nm. The latter change is attributed to the conformational change of the LHCII-bound carotenoid neoxanthin, by analyzing the CD spectra of neoxanthin-deficient plant thylakoid membranes. The neoxanthin-specific band at (-)-494 nm was not pronounced in LHCII in detergent-free gels or solubilized in the ? isomer of DM but was present when LHCII was reconstituted in membranes composed of phosphatidylcholine or plant thylakoid lipids, indicating that the conformation of neoxanthin is sensitive to the molecular environment. Neither the aggregation-specific CD bands, nor the surfactant-specific bands were positively associated with the onset of fluorescence quenching, which could be triggered without invoking such spectral changes. Significant quenching was not active in reconstituted LHCII proteoliposomes, whereas a high degree of energetic connectivity, depending on the lipid:protein ratio, in these membranes allows for efficient light harvesting. PMID:25525277

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

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Han

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

  8. 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 ?m 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.

  9. 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. PMID:26301578

  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 used to characterize part-to-substrate MSA. It is shown that the assembly rate and the yield are most dependent on the rotational symmetry of the magnet pattern. Simultaneous and sequential heterogeneous assembly of two types of parts with selective bonding is also demonstrated, with the average assembly yield of 93% in 60 s and 99% in 3.5 min respectively. Finally, MSA with functional electrical interconnects is also demonstrated with a yield of 90.5%.

  11. 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

  12. 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

  13. Direct observation of ultrafast coherent exciton dynamics in helical ?-stacks of self-assembled perylene bisimides

    PubMed Central

    Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin; Würthner, Frank; Kim, Dongho

    2015-01-01

    Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of ?-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar ?–? stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple ?-stacked dimer, the photoexcitation energy in the columnar ?-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process. PMID:26492820

  14. Department of Chemistry "Self-Assembled Soft Materials from Sugar

    E-print Network

    Mark, James E.

    Department of Chemistry "Self-Assembled Soft Materials from Sugar Amphiphiles, and the In Situ. #12;ABSTRACT: Self-Assembled Soft Materials from Sugar Amphiphiles, and the In Situ Synthesis resources to generate soft materials such as new surfactants, liquid crystals, lipid nanotubes and molecular

  15. Self-Assembly of Dendron Rodcoil Molecules into Nanoribbons

    E-print Network

    Natelson, Douglas

    Self-Assembly of Dendron Rodcoil Molecules into Nanoribbons Eugene R. Zubarev, Martin U. Pralle of Chemistry, Medical School Northwestern UniVersity, EVanston, Illinois 60208 ReceiVed February 9, 2001 One on designed molecules that self-order or fold. The focus on self-assembly throughout the 90s has generated

  16. Self-Assembly: (Adv. Mater. 38/2015).

    PubMed

    2015-10-01

    The self-assembly of molecules at surfaces can be caused by a range of physical mechanisms. Molecular Foundry researchers have described some apparently disparate systems in similar physical terms, indicating that simple factors, such as the geometry and energy scale of intermolecular binding, are key to understanding the self-assembly of those systems. PMID:26448603

  17. PREPARATION OF SELF-ASSEMBLED COBALT NANOCRYSTAL ARRAYS

    E-print Network

    Wang, Zhong L.

    PREPARATION OF SELF-ASSEMBLED COBALT NANOCRYSTAL ARRAYS J.S. Yin and Z.L. Wang School of Materials scientific and technological interests. In this paper, three different kinds of self-assemblies of cobalt nanocrystals were processed using particles processed by thermal decomposition of cobalt carbonyl in toluene

  18. Nanotechnology Applications in Self-Assembly and DNA Computing

    E-print Network

    Akin, Hayri Engin

    2011-01-01

    microprocessor has 2300 to 2500 transistors, and would require approximately 10,000 to 12,500 keyed components in a self-assembly processmicroprocessor has 2300 to 2500 transistors, and would require approximately 10,000 to 12,500 keyed components in a self-assembly process

  19. Self-Assembly Strategy for Fabricating Connected Graphene Nanoribbons.

    PubMed

    Han, Patrick; Akagi, Kazuto; Federici Canova, Filippo; Shimizu, Ryota; Oguchi, Hiroyuki; Shiraki, Susumu; Weiss, Paul S; Asao, Naoki; Hitosugi, Taro

    2015-12-22

    We use self-assembly to fabricate and to connect precise graphene nanoribbons end to end. Combining scanning tunneling microscopy, Raman spectroscopy, and density functional theory, we characterize the chemical and electronic aspects of the interconnections between ribbons. We demonstrate how the substrate effects of our self-assembly can be exploited to fabricate graphene structures connected to desired electrodes. PMID:26588477

  20. Metal-Driven Hierarchical Self-Assembled One-Dimensional

    E-print Network

    Huang, Jianbin

    Metal-Driven Hierarchical Self-Assembled One-Dimensional Nanohelices Yan Qiao, Yiyang Lin, Yijie-dimensional helical nanostructure is presented based on metal-cholate supramolecular self-assembly. Well-defined right-handed helical nanoribbons in calcium-cholate systems are systematically investigated and a series of metal ions

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

    PubMed

    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

    2015-12-17

    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. PMID:26612683

  2. Light-Harvesting Chlorophyll a/b Protein 1

    PubMed Central

    Cline, Kenneth

    1988-01-01

    The apoprotein of the light-harvesting chlorophyll a/b protein (LHCP) is a major integral thylakoid membrane protein that is normally complexed with chlorophyll and xanthophylls and serves as the antenna complex of photosystem II. LHCP is encoded in the nucleus and synthesized in the cytosol as a higher molecular weight precursor that is subsequently imported into chloroplasts and assembled into thylakoids. In a previous study it was established that the LHCP precursor can integrate into isolated thylakoid membranes. The present study demonstrates that under conditions designed to preserve thylakoid structure, the inserted LHCP precursor is processed to mature size, assembled into the LHC II chlorophyll-protein complex, and localized to the appressed thylakoid membranes. Under these conditions, light can partially replace exogenous ATP in the membrane integration process. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 PMID:16666042

  3. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1996-01-01

    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.

  4. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1999-10-12

    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. Self-assembly of active attractive spheres.

    PubMed

    Prymidis, Vasileios; Sielcken, Harmen; Filion, Laura

    2015-06-01

    We study the self-assembly of a system of self-propelled, Lennard-Jones particles using Brownian dynamics simulations. We examine the state diagrams of the system for different rotational diffusion coefficients of the self-propelled motion of the particles. For fast rotational diffusion, the state diagram exhibits a strong similarity to that of the equilibrium Lennard-Jones fluid. As we decrease the rotational diffusion coefficient, the state diagram is slowly transformed. Specifically, the liquid-gas coexistence region is gradually replaced by a highly dynamic percolating network state. We find significant local alignment of the particles in the percolating network state despite the absence of aligning interactions, and propose a simple mechanism to justify the formation of this novel state. PMID:25866369

  6. 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.

  7. 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

  8. 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.

  9. Self-assembly of phospholipids on flat supports.

    PubMed

    Mhashal, Anil R; Roy, Sudip

    2015-11-18

    The current study deals with the self-assembly of phospholipids on flat supports using the Martini coarse grain model. We reported here the effect of the hydrophilic and hydrophobic nature of the solid supports on the lipid self-assembly. The hydrophilic and hydrophobic supports were modeled on the basis of water droplet simulations. The present work addresses the self-assembly mechanism of lipids on eight different supports with different strengths of hydrophilicity and hydrophobicity. We demonstrated how interplay between the interactions of lipid and water with the support can guide the lipid self-assembly process. Thereafter, we calculated the energetics of the components of the system to quantify the competitions between water and a lipid head-group with hydrophilic supports. Finally, the properties of the self-assembled bilayers were also analyzed and reported here. PMID:26540275

  10. Self-assembly of granular crystals

    NASA Astrophysics Data System (ADS)

    Shattuck, Mark

    2015-03-01

    Acoustic meta-materials are engineered materials with the ability to control, direct, and manipulate sound waves. Since the 1990s, several groups have developed acoustic meta-materials with novel capabilities including negative index materials for acoustic super-lenses, phononic crystals with acoustic band gaps for wave guides and mirrors, and acoustic cloaking device. Most previous work on acoustic meta-materials has focused on continuum solids and fluids. In contrast, we report on coordinated computational and experimental studies to use macro-self-assembly of granular materials to produce acoustic meta-materials. The advantages of granular acoustic materials are three-fold: 1) Microscopic control: The discrete nature of granular media allows us to optimize acoustic properties on both the grain and network scales. 2) Tunability: The speed of sound in granular media depends strongly on pressure due to non-linear contact interactions and contact breaking. 3) Direct visualization: The macro-scale size of the grains enables visualization of the structure and stress propagation within granular assemblies. We report simulations and experiments of vibrated particles that form a variety of self-assembled ordered structures in two- and three-dimensions. In the simplest case of mono-disperse spheres, using a combination of pressure and vibration we produce crystals with long-range order on the scale of 100's of particles. Using special particle shapes that form ``lock and key'' structures we are able to make binary crystals with prescribed stoichiometries. We discuss the mechanical properties of these structures and methods to create more complicated structures.

  11. 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 amphiphiles. One possibility is photochemical oxidation of hydrocarbons.

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

    E-print Network

    Efficient light harvesting in multiple-device stacked structure for polymer solar cells Vishal structure of polymer solar cells for efficient light harvesting. Two polymer photovoltaic cells are stacked and the short-circuit current are almost doubled compared to a single cell. © 2006 American Institute of Physics

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

    E-print Network

    Demir, Hilmi Volkan

    Highly efficient nonradiative energy transfer mediated light harvesting in water using aqueous Cd@bilkent.edu.tr Abstract: We present light harvesting of aqueous colloidal quantum dots to nonradiatively transfer.3 ns to 7.2 ns as a result of their energy transfer with efficiency levels up to 86%. Such nonradiative

  14. Large-Area Nanosphere Self-Assembly by a Micro-Propulsive Injection Method for High Throughput Periodic Surface Nanotexturing.

    PubMed

    Gao, Pingqi; He, Jian; Zhou, Suqiong; Yang, Xi; Li, Sizhong; Sheng, Jiang; Wang, Dan; Yu, Tianbao; Ye, Jichun; Cui, Yi

    2015-07-01

    A high throughput surface texturing process for optical and optoelectric devices based on a large-area self-assembly of nanospheres via a low-cost micropropulsive injection (MPI) method is presented. The novel MPI process enables the formation of a well-organized monolayer of hexagonally arranged nanosphere arrays (NAs) with tunable periodicity directly on the water surface, which is then transferred onto the preset substrates. This process can readily reach a throughput of 3000 wafers/h, which is compatible with the high volume photovoltaic manufacturing, thereby presenting a highly versatile platform for the fabrication of periodic nanotexturing on device surfaces. Specifically, a double-sided grating texturing with top-sided nanopencils and bottom-sided inverted-nanopyramids is realized in a thin film of crystalline silicon (28 ?m in thickness) using chemical etching on the mask of NAs to significantly enhance antireflection and light trapping, resulting in absorptions nearly approaching the Lambertian limit over a broad wavelength range of 375-1000 nm and even surpassing this limit beyond 1000 nm. In addition, it is demonstrated that the NAs can serve as templates for replicas of three-dimensional conformal amorphous silicon films with significantly enhanced light harvesting. The MPI induced self-assembly process may provide a universal and cost-effective solution for boosting light utilization, a problem of crucial importance for ultrathin solar cells. PMID:26039258

  15. Self-assembly of Janus particles confined in a channel

    NASA Astrophysics Data System (ADS)

    Sobrino Fernández, M.; Misko, V. R.; Peeters, F. M.

    2014-02-01

    Janus particles present an important class of building blocks for directional assembly. These are compartmentalized colloids with two different hemispheres. Here, we consider a two-dimensional model of Janus disks consisting of a hydrophobic semicircle and an electro-negatively charged one. Placed in a solution, the hydrophobic sides will attract each other while the charged sides will give rise to a repulsive force. Using molecular dynamics simulations, we study the morphology of these particles when confined in a channel-like environment using a one dimensional harmonic confinement potential. The interest to this system is first of all due to the fact that it could serve as a simple model for membrane formation. Indeed, the recently synthesized new class of artificial amphiphiles, known as Janus dendrimers, were shown to self-assemble in bilayer structures mimicking biological membranes. In turn, Janus particles that combine the amphiphilicity and colloidal rigidity serve as a good model for Janus dendrimers. A variety of ordered membrane-like morphologies are found consisting of single and multiple chain configurations with different orientations of the particles with respect to each other that we summarize in a phase diagram.

  16. Controlling decay dynamics of quantum emitters with Plsmonic self assembly templates

    NASA Astrophysics Data System (ADS)

    Indukuri, S. R. K. Chaitanya; Basu, J. K.

    2015-03-01

    Controlling the emission of quantum dots by tailoring local density of states(LDOS) in self assembled plasmonic template. Using very small diameter gold (Au) spherical nanoantenna within a polymer tem plate randomly dispersed with quantum dots, we show how the photoluminescence intensity and lifetime anisotropy of these dots can be significantly enhanced through LDOS tuning. We also studied the effect of dispersion, wider range of geometric and spectral parameters bringing out the versatility of these functional plasmonic templates. We studied the effect of nano antenna distribution on radiative and non radiative decay rates in the templates. We demonstrated that the decay dynamics in the plasmonic templates can be controlled in a facile manner by changing the filling fraction of the Au nanoparticles. This polarization dependent anisotropic decay dynamics for the quantum emitters is determined by polarization dependent LDOS of the plasmonic templates as demonstrated by FDTD simulations. Our work provides a new method to achieve spontaneous emission intensity and anisotropy enhancement with nanoscale plasmon resonators for applications from controlled photon emitters to light harvesting. DST, India Nanomission.

  17. 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

  18. Self-assembled single-crystal silicon circuits on plastic

    PubMed Central

    Stauth, Sean A.; Parviz, Babak A.

    2006-01-01

    We demonstrate the use of self-assembly for the integration of freestanding micrometer-scale components, including single-crystal, silicon field-effect transistors (FETs) and diffusion resistors, onto flexible plastic substrates. Preferential self-assembly of multiple microcomponent types onto a common platform is achieved through complementary shape recognition and aided by capillary, fluidic, and gravitational forces. We outline a microfabrication process that yields single-crystal, silicon FETs in a freestanding, powder-like collection for use with self-assembly. Demonstrations of self-assembled FETs on plastic include logic inverters and measured electron mobility of 592 cm2/V-s. Finally, we extend the self-assembly process to substrates each containing 10,000 binding sites and realize 97% self-assembly yield within 25 min for 100-?m-sized elements. High-yield self-assembly of micrometer-scale functional devices as outlined here provides a powerful approach for production of macroelectronic systems. PMID:16968780

  19. 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.

  20. 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). Using AFM force measurements discrete unbinding forces between surface attached P22 and LPS were obtained. Both whole P22 and tailspike proteins separated from the P22 capsid were used. The unbinding force histograms point to discrete forces between substrate-supported P22 and LPS. The unit unbinding force was found to decrease with decreasing force loading rate and increasing temperature. By fitting the force data with the Bell model, an energy barrier of approximately 55 KJ/mol was obtained. The resilience of phage binding to pH variation and hydration/dehydration cycles argues for the robustness of potential phage-based devices.

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

    PubMed

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

    2013-07-01

    The huge and intelligent processing power of three-dimensional (3D) biological "processors" like the human brain with clock speeds of only 0.1 kHz is an extremely fascinating property, which is based on a massively parallel interconnect strategy. Artificial silicon microprocessors are 7 orders of magnitude faster. Nevertheless, they do not show any indication of intelligent processing power, mostly due to their very limited interconnectivity. Massively parallel interconnectivity can only be realized in three dimensions. Three-dimensional artificial processors would therefore be at the root of fabricating artificially intelligent systems. A first step in this direction would be the self-assembly of silicon based building blocks into 3D structures. We report on the self-assembly of such building blocks by molecular recognition, and on the electrical characterization of the formed assemblies. First, planar silicon substrates were functionalized with self-assembling monolayers of 3-aminopropyltrimethoxysilane for coupling of oligonucleotides (single stranded DNA) with glutaric aldehyde. The oligonucleotide immobilization was confirmed and quantified by hybridization with fluorescence-labeled complementary oligonucleotides. After the individual processing steps, the samples were analyzed by contact angle measurements, ellipsometry, atomic force microscopy, and fluorescence microscopy. Patterned DNA-functionalized layers were fabricated by microcontact printing (?CP) and photolithography. Silicon microcubes of 3 ?m edge length as model objects for first 3D self-assembly experiments were fabricated out of silicon-on-insulator (SOI) wafers by a combination of reactive ion etching (RIE) and selective wet etching. The microcubes were then surface-functionalized using the same protocol as on planar substrates, and their self-assembly was demonstrated both on patterned silicon surfaces (88% correctly placed cubes), and to cube aggregates by complementary DNA functionalization and hybridization. The yield of formed aggregates was found to be about 44%, with a relative fraction of dimers of some 30%. Finally, the electrical properties of the formed dimers were characterized using probe tips inside a scanning electron microscope. PMID:23786592

  2. Peptide-directed self-assembly of hydrogels

    PubMed Central

    Kope?ek, Jind?ich; Yang, Jiyuan

    2009-01-01

    This review focuses on the self-assembly of macromolecules mediated by the biorecognition of peptide/protein domains. Structures forming ?-helices and ?-sheets have been used to mediate self-assembly into hydrogels of peptides, reactive copolymers and peptide motifs, block copolymers, and graft copolymers. Structural factors governing the self-assembly of these molecules into precisely defined three-dimensional structures (hydrogels) are reviewed. The incorporation of peptide motifs into hybrid systems, composed of synthetic and natural macromolecules, enhances design opportunities for new biomaterials when compared to individual components. PMID:18952513

  3. Examples of Molecular Self-Assembly at Surfaces.

    PubMed

    Whitelam, Stephen

    2015-10-01

    The self-assembly of molecules at surfaces can be caused by a range of physical mechanisms. Assembly can be driven by intermolecular forces, or molecule-surface forces, or both; it can result in structures that are in equilibrium or that are kinetically trapped. Here we review examples of self-assembly at surfaces focusing on a physical understanding of what causes patterns seen in experiment. Some apparently disparate systems can be described in similar physical terms, indicating that simple factors - such as the geometry and energy scale of intermolecular binding - are key to understanding the self-assembly of those systems. PMID:25873520

  4. 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

  5. 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 ?-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 ?-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

  6. Molecularly engineered self-assembling membranes for cell-mediated degradation.

    PubMed

    Ferreira, Daniela S; Lin, Yi-An; Cui, Honggang; Hubbell, Jeffrey A; Reis, Rui L; Azevedo, Helena S

    2015-03-11

    The use of peptide engineering to develop self-assembling membranes that are responsive to cellular enzyme activities is reported. The membranes are obtained by combining hyaluronan (HA) and a rationally designed peptide amphiphile (PA) containing a proteolytic domain (GPQGIWGQ octapeptide) sensitive to matrix metalloproteinase-1 (MMP-1). Insertion of an octapeptide in a typical PA structure does not disturb its self-assembly into fibrillar nanostructures neither the ability to form membranes with HA. In vitro enzymatic degradation with hyaluronidase and MMP-1 shows that membranes containing the MMP-1 substrate exhibit enhanced enzymatic degradation, compared with control membranes (absence of MMP-1 cleavable peptide or containing a MMP-1 insensitive sequence), being completely degraded after 7 days. Cell viability and proliferation is minimally affected by the enzymatically cleavable functionality of the membrane, but the presence of MMP-1 cleavable sequence does stimulate the secretion of MMP-1 by fibroblasts and interfere with matrix deposition, particularly the deposition of collagen. By showing cell-responsiveness to biochemical signals presented on self-assembling membranes, this study highlights the ability of modulating certain cellular activities through matrix engineering. This concept can be further explored to understand the cellular remodeling process and as a strategy to develop artificial matrices with more biomimetic degradation for tissue engineering applications. PMID:25413155

  7. Electrostatic self-assembly of biomolecules

    NASA Astrophysics Data System (ADS)

    Olvera de La Cruz, Monica

    2015-03-01

    Charged filaments and membranes are natural structures abundant in cell media. In this talk we discuss the assembly of amphiphiles into biocompatible fibers, ribbons and membranes. We describe one- and two-dimensional assemblies that undergo re-entrant transitions in crystalline packing in response to changes in the solution pH and/or salt concentration resulting in different mesoscale morphologies and properties. In the case of one-dimensional structures, we discuss self-assembled amphiphiles into highly charged nanofibers in water that order into two-dimensional crystals. These fibers of about 6 nm cross-sectional diameter form crystalline arrays with inter-fiber spacings of up to 130 nm. Solution concentration and temperature can be adjusted to control the inter-fiber spacings. The addition of salt destroys crystal packing, indicating that electrostatic repulsions are necessary for the observed ordering. We describe the crystallization of bundles of filament networks interacting via long-range repulsions in confinement by a phenomenological model. Two distinct crystallization mechanisms in the short and large screening length regimes are discussed and the phase diagram is obtained. Simulation of large bundles predicts the existence of topological defects among bundled filaments. Crystallization processes driven by electrostatic attractions are also discussed. Funded by Center for Bio-Inspired Energy Science (CBES), which is an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0000989.

  8. 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.

  9. 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.

  10. Self-assembled biomimetic superhydrophobic hierarchical arrays.

    PubMed

    Yang, Hongta; Dou, Xuan; Fang, Yin; Jiang, Peng

    2013-09-01

    Here, we report a simple and inexpensive bottom-up technology for fabricating superhydrophobic coatings with hierarchical micro-/nano-structures, which are inspired by the binary periodic structure found on the superhydrophobic compound eyes of some insects (e.g., mosquitoes and moths). Binary colloidal arrays consisting of exemplary large (4 and 30 ?m) and small (300 nm) silica spheres are first assembled by a scalable Langmuir-Blodgett (LB) technology in a layer-by-layer manner. After surface modification with fluorosilanes, the self-assembled hierarchical particle arrays become superhydrophobic with an apparent water contact angle (CA) larger than 150°. The throughput of the resulting superhydrophobic coatings with hierarchical structures can be significantly improved by templating the binary periodic structures of the LB-assembled colloidal arrays into UV-curable fluoropolymers by a soft lithography approach. Superhydrophobic perfluoroether acrylate hierarchical arrays with large CAs and small CA hysteresis can be faithfully replicated onto various substrates. Both experiments and theoretical calculations based on the Cassie's dewetting model demonstrate the importance of the hierarchical structure in achieving the final superhydrophobic surface states. PMID:23786830

  11. Self-Assembled Microdisk Lasers of Perylenediimides.

    PubMed

    Yu, Zhenyi; Wu, Yishi; Liao, Qing; Zhang, Haihua; Bai, Shuming; Li, Hui; Xu, Zhenzhen; Sun, Chunlin; Wang, Xuedong; Yao, Jiannian; Fu, Hongbing

    2015-12-01

    Organic solid-state lasers (OSSLs) have been a topic of intensive investigations. Perylenediimide (PDI) derivatives are widely used in organic thin-film transistors and solar cells. However, OSSLs based on neat PDIs have not been achieved yet, owing to the formation of H-aggregates and excimer trap-states. Here, we demonstrated the first PDI-based OSSL from whispering-gallery mode (WGM) hexagonal microdisk (hMD) microcavity of N,N'-bis(1-ethylpropyl)-2,5,8,11-tetrakis(p-methyl-phenyl)-perylenediimide (mp-PDI) self-assembled from solution. Single-crystal data reveal that mp-PDI molecules stack into a loosely packed twisted brickstone arrangement, resulting in J-type aggregates that exhibit a solid-state photoluminescence (PL) efficiency ? > 15%. Moreover, we found that exciton-vibration coupling in J-aggregates leads to an exceptional ultrafast radiative decay, which reduces the exciton diffusion length, in turn, suppresses bimolecular exciton annihilation (bmEA) process. These spectral features, plus the optical feedback provided by WGM-hMD microcavity, enable the observation of multimode lasing as evidenced by nonlinear output, spectral narrowing, and temporal coherence of laser emission. With consideration of high carrier-mobility associated with PDIs, hMDs of mp-PDI are attractive candidates on the way to achieve electrically driven OSSL. PMID:26580969

  12. Electronically Guided Self Assembly within Quantum Corrals

    NASA Astrophysics Data System (ADS)

    Cao, Rongxing; Miao, Bingfeng; Zhong, Zhangfeng; Sun, Liang; You, Biao; Zhang, Wei; Wu, Di; Hu, An; Bader, Samuel; Ding, Haifeng; Center Collaboration; Low Dimensional Magnetism Team

    2013-03-01

    A grand challenge of nanoscience is to master the control of structure and properties in order to go beyond present day functionality. The creation of nanostructures via atom manipulation by means of a scanning probe represents one of the great achievements of the nano era. Here we build on this achievement to self-assemble nanostructures within quantum corrals. We constructed circular and triangular Fe quantum corrals on Ag(111) substrate via STM manipulation and studied the quantum confinement of electronic states and the diffusion of Gd atoms inside the corrals. Statistical results reveal the motion of the Gd atoms forming several individual orbits that are closely related to the local density of states. We experimentally demonstrate that different self-organized Gd atomic structures are formed within 30-nm circular and triangular Fe quantum corrals with a step-by-step guiding process. The findings demonstrate that quantum confinement can be used to engineer atomic structures and atom diffusion. And 30-nm resolution can be reached by means of advanced lithography. Adding quantum engineering to augment it opens new possibilities for local functionality design down to the atomic scale. Work at Nanjing is supported by the State Key Program for Basic Research of China (Grant No. 2010CB923401), NSFC (Grants Nos. 10974087, 10834001, and 11023002) and PAPD.

  13. 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 ?-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. PMID:26419936

  14. 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. PMID:26554000

  15. Excitation migration in fluctuating light-harvesting antenna systems.

    PubMed

    Chmeliov, Jevgenij; Trinkunas, Gediminas; van Amerongen, Herbert; Valkunas, Leonas

    2016-01-01

    Complex multi-exponential fluorescence decay kinetics observed in various photosynthetic systems like photosystem II (PSII) have often been explained by the reversible quenching mechanism of the charge separation taking place in the reaction center (RC) of PSII. However, this description does not account for the intrinsic dynamic disorder of the light-harvesting proteins as well as their fluctuating dislocations within the antenna, which also facilitate the repair of RCs, state transitions, and the process of non-photochemical quenching. Since dynamic fluctuations result in varying connectivity between pigment-protein complexes, they can also lead to non-exponential excitation decay kinetics. Based on this presumption, we have recently proposed a simple conceptual model describing excitation diffusion in a continuous medium and accounting for possible variations of the excitation transfer pathways. In the current work, this model is further developed and then applied to describe fluorescence kinetics originating from very diverse antenna systems, ranging from PSII of various sizes to LHCII aggregates and even the entire thylakoid membrane. In all cases, complex multi-exponential fluorescence kinetics are perfectly reproduced on the entire relevant time scale without assuming any radical pair equilibration at the side of the excitation quencher, but using just a few parameters reflecting the mean excitation energy transfer rate as well as the overall average organization of the photosynthetic antenna. PMID:25605669

  16. DNA-Based Oligochromophores as Light-Harvesting Systems.

    PubMed

    Ensslen, Philipp; Brandl, Fabian; Sezi, Sabrina; Varghese, Reji; Kutta, Roger-Jan; Dick, Bernhard; Wagenknecht, Hans-Achim

    2015-06-22

    The chromophores ethynyl pyrene as blue, ethynyl perylene as green and ethynyl Nile red as red emitter were conjugated to the 5-position of 2'-deoxyuridine via an acetylene bridge. Using phosphoramidite chemistry on solid phase labelled DNA duplexes were prepared that bear single chromophore modifications, and binary and ternary combinations of these chromophore modifications. The steady-state and time-resolved fluorescence spectra of all three chromophores were studied in these modified DNA duplexes. An energy-transfer cascade occurs from ethynyl pyrene over ethynyl perylene to ethynyl Nile red and subsequently an electron-transfer cascade in the opposite direction (from ethynyl Nile red to ethynyl perylene or ethynyl pyrene, but not from ethynyl perylene to ethynyl pyrene). The electron-transfer processes finally provide charge separation. The efficiencies by these energy and electron-transfer processes can be tuned by the distances between the chromophores and the sequences. Most importantly, excitation at any wavelength between 350 and 700?nm finally leads to charge separated states which make these DNA samples promising candidates for light-harvesting systems. PMID:26069203

  17. 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 ?m) 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

  18. Understanding emergent functions in self-assembled fibrous networks

    NASA Astrophysics Data System (ADS)

    Sinko, Robert; Keten, Sinan

    2015-09-01

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

  19. Aqueous self-assembly of chromophore-conjugated amphiphiles.

    PubMed

    Molla, Mijanur Rahaman; Ghosh, Suhrit

    2014-12-28

    The self-assembly of ?-conjugated building blocks has been a topic of interest in last few years owing to their close relevance to optoelectronic device applications. If such building blocks are made amphiphilic by appropriate derivatization, then the self-assembly can be realized in water by the strong hydrophobic repulsive forces between the polar medium and the rigid ?-surface. On the other hand, as ?-? interactions are directional, such self-assembly can produce structurally precise nano-structures, compared to classical surfactants. With these objectives, the self-assembly of several amphiphilic ?-systems has been studied in the recent past and is described in this article. Examples include electron-deficient, electron-rich and also mixed assemblies of donor and acceptor type chromophores which produce many elegant soft structures such as micelles, vesicle, nanotubes and fibres etc. PMID:25375094

  20. Mechanical behavior and microstructure of self-assembling oligopeptide gels

    E-print Network

    Hammond, Nathan Allen

    2010-01-01

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

  1. Host-Guest Self-assembly in Block Copolymer Blends

    E-print Network

    Park, Woon Ik

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

  2. The Statistical Dynamics of Programmed Self-Assembly

    E-print Network

    Klavins, Eric

    The Statistical Dynamics of Programmed Self-Assembly Nils Napp Samuel Burden Eric Klavins Department of Electrical Engineering University of Washington Seattle, WA 98195 klavins- controlled manipulators in a natural way required sub- stantial effort. The analogous theory for programmed

  3. 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 ?–? stacking interactions. The electronic conductivity of the T 1 and T 2 films was tested by a four-probe method.

  4. Self-assembly of helical ribbons from chiral amphiphiles

    E-print Network

    Zastavker, Yevgeniya Vladimirovna, 1971-

    2001-01-01

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

  5. Assessment of colloidal self-assembly for photonic crystal

    E-print Network

    Yip, Chan Hoe

    2006-01-01

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

  6. 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

  7. Self-assembly of globular protein-polymer diblock copolymers

    E-print Network

    Thomas, Carla S. (Carla Stephanie)

    2014-01-01

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

  8. Ordering Control of Self-Assembled Colloidal Crystals

    E-print Network

    Koh, Yaw Koon

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

  9. 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 ?-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

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

    NASA Astrophysics Data System (ADS)

    Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

    2013-05-01

    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.

  11. 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, ?-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

  12. 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 ~\

  13. Optimized Ratiometric Fluorescent Probes by Peptide Self-Assembly.

    PubMed

    Cai, Yanbin; Zhan, Jie; Shen, Haosheng; Mao, Duo; Ji, Shenglu; Liu, Ruihua; Yang, Bing; Kong, Deling; Wang, Ling; Yang, Zhimou

    2016-01-01

    We report in this study on optimized ratiometric fluorescent probes by peptide self-assembly. The resulting self-assembled nanoprobes show extraordinary stability in aqueous solutions and extremely low background fluorescence in buffer solutions. Our optimized probes with much bigger ratiometric fluorescence ratios also show an enhanced cellular uptake, lower background noise, and much brighter fluorescence signal in the cell experiment. Our study provides a versatile and very useful strategy to design and produce fluorescent probes with better performance. PMID:26630460

  14. Self-assembly of amphiphilic peanut-shaped nanoparticles

    E-print Network

    Stephen Whitelam; Stefan A. F. Bon

    2010-02-19

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

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

    PubMed Central

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

    2012-01-01

    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

  16. 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. PMID:26322626

  17. Self assembly: An approach to terascale integration

    SciTech Connect

    Singer, S.

    1993-09-01

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

  18. Light-Harvesting Function in the Diatom Phaeodactylum tricornutum1

    PubMed Central

    Owens, Thomas G.

    1986-01-01

    The distribution of excitation energy between photosystems I and II (PSI and PSII) was investigated in the marine diatom Phaeodactylum tricornutum (Bohlin) using light-induced changes in fluorescence yield and rate of modulated O2 evolution. The intensity dependence of the fast fluorescence rise in dark adapted cells (±DCMU) suggests that light absorbed by the major antenna complex was not delivered preferentially to PSII but is more equally distributed between the photosystems. Reversible, slow fluorescence yield changes measured in the absence of DCMU were correlated with decreased initial fluorescence and rate constants for PSII photochemistry, increased variable fluorescence, alteration of the fluorescence excitation and emission spectra, and could be effected by either 510 nm (PSII) or 704 nm (PSI) light. Slow, reversible fluorescence yield changes were also observed in the presence of DCMU, but were characterized by a loss of both initial and variable fluorescence and could not be induced by PSI light. The absence of slow changes in the yield of fluorescence and rate of modulated O2 evolution, following addition or removal of PSI background light to modulated PSII excitation, does not support regulation of excitation energy density in PSI at the expense of PSII. The results suggest that adjustments are made at the level of excitation energy transfer to the PSII reaction center which prevent prolonged loss of photosynthetic capacity. Energy distribution is regulated by ionic distributions independently of the plastoquinone pool redox state. These differences in light-harvesting function are probably a response to the aquatic light field and may account for the success of diatoms in low and variable light environments. PMID:16664695

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

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

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

    PubMed Central

    Pan, Yong; Mu, Ning; Shao, Shengyu; Yang, Liu; Wang, Wen; Xie, Xiao; He, Shitang

    2015-01-01

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

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

    PubMed

    Pan, Yong; Mu, Ning; Shao, Shengyu; Yang, Liu; Wang, Wen; Xie, Xiao; He, Shitang

    2015-01-01

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

  4. 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 ?-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

  5. Molecular Adaptation of Photoprotection: Triplet States in Light-Harvesting Proteins

    PubMed Central

    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

    2011-01-01

    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. PMID:21843485

  6. Structures Self-Assembled Through Directional Solidification

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2005-01-01

    Nanotechnology has created a demand for new fabrication methods with an emphasis on simple, low-cost techniques. Directional solidification of eutectics (DSE) is an unconventional approach in comparison to low-temperature biomimetic approaches. A technical challenge for DSE is producing microstructural architectures on the nanometer scale. In both processes, the driving force is the minimization of Gibb's free energy. Selfassembly by biomimetic approaches depends on weak interaction forces between organic molecules to define the architectural structure. The architectural structure for solidification depends on strong chemical bonding between atoms. Constituents partition into atomic-level arrangements at the liquid-solid interface to form polyphase structures, and this atomic-level arrangement at the liquid-solid interface is controlled by atomic diffusion and total undercooling due to composition (diffusion), kinetics, and curvature of the boundary phases. Judicious selection of the materials system and control of the total undercooling are the keys to producing structures on the nanometer scale. The silicon-titanium silicide (Si-TiSi2) eutectic forms a rod structure under isothermal cooling conditions. At the NASA Glenn Research Center, directional solidification was employed along with a thermal gradient to promote uniform rods oriented with the thermal gradient. The preceding photomicrograph shows the typical transverse microstructure of a solidified Si-TiSi2 eutectic composition. The dark and light gray regions are Si and TiSi2, respectively. Preferred rod orientation along the thermal gradient was poor. The ordered TiSi2 rods have a narrow distribution in diameter of 2 to 3 m, as shown. The rod diameter showed a weak dependence on process conditions. Anisotropic etch behavior between different phases provides the opportunity to fabricate structures with high aspect ratios. The photomicrographs show the resulting microstructure after a wet chemical etch and a 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.

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

    PubMed Central

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

    2013-01-01

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

  8. Self-Assembly for the Synthesis of Functional Biomaterials

    PubMed Central

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Yaghoubi, Houman

    Harvesting solar energy can potentially be a promising solution to the energy crisis now and in the future. However, material and processing costs continue to be the most important limitations for the commercial devices. A key solution to these problems might lie within the development of bio-hybrid solar cells that seeks to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. The bio-photoelectrochemical cell technologies exploit biomimetic means of energy conversion by utilizing plant-derived photosystems which can be inexpensive and ultimately the most sustainable alternative. Plants and photosynthetic bacteria harvest light, through special proteins called reaction centers (RCs), with high efficiency and convert it into electrochemical energy. In theory, photosynthetic RCs can be used in a device to harvest solar energy and generate 1.1 V open circuit voltage and ~1 mA cm-2 short circuit photocurrent. Considering the nearly perfect quantum yield of photo-induced charge separation, efficiency of a protein-based solar cell might exceed 20%. In practice, the efficiency of fabricated devices has been limited mainly due to the challenges in the electron transfer between the protein complex and the device electrodes as well as limited light absorption. The overarching goal of this work is to increase the power conversion efficiency in protein-based solar cells by addressing those issues (i.e. electron transfer and light absorption). This work presents several approaches to increase the charge transfer rate between the photosynthetic RC and underlying electrode as well as increasing the light absorption to eventually enhance the external quantum efficiency (EQE) of bio-hybrid solar cells. The first approach is to decrease the electron transfer distance between one of the redox active sites in the RC and the underlying electrode by direct attachment of the of protein complex 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. Guided and magnetic self-assembly of tunable magnetoceptive gels.

    PubMed

    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

  11. Hierarchical self-assembly of chiral fibres from achiral particles

    PubMed Central

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

    2012-01-01

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

  12. Self-assembly properties of a model RING domain

    PubMed Central

    Kentsis, Alex; Gordon, Ronald E.; Borden, Katherine L. B.

    2002-01-01

    RING domains act in a variety of essential cellular processes but have no general function ascribed to them. Here, we observe that purified arenaviral protein Z, constituted almost entirely by its RING domain, self-assembles in vitro into spherical structures that resemble functional bodies formed by Z in infected cells. By using a variety of biophysical methods we provide a thermodynamic and kinetic framework for the RING-dependent self-assembly of Z. Assembly appears coupled to substantial conformational reorganization and changes in zinc coordination of site II of the RING. Thus, the rate-limiting nature of conformational reorganization observed in the folding of monomeric proteins can also apply to the assembly of macromolecular scaffolds. These studies describe a unique mechanism of nonfibrillar homogeneous self-assembly and suggest a general function of RINGs in the formation of macromolecular scaffolds that are positioned to integrate biochemical processes in cells. PMID:11792829

  13. Self-assembly of polyhedral shells: A molecular dynamics study

    E-print Network

    D. C. Rapaport

    2004-07-18

    The use of reduced models for investigating the self-assembly dynamics underlying protein shell formation in spherical viruses is described. The spontaneous self-assembly of these polyhedral, supramolecular structures, in which icosahedral symmetry is a conspicuous feature, is a phenomenon whose dynamics remain unexplored; studying the growth process by means of computer simulation provides access to the mechanisms underlying assembly. In order to capture the more universal aspects of self-assembly, namely the manner in which component shapes influence structure and assembly pathway, in this exploratory study low-resolution approximations are used to represent the basic protein building blocks. Alternative approaches involving both irreversible and reversible assembly are discussed, models based on both schemes are introduced, and examples of the resulting behavior described.

  14. 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

  15. 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.

  16. Self-assembly of DNA-functionalized colloids

    E-print Network

    Panagiotis E. Theodorakis; Nikolaos G. Fytas; Gerhard Kahl; Christoph Dellago

    2015-06-16

    Colloidal particles grafted with single-stranded DNA (ssDNA) chains can self-assemble into a number of different crystalline structures, where hybridization of the ssDNA chains creates links between colloids stabilizing their structure. Depending on the geometry and the size of the particles, the grafting density of the ssDNA chains, and the length and choice of DNA sequences, a number of different crystalline structures can be fabricated. However, understanding how these factors contribute synergistically to the self-assembly process of DNA-functionalized nano- or micro-sized particles remains an intensive field of research. Moreover, the fabrication of long-range structures due to kinetic bottlenecks in the self-assembly are additional challenges. Here, we discuss the most recent advances from theory and experiment with particular focus put on recent simulation studies.

  17. 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.

  18. Equation of State for Phospholipid Self-Assembly.

    PubMed

    Marsh, Derek

    2016-01-01

    Phospholipid self-assembly is the basis of biomembrane stability. The entropy of transfer from water to self-assembled micelles of lysophosphatidylcholines and diacyl phosphatidylcholines with different chain lengths converges to a common value at a temperature of 44°C. The corresponding enthalpies of transfer converge at ?-18°C. An equation of state for the free energy of self-assembly formulated from this thermodynamic data depends on the heat capacity of transfer as the sole parameter needed to specify a particular lipid. For lipids lacking calorimetric data, measurement of the critical micelle concentration at a single temperature suffices to define an effective heat capacity according to the model. Agreement with the experimental temperature dependence of the critical micelle concentration is then good. The predictive powers should extend also to amphiphile partitioning and the kinetics of lipid-monomer transfer. PMID:26745421

  19. Recombinant self-assembling peptides as biomaterials for tissue engineering.

    PubMed

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

    2010-12-01

    Synthetic nanostructures based on self-assembling systems that aim to mimic natural extracellular matrix are now being used as substrates in tissue engineering applications. Peptides are excellent starting materials for the self-assembly process as they can be readily synthesised both chemically and biologically. P??-4 is an 11 amino acid peptide that undergoes triggered self-assembly to form a self-supporting hydrogel. It exists as unimers of random coil conformations in water above pH 7.5 but at low pH adopts an antiparallel ?-sheet conformation. It also self-assembles under physiological conditions in a concentration-dependent manner. Here we describe an unimer P??-4 production system and the use of a simple site-directed mutagenesis approach to generate a series of other P??-family peptide expression vectors. We have developed an efficient purification strategy for these peptide biomaterials using a simple procedure involving chemical cleavage with cyanogen bromide then repeated filtration, lyophilisation and wash steps. We report peptide-fusion protein yields of ca. 4.64 g/L and we believe the highest reported recovery of a recombinant self-assembling peptide at 203 mg/L of pure recombinant P??-4. This peptide forms a self-supporting hydrogel under physiological conditions with essentially identical physico-chemical properties to the chemically synthesised peptide. Critically it also displays excellent cytocompatibility when tested with primary human dermal fibroblasts. This study demonstrates that high levels of a series of recombinant self-assembling peptides can be purified using a simple process for applications as scaffolds in tissue engineering. PMID:20932572

  20. Insight into the structure of light-harvesting complex II and its stabilization in detergent solution.

    PubMed

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

    2009-12-24

    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(2)O/D(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(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(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. PMID:19954150

  1. 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.

  2. Self-assembly and manipulation of particles on drop surfaces

    NASA Astrophysics Data System (ADS)

    Janjua, M.; Fischer, I. S.; Singh, P.

    2013-11-01

    We have recently shown that particles adsorbed on the surface of a drop can be self-assembled at the poles or the equator of the drop by applying a uniform electric field, and that this method can be used to separate on the surface of a drop particles experiencing positive dielectrophoresis from those experiencing negative dielectrophoresis. In this talk we show that the frequency of the electric field is an important parameter which can be used to modify the distribution of self-assembled monolayers.

  3. Self-Assembly of Tyrosine into Controlled Supramolecular Nanostructures.

    PubMed

    Ménard-Moyon, Cécilia; Venkatesh, V; Krishna, K Vijaya; Bonachera, Fanny; Verma, Sandeep; Bianco, Alberto

    2015-08-10

    In the context of designing novel amino acid nanostructures, the capacity of tyrosine alone to form well-ordered structures under different conditions was explored. It was observed that Tyr can self-assemble into well-defined morphologies when deposited onto surfaces for transmission electron microscopy, atomic force microscopy, and scanning electron microscopy. The influence of various parameters that can modulate the self-assembly process, including concentration of the amino acid, aging time, and solvent, was studied. Different supramolecular architectures, including nanoribbons, branched structures, and fern-like arrangements were also observed. PMID:26179867

  4. Polymersomes confined self-assembly: micellisation in 2D

    E-print Network

    Ruiz-Perez, Lorena; Gaitzsch, Jens; Joseph, Adrian; Sutto, Ludovico; Gervasio, Francesco Luigi; Battaglia, Giuseppe

    2015-01-01

    Biological systems exploit self-assembly to create complex structures whose arrangements are finely controlled from molecular to mesoscopic level. Herein we report an example of using fully synthetic systems that mimic two levels of self-assembly. We show the formation of vesicles using amphiphilic copolymers whose chemical nature is chosen to control both membrane formation and membrane-confined interactions. We report polymersomes with patterns that emerge by engineering interfacial tension within the polymersome surface. This allows the formation of domains whose topology is tailored by the chemical synthesis paving the avenue to complex supramolecular designs functionally similar to those found in viruses and trafficking vesicles.

  5. 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.

  6. Self-assembly behavior of A( 4-miktoarm star terpolymers

    NASA Astrophysics Data System (ADS)

    Zhou, Ling; Fang, Jinghuai; Peng, Ju; Zhang, Jianguo

    2013-11-01

    The self-assembly of miktoarm star terpolymers provides a powerful route to obtain complex microstructures. Here we use self-consistent field theory to investigate the melt morphologies self-assembled from A( 4-miktoarm star terpolymers composed of a homopolymer arm A and three copolymer arms BC. A variety of ordered microstructures are predicted by controlling the volume fractions of different components and the Flory-Huggins interaction parameters. At the same time a series of order-order and order-disorder transitions are observed. The results may be helpful for the design of novel microstructures.

  7. 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.

  8. Backfilled, self-assembled monolayers and methods of making same

    DOEpatents

    Fryxell, Glen E. (Kennewick, WA); Zemanian, Thomas S. (Richland, WA); Addleman, R. Shane (Benton City, WA); Aardahl, Christopher L. (Sequim, WA); Zheng, Feng (Richland, WA); Busche, Brad (Raleigh, NC); Egorov, Oleg B. (West Richland, WA)

    2009-06-30

    Backfilled, self-assembled monolayers and methods of making the same are disclosed. The self-assembled monolayer comprises at least one functional organosilane species and a substantially random dispersion of at least one backfilling organosilane species among the functional organosilane species, wherein the functional and backfilling organosilane species have been sequentially deposited on a substrate. The method comprises depositing sequentially a first organosilane species followed by a backfilling organosilane species, and employing a relaxation agent before or during deposition of the backfilling organosilane species, wherein the first and backfilling organosilane species are substantially randomly dispersed on a substrate.

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

    E-print Network

    Pan, Keyao

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

  10. 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 compounds has much to do with the breakage of intramolecular pi-stacking interactions and the formation of stronger intermolecular pi-stacking interactions. Finally, the transport of K+ through nanoporous membranes and single nanopores with novel PEG-type polymeric dispersions is demonstrated. This thesis concludes with future work toward developing more advanced transporters and proposes novel uses for anthraquinone-appended polymers as proton exchange membranes and DNA-base pair interchelators.

  11. BULK TITANIUM MICROFLUIDIC NETWORKS FOR PROTEIN SELF-ASSEMBLY STUDIES

    E-print Network

    MacDonald, Noel C.

    BULK TITANIUM MICROFLUIDIC NETWORKS FOR PROTEIN SELF-ASSEMBLY STUDIES E.R. Parker1 , L.S. Hirst2 developed micromachining technique to fabricate microfluidic networks in thin titanium foils. These devices been integrated into the fabrication process in order to minimize protein adsorption to the titanium

  12. Patterned Substrates to Direct Self-Assembly of Particle Monolayers

    NASA Astrophysics Data System (ADS)

    Ferraro, Mark; Truskett, Thomas; Bonnecaze, Roger

    2014-03-01

    As current lithographic techniques approach practical engineering limits for resolution, directed self-assembly of nanoparticles becomes an attractive scalable nanomanufacturing process for creating ordered arrays of particles at a variety of length scales that could be used both as patterning agents and functional materials. However the roles of interparticle forces and external fields on directed self-assembly of particles is not well understood. In this presentation density functional theory (DFT) and Monte Carlo (MC) simulations are used to explore the use of larger scale patterned substrates to drive smaller scale directed self-assembly of particle monolayers. Square patterned substrates with varying energy barriers at length scales N-fold the final desired particle pitch are considered (N>1). Ranges of N, bulk density and patterned substrate field strength are identified that disrupt the entropically favored hexagonally close-packed lattice and promote square lattice formation for hard-spheres. Monte Carlo simulations are then employed to verify the predictions from DFT and to further analyze the self-assembly process. These DFT and MC results are used to discuss and define the energetically and kinetically accessible spaces for non-hexagonal lattice formation.

  13. Submicrometre geometrically encoded fluorescent barcodes self-assembled from DNA

    E-print Network

    Church, George M.

    with features spaced by 40 nm. One species of the barcodes was used to tag yeast surface receptors, which dimensions remains challenging, with only a few reports3,7,8,12 of submicrometre barcodes and no more than 11Submicrometre geometrically encoded fluorescent barcodes self-assembled from DNA Chenxiang Lin1

  14. Energy landscapes for the self-assembly of supramolecular polyhedra

    E-print Network

    Menon, Govind

    Energy landscapes for the self-assembly of supramolecular polyhedra Emily R. Russell , Govind Menon June 10, 2015 Abstract We develop a mathematical model for the energy landscape of poly- hedral the combinatorial configuration space. The energy landscape of our model is the energy of each state in the com

  15. 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

  16. Soft self-assembled nanoparticles with temperature-dependent properties

    E-print Network

    Lorenzo Rovigatti; Barbara Capone; Christos N. Likos

    2015-09-10

    The fabrication of versatile building blocks that are reliably self-assemble into desired ordered and disordered phases is amongst the hottest topics in contemporary material 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 a specific funcionalisation of the building blocks is required. Telechelic star polymers, i.e., star polymers made of a number $f$ of 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, at fixed external conditions the self-assembly behaviour depends only on the number of arms and/or on the ratio of solvophobic to solvophilic monomers. However, changes in temperature and/or solvent quality makes it possible to reliably change the number and size of the attractive patches. This allows to steer 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.

  17. Self-assembled lipid and membrane protein polyhedral nanoparticles

    E-print Network

    Pace, Norman

    Self-assembled lipid and membrane protein polyhedral nanoparticles Tamara Bastaa,1 , Hsin-Jui Wub,1 of small conductance (MscS) as a model protein, we prepared mem- brane protein polyhedral nanoparticles prepared membrane protein polyhedral nanoparticles (MPPNs) of the bacterial mechanosensitive channel of

  18. pH-directed self-assembling helical peptide conformation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The beta-sheet and alpha-helix peptide conformation are two of the most fundamentally ordered secondary structures found in proteins and peptides. They also give rise to self-assembling motifs that form macromolecular channels and nanostructures. Through design these conformations can yield enhance...

  19. Chemical mimicry of viral capsid self-assembly

    PubMed Central

    Olson, Arthur J.; Hu, Yunfeng H. E.; Keinan, Ehud

    2007-01-01

    Stable structures of icosahedral symmetry can serve numerous functional roles, including chemical microencapsulation and delivery of drugs and biomolecules, epitope presentation to allow for an efficient immunization process, synthesis of nanoparticles of uniform size, observation of encapsulated reactive intermediates, formation of structural elements for supramolecular constructs, and molecular computing. By examining physical models of spherical virus assembly we have arrived at a general synthetic strategy for producing chemical capsids at size scales between fullerenes and spherical viruses. Such capsids can be formed by self-assembly from a class of molecules developed from a symmetric pentagonal core. By designing chemical complementarity into the five interface edges of the molecule, we can produce self-assembling stable structures of icosahedral symmetry. We considered three different binding mechanisms: hydrogen bonding, metal binding, and formation of disulfide bonds. These structures can be designed to assemble and disassemble under controlled environmental conditions. We have conducted molecular dynamics simulation on a class of corannulene-based molecules to demonstrate the characteristics of self-assembly and to aid in the design of the molecular subunits. The edge complementarities can be of diverse structure, and they need not reflect the fivefold symmetry of the molecular core. Thus, self-assembling capsids formed from coded subunits can serve as addressable nanocontainers or custom-made structural elements. PMID:18093950

  20. Superstructures of self-assembled cobalt nanocrystals Youhui Gaoa)

    E-print Network

    Krishnan, Kannan M.

    Superstructures of self-assembled cobalt nanocrystals Youhui Gaoa) Institute of Multidisciplinary-dimensional superstructures of spherical cobalt nanocrystals are produced by the interplay between dipolar interaction fabrication, and can be extended to other nanocomposite materials fabrication if cobalt particles can act

  1. 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...

  2. Templated self-assembly for complex pattern fabrication

    E-print Network

    Chang, Jae-Byum

    2014-01-01

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

  3. Self-Assembled Polymer Membrane Capsules Inflated by Osmotic Pressure

    E-print Network

    and delivery of active agents are increasingly vital to technologies as varied as drug delivery, functionalSelf-Assembled Polymer Membrane Capsules Inflated by Osmotic Pressure Vernita D. Gordon,, Xi Chen@deas.harvard.edu Abstract: We fabricate and characterize capsules that are composite membranes, made of a polymer network

  4. Designing Ordered Nucleic Acid Self-Assembly Processes Rebecca Schulmana

    E-print Network

    Doty, David

    is designed and built. Typically, cars or computers are assembled using well- defined, sequential processesDesigning Ordered Nucleic Acid Self-Assembly Processes Rebecca Schulmana , David Dotyb a of biomolecular structures with diverse, intricate features across multiple length scales. Designing self

  5. Self-assembled domain structures: From micro- to nanoscale

    NASA Astrophysics Data System (ADS)

    Shur, Vladimir; Akhmatkhanov, Andrey; Lobov, Alexey; Turygin, Anton

    2015-06-01

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

  6. 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

  7. Self-Assembly of Globular Protein-Polymer Diblock Copolymers

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  8. Self-Assembled Computer Architecture: Design and Fabrication Theory

    E-print Network

    Dwyer, Chris

    : Sean Washburn #12;ii #12;iii © 2003 Christopher Leonard Dwyer ALL RIGHTS RESERVED #12;iv #12;v ABSTRACTSelf-Assembled Computer Architecture: Design and Fabrication Theory by Christopher L. Dwyer CHRISTOPHER L. DWYER: Self-Assembled Computer Architecture: Design and Fabrication Theory (under the direction

  9. Controlling self-assembly within nanospace for peptide nanoparticle fabrication

    E-print Network

    Chau, Ying

    , for the first time, we present a new approach to produce peptide nanoparticles, which involves controlling- cially in tissue engineering, drug delivery and biosensor fabrication.1­4 Self-assembling peptides for biosensor fabrication and nanofibers for tissue engineering. Using processing parameters to control

  10. Bicontinuous Surfaces in Self-assembling Amphiphilic Systems

    E-print Network

    Schwarz, Ulrich

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

  11. Supporting Information Self-Assembled Liquid Crystal Gels in Emulsion

    E-print Network

    Zhao, Yue

    Supporting Information Self-Assembled Liquid Crystal Gels in Emulsion Xia Tong,1 Jong Won Chung,2 emulsion. Fig. S1. Image a is the photomicrograph (reflection mode) of an emulsion cast on a glass slide. Polarizing photomicrographs showing (a) the droplets of liquid crystal emulsion without gelator and (b

  12. 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

  13. Fabrication of a Molecular Self-Assembled Monolayer Diode Using

    E-print Network

    Fabrication of a Molecular Self-Assembled Monolayer Diode Using Nanoimprint Lithography Michael D ABSTRACT We report a simple parallel process for the fabrication of nanoscale electrical contacts to probe), a patterning technology capable of sub-10 nm resolution. We fabricated multiple samples, each with 40 gold

  14. Electrochemical impedance sensing of DNA at PNA self assembled monolayer

    E-print Network

    Kwak, Juhyoun

    Electrochemical impedance sensing of DNA at PNA self assembled monolayer Tesfaye Hailu Degefa was investi- gated using electrochemical impedance spectroscopy (EIS) in the presence of target DNA and redox of the current is simple for such system, electrochemical impedance spectroscopy (EIS) has been shown to provide

  15. 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

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

    PubMed

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

    2012-05-01

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

  17. Linear length-dependent light-harvesting ability of silicon nanowire

    NASA Astrophysics Data System (ADS)

    Li, Yingfeng; Li, Meicheng; Li, Ruike; Fu, Pengfei; Jiang, Bing; Song, Dandan; Shen, Chao; Zhao, Yan; Huang, Rui

    2015-11-01

    Silicon nanowire (SiNW) is of great promising for photovoltaic applications due to its excellent performance in light-harvesting. Some experimental and theoretical results indicate its light-harvesting is dramatically length dependent, while there is still no investigation on this dependency. Through reliable simulations on the optical extinction and absorption spectra of SiNWs with varying lengths, we find that the light-harvesting ability of SiNW is linear with its length. For the SiNWs of the optimal diameter, 80 nm, the linearity between the light-concentration (light-absorption) multiples and length is about 133 ?m-1 (50 ?m-1). This linear relationship can be explained reasonably by the leaky modes theory.

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

    E-print Network

    Krüger, Tjaart P J

    2015-01-01

    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 u...

  19. Simulation and control of dynamic directed self-assembly of nanostructures

    E-print Network

    Ramaswamy, Sivaraman

    2015-01-01

    Self-assembled nanoscale structures are the basis for various technological advancements in functional materials, sensors, and molecular circuits and factories. With significant progress in self-assembly of periodic ...

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

    E-print Network

    Wood, Kris Cameron

    2007-01-01

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

  1. Luminescent Silicon Nanoparticles Capped by Conductive Polyaniline through the Self-Assembly Method

    E-print Network

    Swihart, Mark T.

    Luminescent Silicon Nanoparticles Capped by Conductive Polyaniline through the Self-Assembly Method polymer coating on free-standing luminescent silicon nanoparticles. The silicon nanoparticles maintained electron microscopy. The silane self-assembled monolayer effectively protected the silicon particles

  2. 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 systems in the literature. PMID:26421616

  3. Smart gating membranes with in situ self-assembled responsive nanogels as functional gates

    NASA Astrophysics Data System (ADS)

    Luo, Feng; Xie, Rui; Liu, Zhuang; Ju, Xiao-Jie; Wang, Wei; Lin, Shuo; Chu, Liang-Yin

    2015-10-01

    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.

  4. Self-assembly and mineralization of genetically modifiable biological nanofibers driven by beta-structure formation

    PubMed Central

    Xu, Hong; Cao, Binrui; George, Anne; Mao, Chuanbin

    2011-01-01

    Bio-inspired mineralization is an innovative approach to the fabrication of bone biomaterials mimicking the natural bone. Bone mineral hydroxylapatite (HAP) is preferentially oriented with c-axis parallel to collagen fibers in natural bone. However, such orientation control is not easy to achieve in artificial bone biomaterials. To overcome the lack of such orientation control, we fabricated a phage-HAP composite by genetically engineering M13 phage, a non-toxic bio-nanofiber, with two HAP-nucleating peptides derived from one of the non-collagenous proteins, Dentin Matrix Protein-1 (DMP1). The phage is a biological nanofiber that can be mass produced by infecting bacteria and is non-toxic to human beings. The resultant HAP-nucleating phages are able to self-assemble into bundles by forming ?-structure between the peptides displayed on their side walls. The ?-structure further promotes the oriented nucleation and growth of HAP crystals within the nanofibrous phage bundles with their c-axis preferentially parallel to the bundles. We proposed that the preferred orientation resulted from the stereochemical matching between the negatively charged amino acid residues within the ?-structure and the positively charged calcium ions on the (001) plane of HAP crystals. The self-assembly and mineralization driven by the ?-structure formation represent a new route for fabricating mineralized fibers that can serve as building blocks in forming bone repair biomaterials and mimic the basic structure of natural bones. PMID:21520924

  5. 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

  6. Nanometric self-assembling peptide layers maintain adult hepatocyte phenotype in sandwich cultures

    PubMed Central

    2010-01-01

    Background Isolated hepatocytes removed from their microenvironment soon lose their hepatospecific functions when cultured. Normally hepatocytes are commonly maintained under limited culture medium supply as well as scaffold thickness. Thus, the cells are forced into metabolic stress that degenerate liver specific functions. This study aims to improve hepatospecific activity by creating a platform based on classical collagen sandwich cultures. Results The modified sandwich cultures replace collagen with self-assembling peptide, RAD16-I, combined with functional peptide motifs such as the integrin-binding sequence RGD and the laminin receptor binding sequence YIG to create a cell-instructive scaffold. In this work, we show that a plasma-deposited coating can be used to obtain a peptide layer thickness in the nanometric range, which in combination with the incorporation of functional peptide motifs have a positive effect on the expression of adult hepatocyte markers including albumin, CYP3A2 and HNF4-alpha. Conclusions This study demonstrates the capacity of sandwich cultures with modified instructive self-assembling peptides to promote cell-matrix interaction and the importance of thinner scaffold layers to overcome mass transfer problems. We believe that this bioengineered platform improves the existing hepatocyte culture methods to be used for predictive toxicology and eventually for hepatic assist technologies and future artificial organs. PMID:21143997

  7. 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

  8. Growth, spectroscopy, and quantum optics of self-assembled quantum dot molecules

    NASA Astrophysics Data System (ADS)

    Gerardot, Brian D.

    Since their inception, semiconductor quantum dots (QDs) have attracted much attention due to properties which are analogous with individual atoms. In addition to classical applications, novel applications have been identified which exploit the strong confinement of both electrons and holes in self-assembled QDs. This artificial atom analogy can be extended to artificial molecules by coupling two neighboring quantum dots. This single quantum system has been proposed for entangled photon pair emission and two bit or quantum bit gate operations. This thesis focuses on self-assembled InAs/GaAs QD molecules, which have good optical quality and tunable electronic and optical properties. One significant drawback of the spontaneous nature of self-assembly is random site nucleation. The lateral ordering of epitaxial semiconductor quantum dots is investigated using crystal growth techniques on pre-patterned substrates. Using localized surface chemical potential engineering, the ability to create ordered quantum dot lattices is demonstrated. However, this positioning technique is not precise enough to investigate coupling between neighboring QDs. Therefore, coupling between two vertically stacked QDs is explored. The strain field above the first QD induces a nucleation site for a second QD. The different nucleation conditions naturally yield different optical and electronic properties in the QD pair. By applying an electric field, carrier transfer between two QDs of different confining potentials is measured using micro-photoluminescence. The crystal growth kinetics in each QD were then carefully optimized to independently tune the two QDs ground state transitions to nearly identical energies. Optical spectroscopy of a QD molecule shows that excitons are strongly localized on each QD, therefore minimizing electronic tunneling. However, two types of electrostatic coupling are observed: Coulombic attraction and dipole-dipole interaction. Two-photon emission correlations from the rich spectra exhibit strong antibunching, unambiguously demonstrating the formation of an artificial molecule. Temperature dependent photoluminescence measurements show that directional energy transfer takes place from the high energy QD to the low energy QD. A simple rate-equation model is used to simulate the photon correlation experiment with qualitative agreement.

  9. Heirarchical Self Assembly: Self Organized nano-structures in a nematically ordered matrix of self assembled polymeric chains

    E-print Network

    Shaikh Mubeena; Apratim Chatterji

    2014-12-04

    We report many different nano-structures which are formed when model nano-particles of different sizes (diameter {\\sigma} n ) are allowed to aggregate in a background matrix of semi-flexible self assembled polymeric worm like micellar chains. The different nano-structures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nano-particles. The different mor- phologies 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 nano-particles in the polymer ma- trix and, of course, the ratio of the size of self assembling nano-particles and self avoidance diameter of polymeric chains. We have used a hybrid semi-grand canonical Monte Carlo simulation scheme to obtain the (non-equilibrium) phase diagram of the self-assembled nano-structures. We observe rod-like structures of nano-particles 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 nano-particles and monomers, in which each crytal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the con- dition 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 nano-structures in the lab.

  10. Defects in the Self-Assembly of Block Copolymers and Their Relevance for Directed Self-Assembly.

    PubMed

    Li, Weihua; Müller, Marcus

    2015-07-24

    Block copolymer self-assembly provides a platform for fabricating dense, ordered nanostructures by encoding information in the chemical architecture of multicomponent macromolecules. Depending on the volume fraction of the components and chain topology, these macromolecules form a variety of spatially periodic microphases in thermodynamic equilibrium. The kinetics of self-assembly, however, often results in initial morphologies with defects, and the subsequent ordering is protracted. Different strategies have been devised to direct the self-assembly of copolymer materials by external fields to align and perfect the self-assembled nanostructures. Understanding and controlling the thermodynamics of defects, their response to external fields, and their dynamics is important because applications in microelectronics either require extremely low defect densities or aim at generating specific defects at predetermined locations to fabricate irregular device-oriented structures for integrated circuits. In this review, we discuss defect morphologies of block copolymers in the bulk and thin films, highlighting (a) analogies to and differences from defects in other crystalline materials, (b) the stability of defects and their dynamics, and PMID:25938921

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    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.

  12. Development of self-assembling nanowires containing electronically active oligothiophenes

    NASA Astrophysics Data System (ADS)

    Tsai, Wei-Wen

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

  13. Predicting supramolecular self-assembly on reconstructed metal surfaces

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    SciTech Connect

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

    2008-01-01

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

  15. A Hidden State in Light-Harvesting Complex II Revealed By Multipulse Spectroscopy

    E-print Network

    van Stokkum, Ivo

    ) is pivotal both for collecting solar radiation for photosynthesis, and for protection against photodamage by photosynthesis. In plants most pigments are found in light-harvesting complexes (LHCs): membrane-bound pigment where the rate of photon absorption is high enough to saturate the electron transfer chain between

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

    E-print Network

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

    2013-11-22

    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 amongst 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. Energy transfer is robust on the initial excitation conditions and temperature changes. Moreover, the same mechanism describes the coexistence of multiple timescales 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.

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

    E-print Network

    Distance-Engineered Plasmon-Enhanced Light Harvesting in CdSe Quantum Dots Shengye Jin,,§, Erica De) is essential for the development of efficient QD-based solar energy conversion systems. In this study, plasmon as a function of interparticle (QD to Ag NP) distance. Up to 24-fold plasmonic enhancement of fluorescence from

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

    E-print Network

    Elad Harel

    2011-10-31

    Photosynthesis, the process by which energy from sunlight drives cellular metabolism, relies on a unique organization of light-harvesting and reaction center complexes. Recently, the organization of light-harvesting LH2 complexes and dimeric reaction center-light harvesting I-PufX (RC-LH1-PufX) core complexes in membranes of purple non-sulfur bacteria was revealed by atomic force microscopy (AFM)1. Here, we report that the structure of LH2 and its organization within the membrane can be largely rationalized by a simple physical model that relies primarily on exciton transfer optimization. The process through which the light-harvesting complexes transfer excitation energy has been recognized to incorporate both coherent and incoherent processes mediated by the surrounding protein environment. Using the Haken-Strobl model, we show that the organization of the complexes in the membrane can be almost entirely explained by simple electrostatic considerations and that quantum effects act primarily to enforce robustness with respect to spatial disorder between complexes. The implications of such an arrangement are discussed in the context of biomimetic photosynthetic analogs capable of transferring energy efficiently across tens to hundreds of nanometers

  19. 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…

  20. 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. ...

  1. Population and coherence dynamics in light harvesting complex II (LH2) Shu-Hao Yeh, Jing Zhu, and Sabre Kais

    E-print Network

    Kais, Sabre

    Population and coherence dynamics in light harvesting complex II (LH2) Shu-Hao Yeh, Jing Zhu, 084110 (2012) Population and coherence dynamics in light harvesting complex II (LH2) Shu-Hao Yeh,1 Jing) The electronic excitation population and coherence dynamics in the chromophores of the photosyn- thetic light

  2. Hidden symmetries enhance quantum transport in Light Harvesting systems

    E-print Network

    Tobias Zech; Roberto Mulet; Thomas Wellens; Andreas Buchleitner

    2012-05-23

    For more than 50 years we have known that photosynthetic systems harvest solar energy with almost unit {\\it quantum efficiency}. However, recent experimental evidence of {\\it quantum coherence} during the excitonic energy transport in photosynthetic organisms challenges our understanding of this fundamental biological function. Currently, and despite numerous efforts, the causal connection between coherence and efficiency is still a matter of debate. We show, through the study of extensive simulations of quantum coherent transport on networks, that three dimensional structures characterized by centro-symmetric Hamiltonians are statistically more efficient than random arrangements. Moreover, we demonstrate that the experimental data available for the electronic Hamiltonians of the Fenna-Mathew-Olson (FMO) complex of sulfur bacteria and of the crypophyte PC645 complex of marine algae are consistent with this strong correlation of centro-symmetry with quantum efficiency. These results show that what appears to be geometrically disordered complexes may well exhibit a hidden symmetry which enhances the energy transport between chromophores. We are confident that our results will motivate research to explore the properties of nearly centro-symmetric Hamiltonians in more realistic environments, and to unveil the role of symmetries for quantum effects in biology. The unravelling of such symmetries may open novel perspectives and suggest new design principles in the development of artificial devices.

  3. Chiral plasmonics of self-assembled nanorod dimers

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  4. Control of gene expression by modulated self-assembly

    E-print Network

    Vilar, Jose M G

    2011-01-01

    Numerous transcription factors self-assemble into different order oligomeric species in a way that is actively regulated by the cell. Until now, no general functional role has been identified for this widespread process. Here we capture the effects of modulated self-assembly in gene expression with a novel quantitative framework. We show that this mechanism provides precision and flexibility, two seemingly antagonistic properties, to the sensing of diverse cellular signals by systems that share common elements present in transcription factors like p53, NF-kappaB, STATs, Oct, and RXR. Applied to the nuclear hormone receptor RXR, this framework accurately reproduces a broad range of classical, previously unexplained, sets of gene expression data and corroborates the existence of a precise functional regime with flexible properties that can be controlled both at a genome-wide scale and at the individual promoter level.

  5. Prospects for using self-assembled nucleic acid structures.

    PubMed

    Rudchenko, M N; Zamyatnin, A A

    2015-04-01

    According to the central dogma in molecular biology, nucleic acids are assigned with key functions on storing and executing genetic information in any living cell. However, features of nucleic acids are not limited only with properties providing template-dependent biosynthetic processes. Studies of DNA and RNA unveiled unique features of these polymers able to make various self-assembled three-dimensional structures that, among other things, use the complementarity principle. Here, we review various self-assembled nucleic acid structures as well as application of DNA and RNA to develop nanomaterials, molecular automata, and nanodevices. It can be expected that in the near future results of these developments will allow designing novel next-generation diagnostic systems and medicinal drugs. PMID:25869355

  6. Geometrically Precise Building Blocks: the Self-Assembly of ?-Peptides.

    PubMed

    Gopalan, Romila D; Del Borgo, Mark P; Mechler, Adam I; Perlmutter, Patrick; Aguilar, Marie-Isabel

    2015-11-19

    Peptides comprised entirely of ?-amino acids, or ?-peptides, have attracted substantial interest over the past 25 years due to their unique structural and chemical characteristics. ?-Peptides form well-defined secondary structures that exhibit different geometries compared with their ?-peptide counterparts, giving rise to their foldamer classification. ?-Peptide foldamers can be functionalized easily and are metabolically stable and, together with the predictable side-chain topography, have led to the design of a growing number of bioactive ?-peptides with a range of biological targets. The strategic engineering of chemical and topographic properties has also led to the design of ?-peptide mimics of higher-order oligomers. More recently, the ability of these peptides to self-assemble into complex structures of controlled geometries has been exploited in materials applications. The focus of this mini-review is on how the unique structural features of ?-peptide assemblies have been exploited in the design of self-assembled proteomimetic bundles and nanomaterials. PMID:26584778

  7. 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. PMID:23647410

  8. DNA-Based Self-Assembly of Fluorescent Nanodiamonds.

    PubMed

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

    2015-08-12

    As a step toward deterministic and scalable assembly of ordered spin arrays we here demonstrate a bottom-up approach to position fluorescent nanodiamonds (NDs) with nanometer precision on DNA origami structures. We have realized a reliable and broadly applicable surface modification strategy that results in DNA-functionalized and perfectly dispersed NDs that were then self-assembled in predefined geometries. With optical studies we show that the fluorescence properties of the nitrogen-vacancy color centers in NDs are preserved during surface modification and DNA assembly. As this method allows the nanoscale arrangement of fluorescent NDs together with other optically active components in complex geometries, applications based on self-assembled spin lattices or plasmon-enhanced spin sensors as well as improved fluorescent labeling for bioimaging could be envisioned. PMID:26196373

  9. 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 ×10¹?cm?². We also show that FTS doping of CNT anodes greatly improves the performance of organic solar cells. This large and stable doping effect, easily achieved in large-area samples, makes this approach very attractive for applications of CNTs in transparent and flexible electronics.

  10. Using Markov State Models to Study Self-Assembly

    NASA Astrophysics Data System (ADS)

    Perkett, Matthew; Hagan, Michael

    2014-03-01

    In recent years, a number of algorithms have been developed to study rare events, which has resulted in paradigm shift from running a few long trajectories to gathering statistics from many shorter trajectories. Running many simulations in parallel to build a Markov State Model (MSM) is one such technique, which has been applied to protein folding with great success. We present an adaptation to the MSM framework that enables its application to a wide range of systems undergoing self-assembly. The feasibility of this approach is demonstrated on two different coarse-grained models for virus self-assembly. We find good agreement between the MSM calculations and brute force long simulations, with up to several orders of magnitude reduction in simulation time.

  11. Catalysts from Self-Assembled Organometallic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Durkee, David; Ellsworth, Mark; Balsara, Nitash

    2005-03-01

    Heterogeneous catalysts were prepared by crosslinking the polyisoprene block of a microphase separated poly(vinyl ferrocenium triflate-block-isoprene) copolymer. The poly(vinyl ferrocenium triflate) moieties are responsible for catalytic activity while the polyisoprene block provides the support structure. The efficacy of the catalyst was analyzed by studying the Michael addition of ethyl-2-oxycyclopentane carboxylate and methyl vinyl ketone. The materials were studied via Transmission Electron Microscopy and the reaction rates were monitored by NMR spectroscopy. The activities obtained with our self-assembled heterogeneous catalyst were within experimental error of the rate of monomeric ferrocenium triflate as well as other homogeneous catalyst analogues. Our method for synthesizing catalysts is unique because the structures of both the support and active sites are controlled by molecular self-assembly.

  12. Magnetotactic molecular architectures from self-assembly of ?-peptide foldamers

    NASA Astrophysics Data System (ADS)

    Kwon, Sunbum; Kim, Beom Jin; Lim, Hyung-Kyu; Kang, Kyungtae; Yoo, Sung Hyun; Gong, Jintaek; Yoon, Eunyoung; Lee, Juno; Choi, Insung S.; Kim, Hyungjun; Lee, Hee-Seung

    2015-10-01

    The design of stimuli-responsive self-assembled molecular systems capable of undergoing mechanical work is one of the most important challenges in synthetic chemistry and materials science. Here we report that foldectures, that is, self-assembled molecular architectures of ?-peptide foldamers, uniformly align with respect to an applied static magnetic field, and also show instantaneous orientational motion in a dynamic magnetic field. This response is explained by the amplified anisotropy of the diamagnetic susceptibilities as a result of the well-ordered molecular packing of the foldectures. In addition, the motions of foldectures at the microscale can be translated into magnetotactic behaviour at the macroscopic scale in a way reminiscent to that of magnetosomes in magnetotactic bacteria. This study will provide significant inspiration for designing the next generation of biocompatible peptide-based molecular machines with applications in biological systems.

  13. 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.

  14. Electrostatic Control of Structure in Self-Assembled Membranes

    PubMed Central

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

    2014-01-01

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

  15. Magnetotactic molecular architectures from self-assembly of ?-peptide foldamers

    PubMed Central

    Kwon, Sunbum; Kim, Beom Jin; Lim, Hyung-Kyu; Kang, Kyungtae; Yoo, Sung Hyun; Gong, Jintaek; Yoon, Eunyoung; Lee, Juno; Choi, Insung S.; Kim, Hyungjun; Lee, Hee-Seung

    2015-01-01

    The design of stimuli-responsive self-assembled molecular systems capable of undergoing mechanical work is one of the most important challenges in synthetic chemistry and materials science. Here we report that foldectures, that is, self-assembled molecular architectures of ?-peptide foldamers, uniformly align with respect to an applied static magnetic field, and also show instantaneous orientational motion in a dynamic magnetic field. This response is explained by the amplified anisotropy of the diamagnetic susceptibilities as a result of the well-ordered molecular packing of the foldectures. In addition, the motions of foldectures at the microscale can be translated into magnetotactic behaviour at the macroscopic scale in a way reminiscent to that of magnetosomes in magnetotactic bacteria. This study will provide significant inspiration for designing the next generation of biocompatible peptide-based molecular machines with applications in biological systems. PMID:26510658

  16. 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

  17. Control of gene expression by modulated self-assembly

    E-print Network

    Jose M. G. Vilar; Leonor Saiz

    2011-05-25

    Numerous transcription factors self-assemble into different order oligomeric species in a way that is actively regulated by the cell. Until now, no general functional role has been identified for this widespread process. Here we capture the effects of modulated self-assembly in gene expression with a novel quantitative framework. We show that this mechanism provides precision and flexibility, two seemingly antagonistic properties, to the sensing of diverse cellular signals by systems that share common elements present in transcription factors like p53, NF-kappaB, STATs, Oct, and RXR. Applied to the nuclear hormone receptor RXR, this framework accurately reproduces a broad range of classical, previously unexplained, sets of gene expression data and corroborates the existence of a precise functional regime with flexible properties that can be controlled both at a genome-wide scale and at the individual promoter level.

  18. Reinforcement of Shear Thinning Protein Hydrogels by Responsive Block Copolymer Self-Assembly

    PubMed Central

    Glassman, Matthew J.; Chan, Jacqueline

    2014-01-01

    Shear thinning hydrogels are promising materials that exhibit rapid self-healing following the cessation of shear, making them attractive for a variety of applications including injectable biomaterials. In this work, self-assembly is demonstrated as a strategy to introduce a reinforcing network within shear thinning artificially engineered protein gels, enabling a responsive transition from an injectable state at low temperatures with a low yield stress to a stiffened state at physiological temperatures with resistance to shear thinning, higher toughness, and reduced erosion rates and creep compliance. Protein-polymer triblock copolymers capable of the responsive self-assembly of two orthogonal networks have been synthesized by conjugating poly(N-isopropylacrylamide) to the N- and C- termini of a protein midblock decorated with coiled-coil self-associating domains. Midblock association forms a shear-thinning network, while endblock aggregation at elevated temperatures introduces a second, independent physical network into the protein hydrogel. These new, reversible crosslinks introduce extremely long relaxation times and lead to a five-fold increase in the elastic modulus, significantly larger than is expected from transient network theory. Thermoresponsive reinforcement reduces the high temperature creep compliance by over four orders of magnitude, decreases the erosion rate by at least a factor of five, and increases the yield stress by up to a factor of seven. The reinforced hydrogels also exhibit enhanced resistance to plastic deformation and failure in uniaxial compression. Combined with the demonstrated potential of shear thinning artificial protein hydrogels for various uses, including the minimally-invasive implantation of bioactive scaffolds, this reinforcement mechanism broadens the range of applications that can be addressed with shear-thinning physical gels. PMID:25568642

  19. Logical computation using algorithmic self-assembly of DNA triple-crossover molecules.

    PubMed

    Mao, C; LaBean, T H; Relf, J H; Seeman, N C

    2000-09-28

    Recent work has demonstrated the self-assembly of designed periodic two-dimensional arrays composed of DNA tiles, in which the intermolecular contacts are directed by 'sticky' ends. In a mathematical context, aperiodic mosaics may be formed by the self-assembly of 'Wang' tiles, a process that emulates the operation of a Turing machine. Macroscopic self-assembly has been used to perform computations; there is also a logical equivalence between DNA sticky ends and Wang tile edges. This suggests that the self-assembly of DNA-based tiles could be used to perform DNA-based computation. Algorithmic aperiodic self-assembly requires greater fidelity than periodic self-assembly, because correct tiles must compete with partially correct tiles. Here we report a one-dimensional algorithmic self-assembly of DNA triple-crossover molecules that can be used to execute four steps of a logical (cumulative XOR) operation on a string of binary bits. PMID:11028996

  20. Fibrin self-assembly inhibitor turnover in rats

    SciTech Connect

    Chiryat'ev, E.A.; Umutbaeva, M.K.; Byshevskii, A.Sh.

    1987-10-01

    The aim of this investigation was to study changes in the concentration of the fibrin self-assembly inhibitor and the mechanism of the changes in diametrically opposite states of blood coagulation, namely, the acceleration and restriction of thrombin formation. Fibrin monomer was obtained from bovine plasma. The inhibitor, a polypeptide, was labelled with potassium iodide activated with iodine 131. The radioactive inhibitor was injected and its concentration determined by chromatography and tracer analysis.

  1. 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

  2. Dispersion of nanoparticulate suspensions using self-assembled surfactant aggregates

    NASA Astrophysics Data System (ADS)

    Singh, Pankaj Kumar

    The dispersion of particles is critical for several industrial applications such as paints, inks, coatings, and cosmetics. Several emerging applications such as abrasives for precision polishing, and drug delivery systems are increasingly relying on nanoparticulates to achieve the desired performance. In the case of nanoparticles, the dispersion becomes more challenging because of the lack of fundamental understanding of dispersant adsorption and interparticle force prediction. Additionally, many of these processes use severe processing environments such as high normal forces (>100 mN/m), high shear forces (>10,000 s -1), and high ionic strengths (>0.1 M). Under such processing conditions, traditionally used dispersants based on electrostatics, and steric force repulsion mechanism may not be adequate. Hence, the development of optimally performing dispersants requires a fundamental understanding of the dispersion mechanism at the atomic/molecular scale. This study explores the use of self-assembled surfactant aggregates at the solid-liquid interface for dispersing nanoparticles in severe processing environments. Surfactant molecules can provide a feasible alternative to polymeric or inorganic dispersants for stabilizing ultrafine particles. The barrier to aggregation in the presence of surfactant molecules was measured using atomic force microscopy. The barrier heights correlated to suspension stability. To understand the mechanism for nanoparticulate suspension stability in the presence of surfactant films, the interface was characterized using zeta potential, contact angle, adsorption, and FT-IR (adsorbed surfactant film structure measurements). The effect of solution conditions such as pH and ionic strength on the suspension stability, and the self-assembled surfactant films was also investigated. It was determined that a transition from a random to an ordered orientation of the surfactant molecules at the interface was responsible for stability of nanoparticulates. Additionally, the role of the surface in surfactant self-assembly was investigated. Mechanical and thermodynamic properties of the self-assembled layer at the solid-liquid interface were calculated based on experimental results, and compared to the corresponding properties in the bulk solution.

  3. Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules

    E-print Network

    Parker, Richard M.; Zhang, Jing; Zheng, Yu; Coulston, Roger J.; Smith, Clive A.; Salmon, Andrew R.; Yu, Ziyi; Scherman, Oren A.; Abell, Chris

    2015-05-26

    -linked polymersomes, [ 19 ] covalent reactions, [ 14 ] supramolecular metal–organic fi lms, [ 20 ] or hydrogen bonding. [ 15 ] These approaches often require multiple fabrication steps (e.g., layer-by-layer deposition or removal of a sacrifi cial template... delivery, [ 2 ] catalysis, [ 3,4 ] food additives, [ 5 ] and incorporation within elec- tronic displays. [ 6,7 ] Numerous approaches to microencap- sulation have been reported, ranging from self-assembled polymersomes [ 8,9 ] and vesicles [ 10...

  4. Propagating waves of self-assembly in organosilane monolayers

    PubMed Central

    Douglas, Jack F.; Efimenko, Kirill; Fischer, Daniel A.; Phelan, Fredrick R.; Genzer, Jan

    2007-01-01

    Wavefronts associated with reaction–diffusion and self-assembly processes are ubiquitous in the natural world. For example, propagating fronts arise in crystallization and diverse other thermodynamic ordering processes, in polymerization fronts involved in cell movement and division, as well as in the competitive social interactions and population dynamics of animals at much larger scales. Although it is often claimed that self-sustaining or autocatalytic front propagation is well described by mean-field “reaction–diffusion” or “phase field” ordering models, it has recently become appreciated from simulations and theoretical arguments that fluctuation effects in lower spatial dimensions can lead to appreciable deviations from the classical mean-field theory (MFT) of this type of front propagation. The present work explores these fluctuation effects in a real physical system. In particular, we consider a high-resolution near-edge x-ray absorption fine structure spectroscopy (NEXAFS) study of the spontaneous frontal self-assembly of organosilane (OS) molecules into self-assembled monolayer (SAM) surface-energy gradients on oxidized silicon wafers. We find that these layers organize from the wafer edge as propagating wavefronts having well defined velocities. In accordance with two-dimensional simulations of this type of front propagation that take fluctuation effects into account, we find that the interfacial widths w(t) of these SAM self-assembly fronts exhibit a power-law broadening in time, w(t) ? t?, rather than the constant width predicted by MFT. Moreover, the observed exponent values accord rather well with previous simulation and theoretical estimates. These observations have significant implications for diverse types of ordering fronts that occur under confinement conditions in biological or materials-processing contexts. PMID:17566108

  5. Monodisperse Magnesium Hydride Nanoparticles Uniformly Self-Assembled on Graphene.

    PubMed

    Xia, Guanglin; Tan, Yingbin; Chen, Xiaowei; Sun, Dalin; Guo, Zaiping; Liu, Huakun; Ouyang, Liuzhang; Zhu, Min; Yu, Xuebin

    2015-10-01

    Monodisperse MgH2 nanoparticles with homogeneous distribution and a high loading percent are developed through hydrogenation-induced self-assembly under the structure-directing role of graphene. Graphene acts not only as a structural support, but also as a space barrier to prevent the growth of MgH2 nanoparticles and as a thermally conductive pathway, leading to outstanding performance. PMID:26315783

  6. Facile Self-Assembly of Quantum Plasmonic Circuit Components.

    PubMed

    Tran, Toan Trong; Fang, Jinghua; Zhang, Hao; Rath, Patrik; Bray, Kerem; Sandstrom, Russell G; Shimoni, Olga; Toth, Milos; Aharonovich, Igor

    2015-07-15

    A facile and cost-effective self-assembly route to engineering of vital quantum plasmonic circuit components is reported. By modifying the surface energy of silver nanowires, the position and density of attached nanodiamonds can be maneuvered leading to silver nanowire/nanodiamond(s) hybrid nanostructures. These structures exhibit strong plasmonic coupling effects and thus hold promise to serve as quantum plasmonic components. PMID:26036242

  7. Self-assembly and dynamics of magnetic holes

    E-print Network

    Arne T. Skjeltorp; Jorgen Akselvoll; Kai De Lange Kistiansen; Geir Helgesen; Renaud Toussaint; Eirik Grude Flekkoy; Josef Cernak

    2006-11-01

    Nonmagnetic particles in magnetized ferrofluids have been denoted magnetic holes and are in many ways ideal model systems to test various forms of particle self assembly and dynamics. Some case studies to be reviewed here include: Chaining of magnetic holes Braid theory and Zipf relation used in dynamics of magnetic microparticles Interactions of magnetic holes in ferrofluid layers The objectives of these works have been to find simple characterizations of complex behavior of particles with dipolar interactions.

  8. Cold Atoms and Molecules in Self-Assembled Dipolar Lattices

    SciTech Connect

    Pupillo, G.; Griessner, A.; Micheli, A.; Ortner, M.; Zoller, P.; Wang, D.-W.

    2008-02-08

    We study the realization of lattice models, where cold atoms and molecules move as extra particles in a dipolar crystal of trapped polar molecules. The crystal is a self-assembled floating mesoscopic lattice structure with quantum dynamics given by phonons. We show that within an experimentally accessible parameter regime extended Hubbard models with tunable long-range phonon-mediated interactions describe the effective dynamics of dressed particles.

  9. 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.

  10. 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

  11. 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

  12. 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

  13. Self-assembly of strongly dipolar molecules on metal surfaces.

    PubMed

    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

    2015-03-14

    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. PMID:25770510

  14. 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.

  15. 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 ?-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-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. PMID:24905674

  17. Self-assembly in sugar-oil complex glasses

    NASA Astrophysics Data System (ADS)

    Dave, Hiteshkumar; Gao, Feng; Lee, Jing-Huei; Liberatore, Matthew; Ho, Chia-Chi; Co, Carlos C.

    2007-04-01

    In aqueous systems, the hydrophobic effect drives the self-assembly of amphiphiles into a broad range of micellar, rod-like, bicontinuous and liquid-crystalline complex fluids. Many of these are relevant to biological matter or technological applications. However, amphiphilic self-assembly is not limited to aqueous systems. Replacement of water with supercritical carbon dioxide, for example, results in complex fluids that combine the properties of gases and liquids. Along this vein, we explore the self-assembly of surfactants in anhydrous sugars. Our study reveals that anhydrous powders of sugars and surfactants suspended in oil spontaneously form molten glasses with nanometre-size domains of sugar and liquid oil without mixing. The low cost, water solubility, low toxicity and stabilizing properties of glassy sugars make them ideal water replacements for many pharmaceutical, food and materials synthesis applications. The optical clarity and solid appearance of these glasses at room temperature belie their inclusion of more than 50% (vol.) oil, which confers liquid-like diffusivity. The unique combination of solid- and liquid-like properties may lead to applications in sensors and optical devices.

  18. 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 ?-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

  19. Molecular Motions in Functional Self-Assembled Nanostructures

    PubMed Central

    Dhotel, Alexandre; Chen, Ziguang; Delbreilh, Laurent; Youssef, Boulos; Saiter, Jean-Marc; Tan, Li

    2013-01-01

    The construction of “smart” materials able to perform specific functions at the molecular scale through the application of various stimuli is highly attractive but still challenging. The most recent applications indicate that the outstanding flexibility of self-assembled architectures can be employed as a powerful tool for the development of innovative molecular devices, functional surfaces and smart nanomaterials. Structural flexibility of these materials is known to be conferred by weak intermolecular forces involved in self-assembly strategies. However, some fundamental mechanisms responsible for conformational lability remain unexplored. Furthermore, the role played by stronger bonds, such as coordination, ionic and covalent bonding, is sometimes neglected while they can be employed readily to produce mechanically robust but also chemically reversible structures. In this review, recent applications of structural flexibility and molecular motions in self-assembled nanostructures are discussed. Special focus is given to advanced materials exhibiting significant performance changes after an external stimulus is applied, such as light exposure, pH variation, heat treatment or electromagnetic field. The crucial role played by strong intra- and weak intermolecular interactions on structural lability and responsiveness is highlighted. PMID:23348927

  20. Capillary-based static self-assembly in higher organisms

    PubMed Central

    Voise, Jonathan; Schindler, Michael; Casas, Jérôme; Raphaël, Elie

    2011-01-01

    Organized structures produced by dynamic self-assembly are often observed in animal groups. Static self-assembly, however, has to date only been observed at the cellular and sub-cellular levels. The aim of this study was to analyse organized structures in immobile whirligig beetle groups on the water surface. We used theoretical and computational approaches to model the meniscus around whirligig beetles and to calculate the surface energy for configurations involving two beetles. Theoretical predictions were then tested using live insects and resin casts. Observations were also made for three and more casts. The meniscus of whirligig beetles had a bipolar shape with two concave parts. For two beetles, predicted configurations based on energy minima corresponded to beetles in contact by their extremities, forming lines and arrows, and agreed well with observations. Experimental results for three and more beetle casts revealed new geometrical arrangements similar to those obtained with colloids at interfaces. This study provides the first example of static self-assembly at the inter-organism level and shows the importance of capillary interactions in such formations. We identify the ecological context in which our findings are of relevance. PMID:21367777

  1. 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

  2. Nanoscale templating and self-assembly of organic semiconductors

    NASA Astrophysics Data System (ADS)

    Hulvat, James Francis

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

  3. A simple artificial light-harvesting dyad as a model for excess energy dissipation in

    E-print Network

    van Stokkum, Ivo

    photosynthesis Rudi Berera , Christian Herrero , Ivo H. M. van Stokkum , Mikas Vengris , Gerdenis Kodis , Rodrigo and Center for the Study of Early Events in Photosynthesis, Arizona State University, Tempe, AZ 85287 photosynthesis carotenoid nonphotochemical quenching photoprotection xanthophyll cycle The ubiquity

  4. A Theoretical and Experimental Study of DNA Self-assembly

    NASA Astrophysics Data System (ADS)

    Chandran, Harish

    The control of matter and phenomena at the nanoscale is fast becoming one of the most important challenges of the 21st century with wide-ranging applications from energy and health care to computing and material science. Conventional top-down approaches to nanotechnology, having served us well for long, are reaching their inherent limitations. Meanwhile, bottom-up methods such as self-assembly are emerging as viable alternatives for nanoscale fabrication and manipulation. A particularly successful bottom up technique is DNA self-assembly where a set of carefully designed DNA strands form a nanoscale object as a consequence of specific, local interactions among the different components, without external direction. The final product of the self-assembly process might be a static nanostructure or a dynamic nanodevice that performs a specific function. Over the past two decades, DNA self-assembly has produced stunning nanoscale objects such as 2D and 3D lattices, polyhedra and addressable arbitrary shaped substrates, and a myriad of nanoscale devices such as molecular tweezers, computational circuits, biosensors and molecular assembly lines. In this dissertation we study multiple problems in the theory, simulations and experiments of DNA self-assembly. We extend the Turing-universal mathematical framework of self-assembly known as the Tile Assembly Model by incorporating randomization during the assembly process. This allows us to reduce the tile complexity of linear assemblies. We develop multiple techniques to build linear assemblies of expected length N using far fewer tile types than previously possible. We abstract the fundamental properties of DNA and develop a biochemical system, which we call meta-DNA, based entirely on strands of DNA as the only component molecule. We further develop various enzyme-free protocols to manipulate meta-DNA systems and provide strand level details along with abstract notations for these mechanisms. We simulate DNA circuits by providing detailed designs for local molecular computations that involve spatially contiguous molecules arranged on addressable substrates via enzyme-free DNA hybridization reaction cascades. We use the Visual DSD simulation software in conjunction with localized reaction rates obtained from biophysical modeling to create chemical reaction networks of localized hybridization circuits that are then model checked using the PRISM model checking software. We develop a DNA detection system employing the triggered self-assembly of a novel DNA dendritic nanostructure. Detection begins when a specific, single-stranded target DNA strand triggers a hybridization chain reaction between two distinct DNA hairpins. Each hairpin opens and hybridizes up to two copies of the other, and hence each layer of the growing dendritic nanostructure can in principle accommodate an exponentially increasing number of cognate molecules, generating a nanostructure with high molecular weight. We build linear activatable assemblies employing a novel protection/deprotection strategy to strictly enforce the direction of tiling assembly growth to ensure the robustness of the assembly process. Our system consists of two tiles that can form a linear co-polymer. These tiles, which are initially protected such that they do not react with each other, can be activated to form linear co-polymers via the use of a strand displacing enzyme.

  5. Combustion and self-assembly of nanoenergetic materials

    NASA Astrophysics Data System (ADS)

    Malchi, Jonathan Yaniv

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

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

    PubMed Central

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

    2014-01-01

    As we bring tubulin protein molecules one by one into the vicinity, they self-assemble and entire event we capture live via quantum tunneling. We observe how these molecules form a linear chain and then chains self-assemble into 2D sheet, an essential for microtubule, —fundamental nano-tube in a cellular life form. Even without using GTP, or any chemical reaction, but applying particular ac signal using specially designed antenna around atomic sharp tip we could carry out the self-assembly, however, if there is no electromagnetic pumping, no self-assembly is observed. In order to verify this atomic scale observation, we have built an artificial cell-like environment with nano-scale engineering and repeated spontaneous growth of tubulin protein to its complex with and without electromagnetic signal. We used 64 combinations of plant, animal and fungi tubulins and several doping molecules used as drug, and repeatedly observed that the long reported common frequency region where protein folds mechanically and its structures vibrate electromagnetically. Under pumping, the growth process exhibits a unique organized behavior unprecedented otherwise. Thus, “common frequency point” is proposed as a tool to regulate protein complex related diseases in the future. PMID:25466883

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    PubMed

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

    2014-01-01

    As we bring tubulin protein molecules one by one into the vicinity, they self-assemble and entire event we capture live via quantum tunneling. We observe how these molecules form a linear chain and then chains self-assemble into 2D sheet, an essential for microtubule, --fundamental nano-tube in a cellular life form. Even without using GTP, or any chemical reaction, but applying particular ac signal using specially designed antenna around atomic sharp tip we could carry out the self-assembly, however, if there is no electromagnetic pumping, no self-assembly is observed. In order to verify this atomic scale observation, we have built an artificial cell-like environment with nano-scale engineering and repeated spontaneous growth of tubulin protein to its complex with and without electromagnetic signal. We used 64 combinations of plant, animal and fungi tubulins and several doping molecules used as drug, and repeatedly observed that the long reported common frequency region where protein folds mechanically and its structures vibrate electromagnetically. Under pumping, the growth process exhibits a unique organized behavior unprecedented otherwise. Thus, "common frequency point" is proposed as a tool to regulate protein complex related diseases in the future. PMID:25466883

  9. Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays

    DOEpatents

    Loewe, Robert S.; Tomizaki, Kin-ya; Lindsey, Jonathan S.

    2005-07-12

    The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: wherein m is at least 1; X.sup.1 is a charge separation group, and X.sup.2 through X.sup.m+1 are chromophores. At least one of X.sup.2 through X.sup.m+1 has at least one perylene group coupled thereto.

  10. Phylogenetic viewpoints on regulation of light harvesting and electron transport in eukaryotic photosynthetic organisms.

    PubMed

    Grouneva, Irina; Gollan, Peter J; Kangasjärvi, Saijaliisa; Suorsa, Marjaana; Tikkanen, Mikko; Aro, Eva-Mari

    2013-02-01

    The comparative study of photosynthetic regulation in the thylakoid membrane of different phylogenetic groups can yield valuable insights into mechanisms, genetic requirements and redundancy of regulatory processes. This review offers a brief summary on the current understanding of light harvesting and photosynthetic electron transport regulation in different photosynthetic eukaryotes, with a special focus on the comparison between higher plants and unicellular algae of secondary endosymbiotic origin. The foundations of thylakoid structure, light harvesting, reversible protein phosphorylation and PSI-mediated cyclic electron transport are traced not only from green algae to vascular plants but also at the branching point between the "green" and the "red" lineage of photosynthetic organisms. This approach was particularly valuable in revealing processes that (1) are highly conserved between phylogenetic groups, (2) serve a common physiological role but nevertheless originate in divergent genetic backgrounds or (3) are missing in one phylogenetic branch despite their unequivocal importance in another, necessitating a search for alternative regulatory mechanisms and interactions. PMID:22971817

  11. 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. PMID:25365647

  12. Dynamic, conjugated microporous polymers: visible light harvesting via guest-responsive reversible swelling.

    PubMed

    Venkata Rao, K; Haldar, Ritesh; Maji, Tapas Kumar; George, Subi J

    2016-01-01

    The light-harvesting properties of two fluorescent dynamic conjugated microporous organic polymers (Py-PP and Py-BPP) rendered with pyrene chromophores are described. The hydrophobic and dynamic nature of these porous frameworks allows the selective capture of various organic solvents by instantaneous swelling at room temperature. Moreover, the dynamic nature of these frameworks indicates the swelling process with visible volume expansion and enhanced fluorescence. This was further explored for the rapid encapsulation of various fluorescent chromophoric guests at room temperature and investigated for photoinduced energy transfer process. The resultant host-guest antenna materials showed efficient light-harvesting and funnelling of excitation energy of host framework towards the entrapped guest molecule. This process further yielded solid-state luminescent materials with tunable emission. This work holds a great promise on the design of smart porous organic solids from ?-conjugated small molecules for optoelectronics, sensing and separation. PMID:26604127

  13. Purple-bacterial light harvesting benefits more from energy funnelling than from delocalisation

    E-print Network

    Baghbanzadeh, Sima

    2015-01-01

    Light-harvesting complexes of purple bacteria have two properties that are thought to contribute to the efficiency of their exciton transport: an energy funnel that directs excitons towards the reaction centre as well as substantial excitonic delocalisation, which can enhance transport through supertransfer. To determine the relative importance of these two features, we compared models of the light-harvesting apparatus with thousands of counterfactual situations in which the extent of delocalisation and the energy landscape were altered. We find that the influence of delocalisation is usually minor and sometimes deleterious, especially when compared to the decisive importance of a funnel in the energy landscape. Consequently, delocalisation is most likely a side-effect of the dense chlorophyll packing that evolved to increase light absorption per reaction centre.

  14. 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.

  15. 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.

  16. Purple-bacterial light harvesting benefits more from energy funnelling than from delocalisation

    E-print Network

    Sima Baghbanzadeh; Ivan Kassal

    2015-09-04

    Light-harvesting complexes of purple bacteria have two properties that are thought to contribute to the efficiency of their exciton transport: an energy funnel that directs excitons towards the reaction centre as well as substantial excitonic delocalisation, which can enhance transport through supertransfer. To determine the relative importance of these two features, we compared models of the light-harvesting apparatus with thousands of counterfactual situations in which the extent of delocalisation and the energy landscape were altered. We find that the influence of delocalisation is usually minor and sometimes deleterious, especially when compared to the decisive importance of a funnel in the energy landscape. Consequently, delocalisation is most likely a side-effect of the dense chlorophyll packing that evolved to increase light absorption per reaction centre.

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

    PubMed Central

    Fawley, Marvin W.

    1989-01-01

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

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

    PubMed

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

    2014-12-28

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

  19. Light-harvesting antennae based on photoactive silicon nanocrystals functionalized with porphyrin chromophores.

    PubMed

    Fermi, Andrea; Locritani, Mirko; Di Carlo, Gabriele; Pizzotti, Maddalena; Caramori, Stefano; Yu, Yixuan; Korgel, Brian A; Bergamini, Giacomo; Ceroni, Paola

    2015-12-22

    Silicon nanocrystals functionalized with tetraphenylporphyrin Zn(ii) chromophores at the periphery perform as light harvesting antennae: excitation of the porphyrin units in the visible spectral region yields sensitized emission of the silicon nanocrystal core in the near infrared with a long lifetime (?max = 905 nm, ? = 130 ?s). This result demonstrates that this hybrid material has a potential application as a luminescent probe for bioimaging. PMID:26399301

  20. Dark excited states of carotenoid in light harvesting complex probing with femtosecond stimulated Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoshimatsu, O.; Abe, K.; Sakai, S.; Horibe, T.; Fujii, R.; Nango, M.; Hashimoto, H.; Yoshizawa, M.

    2013-03-01

    Vibrational dynamics of dark excited states in carotenoids have been investigated using tunable Raman pump pulses. The S1 state has same vibrational dynamics in light-harvesting complex (LH1) and solution. The S* state in LH1 has similar vibrational modes with the triplet state of carotenoid. However, the so-called S* state in solution does not have the modes and is concluded to be different from the S* state in LH1.

  1. Large organized surface domains self-assembled from nonpolar amphiphiles.

    PubMed

    Krafft, Marie Pierre

    2012-04-17

    For years, researchers had presumed that Langmuir monolayers of small C(n)F(2n+1)C(m)H(2m+1) (FnHm) diblock molecules (such as F8H16) consisted of continuous, featureless films. Recently we have discovered that they instead form ordered arrays of unusually large (~30-60 nm), discrete self-assembled surface domains or hemimicelles both at the surface of water and on solid substrates. These surface micelles differ in several essential ways from all previously reported or predicted molecular surface aggregates. They self-assemble spontaneously, even at zero surface pressure, depending solely on a critical surface concentration. They are very large (~100 times the length of the diblock) and involve thousands of molecules (orders of magnitude more than classical micelles). At the same time, the surface micelles are highly monodisperse and self-organize in close-packed hexagonal patterns (two-dimensional crystals). Their size is essentially independent from pressure, and they do not coalesce and are unexpectedly sturdy for soft matter (persisting even beyond surface film collapse). We and other researchers have observed large surface micelles for numerous diblocks, using Langmuir-Blodgett (LB) transfer, spin-coating and dip-coating techniques, or expulsion from mixed monolayers, and on diverse supports, establishing that hemimicelle formation and ordering are intrinsic properties of (perfluoroalkyl)alkanes. Notably, they involve "incomplete" surfactants with limited amphiphilic character, which further illustrates the outstanding capacity for perfluoroalkyl chains to promote self-assembly and interfacial film structuring. Using X-ray reflectivity, we determined a perfluoroalkyl-chain-up orientation. Theoretical investigations assigned self-assembly and hemimicelle stability to electrostatic dipole-dipole interactions at the interface between Fn- and Hm-sublayers. Grazing-incidence small-angle X-ray scattering (GISAXS) data collected directly on the surface of water unambiguously demonstrated the presence of surface micelles in monolayers of diblocks prior to LB transfer for atomic force microscopy imaging. We characterized an almost perfect two-dimensional crystal, with 12 assignable diffraction peaks, which established that self-assembly and regular nanopatterning were not caused by transfer or induced by the solid support. These experiments also provide the first direct identification of surface micelles on water, and the first identification of such large-size domains using GISAXS. Revisiting Langmuir film compression behavior after we realized that it actually was a compression of nanometric objects led to further unanticipated observations. These films could be compressed far beyond the documented film "collapse", eventually leading to the buildup of two superimposed, less-organized bilayers of diblocks on top of the initially formed monolayer of hemimicelles. Remarkably, the latter withstood the final, irreversible collapse of the composite films. "Gemini" tetrablocks, di(FnHm), with two Fn-chains and two Hm-chains, provided two superposed layers of discrete micelles, apparently the first example of thin films made of stacked discrete self-assembled nanoobjects. Decoration of solid surfaces with domains of predetermined size of these small "nonpolar" molecules is straightforward. Initial examples of applications include deposition of metal dots and catalytic oxidation of CO, and nanopatterning of SiO(2) films. PMID:22185721

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

    PubMed Central

    Harel, Elad; Engel, Gregory S.

    2012-01-01

    Light-harvesting antenna complexes transfer energy from sunlight to photosynthetic reaction centers where charge separation drives cellular metabolism. The process through which pigments transfer excitation energy involves a complex choreography of coherent and incoherent processes mediated by the surrounding protein and solvent environment. The recent discovery of coherent dynamics in photosynthetic light-harvesting antennae has motivated many theoretical models exploring effects of interference in energy transfer phenomena. In this work, we provide experimental evidence of long-lived quantum coherence between the spectrally separated B800 and B850 rings of the light-harvesting complex 2 (LH2) of purple bacteria. Spectrally resolved maps of the detuning, dephasing, and the amplitude of electronic coupling between excitons reveal that different relaxation pathways act in concert for optimal transfer efficiency. Furthermore, maps of the phase of the signal suggest that quantum mechanical interference between different energy transfer pathways may be important even at ambient temperature. Such interference at a product state has already been shown to enhance the quantum efficiency of transfer in theoretical models of closed loop systems such as LH2. PMID:22215585

  3. Phycobilisome Mobility and Its Role in the Regulation of Light Harvesting in Red Algae.

    PubMed

    Ka?a, Radek; Kotabová, Eva; Lukeš, Martin; Papá?ek, St?pán; Matonoha, Ctirad; Liu, Lu-Ning; Prášil, Ond?ej; Mullineaux, Conrad W

    2014-06-19

    Red algae represent an evolutionarily important group that gave rise to the whole red clade of photosynthetic organisms. They contain a unique combination of light-harvesting systems represented by a membrane-bound antenna and by phycobilisomes situated on thylakoid membrane surfaces. So far, very little has been revealed about the mobility of their phycobilisomes and the regulation of their light-harvesting system in general. Therefore, we carried out a detailed analysis of phycobilisome dynamics in several red alga strains and compared these results with the presence (or absence) of photoprotective mechanisms. Our data conclusively prove phycobilisome mobility in two model mesophilic red alga strains, Porphyridium cruentum and Rhodella violacea. In contrast, there was almost no phycobilisome mobility in the thermophilic red alga Cyanidium caldarium that was not caused by a decrease in lipid desaturation in this extremophile. Experimental data attributed this immobility to the strong phycobilisome-photosystem interaction that highly restricted phycobilisome movement. Variations in phycobilisome mobility reflect the different ways in which light-harvesting antennae can be regulated in mesophilic and thermophilic red algae. Fluorescence changes attributed in cyanobacteria to state transitions were observed only in mesophilic P. cruentum with mobile phycobilisomes, and they were absent in the extremophilic C. caldarium with immobile phycobilisomes. We suggest that state transitions have an important regulatory function in mesophilic red algae; however, in thermophilic red algae, this process is replaced by nonphotochemical quenching. PMID:24948833

  4. Design principles and fundamental trade-offs in biomimetic light harvesting

    E-print Network

    Mohan Sarovar; K. Birgitta Whaley

    2013-03-25

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

  5. Antheraxanthin, a light harvesting carotenoid found in a chromophyte alga. [Chrysophaera magna Becher, Phaeodactylum tricornutum

    SciTech Connect

    Alberte, R.S.; Andersen, R.A.

    1986-02-01

    The pigments of the chromophyte freshwater alga, Chrysophaera magna Belcher were analyzed by thin layer chromatography (TLC) and high performance liquid chromatography (HPLC) to reveal the presence of chlorophylls a and c, ..beta..-carotene, fucoxanthin, and antheraxanthin. The presence of antheraxanthin was verified by comparison of TLC R/sub F/ values, HPLC retention times, and absorption features to those of authentic, synthetic antheraxanthin. Antheraxanthin accounted for about 15% of the total carotenoid content of C. magna. The molar ratio of the major carotenoids was antheraxanthin:fucoxanthin:..beta..-carotene, 1:2.3:3.3. The whole-cell absorption spectrum revealed a broad band between 470 and 520 nanometers which was attributed to fucoxanthin and antheraxanthin in vivo. Upon extraction in hydrocarbon, this broad absorption region was lost. The in vivo fluorescence excitation spectrum for 680 nm emission revealed the energy transfer activities and light harvesting roles of chlorophylls a and c, and fucoxanthin. In addition, an excitation band was resolved at 487 nanometers which could be attributed only to antheraxanthin. Comparison of whole-cell fluorescence excitation spectra of C. magna with the diatom Phaeodactylum tricornutum, which possesses fucoxanthin but not antheraxanthin, supports the assignment of the 487 nm band to antheraxanthin. This is the first report of a photosynthetic light harvesting function of the xanthophyll, antheraxanthin. This carotenoid broadens the absorption cross-section for photosynthesis in C. magna and extends light harvesting into the green portion of the spectrum.

  6. Functional quantum dot-protein nano bio-assembly for superior light harvesting applications

    NASA Astrophysics Data System (ADS)

    Mutlugun, Evren; Ozgur Safak Seker, Urartu; Hernandez-Martinez, Pedro Ludwig; Sharma, Vijay Kumar; Lesnyak, Vladimir; Gaponik, Nikolai; Eychmuller, Alexander; Demir, Hilmi Volkan

    2013-03-01

    The formation of functional bio-assemblies is crucial for the advanced biophotonic applications. In this work, we formed a nano bio-assembly, consisting of green fluorescent protein (GFP) and inorganic quantum dots (QDs), to employ as an excitonic biofunctional composite to use for light harvesting and biosensing applications. Using QDs as donor molecules with the acceptor GFP in the formed bio-assembly, we observed up-to 15-fold enhancement on the GFP emission, mediated by the strong nonradiative energy transfer. The lifetime modifications of the donor-acceptor pair were studied as a function of the number of proteins per quantum dot, and in good agreement with the proposed theoretical model based on the excitonic interaction among the species. Apart from the light harvesting system, a biosensing medium was also established, facilitated by the enzymatic activity destructing the light harvesting complex. The energy transferring QD-GFP complex was controllably modified by the addition of trypsin, by destroying the bond in between the QD-GFP complex, as verified by the observation of lifetime modifications. In summary, we developed functional excitonic nano-bio-assemblies, which we believe will open up new possibilities for advanced biophotonic applications. The author contributed equally to this work

  7. 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.

  8. 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.

  9. A Major Light-Harvesting Polypeptide of Photosystem II Functions in Thermal DissipationW?

    PubMed Central

    Elrad, Dafna; Niyogi, Krishna K.; Grossman, Arthur R.

    2002-01-01

    Under high-light conditions, photoprotective mechanisms minimize the damaging effects of excess light. A primary photoprotective mechanism is thermal dissipation of excess excitation energy within the light-harvesting complex of photosystem II (LHCII). Although roles for both carotenoids and specific polypeptides in thermal dissipation have been reported, neither the site nor the mechanism of this process has been defined precisely. Here, we describe the physiological and molecular characteristics of the Chlamydomonas reinhardtii npq5 mutant, a strain that exhibits little thermal dissipation. This strain is normal for state transition, high light–induced violaxanthin deepoxidation, and low light growth, but it is more sensitive to photoinhibition than the wild type. Furthermore, both pigment data and measurements of photosynthesis suggest that the photosystem II antenna in the npq5 mutant has one-third fewer light-harvesting trimers than do wild-type cells. The npq5 mutant is null for a gene designated Lhcbm1, which encodes a light-harvesting polypeptide present in the trimers of the photosystem II antennae. Based on sequence data, the Lhcbm1 gene is 1 of 10 genes that encode the major LHCII polypeptides in Chlamydomonas. Amino acid alignments demonstrate that these predicted polypeptides display a high degree of sequence identity but maintain specific differences in their N-terminal regions. Both physiological and molecular characterization of the npq5 mutant suggest that most thermal dissipation within LHCII of Chlamydomonas is dependent on the peripherally associated trimeric LHC polypeptides. PMID:12172023

  10. Phycobilisome Mobility and Its Role in the Regulation of Light Harvesting in Red Algae1[W

    PubMed Central

    Ka?a, Radek; Kotabová, Eva; Lukeš, Martin; Papá?ek, Št?pán; Matonoha, Ctirad; Liu, Lu-Ning; Prášil, Ond?ej; Mullineaux, Conrad W.

    2014-01-01

    Red algae represent an evolutionarily important group that gave rise to the whole red clade of photosynthetic organisms. They contain a unique combination of light-harvesting systems represented by a membrane-bound antenna and by phycobilisomes situated on thylakoid membrane surfaces. So far, very little has been revealed about the mobility of their phycobilisomes and the regulation of their light-harvesting system in general. Therefore, we carried out a detailed analysis of phycobilisome dynamics in several red alga strains and compared these results with the presence (or absence) of photoprotective mechanisms. Our data conclusively prove phycobilisome mobility in two model mesophilic red alga strains, Porphyridium cruentum and Rhodella violacea. In contrast, there was almost no phycobilisome mobility in the thermophilic red alga Cyanidium caldarium that was not caused by a decrease in lipid desaturation in this extremophile. Experimental data attributed this immobility to the strong phycobilisome-photosystem interaction that highly restricted phycobilisome movement. Variations in phycobilisome mobility reflect the different ways in which light-harvesting antennae can be regulated in mesophilic and thermophilic red algae. Fluorescence changes attributed in cyanobacteria to state transitions were observed only in mesophilic P. cruentum with mobile phycobilisomes, and they were absent in the extremophilic C. caldarium with immobile phycobilisomes. We suggest that state transitions have an important regulatory function in mesophilic red algae; however, in thermophilic red algae, this process is replaced by nonphotochemical quenching. PMID:24948833

  11. Design principles and fundamental trade-offs in biomimetic light harvesting

    NASA Astrophysics Data System (ADS)

    Sarovar, Mohan; Whaley, K. Birgitta

    2013-01-01

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

  12. 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

  13. Bacterial expression of self-assembling peptide hydrogelators

    NASA Astrophysics Data System (ADS)

    Sonmez, Cem

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

  14. Self-assembly of amorphous biophotonic nanostructures by phase separation

    SciTech Connect

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

    2009-04-23

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

  15. Particle self-assembly at ionic liquid-based interfaces.

    PubMed

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

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. PMID:24230971

  16. Understanding and directing self-assembly of inorganic nanostructures

    NASA Astrophysics Data System (ADS)

    Doshi, Dhaval Arun

    2002-09-01

    Since their initial report in 1992 [1] structure definition of inorganic materials via surfactant templating approaches has seen an explosion in efforts. This new class of mesoporous materials, with uniform pore size in the 16A--500A range, are attractive for their potential application in membranes, catalysis, photonics, low dielectric constant materials (so called low kappa dielectrics), and sensors. Over the last 5 years evaporation induced self-assembly (EISA) approaches have been used to process these materials as thin films---desirable for their integration into devices. Understanding the assembly mechanism and patterning the form and function of these thin-films is essential to promote self-assembly from a lab exercise to a nanofabrication tool. In this work, the self-assembly mechanism during EISA of silica films is elucidated by combining in-situ optical interferometry or gravimetric analysis with grazing incidence x-ray scattering. Effects of the presence of silica, pH, surfactant type and concentration, and the presence of air-liquid and solid-liquid interfaces on the surfactant phase behavior is studied. Photosensitive films incorporating molecular photo-active compounds such as photoacid generators, photoresists; and photo-active swelling agents, compartmentalized within a silica-surfactant mesophase were prepared by EISA. Patterned ultra-violet (UV) exposure results in various modes of patterning. For films that incorporated photoacid generators, UV exposure promoted localized acid-catalyzed siloxane condensation, which can be used for selective etching of unexposed regions; for 'gray-scale' patterning of refractive index, pore size, surface area, and wetting behavior; and for optically defining a mesophase transformation (from hexagonal to tetragonal) within the film. Incorporation of photoactive swelling agents allows patterning of refractive index and pore size, whereas photoresists are used to define optically open and closed mesopore nanocomposites.

  17. Self-assembly of 33-mer gliadin peptide oligomers.

    PubMed

    Herrera, M G; Benedini, L A; Lonez, C; Schilardi, P L; Hellweg, T; Ruysschaert, J-M; Dodero, V I

    2015-11-01

    The 33-mer gliadin peptide, LQLQPF(PQPQLPY)3PQPQPF, is a highly immunogenic peptide involved in celiac disease and probably in other immunopathologies associated with gliadin. Herein, dynamic light scattering measurements showed that 33-mer, in the micromolar concentration range, forms polydisperse nano- and micrometer range particles in aqueous media. This behaviour is reminiscent of classical association of colloids and we hypothesized that the 33-mer peptide self-assembles into micelles that could be the precursors of 33-mer oligomers in water. Deposition of 33-mer peptide aqueous solution on bare mica generated nano- and microstructures with different morphologies as revealed by atomic force microscopy. At 6 ?M, the 33-mer is organised in isolated and clusters of spherical nanostructures. In the 60 to 250 ?M concentration range, the spherical oligomers associated mainly in linear and annular arrangements and structures adopting a "sheet" type morphology appeared. At higher concentrations (610 ?M), mainly filaments and plaques immersed in a background of nanospherical structures were detected. The occurrence of different morphologies of oligomers and finally the filaments suggests that the unique specific geometry of the 33-mer oligomers has a crucial role in the subsequent condensation and organization of their fractal structures into the final filaments. The self-assembly process on mica is described qualitatively and quantitatively by a fractal diffusion limited aggregation (DLA) behaviour with the fractal dimension in the range of 1.62 ± 0.02 to 1.73 ± 0.03. Secondary structure evaluation of the oligomers by Attenuated Total Reflection FTIR spectroscopy (ATR-FTIR) revealed the existence of a conformational equilibrium of self-assembled structures, from an extended conformation to a more folded parallel beta elongated structures. Altogether, these findings provide structural and morphological information about supramolecular organization of the 33-mer peptide, which might offer new perspectives for the understanding and treatment of gliadin intolerance disorders. PMID:26376290

  18. Unifying Interfacial Self-Assembly and Surface Freezing

    SciTech Connect

    B Ocko; H Hlaing; P Jepsen; S Kewalramani; A Tkachenko; D Pontoni; H Reichert; M Deutsch

    2011-12-31

    X-ray investigations reveal that the monolayers formed at the bulk alkanol-sapphire interface are densely packed with the surface-normal molecules hydrogen bound to the sapphire. About 30-35 C above the bulk, these monolayers both melt reversibly and partially desorb. This system exhibits balanced intermolecular and molecule-substrate interactions which are intermediate between self-assembled and surface-frozen monolayers, each dominated by one interaction. The phase behavior is rationalized within a thermodynamic model comprising interfacial interactions, elasticity, and entropic effects. Separating the substrate from the melt leaves the monolayer structurally intact.

  19. Unifying Interfacial Self-Assembly and Surface Freezing

    SciTech Connect

    Ocko, B.M.; Hlaing, H.; Jepsen, P.N.; Kewalramani, S.; Tkachenko, A.; Pontoni, D.; Reichert, H.; Deutsch, M.

    2011-03-30

    X-ray investigations reveal that the monolayers formed at the bulk alkanol-sapphire interface are densely packed with the surface-normal molecules hydrogen bound to the sapphire. About 30-35 C above the bulk, these monolayers both melt reversibly and partially desorb. This system exhibits balanced intermolecular and molecule-substrate interactions which are intermediate between self-assembled and surface-frozen monolayers, each dominated by one interaction. The phase behavior is rationalized within a thermodynamic model comprising interfacial interactions, elasticity, and entropic effects. Separating the substrate from the melt leaves the monolayer structurally intact.

  20. Passivation effects in B doped self-assembled Si nanocrystals

    SciTech Connect

    Puthen Veettil, B. Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Zhang, Tian; Yang, Terry; Johnson, Craig; Conibeer, Gavin; Perez-Würfl, Ivan; McCamey, Dane

    2014-12-01

    Doping of semiconductor nanocrystals has enabled their widespread technological application in optoelectronics and micro/nano-electronics. In this work, boron-doped self-assembled silicon nanocrystal samples have been grown and characterised using Electron Spin Resonance and photoluminescence spectroscopy. The passivation effects of boron on the interface dangling bonds have been investigated. Addition of boron dopants is found to compensate the active dangling bonds at the interface, and this is confirmed by an increase in photoluminescence intensity. Further addition of dopants is found to reduce the photoluminescence intensity by decreasing the minority carrier lifetime as a result of the increased number of non-radiative processes.

  1. Self-assembly of monodisperse clusters: Dependence on target geometry

    NASA Astrophysics Data System (ADS)

    Wilber, Alex W.; Doye, Jonathan P. K.; Louis, Ard A.

    2009-11-01

    We apply a simple model system of patchy particles to study monodisperse self-assembly using the Platonic solids as target structures. We find marked differences between the assembly behaviors of the different systems. Tetrahedra, octahedral, and icosahedra assemble easily, while cubes are more challenging and dodecahedra do not assemble. We relate these differences to the kinetics and thermodynamics of assembly, with the formation of large disordered aggregates a particular important competitor to correct assembly. In particular, the free energy landscapes of those targets that are easy to assemble are funnel-like, whereas for the dodecahedral system the landscape is relatively flat with little driving force to facilitate escape from disordered aggregates.

  2. Manipulation of self-assembly amyloid peptide nanotubes by dielectrophoresis.

    PubMed

    Castillo, Jaime; Tanzi, Simone; Dimaki, Maria; Svendsen, Winnie

    2008-12-01

    Self-assembled amyloid peptide nanotubes (SAPNT) were manipulated and immobilized using dielectrophoresis. Micro-patterned electrodes of Au were fabricated by photolithography and lifted off on a silicon dioxide layer. SAPNT were manipulated by adjusting the amplitude and frequency of the applied voltage. The immobilized SAPNT were evaluated by SEM and atomic force microscopy. The conductivity of the immobilized SAPNT was studied by I-V characterization, for both single SAPNT and bundles. This work illustrates a way to manipulate and integrate biological nanostructures into novel bio-nanoassemblies with concrete applications, such as field-effect transistors, microprobes, microarrays, and biosensing devices. PMID:19130587

  3. Stacking of self-assembled surface micelles in ultrathin films.

    PubMed

    de Gracia Lux, Caroline; Gallani, Jean-Louis; Waton, Gilles; Krafft, Marie Pierre

    2012-04-23

    Nonpolar fluorophilic/lipophilic tetrablock amphiphiles are investigated on the surface of water and on solid substrates using compression isotherms, Brewster angle microscopy, and atomic force microscopy. At low pressures, the tetrablocks form monolayers of closely packed surface hemimicelles. Further compression causes a 2D/3D transition. At the end of the plateau, half of the deposited material is expelled forming a second monolayer on top of the initially formed monolayer. Both layers of the films consist of surface micelles, thus providing the first example of spontaneous or compression-driven stacking of self-assembled nano-objects. PMID:22431371

  4. A self-assembling fluorescent dipeptide conjugate for cell labelling.

    PubMed

    Kirkham, Steven; Hamley, Ian W; Smith, Andrew M; Gouveia, Ricardo M; Connon, Che J; Reza, Mehedi; Ruokolainen, Janne

    2016-01-01

    Derivatives of fluorophore FITC (fluorescein isothiocyanate) are widely used in bioassays to label proteins and cells. An N-terminal leucine dipeptide is attached to FITC, and we show that this simple conjugate molecule is cytocompatible and is uptaken by cells (human dermal and corneal fibroblasts) in contrast to FITC itself. Co-localisation shows that FITC-LL segregates in peri-nuclear and intracellular vesicle regions. Above a critical aggregation concentration, the conjugate is shown to self-assemble into beta-sheet nanostructures comprising molecular bilayers. PMID:25990811

  5. Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters

    SciTech Connect

    Sigmon, Ginger E.; Burns, Peter C.

    2011-06-22

    Clusters built from 32 uranyl peroxide polyhedra self-assemble and crystallize within 15 min after combining uranyl nitrate, ammonium hydroxide, and hydrogen peroxide in aqueous solution under ambient conditions. These novel crown-shaped clusters are remarkable in that they form so quickly, have extraordinarily low aqueous solubility, form with at least two distinct peroxide to hydroxyl ratios, and form in very high yield. The clusters, which have outer diameters of 23 Å, topologically consist of eight pentagons and four hexagons. Their rapid formation and low solubility in aqueous systems may be useful properties at various stages in an advanced nuclear energy system.

  6. Guided Self-Assembly of Nano-Precipitates into Mesocrystals

    PubMed Central

    Liu, H.; Gao, Y.; Xu, Z.; Zhu, Y.M.; Wang, Y.; Nie, J.F.

    2015-01-01

    We show by a combination of computer simulation and experimental characterization guided self-assembly of coherent nano-precipitates into a mesocrystal having a honeycomb structure in bulk materials. The structure consists of different orientation variants of a product phase precipitated out of the parent phase by heterogeneous nucleation on a hexagonal dislocation network. The predicted honeycomb mesocrystal has been confirmed by experimental observations in an Mg-Y-Nd alloy. The structure and lattice parameters of the mesocrystal and the size of the nano-precipitates are readily tuneable, offering ample opportunities to tailor its properties for a wide range of technological applications. PMID:26559002

  7. Programmed self-assembly of complex DNA nanostructures

    NASA Astrophysics Data System (ADS)

    Tian, Cheng

    DNA has served as an excellent building block to self-assemble into a wide range of one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) structures with the bottom-up method. Due to the specificity of base pairing, the DNA assembly system is predictable and robust. These DNA structures with higher diversity and complexity have potential applications as templates to organize guest molecules or nanoparticles for the nanofabrication, as biosensors for the genetic diagnosis and environmental detection, and as nanocarriers to deliver and release drugs for the therapy. My major researches focus on designing a novel building block and assembly strategies to self-assemble DNA into complex nanostructures to increase the diversity and complexity. A novel building block was first constructed, which is a parallel, left-handed DNA helix containing multiple domains of half-turn-long standard B-DNA. Such a structure can be used to introduce left-handed crossings in order to increase the diversity and complexity of DNA nanostructures, and can be taken into consideration when predicting the secondary structure of DNA/RNA molecules in cells. In addition, a tile-based directed self-assembly strategy was developed to construct DNA nanocages. In this strategy, directing building blocks were employed to control the self-assembly process of assembly building blocks. This strategy greatly expands the scope of accessible DNA nanostructures and would facilitate technological applications such as nano-guest encapsulation, drug delivery, and nanoparticle organization. As the complexity of DNA nanostructures increases, more errors might be involved in the assembly process. Therefore, a simplified design system based on T-junction was designed to build DNA arrays and minimize the assembly errors. In such system, due to the sequence symmetry, only one DNA single strand is employed and assembled into predesigned 1D and 2D arrays. This design system can be applied to assemble a wide range of DNA nanostructures with varieties of features.

  8. Self-assembled conducting polypyrrole micro/nanotubes

    NASA Astrophysics Data System (ADS)

    Yang, Yongsheng; Liu, Jin; Wan, Meixiang

    2002-12-01

    Self-assembled polypyrrole (PPy) micro/nanotubes, whose diameters and room temperature conductivities were within the ranges of 50-2000 nm and 2-40 S cm-1 respectively, were successfully synthesized by a chemical and electrochemical method in the presence of ?-naphthalene sulfonic acid or p-toluenesulfonate acid as the dopant. By changing the polymerization method and conditions as well as dopant structures, one can control the morphology, size and electrical properties of the doped PPy. It was proposed that dopant micelles or pyrrole/dopant clusters act as templates in the formation of the micro/nanotubes.

  9. Metal nanowires from self-assembled protein fibers

    NASA Astrophysics Data System (ADS)

    Parthasarathy, Raghuveer; Lin, Xiao-Min; Jaeger, Heinrich M.; Sawicki, George; Scheibel, Thomas; Lindquist, Susan L.

    2002-03-01

    We present gold and silver nanowires formed by metallization of self-assembled yeast prion proteins. The proteins form 10nm wide, microns long fibers, which we metallize by growth of gold or silver crystals from specific nucleation sites on the genetically engineered fiber surface. This site-specific metal decoration is the first step toward more elaborate functionalization of these biological nanostructures. Deposition of fibers onto substrates with in-plane electrodes will allow electronic transport measurements, correlated with images (TEM and AFM) of the nanowire structure.

  10. Crowding induced self-assembly and enthalpy-entropy compensation.

    PubMed

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

    2009-09-25

    We develop a general virial expansion to describe the influence of molecular additives on the equilibrium self-assembly of proteins or other supermolecularly assembling species M in solution. When specialized to high molar mass polymer additives, the cross-virial coefficient between the polymer and M, which dominates this effect, is found to vanish at a particular temperature T_{Theta} corresponding to an enthalpy-entropy compensation condition. Specifically, the increased stability of the assembled form of M, due to the modification of the entropy of the assembly by repulsive polymer-protein interactions, is progressively compensated by attractive interactions that alter the enthalpy of assembly. PMID:19905522

  11. Model for dynamic self-assembled magnetic surface structures.

    SciTech Connect

    Belkin, M.; Glatz, A.; Snezhko, A.; Aranson, I. S.; Materials Science Division; Northwestern Univ.

    2010-07-07

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

  12. Guided Self-Assembly of Nano-Precipitates into Mesocrystals

    NASA Astrophysics Data System (ADS)

    Liu, H.; Gao, Y.; Xu, Z.; Zhu, Y. M.; Wang, Y.; Nie, J. F.

    2015-11-01

    We show by a combination of computer simulation and experimental characterization guided self-assembly of coherent nano-precipitates into a mesocrystal having a honeycomb structure in bulk materials. The structure consists of different orientation variants of a product phase precipitated out of the parent phase by heterogeneous nucleation on a hexagonal dislocation network. The predicted honeycomb mesocrystal has been confirmed by experimental observations in an Mg-Y-Nd alloy. The structure and lattice parameters of the mesocrystal and the size of the nano-precipitates are readily tuneable, offering ample opportunities to tailor its properties for a wide range of technological applications.

  13. Customizing mesoscale self-assembly with 3D printing

    E-print Network

    M. Poty; G. Lumay; N. Vandewalle

    2013-10-17

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

  14. Purification of ethanol for highly sensitive self-assembly experiments

    PubMed Central

    Barbe, Kathrin; Kind, Martin; Pfeiffer, Christian

    2014-01-01

    Summary Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs) of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only show high capacities for surface-active contaminants, such as thiols, but can be fully regenerated via a simple pyrolysis protocol. PMID:25161861

  15. Real time monitoring of superparamagnetic nanoparticle self-assembly on surfaces of magnetic recording media

    SciTech Connect

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

    2014-05-07

    Nanoparticle self-assembly dynamics are monitored in real-time by detecting optical diffraction from an all-nanoparticle grating as it self-assembles on a grating pattern recorded on a magnetic medium. The diffraction efficiency strongly depends on concentration, pH, and colloidal stability of nanoparticle suspensions, demonstrating the nanoparticle self-assembly process is highly tunable. This metrology could provide an alternative for detecting nanoparticle properties such as colloidal stability.

  16. Self-assembly of nanoparticles into nanowires under laser exposure in liquids

    NASA Astrophysics Data System (ADS)

    Serkov, A. A.; Barmina, E. V.; Kuzmin, P. G.; Shafeev, G. A.

    2015-03-01

    Experimental results on the process of self-assembly of Au nanoparticles under their exposure to picosecond laser radiation in water are presented. Self-assembly of Au NPs into nanowires occurs under laser ablation of a bulk Au target, which is cathodically biased with respect to a Pt anode. Similar process is observed in excess of free electrons in solution due to presence of beta-active ions, e.g., Tritium. Self-assembly of Au NPs into nanowires also occurs under laser exposure of their dense colloidal solution to picosecond laser radiation and proceeds in an avalanche-like way. Possible mechanisms of self-assembly are discussed.

  17. Peptide self-assembly for nanomaterials: the old new kid on the block.

    PubMed

    De Santis, Emiliana; Ryadnov, Maxim G

    2015-11-21

    Peptide self-assembly is an increasingly attractive tool for nanomaterials. Perfected in biology peptide self-assembling systems have impacted on nearly any conceivable nanomaterial type. However, with all the information available to us commercialisation of peptide materials remains in its infancy. In an attempt to better understand the reasons behind this shortcoming we categorise peptide self-assembled materials in relation to their non-peptide counterparts. A particular emphasis is placed on the versatility of peptide self-assembly in terms of modularity, responsiveness and functional diversity, which enables direct comparisons with more traditional material chemistries. PMID:26272066

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

    E-print Network

    McCombs, Jessica R. (Jessica Rose)

    2013-01-01

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

  19. Polymer Nanocomposites through Controlled Self-Assembly of Cubic Silsesquioxane Scaffolds

    E-print Network

    Polymer Nanocomposites through Controlled Self-Assembly of Cubic Silsesquioxane Scaffolds Lei Zheng nanocomposites using cubic silsesquioxanes (POSS) nanoparticles as building blocks is reported. The design

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

    E-print Network

    Cleary, Liam

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

  1. Delivery of therapeutics and molecules using self-assembled peptides.

    PubMed

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

    2014-01-01

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

  2. Chiral plasmonics of self-assembled nanorod dimers.

    PubMed

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

    2013-01-01

    Chiral nanoscale photonic systems typically follow either tetrahedral or helical geometries that require four or more different constituent nanoparticles. Smaller number of particles and different chiral geometries taking advantage of the self-organization capabilities of nanomaterials will advance understanding of chiral plasmonic effects, facilitate development of their theory, and stimulate practical applications of chiroplasmonics. Here we show that gold nanorods self-assemble into side-by-side orientated pairs and "ladders" in which chiral properties originate from the small dihedral angle between them. Spontaneous twisting of one nanorod versus the other one breaks the centrosymmetric nature of the parallel assemblies. Two possible enantiomeric conformations with positive and negative dihedral angles were obtained with different assembly triggers. The chiral nature of the angled nanorod pairs was confirmed by 4? full space simulations and the first example of single-particle CD spectroscopy. Self-assembled nanorod pairs and "ladders" enable the development of chiral metamaterials, (bio)sensors, and new catalytic processes. PMID:23752317

  3. Aerosol-Assisted Self-Assembly of Mesostructured Spherical Nanoparticles

    SciTech Connect

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

    1999-03-23

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

  4. Self-assembling and self-limiting monolayer deposition

    NASA Astrophysics Data System (ADS)

    Foest, Rüdiger; Schmidt, Martin; Gargouri, Hassan

    2014-02-01

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

  5. Self-assembled nanostructured aqueous dispersions as dermal delivery systems.

    PubMed

    Hoppel, Magdalena; Caneri, Manuel; Glatter, Otto; Valenta, Claudia

    2015-11-10

    Due to their high interfacial area and capability of loading hydrophobic, hydrophilic and amphiphilic drugs, self-assembled nanoparticles are the subject of much attention in view of an application of these dispersions as carrier systems for a variety of different active ingredients. Therefore, the effect of the internal nanostructure of oil-loaded monoglyceride-based nanoparticles on the dermal delivery of diclofenac sodium was investigated. The different self-assembled phases of the nanostructured aqueous dispersions were characterized by small angle X-ray scattering (SAXS). The influence of the different phases ranging from cubic-bicontinuous, over hexagonal and cubic-micellar phases to emulsified microemulsions on the dermal delivery of the incorporated active was examined by Franz-type diffusion cell and in vitro tape stripping experiments on porcine skin. These studies revealed a dependency of the skin permeation of diclofenac sodium on the formulation's internal structure, which could be modified by varying the amount of R-(+)-limonene in the oil phase. A superiority of the emulsified microemulsion, possessing the highest amount of R-(+)-limonene, over cubic or hexagonal phases was evidenced in terms of dermal drug delivery. PMID:26364712

  6. Self assembly of highly-ordered nanoparticle monolayers.

    SciTech Connect

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago

    2006-01-01

    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

  7. Self-assembled single-phase perovskite nanocomposite thin films.

    PubMed

    Kim, Hyun-Suk; Bi, Lei; Paik, Hanjong; Yang, Dae-Jin; Park, Yun Chang; Dionne, Gerald F; Ross, Caroline A

    2010-02-10

    Thin films of perovskite-structured oxides with general formula ABO(3) have great potential in electronic devices because of their unique properties, which include the high dielectric constant of titanates, (1) high-T(C) superconductivity in cuprates, (2) and colossal magnetoresistance in manganites. (3) These properties are intimately dependent on, and can therefore be tailored by, the microstructure, orientation, and strain state of the film. Here, we demonstrate the growth of cubic Sr(Ti,Fe)O(3) (STF) films with an unusual self-assembled nanocomposite microstructure consisting of (100) and (110)-oriented crystals, both of which grow epitaxially with respect to the Si substrate and which are therefore homoepitaxial with each other. These structures differ from previously reported self-assembled oxide nanocomposites, which consist either of two different materials (4-7) or of single-phase distorted-cubic materials that exhibit two or more variants. (8-12) Moreover, an epitaxial nanocomposite SrTiO(3) overlayer can be grown on the STF, extending the range of compositions over which this microstructure can be formed. This offers the potential for the implementation of self-organized optical/ferromagnetic or ferromagnetic/ferroelectric hybrid nanostructures integrated on technologically important Si substrates with applications in magnetooptical or spintronic devices. PMID:20039695

  8. The surface plasmon modes of self-assembled gold nanocrystals

    NASA Astrophysics Data System (ADS)

    Barrow, Steven J.; Wei, Xingzhan; Baldauf, Julia S.; Funston, Alison M.; Mulvaney, Paul

    2012-12-01

    The three-dimensional (3D) self-assembly of nanocrystals constitutes one of the most important challenges in materials science. A key milestone is the synthesis of simple, regular structures, such as platonic solids, composed of nanocrystal building blocks. Such objects are predicted to have unique optical and electronic properties such as polarization-independent light-scattering and intense local fields. Here we present a two-stage process for fabricating well-defined and highly symmetric, 3D gold nanocrystal structures, including tetrahedra, 3D pentamers and 3D hexamers. Polarized scattering spectra are used to elucidate the plasmon modes present in each structure, and these are compared with computational models. We conclude that self-assembly of highly symmetric, polarization-independent structures with interparticle spacings of order 0.5?nm can now be fabricated. Drastically, enhanced local fields, 1000 times higher than the incident field strength, are produced within the interstices. Fano resonances are generated if the symmetry is broken.

  9. Structure of self - assembled two-dimensional spherical crystals

    NASA Astrophysics Data System (ADS)

    Bausch, Andreas R.

    2004-03-01

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

  10. Precise hierarchical self-assembly of multicompartment micelles

    PubMed Central

    Gröschel, André H.; Schacher, Felix H.; Schmalz, Holger; Borisov, Oleg V.; Zhulina, Ekaterina B.; Walther, Andreas; Müller, Axel H.E.

    2012-01-01

    Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of complex materials. For block copolymers, the last decade witnessed great progress in diversifying the structural complexity of solution-based assemblies into multicompartment micelles. However, a general understanding of what governs multicompartment micelle morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. Here we demonstrate how to create homogeneous multicompartment micelles with unprecedented structural control via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined multicompartment micelles with precisely tunable patchiness, while using simple linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of multicompartment micelles into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects. PMID:22426231

  11. Structural Diversity of Self-Assembled Iridescent Arthropod Biophotonic Nanostructures

    NASA Astrophysics Data System (ADS)

    Saranathan, Vinod Kumar; Prum, Richard O.

    2015-03-01

    Many organisms, especially arthropods, produce vivid interference colors using diverse mesoscopic (100-350 nm) integumentary biophotonic nanostructures that are increasingly being investigated for technological applications. Despite a century of interest, we lack precise structural knowledge of many biophotonic nanostructures and mechanisms controlling their development, when such knowledge can open novel biomimetic routes to facilely self-assemble tunable, multi-functional materials. Here, we use synchrotron small angle X-ray scattering and electron microscopy to characterize the photonic nanostructure of 140 iridescent integumentary scales and setae from 127 species of terrestrial arthropods in 85 genera from 5 orders. We report a rich nanostructural diversity, including triply-periodic bicontinuous networks, close-packed spheres, inverse columnar, perforated lamellar, and disordered sponge-like morphologies, commonly observed as stable phases of amphiphilic surfactants, block copolymer, and lyotropic lipid-water systems. Diverse arthropod lineages appear to have independently evolved to utilize the self-assembly of infolding bilayer membranes to develop biophotonic nanostructures that span the phase-space of amphiphilic morphologies, but at optical length scales.

  12. Glycosylated Self-Assembled Monolayers for Arrays and Surface Analysis

    PubMed Central

    Cheng, Fang; Ratner, Daniel M.

    2013-01-01

    Over the past few decades, carbohydrates (glycans) have received growing attention for their many roles in biological systems, including pathogenesis, receptor-ligand interactions, and cell signaling. To unravel the biology of this important category of biomolecules, a host of new tools have been developed for glycomics investigation. At the forefront is the carbohydrate microarray, developed to immobilize functional glycans on a solid substrate to rapidly screen a variety of potential binding partners (carbohydrates, proteins, nucleic acids, cells, and viruses). The essential role played by surface modification on glycan microarray performance requires new methods to rigorously characterize glycan surface chemistries. Due to their highly reproducible nature and well-studied properties, self-assembled monolayers (SAMs) on gold are powerful models for presenting glycans on a solid substrate, engineering biomimetic microenvironments and exploring the bioactivity of immobilized carbohydrates via surface plasmon resonance (SPR). However, it can be challenging to prepare high quality glycosylated SAMs (glyco-SAMs) that retain their biological function following surface immobilization. Herein, a selection of versatile methods for the preparation of glyco-SAMs using natural and chemically modified glycans is described. This chapter will highlight the following three immobilization techniques: (1) direct self assembly using thiolated glycosides onto gold, (2) tethering aminated glycosides onto amine-reactive SAMs, and (3) conjugating natural glycan onto divinyl sulfone-activated SAMs. PMID:22057519

  13. Molecular Self-Assembly at Metal-Electrolyte Interfaces

    PubMed Central

    Phan, Thanh Hai; Wandelt, Klaus

    2013-01-01

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

  14. On Irregular Interconnect Fabrics for Self-Assembled Nanoscale Electronics

    E-print Network

    Christof Teuscher

    2006-06-22

    Nanoscale electronics and novel fabrication technologies bear unique opportunities for self-assembling multi-billion component systems in a largely random manner, which would likely lower fabrication costs significantly compared to a definite ad hoc assembly. It has been shown that communication networks with the small-world property have major advantages in terms of transport characteristics and robustness over regularly connected systems. In this paper we pragmatically investigate the properties of an irregular, abstract, yet physically plausible small-world interconnect fabric that is inspired by modern network-on-chip paradigms. We vary the framework's key parameters, such as the connectivity, the number of switch blocks, the number of virtual channels, the routing strategy, the distribution of long- and short-range connections, and measure the network's transport characteristics and robustness against failures. We further explore the ability and efficiency to solve two simple toy problems, the synchronization and the density classification task. The results confirm that (1) computation in irregular assemblies is a promising new computing paradigm for nanoscale electronics and (2) that small-world interconnect fabrics have major advantages over local CA-like topologies. Finally, the results will help to make important design decisions for building self-assembled electronics in a largely random manner.

  15. Functional self-assembled DNA nanostructures for molecular recognition

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaojuan; Yadavalli, Vamsi K.

    2012-03-01

    Nucleic acids present a wonderful toolkit of structural motifs for nanoconstruction. Functional DNA nanostructures can enable protein recognition by the use of aptamers attached to a basic core shape formed by DNA self-assembly. Here, we present a facile, programmable strategy for the assembly of discrete aptamer-tagged DNA shapes and nanostructures that can function for molecular recognition and binding in an aqueous environment. These nanostructures, presented here to bind two different protein targets, are easily synthesized in large numbers, and are portable and stable over long periods of time. This construction modality can facilitate on-demand production of libraries of diverse shapes to recognize and bind proteins or catalyze reactions via functional nucleic acid tags.Nucleic acids present a wonderful toolkit of structural motifs for nanoconstruction. Functional DNA nanostructures can enable protein recognition by the use of aptamers attached to a basic core shape formed by DNA self-assembly. Here, we present a facile, programmable strategy for the assembly of discrete aptamer-tagged DNA shapes and nanostructures that can function for molecular recognition and binding in an aqueous environment. These nanostructures, presented here to bind two different protein targets, are easily synthesized in large numbers, and are portable and stable over long periods of time. This construction modality can facilitate on-demand production of libraries of diverse shapes to recognize and bind proteins or catalyze reactions via functional nucleic acid tags. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11711h

  16. Self-assembly of Giant Molecular Shape Amphiphiles in Solution

    NASA Astrophysics Data System (ADS)

    Wang, Rong; Ma, Shiying

    2015-03-01

    The self-assembly of giant molecular shape amphiphiles consisting of a hydrophilic head and one or more hydrophobic tails is investigated by dissipative particle dynamics. The morphology can transform from vesicles to worm-like cylinders and further to spheres by increasing the interaction parameter between the hydrophilic heads. The results are in agreement with the experimental observations. Through changing the interaction parameter between hydrophilic head and solvents, the length of hydrophobic tail and the size of hydrophilic head, the self-assembled aggregates exhibit a rich variety of morphological structures, such as, spheres, vesicles, worm-like cylinders, disk-like micelles and layered-rod-like micelles. Vesicles form for short hydrophobic tail, while disk-like micelles are taken shape for longer hydrophobic tail. As further increasing the diameter of hydrophilic head, large compound micelles are obtained for short hydrophobic tail, however layered-rod-like micelles form for longer tail. The simulation findings might be valuable for guiding the experimental studies and fascinating new possibility and applications in material science. This work was financially supported by NNSFC (21474051 and 21074053), NBRPC (2010CB923303) and PCSIRT.

  17. Silver nanoprisms self-assembly on differently functionalized silica surface

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  18. Molecular Self-Assembly Driven by London Dispersion Forces

    SciTech Connect

    Li, Guo; Cooper, Valentino R; Cho, Jun-Hyung; Du, Shixuan; Gao, Hongjun; Zhang, Zhenyu

    2011-01-01

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

  19. Engineering protocells: prospects for self-assembly and nanoscale production-lines.

    PubMed

    Miller, David M; Gulbis, Jacqueline M

    2015-01-01

    The increasing ease of producing nucleic acids and proteins to specification offers potential for design and fabrication of artificial synthetic "organisms" with a myriad of possible capabilities. The prospects for these synthetic organisms are significant, with potential applications in diverse fields including synthesis of pharmaceuticals, sources of renewable fuel and environmental cleanup. Until now, artificial cell technology has been largely restricted to the modification and metabolic engineering of living unicellular organisms. This review discusses emerging possibilities for developing synthetic protocell "machines" assembled entirely from individual biological components. We describe a host of recent technological advances that could potentially be harnessed in design and construction of synthetic protocells, some of which have already been utilized toward these ends. More elaborate designs include options for building self-assembling machines by incorporating cellular transport and assembly machinery. We also discuss production in miniature, using microfluidic production lines. While there are still many unknowns in the design, engineering and optimization of protocells, current technologies are now tantalizingly close to the capabilities required to build the first prototype protocells with potential real-world applications. PMID:25815781

  20. Engineering Protocells: Prospects for Self-Assembly and Nanoscale Production-Lines

    PubMed Central

    Miller, David M.; Gulbis, Jacqueline M.

    2015-01-01

    The increasing ease of producing nucleic acids and proteins to specification offers potential for design and fabrication of artificial synthetic “organisms” with a myriad of possible capabilities. The prospects for these synthetic organisms are significant, with potential applications in diverse fields including synthesis of pharmaceuticals, sources of renewable fuel and environmental cleanup. Until now, artificial cell technology has been largely restricted to the modification and metabolic engineering of living unicellular organisms. This review discusses emerging possibilities for developing synthetic protocell “machines” assembled entirely from individual biological components. We describe a host of recent technological advances that could potentially be harnessed in design and construction of synthetic protocells, some of which have already been utilized toward these ends. More elaborate designs include options for building self-assembling machines by incorporating cellular transport and assembly machinery. We also discuss production in miniature, using microfluidic production lines. While there are still many unknowns in the design, engineering and optimization of protocells, current technologies are now tantalizingly close to the capabilities required to build the first prototype protocells with potential real-world applications. PMID:25815781

  1. Ionic self-assembly for functional hierarchical nanostructured materials.

    PubMed

    Faul, Charl F J

    2014-12-16

    CONSPECTUS: The challenge of constructing soft functional materials over multiple length scales can be addressed by a number of different routes based on the principles of self-assembly, with the judicious use of various noncovalent interactions providing the tools to control such self-assembly processes. It is within the context of this challenge that we have extensively explored the use of an important approach for materials construction over the past decade: exploiting electrostatic interactions in our ionic self-assembly (ISA) method. In this approach, cooperative assembly of carefully chosen charged surfactants and oppositely charged building blocks (or tectons) provides a facile noncovalent route for the rational design and production of functional nanostructured materials. Generally, our research efforts have developed with an initial focus on establishing rules for the construction of novel noncovalent liquid-crystalline (LC) materials. We found that the use of double-tailed surfactant species (especially branched double-tailed surfactants) led to the facile formation of thermotropic (and, in certain cases, lyotropic) phases, as demonstrated by extensive temperature-dependent X-ray and light microscopy investigations. From this core area of activity, research expanded to cover issues beyond simple construction of anisotropic materials, turning to the challenge of inclusion and exploitation of switchable functionality. The use of photoactive azobenzene-containing ISA materials afforded opportunities to exploit both photo-orientation and surface relief grating formation. The preparation of these anisotropic LC materials was of interest, as the aim was the facile production of disposable and low-cost optical components for display applications and data storage. However, the prohibitive cost of the photo-orientation processes hampered further exploitation of these materials. We also expanded our activities to explore ISA of biologically relevant tectons, specifically deoxyguanosine monophosphate. This approach proved, in combination with block copolymer (BCP) self-assembly, very fruitful for the construction of complex and hierarchical functional materials across multiple length scales. Molecular frustration and incommensurability, which played a major role in structure formation in combination with nucleotide assembly, have now become important tools to tune supramolecular structure formation. These concepts, that is, the use of BCP assembly and incommensurability, in combination with metal-containing polymeric materials, have provided access to novel supramolecular morphologies and, more importantly, design rules to prepare such constructs. These design rules are now also being applied to the assembly of electroactive oligo(aniline)-based materials for the preparation of highly ordered functional soft materials, and present an opportunity for materials development for applications in energy storage. In this Account, we therefore discuss investigations into (i) the inclusion and preparation of supramolecular photoactive and electroactive materials; (ii) the exploitation and control over multiple noncovalent interactions to fine-tune function, internal structure, and long-range order and (iii) exploration of construction over multiple length scales by combination of ISA with well-known BCP self-assembly. Combination of ISA with tuning of volume fractions, mutual compatibility, and molecular frustration now provides a versatile tool kit to construct complex and hierarchical functional materials in a facile noncovalent way. A direct challenge for future ISA activities would certainly be the construction of functional mesoscale objects. However, within a broader scientific context, the challenge would be to exploit this powerful assembly tool for application in areas of research with societal impact, for example, energy storage and generation. The hope is that this Account will provide a platform for such future research activities and opportunities. PMID:25191750

  2. Applications of molecular self-assembly in tissue engineering

    NASA Astrophysics Data System (ADS)

    Harrington, Daniel Anton

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

  3. Principles Governing the Self Assembly of Polypeptide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wahome, Newton

    Self assembling systems on the nanometer scale afford the advantage of being able to control submicron level events. In this study, we focus on the self-assembling polypeptide nanoparticles (SAPN). The SAPN scaffold is made up of oligomerizing domains that align along the principle rotational axes of icosahedral symmetry. By aligning them along these axes, a particle with spherical geometry can be achieved. This particle can be utilized as a vaccine, as a drug delivery vehicle, or as a biomedical imaging device. This research will try to answer why the SAPN self-assembles into distinct molecular weight ranges while mostly maintaining a spherical morphology. The first means will be theoretical and computational, where we will utilize a mathematical formalism to find out how the packing of SAPN's monomeric units can occur within symmetric space. Then molecular dynamics will be run within this symmetric space to test the per amino acid residue susceptibility of SAPN towards becoming polymorphic in nature. Means for examining the aggregation propensity of SAPN will be also be tested. Specifically, the relationship of different sequences of SAPN with pH will be elucidated. Co-assembly of SAPN to reduce the surface density of an aggregation prone epitope will be tested. Also, aggregation reduction consisting of the exchange of an anionic denaturant with a positively charged suppressor in order to mitigate a priori peptide association and misfolding, will also be attempted. SAPN has been shown to be an immunogenic platform for the presentation of pathogen derived antigens. We will attempt to show the efficacy of presenting an antigen from HIV-1 which is structurally restrained to best match the native conformation on the virus. Immunological studies will be performed to test the effect of this approach, as well testing the antigenicity of the nanoparticle in the absence of adjuvant. Finally, the antigen presenting nanoparticles will undergo formulation testing, to measure the feasibility of SAPN for lyophilization. The regular buffers for refolding will be optimized, or replaced, in order to enhance the formation of a uniform powder, one that will not enhance the aggregation potential of the peptide species once freeze-drying has occurred.

  4. Molecular engineering and characterization of self-assembled biorecognition surfaces

    NASA Astrophysics Data System (ADS)

    Pan, Sheng

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

  5. Shape-and-solder-directed self-assembly to package semiconductor device segments

    E-print Network

    Jacobs, Heiko O.

    Shape-and-solder-directed self-assembly to package semiconductor device segments Wei Zheng recognition with site specific wetting and binding involving liquid solder. Components with complementary forces,3,4 liquid solder-based self-assemblies that use the surface tension between pairs of molten

  6. Energy transfer in self-assembled [N]-acene fibers involving > or =100 donors per acceptor.

    PubMed

    Del Guerzo, André; Olive, Alexandre G L; Reichwagen, Jens; Hopf, Henning; Desvergne, Jean-Pierre

    2005-12-28

    Anthracene derivatives self-assemble into fibers with a high molecular order, as is evidenced by probing the structure with energy-trapping tetracene analogues. Efficient energy transfer processes involving tens to hundreds of donors per acceptor and high emission quantum yields are outstanding characteristics displayed in these self-assembled fibers. PMID:16366532

  7. Self-Assembly of a Swarm of Autonomous Boats into Floating Structures

    E-print Network

    Napp, Nils

    Self-Assembly of a Swarm of Autonomous Boats into Floating Structures Ian O'Hara, James Paulos, Jay and Mark Yim Abstract-- This paper addresses the self-assembly of a large team of autonomous boats into floating platforms. We describe the design of individual boats, the systems concept, the al- gorithms

  8. Integration of Self-Assembled Three-Dimensional Photonic Crystals onto Structured Silicon Wafers

    E-print Network

    Jonsson, Fredrik

    Integration of Self-Assembled Three-Dimensional Photonic Crystals onto Structured Silicon Wafers silica spheres (diameter of 890 nm), self-assembled in hydrophilic trenches of silicon wafers by using a spatial selectivity of opal crystallization without special treatment of the wafer surface, a filling

  9. RPM-2: A recyclable porous material with unusual adsorption capability: self assembly via structural transformations

    E-print Network

    Li, Jing

    , effective control of a self-organization process towards targeted products still remains an enormous challenge in both static self- assembly and dynamic self-assembly.2 Realization of new crystalline that are difficult to control, for example, various ways in which a metal and a ligand may form a bond and different

  10. Programming Methodology for Biologically-Inspired Self-Assembling Systems Radhika Nagpal, Attila Kondacs, Catherine Chang

    E-print Network

    Batzoglou, Serafim

    Programming Methodology for Biologically-Inspired Self-Assembling Systems Radhika Nagpal, Attila@mit.edu Abstract We present a programming methodology for self-assembling complex structures from vast numbers of locally-interacting identically-programmed agents, using techniques inspired by developmental biology. We

  11. On the Manipulation of Nanoscale Self-Assembly by Elastic Field Division of Engineering,

    E-print Network

    Gao, Yanfei

    On the Manipulation of Nanoscale Self-Assembly by Elastic Field Y.F. Gao Division of Engineering-assembly can be manipulated by the long-range elastic field. This paper gives a universal formulation to manipulate nanoscale self-assembly by engineering the long-range elastic field. We focus our attention

  12. Coarse-grained lattice models for drying-mediated self-assembly of nanoparticles

    E-print Network

    Rabani, Eran

    Coarse-grained lattice models for drying- mediated self-assembly of nanoparticles Orly Kletenik-Edelman, Claudia G. Sztrum-Vartash and Eran Rabani DOI: 10.1039/b817439c We present a coarse-grained lattice gas approach applicable for modelling the drying- mediated self-assembly of nanoparticles. The approach

  13. Drying-Mediated Hierarchical Self-Assembly of Nanoparticles: A Dynamical Coarse-Grained Approach

    E-print Network

    Rabani, Eran

    Drying-Mediated Hierarchical Self-Assembly of Nanoparticles: A Dynamical Coarse-Grained Approach 91904, Israel ReceiVed: October 1, 2007 A coarse-grained lattice gas model is developed to study the drying-mediated self-assembly of nanoparticles on diblock copolymer substrates. The model describes

  14. The evolution of self-assemblies in the mixed system of oleic aciddiethylenetriamine based on

    E-print Network

    Huang, Jianbin

    The evolution of self-assemblies in the mixed system of oleic acid­diethylenetriamine based attraction between the oppositely charged headgroups.16,17 The construction and evolution of the self the evolution of self-assemblies based on the transformation of the electrostatic interaction and hydrogen bond

  15. Post-Self-Assembly Cross-Linking of Molecular Nanofibers for Oscillatory Hydrogels

    E-print Network

    Epstein, Irving R.

    Post-Self-Assembly Cross-Linking of Molecular Nanofibers for Oscillatory Hydrogels Ye Zhang, Ning in water to form molecular nanofibers, post-self-assembly cross-linking allows the catalyst of the Belousov-Zhabotinsky (BZ) reaction to be attached to the nanofibers, resulting in a hydrogel that exhibits concentration

  16. Post-Self-Assembly Cross-Linking to Integrate Molecular Nanofibers with Copolymers in Oscillatory Hydrogels

    E-print Network

    Epstein, Irving R.

    Post-Self-Assembly Cross-Linking to Integrate Molecular Nanofibers with Copolymers in Oscillatory Information ABSTRACT: We study the use of post-self-assembly cross- linking to combine molecular nanofibers. The formation of nanofibers from designed hydrogelators provides multiple polymerizable sites for copolymerizing

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

    E-print Network

    Salaita, Khalid

    Structurally Defined Nanoscale Sheets from Self-Assembly of Collagen-Mimetic Peptides Tao Jiang of two collagen-mimetic peptide sequences, NSI and NSII, that self-assemble into structurally defined packing of collagen triple helices in two dimensions. These nanosheet assemblies represent a novel

  18. Geometric Binding Site Design for Surface-Tension Driven Self-Assembly

    E-print Network

    Geometric Binding Site Design for Surface-Tension Driven Self-Assembly Xiaorong Xiong, Sheng 98195-2500 Email: xrxiong@u.washington.edu Abstract-- Surface-tension driven self-assembly techniques-assembly, micro assembly, MEMS, hy- drophobic, hydrophilic, surface energy, surface tension force, binding site

  19. Novel Polymer Patterns Formed by Lithographically Induced Self-Assembly (LISA)

    E-print Network

    Novel Polymer Patterns Formed by Lithographically Induced Self-Assembly (LISA) Lei Chen,* Lei film have been achieved by lithographically induced self-assembly (LISA) in this study. The variations of the LISA patterns are controlled by many operation factors, such as the choice of the polymers, mask

  20. Student Learning about Biomolecular Self-Assembly Using Two Different External Representations

    ERIC Educational Resources Information Center

    Host, Gunnar E.; Larsson, Caroline; Olson, Arthur; Tibell, Lena A. E.

    2013-01-01

    Self-assembly is the fundamental but counterintuitive principle that explains how ordered biomolecular complexes form spontaneously in the cell. This study investigated the impact of using two external representations of virus self-assembly, an interactive tangible three-dimensional model and a static two-dimensional image, on student learning…

  1. Nanostructured Polymers Prepared Using a Self-Assembled Nanofibrillar Scaffold as a Reverse Template

    E-print Network

    Raghavan, Srinivasa

    Nanostructured Polymers Prepared Using a Self-Assembled Nanofibrillar Scaffold as a Reverse describe the preparation of nanostructured polymeric materials by polymerizing a monomer within a scaffold composed of self-assembled nanofibrils. 1,3:2,4-Dibenzylidene sorbitol (DBS) is an inexpensive sugar

  2. The Self-Assembly Properties of a Benzene-1,3,5-tricarboxamide Derivative

    ERIC Educational Resources Information Center

    Stals, Patrick J. M.; Haveman, Jan F.; Palmans, Anja R. A.; Schenning, Albertus P. H. J.

    2009-01-01

    A series of experiments involving the synthesis and characterization of a benzene-1,3,5-tricarboxamide derivative and its self-assembly properties are reported. These laboratory experiments combine organic synthesis, self-assembly, and physical characterization and are designed for upper-level undergraduate students to introduce the topic of…

  3. Self-assembling tryptophan-based designer peptides as intracellular delivery vehicles.

    PubMed

    Bhardwaj, Ishanki; Jha, Divya; Admane, Prasad; Panda, Amulya K; Haridas, V

    2016-01-15

    A series of tryptophan-based peptides W1a, b-W4a, b, with diverse architectures were designed and synthesized. These tryptophan containing peptides can self-assemble to spherical particle. This self-assembled system was demonstrated to encapsulate rhodamine B and penetrate the cell membrane. PMID:26631316

  4. Functional Nanocomposites Prepared by Self-Assembly and Polymerization of Diacetylene Surfactants and Silicic Acid

    E-print Network

    Brinker, C. Jeffrey

    Functional Nanocomposites Prepared by Self-Assembly and Polymerization of Diacetylene Surfactants/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique

  5. Self-assembly of triangular polyoxometalate-organic hybrid macroions in mixed solvents.

    PubMed

    Zhang, Baofang; Pradeep, Chullikkattil P; Cronin, Leroy; Liu, Tianbo

    2015-05-21

    Triangular-shaped inorganic-organic hybrids with three polyoxometalate (POM) clusters as polar head groups are found to self-assemble into blackberry structures in water-acetone solvent mixtures containing 65-95 vol% acetone. The driving force for the self-assembly of the hybrids is shown to originate from the electrostatic counterion-cluster interactions. PMID:25900154

  6. Denaturation and Renaturation of Self-Assembled Yeast Iso-1-cytochrome c on Au

    E-print Network

    Zare, Richard N.

    Denaturation and Renaturation of Self-Assembled Yeast Iso-1-cytochrome c on Au Soonwoo Chah, Challa before and after self- assembly of the Cyt c. Exposure to a urea solution causes denaturation of Cyt c. The Gibbs free energy change for denaturation of the protein on Au is calculated from the change of the SPR

  7. Atomically precise self-assembly of one-dimensional structures on silicon

    E-print Network

    Himpsel, Franz J.

    Atomically precise self-assembly of one-dimensional structures on silicon I. Barke, T.K. Ru-magnetic surface. An interesting by-product is a memory structure with self-assembled tracks that are five atom: Low-dimensional structures; Atomic wires; Silicon surfaces; One-dimensional physics; Scanning

  8. A case of cyclodextrin-catalyzed self-assembly of an amphiphile into microspheres

    E-print Network

    Huang, Jianbin

    A case of cyclodextrin-catalyzed self-assembly of an amphiphile into microspheres Li Zhao-containing amphiphile TTC4L into microspheres. TT4CL can form precipitates when CDs are not present, whereas it self-assembly of cucurbit[n]uril. An amphiphile is required to form host­guest inclusion complexes before the self

  9. Controllable self-assembled laminated nanoribbons from dipeptide-amphiphile bearing azobenzene moiety

    E-print Network

    Huang, Jianbin

    Controllable self-assembled laminated nanoribbons from dipeptide-amphiphile bearing azobenzene nanostructures and biomaterials. In this paper, a dipeptide- amphiphile incorporated with an azobenzene moiety, Stupp has reported pH-induced self-assembly of a peptide-amphiphile to make nanostructured fibrous

  10. Synthesis and Self-Assembly of Amphiphilic Dendrimers Based on Aliphatic Polyether-Type Dendritic Cores

    E-print Network

    Gruner, Sol M.

    Synthesis and Self-Assembly of Amphiphilic Dendrimers Based on Aliphatic Polyether-Type Dendritic Manuscript Received February 22, 2004 ABSTRACT: We have prepared a series of amphiphilic dendrimers-angle X-ray scattering (WAXS) experiments. Amphiphilic dendrimer self-assembly in the solid state

  11. Self-Assembly of Regioregular, Amphiphilic Polythiophenes into Highly Ordered -Stacked

    E-print Network

    McCullough, Richard D.

    Self-Assembly of Regioregular, Amphiphilic Polythiophenes into Highly Ordered -Stacked Conjugated surfactants8 as well as nonamphiphilic polymers decorated with alkyl chains.9 Here we present amphiphilic. These amphiphilic polythiophenes self- assemble into -stacked conjugated chains that form a very stable cell

  12. Structure of cholesterol helical ribbons and self-assembling biological springs and George B. Benedek

    E-print Network

    Benedek, George B.

    Structure of cholesterol helical ribbons and self-assembling biological springs and George B of cholesterol helical ribbons and self-assembling biological springs Boris Khaykovich , Chintan Hossain of individual helical ribbons formed in multicomponent solutions of cholesterol solubilized by various

  13. Self-Assembly of 10-m-Sized Objects into Ordered Three-Dimensional Arrays

    E-print Network

    Tien, Joe

    functionalized to be hydrophobic or hydrophilic using self-assembled monolayers (SAMs). Self-assembly occurs in water through capillary interactions between thin films of a hydrophobic liquid (a liquid prepolymer open, three-dimensional microstructures. This work validates the use of capillary interactions

  14. Ultralow Thermal Conductivity in Organoclay Nanolaminates Synthesized via Simple Self-Assembly

    E-print Network

    Braun, Paul

    Ultralow Thermal Conductivity in Organoclay Nanolaminates Synthesized via Simple Self-Assembly Mark transform fully dense solids into ultralow thermal conductivity materials. Here we report a simple self-assembly approach to synthesizing organoclay nanolaminates with cross-planar thermal conductivities below 0.10 W m-1

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

    PubMed Central

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

    2014-01-01

    In plants and green algae, light is captured by the light-harvesting complexes (LHCs), a family of integral membrane proteins that coordinate chlorophylls and carotenoids. In vivo, these proteins are folded with pigments to form complexes which are inserted in the thylakoid membrane of the chloroplast. The high similarity in the chemical and physical properties of the members of the family, together with the fact that they can easily lose pigments during isolation, makes their purification in a native state challenging. An alternative approach to obtain homogeneous preparations of LHCs was developed by Plumley and Schmidt in 19871, who showed that it was possible to reconstitute these complexes in vitro starting from purified pigments and unfolded apoproteins, resulting in complexes with properties very similar to that of native complexes. This opened the way to the use of bacterial expressed recombinant proteins for in vitro reconstitution. The reconstitution method is powerful for various reasons: (1) pure preparations of individual complexes can be obtained, (2) pigment composition can be controlled to assess their contribution to structure and function, (3) recombinant proteins can be mutated to study the functional role of the individual residues (e.g., pigment binding sites) or protein domain (e.g., protein-protein interaction, folding). This method has been optimized in several laboratories and applied to most of the light-harvesting complexes. The protocol described here details the method of reconstituting light-harvesting complexes in vitro currently used in our laboratory,and examples describing applications of the method are provided. PMID:25350712

  16. Molecular self-assembly of amphiphilic cyclic phosphoryl gemcitabine with different N-fatty acyl tails and enhanced anticancer effects of the self-assembled nanostructures.

    PubMed

    Jin, Yiguang; Wang, Shan; Yao, Weishang; Du, Lina

    2015-09-01

    Molecular self-assembly of nucleosides is important, and the self-assembled nanostructures may be used for drug delivery and targeting. Gemcitabine (GEM) is an important anticancer nucleoside analog though deactivation and multi-drug resistance frequently happen. Four N-fatty acyl derivatives of cyclic phosphoryl GEM were prepared based on the theory of self-assembled drug delivery systems and the HepDirect prodrug technique wherein the prodrug could be degraded by the cytochrome P450 isozymes in hepatocytes to release active drugs. They are cyclic phosphoryl N-octyl gemcitabine (CPOG), cyclic phosphoryl N-dodecanoyl gemcitabine (CPDG), cyclic phosphoryl N-hexadecanoyl gemcitabine (CPHG), and cyclic phosphoryl N-octadecanoyl gemcitabine (CPODG). Their amphiphilicity and self-assembling property were explored. The self-assembled nanostructures of them were prepared and simulated. The in vitro anticancer activities of the nanostructures were investigated. The derivatives formed the Langmuir monolayers at the air/water interface, though their surface pressure-molecular area isotherms were different with dependency of the length of lipid chains. The derivatives self-assembled into the vesicular or rice-like nanostructures based on the hydrophobic interaction between lipid chains when injected into water, in accordance with the results of computer simulation. The nanostructures showed higher anticancer effects on HepG2 cells than GEM. The nanostructures are promising anticancer nanomedicines. PMID:26143151

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

    SciTech Connect

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

    2011-10-24

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

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

    E-print Network

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

    2010-03-11

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  20. Novel techniques to improve the light harvesting of thin film solar cells

    NASA Astrophysics Data System (ADS)

    Castelletto, Stefania; Boretti, Alberto

    2012-10-01

    Thin film solar cells are novel technologies receiving particular attention for their potentials to produce less expensive and more environmentally friendly renewable electricity from the sun light. This paper reports on different techniques that have been considered to improve the light harvesting, from the plasmonic resonance of noble metal nanoparticles, to the nanoparticles of a different semiconductor with different refractive index and band gap, to the anti-reflection surface textures as moth-eye-like shapes. Results of novel simulations solving the Maxwell's equations are compared to previous simulations.

  1. Up-converted fluorescence from photosynthetic light-harvesting complexes linearly dependent on excitation intensity.

    PubMed

    Leiger, Kristjan; Freiberg, Arvi

    2016-01-01

    Weak up-converted fluorescence related to bacteriochlorophyll a was recorded from various detergent-isolated and membrane-embedded light-harvesting pigment-protein complexes as well as from the functional membranes of photosynthetic purple bacteria under continuous-wave infrared laser excitation at 1064 nm, far outside the optically allowed singlet absorption bands of the chromophore. The fluorescence increases linearly with the excitation power, distinguishing it from the previously observed two-photon excited fluorescence upon femtosecond pulse excitation. Possible mechanisms of this excitation are discussed. PMID:25764015

  2. Light-harvesting in single conjugated polymer chains and semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Walter, Manfred J.

    Light-harvesting characterizes the efficient absorption of light and subsequent transport of excitation energy to a reaction center and thus the two basic processes relevant to photovoltaics. In this work, light-harvesting is studied on the fundamental single particle level of two technologically relevant semiconducting material classes---nanocrystals and conjugated polymers. The approach allows for the identification of structure-property relations which can usually not be resolved in ensembles of the same materials. Specifically, photoluminescence excitation (PLE) spectroscopy under intraparticle energy transfer conditions is performed on semiconductor nanotetrapods and dye-endcapped polymer chains, both model light-harvesting systems. This way, the structural origin of hampered energy funneling to the tetrapod core as well as the distribution and interaction of polymer chain subunits (chromophores) is resolved, respectively. For the first time, the energetic distribution and vibronic coupling of absorbing chromophores is measured on single polymer chains. While the conventional chromophore picture can be confirmed by several excitation properties, unexpectedly broad single chain absorption, remote interchromophoric coupling, and a correlation between chromophore length and exciton funneling efficiency offer valuable experimental results leading to a better understanding of intrachain excitation energy transfer. For the study of this process as well as exciton self-trapping in single polymer chains, a new spectroscopic method is established: combined single molecule fluorescence and surface-enhanced Raman scattering (SERS) spectroscopy. A comparison of both simultaneously acquired spectral signatures in the time or frequency domain can track excited state relaxation within a single polymer chain. The work is complemented by a simple screening method to identify substrates which are well suited for SERS. In short, the main results comprise (1) a tool to track intramolecular energy transfer in single polymer chains; (2) aspects for a better understanding of intrachain energy transfer; (3) the confirmation of an oligomer-like chromophore picture in single polymer absorption which, however, demands some alterations; and (4) an all-optical classification to identify and structurally characterize subgroups of nanocrystals with favorable light-harvesting properties.

  3. Vortices in dense self-assembled hole arrays.

    SciTech Connect

    Crabtree, G. W.; Welp, U.; Xiao, Z. L.; Jiang, J. S.; Vlasko-Vlasov, V. K.; Bader, S. D.; Liang, J.; Chik, H.; Xu, J. M.

    2002-10-09

    We present a study of the upper critical field and pinning strength from the resistivity and magnetization of a Nb film containing a dense array of 45 nm diameter holes on a hexagonal lattice with a spacing of 101 nm. The holes were formed by self-assembly in anodic aluminum oxide (AAO) using an electrochemical procedure. Confinement effects and Little-Parks oscillations are seen above 6 K, and strong pinning with matching field effects is seen below 6 K. Above the first matching field interstitial vortices coexist with vortices trapped in the hole array. Pinning in the Nb films with hole arrays is enhanced by two orders of magnitude over that in continuous Nb films. At low temperature, flux avalanches are observed and imaged using the magneto-optical Faraday effect.

  4. A single metal layer MEMS self-assembling coplanar structure

    NASA Astrophysics Data System (ADS)

    Bagolini, A.; Giacomozzi, F.; Margesin, B.; Bellutti, P.

    2007-05-01

    Self-assembling perforated microplates modeled and fabricated on silicon wafers by means of surface micromachining are presented. The structures consist of a single Cr/Au metal layer and are set into position by the residual tensile in-plane stress of the material; the geometry is designed to obtain a lifted microplate coplanar to the surface of the wafer. The structures are modeled both analytically and by finite element simulation to correlate the displacement with the strain of the structural material. Samples are fabricated using IC technology on standard 4-inch silicon wafers by surface micromachining; a photoresist is used as a sacrificial layer and electroplated gold is used as a structural layer on a chromium-gold PVD seedlayer. The fabricated structures exhibit a vertical displacement of 38 µm. The resulting estimated strain is 0.001 66, which corresponds to a tensile stress of 173 MPa and is consistent with thermal residual strain.

  5. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hamoudi, Hicham

    2014-06-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5'-bis (mercaptomethyl)-2,2'-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing.

  6. Charged triblock copolymer self-assembly into charged micelles

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  7. Supramolecular amplification of amyloid self-assembly by iodination

    PubMed Central

    Bertolani, Arianna; Pirrie, Lisa; Stefan, Loic; Houbenov, Nikolay; Haataja, Johannes S.; Catalano, Luca; Terraneo, Giancarlo; Giancane, Gabriele; Valli, Ludovico; Milani, Roberto; Ikkala, Olli; Resnati, Giuseppe; Metrangolo, Pierangelo

    2015-01-01

    Amyloid supramolecular assemblies have found widespread exploitation as ordered nanomaterials in a range of applications from materials science to biotechnology. New strategies are, however, required for understanding and promoting mature fibril formation from simple monomer motifs through easy and scalable processes. Noncovalent interactions are key to forming and holding the amyloid structure together. On the other hand, the halogen bond has never been used purposefully to achieve control over amyloid self-assembly. Here we show that single atom replacement of hydrogen with iodine, a halogen-bond donor, in the human calcitonin-derived amyloidogenic fragment DFNKF results in a super-gelator peptide, which forms a strong and shape-persistent hydrogel at 30-fold lower concentration than the wild-type pentapeptide. This is remarkable for such a modest perturbation in structure. Iodination of aromatic amino acids may thus develop as a general strategy for the design of new hydrogels from unprotected peptides and without using organic solvents. PMID:26123690

  8. Peptide Self-Assembly for Crafting Functional Biological Materials

    PubMed Central

    Matson, John B.; Zha, R. Helen; Stupp, Samuel I.

    2011-01-01

    Self-assembling, peptide-based scaffolds are frontrunners in the search for biomaterials with widespread impact in regenerative medicine. The inherent biocompatibility and cell signaling capabilities of peptides, in combination with control of secondary structure, has led to the development of a broad range of functional materials with potential for many novel therapies. More recently, membranes formed through complexation of peptide nanostructures with natural biopolymers have led to the development of hierarchically-structured constructs with potentially far-reaching applications in biology and medicine. In this review, we highlight recent advances in peptide-based gels and membranes, including work from our group and others. Specifically, we discuss the application of peptide-based materials in the regeneration of bone and enamel, cartilage, and the central nervous system, as well as the transplantation of islets, wound-healing, cardiovascular therapies, and treatment of erectile dysfunction after prostatectomy PMID:22125413

  9. DNA directed self-assembly of shape-controlled hydrogels

    PubMed Central

    Qi, Hao; Ghodousi, Majid; Du, Yanan; Grun, Casey; Bae, Hojae; Yin, Peng; Khademhosseini, Ali

    2013-01-01

    Using DNA as programmable, sequence specific ‘glues’, shape-controlled hydrogel units are self-assembled into prescribed structures. Here we report that aggregates are produced using hydrogel cubes with edge length ranging from 30 micrometers to 1 millimeter, demonstrating assembly across scales. In a simple one-pot agitation reaction, 25 dimers are constructed in parallel from 50 distinct hydrogel cube species, demonstrating highly multiplexed assembly. Using hydrogel cuboids displaying face-specific DNA glues, diverse structures are achieved in aqueous and in interfacial agitation systems. These include dimers, extended chains, and open network structures in an aqueous system; and dimers, chains of fixed length, T-junctions, and square shapes in the interfacial system, demonstrating the versatility of the assembly system. PMID:24013352

  10. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping

    2015-07-01

    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66?×?10-15?cm2?s-1, 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189?meV below the conduction band, consistent with the literature value.

  11. Phase Diagrams of Electrostatically Self-Assembled Amphiplexes

    SciTech Connect

    V Stanic; M Mancuso; W Wong; E DiMasi; H Strey

    2011-12-31

    We present the phase diagrams of electrostatically self-assembled amphiplexes (ESA) comprised of poly(acrylic acid) (PAA), cetyltrimethylammonium chloride (CTACl), dodecane, pentanol, and water at three different NaCl salt concentrations: 100, 300, and 500 mM. This is the first report of phase diagrams for these quinary complexes. Adding a cosurfactant, we were able to swell the unit cell size of all long-range ordered phases (lamellar, hexagonal, Pm3n, Ia3d) by almost a factor of 2. The added advantage of tuning the unit cell size makes such complexes (especially the bicontinuous phases) attractive for applications in bioseparation, drug delivery, and possibly in oil recovery.

  12. Supramolecular self-assembly of conjugated diblock copolymers.

    SciTech Connect

    Wang, H.; You, W.; Jiang, P.; Yu, L.; Wang, H. H.; Univ. of Chicago

    2004-02-20

    This paper describes the synthesis and characterization of a novel series of copolymers with different lengths of oligo(phenylene vinylene) (OPV) as the rod block, and poly(propylene oxide) as the coil block. Detailed characterization by means of transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle neutron scattering (SANS) revealed the strong tendency of these copolymers to self-assemble into cylindrical micelles in solution and as-casted films on a nanometer scale. These micelles have a cylindrical OPV core surrounded by a poly(propylene glycol) (PPG) corona and readily align with each other to form parallel packed structures when mica is used as the substrate. A packing model has been proposed for these cylindrical micelles.

  13. Nanowire Transistors, Gate Electrodes, and Their Directed Self-Assembly

    NASA Astrophysics Data System (ADS)

    Skinner, K.; Carroll, R. L.; Washburn, Sean; Dwyer, C.

    2005-11-01

    Lithographic processes used in the fabrication of current CMOS technology for microprocessors are rapidly approaching both fundamental and practical limitations. Nanowires capable of acting as either transistors or interconnects are one set of resources currently undergoing heavy research as a possible alternative for lithographic limitations. We present a method for the fabrication of multi-material, segmented nanowires composed of Au and CdSe that display non-linear current-voltage characteristics, and the selective functionalization of these nanowires with DNA by first blocking the Au sites we wish to be non-reactive with 6-mercapto 1-hexanol. Single material, conductive nanowires were then selectively functionalized at only the ends with complementary strands of DNA and were directed to self-assemble with the bound DNA on the segmented nanowires to serve as gate electrodes for the transistors.

  14. Self-Assembly of Cerium Oxide Nanostructures in Ice Molds

    SciTech Connect

    Karakoti, Ajay S.; Kuchibhatla, Satyanarayana V N T; Baer, Donald R.; Thevuthasan, Suntharampillai; Sayle, Dean C.; Seal, Sudipta

    2008-08-01

    The formation of nanorods, driven by the physico-chemical phenomena during the freezing of ceria nanoparticle suspension is reported. During freezing a dilute solution of CeO2 nanocrystals, some nuclei remain in solution while others are trapped inside the voids formed within the growing ice front. Over time the particles trapped within the constrained geometries combined by an oriented attachment process to form ceria nanorods. The experimental observations are further supported through Molecular Dynamics (MD) simulations. These observations suggest a new possible strategy for the templated formation of nanostructures through self assembly by exploiting natural phenomena such as freezing of water. "(A portion of) The research described in this paper (poster or presentation) was performed in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory."

  15. Self-assembly of tetrahedral plasmonic nanoclusters for optical metafluids

    NASA Astrophysics Data System (ADS)

    Schade, Nicholas; Manoharan, Vinothan

    2015-03-01

    We direct the assembly of clusters of gold nanospheres that behave as nanoscale electromagnetic resonators. We use spherical gold nanoparticles that are exceptionally smooth, monocrystalline, and monodisperse. These particles exhibit highly reproducible scattering spectra compared with gold colloids that are available commercially. We mix these positively charged particles with negatively charged dielectric particles. The gold particles stick to the dielectric particles permanently and randomly in a process that can be modeled mathematically as ``random parking,'' a type of non-equilibrium self-assembly. By controlling the particles' sizes, stoichiometry, and interactions, we maximize the yield of tetrahedral clusters, the ideal structures for isotropic metamaterials. We measure the optical properties of these structures with dark-field spectroscopy to characterize their suitability as building blocks for a bulk, isotropic, optical metafluid.

  16. Nanostructuring of diamond films using self-assembled nanoparticles

    NASA Astrophysics Data System (ADS)

    Babchenko, Oleg; Kromka, Alexander; Hruska, Karel; Michalka, Miroslav; Potmesil, Jiri; Vanecek, Milan

    2009-06-01

    We report the use of gold, nickel and diamond nanoparticles as a masking material for realization of diamond nano-structures by applying the dry plasma etching process. Applying low power plasma (100 W) in a gas mixture of CF4/O2 for 5 minutes results in a formation of three different types of diamond nanostructures, depending on the mask type material and particle size. Using of the Ni mask results in realization of diamond nano-rods, applying of the Au mask brings cauliflower-like structures, and using the diamond powder allows the production of irregular nano-structures. The main advance of the presented etching procedure is use of a self-assembly strategy where no lithographic steps are implemented.

  17. A self-assembled metamaterial for Lamb waves

    NASA Astrophysics Data System (ADS)

    Khanolkar, A.; Wallen, S.; Abi Ghanem, M.; Jenks, J.; Vogel, N.; Boechler, N.

    2015-08-01

    We report the design and characterization of a self-assembled, locally resonant acoustic metamaterial for Lamb waves, composed of a monolayer of 1.02 ?m polystyrene microspheres adhered to a 1.27 ?m thick free-standing silicon membrane. A laser-induced transient grating technique is used to generate Lamb waves in the metamaterial and to measure its acoustic response. The measurements reveal a microsphere contact resonance and the lowest frequency spheroidal microsphere resonance. The measured dispersion curves show hybridization of flexural Lamb waves with the microsphere contact resonance. We compare the measured dispersion with an analytical model using the contact resonance frequency as a single fitting parameter, and find that it well describes the observed hybridization. This study may lead to an improved understanding of microscale contact mechanics and to the design of new types of acoustic metamaterials.

  18. A Self-Assembled Metamaterial for Lamb Waves

    E-print Network

    Amey Khanolkar; Samuel Wallen; Maroun Abi Ghanem; Jennifer Jenks; Nicolas Vogel; Nicholas Boechler

    2015-05-22

    We report the design and characterization of a self-assembled, locally resonant acoustic metamaterial for Lamb waves, composed of a monolayer of $1.02$ $\\mu$m polystyrene microspheres adhered to a $1.3$ $\\mu$m thick free-standing silicon membrane. A laser-induced transient grating technique is used to generate Lamb waves in the metamaterial and measure its acoustic response. The measurements reveal a microsphere contact resonance and the lowest frequency spheroidal microsphere resonance. The measured dispersion curves show hybridization of flexural Lamb waves with the microsphere contact resonance. We compare the measured dispersion with an analytical model using the contact resonance frequency as a single fitting parameter, and find that it well describes the observed hybridization. Results from this study can lead to an improved understanding of microscale contact mechanics and to the design of new types of acoustic metamaterials.

  19. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

    Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H

    2015-12-01

    Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid. PMID:26565433

  20. Self-assembled hydrogels utilizing polymer-nanoparticle interactions

    NASA Astrophysics Data System (ADS)

    Appel, Eric A.; Tibbitt, Mark W.; Webber, Matthew J.; Mattix, Bradley A.; Veiseh, Omid; Langer, Robert

    2015-02-01

    Mouldable hydrogels that flow on applied stress and rapidly self-heal are increasingly utilized as they afford minimally invasive delivery and conformal application. Here we report a new paradigm for the fabrication of self-assembled hydrogels with shear-thinning and self-healing properties employing rationally engineered polymer-nanoparticle (NP) interactions. Biopolymer derivatives are linked together by selective adsorption to NPs. The transient and reversible interactions between biopolymers and NPs enable flow under applied shear stress, followed by rapid self-healing when the stress is relaxed. We develop a physical description of polymer-NP gel formation that is utilized to design biocompatible gels for drug delivery. Owing to the hierarchical structure of the gel, both hydrophilic and hydrophobic drugs can be entrapped and delivered with differential release profiles, both in vitro and in vivo. The work introduces a facile and generalizable class of mouldable hydrogels amenable to a range of biomedical and industrial applications.

  1. Nonlinear Analysis of the Self-assembly of Nanostructures

    NASA Astrophysics Data System (ADS)

    Hu, Shaowen; Nathan, Girish; Gunaratne, Gemunu; Kouri, Donald

    2006-03-01

    We investigate properties of a model of nanoscale pattern formation on a uniform substrate. The coefficients of the Ginzburg-Landau equations are concentration dependent. We find that, above the threshold, there are two branches of solutions corresponding to the up and down hexagonal structures; their appearance is related to the initial concentration of the system. The stability of such structures is confirmed by the analysis of the phase dynamics. When system is away from the threshold, the theory predicts a competition of stripe and hexagonal structures. The predicted stability domain of the stripe structures is consistent with numerical simulations. This provides a framework to understand the guided self-assembly technology, e.g., by the photolithography, at a coarse scale. The possible interaction of a large scale mode with the pattern mode is also discussed.

  2. Electrochemical metal speciation using self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Mandler, D.; Gal-Oz, R.; Burshtain, D.; Turyan, I.

    2003-05-01

    The application of self-assembled monolayers (SAMs) as a means of achieving speciation in heavy metal electrochemical determination is demonstrated. SAMs are monomolecular organic layers that can be chemically attached onto different electrode materials and used for the selective extraction of heavy metals. The selectivity is achieved by assembling monolayers that have pendant ligands, which interact selectively with the analytes in the solution. For example, the formation of a monolayer comprising a pyridine group was used to selectively extract Cr(VI) from aqueous solutions, whereas the selective determination of Fe(II) was accomplished using a covalently bound terpyridine monolayer. Yet, determining the heterogeneous binding constants of the metallic species by the SAMs is of significant importance and allows studying quantitatively the interactions between the monolayer and the metal ions. We have developed a few methods for determining the binding constants of heavy metal ions by SAMs of which two of them are briefly discussed here.

  3. Piezoelectric resonators based on self-assembled diphenylalanine microtubes

    NASA Astrophysics Data System (ADS)

    Bosne, E. D.; Heredia, A.; Kopyl, S.; Karpinsky, D. V.; Pinto, A. G.; Kholkin, A. L.

    2013-02-01

    Piezoelectric actuation has been widely used in microelectromechanical devices including resonance-based biosensors, mass detectors, resonators, etc. These were mainly produced by micromachining of Si and deposited inorganic piezoelectrics based on metal oxides or perovskite-type materials which have to be further functionalized in order to be used in biological applications. In this work, we demonstrate piezoelectrically driven micromechanical resonators based on individual self-assembled diphenylalanine microtubes with strong intrinsic piezoelectric effect. Tubes of different diameters and lengths were grown from the solution and assembled on a rigid support. The conducting tip of the commercial atomic force microscope was then used to both excite vibrations and study resonance behavior. Efficient piezoelectric actuation at the fundamental resonance frequency ?2.7 MHz was achieved with a quality factor of 114 for a microtube of 277 ?m long. A possibility of using piezoelectric dipeptides for biosensor applications is discussed.

  4. Adsorption of self-assembled monolayers of mercaptan on gold.

    PubMed

    De Weldige, K; Rohwerder, M; Vago, E; Viefhaus, H; Stratmann, M

    1995-10-01

    XPS and AES are suitable techniques for studying organic monolayers on metals if radiation doses are kept low. The adsorption of self-assembled (SA) mercaptan monolayers on gold is a process in two stages. The adsorption to near completeness is very rapid. However, the process of orientation of the carbon chains, which is responsible for the blocking of electrochemical reactions takes much longer, as could be shown by ARXPS (angle resolved X-ray photo electron spectroscopy). Adsorption under potential control allows electrochemical experiments during the adsorption process as e.g. the measurement of the capacity of the electric double layer. Furthermore the control of the potential guarantees sure that the metal/liquid interface is well defined during the adsorption process. PMID:15048492

  5. Lithographically-directed self-assembly of nanostructures

    SciTech Connect

    Liddle, J. Alexander; Cui, Yi; Alivisatos, Paul

    2004-09-21

    The combination of lithography and self-assembly provides apowerful means of organizing solution-synthesized nanostructures for awide variety of applications. We have developed a fluidic assembly methodthat relies on the local pinning of a moving liquid contact line bylithographically produced topographic features to concentratenanoparticles at those features. The final stages of the assembly processare controlled first by long-range immersion capillary forces and then bythe short-range electrostatic and Van der Waal's interactions. We havesuccessfully assembled nanoparticles from 50 nm to 2 nm in size usingthis technique and have also demonstrated the controlled positioning ofmore complex nanotetrapod structures. We have used this process toassemble Au nanoparticles into pre-patterned electrode structures andhave performed preliminary electrical characterization of the devices soformed. The fluidic assembly method is capable of very high yield, interms of positioning nanostructures at each lithographically-definedlocation, and of excellent specificity, with essentially no particledeposition between features.

  6. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    PubMed Central

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5?-bis (mercaptomethyl)-2,2?-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing. PMID:24994952

  7. Self-assembly of ABA triblock copolymers under soft confinement

    NASA Astrophysics Data System (ADS)

    Sheng, Yuping; An, Jian; Zhu, Yutian

    2015-05-01

    Using Monte Carlo method, the self-assembly of ABA triblock copolymers under soft confinement is investigated in this study. The soft confinement is achieved by a poor solvent environment for the polymer, which makes the polymer aggregate into a droplet. Various effects, including the block length ratio, the solvent quality for the blocks B, and the incompatibility between blocks A and B, on the micellar structures induced by soft confinement are examined. By increasing the solvent quality of B blocks, the micellar structure transforms from stacked lamella to bud-like structure, and then to onion-like structure for A5B8A5 triblock copolymers, while the inner micellar structure changes from spherical phase to various cylindrical phase, such as inner single helix, double helixes, stacked rings and cage-like structures, for A7B4A7 triblock copolymers. Moreover, the formation pathways of some typical aggregates are examined to illustrate their growth mechanisms.

  8. Self-assembly of anisotropic soft particles in two dimensions.

    PubMed

    Salgado-Blanco, Daniel; I Mendoza, Carlos

    2013-04-01

    The self-assembly of core-corona discs interacting via anisotropic potentials is investigated using Monte Carlo computer simulations. A minimal interaction potential that incorporates anisotropy in a simple way is introduced. It consists in a core-corona architecture in which the center of the core is shifted with respect to the center of the corona. Anisotropy can thus be tuned by progressively shifting the position of the core. Despite its simplicity, the system self-organizes in a rich variety of structures including stripes, triangular and rectangular lattices, cluster crystals, unusual plastic crystals, and geometrically frustrated phases. Our results indicate that the amount of anisotropy does not alter the lattice spacing and only influences the type of clustering (stripes, micelles, etc.) of the individual particles. PMID:23605567

  9. Three-Dimensional Structures Self-Assembled from DNA Bricks

    PubMed Central

    Ke, Yonggang; Ong, Luvena L.; Shih, William M.; Yin, Peng

    2013-01-01

    We describe a simple and robust method to construct complex three-dimensional (3D) structures using short synthetic DNA strands that we call “DNA bricks”. In one-step annealing reactions, bricks with hundreds of distinct sequences self-assemble into prescribed 3D shapes. Each 32-nucleotide brick is a modular component; it binds to four local neighbors and can be removed or added independently. Each 8-base-pair interaction between bricks defines a voxel with dimensions 2.5 nanometers by 2.5 nanometers by 2.7 nanometers, and a master brick collection defines a “molecular canvas” with dimensions of 10 by 10 by 10 voxels. By selecting subsets of bricks from this canvas, we constructed a panel of 102 distinct shapes exhibiting sophisticated surface features as well as intricate interior cavities and tunnels. PMID:23197527

  10. Alkyl Chain Dependent Alkanethiol Self-Assembled Adsorption Dynamics

    NASA Astrophysics Data System (ADS)

    Guo, Yan; Chen, Mingdong; He, Hui

    2015-10-01

    The adsorption dynamics for the formation of self-assembled monolayer of alkanethiols has been investigated by electrochemical method, water contact angle and scanning tunneling microscopy. Thiols with three alkyl chains, including short chain hexanethiol, middle chain dodecanethiol, and long chain octadecanethiol are examined. The experimental results indicate that the adsorption of thiols onto Au substrate consists of two process, a rapid adsorption and a slow reorganization. The rapid adsorption process is demonstrated to follow the diffusion-controlled Langmuir model. The apparent adsorption rate constant is obtained from the slopes, which is related to the concentration. According to our results, the difference of activation energy per methylene unit is 89 J/mol.

  11. Protein machines and self assembly in muscle organization

    NASA Technical Reports Server (NTRS)

    Barral, J. M.; Epstein, H. F.

    1999-01-01

    The remarkable order of striated muscle is the result of a complex series of protein interactions at different levels of organization. Within muscle, the thick filament and its major protein myosin are classical examples of functioning protein machines. Our understanding of the structure and assembly of thick filaments and their organization into the regular arrays of the A-band has recently been enhanced by the application of biochemical, genetic, and structural approaches. Detailed studies of the thick filament backbone have shown that the myosins are organized into a tubular structure. Additional protein machines and specific myosin rod sequences have been identified that play significant roles in thick filament structure, assembly, and organization. These include intrinsic filament components, cross-linking molecules of the M-band and constituents of the membrane-cytoskeleton system. Muscle organization is directed by the multistep actions of protein machines that take advantage of well-established self-assembly relationships. Copyright 1999 John Wiley & Sons, Inc.

  12. Self-assembly and emulsification of dopamine-modified hyaluronan.

    PubMed

    Zhu, Ye; Wang, Juanqin; Li, Xiaojie; Zhao, Donghua; Sun, Jianhua; Liu, Xiaoya

    2015-06-01

    Dopamine modified hyaluronan (HA-DOPA) with different grafting degree were synthesized and self-assembled into nanoparticles. The effects of pH and salinity changes on the structure of the HA-DOPA nanoparticles were investigated. Nanoparticles swelled under increased pH values, and disassociation started at pH values above 6.20. At a fixed pH of 6.20, the size of the nanoparticles decreased with increased salinity, and flocculation occurred when the salt concentration was higher than 0.3M. The emulsification performance of HA-DOPA nanoparticles at different pH values and salt concentrations demonstrated that nanoparticles with moderately swollen structures possess better emulsifying efficiency and emulsion stability. Additionally, HA-DOPA nanoparticles were able to stabilize various types of oils. These results suggest that HA-DOPA nanoparticles have promising potential as Pickering emulsifiers for applications in the cosmetics, medical, and food industries. PMID:25843836

  13. A self-assembly pathway to aligned monodomain gels

    SciTech Connect

    Zhang, Shuming; Greenfield, Megan A.; Mata, Alvaro; Palmer, Liam C.; Bitton, Ronit; Mantei, Jason R.; Aparicio, Conrado; Olvera de la Cruz, Monica; Stupp, Samuel I.

    2010-09-27

    Aggregates of charged amphiphilic molecules have been found to access a structure at elevated temperature that templates alignment of supramolecular fibrils over macroscopic scales. The thermal pathway leads to a lamellar plaque structure with fibrous texture that breaks on cooling into large arrays of aligned nanoscale fibres and forms a strongly birefringent liquid. By manually dragging this liquid crystal from a pipette onto salty media, it is possible to extend this alignment over centimetres in noodle-shaped viscoelastic strings. Using this approach, the solution of supramolecular filaments can be mixed with cells at physiological temperatures to form monodomain gels of aligned cells and filaments. The nature of the self-assembly process and its biocompatibility would allow formation of cellular wires in situ that have any length and customized peptide compositions for use in biological applications.

  14. Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

    NASA Astrophysics Data System (ADS)

    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.

    2014-11-01

    Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.

  15. Entropic control of particle sizes during viral self-assembly

    NASA Astrophysics Data System (ADS)

    Castelnovo, M.; Muriaux, D.; Faivre-Moskalenko, C.

    2013-03-01

    Morphologic diversity is observed across all families of viruses. However, these supra-molecular assemblies are produced most of the time in a spontaneous way through complex molecular self-assembly scenarios. The modeling of these phenomena remains a challenging problem within the emerging field of physical virology. We present in this work a theoretical analysis aiming at highlighting the particular role of configuration entropy in the control of viral particle size distribution. Specializing this model to retroviruses such as HIV-1, we predict a new mechanism of entropic control of both RNA uptake into the viral particle and of the particle's size distribution. Evidence of this peculiar behavior has recently been reported experimentally.

  16. Supramolecular amplification of amyloid self-assembly by iodination.

    PubMed

    Bertolani, Arianna; Pirrie, Lisa; Stefan, Loic; Houbenov, Nikolay; Haataja, Johannes S; Catalano, Luca; Terraneo, Giancarlo; Giancane, Gabriele; Valli, Ludovico; Milani, Roberto; Ikkala, Olli; Resnati, Giuseppe; Metrangolo, Pierangelo

    2015-01-01

    Amyloid supramolecular assemblies have found widespread exploitation as ordered nanomaterials in a range of applications from materials science to biotechnology. New strategies are, however, required for understanding and promoting mature fibril formation from simple monomer motifs through easy and scalable processes. Noncovalent interactions are key to forming and holding the amyloid structure together. On the other hand, the halogen bond has never been used purposefully to achieve control over amyloid self-assembly. Here we show that single atom replacement of hydrogen with iodine, a halogen-bond donor, in the human calcitonin-derived amyloidogenic fragment DFNKF results in a super-gelator peptide, which forms a strong and shape-persistent hydrogel at 30-fold lower concentration than the wild-type pentapeptide. This is remarkable for such a modest perturbation in structure. Iodination of aromatic amino acids may thus develop as a general strategy for the design of new hydrogels from unprotected peptides and without using organic solvents. PMID:26123690

  17. Aqueous Gemini Surfactant Self-Assembly into Complex Lyotropic Phases

    NASA Astrophysics Data System (ADS)

    Mahanthappa, Mahesh; Sorenson, Gregory

    2012-02-01

    In spite of the potentially wide-ranging applications of aqueous bicontinuous lyotropic liquid crystals (LLCs), the discovery of amphiphiles that reliably form these non-constant mean curvature morphologies over large phase windows remains largely serendipitous. Recent work has established that cationic gemini surfactants exhibit a pronounced tendency to form bicontinuous cubic (e.g. gyroid) phases as compared to their parent single-tail amphiphiles. The universality of this phenomenon in other surfactant systems remains untested. In this paper, we will report the aqueous LLC phase behavior of a new class of anionic gemini surfactants derived from long chain carboxylic acids. Our studies show that these new surfactants favor the formation of non-constant mean curvature gyroid and primitive (``Plumber's Nightmare'') structures over amphiphile concentration windows up to 20 wt% wide. Based on these observations, we will discuss insights gained into the delicate force balance governing the self-assembly of these surfactants into aqueous bicontinuous LLCs.

  18. A Self-Assembly Pathway to Aligned Monodomain Gels

    PubMed Central

    Zhang, Shuming; Greenfield, Megan A.; Mata, Alvaro; Palmer, Liam C.; Bitton, Ronit; Mantei, Jason R.; Aparicio, Conrado; de la Cruz, Monica Olvera; Stupp, Samuel I.

    2011-01-01

    Aggregates of charged amphiphilic molecules have been found to access a structure at elevated temperature that templates alignment of supramolecular fibrils over macroscopic scales. The thermal pathway leads to a lamellar plaque structure with fibrous texture that breaks upon cooling into large arrays of aligned nanoscale fibres and forms a strongly birefringent liquid. By manually dragging this liquid crystal from a pipette onto salty media, it is possible to extend this alignment over centimetres in noodle-shaped viscoelastic strings. Using this approach, the solution of supramolecular filaments can be mixed with cells at physiological temperatures to form monodomain gels of aligned cells and filaments. The nature of the self-assembly process and its biocompatibility would allow formation of cellular wires in situ that have any length and customized peptide compositions for use in biological applications. PMID:20543836

  19. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers.

    PubMed

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping

    2015-01-01

    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10(-15) cm(2) s(-1), 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value. PMID:26227342

  20. Self-assembled cellular microarrays patterned using DNA barcodes.

    PubMed

    Douglas, Erik S; Chandra, Ravi A; Bertozzi, Carolyn R; Mathies, Richard A; Francis, Matthew B

    2007-11-01

    The successful integration of living cells into synthetic devices requires precise control over cell patterning. Here we describe a versatile platform that can accomplish this goal through DNA hybridization. Living cells functionalized with exogenous cell-surface DNA strands bind to cognate sequences of DNA printed on glass slides. Attachment via these "cell-adhesion barcodes" is rapid and specific, with close-packed arrays of cells forming within minutes. The biophysical properties of the system are characterized, and the technique is used to form complex cellular patterns with single-cell line widths and self-assembled cellular microarrays. Key advantages of DNA-directed cell binding include the ability to immobilize both adherent and non-adherent cells, to capture cells selectively from a mixed population, to tune the binding properties of the cells, and to reuse substrates prepared with widely available DNA printing technologies. PMID:17960269