phase separating self-assembled: Topics by Science.gov

Sample records for phase separating self-assembled

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

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

2009-04-01

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

NASA Astrophysics Data System (ADS)

Reinhardt, Aleks; Williamson, Alexander J.; Doye, Jonathan P. K.; Carrete, Jesús; Varela, Luis M.; Louis, Ard A.

2011-03-01

In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.
Programming molecular self-assembly of intrinsically disordered proteins containing sequences of low complexity

NASA Astrophysics Data System (ADS)

Simon, Joseph R.; Carroll, Nick J.; Rubinstein, Michael; Chilkoti, Ashutosh; López, Gabriel P.

2017-06-01

Dynamic protein-rich intracellular structures that contain phase-separated intrinsically disordered proteins (IDPs) composed of sequences of low complexity (SLC) have been shown to serve a variety of important cellular functions, which include signalling, compartmentalization and stabilization. However, our understanding of these structures and our ability to synthesize models of them have been limited. We present design rules for IDPs possessing SLCs that phase separate into diverse assemblies within droplet microenvironments. Using theoretical analyses, we interpret the phase behaviour of archetypal IDP sequences and demonstrate the rational design of a vast library of multicomponent protein-rich structures that ranges from uniform nano-, meso- and microscale puncta (distinct protein droplets) to multilayered orthogonally phase-separated granular structures. The ability to predict and program IDP-rich assemblies in this fashion offers new insights into (1) genetic-to-molecular-to-macroscale relationships that encode hierarchical IDP assemblies, (2) design rules of such assemblies in cell biology and (3) molecular-level engineering of self-assembled recombinant IDP-rich materials.
End Groups of Functionalized Siloxane Oligomers Direct Block-Copolymeric or Liquid-Crystalline Self-Assembly Behavior

PubMed Central

2016-01-01

Monodisperse oligodimethylsiloxanes end-functionalized with the hydrogen-bonding ureidopyrimidinone (UPy) motif undergo phase separation between their aromatic end groups and dimethylsiloxane midblocks to form ordered nanostructures with domain spacings of <5 nm. The self-assembly behavior of these well-defined oligomers resembles that of high degree of polymerization (N)–high block interaction parameter (χ) linear diblock copolymers despite their small size. Specifically, the phase morphology varies from lamellar to hexagonal to body-centered cubic with increasing asymmetry in molecular volume fraction. Mixing molecules with different molecular weights to give dispersity >1.13 results in disorder, showing importance of molecular monodispersity for ultrasmall ordered phase separation. In contrast, oligodimethylsiloxanes end-functionalized with an O-benzylated UPy derivative self-assemble into lamellar nanostructures regardless of volume fraction because of the strong preference of the end groups to aggregate in a planar geometry. Thus, these molecules display more classically liquid-crystalline self-assembly behavior where the lamellar bilayer thickness is determined by the siloxane midblock. Here the lamellar nanostructure is tolerant to molecular polydispersity. We show the importance of end groups in high χ–low N block molecules, where block-copolymer-like self-assembly in our UPy-functionalized oligodimethylsiloxanes relies upon the dominance of phase separation effects over directional end group aggregation. PMID:27054381
A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces

NASA Astrophysics Data System (ADS)

Ong, Quy; Nianias, Nikolaos; Stellacci, Francesco

2017-09-01

Binary self-assembled monolayers (SAMs) on gold surfaces have been known to undergo molecular phase separation to various degrees and have been subject to both experimental and theoretical studies. On gold nanoparticles in particular, binary SAMs ligand shells display intriguing morphologies. Consequently, unexpected behaviors of the nanoparticles with respect to their biological, chemical, and interfacial properties have been observed. It is critical that the phase separation of binary SAMs be understood at both molecular and macroscopic level to create, and then manipulate, the useful properties of the functionalized surfaces. We look into the current understanding of molecular phase separation of binary SAMs on gold surfaces, represented by Au(111) flat surfaces and Au nanoparticles, from both theoretical and experimental aspects. We point out shortcomings and describe several research strategies that will address them in the future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Pule Pileni.
Conserved interdomain linker promotes phase separation of the multivalent adaptor protein Nck

PubMed Central

Banjade, Sudeep; Wu, Qiong; Mittal, Anuradha; Peeples, William B.; Pappu, Rohit V.; Rosen, Michael K.

2015-01-01

The organization of membranes, the cytosol, and the nucleus of eukaryotic cells can be controlled through phase separation of lipids, proteins, and nucleic acids. Collective interactions of multivalent molecules mediated by modular binding domains can induce gelation and phase separation in several cytosolic and membrane-associated systems. The adaptor protein Nck has three SRC-homology 3 (SH3) domains that bind multiple proline-rich segments in the actin regulatory protein neuronal Wiskott-Aldrich syndrome protein (N-WASP) and an SH2 domain that binds to multiple phosphotyrosine sites in the adhesion protein nephrin, leading to phase separation. Here, we show that the 50-residue linker between the first two SH3 domains of Nck enhances phase separation of Nck/N-WASP/nephrin assemblies. Two linear motifs within this element, as well as its overall positively charged character, are important for this effect. The linker increases the driving force for self-assembly of Nck, likely through weak interactions with the second SH3 domain, and this effect appears to promote phase separation. The linker sequence is highly conserved, suggesting that the sequence determinants of the driving forces for phase separation may be generally important to Nck functions. Our studies demonstrate that linker regions between modular domains can contribute to the driving forces for self-assembly and phase separation of multivalent proteins. PMID:26553976
Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains

NASA Astrophysics Data System (ADS)

Mubeena, Shaikh; Chatterji, Apratim

2015-03-01

We report many different nanostructures which are formed when model nanoparticles of different sizes (diameter σn) are allowed to aggregate in a background matrix of semiflexible self-assembled polymeric wormlike micellar chains. The different nanostructures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nanoparticles. The different morphologies obtained are the result of an interplay of the available free volume, the elastic energy of deformation of polymers, the density (chemical potential) of the nanoparticles in the polymer matrix, and, of course, the ratio of the size of self-assembling nanoparticles and self-avoidance diameter of polymeric chains. We have used a hybrid semi-grand-canonical Monte Carlo simulation scheme to obtain the (nonequilibrium) phase diagram of the self-assembled nanostructures. We observe rodlike structures of nanoparticles which get self-assembled in the gaps between the nematically ordered chains, as well as percolating gel-like network of conjoined nanotubes. We also find a totally unexpected interlocked crystalline phase of nanoparticles and monomers, in which each crystal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the condition which leads to such interlocked crystal structure. We suggest experimental possibilities of how the results presented in this paper could be used to obtain different nanostructures in the laboratory.
Self-assembly of amorphous biophotonic nanostructures by phase separation

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

Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar

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 rolesmore » 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.« less
Grooved nanowires from self-assembling hairpin molecules for solar cells.

PubMed

Tevis, Ian D; Tsai, Wei-Wen; Palmer, Liam C; Aytun, Taner; Stupp, Samuel I

2012-03-27

One of the challenges facing bulk heterojunction organic solar cells is obtaining organized films during the phase separation of intimately mixed donor and acceptor components. We report here on the use of hairpin-shaped sexithiophene molecules to generate by self-assembly grooved nanowires as the donor component in bulk heterojunction solar cells. Photovoltaic devices were fabricated via spin-casting to produce by solvent evaporation a percolating network of self-assembled nanowires and fullerene acceptors. Thermal annealing was found to increase power conversion efficiencies by promoting domain growth while still maintaining this percolating network of nanostructures. The benefits of self-assembly and grooved nanowires were examined by building devices from a soluble sexithiophene derivative that does not form one-dimensional structures. In these systems, excessive phase separation caused by thermal annealing leads to the formation of defects and lower device efficiencies. We propose that the unique hairpin shape of the self-assembling molecules allows the nanowires as they form to interact well with the fullerenes in receptor-ligand type configurations at the heterojunction of the two domains, thus enhancing device efficiencies by 23%. © 2012 American Chemical Society
Theoretical study of the self-assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers

NASA Astrophysics Data System (ADS)

Gadelrab, Karim; Alexander-Katz, Alfredo; LaboratoryTheoretical Soft Materials Team

The self-assembly of block copolymers BCP has provided an impressive control over the nanoscale structure of soft matter. While the main focus of the research in the field has been directed towards simple linear diblocks, the development of advanced polymer architecture provided improved performance and access to new structures. In particular, bottlebrush BCPs (BBCPs) have interesting characteristics due to their dense functionality, high molecular weight, low levels of entanglement, and tendency to efficiently undergo rapid bulk phase separation. In this work, we are interested in theoretically studying the self-assembly of Janus-type ``A-branch-B'' BBCPs where A and B blocks can phase separate with the bottlebrush polymer backbone serving as the interface between the two blocks. Hence, the polymer backbone adds an extra constraint on the equilibrium spacing between neighboring linear diblock chains. In this regard, the segment length of the backbone separating the AB junctions has a direct effect of the observed domain spacing and effective segregation strength of the AB blocks. We employ self-consistent field theoretic SCFT simulations to capture the effect of volume fraction of different constituents and construct a phase diagram of the accessible morphologies of these BBCPs.
Block copolymer self-assembly derived ultrafiltration membranes: From science to start-up

NASA Astrophysics Data System (ADS)

Wiesner, Ulrich

In the last ten years a novel method to generate asymmetric ultrafiltration membranes has been established. It is based on the combination of block copolymer self-assembly with non-solvent induced phase separation (NIPS) and is now referred to as SNIPS. NIPS as an industry proven method for the formation of phase inversion membranes opening a pathway to scale up and commercialization of these membranes. The combination of NIPS with block copolymer self-assembly leads to asymmetric membranes with narrow pore size distributions in the top surface layer (so called isoporous membranes) as well as high pore densities, thereby potentially combining high resolution with high flux in membrane separation processes. Such membranes have potential applications in the biopharmaceutical industry where a large fraction of the costs are currently associated with time-consuming non-membrane based separation processes. This talk will describe a family of isoporous ultrafiltration membranes based on the self-assembly behavior of an ABC triblock terpolymer which has led to the formation of a start-up company out of Cornell University. After introduction of the SNIPS process in general, and its application to such ABC triblock terpolymers in particular, open scientific questions associated with the formation mechanisms of the top surface separation layer in such membranes is discussed, which is at the heart of enabling high performance separation behavior. Furthermore, challenges translating scientific work into industrial settings are highlighted.
Gel phase formation in dilute triblock copolyelectrolyte complexes

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

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less
Gel phase formation in dilute triblock copolyelectrolyte complexes

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

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less
Gel phase formation in dilute triblock copolyelectrolyte complexes

DOE PAGES

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; ...

2017-02-23

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less
Gel Phase Formation in Dilute Triblock Copolyelectrolyte Complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Prabhu, Vivek; de Pablo, Juan; Tirrell, Matthew

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at extremely low polymer concentrations (<1 % by mass) has been observed in scattering experiments and molecular dynamics simulations. In contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing polymer concentrations, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assemblies of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously upon solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of triblock copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries not only contribute to our fundamental understanding of the structure and pathways of complexation driven assemblies, but also raise intriguing prospects for formation of gel structures at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.
Gel phase formation in dilute triblock copolyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

2017-02-01

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.
Molecular Effects on Coacervate-Driven Block Copolymer Self Assembly

NASA Astrophysics Data System (ADS)

Lytle, Tyer; Radhakrishna, Mithun; Sing, Charles

Two oppositely charged polymers can undergo associative phase separation in a salt solution in a process known as \\x98complex coacervation. Recent work has used this as a motif to control the self-assembly behavior of a mixture of oppositely-charged block copolymers which form nanoscale structures. The materials formed from these complex coacervate-block copolymers (BCPs) have potential use as drug delivery systems, gels, and sensors. We have developed a hybrid Monte Carlo-Single Chain in a Mean Field (MC-SCMF) simulation method that is able to determine morphological phase diagrams for BCPs. This technique is an efficient way to calculate morphological phase diagrams and provides a clear link between molecular level features and self-assembly behaviors. Morphological phase diagrams showing the effects of polymer concentration, salt concentration, chain length, and charge-block fraction at large charge densities on self-assembly behavior have been determined. An unexpected phase transition from disorder to hexagonal packing at large salt concentrations has been observed for charge-block fractions equal to and larger than 0.5. This is attributed to the salt filling space stabilizing the morphology of the BCP.
Temperature-Induced Phase Separation in Molecular Assembly of Nanotubes Comprising Amphiphilic Polypeptide with Poly( N-Ethyl Glycine) in Water by a Hydrophilic-Region Driven Type Mechanism.

PubMed

Hattori, Tetsuya; Itagaki, Toru; Uji, Hirotaka; Kimura, Shunsaku

2018-06-20

Two kinds of amphiphilic polypeptides having different types of hydrophilic polypeptoids, poly(sarcosine)-b-(L-Leu-Aib)6 (ML12) and poly(N-ethyl glycine)-b-(L-Leu-Aib)6 (EL12), were self-assembled via two paths to phase-separated nanotubes. One path was via sticking ML12 nanotubes with EL12 nanotubes, and the other was a preparation from a mixture of ML12 and EL12 in solution. In either case, nanotubes showed temperature-induced phase separation along the long axis, which was observed by two methods of labeling one phase with gold nanoparticles and fluorescence resonance energy transfer between the components. The phase-separation was ascribed to aggregation of poly(N-ethyl glycine) blocks over the cloud point temperature. The addition of 5% trifluoroethanol was needed for the phase separation, because the tight association of the helices in the hydrophobic region should be loosened to allow lateral diffusion of the components to be separated. The phase-separation in molecular assemblies in water based on the hydrophilic-region driven type mechanism therefore requires sophisticated balances of association forces exerting among the hydrophilic and hydrophobic regions of the amphiphilic polypeptoids.
Crystallization and Microphase Separation in Chiral Block Copolymers

NASA Astrophysics Data System (ADS)

Ho, Rong-Ming

2012-02-01

Block copolymers composed of chiral entities, denoted as chiral block copolymers (BCP*s), were designed to fabricate helical architectures from self-assembly. A helical phase (denoted H*) was discovered in the self-assembly of poly(styrene)-b-poly(L-lactide) (PS-PLLA) BCPs*. To examine the phase behavior of the PS-PLLA, self-assembled superstructures resulting from the competition between crystallization and microphase separation of the PS-PLLA in solution were examined. A kinetically controlled process by changing non-solvent addition rate was utilized to control the BCP* self-assembly. Single-crystal lozenge lamellae were obtained by the slow self-assembly (i.e., slow non-solvent addition rate) of PS-PLLA whereas amorphous helical ribbon superstructures were obtained from the fast self-assembly (i.e., fast non-solvent addition rate). As a result, the formation of helical architectures from the self-assembly of the PS-PLLA reflects the impact of chirality on microphase separation, but the chiral effect might be overwhelmed by crystallization. Consequently, various crystalline PS-PLLA nanostructures in bulk were obtained by controlling the crystallization temperature of PLLA (Tc,PLLA) at which crystalline helices and crystalline cylinders occur while Tc,PLLA=x Tg,PS, respectively. Anisotropic arrangement of the PLLA crystallites grown within the microdomains was identified. The formation of this exclusive crystalline growth is attributed to the spatial confinement effect for crystallization. While Tc,PLLA=x Tg,PS, the preferential growth may modulate the curvature of microdomains by shifting the molecular chains to access the fast path for crystalline growth due to the increase in chain mobility. As a result, a spring-like behavior of the helical nanostructure can be driven by crystallization so as to dictate the transformation of helices and to result in crystalline cylinders.
Chemically programmed self-sorting of gelator networks.

PubMed

Morris, Kyle L; Chen, Lin; Raeburn, Jaclyn; Sellick, Owen R; Cotanda, Pepa; Paul, Alison; Griffiths, Peter C; King, Stephen M; O'Reilly, Rachel K; Serpell, Louise C; Adams, Dave J

2013-01-01

Controlling the order and spatial distribution of self-assembly in multicomponent supramolecular systems could underpin exciting new functional materials, but it is extremely challenging. When a solution of different components self-assembles, the molecules can either coassemble, or self-sort, where a preference for like-like intermolecular interactions results in coexisting, homomolecular assemblies. A challenge is to produce generic and controlled 'one-pot' fabrication methods to form separate ordered assemblies from 'cocktails' of two or more self-assembling species, which might have relatively similar molecular structures and chemistry. Self-sorting in supramolecular gel phases is hence rare. Here we report the first example of the pH-controlled self-sorting of gelators to form self-assembled networks in water. Uniquely, the order of assembly can be predefined. The assembly of each component is preprogrammed by the pK(a) of the gelator. This pH-programming method will enable higher level, complex structures to be formed that cannot be accessed by simple thermal gelation.

Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers.

PubMed

Huang, Shuai; Pang, Linlin; Chen, Yuxuan; Zhou, Liming; Fang, Shaoming; Yu, Haifeng

2018-03-01

Microphase-separated structures of block copolymers (BCs) with a size of sub-10 nm are usually obtained by hydrogen-bond-induced self-assembly of BCs through doping with small molecules as functional additives. Here, fabrication of hierarchically self-assembled sub-10 nm structures upon microphase separation of amphiphilic liquid-crystalline BCs (LCBCs) at the existence of hydrogen bonds but without any dopants is reported. The newly introduced urethane groups in the side chain of the hydrophobic block of LCBCs interact with the ether groups of the hydrophilic poly(ethylene oxide) (PEO) block, leading to imperfect crystallization of the PEO blocks. Both crystalline and amorphous domains coexist in the separated PEO phase, enabling a lamellar structure to appear inside the PEO nanocylinders. This provides an elegant method to fabricate controllable sub-10 nm microstructures in well-defined polymer systems without the introduction of any dopants. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ultrahigh PEMFC performance of a thin-film, dual-electrode assembly with tailored electrode morphology.

PubMed

Jung, Chi-Young; Kim, Tae-Hyun; Yi, Sung-Chul

2014-02-01

A dual-electrode membrane electrode assembly (MEA) for proton exchange membrane fuel cells with enhanced polarization under zero relative humidity (RH) is fabricated by introducing a phase-separated morphology in an agglomerated catalyst layer of Pt/C (platinum on carbon black) and Nafion. In the catalyst layer, a sufficient level of phase separation is achieved by dispersing the Pt catalyst and the Nafion dispersion in a mixed-solvent system (propane-1,2,3-triol/1-methyl-2-pyrrolidinone).The high polymer chain mobility results in improved water uptake and regular pore-size distribution with small pore diameters. The electrochemical performance of the dual-film electrode assembly with different levels of phase separation is compared to conventional electrode assemblies. As a result, good performance at 0 % RH is obtained because self-humidification is dramatically improved by attaching this dense and phase-separated catalytic overlayer onto the conventional catalyst layer. A MEA prepared using the thin-film, dual-layered electrode exhibits 39-fold increased RH stability and 28-fold improved start-up recovery time during the on-off operation relative to the conventional device. We demonstrate the successful operation of the dual-layered electrode comprised of discriminatively phase-separated agglomerates with an ultrahigh zero RH fuel-cell performance reaching over 95 % performance of a fully humidified MEA. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Supramolecular guests in solvent driven block copolymer assembly: From internally structured nanoparticles to micelles

PubMed Central

Klinger, Daniel; Robb, Maxwell J.; Spruell, Jason M.; Lynd, Nathaniel A.; Hawker, Craig J.

2014-01-01

Supramolecular interactions between different hydrogen-bonding guests and poly(2-vinyl pyridine)-block-poly (styrene) can be exploited to prepare remarkably diverse self-assembled nanostructures in dispersion from a single block copolymer (BCP). The characteristics of the BCP can be efficiently controlled by tailoring the properties of a guest which preferentially binds to the P2VP block. For example, the incorporation of a hydrophobic guest creates a hydrophobic BCP complex that forms phase separated nanoparticles upon self-assembly. Conversely, the incorporation of a hydrophilic guest results in an amphiphilic BCP complex that forms spherical micelles in water. The ability to tune the self-assembly behavior and access dramatically different nanostructures from a single BCP substrate demonstrates the exceptional versatility of the self-assembly of BCPs driven by supramolecular interactions. This approach represents a new methodology that will enable the further design of complex, responsive self-assembled nanostructures. PMID:25525473
Characterization of charged polymer self-assemblies by multidetector thermal field-flow fractionation in aqueous mobile phases.

PubMed

Greyling, Guilaume; Pasch, Harald

2018-01-12

Charged block copolymer self-assemblies, such as charged micelles, have attracted much attention as versatile drug delivery systems due to their readily tunable characteristics such as size and surface charge. However, current column-based analytical techniques are not suitable to fractionate and comprehensively characterize charged micelles in terms of size, molar mass, chemical composition and morphology. Multidetector thermal field-flow fractionation (ThFFF) is shown to be a unique characterization platform that can be used to characterize charged micelles in terms of size, molar mass, chemical composition and morphology in aqueous mobile phases with various ionic strengths and pH. This is demonstrated by the characterization of poly(methacrylic acid)-b-poly(methyl methacrylate) self-assemblies in high pH buffers as well as the characterization of cationic poly(2-vinyl pyridine)-b-polystyrene and poly(4-vinyl pyridine)-b-polystyrene self-assemblies in low pH buffers. Moreover, it is shown that ThFFF is capable of separating charged micelles according to the corona composition. These investigations prove convincingly that ThFFF is broadly applicable to the comprehensive characterization of amphiphilic self-assemblies even when aqueous mobile phases are used. Copyright © 2017 Elsevier B.V. All rights reserved.
Novel agrochemical conjugates with self-assembling behaviour.

PubMed

Liu, Qingtao; Graham, Bim; Hawley, Adrian; Dong, Yao-Da; Boyd, Ben J

2018-02-15

That conjugation of agrichemicals to pro-assembly hydrophobic moieties will enable enhanced compatibility and loading with host lyotropic liquid crystalline carrier matrix, and potentially self-assemble in their own right in aqueous environments. A series of lipid-like agrochemical-conjugates were synthesized using specific amphiphilic entities conjugated onto the agrochemicals, picloram and 2,4-dichlorophenoxyacetic acid (2,4-D). The self-assembly behaviour and compatibility of the novel entities when incorporated into phytantriol and monoolein-based liquid crystalline systems were examined using small angle X-ray scattering, cryo-TEM and polarized optical microscopy. Compared to agrochemical-conjugates with simple alkyl ester groups, the esterification of the agrochemicals with amphiphilic groups such as phytantriol and monoolein led to greater structural compatibility and consequently a greater loading of the agrochemicals in the liquid crystalline systems without destabilizing phase structure. Picloram-monoolein and picloram-monoelaidin can self-assemble to form lamellar structures in water. However, certain agrochemical-conjugates such as picloram-monoelaidin and picloram-PEGn-oleate showed poor compatibility with liquid crystalline systems, resulting in phase separation. Copyright © 2017 Elsevier Inc. All rights reserved.
Nonionic amphiphile nanoarchitectonics: self-assembly into micelles and lyotropic liquid crystals

NASA Astrophysics Data System (ADS)

Shrestha, Lok Kumar; Strzelczyk, Karolina Maria; Goswami Shrestha, Rekha; Ichikawa, Kotoko; Aramaki, Kenji; Hill, Jonathan P.; Ariga, Katsuhiko

2015-05-01

Amphiphiles, molecules that possess both hydrophilic and hydrophobic moieties, are architecturally simple molecules that can spontaneously self-assemble into complex hierarchical structures from lower to higher dimensions either in the bulk phase or at an interface. Recent developments in multifunctional nanostructure design using the advanced concept of nanoarchitectonics utilize this simple process of assembly. Amphiphilic self-assemblies involving lipids or proteins mimic the structure of biological systems, thus highlighting the necessity of a fundamental physical understanding of amphiphilic self-assembly towards a realization of the complex mechanisms operating in nature. Herein, we describe self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system. Temperature-composition analyses of equilibrium phases identified by using small-angle x-ray scattering (SAXS) provide strong evidence of various spontaneously self-assembled mesostructures, such as normal micelles (Wm), hexagonal liquid crystal (H1), and reverse micelles (Om). In contrast to conventional poly(oxyethylene) nonionic surfactants, C12G4 did not exhibit the clouding phenomenon at higher temperatures (phase separation was not observed up to 100 °C), demonstrating the greater thermal stability of the self-assembled mesophases. Generalized indirect Fourier transformation (GIFT) evaluation of the SAXS data confirmed the formation of core-shell-type spherical micelles with a maximum dimension ca. 8.7 nm. The shape and size of the C12G4 micelles remained apparently unchanged over a wide range of concentrations (up to 20%), but intermicellar interactions increased and could be described by the Percus-Yevick (PY) theory (after Carnahan and Starling), which provides a very accurate analytical expression for the osmotic pressure of a monodisperse hard sphere.
Sericin Promotes Fibroin Silk I Stabilization Across a Phase-Separation.

PubMed

Kwak, Hyo Won; Ju, Ji Eun; Shin, Munju; Holland, Chris; Lee, Ki Hoon

2017-08-14

Natural silk spinning offers several advantages over the synthetic fiber spinning, although the underlying mechanisms of this process are yet to be fully elucidated. Silkworm silks, specifically B. mori, comprise two main proteins: fibroin, which forms the fiber, and sericin, a coextruded coating that acts as a matrix in the resulting nonwoven composite cocoon. To date, most studies have focused on fibroin's self-assembly and gelation, with the influence of sericin during spinning receiving little to no attention. This study investigates sericin's effects on the self-assembly of fibroin via their natural phase-separation. Through changes in sample opacity, FTIR, and XRD, we report that increasing sericin concentration retards the time to gelation and β-sheet formation of fibroin, causing it to adopt a Silk I conformation. Such findings have important implications for both the natural silk spinning process and any future industrial applications, suggesting that sericin may be able to induce long-range conformational and stability control in silk fibroin, while being in a separate phase, a factor that would facilitate long-term storage or silk feedstocks.
Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers.

PubMed

Siddique, Radwanul H; Donie, Yidenekachew J; Gomard, Guillaume; Yalamanchili, Sisir; Merdzhanova, Tsvetelina; Lemmer, Uli; Hölscher, Hendrik

2017-10-01

The wings of the black butterfly, Pachliopta aristolochiae , are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells.
Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers

PubMed Central

Siddique, Radwanul H.; Donie, Yidenekachew J.; Gomard, Guillaume; Yalamanchili, Sisir; Merdzhanova, Tsvetelina; Lemmer, Uli; Hölscher, Hendrik

2017-01-01

The wings of the black butterfly, Pachliopta aristolochiae, are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells. PMID:29057320
A Facile Synthesis of Dynamic, Shape-Changing Polymer Particles

DTIC Science & Technology

2014-04-02

utilizing functional surfactants to control the phase separation of symmetric polystyrene- b -poly(2-vinylpyr- idine) ( PS - b - P2VP ) in dispersed droplets...Figure 1. Schematic representation of a mixed surfactant strategy for controlling the self-assembly of PS - b - P2VP and the generation of particles with...surfactant mixtures to control the phase separation of the symmetric polystyrene- b -poly(2-vinylpyridine) ( PS - b - P2VP ) block copolymers (BCPs) within
Thermoelectric Properties of Self Assembled TiO2/SnO2 Nanocomposites

NASA Technical Reports Server (NTRS)

Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

2008-01-01

Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 W/mK2 at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.
Thermoelectric Properties of Self Assemble TiO2/SnO2 Nanocomposites

NASA Technical Reports Server (NTRS)

Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

2008-01-01

Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 (mu)W/m sq K at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.
Guiding nanocrystal organization within mesoscale lipid thin-film templates

NASA Astrophysics Data System (ADS)

Steer, Dylan; Zhai, You; Oh, Nuri; Shim, Moonsub; Leal, Cecilia

Recently a great deal of interest has been established in the cooperative intermolecular interactions in hard and soft meso-structured composite materials. Much of this research has focused on the effects of nanoparticle incorporation into block copolymers that otherwise self-assemble into periodic mesostructures through microphase separation. Through careful selection of the polymer components the nanoparticles can be directed to also microphase separate and therefore exhibit symmetry induced by the block copolymers. Such systems are promising for enabling the organization of nanoparticle superstructures. Although this is useful in many applications such as in bottom-up assembly of opti-electronic materials, most of these applications would benefit from interplay between structure and dynamics. Much like block-copolymers, lipids can self-assembly into a variety of structures with 1D lamellar, 2D Hexagonal, and 3D cubic symmetry. However, unlike block-copolymers phase stabilization and conversion from one geometry to another happens under a minute. We will show our recent efforts into using lipid thin films to guide the assembly of nanoparticle superstructures resembling those displayed by lipid polymorphs and how they distort lipid equilibrium phase behavior. Funding from the Office of Naval Research.
Nanopatterns by phase separation of patterned mixed polymer monolayers

DOEpatents

Huber, Dale L; Frischknecht, Amalie

2014-02-18

Micron-size and sub-micron-size patterns on a substrate can direct the self-assembly of surface-bonded mixed polymer brushes to create nanoscale patterns in the phase-separated mixed polymer brush. The larger scale features, or patterns, can be defined by a variety of lithographic techniques, as well as other physical and chemical processes including but not limited to etching, grinding, and polishing. The polymer brushes preferably comprise vinyl polymers, such as polystyrene and poly(methyl methacrylate).
Crystalline modification of a rare earth nucleating agent for isotactic polypropylene based on its self-assembly.

PubMed

Zhang, Yuanming; Sun, Tingting; Jiang, Wei; Han, Guangting

2018-05-01

In this paper, the crystalline modification of a rare earth nucleating agent (WBG) for isotactic polypropylene (PP) based on its supramolecular self-assembly was investigated by differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscopy. In addition, the relationship between the self-assembly structure of the nucleating agent and the crystalline structure, as well as the possible reason for the self-assembly behaviour, was further studied. The structure evolution of WBG showed that the self-assembly structure changed from a needle-like structure to a dendritic structure with increase in the content of WBG. When the content of WBG exceeded a critical value (0.4 wt%), it self-assembled into a strip structure. This revealed that the structure evolution of WBG contributed to the K β and the crystallization morphology of PP with different content of WBG. In addition, further studies implied that the behaviour of self-assembly was a liquid-solid transformation of WBG, followed by a liquid-liquid phase separation of molten isotactic PP and WBG. The formation of the self-assembly structure was based on the free molecules by hydrogen bond dissociation while being heated, followed by aggregation into another structure by hydrogen bond association while being cooled. Furthermore, self-assembly behaviour depends largely on the interaction between WBG themselves.
Extremely asymmetric phase diagram of homopolymer-monotethered nanoparticles: Competition between chain conformational entropy and particle steric interaction.

PubMed

Zhang, Tiancai; Fu, Chao; Yang, Yingzi; Qiu, Feng

2017-02-07

The phase behaviors of homopolymer-monotethered nanoparticles (HMNs) in melt are investigated via a theoretical method combining self-consistent field theory for polymers and density functional theory for hard spheres. An extremely asymmetric phase diagram is observed: (i) microphases are only possible for the volume fraction of the tethered polymer f A > 0.35; (ii) in addition to lamellar phase, the system can only self-assemble into various morphologies with a polymer-rich matrix, including gyroid phase, cylindrical phase, and spherical phase. In the frame of this theory, the critical point for HMNs' microphase separation is significantly lower than that of linear diblock copolymers. Furthermore, the characteristic length of microphase-separated structures of HMNs is much smaller than that of linear diblock copolymers with the same molecular weight. Our calculation results on morphologies and characteristic length agree well with recent simulations and experimental observations.
Ultrafast Self-Assembly of Sub-10 nm Block Copolymer Nanostructures by Solvent-Free High-Temperature Laser Annealing.

PubMed

Jiang, Jing; Jacobs, Alan G; Wenning, Brandon; Liedel, Clemens; Thompson, Michael O; Ober, Christopher K

2017-09-20

Laser spike annealing was applied to PS-b-PDMS diblock copolymers to induce short-time (millisecond time scale), high-temperature (300 to 700 °C) microphase segregation and directed self-assembly of sub-10 nm features. Conditions were identified that enabled uniform microphase separation in the time frame of tens of milliseconds. Microphase ordering improved with increased temperature and annealing time, whereas phase separation contrast was lost for very short annealing times at high temperature. PMMA brush underlayers aided ordering under otherwise identical laser annealing conditions. Good long-range order for sub-10 nm cylinder morphology was achieved using graphoepitaxy coupled with a 20 ms dwell laser spike anneal above 440 °C.
Nanocomposites for ultra high density information storage, devices including the same, and methods of making the same

DOEpatents

Goyal, Amit; Shin, Junsoo

2014-04-01

A nanocomposite article that includes a single-crystal or single-crystal-like substrate and heteroepitaxial, phase-separated layer supported by a surface of the substrate and a method of making the same are described. The heteroepitaxial layer can include a continuous, non-magnetic, crystalline, matrix phase, and an ordered, magnetic magnetic phase disposed within the matrix phase. The ordered magnetic phase can include a plurality of self-assembled crystalline nanostructures of a magnetic material. The phase-separated layer and the single crystal substrate can be separated by a buffer layer. An electronic storage device that includes a read-write head and a nanocomposite article with a data storage density of 0.75 Tb/in.sup.2 is also described.
Ternary blend polymer solar cells with self-assembled structure for enhancing power conversion efficiency

NASA Astrophysics Data System (ADS)

Yang, Zhenhua; Li, Hongfei; Nam, Chang-Yong; Kisslinger, Kim; Satija, Sushil; Rafailovich, Miriam

Bulk heterojunction (BHJ) polymer solar cells are an area of intense interest due to their advantages such as mechanical flexibility. The active layer is typically spin coated from the solution of polythiophene derivatives (donor) and fullerenes (acceptor) and interconnected domains are formed because of phase separation. However, the power conversion efficiency (PCE) of BHJ solar cell is restricted by the disordered inner structures in the active layer, donor or acceptor domains isolated from electrodes. Here we report a self-assembled columnar structure formed by phase separation between (PCDTBT) and polystyrene (PS) for the active layer morphology optimization. The BHJ solar cell device based on this structure is promising for exhibiting higher performance due to the shorter carrier transportation pathway and larger interfacial area between donor and acceptor. The surface morphology is investigated with atomic force microscopy (AFM) and the columnar structure is studied by investigation of cross-section of the blend thin film of PCDTBT and PS under the transmission electron microscopy (TEM). The different morphological structures formed via phase segregation are correlated with the performance of the BHJ solar cells.
Stable, Metastable, and Kinetically Trapped Amyloid Aggregate Phases

PubMed Central

2015-01-01

Self-assembly of proteins into amyloid fibrils plays a key role in a multitude of human disorders that range from Alzheimer’s disease to type II diabetes. Compact oligomeric species, observed early during amyloid formation, are reported as the molecular entities responsible for the toxic effects of amyloid self-assembly. However, the relation between early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. We show that these different structures occupy well-defined regions in a peculiar phase diagram. Lysozyme amyloid oligomers and their curvilinear fibrils only form after they cross a salt and protein concentration-dependent threshold. We also determine a boundary for the onset of amyloid oligomer precipitation. The oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. These experimentally determined boundaries match well with colloidal model predictions that account for salt-modulated charge repulsion. The model also incorporates the metastable and kinetic character of oligomer phases. Similarities and differences of amyloid oligomer assembly to metastable liquid–liquid phase separation of proteins and to surfactant aggregation are discussed. PMID:25469942

Stable, metastable, and kinetically trapped amyloid aggregate phases.

PubMed

Miti, Tatiana; Mulaj, Mentor; Schmit, Jeremy D; Muschol, Martin

2015-01-12

Self-assembly of proteins into amyloid fibrils plays a key role in a multitude of human disorders that range from Alzheimer's disease to type II diabetes. Compact oligomeric species, observed early during amyloid formation, are reported as the molecular entities responsible for the toxic effects of amyloid self-assembly. However, the relation between early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. We show that these different structures occupy well-defined regions in a peculiar phase diagram. Lysozyme amyloid oligomers and their curvilinear fibrils only form after they cross a salt and protein concentration-dependent threshold. We also determine a boundary for the onset of amyloid oligomer precipitation. The oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. These experimentally determined boundaries match well with colloidal model predictions that account for salt-modulated charge repulsion. The model also incorporates the metastable and kinetic character of oligomer phases. Similarities and differences of amyloid oligomer assembly to metastable liquid-liquid phase separation of proteins and to surfactant aggregation are discussed.
Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants

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

Yue, Kan; Huang, Mingjun; Marson, Ryan L.

Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results frommore » nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.« less
Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants

PubMed Central

Yue, Kan; Huang, Mingjun; Marson, Ryan L.; He, Jinlin; Huang, Jiahao; Zhou, Zhe; Wang, Jing; Liu, Chang; Yan, Xuesheng; Wu, Kan; Guo, Zaihong; Liu, Hao; Ni, Peihong; Wesdemiotis, Chrys; Zhang, Wen-Bin; Glotzer, Sharon C.; Cheng, Stephen Z. D.

2016-01-01

Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures. PMID:27911786
Simulations to Predict the Phase Behavior and Structure of Multipolar Colloidal Particles

NASA Astrophysics Data System (ADS)

Rutkowski, David Matthew

Colloidal particles with anisotropic charge distributions can assemble into a number of interesting structures including chains, lattices and micelles that could be useful in biotechnology, optics and electronics. The goal of this work is to understand how the properties of the colloidal particles, such as their charge distribution or shape, affect the selfassembly and phase behavior of collections of such particles. The specific aim of this work is to understand how the separation between a pair of oppositely signed charges affects the phase behavior and structure of assemblies of colloidal particles. To examine these particles, we have used both discontinuous molecular dynamics (DMD) and Monte Carlo (MC) simulation techniques. In our first study of colloidal particles with finite charge separation, we simulate systems of 2-D colloidal rods with four possible charge separations. Our simulations show that the charge separation does indeed have a large effect on the phase behavior as can be seen in the phase diagrams we construct for these four systems in the area fraction-reduced temperature plane. The phase diagrams delineate the boundaries between isotropic fluid, string-fluid and percolated fluid for all systems considered. In particular, we find that coarse gel-like structures tend to form at large charge separations while denser aggregates form at small charge separations, suggesting a route to forming low volume gels by focusing on systems with large charge separations. Next we examine systems of circular particles with four embedded charges of alternating sign fixed to a triangular lattice. This system is found to form a limit periodic structure, a theoretical structure with an infinite number of phase transitions, under specific conditions. The limit-periodic structure only forms when the rotation of the particles in the system is restricted to increments of pi/3. When the rotation is restricted to increments of th/6 or the rotation is continuous, related structures form including a striped phase and a phase with nematic order. Neither the distance from the point charges to the center of the particle nor the angle between the charges influences whether the system forms a limit-periodic structure, suggesting that point quadrupoles may also be able to form limit-periodic structures. Results from these simulations will likely aid in the quest to find an experimental realization of a limit-periodic structure. Next we examine the effect of charge separation on the self-assembly of systems of 2-D colloidal particles with off-center extended dipoles. We simulate systems with both small and large charge separations for a set of displacements of the dipole from the particle center. Upon cooling, these particles self-assemble into closed, cyclic structures at large displacements including dimers, triangular shapes and square shapes, and chain-like structures at small displacements. At extremely low temperatures, the cyclic structures form interesting lattices with particles of similar chirality grouped together. Results from this work could aid in the experimental construction of open lattice-like structures that could find use in photonic applications. Finally, we present work in collaboration with Drs. Bhuvnesh Bharti and Orlin Velev in which we investigate how the surface coverage affects the self-assembly of systems of Janus particles coated with both an iron oxide and fatty acid chain layer. We model these particles by decorating a sphere with evenly dispersed points that interact with points on other spheres through square-well interactions. The interactions are designed to mimic specific coverage values for the iron oxide/fatty acid chain layer. Structures similar to those found in experiment form readily in the simulations. The number of clusters formed as a function of surface coverage agrees well with experiment. The aggregation behavior of these novel particles can therefore, be described by a relatively simple model.
Effect of double-tailed surfactant architecture on the conformation, self-assembly, and processing in polypeptide-surfactant complexes.

PubMed

Junnila, Susanna; Hanski, Sirkku; Oakley, Richard J; Nummelin, Sami; Ruokolainen, Janne; Faul, Charl F J; Ikkala, Olli

2009-10-12

This work describes the solid-state conformational and structural properties of self-assembled polypeptide-surfactant complexes with double-tailed surfactants. Poly(L-lysine) was complexed with three dialkyl esters of phosphoric acid (i.e., phosphodiester surfactants), where the surfactant tail branching and length was varied to tune the supramolecular architecture in a facile way. After complexation with the branched surfactant bis(2-ethylhexyl) phosphate in an aqueous solution, the polypeptide chains adopted an alpha-helical conformation. These rod-like helices self-assembled into cylindrical phases with the amorphous alkyl tails pointing outward. In complexes with dioctyl phosphate and didodecyl phosphate, which have two linear n-octyl or n-dodecyl tails, respectively, the polypeptide formed antiparallel beta-sheets separated by alkyl layers, resulting in well-ordered lamellar self-assemblies. By heating, it was possible to trigger a partial opening of the beta-sheets and disruption of the lamellar phase. After repeated heating/cooling, all of these complexes also showed a glass transition between 37 and 50 degrees C. Organic solvent treatment and plasticization by overstoichiometric amount of surfactant led to structure modification in poly(L-lysine)-dioctyl phosphate complexes, PLL(diC8)(x) (x = 1.0-3.0). Here, the alpha-helical PLL is surrounded by the surfactants and these bottle-brush-like chains self-assemble in a hexagonal cylindrical morphology. As x is increased, the materials are clearly plasticized and the degree of ordering is improved: The stiff alpha-helical backbones in a softened surfactant matrix give rise to thermotropic liquid-crystalline phases. The complexes were examined by Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry, polarized optical microscopy, and circular dichroism.
Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

PubMed

Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

2016-11-01

A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.
From Vesicles to Protocells: The Roles of Amphiphilic Molecules

PubMed Central

Sakuma, Yuka; Imai, Masayuki

2015-01-01

It is very challenging to construct protocells from molecular assemblies. An important step in this challenge is the achievement of vesicle dynamics that are relevant to cellular functions, such as membrane trafficking and self-reproduction, using amphiphilic molecules. Soft matter physics will play an important role in the development of vesicles that have these functions. Here, we show that simple binary phospholipid vesicles have the potential to reproduce the relevant functions of adhesion, pore formation and self-reproduction of vesicles, by coupling the lipid geometries (spontaneous curvatures) and the phase separation. This achievement will elucidate the pathway from molecular assembly to cellular life. PMID:25738256
Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Liu, Shujuan; Song, Xinwang; Zhu, Yangwen; Jiang, Shengxiang

2012-11-21

Graphene oxide (GO) has been layer-by-layer assembled onto silica microspheres to form a GO/SiO(2) composite stationary phase. All the characterizations of GO/SiO(2) by elemental analysis, Raman spectroscopy and Fourier transformed infrared spectrometry confirmed that with the increase of the assembled layer, GO gradually increases on the silica surface. The chromatographic properties of bare SiO(2) and GO/SiO(2) with different GO assembled layers show that the amount of GO plays an important role in the separation of analytes. Only the appropriate amount of GO on SiO(2) can perform a good chromatographic separation. The comparison between chromatographic performances of bare SiO(2) column, GO/SiO(2)-2 column and C18 commercial column clearly show that GO/SiO(2)-2 and C18 columns obtained a better separation; GO/SiO(2)-2 exhibits a large π-electron system and C18 exhibits hydrophobicity. The eluting order, peak width and resolution of analyte on GO/SiO(2)-2 column was highly dependent on the size of its π-electron system, while on the C18 column the decisive factor is its hydrophobic property.
Block copolymer templated self-assembly of disk-shaped molecules

NASA Astrophysics Data System (ADS)

Aragones, J. L.; Alexander-Katz, A.

2017-08-01

Stacking of disk-shaped organic molecules is a promising strategy to develop electronic and photovoltaic devices. Here, we investigate the capability of a soft block copolymer matrix that microphase separates into a cylindrical phase to direct the self-assembly of disk-shaped molecules by means of molecular simulations. We show that two disk molecules confined in the cylinder domain experience a depletion force, induced by the polymer chains, which results in the formation of stacks of disks. This entropic interaction and the soft confinement provided by the matrix are both responsible for the structures that can be self-assembled, which include slanted or columnar stacks. In addition, we evidence the transmission of stresses between the different minority domains of the microphase, which results in the establishment of a long-ranged interaction between disk molecules embedded in different domains; this interaction is of the order of the microphase periodicity and may be exploited to direct assembly of disks at larger scales.
Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

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

Richter, Andrew; Dergunov, Sergey; Ganus, Bill

2011-01-01

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less
Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

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

Richter, Andrew G.; Dergunov, Sergey A.; Ganus, Bill

2011-03-10

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Finally, pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less
Ultrathin self-assembled anionic polymer membranes for superfast size-selective separation

NASA Astrophysics Data System (ADS)

Deng, Chao; Zhang, Qiu Gen; Han, Guang Lu; Gong, Yi; Zhu, Ai Mei; Liu, Qing Lin

2013-10-01

Nanoporous membranes with superior separation performance have become more crucial with increasing concerns in functional nanomaterials. Here novel ultrahigh permeable nanoporous membranes have been fabricated on macroporous supports by self-assembly of anionic polymer on copper hydroxide nanostrand templates in organic solution. This facile approach has a great potential for the fabrication of ultrathin anionic polymer membranes as a general method. The as-fabricated self-assembled membranes have a mean pore size of 5-12 nm and an adjustable thickness as low as 85 nm. They allow superfast permeation of water, and exhibit excellent size-selective separation properties and good fouling resistance for negatively-charged solutes during filtration. The 85 nm thick membrane has an ultrahigh water flux (3306 l m-2 h-1 bar-1) that is an order of magnitude larger than commercial membranes, and can highly efficiently separate 5 and 15 nm gold nanoparticles from their mixtures. The newly developed nanoporous membranes have a wide application in separation and purification of biomacromolecules and nanoparticles.Nanoporous membranes with superior separation performance have become more crucial with increasing concerns in functional nanomaterials. Here novel ultrahigh permeable nanoporous membranes have been fabricated on macroporous supports by self-assembly of anionic polymer on copper hydroxide nanostrand templates in organic solution. This facile approach has a great potential for the fabrication of ultrathin anionic polymer membranes as a general method. The as-fabricated self-assembled membranes have a mean pore size of 5-12 nm and an adjustable thickness as low as 85 nm. They allow superfast permeation of water, and exhibit excellent size-selective separation properties and good fouling resistance for negatively-charged solutes during filtration. The 85 nm thick membrane has an ultrahigh water flux (3306 l m-2 h-1 bar-1) that is an order of magnitude larger than commercial membranes, and can highly efficiently separate 5 and 15 nm gold nanoparticles from their mixtures. The newly developed nanoporous membranes have a wide application in separation and purification of biomacromolecules and nanoparticles. Electronic supplementary information (ESI) available: Synthesis and characterization of SPEK-C; effect of the sulfonation degree on membrane formation; structure and properties of the self-assembled membranes; separation of cyt.c by the self-assembled membranes; size-selective separation of gold nanoparticles by the self-assembled membranes; comparison with commercial flat sheet ultrafiltration membranes. See DOI: 10.1039/c3nr03362g
Self assembly of oppositely charged latex particles at oil-water interface.

PubMed

Nallamilli, Trivikram; Ragothaman, Srikanth; Basavaraj, Madivala G

2017-01-15

In this study we explore the self assembly of oppositely charged latex particles at decane water interfaces. Two spreading protocols have been proposed in this context. In the first method oppositely charged particles are mixed prior to spreading at the interface, this is called "premixed-mixtures". In the second protocol negatively charged particles are first spread at the interface at known coverage followed by spreading positively charged particles at known coverage and this is called "sequential-mixtures". In premixed mixtures depending on particle mixing ratio (composition) and total surface coverage a number of 2d structures ranging from 2d crystals, aggregate-crystal coexistence and 2d-gels are observed. A detailed phase diagram of this system has been explored. In sequential-mixtures for the first time we observed a new phase in colloidal monolayers called 2d-bi crystalline domains. These structures consisted regions of two crystal phases of oppositely charged particles separated by a one dimensional chain of alternating positive and negative particles. Phase diagram of this system has also been explored at various combinations of first spread and second spread particles. A possible mechanism leading to formation of these 2d bi crystalline structures has been discussed. A direct visualization of breakage and reformation of particle barriers separating the crystal phases has been demonstrated through videos. Effect of salt in the water sub phase and particle hydrophobicity on domain formation is also investigated. Copyright © 2016 Elsevier Inc. All rights reserved.
Nanoporous Membranes with Chemically-Tailored Pore Walls from Triblock Terpolymer Templates

NASA Astrophysics Data System (ADS)

Mulvenna, Ryan; Weidman, Jacob; Pople, John; Boudouris, Bryan; Phillip, William

2014-03-01

Membranes generated from self-assembled block polymers have shown promise as highly permeable and selective filters; however, current syntheses of such materials lack diverse pore wall chemical functionality. Here, we report the facile synthesis of polyisoprene- b-polystyrene- b-poly(N , N -dimethylacrylamide) (PI-PS-PDMA) using a controlled reversible addition-fragmentation chain transfer (RAFT) polymerization mechanism to yield a macromolecule with an easily-tunable molecular weight and a narrow molecular weight distribution. The PI-PS-PDMA is then cast into an anisotropic membrane using the self-assembly and non-solvent induced phase separation process (SNIPS) protocol. These membranes can be used in size-selective separations for particles as small as 8 nm in diameter. Furthermore, the PDMA block can be converted to poly(acrylic acid) (PAA) readily in the solid state, and this PI-PS-PAA terpolymer membrane can separate particles as low as 2 nm in diameter while still retaining a relatively high flux. This is the smallest reported separation for a block polymer-based membrane to date. Additionally, the PAA-lined pores serve as a conversion platform to be tuned to any other pore chemistry, which allows the membrane to be of great utility in optimizing chemistry-specific separations.
Supramolecular Differentiation for Construction of Anisotropic Fullerene Nanostructures by Time-Programmed Control of Interfacial Growth.

PubMed

Bairi, Partha; Minami, Kosuke; Hill, Jonathan P; Nakanishi, Waka; Shrestha, Lok Kumar; Liu, Chao; Harano, Koji; Nakamura, Eiichi; Ariga, Katsuhiko

2016-09-27

Supramolecular assembly can be used to construct a wide variety of ordered structures by exploiting the cumulative effects of multiple noncovalent interactions. However, the construction of anisotropic nanostructures remains subject to some limitations. Here, we demonstrate the preparation of anisotropic fullerene-based nanostructures by supramolecular differentiation, which is the programmed control of multiple assembly strategies. We have carefully combined interfacial assembly and local phase separation phenomena. Two fullerene derivatives, PhH and C12H, were together formed into self-assembled anisotropic nanostructures by using this approach. This technique is applicable for the construction of anisotropic nanostructures without requiring complex molecular design or complicated methodology.
Probing Phase Evolutions of Au-Methyl-Propyl-Thiolate Self-Assembled Monolayers on Au(111) at the Molecular Level.

PubMed

Gao, Jianzhi; Lin, Haiping; Qin, Xuhui; Zhang, Xin; Ding, Haoxuan; Wang, Yitao; Rokni Fard, Mahroo; Kaya, Dogan; Zhu, Gangqiang; Li, Qing; Li, Youyong; Pan, Minghu; Guo, Quanmin

2018-06-18

A self-assembled monolayer (SAM) consisting of a mixture of CH 3 S-Au-SCH 3 , CH 3 S-Au-S(CH 2 ) 2 CH 3 , and CH 3 (CH 2 ) 2 S-Au-S(CH 2 ) 2 CH 3 was studied systematically using scanning tunneling microscopy and density functional calculations. We find that the SAM is subjected to frequent changes at the molecular level on the time scale of ∼minutes. The presence of CH 3 S or CH 3 S-Au as a dissociation product of CH 3 S-Au-SCH 3 plays a key role in the dynamical behavior of the mixed SAM. Slow phase separation takes place at room temperature over hours to days, leading to the formation of methyl-thiolate-rich and propyl-thiolate-rich phases. Our results provide new insights into the chemistry of the thiolate-Au interface, especially for ligand exchange reaction in the RS-Au-SR staple motif.
Separating homeologs by phasing in the tetraploid wheat transcriptome.

PubMed

Krasileva, Ksenia V; Buffalo, Vince; Bailey, Paul; Pearce, Stephen; Ayling, Sarah; Tabbita, Facundo; Soria, Marcelo; Wang, Shichen; Akhunov, Eduard; Uauy, Cristobal; Dubcovsky, Jorge

2013-06-25

The high level of identity among duplicated homoeologous genomes in tetraploid pasta wheat presents substantial challenges for de novo transcriptome assembly. To solve this problem, we develop a specialized bioinformatics workflow that optimizes transcriptome assembly and separation of merged homoeologs. To evaluate our strategy, we sequence and assemble the transcriptome of one of the diploid ancestors of pasta wheat, and compare both assemblies with a benchmark set of 13,472 full-length, non-redundant bread wheat cDNAs. A total of 489 million 100 bp paired-end reads from tetraploid wheat assemble in 140,118 contigs, including 96% of the benchmark cDNAs. We used a comparative genomics approach to annotate 66,633 open reading frames. The multiple k-mer assembly strategy increases the proportion of cDNAs assembled full-length in a single contig by 22% relative to the best single k-mer size. Homoeologs are separated using a post-assembly pipeline that includes polymorphism identification, phasing of SNPs, read sorting, and re-assembly of phased reads. Using a reference set of genes, we determine that 98.7% of SNPs analyzed are correctly separated by phasing. Our study shows that de novo transcriptome assembly of tetraploid wheat benefit from multiple k-mer assembly strategies more than diploid wheat. Our results also demonstrate that phasing approaches originally designed for heterozygous diploid organisms can be used to separate the close homoeologous genomes of tetraploid wheat. The predicted tetraploid wheat proteome and gene models provide a valuable tool for the wheat research community and for those interested in comparative genomic studies.
Separating homeologs by phasing in the tetraploid wheat transcriptome

PubMed Central

2013-01-01

Background The high level of identity among duplicated homoeologous genomes in tetraploid pasta wheat presents substantial challenges for de novo transcriptome assembly. To solve this problem, we develop a specialized bioinformatics workflow that optimizes transcriptome assembly and separation of merged homoeologs. To evaluate our strategy, we sequence and assemble the transcriptome of one of the diploid ancestors of pasta wheat, and compare both assemblies with a benchmark set of 13,472 full-length, non-redundant bread wheat cDNAs. Results A total of 489 million 100 bp paired-end reads from tetraploid wheat assemble in 140,118 contigs, including 96% of the benchmark cDNAs. We used a comparative genomics approach to annotate 66,633 open reading frames. The multiple k-mer assembly strategy increases the proportion of cDNAs assembled full-length in a single contig by 22% relative to the best single k-mer size. Homoeologs are separated using a post-assembly pipeline that includes polymorphism identification, phasing of SNPs, read sorting, and re-assembly of phased reads. Using a reference set of genes, we determine that 98.7% of SNPs analyzed are correctly separated by phasing. Conclusions Our study shows that de novo transcriptome assembly of tetraploid wheat benefit from multiple k-mer assembly strategies more than diploid wheat. Our results also demonstrate that phasing approaches originally designed for heterozygous diploid organisms can be used to separate the close homoeologous genomes of tetraploid wheat. The predicted tetraploid wheat proteome and gene models provide a valuable tool for the wheat research community and for those interested in comparative genomic studies. PMID:23800085
Tunable self-organization of nanocomposite multilayers

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

Chen, C. Q.; Pei, Y. T.; Shaha, K. P.

In this letter we report the controlled growth and microstructural evolution of self-assembled nanocomposite multilayers that are induced by surface ion-impingement. The nanoscale structures together with chemical composition, especially at the growing front, have been investigated with high-resolution transmission electron microscopy. Concurrent ion impingement of growing films produces an amorphous capping layer 3 nm in thickness where spatially modulated phase separation is initiated. It is shown that the modulation of multilayers as controlled by the self-organization of nanocrystallites below the capping layer, can be tuned through the entire film.
Highly tensile-strained Ge/InAlAs nanocomposites

NASA Astrophysics Data System (ADS)

Jung, Daehwan; Faucher, Joseph; Mukherjee, Samik; Akey, Austin; Ironside, Daniel J.; Cabral, Matthew; Sang, Xiahan; Lebeau, James; Bank, Seth R.; Buonassisi, Tonio; Moutanabbir, Oussama; Lee, Minjoo Larry

2017-01-01

Self-assembled nanocomposites have been extensively investigated due to the novel properties that can emerge when multiple material phases are combined. Growth of epitaxial nanocomposites using lattice-mismatched constituents also enables strain-engineering, which can be used to further enhance material properties. Here, we report self-assembled growth of highly tensile-strained Ge/In0.52Al0.48As (InAlAs) nanocomposites by using spontaneous phase separation. Transmission electron microscopy shows a high density of single-crystalline germanium nanostructures coherently embedded in InAlAs without extended defects, and Raman spectroscopy reveals a 3.8% biaxial tensile strain in the germanium nanostructures. We also show that the strain in the germanium nanostructures can be tuned to 5.3% by altering the lattice constant of the matrix material, illustrating the versatility of epitaxial nanocomposites for strain engineering. Photoluminescence and electroluminescence results are then discussed to illustrate the potential for realizing devices based on this nanocomposite material.

Highly tensile-strained Ge/InAlAs nanocomposites

PubMed Central

Jung, Daehwan; Faucher, Joseph; Mukherjee, Samik; Akey, Austin; Ironside, Daniel J.; Cabral, Matthew; Sang, Xiahan; Lebeau, James; Bank, Seth R.; Buonassisi, Tonio; Moutanabbir, Oussama; Lee, Minjoo Larry

2017-01-01

Self-assembled nanocomposites have been extensively investigated due to the novel properties that can emerge when multiple material phases are combined. Growth of epitaxial nanocomposites using lattice-mismatched constituents also enables strain-engineering, which can be used to further enhance material properties. Here, we report self-assembled growth of highly tensile-strained Ge/In0.52Al0.48As (InAlAs) nanocomposites by using spontaneous phase separation. Transmission electron microscopy shows a high density of single-crystalline germanium nanostructures coherently embedded in InAlAs without extended defects, and Raman spectroscopy reveals a 3.8% biaxial tensile strain in the germanium nanostructures. We also show that the strain in the germanium nanostructures can be tuned to 5.3% by altering the lattice constant of the matrix material, illustrating the versatility of epitaxial nanocomposites for strain engineering. Photoluminescence and electroluminescence results are then discussed to illustrate the potential for realizing devices based on this nanocomposite material. PMID:28128282
Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

NASA Astrophysics Data System (ADS)

Radhakrishna, Mithun; Sing, Charles E.

Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.
Phase behavior and transitions of self-assembling nano-structured materials

NASA Astrophysics Data System (ADS)

Duan, Hu

Homologous series of supramolecular nanostructures have been investigated by a combination of transmission electron microscopy (TEM), electron diffraction (ED), thermal polarized optical microscopy and X-ray diffraction (XRD). Materials include amphiphilic oligomers and polymer such as charged complexes, dipeptide dendrons semi-fluorinated dendron and polyethyleneimines. Upon microphase separation, they self-assemble into either cylindrical or spherical shapes, which co-organize into a 2D P6mm hexagonal columnar phase or 3D Pm 3¯ n and Im 3¯ m cubic phases. Correlation between the phase selection and molecular architecture is established accordingly. The order-disorder transition (ODT) is explored by rheometry and rheo-optical microscopy in a model polymeric compound poly(N-[3,4-bis(n-dodecan-1-yloxy)benzoyl]ethyleneimine). Shear alignment of the hexagonal columnar liquid crystalline phase along the velocity direction at low temperature and shear disordering in the vicinity of the ODT were observed. After cessation of shear, transformation back to the stable columnar phase follows a row-nucleation mechanism. The order-order transition process is explored in a monodendron that exhibits a hexagonal columnar and a weakly birefringent mesophase. Polarized DIC microscopy strongly supports an epitaxial relationship between them.
A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly.

PubMed

Zhang, Xun; Zhang, Junhu; Zhu, Difu; Li, Xiao; Zhang, Xuemin; Wang, Tieqiang; Yang, Bai

2010-12-07

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.
Self-assembly of Nano-rods in Photosensitive Phase Separation

NASA Astrophysics Data System (ADS)

Liu, Ya; Kuksenok, Olga; Maresov, Egor; Balazs, Anna

2012-02-01

Computer simulations reveal how photo-induced chemical reactions in polymeric mixtures can be exploited to create long-range order in materials whose features range from the sub-micron to the nanoscale. The process is initiated by shining a spatially uniform light on a photosensitive AB binary blend, which thereby undergoes both a reversible chemical reaction and phase separation. When a well-collimated, higher intensity light is rastered over the sample, the system forms defect-free, spatially periodic structures. We now build on this approach by introducing nanorods that have a preferential affinity for one the phases in a binary mixture. By rastering over the sample with the higher intensity light, we can create ordered arrays of rods within periodically ordered materials in essentially one processing step.
Chiral recognition and selection during the self-assembly process of protein-mimic macroanions

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

Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin

The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24]20- (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis ofmore » the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.« less
A technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates.

PubMed

Fontana, Jake; Spillmann, Christopher; Naciri, Jawad; Ratna, Banahalli R

2014-05-09

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface. The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates. The flow is mediated by a surface tension gradient and creates macroscopic, high-density, monolayer nanoparticle-ligand films. This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.
Hierarchically self-assembled hexagonal honeycomb and kagome superlattices of binary 1D colloids.

PubMed

Lim, Sung-Hwan; Lee, Taehoon; Oh, Younghoon; Narayanan, Theyencheri; Sung, Bong June; Choi, Sung-Min

2017-08-25

Synthesis of binary nanoparticle superlattices has attracted attention for a broad spectrum of potential applications. However, this has remained challenging for one-dimensional nanoparticle systems. In this study, we investigate the packing behavior of one-dimensional nanoparticles of different diameters into a hexagonally packed cylindrical micellar system and demonstrate that binary one-dimensional nanoparticle superlattices of two different symmetries can be obtained by tuning particle diameter and mixing ratios. The hexagonal arrays of one-dimensional nanoparticles are embedded in the honeycomb lattices (for AB 2 type) or kagome lattices (for AB 3 type) of micellar cylinders. The maximization of free volume entropy is considered as the main driving force for the formation of superlattices, which is well supported by our theoretical free energy calculations. Our approach provides a route for fabricating binary one-dimensional nanoparticle superlattices and may be applicable for inorganic one-dimensional nanoparticle systems.Binary mixtures of 1D particles are rarely observed to cooperatively self-assemble into binary superlattices, as the particle types separate into phases. Here, the authors design a system that avoids phase separation, obtaining binary superlattices with different symmetries by simply tuning the particle diameter and mixture composition.
Self-assembly of three-dimensional open structures using patchy colloidal particles.

PubMed

Rocklin, D Zeb; Mao, Xiaoming

2014-10-14

Open structures can display a number of unusual properties, including a negative Poisson's ratio, negative thermal expansion, and holographic elasticity, and have many interesting applications in engineering. However, it is a grand challenge to self-assemble open structures at the colloidal scale, where short-range interactions and low coordination number can leave them mechanically unstable. In this paper we discuss the self-assembly of three-dimensional open structures using triblock Janus particles, which have two large attractive patches that can form multiple bonds, separated by a band with purely hard-sphere repulsion. Such surface patterning leads to open structures that are stabilized by orientational entropy (in an order-by-disorder effect) and selected over close-packed structures by vibrational entropy. For different patch sizes the particles can form into either tetrahedral or octahedral structural motifs which then compose open lattices, including the pyrochlore, the hexagonal tetrastack and the perovskite lattices. Using an analytic theory, we examine the phase diagrams of these possible open and close-packed structures for triblock Janus particles and characterize the mechanical properties of these structures. Our theory leads to rational designs of particles for the self-assembly of three-dimensional colloidal structures that are possible using current experimental techniques.
Understanding self-assembly of charged-neutral block copolymer (BCP) and surfactant complexes using molecular dynamics (MD) simulation

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Sumpter, Bobby; Kilbey, Michael

Here we report the formation of phase separated BCP-surfactant complexes resulting from the electrostatic self-assembly of charge-neutral block copolymers with oppositely charged surfactants. Complexation behaviors of oppositely charged polyelectrolytes has gained considerable attention in the field of soft condensed matter physics due to their potential application as functional nanomaterials for batteries, wastewater treatment and drug delivery systems. Numerous experiments have examined the self-assembled structures resulting from complexation of charge-neutral BCP and surfactants, however, there is a lack of comprehensive understanding at the fundamental level. To help bridge this gap, we use, MD simulations to study self-assembly and dynamics of the BCP-surfactant complex at the molecular level. Our results show an overcharging effect in BCPs with hydrophobic neutral blocks and a formation of core-shell colloidal structure. Hydrophilic neutral blocks, on the other hand, show stable, hairy colloidal structures with neutral blocks forming a loosely-bound, fuzzy outer layer. Our results qualitatively agree with previous SANS and SAXS experiments. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Materials Science and Engineering Division.
Dynamics of self-assembled cytosine nucleobases on graphene

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

NASA Astrophysics Data System (ADS)

Kang, Minjee; Leal, Cecilia

The cell membrane is highly compartmentalized over micro-and nano scale. The compartmentalized domains play an important role in regulating the diffusion and distribution of species within and across the membrane. In this work, we introduced nanoscale heterogeneities into lipid films for the purpose of developing nature-mimicking phase-separated materials. The mixtures of phospholipids and amphiphilic block copolymers self-assemble into supported 1D multi-bilayers. We observed that in each lamella, mixtures of lipid and polymer phase-separate into domains that differ in their composition akin to sub-phases in cholesterol-containing lipid bilayers. Interestingly, we found evidence that like-domains are in registry across multilayers, making phase separation three-dimensional. To exploit such distinctive domain structure for surface-mediated drug delivery, we incorporated pharmaceutical molecules into the films. The drug release study revealed that the presence of domains in hybrid films modifies the diffusion pathways of drugs that become confined within phase-separated domains. A comprehensive domain structure coupled with drug diffusion pathways in films will be presented, offering new perspectives in designing a thin-film matrix system for controlled drug delivery. This work was supported by the National Science Foundation under Grant No. DMR-1554435.
Asymmetric organic-inorganic hybrid membrane formation via block copolymer-nanoparticle co-assembly.

PubMed

Gu, Yibei; Dorin, Rachel M; Wiesner, Ulrich

2013-01-01

A facile method for forming asymmetric organic-inorganic hybrid membranes for selective separation applications is developed. This approach combines co-assembly of block copolymer (BCP) and inorganic nanoparticles (NPs) with non-solvent induced phase separation. The method is successfully applied to two distinct molar mass BCPs with different fractions of titanium dioxide (TiO2) NPs. The resulting hybrid membranes exhibit structural asymmetry with a thin nanoporous surface layer on top of a macroporous fingerlike support layer. Key parameters that dictate membrane surface morphology include the fraction of inorganics used and the length of time allowed for surface layer development. The resulting membranes exhibit both good selectivity and high permeability (3200 ± 500 Lm(-2) h(-1) bar(-1)). This fast and straightforward synthesis method for asymmetric hybrid membranes provides a new self-assembly platform upon which multifunctional and high-performance organic-inorganic hybrid membranes can be formed.
Bottom-up multiferroic nanostructures

NASA Astrophysics Data System (ADS)

Ren, Shenqiang

Multiferroic and especially magnetoelectric (ME) nanocomposites have received extensive attention due to their potential applications in spintronics, information storage and logic devices. The extrinsic ME coupling in composites is strain mediated via the interface between the piezoelectric and magnetostrictive components. However, the design and synthesis of controlled nanostructures with engineering enhanced coupling remain a significant challenge. The purpose of this thesis is to create nanostructures with very large interface densities and unique connectivities of the two phases in a controlled manner. Using inorganic solid state phase transformations and organic block copolymer self assembly methodologies, we present novel self assembly "bottom-up" techniques as a general protocol for the nanofabrication of multifunctional devices. First, Lead-Zirconium-Titanate/Nickel-Ferrite (PZT/NFO) vertical multilamellar nanostructures have been produced by crystallizing and decomposing a gel in a magnetic field below the Curie temperature of NFO. The ensuing microstructure is nanoscopically periodic and anisotropic. The wavelength of the PZT/NFO alternation, 25 nm, agrees within a factor of two with the theoretically estimated value. The macroscopic ferromagnetic and magnetoelectric responses correspond qualitatively and semi-quantitatively to the features of the nanostructure. The maximum of the field dependent magnetoelectric susceptibility equals 1.8 V/cm Oe. Second, a magnetoelectric composite with controlled nanostructures is synthesized using co-assembly of two inorganic precursors with a block copolymer. This solution processed material consists of hexagonally arranged ferromagnetic cobalt ferrite (CFO) nano-cylinders within a matrix of ferroelectric Lead-Zirconium-Titanate (PZT). The initial magnetic permeability of the self-assembled CFO/PZT nanocomposite changes by a factor of 5 through the application of 2.5 V. This work may have significant impact on the development of novel memory or logic devices through self assembly techniques. It also demonstrates a universal two-phase hard template application. Last, solid-state self assembly had been used recently to form pseudoperiodic chessboard-like nanoscale morphologies in a series of chemically homogeneous complex oxide systems. We improved on this approach by synthesizing a spontaneously phase separated nanolamellar BaTiO3-CoFe2O4 bi-crystal. The superlattice is magnetoelectric with a frequency dependent coupling. The BaTiO3 component is a ferroelectric relaxor with a Vogel-Fulcher temperature of 311 K. Since the material can be produced by standard ceramic processing methods, the discovery represents great potential for magnetoelectric devices.
Inter and Intra Molecular Phase Separation Environment Effects on PI-PEO Block Copolymers for Batteries and Fuel Cells

NASA Technical Reports Server (NTRS)

Xue, Chen-Chen; Meador, Mary Ann B.; Eby, R. K.; Cheng, Stephen Z. D.; Ge, Jason J.; Cubon, Valerie A.

2002-01-01

Rod-coil molecules have been introduced as a novel type of block copolymers with unique microstructure due to their ability to self-assemble to various ordered morphologies on a nanometer length scale. These molecules, comprised two homo polymers joined together at one end, microphase separate into ordered, periodic arrays of spheres, cylinders in the bulk state and or solution. To get ordered structure in a reasonable scale, additional force field are applied, such as mechanical shearing, electric field and magnetic field. Recently, progress has made it a possible to develop a new class of polyimides (PI)-Polyethylene oxide (PEO) that are soluble in polar organic solvents. The solvent-soluble PI-PEO has a wide variety of applications in microelectronics, since these PI-PEO films exhibit a high degree of thermal and chemical stability. In this paper, we report the self-assembled ordered structure of PI-PEO molecules formed from concentrate solution.
Watching Nanoscale Self-Assembly Kinetics of Gold Prisms in Liquids

NASA Astrophysics Data System (ADS)

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

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

PubMed Central

Hagan, Michael F.; Elrad, Oren M.; Jack, Robert L.

2011-01-01

In self-assembly processes, kinetic trapping effects often hinder the formation of thermodynamically stable ordered states. In a model of viral capsid assembly and in the phase transformation of a lattice gas, we show how simulations in a self-assembling steady state can be used to identify two distinct mechanisms of kinetic trapping. We argue that one of these mechanisms can be adequately captured by kinetic rate equations, while the other involves a breakdown of theories that rely on cluster size as a reaction coordinate. We discuss how these observations might be useful in designing and optimising self-assembly reactions. PMID:21932884
Pre-biotic stage of life origin under non-photosynthetic conditions

NASA Technical Reports Server (NTRS)

Bartsev, S. I.; Mezhevikin, V. V.

2005-01-01

Spontaneous assembling of a simplest bacterial cell even if all necessary molecules are present in a solution seems to be extremely rare event and from the scientific standpoint has to be considered as impossible. Therefore, a predecessor of a living cell has to be very simple for providing its self-assembling and at the same time it should be able of progressive increase in complexity. Now phase-separated particles, first of all micelles, are put forward as possible predecessors of living cell. According to the offered working concept only phase-separated particles possessing autocatalytic properties can be considered as predecessors of living cells. The first stage of evolution of these phase-separated autocatalytic systems is the appearance of pre-biotic metabolism providing synthesis of amphiphiles for formation of capsules of these systems. This synthesis is maintained by the energy of a base reaction being a component of a planet-chemical cycle. Catalytic system providing functioning of pre-biotic metabolism is based on multivariate oligomeric autocatalyst, which reproduces itself from monomers, penetrating the particles from the outside. Since the autocatalyst realizes random polymerization then a collection of other oligomers possessing different catalytic functions is produced. In the paper the functioning of multivariate oligomeric autocatalyst in flow reactor is analyzed. c2005 Published by Elsevier Ltd on behalf of COSPAR.
Balancing the intermolecular forces in peptide amphiphiles for controlling self-assembly transitions.

PubMed

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

2017-06-21

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

NASA Astrophysics Data System (ADS)

Mahynski, Nathan Alexander

In this dissertation I use computational tools to study the structure and thermodynamics of colloid-polymer mixtures. I show that fluid-fluid phase separation in mixtures of colloids and linear polymers cannot be universally reduced using polymer-based scaling principles since these assume the binodals exist in a single scaling regime, whereas accurate simulations clearly demonstrate otherwise. I show that rethinking these solutions in terms of multiple length scales is necessary to properly explain the thermodynamic stability and structure of these fluid phases, and produce phase diagrams in nearly quantitative agreement with experimental results. I then extend this work to encompass more geometrically complex "star" polymers revealing how the phase behavior for many of these binary mixtures may be mapped onto that of mixtures containing only linear polymers. I further consider the depletion-driven crystallization of athermal colloidal hard spheres induced by polymers. I demonstrate how the partitioning of a finite amount of polymer into the colloidal crystal phase implies that the polymer's architecture can be tailored to interact with the internal void structure of different crystal polymorphs uniquely, thus providing a direct route to thermodynamically stabilizing one arbitrarily chosen structure over another, e.g., the hexagonal close-packed crystal over the face-centered cubic. I then begin to generalize this result by considering the consequences of thermal interactions and complex polymer architectures. These principles lay the groundwork for intelligently engineering co-solute additives in crystallizing colloidal suspensions that can be used to thermodynamically isolate single crystal morphologies. Finally, I examine the competition between self-assembly and phase separation in polymer-grafted nanoparticle systems by comparing and contrasting the validity of two different models for grafted nanoparticles: "nanoparticle amphiphiles" versus "patchy particles." The latter suggests these systems have some utility in forming novel "equilibrium gel" phases, however, I find that considering grafted nanoparticles as amphiphiles provides a qualitatively accurate description of their thermodynamics revealing either first-order phase separation into two isotropic phases or continuous self-assembly. I find no signs of empty liquid formation, suggesting that these nanoparticles do not provide a route to such phases.

Independent active and thermodynamic processes govern the nucleolus assembly in vivo

PubMed Central

Falahati, Hanieh; Wieschaus, Eric

2017-01-01

Membraneless organelles play a central role in the organization of protoplasm by concentrating macromolecules, which allows efficient cellular processes. Recent studies have shown that, in vitro, certain components in such organelles can assemble through phase separation. Inside the cell, however, such organelles are multicomponent, with numerous intermolecular interactions that can potentially affect the demixing properties of individual components. In addition, the organelles themselves are inherently active, and it is not clear how the active, energy-consuming processes that occur constantly within such organelles affect the phase separation behavior of the constituent macromolecules. Here, we examine the phase separation model for the formation of membraneless organelles in vivo by assessing the two features that collectively distinguish it from active assembly, namely temperature dependence and reversibility. We use a microfluidic device that allows accurate and rapid manipulation of temperature and examine the quantitative dynamics by which six different nucleolar proteins assemble into the nucleoli of Drosophila melanogaster embryos. Our results indicate that, although phase separation is the main mode of recruitment for four of the studied proteins, the assembly of the other two is irreversible and enhanced at higher temperatures, behaviors indicative of active recruitment to the nucleolus. These two subsets of components differ in their requirements for ribosomal DNA; the two actively assembling components fail to assemble in the absence of ribosomal DNA, whereas the thermodynamically driven components assemble but lose temporal and spatial precision. PMID:28115706
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.
"Self-Shaping" of Multicomponent Drops.

PubMed

Cholakova, Diana; Valkova, Zhulieta; Tcholakova, Slavka; Denkov, Nikolai; Smoukov, Stoyan K

2017-06-13

In our recent study we showed that single-component emulsion drops, stabilized by proper surfactants, can spontaneously break symmetry and transform into various polygonal shapes during cooling [ Denkov Nature 2015 , 528 , 392 - 395 ]. This process involves the formation of a plastic rotator phase of self-assembled oil molecules beneath the drop surface. The plastic phase spontaneously forms a frame of plastic rods at the oil drop perimeter which supports the polygonal shapes. However, most of the common substances used in industry appear as mixtures of molecules rather than pure substances. Here we present a systematic study of the ability of multicomponent emulsion drops to deform upon cooling. The observed trends can be summarized as follows: (1) The general drop-shape evolution for multicomponent drops during cooling is the same as with single-component drops; however, some additional shapes are observed. (2) Preservation of the particle shape upon freezing is possible for alkane mixtures with chain length difference Δn ≤ 4; for greater Δn, phase separation within the droplet is observed. (3) Multicomponent particles prepared from alkanes with Δn ≤ 4 plastify upon cooling due to the formation of a bulk rotator phase within the particles. (4) If a compound, which cannot induce self-shaping when pure, is mixed with a certain amount of a compound which induces self-shaping, then drops prepared from this mixture can also self-shape upon cooling. (5) Self-emulsification phenomena are also observed for multicomponent drops. In addition to the three recently reported mechanisms of self-emulsification [ Tcholakova Nat. Commun. 2017 , ( 8 ), 15012 ], a new (fourth) mechanism is observed upon freezing for alkane mixtures with Δn > 4. It involves disintegration of the particles due to a phase separation of alkanes upon freezing.
Self-Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate.

PubMed

Schreiber, Roy E; Avram, Liat; Neumann, Ronny

2018-01-09

High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H 2 F 6 NaW 18 O 56 ] 7- from simple tungstate Na 2 WO 2 F 4 was demonstrated by using 2D 19 F- 19 F NOESY, 2D 19 F- 19 F COSY NMR spectroscopy, a new 2D 19 F{ 183 W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Photocatalytic activity of self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition

NASA Astrophysics Data System (ADS)

Shi, Pengjun; Li, Xibo; Zhang, Qiuju; Yi, Zao; Luo, Jiangshan

2018-04-01

A well-separated and oriented TiO2 nano-columns arrays with porous structure were fabricated by the oblique angle sputter deposition technique and subsequently annealing at 450 °C in Ar/O2 mixed atmosphere. The deposited substrate was firstly modified by a template of self-assembled close-packed arrays of 500 nm-diameter silica (SiO2) spheres. Scanning electronic microscopic (SEM) images show that the porous columnar nanostructure is formed as a result of the geometric shadowing effect and surface diffusion of the adatoms in oblique angle deposition (OAD). X-ray diffraction (XRD) measurements reveal that the physically OAD film with annealing treatment are generally mixed phase of rutile and anatase TiO2 polymorphic forms. The morphology induced absorbance and band gap tuning by different substrates was demonstrated by the UV–vis spectroscopy. The well-separated one-dimensional (1D) nano-columns array with specific large porous surface area is beneficial for charge separation in photocatalytic degradation. Compared with compact thin film, such self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition performed an enhanced visible light induced photocatalytic activity by decomposing methyl orange (MO) solution. The well-designed periodic array-structured porous TiO2 films by using modified patterned substrates has been demonstrated significantly increased absorption edge in the UV-visible light region with a narrower optical band gap, which are expected to be favorable for application in photovoltaic, lithium-ion insertion and photocatalytic, etc.
Centrifugal contactor modified for end stage operation in a multistage system

DOEpatents

Jubin, Robert T.

1990-01-01

A cascade formed of a plurality of centrifugal contactors useful for countercurrent solvent extraction processes such as utilizable for the reprocessing of nuclear reactor fuels is modified to permit operation in the event one or both end stages of the cascade become inoperative. Weir assemblies are connected to each of the two end stages by suitable conduits for separating liquids discharged from an inoperative end stage based upon the weight of the liquid phases uses in the solvent extraction process. The weir assembly at one end stage is constructed to separate and discharge the heaviest liquid phase while the weir assembly at the other end stage is constructed to separate and discharge the lightest liquid phase. These weir assemblies function to keep the liquid discharge from an inoperative end stages on the same weight phase a would occur from an operating end stage.
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…
Separation and characterization of metallosupramolecular libraries by ion mobility mass spectrometry.

PubMed

Li, Xiaopeng; Chan, Yi-Tsu; Casiano-Maldonado, Madalis; Yu, Jing; Carri, Gustavo A; Newkome, George R; Wesdemiotis, Chrys

2011-09-01

The self-assembly of Zn(II) ions and bis(terpyridine) (tpy) ligands carrying 120° or 180° angles between their metal binding sites was utilized to prepare metallosupramolecular libraries with the connectivity. These combinatorial libraries were separated and characterized by ion mobility mass spectrometry (IM MS) and tandem mass spectrometry (MS(2)). The 180°-angle building blocks generate exclusively linear complexes, which were used as standards to determine the architectures of the assemblies resulting from the 120°-angle ligands. The latter ligand geometry promotes the formation of macrocyclic hexamers, but other n-mers with smaller (n = 5) or larger ring sizes (n = 7-9) were identified as minor products, indicating that the angles in the bis(terpyridine) ligand and within the coordinative tpy-Zn(II)-tpy bonds are not as rigid, as previously believed. Macrocyclic and linear isomers were detected in penta- and heptameric assemblies; in the larger octa- and nonameric assemblies, ring-opened conformers with compact and folded geometries were observed in addition to linear extended and cyclic architectures. IM MS(2) experiments provided strong evidence that the macrocycles present in the libraries were already formed in solution, during the self-assembly process, not by dissociation of larger complexes in the gas phase. The IM MS/MS(2) methods provide a means to analyze, based on size and shape (architecture), supramolecular libraries that are not amenable to liquid chromatography, LC-MS, NMR, and/or X-ray techniques.
Self-assembly concepts in the formation of nanostructured particles using a liquid-phase synthesis method

NASA Astrophysics Data System (ADS)

Nandiyanto, Asep Bayu Dani

2016-02-01

When synthesizing particles using a liquid-phase synthesis method, reactant components show interaction with the reaction system itself. However, current reports described successful synthesis of material with only partial information on the component-component interaction and possible self-assembly mechanism occurring during the material synthesis process. Here, self-assembly concepts in the formation of nanostructured particles are presented. Influences of self-assembly parameters (i.e., surface charge, size, and concentration of components involving the reaction) on self-organized material fabrication are described. Because understanding the interaction of the component provides significant information in regard to practical uses, this report can be relevant to further material development and fabrication.
The self-assembly structure and the CO2-philicity of a hybrid surfactant in supercritical CO2: effects of hydrocarbon chain length.

PubMed

Wang, Muhan; Fang, Timing; Wang, Pan; Tang, Xinpeng; Sun, Baojiang; Zhang, Jun; Liu, Bing

2016-10-04

Hybrid surfactants containing both fluorocarbon (FC) and hydrocarbon (HC) chains, as effective CO 2 -philic surfactants, could improve the solubility of polar substances in supercritical CO 2 . Varying the length of the HC of hybrid surfactants is an effective way to improve the CO 2 -philicity. In this paper, we have investigated the effects of the HC length on the self-assembly process and the CO 2 -philicity of hybrid surfactants (F7Hn, n = 1, 4, 7 and 10) in water/CO 2 mixtures using molecular dynamics simulations. It is found that the self-assembly time of F7Hn exhibits a maximum when the length of the HC is equal to that of the FC (F7H7). In this case, the investigation of H-bonds between the water core and CO 2 phase shows that F7H7 has the strongest CO 2 -philicity because it has the best ability to separate water and CO 2 . To explain the origin of the differences in separation ability, the analysis of the structures of the reverse micelles shows that there are two competing mechanisms with a shortening HC. Firstly, the volume of F7Hn is reduced, which thus decreases the separation ability. Moreover, this also leads to the curved conformation of the FC. As a result, the separation ability is enhanced. These two mechanisms are balanced in F7H7, which has the best ability to separate water and CO 2 . Our simulation results demonstrate that the increased volume and the curved conformation of the hybrid surfactant tail could enhance the CO 2 -philicity in F7Hn surfactants. It is expected that this work will provide valuable information for the design of CO 2 -philic surfactants.
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.
Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

PubMed

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

2017-04-18

The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical chains from self-assembly. The handedness of the twisted lamella can be determined by using rotation experiment of polarized light microscopy (PLM). Similar to the self-assembly of BCPs*, the examined results suggest the homochiral evolution in the crystallized chiral polylactides. The results presented in this Account demonstrate the notable progress in the spectral and morphological determination for the examination of molecular, conformational, and hierarchical chirality in self-assembled twisted superstructures of chiral polymers and helical phases of block copolymers and suggest the attainability of homochiral evolution in the self-assembly of chiral homopolymers and BCPs*. The suggested methodologies for the understanding of the mechanisms of the chirality transfer at different length scales provide the approaches to give Supporting Information for disclosing the mysteries of the homochiral evolution from molecular level.
Multiscale and Multifunctional Emulsions by Host–Guest Interaction-Mediated Self-Assembly

PubMed Central

2018-01-01

Emulsions are widely used in numerous fields. Therefore, there has been increasing interest in the development of new emulsification strategies toward emulsions with advanced functions. Herein we report the formation of diverse emulsions by host–guest interaction-mediated interfacial self-assembly under mild conditions. In this strategy, a hydrophilic diblock copolymer with one block containing β-cyclodextrin (β-CD) can assemble at the oil/water interface when its aqueous solution is mixed with an oil phase of benzyl alcohol (BA), by host–guest interactions between β-CD and BA. This results in significantly reduced interfacial tension and the formation of switchable emulsions with easily tunable droplet sizes. Furthermore, nanoemulsions with excellent stability are successfully prepared simply via vortexing. The self-assembled oil-in-water emulsions also show catastrophic phase inversion, which can generate stable bicontinuous phase and water-in-oil emulsions, thereby further extending phase structures that can be realized by this host–guest self-assembly approach. Moreover, the host–guest nanoemulsions are able to engineer different nanoparticles and microstructures as well as solubilize a diverse array of hydrophobic drugs and dramatically enhance their oral bioavailability. The host–guest self-assembly emulsification is facile, energetically friendly, and fully translatable to industry, therefore representing a conceptually creative approach toward advanced emulsions. PMID:29806006
Functional Domains of NEAT1 Architectural lncRNA Induce Paraspeckle Assembly through Phase Separation.

PubMed

Yamazaki, Tomohiro; Souquere, Sylvie; Chujo, Takeshi; Kobelke, Simon; Chong, Yee Seng; Fox, Archa H; Bond, Charles S; Nakagawa, Shinichi; Pierron, Gerard; Hirose, Tetsuro

2018-06-21

A class of long noncoding RNAs (lncRNAs) has architectural functions in nuclear body construction; however, specific RNA domains dictating their architectural functions remain uninvestigated. Here, we identified the domains of the architectural NEAT1 lncRNA that construct paraspeckles. Systematic deletion of NEAT1 portions using CRISPR/Cas9 in haploid cells revealed modular domains of NEAT1 important for RNA stability, isoform switching, and paraspeckle assembly. The middle domain, containing functionally redundant subdomains, was responsible for paraspeckle assembly. Artificial tethering of the NONO protein to a NEAT1_2 mutant lacking the functional subdomains rescued paraspeckle assembly, and this required the NOPS dimerization domain of NONO. Paraspeckles exhibit phase-separated properties including susceptibility to 1,6-hexanediol treatment. RNA fragments of the NEAT1_2 subdomains preferentially bound NONO/SFPQ, leading to phase-separated aggregates in vitro. Thus, we demonstrate that the enrichment of NONO dimers on the redundant NEAT1_2 subdomains initiates construction of phase-separated paraspeckles, providing mechanistic insights into lncRNA-based nuclear body formation. Copyright © 2018 Elsevier Inc. All rights reserved.
Kinetic control of block copolymer self-assembly into multicompartment and novel geometry nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Yingchao; Wang, Xiaojun; Zhang, Ke; Wooley, Karen; Mays, Jimmy; Percec, Virgil; Pochan, Darrin

2012-02-01

Micelles with the segregation of hydrophobic blocks trapped in the same nanoparticle core have been produced through co-self-assembly of two block copolymers in THF/water dilute solution. The dissolution of two block copolymer sharing the same polyacrylic acid PAA blocks in THF undergoes consequent aggregation and phase separation through either slow water titration or quick water addition that triggers the micellar formation. The combination and comparison of the two water addition kinetic pathways are the keys of forming multicompartment structures at high water content. Importantly, the addition of organic diamine provides for acid-base complexation with the PAA side chains which, in turn, plays the key role of trapping unlike hydrophobic blocks from different block copolymers into one nanoparticle core. The kinetic control of solution assembly can be applied to other molecular systems such as dendrimers as well as other block copolymer molecules. Transmission electron microscopy, cryogenic transmission electron microscopy, light scattering have been applied to characterize the micelle structures.
Hemicellulose block copolymers made from woods for wide-range directed self-assembly lithography enabling wider range of applicable patterning size

NASA Astrophysics Data System (ADS)

Morita, Kazuyo; Yamamoto, Kimiko

2017-03-01

Xylan, one of hemicellulose family, block copolymer was newly developed for wide-range directed self-assembly lithography (DSA). Xylan is higher hydrophilic material because of having many hydroxy groups in one molecule. It means that xylan block copolymer has a possibility of high-chi block copolymer. Generally, DSA is focused on microphase separation for smaller size with high-chi block copolymer and not well known for larger size. In this study, xylan block copolymer was confirmed enabling wider range of patterning size, from smaller size to larger size. The key of xylan block copolymer is a new molecular structure of block copolymer and sugar chain control technology. Sugar content is the important parameter for not only micro-phase separation property but also line edge roughness (LER) and defects. Based on the sugar control technology, wide-range (hp 8.3nm to 26nm L/S and CD 10nm to 51nm hole) DSA patterning was demonstrated. Additionally it was confirmed that xylan block copolymer is suitable for sequential infiltration synthesis (SIS) process.
Self Assembly of Hard, Space-Filling Polytopes

NASA Astrophysics Data System (ADS)

Schultz, Benjamin; Damasceno, Pablo; Engel, Michael; Glotzer, Sharon

2012-02-01

The thermodynamic behavior of systems of hard particles in the limit of infinite pressure is known to yield the densest possible packing [1,2]. Hard polytopes that tile or fill space in two or three spatial dimensions are guaranteed to obtain packing fractions of unity in the infinite pressure limit. Away from this limit, however, other structures may be possible [3]. We present the results of a simulation study of the thermodynamic self-assembly of hard, space-filling particles from disordered initial conditions. We show that for many polytopes, the infinite pressure structure readily assembles at intermediate pressures and packing fractions significantly less than one; in others, assembly of the infinite pressure structure is foiled by mesophases, jamming and phase separation. Common features of these latter systems are identified and strategies for enhancing assembly of the infinite pressure structure at intermediate pressures through building block modification are discussed.[4pt] [1] P. F. Damasceno, M. Engel, S.C. Glotzer arXiv:1109.1323v1 [cond-mat.soft][0pt] [2] A. Haji-Akbari, M. Engel, S.C. Glotzer arXiv:1106.4765v2 [cond-mat.soft][0pt] [3] U. Agarwal, F.A. Escobedo, Nature Materials 10, 230--235 (2011)
Self-Assembly and Crystallization of Hairy (f-Star) and DNA-Grafted Nanocubes

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

Knorowski, Christopher; Travesset, Alex

Nanoparticle superlattices are key to realizing many of the materials that will solve current technological challenges. Particularly important for their optical, mechanical or catalytic properties are superlattices of anisotropic (nonspherical) nanoparticles. The key challenge is how to program anisotropic nanoparticles to self-assemble into the relevant structures. In this Article, using numerical simulations, we show that “hairy” (f-star) or DNA grafted on nanocubes provides a general framework to direct the self-assembly into phases with crystalline, liquid crystalline, rotator, or noncrystalline phases with both long-range positional and orientational order. We discuss the relevance of these phases for engineering nanomaterials or micromaterials displayingmore » precise orientational order, realization of dry superlattices as well as for the field of programmed self-assembly of anisotropic nanoparticles in general.« less
Tuning the self-assembled 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol nanoarchitectures using the phase inversion method

NASA Astrophysics Data System (ADS)

Lai, Wei-Chi; Tseng, Shen-Jhen

2013-11-01

1,3:2,4-Di(3,4-dimethylbenzylidene) sorbitol (DMDBS) molecules can self-assemble into nanoscaled structures in organic solvents and polymer melts. The nanofibril structures were the mostly found. In this study, we used two phase inversion methods, i.e., dry and wet methods, to obtain different DMDBS nanoarchitectures. Poly(vinylidene fluoride) (PVDF) was chosen as polymer matrix, and the DMDBS structures were tuned by the process of PVDF membrane formation (crystallization and liquid-liquid demixing). When the membrane was prepared using the dry method, the DMDBS structure is controlled by the PVDF crystallization. Fewer DMDBS nanofibrils formed on the surfaces, and no nanofibrils were found in the cross-sections. On the other hand, when the membrane was prepared using the wet method, the liquid-liquid demixing (nonsolvent induced phase separation) occurred simultaneously as PVDF crystallized, and thus influenced the aggregation of DMDBS molecules. DMDBS is an amphiphilic molecule with two hydrophilic hydroxyl groups. The addition of nonsolvent (water) caused a large number of DMDBS molecules to aggregate outside the hydrophobic PVDF. In addition, a new structure "nanomat" was found. The mat was composed of DMDBS nanofibrils with diameters of 10-20 nm, similar to those observed in the dry method membranes. Fourier transform infra-red spectroscopy indicates that the DMDBS molecules self-assembled (aggregated) mainly through intermolecular hydrogen bonding in the presence of PVDF. The more intermolecular hydrogen bonding between DMDBS existed, the more excessive amounts of DMDBS molecules were, leading to the formation of nanomats.
Freezing-induced self-assembly of amphiphilic molecules

NASA Astrophysics Data System (ADS)

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

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

Freezing-induced self-assembly of amphiphilic molecules.

PubMed

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

2017-03-01

The self-assembly of amphiphilic molecules usually takes place in a liquid phase, near room temperature. Here, using small angle X-ray scattering (SAXS) experiments performed in real time, we show that freezing of aqueous solutions of copolymer amphiphilic molecules can induce self-assembly below 0 °C.
Colloidal Material Box: In-situ Observations of Colloidal Self-Assembly and Liquid Crystal Phase Transitions in Microgravity

NASA Astrophysics Data System (ADS)

Li, WeiBin; Lan, Ding; Sun, ZhiBin; Geng, BaoMing; Wang, XiaoQing; Tian, WeiQian; Zhai, GuangJie; Wang, YuRen

2016-05-01

To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg2Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.
Photoinitated charge separation in a hybrid titanium dioxide metalloporphyrin peptide material

NASA Astrophysics Data System (ADS)

Fry, H. Christopher; Liu, Yuzi; Dimitrijevic, Nada M.; Rajh, Tijana

2014-08-01

In natural systems, electron flow is mediated by proteins that spatially organize donor and acceptor molecules with great precision. Achieving this guided, directional flow of information is a desirable feature in photovoltaic media. Here, we design self-assembled peptide materials that organize multiple electronic components capable of performing photoinduced charge separation. Two peptides, c16-AHL3K3-CO2H and c16-AHL3K9-CO2H, self-assemble into fibres and provide a scaffold capable of binding a metalloporphyrin via histidine axial ligation and mineralize titanium dioxide (TiO2) on the lysine-rich surface of the resulting fibrous structures. Electron paramagnetic resonance studies of this self-assembled material under continuous light excitation demonstrate charge separation induced by excitation of the metalloporphyrin and mediated by the peptide assembly structure. This approach to dye-sensitized semiconducting materials offers a means to spatially control the dye molecule with respect to the semiconducting material through careful, strategic peptide design.
CHEMO/mechanical energy conversiona via supramolecular self-assembly

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

Lynn, David G.; Conticello, Vincent

With the assembly codes for protein/peptide self-assembly sufficiently developed to control these phases, we are positioned to address critical requirements for generating unique self-propagating functional assemblies such as chemical batteries and engines that can be used to extend the capability of living cells. These integrative functional assemblies can then be used within cells to create new functions that will address the world’s energy challenges.
Driving Forces of the Self-Assembly of Supramolecular Systems: Partially Ordered Mesophases

NASA Astrophysics Data System (ADS)

Shcherbina, M. A.; Chvalun, S. N.

2018-06-01

The main aspects are considered of the self-organization of a new class of liquid crystalline compounds, rigid sector-shaped and cone-shaped dendrons. Theoretical approaches to the self-assembly of different amphiphilic compounds (lipids, bolaamphiphiles, block copolymers, and polyelectrolytes) are described. Particular attention is given to the mesophase structures that emerge during the self-organization of mesophases characterized by intermediate degrees of ordering, e.g., plastic crystals, the rotation-crystalline phase in polymers, ordered and disordered two-dimensional columnar phases, and bicontinuous cubic phases of different symmetry.
Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions.

PubMed

Abraham, Alex; Chatterji, Apratim

2018-04-21

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.
Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions

NASA Astrophysics Data System (ADS)

Abraham, Alex; Chatterji, Apratim

2018-04-01

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.
Fully packed capillary electrochromatographic microchip with self-assembly colloidal silica beads.

PubMed

Park, Jongman; Lee, Dami; Kim, Won; Horiike, Shigeyoshi; Nishimoto, Takahiro; Lee, Se Hwan; Ahn, Chong H

2007-04-15

A fully packed capillary electrochromatographic (CEC) microchip showing improved solution and chip handling was developed. Microchannels for the CEC microchip were patterned on a cyclic olefin copolymer substrate by injection molding and packed fully with 0.8-microm monodisperse colloidal silica beads utilizing a self-assembly packing technique. The silica packed chip substrate was covered and thermally press-bonded. After fabrication, the chip was filled with buffer solution by self-priming capillary action. The self-assembly packing at each channel served as a built-in nanofilter allowing quick loading of samples and running buffer solution without filtration. Because of a large surface area-to-volume ratio of the silica packing, reproducible control of electroosmotic flow was possible without leveling of the solutions in the reservoirs resulting 1.3% rsd in migration rate. The capillary electrophoretic separation characteristics of the chip were studied using fluorescein isothiocyanate (FITC)-derivatized amino acids as probe molecules. A mixture of FITC and four FITC-derivatized amino acids was successfully separated with 2-mm separation channel length.
Understanding and Controlling Nanoscale Morphology in Self-Assembled Semiconducting Materials

NASA Astrophysics Data System (ADS)

Kang, Hyeyeon

Self-assembled semiconducting materials have been rapidly developed for a range of applications. This work aims to control the morphology of nanostructured semiconductors to understand how their functions arise from the structural properties. The first part of this dissertation focuses on the formation of a bulk-heterojunction (BHJ) in the active layer of organic photovoltaics (OPV). A BHJ is a bicontinuous interpenetrating network of organic components. The phase separation of the electron donor and the acceptor is required to achieve a BHJ structure in the nanostructured morphology, which promotes an efficient charge transportation. The use of solvent additive is one of the strategies to control the spontaneous phase separation during the film formation. Low vapor pressure solvent additives are introduced to a polymer casting solution in a sequentially processed OPV system, to study the swelling effect on the phase separation. In particular, the change in crystallinity and vertical mixing will be intensively studied upon polymer swelling. As another strategy, we introduce a molecular structure change to fullerene derivatives. A small structural variation leads to a large enough contrast of their surface energy, which is attributed to different vertical phase separation in the active layer. It eventually allows us to examine photovoltaic performance and device physics. In the second part, mesoporous inorganic films are investigated by preparation from a nanocrystal solution or sol-gel precursors for solar energy applications. Mesoporous nanocrystal-based titania is synthesized for inorganic/organic hybrid solar cells. The effect of surface modification is examined by anchoring a fullerene derivative on to titania surface. 3D interconnected mesoporous tantalum nitride films are prepared via sol-gel method as photoanodes in solar water splitting. The simple synthetic method using polymer template enables us to successfully prepare nitride films with excellent pore periodicity. The porous tantalum nitride film is examined with photoelectrochemical measurement to investigate the correlation between nanostructuring and photocatalytic activity. For the final part of this dissertation, porous cobalt ferrite and cadmium sulfide films are studied using ellipsometric porosimetry. Understanding the nature of their pores allows us to tune the intrinsic properties of the materials or prove the newly designed synthetic method.
Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems

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

Wasielewski, Michael R.

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 ofmore » 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.« less
Self-assembled Co-BaZrO 3 nanocomposite thin films with ultra-fine vertically aligned Co nanopillars

DOE PAGES

Huang, Jijie; Li, Leigang; Lu, Ping; ...

2017-05-11

A simple one-step pulsed laser deposition (PLD) method has been applied to grow self-assembled metal-oxide nanocomposite thin films. The as-deposited Co-BaZrO 3 films show high epitaxial quality with ultra-fine vertically aligned Co nanopillars (diameter <5 nm) embeded in BZO matrix. The diameter of the nanopillars can be further tuned by varying the deposition frequency. The metal and oxide phases grow separately without inter-diffusion or mixing. Taking advantage of this unique structure, a high saturation magnetization of ~1375 emu/cm 3 in the Co- BaZrO 3 nanocomposites has been achieved and further confirmed by Lorentz microscopy imaging in TEM. Furthermore, the coercivitymore » values of this nanocomposite thin films range from 600 Oe (20 Hz) to 1020 Oe (2 Hz), which makes the nanocomposite an ideal candidate for high-density perpendicular recording media.« less
Waveguide electro-optic modulators based on intrinsically polar self-assembled superlattices (SASs)

NASA Astrophysics Data System (ADS)

Liu, Zhifu; Ho, Seng Tiong; Chang, Seongsik; Zhao, Yiguang; Marks, Tobin J.; Kang, Hu; van der Boom, Milko E.; Zhu, Peiwang

2002-12-01

In this paper we describe methods of fabricating and characterizing organic electro-optic modulators based on intrinsically polar self-assembled superlattices. These structures are intrinsically acentric, and exhibit large second harmonic generation and electro-optic responses without the requirement of poling by an external electric field. A novel wet chemical protection-deprotection approach for the growth of self-assembled superlattices have been developed, and the refractive indices of self-assembled organic electro-optic superlattices may be tuned during the self-assembly process. Prototype electro-optic modulators based on chromophoric self-assembled superlattices have been designed and fabricated. The effective electro-optic coefficient of the self-assembled superlattice film in a phase modulator is estimated as about 20 pm/V at a wavelength of 1064 nm.
Self-assembling DNA nanotubes to connect molecular landmarks

NASA Astrophysics Data System (ADS)

Mohammed, Abdul M.; Šulc, Petr; Zenk, John; Schulman, Rebecca

2017-05-01

Within cells, nanostructures are often organized using local assembly rules that produce long-range order. Because these rules can take into account the cell's current structure and state, they can enable complexes, organelles or cytoskeletal structures to assemble around existing cellular components to form architectures. Although many methods for self-assembling biomolecular nanostructures have been developed, few can be programmed to assemble structures whose form depends on the identity and organization of structures already present in the environment. Here, we demonstrate that DNA nanotubes can grow to connect pairs of molecular landmarks with different separation distances and relative orientations. DNA tile nanotubes nucleate at these landmarks and grow while their free ends diffuse. The nanotubes can then join end to end to form stable connections, with unconnected nanotubes selectively melted away. Connections form between landmark pairs separated by 1-10 µm in more than 75% of cases and can span a surface or three dimensions. This point-to-point assembly process illustrates how self-assembly kinetics can be designed to produce structures with a desired physical property rather than a specific shape.
Memory effects in annealed hybrid gold nanoparticles/block copolymer bilayers

PubMed Central

2011-01-01

We report on the use of the self-organization process of sputtered gold nanoparticles on a self-assembled block copolymer film deposited by horizontal precipitation Langmuir-Blodgett (HP-LB) method. The morphology and the phase-separation of a film of poly-n-butylacrylate-block-polyacrylic acid (PnBuA-b-PAA) were studied at the nanometric scale by using atomic force microscopy (AFM) and Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS). The templating capability of the PnBuA-b-PAA phase-separated film was studied by sputtering gold nanoparticles (NPs), forming a film of nanometric thickness. The effect of the polymer chain mobility onto the organization of gold nanoparticle layer was assessed by heating the obtained hybrid PnBuA-b-PAA/Au NPs bilayer at T >Tg. The nanoparticles' distribution onto the different copolymer domains was found strongly affected by the annealing treatment, showing a peculiar memory effect, which modifies the AFM phase response of the Au NPs layer onto the polar domains, without affecting their surfacial composition. The effect is discussed in terms of the peculiar morphological features induced by enhanced mobility of polymer chains on the Au NPs layer. PMID:21711674
Ordered Nanostructured Amphiphile Self-Assembly Materials from Endogenous Nonionic Unsaturated Monoethanolamide Lipids in Water

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

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

2010-08-23

The self-assembly, solid state and lyotropic liquid crystalline phase behavior of a series of endogenous n-acylethanolamides (NAEs) with differing degrees of unsaturation, viz., oleoyl monoethanolamide, linoleoyl monoethanolamide, and linolenoyl monoethanolamide, have been examined. The studied molecules are known to possess inherent biological function. Both the monoethanolamide headgroup and the unsaturated hydrophobe are found to be important in dictating the self-assembly behavior of these molecules. In addition, all three molecules form lyotropic liquid crystalline phases in water, including the inverse bicontinuous cubic diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) phases. The ability of the NAE's to form inverse cubicmore » phases and to be dispersed into ordered nanostructured colloidal particles, cubosomes, in excess water, combined with their endogenous nature and natural medicinal properties, makes this new class of soft mesoporous amphiphile self-assembly materials suitable candidates for investigation in a variety of advanced multifunctional applications, including encapsulation and controlled release of therapeutic agents and incorporation of medical imaging agents.« less
Design, Synthesis, and Self-Assembly of Well-Defined Hybrid Materials Including Polymer Amphiphiles and Giant Tetrahedra Molecules Based on Poss Nanoparticles

NASA Astrophysics Data System (ADS)

Huang, Mingjun

"Bottom-up" techniques-based self-assembly are always attracting people's interests since this technology provides relatively low economic cost and fast route to construct organized structures at different scales. Considering unprecedented benefits from polymer materials, self-assemblies utilizing polymer building blocks have been extensively studied to achieve diverse hierarchical structures and various attractive properties. However, precise controls of chemical primary structures and compositions and exact constructions of hierarchal ordered structures in synthetic polymers are far from being fully appreciated. In this dissertation, a novel approach has been utilized to construct diverse well-defined nano-building blocks, giant molecules, via conjugating different, and functionalized molecular nanoparticles (MNPs) which are shape- and volume-persistent nano-objects with precise molecular structure and specific symmetry. The representative examples of the three basic categories of giant molecules, "giant polyhedra", "giant surfactants", and "giant shape amphiphiles" were discussed in details. First, a class of precisely defined, nanosized giant tetrahedra was constructed by placing different polyhedral oligomeric silsesquioxane (POSS) molecular nanoparticles at the vertices of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces accurate positional interactions and results in diverse selectively assembled, highly ordered supramolecular lattices including a Frank-Kasper (FK) A15 phase. The FK and quasicrystal phases are originally identified in metal alloys and only sporadically observed in soft matters. It remains unclear how to correlate their stability with the chemical composition and molecular topology in the self-assembling systems. We then for this purpose designed and studied the self-assembly phase transition sequences of four series of hybrid giant surfactants based on hydrophilic POSS cages tethered with one to four polystyrene (PS) tails. With increasing the number of tails, molecular topological variations not only affect phase boundaries in terms of the PS volume fraction, but also open a window to stabilize supramolecular FK and quasicrystal phases in the spherical phase region, demonstrating the critical role of molecular topology in dictating the formation of unconventional supramolecular lattices of "soft" spherical motifs. The FK A15 phase was even surprisingly observed in the giant shape amphiphile molecule, triphenylene-6BPOSS, which has a disk-like flat triphenylene core connected with six hydrophobic POSS cages by sides. Without conical molecular shape, triphenylene-6BPOSS self-assembled and stabilized into supramolecular sphere via pi-pi interactions through a completely different mechanism with precious two cases. These studies indicate that "bottom-up" self-assemble based on well-defined giant molecules approach can be rather powerful to fabricate usually complicated hierarchical structures and open up a wide field of supramolecular self-assembly with unexpected structure and properties.
Influence of Geometries on the Assembly of Snowman-Shaped Janus Nanoparticles.

PubMed

Kang, Chengjun; Honciuc, Andrei

2018-04-24

The self-assembly of micro/nanoparticles into suprastructures is a promising way to develop reconfigurable materials and to gain insights into the fundamental question of how matter organizes itself. The geometry of particles, especially those deviating from perfectly spherical shapes, is of significant importance in colloidal assembly because it influences the particle "recognition", determines the particle packing, and ultimately dictates the formation of assembled suprastructures. In order to organize particles into desired structures, it is of vital importance to understand the relationship between the shape of the colloidal building blocks and the assembled suprastructures. This fundamental issue is an enduring topic in the assembly of molecular surfactants, but it remained elusive in colloidal assembly. To address this issue, we use snowman-shaped Janus nanoparticles (JNPs) as a model to systematically study the effect of colloidal geometries on their assembled suprastructures. Ten types of JNPs with identical chemical compositions but with different geometries were synthesized. Specifically, the synthesized JNPs differ in their lobe size ratios, phase separation degrees, and overall sizes. We show that by altering these parameters, both finite suprastructures, such as capsules with different curvatures, and nonfinite suprastructures, including free-standing single-layered or double-layered JNPs sheets, can be obtained via self-assembly. All these different types of suprastructures are constituted by highly oriented and hexagonally packed JNPs. These findings demonstrate the significance of geometries in colloidal assembly, such that slightly changing the building block geometries could result in a large variety of very different assembled structures, without altering the chemistry of the particles.
An improved design of spiral tube assembly for separation of proteins by high-speed counter-current chromatography.

PubMed

Dasarathy, Dhweeja; Ito, Yoichiro

2015-10-30

A new spiral tube assembly was designed to improve the column capacity and partition efficiency for protein separation. This spiral tube assembly has greater column capacity than the original tubing because of an increase in radial grooves from 4 to 12 to accommodate more spiral layers and 12 narrow spots instead of 4 in each circular loop to interrupt the laminar flow that causes sample band broadening. Standard PTFE tubing (1.6mm ID) and the modified flat-twisted tubing were used as the separation column. The performances of both assemblies were compared for separating three stable test proteins including cytochrome c, myoglobin, and lysozyme using a two phase aqueous-aqueous solvent system composed of polyethylene glycol 1000 (12.5% w/w) and dibasic potassium phosphate (12.5% w/w). All samples were run at 1, 2, 3, and 5mL/min at both 800rpm and 1000rpm. The separation of these three protein samples produced high stationary phase retentions at 1, 2, and 3mL/min, yet separated efficiently at 5mL/min in 40min. After comparing the separation efficiency in terms of the peak resolutions, theoretical plate numbers, and separation times, it was determined that the flat-twisted tubing was more effective in separating these protein samples. In order to validate the efficacy of this novel assembly, a mixture of five protein samples (cytochrome c, myoglobin, ovalbumin, lysozyme, and hemoglobin) were separated, under the optimal conditions established with these three protein samples, at 1mL/min with a revolution speed of 1000rpm. There were high stationary phase retentions of around 60%, with effective separations, demonstrating the efficiency of the flat-twisted spiral tube assembly. The separation time of 6h was a limitation but can potentially be shortened by improving the strength of the column that will permit an increase in revolution speed and flow rate. This novel spiral separation column will allow rapid and efficient separation of mixtures with high yield of the constituent components. Published by Elsevier B.V.
Self-organization of a wedge-shaped surfactant in monolayers and multilayers.

PubMed

Cain, Nicholas; Van Bogaert, Josh; Gin, Douglas L; Hammond, Scott R; Schwartz, Daniel K

2007-01-16

The self-organization behavior of a wedge-shaped surfactant, disodium-3,4,5-tris(dodecyloxy)phenylmethylphosphonate, was studied in Langmuir monolayers (at the air-water interface), Langmuir-Blodgett (LB) monolayers and multilayers, and films adsorbed spontaneously from isooctane solution onto a mica substrate (self-assembled films). This compound forms an inverted hexagonal lyotropic liquid crystal phase in the bulk and in thick adsorbed films. Surface pressure isotherm and Brewster angle microscope (BAM) studies of Langmuir monolayers revealed three phases: gas (G), liquid expanded (LE), and liquid condensed (LC). The surface pressure-temperature phase diagram was determined in detail; a triple point was found at approximately 10 degrees C. Atomic force microscope (AFM) images of LB monolayers transferred from various regions of the phase diagram were consistent with the BAM images and indicated that the LE regions are approximately 0.5 nm thinner than the LC regions. AFM images were also obtained of self-assembled films after various adsorption times. For short adsorption times, when monolayer self-assembly was incomplete, the film topography indicated the coexistence of two distinct monolayer phases. The height difference between these two phases was again 0.5 nm, suggesting a correspondence with the LE/LC coexistence observed in the Langmuir monolayers. For longer immersion times, adsorbed multilayers assembled into highly organized periodic arrays of inverse cylindrical micelles. Similar periodic structures, with the same repeat distance of 4.5 nm, were also observed in three-layer LB films. However, the regions of organized periodic structure were much smaller and more poorly correlated in the LB multilayers than in the films adsorbed from solution. Collectively, these observations indicate a high degree of similarity between the molecular organization in Langmuir layers/LB films and adsorbed self-assembled films. In both cases, monolayers progress through an LE phase, into LE/LC coexistence, and finally into LC phase as surface density increases. Following the deposition of an additional bilayer, the film reorganizes to form an array of inverted cylindrical micelles.
Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

PubMed

Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

2018-04-11

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies

NASA Astrophysics Data System (ADS)

Fèvre, Mathieu; Le Bouar, Yann; Finel, Alphonse

2018-05-01

The aim of this paper is to investigate the consequences of finite-size effects on the thermodynamics of nanoparticle assemblies and isolated particles. We consider a binary phase-separating alloy with a negligible atomic size mismatch, and equilibrium states are computed using off-lattice Monte Carlo simulations in several thermodynamic ensembles. First, a semi-grand-canonical ensemble is used to describe infinite assemblies of particles with the same size. When decreasing the particle size, we obtain a significant decrease of the solid/liquid transition temperatures as well as a growing asymmetry of the solid-state miscibility gap related to surface segregation effects. Second, a canonical ensemble is used to analyze the thermodynamic equilibrium of finite monodisperse particle assemblies. Using a general thermodynamic formulation, we show that a particle assembly may split into two subassemblies of identical particles. Moreover, if the overall average canonical concentration belongs to a discrete spectrum, the subassembly concentrations are equal to the semi-grand-canonical equilibrium ones. We also show that the equilibrium of a particle assembly with a prescribed size distribution combines a size effect and the fact that a given particle size assembly can adopt two configurations. Finally, we have considered the thermodynamics of an isolated particle to analyze whether a phase separation can be defined within a particle. When studying rather large nanoparticles, we found that the region in which a two-phase domain can be identified inside a particle is well below the bulk phase diagram, but the concentration of the homogeneous core remains very close to the bulk solubility limit.
Self-assembled nanomaterials for photoacoustic imaging

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

PubMed

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

2016-02-07

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

NASA Astrophysics Data System (ADS)

Parnell, Andrew

The vibrancy and variety of structural color found in nature has long been well-known; what has only recently been discovered is the sophistication of the physics that underlies these effects. In the talk I will discuss some of our recent studies of the structures responsible for color in bird feathers and beetle elytra, based on structural characterization using small angle x-ray scattering, x-ray tomography and optical modeling. These have enabled us to study a large number of structural color exhibiting materials and look for trends in the structures nature uses to provide these optical effects. In terms of creating the optical structure responsible for the color of the Eurasian Jay feathers (Garrulus glandarius) the nanostructure is produced by a phase-separation process that is arrested at a late stage; mastery of the color is achieved by control over the duration of this phase-separation process. Our analysis shows that nanostructure in single bird feather barbs can be varied continuously by controlling the time the keratin network is allowed to phase separate before mobility in the system is arrested. Dynamic scaling analysis of the single barb scattering data implies that the phase separation arrest mechanism is rapid and also distinct from the spinodal phase separation mechanism i.e. it is not gelation or intermolecular re-association. Any growing lengthscale using this spinodal phase separation approach must first traverse the UV and blue wavelength regions, growing the structure by coarsening, resulting in a broad distribution of domain sizes. AJP acknowledges financial support via the APS/DPOLY exchange lectureship 2017.
Formation and Maturation of Phase Separated Liquid Droplets by RNA Binding Proteins

PubMed Central

Lin, Yuan; Protter, David S. W.; Rosen, Michael K.; Parker, Roy

2015-01-01

Eukaryotic cells possess numerous dynamic membrane-less organelles, RNP granules, enriched in RNA and RNA binding proteins containing disordered regions. We demonstrate that the disordered regions of key RNP granule components, and the full-length granule protein hnRNPA1, can phase separate in vitro, producing dynamic liquid droplets. Phase separation is promoted by low salt concentrations or RNA. Over time, the droplets mature to more stable states, as assessed by slowed fluorescence recovery after photobleaching and resistance to salt. Maturation often coincides with formation of fibrous structures. Different disordered domains can co-assemble into phase-separated droplets. These biophysical properties demonstrate a plausible mechanism by which interactions between disordered regions, coupled with RNA binding, could contribute to RNP granule assembly in vivo through promoting phase separation. Progression from dynamic liquids to stable fibers may be regulated to produce cellular structures with diverse physiochemical properties and functions. Misregulation could contribute to diseases involving aberrant RNA granules. PMID:26412307
When lithography meets self-assembly: a review of recent advances in the directed assembly of complex metal nanostructures on planar and textured surfaces

NASA Astrophysics Data System (ADS)

Hughes, Robert A.; Menumerov, Eredzhep; Neretina, Svetlana

2017-07-01

One of the foremost challenges in nanofabrication is the establishment of a processing science that integrates wafer-based materials, techniques, and devices with the extraordinary physicochemical properties accessible when materials are reduced to nanoscale dimensions. Such a merger would allow for exacting controls on nanostructure positioning, promote cooperative phenomenon between adjacent nanostructures and/or substrate materials, and allow for electrical contact to individual or groups of nanostructures. With neither self-assembly nor top-down lithographic processes being able to adequately meet this challenge, advancements have often relied on a hybrid strategy that utilizes lithographically-defined features to direct the assembly of nanostructures into organized patterns. While these so-called directed assembly techniques have proven viable, much of this effort has focused on the assembly of periodic arrays of spherical or near-spherical nanostructures comprised of a single element. Work directed toward the fabrication of more complex nanostructures, while still at a nascent stage, has nevertheless demonstrated the possibility of forming arrays of nanocubes, nanorods, nanoprisms, nanoshells, nanocages, nanoframes, core-shell structures, Janus structures, and various alloys on the substrate surface. In this topical review, we describe the progress made in the directed assembly of periodic arrays of these complex metal nanostructures on planar and textured substrates. The review is divided into three broad strategies reliant on: (i) the deterministic positioning of colloidal structures, (ii) the reorganization of deposited metal films at elevated temperatures, and (iii) liquid-phase chemistry practiced directly on the substrate surface. These strategies collectively utilize a broad range of techniques including capillary assembly, microcontact printing, chemical surface modulation, templated dewetting, nanoimprint lithography, and dip-pen nanolithography and employ a wide scope of chemical processes including redox reactions, alloying, dealloying, phase separation, galvanic replacement, preferential etching, template-mediated reactions, and facet-selective capping agents. Taken together, they highlight the diverse toolset available when fabricating organized surfaces of substrate-supported nanostructures.
Local Crystalline Structure in an Amorphous Protein Dense Phase

PubMed Central

Greene, Daniel G.; Modla, Shannon; Wagner, Norman J.; Sandler, Stanley I.; Lenhoff, Abraham M.

2015-01-01

Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein. PMID:26488663
Functional Nanostructured Materials Based on Polymerized Surfactant Liquid Crystal Assemblies Liquid Crystal Assemblies

NASA Astrophysics Data System (ADS)

Gin, Douglas

2003-03-01

The development of materials with controlled nanostructures is one of the most important new areas of scientific research in chemistry and engineering. Our research group has developed a novel approach for making nanostructured polymer materials with unique functional properties using liquid crystals as starting materials. In this approach, we design polymerizable organic building blocks based on lyotropic liquid crystals (LLCs) (i.e., amphiphiles or surfactants) that carry, or can accommodate, a functional property of general interest. Through appropriate molecular design, these monomers self-assemble in the presence of water into fluid, yet ordered phase-separated, water-hydrocarbon assemblies with predictable nanoscale geometries. The architectures of these LLC phases can range from stacked two-dimensional lamellae to hexagonally ordered cylindrical channels with uniform feature sizes in the 1-10 nm range. These LLC phases are then photopolymerized into robust polymer networks with preservation of their small-scale structures. This approach allows us to investigate the effect of nanometer-scale architecture on important bulk properties, as well as to engineer chemical environments on the nanometer-scale for several areas of application. In this talk, new functional materials based on the polymerization of the lyotropic inverted hexagonal phase will be presented as one example of our general approach. Issues in the design and photopolymerization of functional amphiphilic monomers that adopt this LC architecture will be discussed. More importantly, the use of the resulting nanostructured polymer networks in three areas of application will be presented: (1) as templates for the synthesis of functional nanocomposites; (2) as tunable heterogeneous catalysts, and (3) as nanoporous membrane and separation media. In particular, issues pertaining to the contribution of nanoscale architecture to the performance of these systems will be highlighted. Opportunities for tailoring the nanoscale chemical environment and architecture of these materials through molecular design will be presented. Finally, the development of methods for controlling macroscopic orientation through processing will also be discussed.
Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

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

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less
Synthesis of monodisperse silica microspheres and modification with diazoresin for mixed-mode ultra high performance liquid chromatography separations.

PubMed

Cong, Hailin; Yu, Bing; Tian, Chao; Zhang, Shuai; Yuan, Hua

2017-11-01

Monodisperse silica particles with average diameters of 1.9-2.9 μm were synthesized by a modified Stöber method, in which tetraethyl orthosilicate was continuously supplied to the reaction mixture containing KCl electrolyte, water, ethanol, and ammonia. The obtained silica particles were modified by self-assembly with positively charged photosensitive diazoresin on the surface. After treatment with ultraviolet light, the ionic bonding between silica and diazoresin was converted into covalent bonding through a unique photochemistry reaction of diazoresin. Depending on the chemical structure of diazoresin and mobile phase composition, the diazoresin-modified silica stationary phase showed different separation mechanisms, including reversed phase and hydrophilic interactions. Therefore, a variety of baseline separation of benzene analogues and organic acids was achieved by using the diazoresin-modified silica particles as packing materials in ultra high performance liquid chromatography. According to the π-π interactional difference between carbon rings of fullerenes and benzene rings of diazoresin, C 60 and C 70 were also well separated by ultra-high performance liquid chromatography. Because it has a small size, the ∼2.5 μm monodisperse diazoresin-modified silica stationary phase shows ultra-high efficiency compared with the commercial C 18 -silica high-performance liquid chromatography stationary phase with average diameters of ∼5 μm. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Self-assembly and electrostriction of arrays and chains of hopfion particles in chiral liquid crystals

PubMed Central

Ackerman, Paul J.; van de Lagemaat, Jao; Smalyukh, Ivan I.

2015-01-01

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains that exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields. PMID:25607778
Hierarchical Self-Organization of Perylene Bisimides into Supramolecular Spheres and Periodic Arrays Thereof.

PubMed

Sahoo, Dipankar; Peterca, Mihai; Aqad, Emad; Partridge, Benjamin E; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Percec, Virgil

2016-11-09

Perylene bisimide derivatives (PBIs) are known to form only columnar or lamellar assemblies. There is no known example of a PBI self-assembling into a supramolecular sphere. Therefore, periodic and quasiperiodic arrays generated from spherical assemblies produced from PBIs are also not known. Here, a PBI functionalized at its imide groups with a second generation self-assembling dendron is reported to self-assemble into supramolecular spheres. These spheres self-organize in a body-centered cubic (BCC) periodic array, rarely encountered for self-assembling dendrons but often encountered in block copolymers. These supramolecular spheres also assemble into a columnar hexagonal array in which the supramolecular columns are unexpectedly and unprecedentedly made from spheres. At lower temperature, two additional columnar hexagonal phases consisting of symmetric and asymmetric tetrameric crowns of PBI are observed. Structural and retrostructural analysis via X-ray diffraction (XRD), molecular modeling, molecular simulation, and solid state NMR suggests that inversion of the symmetric tetrameric crowns at high temperature mediates their transformation into supramolecular spheres. The tetrameric crowns of PBIs are able to form an isotropic sphere in the cubic phase due to rapid molecular motion at high temperature, unobservable by XRD but demonstrated by solid state NMR studies. This mechanism of hierarchical self-organization of PBI into supramolecular spheres is most probably general and can be applied to other related planar molecules to generate new functions.
Ultrahigh-density sub-10 nm nanowire array formation via surface-controlled phase separation.

PubMed

Tian, Yuan; Mukherjee, Pinaki; Jayaraman, Tanjore V; Xu, Zhanping; Yu, Yongsheng; Tan, Li; Sellmyer, David J; Shield, Jeffrey E

2014-08-13

We present simple, self-assembled, and robust fabrication of ultrahigh density cobalt nanowire arrays. The binary Co-Al and Co-Si systems phase-separate during physical vapor deposition, resulting in Co nanowire arrays with average diameter as small as 4.9 nm and nanowire density on the order of 10(16)/m(2). The nanowire diameters were controlled by moderating the surface diffusivity, which affected the lateral diffusion lengths. High resolution transmission electron microscopy reveals that the Co nanowires formed in the face-centered cubic structure. Elemental mapping showed that in both systems the nanowires consisted of Co with undetectable Al or Si and that the matrix consisted of Al with no distinguishable Co in the Co-Al system and a mixture of Si and Co in the Co-Si system. Magnetic measurements clearly indicate anisotropic behavior consistent with shape anisotropy. The dynamics of nanowire growth, simulated using an Ising model, is consistent with the experimental phase and geometry of the nanowires.
Self-assembly of ordered nanostructures

NASA Astrophysics Data System (ADS)

Yin, Jinsong

2000-10-01

Several different kinds of nanostructure materials were studied in this thesis: self-assembled monodispersive nanocrystals, photonic crystals, ordered mesoporous silica and hierarchically ordered nanostructured materials. Tetrahedral nanocrystals of CoO, with edge-lengths of 4.4 +/- 0.2 nm, were synthesized at high purity and monodispersity. The size, shape and phase selections of the nanocrystals were performed using a novel magnetic field separation technique. These nanocrystals behave like molecules, forming a face-centered cubic self-assembly of nanocrystal superlattices. In-situ behavior of self-assembled CoO nanocrystal arrays was also analyzed using transmission electron microscopy and associated techniques. The surface passivation layer started to evaporate/decompose at temperatures as low as ˜200°C, but the exposed cores of nanocrystals preserved the geometrical configuration of the assembly due to the strong adhesion of the carbon substrate. As the temperature is further increased from 300 to 600°C, the intrinsic crystal structure of the CoO nanoparticles experiences a replacement reaction, resulting in the formation of cobalt carbides. Two-dimensional self-assembling of cobalt nanocrystals with an average particle size of 9.2 nm and polydispersity of 9% is processed. Phtonic crystals were processed by a template-assisted method. Ordered self-assembly of pores of titania nanocrystals formed a face-centered cubic packing structure. The walls of the pores were made of anatase nanocrystals of ˜8 nm in diameter. Cobalt can be doped into the walls of the pores by solution infiltration of cobalt carbonyl. Cobalt titanium oxide may be formed on the internal surface of the ordered pore structure. This type of structure is likely to be an excellent supporting material for catalysis. The experimental results suggest that transition metal elements can be incorporated into porous titania without blocking the interconnected pores. Hierarchically ordered nanostructured materials with high porosity at dual length-scale were prepared by a single annealing procedure. The plasma energy of this porous materials shifts about 1.2 eV to lower energy, compared to the fully densed silica spheres. This type of material is expected to have not only large surface area for catalysis, but also low dielectric constant for low-loss dielectric applications.
Directed Self-Assembly of Star-Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism.

PubMed

Krishnan, Mohan Raj; Lu, Kai-Yuan; Chiu, Wen-Yu; Chen, I-Chen; Lin, Jheng-Wei; Lo, Ting-Ya; Georgopanos, Prokopios; Avgeropoulos, Apostolos; Lee, Ming-Chang; Ho, Rong-Ming

2018-04-01

Exploring the ordering mechanism and dynamics of self-assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self-assembling mechanism and kinetics of silicon-containing 3-arm star-block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self-assembly using topographically patterned substrates. The ordering process of the star-block copolymer within fabricated topographic patterns with PS-functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well-ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self-assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top-down and bottom-up approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
High quality factor whispering gallery modes from self-assembled hexagonal GaN rods grown by metal-organic vapor phase epitaxy.

PubMed

Tessarek, C; Sarau, G; Kiometzis, M; Christiansen, S

2013-02-11

Self-assembled GaN rods were grown on sapphire by metal-organic vapor phase epitaxy using a simple two-step method that relies first on a nitridation step followed by GaN epitaxy. The mask-free rods formed without any additional catalyst. Most of the vertically aligned rods exhibit a regular hexagonal shape with sharp edges and smooth sidewall facets. Cathodo- and microphotoluminescence investigations were carried out on single GaN rods. Whispering gallery modes with quality factors greater than 4000 were measured demonstrating the high morphological and optical quality of the self-assembled GaN rods.
The unusual dynamics of parasite actin result from isodesmic polymerization

PubMed Central

Skillman, Kristen M.; Ma, Christopher I.; Fremont, Daved H.; Diraviyam, Karthikeyan; Cooper, John A.; Sept, David; Sibley, L. David

2013-01-01

Previous reports have indicated that parasite actins are short and inherently unstable, despite being required for motility. Here, we re-examine the polymerization properties of actin in Toxoplasma gondii (TgACTI), unexpectedly finding that it exhibits isodesmic polymerization in contrast to the conventional nucleation-elongation process of all previously studied actins from both eukaryotes and bacteria. TgACTI polymerization kinetics lacks both a lag phase and critical concentration, normally characteristic of actins. Unique among actins, the kinetics of assembly can be fit with a single set of rate constants for all subunit interactions, without need for separate nucleation and elongation rates. This isodesmic model accurately predicts the assembly, disassembly, and the size distribution of TgACTI filaments in vitro, providing a mechanistic explanation for actin dynamics in vivo. Our findings expand the repertoire of mechanisms by which actin polymerization is governed and offer clues about the evolution of self-assembling, stabilized protein polymers. PMID:23921463
Recent highlights in electro-driven separations- selected applications of alkylthiol gold nanoparticles in capillary electrophoresis and capillary electro-chromatography.

PubMed

Guihen, Elizabeth

2017-09-01

To date, alkylthiol gold nanoparticles (AuNPs) have been widely used in electro-chromatographic separation techniques as a viable alternative to traditional stationary phases. This is mainly due to their stability, chemical inertness, ease of functionality, increased phase ratio, ability to form self-assembled monolayers. They also yield versatile stationary phases with highly specific targeted functionalities. At the nanoscale region, the chemical and physical properties of a molecule display different attributes to that of the parent molecules or material, hence these features can be harnessed in electro-driven chromatographic separations. Application areas illustrating the use of AuNPs in separation science continue to grow and expand to cover many different kinds of analysis. The last decade has witnessed a successful trend in miniaturisation of chemical separation systems toward the micro and nanoscale ranges. Nanoparticle-based stationary phases fit well with performing chemical separations on microfluidic and capillary platforms. In this review the theory of the use of alkylthiol gold nanoparticles in electro-chromatographic driven separation methods will be discussed. This will be followed by details of recent and selected applications showing alkylthiol gold nanoparticles in capillary electrophoretic and open-tubular electro-chromatographic separations. This review will focus solely on alkylthiol based gold nanoparticles, therefore other kinds of chemical moieties bonded to gold nanoparticles are outside the scope of this review. Finally the future outlook of this exciting technology will be outlined in some detail in the final section. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Self-interaction of NPM1 modulates multiple mechanisms of liquid-liquid phase separation.

PubMed

Mitrea, Diana M; Cika, Jaclyn A; Stanley, Christopher B; Nourse, Amanda; Onuchic, Paulo L; Banerjee, Priya R; Phillips, Aaron H; Park, Cheon-Gil; Deniz, Ashok A; Kriwacki, Richard W

2018-02-26

Nucleophosmin (NPM1) is an abundant, oligomeric protein in the granular component of the nucleolus with roles in ribosome biogenesis. Pentameric NPM1 undergoes liquid-liquid phase separation (LLPS) via heterotypic interactions with nucleolar components, including ribosomal RNA (rRNA) and proteins which display multivalent arginine-rich linear motifs (R-motifs), and is integral to the liquid-like nucleolar matrix. Here we show that NPM1 can also undergo LLPS via homotypic interactions between its polyampholytic intrinsically disordered regions, a mechanism that opposes LLPS via heterotypic interactions. Using a combination of biophysical techniques, including confocal microscopy, SAXS, analytical ultracentrifugation, and single-molecule fluorescence, we describe how conformational changes within NPM1 control valency and switching between the different LLPS mechanisms. We propose that this newly discovered interplay between multiple LLPS mechanisms may influence the direction of vectorial pre-ribosomal particle assembly within, and exit from the nucleolus as part of the ribosome biogenesis process.
Cooperativity in self-limiting equilibrium self-associating systems

NASA Astrophysics Data System (ADS)

Freed, Karl F.

2012-11-01

A wide variety of highly cooperative self-assembly processes in biological and synthetic systems involve the assembly of a large number (m) of units into clusters, with m narrowly peaked about a large size m0 ≫ 1 and with a second peak centered about the m = 1 unassembled monomers. While very specific models have been proposed for the assembly of, for example, viral capsids and core-shell micelles of ß-casein, no available theory describes a thermodynamically general mechanism for this double peaked, highly cooperative equilibrium assembly process. This study provides a general mechanism for these cooperative processes by developing a minimal Flory-Huggins type theory. Beginning from the simplest non-cooperative, free association model in which the equilibrium constant for addition of a monomer to a cluster is independent of cluster size, the new model merely allows more favorable growth for clusters of intermediate sizes. The theory is illustrated by computing the phase diagram for cases of self-assembly on cooling or heating and for the mass distribution of the two phases.

RNA transcription modulates phase transition-driven nuclear body assembly

PubMed Central

Berry, Joel; Weber, Stephanie C.; Vaidya, Nilesh; Haataja, Mikko; Brangwynne, Clifford P.

2015-01-01

Nuclear bodies are RNA and protein-rich, membraneless organelles that play important roles in gene regulation. The largest and most well-known nuclear body is the nucleolus, an organelle whose primary function in ribosome biogenesis makes it key for cell growth and size homeostasis. The nucleolus and other nuclear bodies behave like liquid-phase droplets and appear to condense from the nucleoplasm by concentration-dependent phase separation. However, nucleoli actively consume chemical energy, and it is unclear how such nonequilibrium activity might impact classical liquid–liquid phase separation. Here, we combine in vivo and in vitro experiments with theory and simulation to characterize the assembly and disassembly dynamics of nucleoli in early Caenorhabditis elegans embryos. In addition to classical nucleoli that assemble at the transcriptionally active nucleolar organizing regions, we observe dozens of “extranucleolar droplets” (ENDs) that condense in the nucleoplasm in a transcription-independent manner. We show that growth of nucleoli and ENDs is consistent with a first-order phase transition in which late-stage coarsening dynamics are mediated by Brownian coalescence and, to a lesser degree, Ostwald ripening. By manipulating C. elegans cell size, we change nucleolar component concentration and confirm several key model predictions. Our results show that rRNA transcription and other nonequilibrium biological activity can modulate the effective thermodynamic parameters governing nucleolar and END assembly, but do not appear to fundamentally alter the passive phase separation mechanism. PMID:26351690
Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

DOE PAGES

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

2016-07-19

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less
Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

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

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less
Rational Self-Assembly of Nano-Colloids using DNA Interaction

NASA Astrophysics Data System (ADS)

Ung, Marie T.; Scarlett, Raynaldo; Sinno, Talid R.; Crocker, John C.

2010-03-01

DNA is an attractive tool to direct the rational self-assembly of nano-colloids since its interaction is specific and reversible. This tunable attractive interaction should lead to a diverse and rich phase diagram of higher ordered structures which would not otherwise be entropically favored.footnotetextTkachenko AV, Morphological Diversity of DNA-Colloidal Self-Assembly, Phys. Rev. Lett 89 (2002) We compare our latest experimental observations to a simulation framework that precisely replicates the experimental phase behavior and the crystal growth kinetics.footnotetextKim AJ, Scarlett R., Biancaniello PL, Sinno T, Crocker JC, Probing interfacial equilibration in microsphere crystals formed by DNA-directed assembly, Nature Materials 8, 52-55 (2009) We will discuss the crystallography of novel structures and address how particle size and heterogeneity affect nucleation and growth rates.
Spiral Countercurrent Chromatography

PubMed Central

Ito, Yoichiro; Knight, Martha; Finn, Thomas M.

2013-01-01

For many years, high-speed countercurrent chromatography conducted in open tubing coils has been widely used for the separation of natural and synthetic compounds. In this method, the retention of the stationary phase is solely provided by the Archimedean screw effect by rotating the coiled column in the centrifugal force field. However, the system fails to retain enough of the stationary phase for polar solvent systems such as the aqueous–aqueous polymer phase systems. To address this problem, the geometry of the coiled channel was modified to a spiral configuration so that the system could utilize the radially acting centrifugal force. This successfully improved the retention of the stationary phase. Two different types of spiral columns were fabricated: the spiral disk assembly, made by stacking multiple plastic disks with single or four interwoven spiral channels connected in series, and the spiral tube assembly, made by inserting the tetrafluoroethylene tubing into a spiral frame (spiral tube support). The capabilities of these column assemblies were successfully demonstrated by separations of peptides and proteins with polar two-phase solvent systems whose stationary phases had not been well retained in the earlier multilayer coil separation column for high-speed countercurrent chromatography. PMID:23833207
Naturally engineered glycolipid biosurfactants leading to distinctive self-assembled structures.

PubMed

Imura, Tomohiro; Ohta, Noboru; Inoue, Katsuaki; Yagi, Naoto; Negishi, Hideyuki; Yanagishita, Hiroshi; Kitamoto, Dai

2006-03-08

Self-assembling properties of "natural" glycolipid biosurfactants, mannosyl-erythritol lipids A and B (MEL-A, MEL-B), which are abundantly produced from yeast strains, were investigated by using the fluorescence-probe method, dynamic light-scattering (DLS) analysis, freeze-fracture transmission electron microscopy (FF-TEM), and synchrotron small/wide-angle X-ray scattering (SAXS/WAXS) analysis, among other methods. Both MEL-A and MEL-B exhibit excellent self-assembly properties at extremely low concentrations; they self-assemble into large unilamellar vesicles (LUV) just above their critical-aggregation concentration (CAC). The CAC(I) value was found to be 4.0x10(-6) M for MEL-A and 6.0x10(-6) M for MEL-B. Moreover, the self-assembled structure of MEL-A above a CAC(II) value of 2.0x10(-5) M was found to drastically change into sponge structures (L3) composed of a network of randomly connected bilayers that are usually obtained from a complicated multicomponent "synthetic" surfactant system. Interestingly, the average water-channel diameter of the sponge structure was 100 nm. This is relatively large compared with those obtained from "synthetic" surfactant systems. In addition, MEL-B, which has a hydroxyl group at the C-4' position on mannose instead of an acetyl group, gives only one CAC; the self-assembled structure of MEL-B seems to gradually move from LUV to multilamellar vesicles (MLV) with lattice constants of 4.4 nm, depending on the concentration. Furthermore, the lyotropic-liquid-crystal-phase observation at high concentrations demonstrates the formation of an inverted hexagonal phase (H2) for MEL-A, together with a lamella phase (L(alpha)) for MEL-B, indicating a difference between MEL-A and MEL-B molecules in the spontaneous curvature of the assemblies. These results clearly show that the difference in spontaneous curvature caused by the single acetyl group on the head group probably decides the direction of self-assembly of glycolipid biosurfactants. The unique and complex molecular structures with several chiral centers that are molecularly engineered by microorganisms must have led to the sophisticated self-assembling properties of the glycolipid biosurfactants.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Amdursky, Nadav; Gazit, Ehud; Rosenman, Gil, E-mail: gilr@eng.tau.ac.il

Highlights: Black-Right-Pointing-Pointer We observe lag-phase crystallization process in insulin. Black-Right-Pointing-Pointer The crystallization is a result of the formation of higher order oligomers. Black-Right-Pointing-Pointer The crystallization also changes the secondary structure of the protein. Black-Right-Pointing-Pointer The spectroscopic signature can be used for amyloid inhibitors assay. -- Abstract: Insulin, as other amyloid proteins, can form amyloid fibrils at certain conditions. The self-assembled aggregation process of insulin can result in a variety of conformations, starting from small oligomers, going through various types of protofibrils, and finishing with bundles of fibrils. One of the most common consensuses among the various self-assembly processes that aremore » suggested in the literature is the formation of an early stage nucleus conformation. Here we present an additional insight for the self-assembly process of insulin. We show that at the early lag phase of the process (prior to fibril formation) the insulin monomers self-assemble into ordered nanostructures. The most notable feature of this early self-assembly process is the formation of nanocrystalline nucleus regions with a strongly bound electron-hole confinement, which also change the secondary structure of the protein. Each step in the self-assembly process is characterized by an optical spectroscopic signature, and possesses a narrow size distribution. By following the spectroscopic signature we can measure the potency of amyloid fibrils inhibitors already at the lag phase. We further demonstrate it by the use of epigallocatechin gallate, a known inhibitor for insulin fibrils. The findings can result in a spectroscopic-based application for the analysis of amyloid fibrils inhibitors.« less
Catalytic diversity in self-propagating peptide assemblies

NASA Astrophysics Data System (ADS)

Omosun, Tolulope O.; Hsieh, Ming-Chien; Childers, W. Seth; Das, Dibyendu; Mehta, Anil K.; Anthony, Neil R.; Pan, Ting; Grover, Martha A.; Berland, Keith M.; Lynn, David G.

2017-08-01

The protein-only infectious agents known as prions exist within cellular matrices as populations of assembled polypeptide phases ranging from particles to amyloid fibres. These phases appear to undergo Darwinian-like selection and propagation, yet remarkably little is known about their accessible chemical and biological functions. Here we construct simple peptides that assemble into well-defined amyloid phases and define paracrystalline surfaces able to catalyse specific enantioselective chemical reactions. Structural adjustments of individual amino acid residues predictably control both the assembled crystalline order and their accessible catalytic repertoire. Notably, the density and proximity of the extended arrays of enantioselective catalytic sites achieve template-directed polymerization of new polymers. These diverse amyloid templates can now be extended as dynamic self-propagating templates for the construction of even more complex functional materials.
Competing processes of micellization and fibrillization in native and reduced casein proteins.

PubMed

Portnaya, Irina; Avni, Sharon; Kesselman, Ellina; Boyarski, Yoav; Sukenik, Shahar; Harries, Daniel; Dan, Nily; Cogan, Uri; Danino, Dganit

2016-08-10

Kappa-casein (κCN) and beta-casein (βCN) are disordered proteins present in mammalian milk. In vitro, βCN self-assembles into core-shell micelles. κCN self assembles into similar micelles, as well as into amyloid-like fibrils. Recent studies indicate that fibrillization can be suppressed by mixing βCN and κCN, but the mechanism of fibril inhibition has not been identified. Examining the interactions of native and reduced kappa-caseins (N-κCN and R-κCN) with βCN, we expose a competition between two different self-assembly processes: micellization and fibrillization. Quite surprisingly, however, we find significant qualitative and quantitative differences in the self-assembly between the native and reduced κCN forms. Specifically, thermodynamic analysis reveals exothermic demicellization for βCN and its mixtures with R-κCN, as opposed to endothermic demicellization of N-κCN and its mixtures with βCN at the same temperature. Furthermore, with time, R-κCN/βCN mixtures undergo phase separation into pure βCN micelles and R-κCN fibrils, while in the N-κCN/βCN mixtures fibril formation is considerably delayed and mixed micelles persist for longer periods of time. Fibrils formed in N-κCN/βCN mixtures are shorter and more flexible than those formed in R-κCN/βCN systems. Interestingly, in the N-κCN/βCN mixtures, the sugar moieties of N-κCN oligomers seem to organize on the mixed micelles surface in a manner similar to the organization of κCN in milk casein micelles.
Optical critical dimension metrology for directed self-assembly assisted contact hole shrink

NASA Astrophysics Data System (ADS)

Dixit, Dhairya; Green, Avery; Hosler, Erik R.; Kamineni, Vimal; Preil, Moshe E.; Keller, Nick; Race, Joseph; Chun, Jun Sung; O'Sullivan, Michael; Khare, Prasanna; Montgomery, Warren; Diebold, Alain C.

2016-01-01

Directed self-assembly (DSA) is a potential patterning solution for future generations of integrated circuits. Its main advantages are high pattern resolution (˜10 nm), high throughput, no requirement of high-resolution mask, and compatibility with standard fab-equipment and processes. The application of Mueller matrix (MM) spectroscopic ellipsometry-based scatterometry to optically characterize DSA patterned contact hole structures fabricated with phase-separated polystyrene-b-polymethylmethacrylate (PS-b-PMMA) is described. A regression-based approach is used to calculate the guide critical dimension (CD), DSA CD, height of the PS column, thicknesses of underlying layers, and contact edge roughness of the post PMMA etch DSA contact hole sample. Scanning electron microscopy and imaging analysis is conducted as a comparative metric for scatterometry. In addition, optical model-based simulations are used to investigate MM elements' sensitivity to various DSA-based contact hole structures, predict sensitivity to dimensional changes, and its limits to characterize DSA-induced defects, such as hole placement inaccuracy, missing vias, and profile inaccuracy of the PMMA cylinder.
Pattern Driven Stress Localization

NASA Astrophysics Data System (ADS)

Croll, Andrew; Crosby, Alfred

2010-03-01

The self-assembly of patterns from isotropic initial states is a major driver of modern soft-matter research. This avenue of study is directed by the desire to understand the complex physics of the varied structures found in Nature, and by technological interest in functional materials that may be derived through biomimicry. In this work we show how a simple striped phase can respond with significant complexity to an appropriately chosen perturbation. In particular, we show how a buckled elastic plate transitions into a state of stress localization using a simple, self-assembled variation in surface topography. The collection of topographic boundaries act in concert to change the state from isotropic sinusoidal wrinkles, to sharp folds or creases separated by relatively flat regions. By varying the size of the imposed topographic pattern or the wavelength of the wrinkles, we construct a state diagram of the system. The localized state has implications for both biological systems, and for the control of non-linear pattern formation.
Solid-phase synthesis of self-assembling multivalent π-conjugated peptides

DOE PAGES

Sanders, Allix M.; Kale, Tejaswini S.; Katz, Howard E.; ...

2017-02-07

Here, we present a completely solid-phase synthetic strategy to create three- and four-fold peptide-appended π-electron molecules, where the multivalent oligopeptide presentation is dictated by the symmetries of reactive handles placed on discotic π-conjugated cores. Carboxylic acid and anhydride groups were viable amidation and imidation partners, respectively, and oligomeric π-electron discotic cores were prepared through Pd-catalyzed cross-couplings. Due to intermolecular hydrogen bonding between the three or four peptide axes, these π-peptide hybrids self-assemble into robust one-dimensional nanostructures with high aspect ratios in aqueous solution. The preparation of these systems via solid-phase methods will be detailed along with their self-assembly properties, asmore » revealed by steady-state spectroscopy and transmission electron microscopy and electrical characterization using field-effect transistor measurements.« less
Self-assembled ordered carbon-nanotube arrays and membranes.

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

Overmyer, Donald L.; Siegal, Michael P.; Yelton, William Graham

2004-11-01

Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growthmore » and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis.« less
Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces.

PubMed

Yuan, Qun-Hui; Wan, Li-Jun; Jude, Hershel; Stang, Peter J

2005-11-23

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.
Sequence-Mandated, Distinct Assembly of Giant Molecules

DOE PAGES

Zhang, Wei; Lu, Xinlin; Mao, Jialin; ...

2017-10-24

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collectivemore » hydrogen bonding and the sequence-mandated topology of the molecules. Lastly, these results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.« less
Sequence-Mandated, Distinct Assembly of Giant Molecules

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

Zhang, Wei; Lu, Xinlin; Mao, Jialin

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collectivemore » hydrogen bonding and the sequence-mandated topology of the molecules. Lastly, these results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.« less
Self-Assembly and Electrostriction of Arrays and Chains of Hopfion Particles in Chiral Liquid Crystals

DOE PAGES

Ackerman, P. J.; van de Lagemaat, J.; Smalyukh, I. I.

2015-01-21

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains thatmore » exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields.« less
A π-gel scaffold for assembling fullerene to photoconducting supramolecular rods

PubMed Central

Nair, Vishnu Sukumaran; Mukhopadhyay, Rahul Dev; Saeki, Akinori; Seki, Shu; Ajayaghosh, Ayyappanpillai

2016-01-01

Nonequilibrium self-assembly of molecules holds a huge prospect as a tool for obtaining new-generation materials for future applications. Crystallization of neutral molecules within a supramolecular gel matrix is one example in which two nonequilibrium processes occur orthogonal to each other. On the other hand, electronically interacting donor-acceptor two-component systems are expected to form phase-miscible hybrid systems. Contrary to the expectation, we report the behavior of a π-gel, derived from oligo(p-phenylenevinylene), OPVA, as a scaffold for the phase separation and crystallization of fullerene (C60) to supramolecular rods with increased transient photoconductivity (φƩμmax = 2.4 × 10−4 cm2 V−1 s−1). The C60 supramolecular rods in the π-gel medium exhibited high photocurrent in comparison to C60 loaded in a non–π-gel medium. This finding provides an opportunity for large-scale preparation of micrometer-sized photoconducting rods of fullerenes for device application. PMID:27679815
Spontaneously formed high-performance charge-transport layers of organic single-crystal semiconductors on precisely synthesized insulating polymers

NASA Astrophysics Data System (ADS)

Makita, Tatsuyuki; Sasaki, Masayuki; Annaka, Tatsuro; Sasaki, Mari; Matsui, Hiroyuki; Mitsui, Chikahiko; Kumagai, Shohei; Watanabe, Shun; Hayakawa, Teruaki; Okamoto, Toshihiro; Takeya, Jun

2017-04-01

Charge-transporting semiconductor layers with high carrier mobility and low trap-density, desired for high-performance organic transistors, are spontaneously formed as a result of thermodynamic phase separation from a blend of π-conjugated small molecules and precisely synthesized insulating polymers dissolved in an aromatic solvent. A crystal film grows continuously to the size of centimeters, with the critical conditions of temperature, concentrations, and atmosphere. It turns out that the molecular weight of the insulating polymers plays an essential role in stable film growth and interfacial homogeneity at the phase separation boundary. Fabricating the transistor devices directly at the semiconductor-insulator boundaries, we demonstrate that the mixture of 3,11-didecyldinaphtho[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and poly(methyl methacrylate) with the optimized weight-average molecular weight shows excellent device performances. The spontaneous phase separation with a one-step fabrication process leads to a high mobility up to 10 cm2 V-1 s-1 and a low subthreshold swing of 0.25 V dec-1 even without any surface treatment such as self-assembled monolayer modifications on oxide gate insulators.
Clustering and heterogeneous dynamics in a kinetic Monte Carlo model of self-propelled hard disks

NASA Astrophysics Data System (ADS)

Levis, Demian; Berthier, Ludovic

2014-06-01

We introduce a kinetic Monte Carlo model for self-propelled hard disks to capture with minimal ingredients the interplay between thermal fluctuations, excluded volume, and self-propulsion in large assemblies of active particles. We analyze in detail the resulting (density, self-propulsion) nonequilibrium phase diagram over a broad range of parameters. We find that purely repulsive hard disks spontaneously aggregate into fractal clusters as self-propulsion is increased and rationalize the evolution of the average cluster size by developing a kinetic model of reversible aggregation. As density is increased, the nonequilibrium clusters percolate to form a ramified structure reminiscent of a physical gel. We show that the addition of a finite amount of noise is needed to trigger a nonequilibrium phase separation, showing that demixing in active Brownian particles results from a delicate balance between noise, interparticle interactions, and self-propulsion. We show that self-propulsion has a profound influence on the dynamics of the active fluid. We find that the diffusion constant has a nonmonotonic behavior as self-propulsion is increased at finite density and that activity produces strong deviations from Fickian diffusion that persist over large time scales and length scales, suggesting that systems of active particles generically behave as dynamically heterogeneous systems.

Thermoresponsive wettability of photonic crystals fabricated by core-shell poly(styrene-acrylamide) nano/microspheres.

PubMed

Zhang, Yuqi; Gao, Loujun; Heng, Liping; Wei, Qingbo; Yang, Hua; Wang, Qiao

2013-03-01

The photonic crystals (PCs) films with tunable wettability were fabricated from self-assembly of an amphiphilic latex nano/microspheres poly(styrene-acrylamide) at different temperatures. The results demonstrate that the surface wettability of the PCs film can be tuned from high hydrophilic (CA, 17 degrees) to high hydrophobic (CA, 127.8 degrees) by controlling the assembly temperature from 30 degrees C to 90 degrees C, while the position of the photonic stopbands of the PCs films unchanged virtually. The obvious wettability transition is due to the change of the surface chemical component of the latex spheres, which mainly derives from the phase separation of polymer segments driven toward minimum interfacial energy. The facile method could open new application fields of PCs in diverse environments.
Non-native three-dimensional block copolymer morphologies

DOE PAGES

Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory; ...

2016-12-22

Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers throughmore » subtle surface topography. As a result, this strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.« less
Non-native three-dimensional block copolymer morphologies

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

Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory

Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers throughmore » subtle surface topography. As a result, this strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.« less
Panoramic View of Electrochemical Pseudocapacitor and Organic Solar Cell Research in Molecularly Engineered Energy Materials (MEEM)

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

Aguirre, Jordan C.; Ferreira, Amy; Ding, Hong

2014-07-09

Our program on capacitive energy storage is a comprehensive one that combines experimental and computational components to achieve a fundamental understanding of charge storage processes in redox-based materials, specifically transition metal oxides. Some of the highlights of this program are the identification of intercalation pseudocapacitance in Nb2O5, which enables high energy density to be achieved at high rates, and the development of a new route for synthesizing mesoporous films in which preformed nanocrystal building blocks are used in combination with polymer templating. The resulting material architectures have large surface areas and enable electrolyte access to the redox active pore walls,more » while the interconnected mesoporous film provides good electronic conductivity. Select first-principles density-functional theory studies of prototypical pseudocapacitor materials are reviewed, providing insight into the key physical and chemical features involved in charge transfer and ion diffusion. Rigorous multiscale physical models and numerical tools have been developed and used to reproduce electrochemical properties of carbon-based electrochemical capacitors with the ultimate objective of facilitating the optimization of electrode design. For the organic photovoltaic (OPV) program, our focus has been ongoing beyond the trial-and-error Edisonian approaches that have been responsible for the increase in power conversion efficiency of blend-cast (BC) bulk heterojunction blends of polymers and fullerenes. Our first approach has been to use molecular self-assembly to create the ideal nanometer-scale architecture using thermodynamics rather than relying on the kinetics of spontaneous phase segregation. We have created fullerenes that self-assemble into one-dimensional stacks and have shown that use of these self-assembled fullerenes lead to dramatically enhanced OPV performance relative to fullerenes that do not assemble. We also have created self-assembling conjugated polymers that form gels based on electrically continuous cross-linked micelles in solution, opening the possibility for water-processable “green” production of OPVs based on these materials. Our second approach has been to avoid kinetic control over phase separation by using a sequential processing (SqP) technique to deposit the polymer and fullerene materials in separate deposition steps. The polymer layer is deposited first, using solvents and deposition conditions that optimize the polymer crystallinity for swelling and hole mobility. The fullerene layer is then deposited in a second step from a solvent that swells the polymer but does not dissolve it, allowing the fullerene to penetrate into the polymer underlayer to the desired degree. Careful comparison of composition- and thickness-matched BC and SqP devices shows that SqP not only produces more efficient devices but also leads to devices that behave more consistently.« less
Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates

PubMed Central

Xie, Yujiao; Liu, Xiaofeng; Hu, Zhuang; Hou, Zhipeng; Chen, Zhangpei; Hu, Jianshe; Yang, Liqun

2018-01-01

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, 1H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications. PMID:29584691
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 without regular shapes. We believe these effects are steric in nature that changes the beta-sheet sub-structure within the nanofibers. These principles could be utilized as strategies to optimize the morphologies and properties of nanostructures based on these amphiphilic molecules.
Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.
Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.
Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.
Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.
Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

NASA Astrophysics Data System (ADS)

Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

2016-06-01

Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.
Micro Galvanic Cell To Generate PtO and Extend the Triple-Phase Boundary during Self-Assembly of Pt/C and Nafion for Catalyst Layers of PEMFC.

PubMed

Long, Zhi; Gao, Liqin; Li, Yankai; Kang, Baotao; Lee, Jin Yong; Ge, Junjie; Liu, Changpeng; Ma, Shuhua; Jin, Zhao; Ai, Hongqi

2017-11-08

The self-assembly powder (SAP) with varying Nafion content was synthesized and characterized by XRD, XPS, HRTEM, and mapping. It is observed that the oxygen from oxygen functional groups transfers to the surface of Pt and generate PtO during the process of self-assembly with the mechanism of micro galvanic cell, where Pt, carbon black, and Nafion act as the anode, cathode and electrolyte, respectively. The appearance of PtO on the surface of Pt leads to a turnover of Nafion structure, and therefore more hydrophilic sulfonic groups directly contact with Pt, and thus the triple-phase boundary (TPB) has been expanded.
Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties

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

Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu; Freed, Karl F., E-mail: freed@uchicago.edu; Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

2015-07-14

The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chainmore » stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.« less
Self-assembly of gold nanorods into symmetric superlattices directed by OH-terminated hexa(ethylene glycol) alkanethiol.

PubMed

Xie, Yong; Guo, Shengming; Ji, Yinglu; Guo, Chuanfei; Liu, Xinfeng; Chen, Ziyu; Wu, Xiaochun; Liu, Qian

2011-09-20

The self-assembly of anisotropic gold nanorods (GNRs) into ordered phases remains a challenge. Herein, we demonstrated the fabrication of symmetric circular- or semicircular-like self-assembled superlattices composed of multilayers of standing GNRs by fine-tuning the repulsive interactions among GNRs. The repulsive force is tailored from electrostatic interaction to steric force by replacing the surface coating of cetyltrimethylammonium bromide (CTAB) (ζ potential of 20-50 mV) with an OH-terminated hexa(ethylene glycol) alkanethiol (here termed as EG(6)OH, ζ potential of -10 mV). The assembly mechanism is discussed via theoretical analyses of the major interactions, and an effective balance between the repulsive steric and attractive depletion interactions is the main driving force for the self-assembly. The real-time observations of solution assembly (UV-vis-NIR absorption spectroscopy) supports the mechanism that we suggested. The superlattices obtained here not only enrich the categories of the self-assembled structures but more importantly deepen the insight of the self-assembly process and pave the way for various potential applications. © 2011 American Chemical Society
Adjustable bridge blocks make huge difference to the self-assembly of multiblock copolymers

NASA Astrophysics Data System (ADS)

Li, Weihua

We present theoretical studies on two types of multiblock copolymers, whose self-assemblies lead to a lot of novel ordered nanostructures. The first example is BABCB multiblock terpolymer, where A- and C-blocks separately aggregate into isolated domains and the three B-blocks with adjustable lengths form the matrix. As a result, the middle B-block forms a natural bridge connecting A- and C-domains. In contrast to ABC, the BABCB can form many binary spherical and cylindrical phases with tunable coordination numbers. In addition, the ABCB solution can form a lot of planet-satellite micellar superstructures with tunable number of satellites that varies from 3 to 20. The another system is AB-type multiblock copolymers. In contrast to the above system, there is no natural bridge. Accordingly, we introduce multiple arms into the architecture which tend to partition themselves into different domains to maximize their configurational entropy, thus forming effective bridges. Furthermore, each arm is devised as BAB triblock to enable adjustable length of bridges. With this copolymer, we predict a few non-classical ordered phases, including a square array cylinder. Our study opens the possibilities of fabricating desired nanostructures using designed block copolymers. National Natural Science Foundation of China (No. 21322407, 21574026).
Toluene diisocyanate based phase-selective supramolecular oil gelator for effective removal of oil spills from polluted water.

PubMed

Wang, Yongzhen; Wang, Youshan; Yan, Xingru; Wu, Songquan; Shao, Lu; Liu, Yuyan; Guo, Zhanhu

2016-06-01

Due to tremendous resource wastes and great harm to ecological environment caused by the accidental oil spills, an alkyl bicarbamate supramolecular oil gelator was synthesized and applied to selectively gelate oils from oil/water mixtures. Interestingly, the oil gelator could be self-assembled in a series of organic solvents, i.e., edible oils and fuel oils to form 3D networks and then turned into thermally reversible organogels, allowing easy separation and removal of oil spills from oil/water mixtures. The possible self-assembly mode for the formation of organogels was proposed. What's more, the optimal conditions for using the oil gelator to recover oils were experimentally determined. Inspiringly, taking gasoline as the co-congealed solvent, a complete gelation of oil phase was achieved within 15 min with high oil removal rate and oil retention rate after convenient salvage and cleanup of oil gels from oil/water mixtures. The oil gelator had some advantages in solidifying oil spills on water surface, exhibiting fast oil gelation, convenient and thorough oil removal and easy recovery. This work illustrates the significant role of oil gelators in the potential cleanup of spilled oils for water purification. Copyright © 2016 Elsevier Ltd. All rights reserved.
Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

PubMed

Khani, Shaghayegh; Jamali, Safa; Boromand, Arman; Hore, Michael J A; Maia, Joao

2015-09-14

Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.
Monte Carlo and mean-field studies of phase evolution in concentrated surfactant solutions

NASA Astrophysics Data System (ADS)

Bohbot, Yardena; Ben-Shaul, Avinoam; Granek, Rony; Gelbart, William M.

1995-11-01

A two-dimensional lattice model, originally introduced by Granek et al. [J. Chem. Phys. 101, 4331 (1994)], is used to demonstrate the intricate coupling between the intramicellar interactions that determine the optimal aggregation geometry of surfactant molecules in dilute solution, and the intermicellar interactions that govern the phase behavior at higher concentrations. Three very different scenarios of self-assembly and phase evolution are analyzed in detail, based on Monte Carlo studies and theoretical interpretations involving mean-field, Landau-Ginzburg, Bethe-Peierls, and virial expansion schemes. The basic particles in the model are ``unit micelles'' which, due to spontaneous self-assembly or because of excluded area interactions, can fuse to form larger aggregates. These aggregates are envisaged as flat micelles composed of a bilayerlike body surrounded by a curved semitoroidal rim. The system's Hamiltonian involves one- through four-body potentials between the unit micelles, which account for their tendency to form aggregates of different shapes, e.g., elongated vs disklike micelles. Equivalently, the configurational energy of the system is a sum of micellar self-energies involving the packing free energies of the constituent molecules in the bilayer body and in rim segments of different local curvature. The rim energy is a sum of a line tension term and a 1D curvature energy which depends on the rim spontaneous curvature and bending rigidity. Different combinations of these molecular parameters imply different optimal packing geometries and hence different self-assembly and phase behaviors. The emphasis in this paper is on systems of ``curvature loving'' amphiphiles which, in our model, are characterized by negative line tension. The three systems studied are: (i) A dilute solution of stable disklike micelles which, upon increasing the concentration, undergoes a first-order phase transition to a continuous bilayer with isolated hole defects. An intermediate modulated ``checkerboard'' phase appears under certain conditions at low temperatures. (ii) A system of unit micelles which in dilute solution tend to associate into linear micelles. These micelles are rodlike at low temperatures, becoming increasingly more flexible as the temperature increases. Upon increasing the concentration the micelles grow and undergo (in 2D) a continuous transition into nematic and ``stripe'' phases of long rods. At still higher concentrations the micellar stripes fuse into continuous sheets with line defects. (iii) A system in which, already in dilute solution, the micelles favor the formation of branched aggregates, analogous to the branched cylindrical micelles recently observed in certain surfactant solutions. As the concentration increases the micelles associate into networks (``gels'') composed of a mesh of linear micelles linked by ``T-like'' intermicellar junctions. The network may span the entire system or phase separate and coexist with a dilute micellar phase, depending on the details of the molecular packing parameters.
Hierarchical self-assembly, coassembly, and self-organization of novel liquid crystalline lattices and superlattices from a twin-tapered dendritic benzamide and its four-cylinder-bundle supramolecular polymer.

PubMed

Percec, Virgil; Bera, Tushar K; Glodde, Martin; Fu, Qiongying; Balagurusamy, Venkatachalapathy S K; Heiney, Paul A

2003-02-17

The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.
Graded porous inorganic materials derived from self-assembled block copolymer templates.

PubMed

Gu, Yibei; Werner, Jörg G; Dorin, Rachel M; Robbins, Spencer W; Wiesner, Ulrich

2015-03-19

Graded porous inorganic materials directed by macromolecular self-assembly are expected to offer unique structural platforms relative to conventional porous inorganic materials. Their preparation to date remains a challenge, however, based on the sparsity of viable synthetic self-assembly pathways to control structural asymmetry. Here we demonstrate the fabrication of graded porous carbon, metal, and metal oxide film structures from self-assembled block copolymer templates by using various backfilling techniques in combination with thermal treatments for template removal and chemical transformations. The asymmetric inorganic structures display mesopores in the film top layers and a gradual pore size increase along the film normal in the macroporous sponge-like support structure. Substructure walls between macropores are themselves mesoporous, constituting a structural hierarchy in addition to the pore gradation. Final graded structures can be tailored by tuning casting conditions of self-assembled templates as well as the backfilling processes. We expect that these graded porous inorganic materials may find use in applications including separation, catalysis, biomedical implants, and energy conversion and storage.

Systems and methods for creation of conducting networks of magnetic particles through dynamic self-assembly process

DOEpatents

Snezhko, Oleksiy [Woodridge, IL; Aronson, Igor [Darien, IL; Kwok, Wai-Kwong [Downers Grove, IL

2011-01-25

Self-assembly of magnetic microparticles in AC magnetic fields. Excitation of the system by an AC magnetic field provides a variety of patterns that can be controlled by adjusting the frequency and the amplitude of the field. At low particle densities the low-frequency magnetic excitation favors cluster phase formation, while high frequency excitation favors chains and netlike structures. For denser configurations, an abrupt transition to the network phase was obtained.
Traveling wave electro-optic phase modulators based on intrinsically polar self-assembled chromophoric superlattices

NASA Astrophysics Data System (ADS)

Zhao, Y.-G.; Wu, A.; Lu, H.-L.; Chang, S.; Lu, W.-K.; Ho, S. T.; van der Boom, M. E.; Marks, T. J.

2001-07-01

Traveling-wave electro-optic modulators based on chromophoric self-assembled superlattices (SASs) possessing intrinsically polar microstructures have been designed and fabricated. Although the thickness of the SAS layer is only ˜150 nm, a π-phase shift is clearly observed. From the measured Vπ value, the effective electro-optic coefficient of the SAS film is determined to be ˜21.8 pm/V at an input wavelength of 1064 nm.
Method for making nanoporous hydrophobic coatings

DOEpatents

Fan, Hongyou; Sun, Zaicheng

2013-04-23

A simple coating method is used to form nanoporous hydrophobic films that can be used as optical coatings. The method uses evaporation-induced self-assembly of materials. The coating method starts with a homogeneous solution comprising a hydrophobic polymer and a surfactant polymer in a selective solvent. The solution is coated onto a substrate. The surfactant polymer forms micelles with the hydrophobic polymer residing in the particle core when the coating is dried. The surfactant polymer can be dissolved and selectively removed from the separated phases by washing with a polar solvent to form the nanoporous hydrophobic film.
Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

NASA Astrophysics Data System (ADS)

Velayutham, T. S.; Ng, B. K.; Gan, W. C.; Majid, W. H. Abd.; Hashim, R.; Zahid, N. I.; Chaiprapa, Jitrin

2014-08-01

Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10-2-106 Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.
Organised surfactant assemblies in analytical atomic spectrometry

NASA Astrophysics Data System (ADS)

Sanz-Medel, Alfredo; Fernandez de la Campa, Maria del Rosario; Gonzalez, Elisa Blanco; Fernandez-Sanchez, Maria Luisa

1999-02-01

The use of surfactant-based organised assemblies in analytical atomic spectroscopy is extensively and critically reviewed along three main lines: first, the ability of organised media to enhance detection of atomic spectroscopic methods by favourable manipulation of physical and chemical properties of the sample solution second, the extension of separation mechanisms by resorting to organised media and third a discussion of synergistic combinations of liquid chromatography separations and atomic detectors via the use of vesicular mobile phases. Changes in physical properties of sample solutions aspirated in atomic spectrometry by addition of surfactants can be advantageously used in at least four different ways: (i) to improve nebulisation efficiency; (ii) to enhance wettability of solid surfaces used for atomisation; (iii) to improve compatibility between aqueous and organic phases; and (iv) to achieve good dispersion of small particles in "slurry" techniques. Controversial results and statements published so far are critically discussed. The ability of surfactant-based organised assemblies, such as micelles and vesicles, to organise reactants at the molecular level has also been applied to enhance the characteristics of chemical generation of volalite species of metals and semi-metals (e.g., hydride or ethylide generation of As, Pb, Cd, Se, Sn, and cold vapour Hg generation) used in atomic methods. Enhancements in efficiency/transport of volatile species, increases in the reaction kinetics, stabilisation of some unstable species and changes in the selectivity of the reactions by surfactants are dealt with. Non-chromatographic cloud-point separations to design pre-concentration procedures with subsequent metal determination by atomic methods are addressed along with chromatographic separations of expanded scope by addition of surfactants to the conventional aqueous mobile phases of reversed-phase high-performance liquid chromatography. Finally, the synergistic effect of using vesicles to improve both the separation capabilities of reversed-phase HPLC and the detectability of atomic detectors by on-line vesicular hydride generation is described. In particular, the possible separation mechanisms responsible for micellar and vesicular mobile phases in reversed-phase chromatographies are analysed and compared. The possible effect of modification of stationary phases by monomers of the surfactants should also be taken into account. The application of such on-line couplings to develop new hybrid approaches to tackle modern problems of trace element speciation for As, Hg, Se, and Cd completes this revision of the present interface between analytical atomic spectroscopy and surfactant-based organised assemblies.
Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

PubMed

Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

2017-02-01

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ion-Specific Interfacial Crystallization of Polymer-Grafted Nanoparticles

DOE PAGES

Zhang, Honghu; Wang, Wenjie; Mallapragada, Surya; ...

2017-06-27

In this study, ion-specific effects on the assembly and crystallization of polyethylene-glycol-grafted Au nanoparticles (PEG-AuNPs) at the vapor–liquid interface are examined by surface sensitive synchrotron X-ray scattering methods. We show that monovalent salts, such as KCl and NaCl, that do not advance phase separation of pure PEG at room temperature induce two-dimensional (2D) self-assembly and crystallization of PEG-AuNPs with some distinctions. Whereas for KCl the 2D hexagonal coherence length of the PEG-AuNP superlattices is remarkably large compared to other salts (over micron-sized crystalline grains), NaCl induces coexistence of two hexagonal structures. Using various salts, we find that the value ofmore » the lattice constant is correlated to the ionic hydration entropy consistent with the Hofmeister series.« less
Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

PubMed

Zhang, Ren; Lee, Bongjoon; Bockstaller, Michael R; Douglas, Jack F; Stafford, Christopher M; Kumar, Sanat K; Raghavan, Dharmaraj; Karim, Alamgir

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.
Self-assembly of silica nanoparticles by tuning substrate-adsorbate interaction

NASA Astrophysics Data System (ADS)

Utsav, Khanna, Sakshum; Mukhopadhayay, Indrajit; Banerjee, Rupak

2018-05-01

We report on self-assembled nanodisc formations of silica nanoparticles on a surface modified silicon substrate using modified Langmuir-Schafer deposition technique (stamping). The size, inter-particle separation as well as the packing of the silica nanoparticles within the nanodiscs formed spontaneously can be tuned by the surface pressure applied on the water surface. We obtain self-assembled nanodiscs of silica nanoparticle arranged in a hexagonal symmetry. We also observe that by varying the surface pressure of deposition at the water-molecule-air interface we obtain such 2D disc-shaped structure with varying sizes and a packing ratio of the silica nanoparticle.
Self-interaction of NPM1 modulates multiple mechanisms of liquid–liquid phase separation

DOE PAGES

Mitrea, Diana M.; Cika, Jaclyn A.; Stanley, Christopher B.; ...

2018-02-26

Nucleophosmin (NPM1) is an abundant, oligomeric protein in the granular component of the nucleolus with roles in ribosome biogenesis. Pentameric NPM1 undergoes liquid–liquid phase separation (LLPS) via heterotypic interactions with nucleolar components, including ribosomal RNA (rRNA) and proteins which display multivalent arginine-rich linear motifs (R-motifs), and is integral to the liquid-like nucleolar matrix. Here we show that NPM1 can also undergo LLPS via homotypic interactions between its polyampholytic intrinsically disordered regions, a mechanism that opposes LLPS via heterotypic interactions. Using a combination of biophysical techniques, including confocal microscopy, SAXS, analytical ultracentrifugation, and single-molecule fluorescence, we describe how conformational changes withinmore » NPM1 control valency and switching between the different LLPS mechanisms. We propose that this newly discovered interplay between multiple LLPS mechanisms may influence the direction of vectorial pre-ribosomal particle assembly within, and exit from the nucleolus as part of the ribosome biogenesis process.« less
Self-interaction of NPM1 modulates multiple mechanisms of liquid–liquid phase separation

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

Mitrea, Diana M.; Cika, Jaclyn A.; Stanley, Christopher B.

Nucleophosmin (NPM1) is an abundant, oligomeric protein in the granular component of the nucleolus with roles in ribosome biogenesis. Pentameric NPM1 undergoes liquid–liquid phase separation (LLPS) via heterotypic interactions with nucleolar components, including ribosomal RNA (rRNA) and proteins which display multivalent arginine-rich linear motifs (R-motifs), and is integral to the liquid-like nucleolar matrix. Here we show that NPM1 can also undergo LLPS via homotypic interactions between its polyampholytic intrinsically disordered regions, a mechanism that opposes LLPS via heterotypic interactions. Using a combination of biophysical techniques, including confocal microscopy, SAXS, analytical ultracentrifugation, and single-molecule fluorescence, we describe how conformational changes withinmore » NPM1 control valency and switching between the different LLPS mechanisms. We propose that this newly discovered interplay between multiple LLPS mechanisms may influence the direction of vectorial pre-ribosomal particle assembly within, and exit from the nucleolus as part of the ribosome biogenesis process.« less
Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing.

PubMed

Xiong, Shisheng; Wan, Lei; Ishida, Yoshihito; Chapuis, Yves-Andre; Craig, Gordon S W; Ruiz, Ricardo; Nealey, Paul F

2016-08-23

Directed self-assembly (DSA) of block copolymers (BCPs) is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. While great progress has been made to implement block copolymer lithography with features in the range of 10-20 nm, patterning solutions below 10 nm are still not mature. Many BCP systems self-assemble at this length scale, but challenges remain in simultaneously tuning the interfacial energy atop the film to control the orientation of BCP domains, designing materials, templates, and processes for ultra-high-density DSA, and establishing a robust pattern transfer strategy. Among the various solutions to achieve domains that are perpendicular to the substrate, solvent annealing is advantageous because it is a versatile method that can be applied to a diversity of materials. Here we report a DSA process based on chemical contrast templates and solvent annealing to fabricate 8 nm features on a 16 nm pitch. To make this possible, a number of innovations were brought in concert with a common platform: (1) assembling the BCP in the phase-separated, solvated state, (2) identifying a larger process window for solvated triblock vs diblock BCPs as a function of solvent volume fraction, (3) employing templates for sub-10-nm BCP systems accessible by lithography, and (4) integrating a robust pattern transfer strategy by vapor infiltration of organometallic precursors for selective metal oxide synthesis to prepare an inorganic hard mask.
Inducing Order from Disordered Copolymers: On Demand Generation of Triblock Morphologies Including Networks

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

Tureau, Maëva S.; Kuan, Wei-Fan; Rong, Lixia

Disordered block copolymers are generally impractical in nanopatterning applications due to their inability to self-assemble into well-defined nanostructures. However, inducing order in low molecular weight disordered systems permits the design of periodic structures with smaller characteristic sizes. Here, we have induced nanoscale phase separation from disordered triblock copolymer melts to form well-ordered lamellae, hexagonally packed cylinders, and a triply periodic gyroid network structure, using a copolymer/homopolymer blending approach, which incorporates constituent homopolymers into selective block domains. This versatile blending approach allows one to precisely target multiple nanostructures from a single disordered material and can be applied to a wide varietymore » of triblock copolymer systems for nanotemplating and nanoscale separation applications requiring nanoscale feature sizes and/or high areal feature densities.« less
Noncovalent Derivatization: A Laboratory Experiment for Understanding the Principles of Molecular Recognition and Self-Assembly through Phase Behavior

ERIC Educational Resources Information Center

Cannon, Amy S.; Warner, John C.; Koraym, Smaa A.; Marteel-Parrish, Anne E.

2014-01-01

An experiment focusing on the creation of phase diagrams involving nonconvalent derivatives of hydroquinone and bis[N,N-diethyl]terephthalamide (HQ-DETPA) is presented. A phase diagram was assembled by taking samples of different compositions (i.e., 40% hydroquinone and 60% bis[N,N-diethyl]terephthalamide, 70%/30%, etc.) and determining the…
Coarse-Graining Polymer Field Theory for Fast and Accurate Simulations of Directed Self-Assembly

NASA Astrophysics Data System (ADS)

Liu, Jimmy; Delaney, Kris; Fredrickson, Glenn

To design effective manufacturing processes using polymer directed self-assembly (DSA), the semiconductor industry benefits greatly from having a complete picture of stable and defective polymer configurations. Field-theoretic simulations are an effective way to study these configurations and predict defect populations. Self-consistent field theory (SCFT) is a particularly successful theory for studies of DSA. Although other models exist that are faster to simulate, these models are phenomenological or derived through asymptotic approximations, often leading to a loss of accuracy relative to SCFT. In this study, we employ our recently-developed method to produce an accurate coarse-grained field theory for diblock copolymers. The method uses a force- and stress-matching strategy to map output from SCFT simulations into parameters for an optimized phase field model. This optimized phase field model is just as fast as existing phenomenological phase field models, but makes more accurate predictions of polymer self-assembly, both in bulk and in confined systems. We study the performance of this model under various conditions, including its predictions of domain spacing, morphology and defect formation energies. Samsung Electronics.
Prediction of binary nanoparticle superlattices from soft potentials

DOE PAGES

Horst, Nathan; Travesset, Alex

2016-01-07

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. From a pool of 24 candidate lattices, the free energy is optimized with respect to additional internal parameters and the p-exponent, determining the short-range properties of the potential, is varied between p = 12 and p = 6. The phase diagrams contain the phases found in ongoingmore » self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. Thus, the resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: Nanoparticle radius ratio (γ) and softness asymmetry.« less
Prediction of Binary Nanoparticle Superlattices from Soft Potentials

NASA Astrophysics Data System (ADS)

Horst, Nathan; Travesset, Alex

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. We explore 24 candidate lattices where the p-exponent, determining the short-range properties of the potential, is varied between p=12 and p=6, and optimize the free energy with respect to additional internal parameters. The phase diagrams contain the phases found in ongoing self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. The resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: nanoparticle radius ratio (γ) and softness asymmetry (SA). Supported by DOE under Contract Number DE-AC02-07CH11358.
Prediction of binary nanoparticle superlattices from soft potentials

NASA Astrophysics Data System (ADS)

Horst, Nathan; Travesset, Alex

2016-01-01

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. From a pool of 24 candidate lattices, the free energy is optimized with respect to additional internal parameters and the p-exponent, determining the short-range properties of the potential, is varied between p = 12 and p = 6. The phase diagrams contain the phases found in ongoing self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. The resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: Nanoparticle radius ratio (γ) and softness asymmetry.
Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge.

PubMed

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-10-21

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm(-1)). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.
Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge

NASA Astrophysics Data System (ADS)

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-09-01

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm-1). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

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
Phase behavior of model ABC triblock copolymers

NASA Astrophysics Data System (ADS)

Chatterjee, Joon

The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that was mixed. The results provide insight into the chain conformation of ABC triblock copolymers, where the B blocks are completely bridged across the adjacent A and C domains. In the final part of the thesis, the swelling properties were used to study the directed assembly of ABC triblock copolymers on chemically nanopatterned surfaces.
Structure and optical function of amorphous photonic nanostructures from avian feather barbs: a comparative small angle X-ray scattering (SAXS) analysis of 230 bird species

PubMed Central

Saranathan, Vinodkumar; Forster, Jason D.; Noh, Heeso; Liew, Seng-Fatt; Mochrie, Simon G. J.; Cao, Hui; Dufresne, Eric R.; Prum, Richard O.

2012-01-01

Non-iridescent structural colours of feathers are a diverse and an important part of the phenotype of many birds. These colours are generally produced by three-dimensional, amorphous (or quasi-ordered) spongy β-keratin and air nanostructures found in the medullary cells of feather barbs. Two main classes of three-dimensional barb nanostructures are known, characterized by a tortuous network of air channels or a close packing of spheroidal air cavities. Using synchrotron small angle X-ray scattering (SAXS) and optical spectrophotometry, we characterized the nanostructure and optical function of 297 distinctly coloured feathers from 230 species belonging to 163 genera in 51 avian families. The SAXS data provided quantitative diagnoses of the channel- and sphere-type nanostructures, and confirmed the presence of a predominant, isotropic length scale of variation in refractive index that produces strong reinforcement of a narrow band of scattered wavelengths. The SAXS structural data identified a new class of rudimentary or weakly nanostructured feathers responsible for slate-grey, and blue-grey structural colours. SAXS structural data provided good predictions of the single-scattering peak of the optical reflectance of the feathers. The SAXS structural measurements of channel- and sphere-type nanostructures are also similar to experimental scattering data from synthetic soft matter systems that self-assemble by phase separation. These results further support the hypothesis that colour-producing protein and air nanostructures in feather barbs are probably self-assembled by arrested phase separation of polymerizing β-keratin from the cytoplasm of medullary cells. Such avian amorphous photonic nanostructures with isotropic optical properties may provide biomimetic inspiration for photonic technology. PMID:22572026
In situ microscopy of the self-assembly of branched nanocrystals in solution

DOE PAGES

Sutter, Eli; Tkachenko, Alexei V.; Sutter, Peter; ...

2016-04-04

Here, solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifiesmore » the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.« less
In situ microscopy of the self-assembly of branched nanocrystals in solution

NASA Astrophysics Data System (ADS)

Sutter, Eli; Sutter, Peter; Tkachenko, Alexei V.; Krahne, Roman; de Graaf, Joost; Arciniegas, Milena; Manna, Liberato

2016-04-01

Solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifies the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.
Self-assembly of nanocomposite materials

DOEpatents

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

2001-01-01

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

NASA Astrophysics Data System (ADS)

Weiss, Marian; Frohnmayer, Johannes Patrick; Benk, Lucia Theresa; Haller, Barbara; Janiesch, Jan-Willi; Heitkamp, Thomas; Börsch, Michael; Lira, Rafael B.; Dimova, Rumiana; Lipowsky, Reinhard; Bodenschatz, Eberhard; Baret, Jean-Christophe; Vidakovic-Koch, Tanja; Sundmacher, Kai; Platzman, Ilia; Spatz, Joachim P.

2018-01-01

Compartments for the spatially and temporally controlled assembly of biological processes are essential towards cellular life. Synthetic mimics of cellular compartments based on lipid-based protocells lack the mechanical and chemical stability to allow their manipulation into a complex and fully functional synthetic cell. Here, we present a high-throughput microfluidic method to generate stable, defined sized liposomes termed `droplet-stabilized giant unilamellar vesicles (dsGUVs)’. The enhanced stability of dsGUVs enables the sequential loading of these compartments with biomolecules, namely purified transmembrane and cytoskeleton proteins by microfluidic pico-injection technology. This constitutes an experimental demonstration of a successful bottom-up assembly of a compartment with contents that would not self-assemble to full functionality when simply mixed together. Following assembly, the stabilizing oil phase and droplet shells are removed to release functional self-supporting protocells to an aqueous phase, enabling them to interact with physiologically relevant matrices.
A new three-phase heterocrystal catalysts and their superior treatment efficiency for tetracycline

NASA Astrophysics Data System (ADS)

Wang, Feng-Rui; Sun, Hui-Ping; Wang, Yan; Liu, Jin-Ku; Fang, Yi; Wang, Jian-Dong

An easy recyclable and interesting Ag3PO4@Pt@TiO2 (APTP) three-phase heterocrystal chains were self-assembled by the cohesive action and chemical construction of polyvinylpyrrolidone (PVP). We found that a new electron-hole transmission path has been built via the rematch of the band structure of Ag3PO4, Pt and TiO2 which extends the light absorption and promoted the electron-hole separation to treat the antibiotic residues in the water. Based on the thorough investigations, a new catalytic material was provided for antibiotics degradation. The catalytic activity of APTP toward the degradation of tetracycline solution was enhanced by 166.67% and the stability increased remarkably compared with pure Ag3PO4 through the integration of different functional components.
Uniform discotic wax particles via electrospray emulsification.

PubMed

Mejia, Andres F; He, Peng; Luo, Dawei; Marquez, Manuel; Cheng, Zhengdong

2009-06-01

We present a novel colloidal discotic system: the formation and self-assembling of wax microdisks with a narrow size distribution. Uniform wax emulsions are first fabricated by electrospraying of melt alpha-eicosene. The size of the emulsions can be flexibly tailored by varying the flow rate of the discontinuous phase, its electric conductivity, and the applied voltage. The process of entrainment of wax droplets, vital for obtaining uniform emulsions, is facilitated by the reduction of air-water surface tension and the density of the continuous phase. Then uniform wax discotic particles are produced via phase transition, during which the formation of a layered structure of the rotator phase of wax converts the droplets, one by one, into oblate particles. The time span for the conversion from spherical emulsions to disk particles is linearly dependent on the size of droplets in the emulsion, indicating the growth of a rotator phase from surface to the center is the limiting step in the shape transition. Using polarized light microscopy, the self-assembling of wax disks is observed by increasing disk concentration and inducing depletion attraction among disks, where several phases, such as isotropic, condensed, columnar stacking, and self-assembly of columnar rods are present sequentially during solvent evaporation of a suspension drop.
Electrostatically Driven Assembly of Charged Amphiphiles Forming Crystallized Membranes, Vesicles and Nanofiber Arrays

NASA Astrophysics Data System (ADS)

Leung, Cheuk Yui Curtis

Charged amphiphilic molecules can self-assemble into a large variety of objects including membranes, vesicles and fibers. These micro to nano-scale structures have been drawing increasing attention due to their broad applications, especially in biotechnology and biomedicine. In this dissertation, three self-assembled systems were investigated: +3/-1 self-assembled catanionic membranes, +2/-1 self-assembled catanionic membranes and +1 self-assembled nanofibers. Transmission electron microscopy (TEM) combined with synchrotron small and wide angle x-ray scattering (SAXS and WAXS) were used to characterize the coassembled structures from the mesoscopic to nanometer scale. We designed a system of +3 and -1 ionic amphiphiles that coassemble into crystalline ionic bilayer vesicles with large variety of geometries that resemble polyhedral cellular crystalline shells and archaea wall envelopes. The degree of ionization of the amphiphiles and their intermolecular electrostatic interactions can be controlled by varying pH. The molecular packing of these membranes showed a hexagonal to rectangular-C to hexagonal phase transition with increasing pH, resulting in significant changes to the membrane morphology. A similar mixture of +2 and -1 ionic amphiphiles was also investigated. In addition to varying pH, which controls the headgroup attractions, we also adjust the tail length of the amphiphiles to control the van der Waals interactions between the tails. A 2D phase diagram was developed to show how pH and tail length can be used to control the intermolecular packing within the membranes. Another system of self-assembled nanofiber network formed by positively charged amphiphiles was also studied. These highly charged fibers repel each other and are packed in hexagonal lattice with lattice constant at least eight times of the fiber diameter. The d-spacing and the crystal structure can be controlled by varying the solution concentration and temperature.
Effects of Coulomb Repulsion on the Phase Diagram of the Asakura-Oosawa Model

NASA Astrophysics Data System (ADS)

Haaga, Jason; Pemberton, Elizabeth; Gunton, James; Rickman, Jeffrey

We investigate the effect of adding a screened Coulomb charge to a model colloidal system interacting via the Asakura-Oosawa depletion potential. This model has previously been used to study the early stages of amelogenin self-assembly, a crucial process in the formation of dental enamel, by Li et al (BiophysicalJournal 101, 2502 (2011). By employing Monte Carlo simulations, we explore the role of interaction strengths and ranges on phase behavior. We find that charge strength and range have a strong influence on the stable, in the case of long range depletion potential, or metastable, in the case of short range depletion, fluid-fluid phase separation. Coulomb repulsion narrows and flattens the coexistence curve with increasing charge. This talk will also discuss solid-solid transitions present for certain interaction ranges. This work is supported by the G. Harold and Leila Y. Mathers Foundation.
Selective directed self-assembly of coexisting morphologies using block copolymer blends

NASA Astrophysics Data System (ADS)

Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

2016-08-01

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.
Hierarchical nanoparticle assemblies formed by decorating breath figures.

PubMed

Böker, Alexander; Lin, Yao; Chiapperini, Kristen; Horowitz, Reina; Thompson, Mike; Carreon, Vincent; Xu, Ting; Abetz, Clarissa; Skaff, Habib; Dinsmore, A D; Emrick, Todd; Russell, Thomas P

2004-05-01

The combination of two self-assembly processes on different length scales leads to the formation of hierarchically structured nanoparticle arrays. Here, the formation of spherical cavities, or 'breath figures'-made by the condensation of micrometre-sized water droplets on the surface of a polymer solution-that self-assemble into a well-ordered hexagonal array, is combined with the self-assembly of CdSe nanoparticles at the polymer solution-water droplet interface. Complete evaporation of the solvent and water confines the particle assembly to an array of spherical cavities and allows for ex situ investigation. Fluorescence confocal, transmission electron and scanning electron microscope images show the preferential segregation of the CdSe nanoparticles to the polymer solution-water interface where they form a 5-7-nm-thick layer, thus functionalizing the walls of the holes. This process opens a new route to fabricating highly functionalized ordered microarrays of nanoparticles, potentially useful in sensory, separation membrane or catalytic applications.
The self-assembly of particles with isotropic interactions: Using DNA coated colloids to create designer nanomaterials

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

Thompson, R. B.; Dion, S.; Konigslow, K. von

Self-consistent field theory equations are presented that are suitable for use as a coarse-grained model for DNA coated colloids, polymer-grafted nanoparticles and other systems with approximately isotropic interactions. The equations are generalized for arbitrary numbers of chemically distinct colloids. The advantages and limitations of such a coarse-grained approach for DNA coated colloids are discussed, as are similarities with block copolymer self-assembly. In particular, preliminary results for three species self-assembly are presented that parallel results from a two dimensional ABC triblock copolymer phase. The possibility of incorporating crystallization, dynamics, inverse statistical mechanics and multiscale modelling techniques are discussed.
Mesoscale Simulation and Machine Learning of Asphaltene Aggregation Phase Behavior and Molecular Assembly Landscapes.

PubMed

Wang, Jiang; Gayatri, Mohit A; Ferguson, Andrew L

2017-05-11

Asphaltenes constitute the heaviest fraction of the aromatic group in crude oil. Aggregation and precipitation of asphaltenes during petroleum processing costs the petroleum industry billions of dollars each year due to downtime and production inefficiencies. Asphaltene aggregation proceeds via a hierarchical self-assembly process that is well-described by the Yen-Mullins model. Nevertheless, the microscopic details of the emergent cluster morphologies and their relative stability under different processing conditions remain poorly understood. We perform coarse-grained molecular dynamics simulations of a prototypical asphaltene molecule to establish a phase diagram mapping the self-assembled morphologies as a function of temperature, pressure, and n-heptane:toluene solvent ratio informing how to control asphaltene aggregation by regulating external processing conditions. We then combine our simulations with graph matching and nonlinear manifold learning to determine low-dimensional free energy surfaces governing asphaltene self-assembly. In doing so, we introduce a variant of diffusion maps designed to handle data sets with large local density variations, and report the first application of many-body diffusion maps to molecular self-assembly to recover a pseudo-1D free energy landscape. Increasing pressure only weakly affects the landscape, serving only to destabilize the largest aggregates. Increasing temperature and toluene solvent fraction stabilizes small cluster sizes and loose bonding arrangements. Although the underlying molecular mechanisms differ, the strikingly similar effect of these variables on the free energy landscape suggests that toluene acts upon asphaltene self-assembly as an effective temperature.
Homopolymer self-assembly into stable nanoparticles: concerted action of hydrophobic association and hydrogen bonding in thermoresponsive poly(alkylacrylic acid)s.

PubMed

Sedlák, Marián

2012-03-01

A new approach to polymer self-assembly was presented recently [M. Sedlák, Č. Koňák, J. Dybal, Macromolecules 2009, 2, 7430-7438 and 7439-7446.] (1, 2) where stable polymeric nanoparticles were formed from poly(ethylacrylic acid) homopolymers without any assembly triggering additives, simply by heating polymer solution under conditions of thermosensitivity to certain temperature. In the current Article, we present successful results on poly(propylacrylic acid), which is a more hydrophobic polymer. We also present results on a less hydrophobic polymer from this series, poly(methacrylic acid), from which nanoparticles cannot be formed. Comparison of results on all three polymers gives a solid physicochemical insight and supports the molecular mechanism of the self-assembly previously suggested: The solvent quality gradually worsens upon heating of a thermosensitive polymer solution, and polymer-polymer contacts are preferred over polymer-solvent contacts, which leads to the formation of polymer assemblies. The presence of a significant amount of charge on chains prevents macroscopic phase separation. Upon subsequent cooling to laboratory temperature, the assemblies (nanoparticles) should eventually dissolve; however, this is not the case due to the fact that polymer chains brought to a close proximity at elevated temperatures become hydrogen-bonded. In addition, hydrogen bonds strengthen upon cooling. Mainly carboxylic-carboxylate hydrogen bonds (COOH····COO(-)) are responsible for the irreversibility of the process and the stability of nanoparticles. Conclusions are supported by results from static and dynamic light scattering, FTIR spectroscopy, and cryo-TEM microscopy. Size of nanoparticles can be monitored during the growth and custom-tailored by tuning critical parameters, especially the degree of ionization, temperature, and time of heating. Nanoparticles are stable over long periods of time. They are stable in a broad range of salt concentrations, including physiological conditions, and possess a mild acceptable degree of polydispersity.
Multimodal Responses of Self-Organized Circuitry in Electronically Phase Separated Materials

DOE PAGES

Herklotz, Andreas; Guo, Hangwen; Wong, Anthony T.; ...

2016-07-13

When confining an electronically phase we separated manganite film to the scale of its coexisting self-organized metallic and these insulating domains allows resistor-capacitor circuit-like responses while providing both electroresistive and magnetoresistive switching functionality.
Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors.

PubMed

Xiang, Yan; Lu, Shanfu; Jiang, San Ping

2012-11-07

As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).
MURI Center for Materials Chemistry in the Space Environment

DTIC Science & Technology

2006-11-30

ionic species in relevant reaction environments, surface photochemistry expertise, synchrotron-based measurement and irradiation, synthesis of structural...and Ne+ ions with dodecanethiolate and semifluorinated dodecanethiolate self-assembled monolayers (SAM), polyhedral oligomeric silsesquioxane (POSS...POSS/Kapton models as gas phase species, and with alkane thiol self assembled monolayers on gold surfaces, and with liquid squalane. We have also
Infrared Focal Plane Arrays Based on Semiconductor Quantum Dots

DTIC Science & Technology

2002-01-01

an ensemble of self -assembled InAs/GaAs or InAs/InP quantum dots (QDs) are typically in the range of 10-30 monolayers [1]. Here, we report on InAs...photoconductive properties of QDIPs based on self organized InAs quantum dots grown on In.52Al.48As/InP(100), using the MBE technique. Dr. Gendry grew the...composed of 10 layers of self assembled InAs dots, separated by 500 Å thick InAlAs (lattice matched to the semi-insulating InP substrate) barrier

Self-assembly of myristic acid in the presence of choline hydroxide: effect of molar ratio and temperature.

PubMed

Arnould, Audrey; Perez, Adrian A; Gaillard, Cédric; Douliez, Jean-Paul; Cousin, Fabrice; Santiago, Liliana G; Zemb, Thomas; Anton, Marc; Fameau, Anne-Laure

2015-05-01

Salt-free catanionic systems based on fatty acids exhibit a broad polymorphism by simply tuning the molar ratio between the two components. For fatty acid combined with organic amino counter-ions, very few data are available on the phase behavior obtained as a function of the molar ratio between the counter-ion and the fatty acid. We investigated the choline hydroxide/myristic acid system by varying the molar ratio, R=n(choline hydroxide)/n(myristic acid), and the temperature. Myristic acid ionization state was determined by coupling pH, conductivity and infra-red spectroscopy measurements. Self-assemblies were characterized by small angle neutron scattering and microscopy experiments. Self-assembly thermal behavior was investigated by differential scanning calorimetry, wide angle X-ray scattering and nuclear magnetic resonance. For R<1, ionized and protonated myristic acid molecules coexisted leading to the formation of facetted self-assemblies and lamellar phases. The melting process between the gel and the fluid state of these bilayers induced a structural change from facetted or lamellar objects to spherical vesicles. For R>1, myristic acid molecules were ionized and formed spherical micelles. Our study highlights that both R and temperature are two key parameters to finely control the self-assembly structure formed by myristic acid in the presence of choline hydroxide. Copyright © 2015 Elsevier Inc. All rights reserved.
Lag periods during the self-assembly of {Mo(72)Fe(30)} macroions: connection to the virus capsid formation process.

PubMed

Zhang, Jie; Li, Dong; Liu, Guang; Glover, Kerney Jebrell; Liu, Tianbo

2009-10-28

The kinetic properties of the self-assembly of hydrophilic Keplerate-type polyoxometalate (POM) {Mo(72)Fe(30)} macroanions into single-layer, vesicle-like blackberry structures in solutions were monitored by the static and dynamic laser light scattering techniques. In the presence of additional electrolytes, an obvious lag period at the initial stage of self-assembly was observed, followed by a fast increase of the scattered intensity. The whole kinetic curve is sigmoidal with a lag phase. A two-step nucleation-growth mechanism is proposed to explain this lag phase: the {Mo(72)Fe(30)} macroanions slowly associate into oligomers (mostly dimers), which are the thermodynamically unfavorable intermediates, at the initial stage; once the oligomers reach a critical concentration, the blackberry formation process is accelerated. Analytical ultracentrifugation (AUC) was used to confirm the oligomeric state in {Mo(72)Fe(30)} solution during the lag period. The length of the lag period is dependent on temperature, ionic strength, and the valent states of the additional salts, as well as the solvent content. The kinetics (including the lag period) of the blackberry formation of the {Mo(72)Fe(30)} macroanions show similarities to the self-assembly of virus capsid proteins (which are also soluble macroions) into spherical capsid shells, suggesting possible connections between the self-assembly behaviors of inorganic species and biological macromolecules.
Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

DOE PAGES

Li, Guo; Rangel, Tonatiuh; Liu, Zhen -Fei; ...

2016-03-24

Using density functional theory (DFT) with van der Waals functionals, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously-studied monomeric phases. Moreover, using a model based on many-body perturbation theory within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. As a result, we find that, independent of coverage, the HOMO energy of the linear chain phase ismore » lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy.« less
Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

NASA Astrophysics Data System (ADS)

Li, Guo; Rangel, Tonatiuh; Liu, Zhen-Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

2016-03-01

Using density functional theory (DFT) with a van der Waals density functional, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously studied monomeric phases. Moreover, using a model, which includes nonlocal polarization effects from the substrate and the neighboring molecules and incorporates many-body perturbation theory calculations within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. We find that, independent of coverage, the HOMO energy of the linear chain phase is lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy.
Switchable pH-responsive polymeric membranes prepared via block copolymer micelle assembly.

PubMed

Nunes, Suzana P; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; Karunakaran, Madhavan; Pradeep, Neelakanda; Vainio, Ulla; Peinemann, Klaus-Viktor

2011-05-24

A process is described to manufacture monodisperse asymmetric pH-responsive nanochannels with very high densities (pore density >2 × 10(14) pores per m(2)), reproducible in m(2) scale. Cylindric pores with diameters in the sub-10 nm range and lengths in the 400 nm range were formed by self-assembly of metal-block copolymer complexes and nonsolvent-induced phase separation. The film morphology was tailored by taking into account the stability constants for a series of metal-polymer complexes and confirmed by AFM. The distribution of metal-copolymer micelles was imaged by transmission electron microscopy tomography. The pH response of the polymer nanochannels is the strongest reported with synthetic pores in the nm range (reversible flux increase of more than 2 orders of magnitude when switching the pH from 2 to 8) and could be demonstrated by cryo-field emission scanning electron microscopy, SAXS, and ultra/nanofiltration experiments.
Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A. Paul; Colvin, Vicki L.

1998-01-01

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.
The role of ultra-fast solvent evaporation on the directed self-assembly of block polymer thin films

NASA Astrophysics Data System (ADS)

Drapes, Chloe; Nelson, G.; Grant, M.; Wong, J.; Baruth, A.

The directed self-assembly of nano-structures in block polymer thin films viasolvent vapor annealing is complicated by several factors, including evaporation rate. Solvent vapor annealing exposes a disordered film to solvent(s) in the vapor phase, increasing mobility and tuning surface energy, with the intention of producing an ordered structure. Recent theoretical predictions reveal the solvent evaporation affects the resultant nano-structuring. In a competition between phase separation and kinetic trapping during drying, faster solvent removal can enhance the propagation of a given morphology into the bulk of the thin film down to the substrate. Recent construction of a purpose-built, computer controlled solvent vapor annealing chamber provides control over forced solvent evaporation down to 15 ms. This is accomplished using pneumatically actuated nitrogen flow into and out of the chamber. Furthermore, in situ spectral reflectance, with 10 ms temporal resolution, monitors the swelling and evaporation. Presently, cylinder-forming polystyrene-block-polylactide thin films were swollen with 40% (by volume) tetrahydrofuran, followed by immediate evaporation under a variety of designed conditions. This includes various evaporation times, ranging from 15 ms to several seconds, and four unique rate trajectories, including linear, exponential, and combinations. Atomic force microscopy reveals specific surface, free and substrate, morphologies of the resultant films, dependent on specific evaporation conditions. Funded by the Clare Boothe Luce Foundation and Nebraska EPSCoR.
Rotary drum separator system

NASA Technical Reports Server (NTRS)

Barone, Michael R. (Inventor); Murdoch, Karen (Inventor); Scull, Timothy D. (Inventor); Fort, James H. (Inventor)

2009-01-01

A rotary phase separator system generally includes a step-shaped rotary drum separator (RDS) and a motor assembly. The aspect ratio of the stepped drum minimizes power for both the accumulating and pumping functions. The accumulator section of the RDS has a relatively small diameter to minimize power losses within an axial length to define significant volume for accumulation. The pumping section of the RDS has a larger diameter to increase pumping head but has a shorter axial length to minimize power losses. The motor assembly drives the RDS at a low speed for separating and accumulating and a higher speed for pumping.
Controlled electron doping into metallic atomic wires: Si(111)4×1-In

NASA Astrophysics Data System (ADS)

Morikawa, Harumo; Hwang, C. C.; Yeom, Han Woong

2010-02-01

We demonstrate the controllable electron doping into metallic atomic wires, indium wires self-assembled on the Si(111) surface, which feature one-dimensional (1D) band structure and temperature-driven metal-insulator transition. The electron filling of 1D metallic bands is systematically increased by alkali-metal adsorption, which, in turn, tunes the macroscopic property, that is, suppresses the metal-insulator transition. On the other hand, the dopant atoms induce a local lattice distortion without a band-gap opening, leading to a microscopic phase separation on the surface. The distinct bifunctional, electronic and structural, roles of dopants in different length scales are thus disclosed.
3D investigation on polystyrene colloidal crystals by floatage self-assembly with mixed solvent via synchrotron radiation x-ray phase-contrast computed tomography

NASA Astrophysics Data System (ADS)

Fu, Yanan; Xie, Honglan; Deng, Biao; Du, Guohao; Xiao, Tiqiao

2017-06-01

The floatage self-assembly method was introduced with mixed solvent as the medium of polystyrene sphere suspension to fabricate the colloidal crystal. The three dimensional (3D) void system of the colloidal crystal was noninvasively characterized by synchrotron radiation phase-contrast computed tomography, and the quantitative image analysis was implemented aiming to the polystyrene sphere colloidal crystal. Comparing with gravity sedimentation method, the three samples fabricated from floatage self-assembly with mixed solvents have the lowest porosity, and when ethylene glycol and water were mixed with ratio of 1:1, the lowest porosity of 27.49% could be achieved, that has been very close to the minimum porosity of ordered 3D monodisperse sphere array (26%). In single slices, the porosities and fractal dimension for the voids were calculated. The results showed that two factors would significantly influence the porosity of the whole colloidal crystal: the first deposited sphere layer's orderliness and the sedimentation speed of the spheres. The floatage self-assembly could induce a stable close-packing process, resulted from the powerful nucleation force-lateral capillary force coupled with the mixed solvent to regulate the floating upward speed for purpose of matching the assembly rate.
Phase separation and the formation of cellular bodies

NASA Astrophysics Data System (ADS)

Xu, Bin; Broedersz, Chase P.; Meir, Yigal; Wingreen, Ned S.

Cellular bodies in eukaryotic cells spontaneously assemble to form cellular compartments. Among other functions, these bodies carry out essential biochemical reactions. Cellular bodies form micron-sized structures, which, unlike canonical cell organelles, are not surrounded by membranes. A recent in vitro experiment has shown that phase separation of polymers in solution can explain the formation of cellular bodies. We constructed a lattice-polymer model to capture the essential mechanism leading to this phase separation. We used both analytical and numerical tools to predict the phase diagram of a system of two interacting polymers, including the concentration of each polymer type in the condensed and dilute phase.
Dendronization-induced phase-transfer, stabilization and self-assembly of large colloidal Au nanoparticles

NASA Astrophysics Data System (ADS)

Malassis, Ludivine; Jishkariani, Davit; Murray, Christopher B.; Donnio, Bertrand

2016-07-01

The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates.The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates. Electronic supplementary information (ESI) available: TEM microscope images. See DOI: 10.1039/c6nr03404g
Self-assembled morphologies of an amphiphilic Y-shaped weak polyelectrolyte in a thin film.

PubMed

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2017-11-29

Different from the self-assembly of neutral polymers, polyelectrolytes self-assemble into smaller aggregates with a more loosely assembled structure, which results from the repulsive forces acting between similar electrical compositions with the introduction of ions. The Y-shaped weak polyelectrolytes self-assemble into a core-shell type cylindrical structure with a hexagonal arrangement in a thin film, whose thickness is smaller than the gyration radius of the polymer chain. The corresponding formation mechanism consists of enrichment of the same components, adjustment of the shape of the aggregate, and the subsequent separation into individual aggregates. With the increase in the thickness of the thin film until it exceeds the gyration radius of the polymer chain, combined with the greater freedom of movement along the direction of thin film thickness, the self-assembled structure changes into a micellar structure. Under confinement, the repulsive force to the polymeric components is weakened by the repulsive forces among polyelectrolyte components with like charges, and this helps in generating aggregates with more uniform size and density distribution. In particular, when the repulsive force between the walls and the core forming components is greater than that between the walls and the shell forming components, such asymmetric confinement produces a crossed-cylindrical structure with nearly perpendicular arrangement of two cylinder arrays. Similarly, a novel three-crossed cylinder morphology is self-assembled upon removal of confinement.
Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes.

PubMed

Moghaddam, Minoo J; de Campo, Liliana; Kirby, Nigel; Drummond, Calum J

2012-10-05

A series of chelating amphiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.
Micellar Self-Assembly of Recombinant Resilin-/Elastin-Like Block Copolypeptides.

PubMed

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

2017-08-14

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

NASA Astrophysics Data System (ADS)

Ronti, Michela; Kantorovich, Sofia

We are studying low temperature structural transitions in dipolar hard spheres (DHS), combining grand-canonical Monte Carlo simulations and direct analytical theoretical calculations. DHS is characterized by long-range anisotropic interactions: it consists of a point dipole at the center of a hard sphere. We are interested in low temperature and low density phase behaviour of DHS systems. From a theoretical point of view the process of self-assembly is not responsible for a phase transition; this belief was completely reverted by theoretical studies showing that the process of self-assembly is alone capable to induce phase transition. On the other hand in the last years it was proved that no sign of critical behaviour is observed, implementing efficient and tailored Monte Carlo algorithms. Moreover a theoretical approach based on Density Functional Theory was developed: a series of structural transitions were discovered providing evidence of a hierarchy in the structures on cooling. We are performing free-energy calculations in order to draw the phase diagram of DHS model. Comparing the numerical results with the theoretical ones shed light on the scenario of temperature induced structural transitions in magnetic nanocolloids. Etn-COLLDENSE (H2020-MCSA-ITN-2014, Grant No. 642774).
Large three-dimensional photonic crystals based on monocrystalline liquid crystal blue phases.

PubMed

Chen, Chun-Wei; Hou, Chien-Tsung; Li, Cheng-Chang; Jau, Hung-Chang; Wang, Chun-Ta; Hong, Ching-Lang; Guo, Duan-Yi; Wang, Cheng-Yu; Chiang, Sheng-Ping; Bunning, Timothy J; Khoo, Iam-Choon; Lin, Tsung-Hsien

2017-09-28

Although there have been intense efforts to fabricate large three-dimensional photonic crystals in order to realize their full potential, the technologies developed so far are still beset with various material processing and cost issues. Conventional top-down fabrications are costly and time-consuming, whereas natural self-assembly and bottom-up fabrications often result in high defect density and limited dimensions. Here we report the fabrication of extraordinarily large monocrystalline photonic crystals by controlling the self-assembly processes which occur in unique phases of liquid crystals that exhibit three-dimensional photonic-crystalline properties called liquid-crystal blue phases. In particular, we have developed a gradient-temperature technique that enables three-dimensional photonic crystals to grow to lateral dimensions of ~1 cm (~30,000 of unit cells) and thickness of ~100 μm (~ 300 unit cells). These giant single crystals exhibit extraordinarily sharp photonic bandgaps with high reflectivity, long-range periodicity in all dimensions and well-defined lattice orientation.Conventional fabrication approaches for large-size three-dimensional photonic crystals are problematic. By properly controlling the self-assembly processes, the authors report the fabrication of monocrystalline blue phase liquid crystals that exhibit three-dimensional photonic-crystalline properties.
Fabrication of MTN-type zeolite by self-assembling of supramolecular compound

NASA Astrophysics Data System (ADS)

Huang, Aisheng; Caro, Jürgen

2009-10-01

MTN-type (Zeolite Socony Mobil Thirty-Nine) zeolite was prepared at 473 K by a novel method through self-assembling of a supramolecular compound called 2,4,6-tris (4-pyridyl) triazine (TPT) in DMF (N,N-dimethylformamide). The effects of fluoride, DMF and germanium on the synthesis of MTN-type zeolite were investigated. The crystallization was facilitated by adding fluoride to the synthesis solution, resulting in the formation of highly crystalline MTN samples, while some amorphous phase was observed in fluoride-free batches. DMF was required to obtain a highly crystalline MTN sample, since TPT dissolves easier in DMF than in water, thus facilitating the self-assembling of TPT into a 3D network to structure the MTN framework. The MTN structure could be synthesized at low germanium content (Ge/Si≤0.18), while AST (AlPO 4-sixteen) as a foreign phase is formed at high germanium substitution (Ge/Si≥0.5).
Arbitrary lattice symmetries via block copolymer nanomeshes

PubMed Central

Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

2015-01-01

Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566
Water ordering controls the dynamic equilibrium of micelle-fibre formation in self-assembly of peptide amphiphiles.

PubMed

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

2016-08-24

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

New support for high-performance liquid chromatography based on silica coated with alumina particles.

PubMed

Silveira, José Leandro R; Dib, Samia R; Faria, Anizio M

2014-01-01

A new material based on silica coated with alumina nanoparticles was proposed for use as a chromatographic support for reversed-phase high-performance liquid chromatography. Alumina nanoparticles were synthesized by a sol-gel process in reversed micelles composed of sodium bis(2-ethylhexyl)sulfosuccinate, and the support material was formed by the self-assembly of alumina layers on silica spheres. Spectroscopic and (29)Si nuclear magnetic resonance results showed evidence of chemical bonds between the alumina nanoparticles and the silica spheres, while morphological characterizations showed that the aluminized silica maintained the morphological properties of silica desired for chromatographic purposes after alumina incorporation. Stability studies indicated that bare silica showed high dissolution (~83%), while the aluminized silica remained practically unchanged (99%) after passing one liter of the alkaline mobile phase, indicating high stability under alkaline conditions. The C18 bonded aluminized silica phase showed great potential for use in high-performance liquid chromatography to separate basic molecules in the reversed-phase mode.
Computer-aided design of nano-filter construction using DNA self-assembly

NASA Astrophysics Data System (ADS)

Mohammadzadegan, Reza; Mohabatkar, Hassan

2007-01-01

Computer-aided design plays a fundamental role in both top-down and bottom-up nano-system fabrication. This paper presents a bottom-up nano-filter patterning process based on DNA self-assembly. In this study we designed a new method to construct fully designed nano-filters with the pores between 5 nm and 9 nm in diameter. Our calculations illustrated that by constructing such a nano-filter we would be able to separate many molecules.
Phase separation of self-propelled ballistic particles

NASA Astrophysics Data System (ADS)

Bruss, Isaac R.; Glotzer, Sharon C.

2018-04-01

Self-propelled particles phase-separate into coexisting dense and dilute regions above a critical density. The statistical nature of their stochastic motion lends itself to various theories that predict the onset of phase separation. However, these theories are ill-equipped to describe such behavior when noise becomes negligible. To overcome this limitation, we present a predictive model that relies on two density-dependent timescales: τF, the mean time particles spend between collisions; and τC, the mean lifetime of a collision. We show that only when τF<τC do collisions last long enough to develop a growing cluster and initiate phase separation. Using both analytical calculations and active particle simulations, we measure these timescales and determine the critical density for phase separation in both two and three dimensions.
Prawn Shell Derived Chitin Nanofiber Membranes as Advanced Sustainable Separators for Li/Na-Ion Batteries.

PubMed

Zhang, Tian-Wen; Shen, Bao; Yao, Hong-Bin; Ma, Tao; Lu, Lei-Lei; Zhou, Fei; Yu, Shu-Hong

2017-08-09

Separators, necessary components to isolate cathodes and anodes in Li/Na-ion batteries, are consumed in large amounts per year; thus, their sustainability is a concerning issue for renewable energy storage systems. However, the eco-efficient and environmentally friendly fabrication of separators with a high mechanical strength, excellent thermal stability, and good electrolyte wettability is still challenging. Herein, we reported the fabrication of a new type of separators for Li/Na-ion batteries through the self-assembly of eco-friendly chitin nanofibers derived from prawn shells. We demonstrated that the pore size in the chitin nanofiber membrane (CNM) separator can be tuned by adjusting the amount of pore generation agent (sodium dihydrogen citrate) in the self-assembly process of chitin nanofibers. By optimizing the pore size in CNM separators, the electrochemical performance of the LiFePO 4 /Li half-cell with a CNM separator is comparable to that with a commercialized polypropylene (PP) separator. More attractively, the CNM separator showed a much better performance in the LiFePO 4 /Li cell at 120 °C and Na 3 V 2 (PO 4 ) 3 /Na cell than the PP separator. The proposed fabrication of separators by using natural raw materials will play a significant contribution to the sustainable development of renewable energy storage systems.
Inverse design of multicomponent assemblies

NASA Astrophysics Data System (ADS)

Piñeros, William D.; Lindquist, Beth A.; Jadrich, Ryan B.; Truskett, Thomas M.

2018-03-01

Inverse design can be a useful strategy for discovering interactions that drive particles to spontaneously self-assemble into a desired structure. Here, we extend an inverse design methodology—relative entropy optimization—to determine isotropic interactions that promote assembly of targeted multicomponent phases, and we apply this extension to design interactions for a variety of binary crystals ranging from compact triangular and square architectures to highly open structures with dodecagonal and octadecagonal motifs. We compare the resulting optimized (self- and cross) interactions for the binary assemblies to those obtained from optimization of analogous single-component systems. This comparison reveals that self-interactions act as a "primer" to position particles at approximately correct coordination shell distances, while cross interactions act as the "binder" that refines and locks the system into the desired configuration. For simpler binary targets, it is possible to successfully design self-assembling systems while restricting one of these interaction types to be a hard-core-like potential. However, optimization of both self- and cross interaction types appears necessary to design for assembly of more complex or open structures.
Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

NASA Astrophysics Data System (ADS)

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

Self-assembly of block copolymers provides opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. The conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.
Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities.

PubMed

Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B; Pink, David A

2014-11-19

Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid component, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness ?. We modelled three cases: (i) liquid?liquid nano-phase separation, (ii) solid?liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ < 0.0701 u (b) transition regime, 0.0701 u ≤ Δ ≤ 0.0916 u and (c) thick coating regime, Δ > 0.0916 u. (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0 < Δ < 7.0 nm transition regime, 7.0 < Δ < 9.2 nm and thick coating, Δ > 9.2 nm (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin coatings) and 0.94% (thick coatings). Minority components can have substantial effects upon aggregation for concentrations less than 1%.
Self-Functionalization Behind a Solution-Processed NiOx Film Used As Hole Transporting Layer for Efficient Perovskite Solar Cells.

PubMed

Ciro, John; Ramírez, Daniel; Mejía Escobar, Mario Alejandro; Montoya, Juan Felipe; Mesa, Santiago; Betancur, Rafael; Jaramillo, Franklin

2017-04-12

Fabrication of solution-processed perovskite solar cells (PSCs) requires the deposition of high quality films from precursor inks. Frequently, buffer layers of PSCs are formed from dispersions of metal oxide nanoparticles (NPs). Therefore, the development of trustable methods for the preparation of stable colloidal NPs dispersions is crucial. In this work, a novel approach to form very compact semiconducting buffer layers with suitable optoelectronic properties is presented through a self-functionalization process of the nanocrystalline particles by their own amorphous phase and without adding any other inorganic or organic functionalization component or surfactant. Such interconnecting amorphous phase composed by residual nitrate, hydroxide, and sodium ions, proved to be fundamental to reach stable colloidal dispersions and contribute to assemble the separate crystalline nickel oxide NPs in the final film, resulting in a very homogeneous and compact layer. A proposed mechanism behind the great stabilization of the nanoparticles is exposed. At the end, the self-functionalized nickel oxide layer exhibited high optoelectronic properties enabling perovskite p-i-n solar cells as efficient as 16.6% demonstrating the pertinence of the presented strategy to obtain high quality buffer layers processed in solution at room temperature.
Lyotropic liquid crystal engineering moving beyond binary compositional space - ordered nanostructured amphiphile self-assembly materials by design.

PubMed

van 't Hag, Leonie; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

2017-05-22

Ordered amphiphile self-assembly materials with a tunable three-dimensional (3D) nanostructure are of fundamental interest, and crucial for progressing several biological and biomedical applications, including in meso membrane protein crystallization, as drug and medical contrast agent delivery vehicles, and as biosensors and biofuel cells. In binary systems consisting of an amphiphile and a solvent, the ability to tune the 3D cubic phase nanostructure, lipid bilayer properties and the lipid mesophase is limited. A move beyond the binary compositional space is therefore required for efficient engineering of the required material properties. In this critical review, the phase transitions upon encapsulation of more than 130 amphiphilic and soluble additives into the bicontinuous lipidic cubic phase under excess hydration are summarized. The data are interpreted using geometric considerations, interfacial curvature, electrostatic interactions, partition coefficients and miscibility of the alkyl chains. The obtained lyotropic liquid crystal engineering design rules can be used to enhance the formulation of self-assembly materials and provides a large library of these materials for use in biomedical applications (242 references).
Nucleation by rRNA Dictates the Precision of Nucleolus Assembly.

PubMed

Falahati, Hanieh; Pelham-Webb, Bobbie; Blythe, Shelby; Wieschaus, Eric

2016-02-08

Membrane-less organelles are intracellular compartments specialized to carry out specific cellular functions. There is growing evidence supporting the possibility that such organelles form as a new phase, separating from cytoplasm or nucleoplasm. However, a main challenge to such phase separation models is that the initial assembly, or nucleation, of the new phase is typically a highly stochastic process and does not allow for the spatiotemporal precision observed in biological systems. Here, we investigate the initial assembly of the nucleolus, a membrane-less organelle involved in different cellular functions including ribosomal biogenesis. We demonstrate that the nucleolus formation is precisely timed in D. melanogaster embryos and follows the transcription of rRNA. We provide evidence that transcription of rRNA is necessary for overcoming the highly stochastic nucleation step in the formation of the nucleolus, through a seeding mechanism. In the absence of rDNA, the nucleolar proteins studied are able to form high-concentration assemblies. However, unlike the nucleolus, these assemblies are highly variable in number, location, and time at which they form. In addition, quantitative study of the changes in the nucleoplasmic concentration and distribution of these nucleolar proteins in the wild-type embryos is consistent with the role of rRNA in seeding the nucleolus formation. Copyright © 2016 Elsevier Ltd. All rights reserved.
Core microstructure, morphology and chain arrangement of block copolymer self-assemblies as investigated by thermal field-flow fractionation.

PubMed

Muza, U L; Greyling, G; Pasch, H

2018-08-10

The self-assembly of block copolymers (BCPs), as a result of solvent selectivity for one block, has recently received significant attention due to novel applications of BCPs in pharmaceuticals, biomedicine, cosmetics, electronics and nanotechnology. The correlation of BCP microstructure and the structure of the resulting self-assemblies requires advanced analytical methods. However, traditional bulk characterization techniques are limited in the quest of providing detailed information regarding molar mass (M w ), hydrodynamic size (D h ), chemical composition, and morphology for these self-assemblies. In the present study, thermal field-flow fractionation (ThFFF) is utilised to investigate the impact of core microstructure on the resultant solution properties of vesicles prepared from polystyrene-polybutadiene block copolymers (PS-b-PBd) with 1.2- and 1.4-polybutadiene blocks, respectively. As compared to investigations on the impact of the corona microstructure, the impact of core microstructure on micellar properties has largely been neglected in previous work. In N,N-dimethylacetamide (DMAc) these BCPs form vesicles having PS shells and PBd cores. D h , M w , aggregation number, and critical micelle concentration of these micelles are shown to be sensitive to the core microstructure, therefore, demonstrating the potential of microstructural differences to be used for providing tuneable pathways to specific self-assemblies. It is shown that micelles prepared from BCPs of similar PS and PBd block sizes are successfully separated by ThFFF. It is further demonstrated in this study that PS-b-PBd vesicles and PS homopolymers of identical surface chemistry (PS) and comparable D h in DMAc, can be separated by ThFFF. Copyright © 2018 Elsevier B.V. All rights reserved.
Self-assembled multicompartment liquid crystalline lipid carriers for protein, peptide, and nucleic acid drug delivery.

PubMed

Angelova, Angelina; Angelov, Borislav; Mutafchieva, Rada; Lesieur, Sylviane; Couvreur, Patrick

2011-02-15

Lipids and lipopolymers self-assembled into biocompatible nano- and mesostructured functional materials offer many potential applications in medicine and diagnostics. In this Account, we demonstrate how high-resolution structural investigations of bicontinuous cubic templates made from lyotropic thermosensitive liquid-crystalline (LC) materials have initiated the development of innovative lipidopolymeric self-assembled nanocarriers. Such structures have tunable nanochannel sizes, morphologies, and hierarchical inner organizations and provide potential vehicles for the predictable loading and release of therapeutic proteins, peptides, or nucleic acids. This Account shows that structural studies of swelling of bicontinuous cubic lipid/water phases are essential for overcoming the nanoscale constraints for encapsulation of large therapeutic molecules in multicompartment lipid carriers. For the systems described here, we have employed time-resolved small-angle X-ray scattering (SAXS) and high-resolution freeze-fracture electronic microscopy (FF-EM) to study the morphology and the dynamic topological transitions of these nanostructured multicomponent amphiphilic assemblies. Quasi-elastic light scattering and circular dichroism spectroscopy can provide additional information at the nanoscale about the behavior of lipid/protein self-assemblies under conditions that approximate physiological hydration. We wanted to generalize these findings to control the stability and the hydration of the water nanochannels in liquid-crystalline lipid nanovehicles and confine therapeutic biomolecules within these structures. Therefore we analyzed the influence of amphiphilic and soluble additives (e.g. poly(ethylene glycol)monooleate (MO-PEG), octyl glucoside (OG), proteins) on the nanochannels' size in a diamond (D)-type bicontinuous cubic phase of the lipid glycerol monooleate (MO). At body temperature, we can stabilize long-living swollen states, corresponding to a diamond cubic phase with large water channels. Time-resolved X-ray diffraction (XRD) scans allowed us to detect metastable intermediate and coexisting structures and monitor the temperature-induced phase sequences of mixed systems containing glycerol monooleate, a soluble protein macromolecule, and an interfacial curvature modulating agent. These observed states correspond to the stages of the growth of the nanofluidic channel network. With the application of a thermal stimulus, the system becomes progressively more ordered into a double-diamond cubic lattice formed by a bicontinuous lipid membrane. High-resolution freeze-fracture electronic microscopy indicates that nanodomains are induced by the inclusion of proteins into nanopockets of the supramolecular cubosomic assemblies. These results contribute to the understanding of the structure and dynamics of functionalized self-assembled lipid nanosystems during stimuli-triggered LC phase transformations.
Chiral self-assembly of helical particles.

PubMed

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

2016-01-01

The shape of the building blocks plays a crucial role in directing self-assembly towards desired architectures. Out of the many different shapes, the 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, an 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.
Self-assembly of Archimedean tilings with enthalpically and entropically patchy polygons.

PubMed

Millan, Jaime A; Ortiz, Daniel; van Anders, Greg; Glotzer, Sharon C

2014-03-25

Considerable progress in the synthesis of anisotropic patchy nanoplates (nanoplatelets) promises a rich variety of highly ordered two-dimensional superlattices. Recent experiments of superlattices assembled from nanoplates confirm the accessibility of exotic phases and motivate the need for a better understanding of the underlying self-assembly mechanisms. Here, we present experimentally accessible, rational design rules for the self-assembly of the Archimedean tilings from polygonal nanoplates. The Archimedean tilings represent a model set of target patterns that (i) contain both simple and complex patterns, (ii) are comprised of simple regular shapes, and (iii) contain patterns with potentially interesting materials properties. Via Monte Carlo simulations, we propose a set of design rules with general applicability to one- and two-component systems of polygons. These design rules, specified by increasing levels of patchiness, correspond to a reduced set of anisotropy dimensions for robust self-assembly of the Archimedean tilings. We show for which tilings entropic patches alone are sufficient for assembly and when short-range enthalpic interactions are required. For the latter, we show how patchy these interactions should be for optimal yield. This study provides a minimal set of guidelines for the design of anisostropic patchy particles that can self-assemble all 11 Archimedean tilings.
Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A.P.; Colvin, V.L.

1998-05-12

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed. 10 figs.
General Mechanism of Morphology Transition and Spreading Area-dependent Phase Diagram of Block Copolymer Self-assembly at the Air/Water Interface

NASA Astrophysics Data System (ADS)

Kim, Dong Hyup; Kim, So Youn

Block copolymers (BCPs) can be self-assembled forming periodic nanostructures, which have been employed in many applications. While general agreements exist for the phase diagrams of BCP self-assembly in bulk or thin films, a fundamental understanding of BCP structures at the air/water interface still remain elusive. The current study explains morphology transition of BCPs with relative fraction of each block at the air/water interface: block fraction is the only parameter to control the morphology. In this study, we show morphology transitions from spherical to cylindrical and planar structures with neat polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) via reducing the spreading area of BCP solution at the air/water interface. For example, PS-b-P2VP in a fixed block fraction known to form only spheres can experience sphere to cylinder or lamellar transitions depending on the spreading area at the air/water interface. Suggesting a new parameter to control the interfacial assembly of BCPs, a complete phase diagram is drawn with two paramters: relative block fraction and spreading area. We also explain the morphology transition with the combinational description of dewetting mechanism and spring effect of hydrophilic block.
Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity

NASA Astrophysics Data System (ADS)

Yu, Haizhou; Qiu, Xiaoyan; Nunes, Suzana P.; Peinemann, Klaus-Viktor

2014-06-01

The design of micro- or nanoparticles that can encapsulate sensitive molecules such as drugs, hormones, proteins or peptides is of increasing importance for applications in biotechnology and medicine. Examples are micelles, liposomes and vesicles. The tiny and, in most cases, hollow spheres are used as vehicles for transport and controlled administration of pharmaceutical drugs or nutrients. Here we report a simple strategy to fabricate microspheres by block copolymer self-assembly. The microsphere particles have monodispersed nanopores that can act as pH-responsive gates. They contain a highly porous internal structure, which is analogous to the Schwarz P structure. The internal porosity of the particles contributes to their high sorption capacity and sustained release behaviour. We successfully separated similarly sized proteins using these particles. The ease of particle fabrication by macrophase separation and self-assembly, and the robustness of the particles makes them ideal for sorption, separation, transport and sustained delivery of pharmaceutical substances.
Nanostructure Control of Biologically Inspired Polymers

NASA Astrophysics Data System (ADS)

Rosales, Adrianne Marie

Biological polymers, such as polypeptides, are responsible for many of life's most sophisticated functions due to precisely evolved hierarchical structures. These protein structures are the result of monodisperse sequences of amino acids that fold into well-defined chain shapes and tertiary structures. Recently, there has been much interest in the design of such sequence-specific polymers for materials applications in fields ranging from biotechnology to separations membranes. Non-natural polymers offer the stability and robustness necessary for materials applications; however, our ability to control monomer sequence in non-natural polymers has traditionally operated on a much simpler level. In addition, the relationship between monomer sequence and self-assembly is not well understood for biological molecules, much less synthetic polymers. Thus, there is a need to explore self-assembly phase space with sequence using a model system. Polypeptoids are non-natural, sequence-specific polymers that offer the opportunity to probe the effect of sequence on self-assembly. A variety of monomer interactions have an impact on polymer properties, such as chirality, hydrophobicity, and electrostatic interactions. Thus, a necessary starting point for this project was to investigate monomer sequence effects on the bulk properties of polypeptoid homopolymers. It was found that several polypeptoids have experimentally accessible melting transitions that are dependent on the choice of side chains, and it was shown that this transition is tuned by the incorporation of "defects" or a comonomer. The polypeptoid chain shape is also controlled with the choice of monomer and monomer sequence. By using at least 50% monomers with bulky, chiral side chains, the polypeptoid backbone is sterically twisted into a helix, and as found for the first time in this work, the persistence length is increased. However, this persistence length, which is a measure of the stiffness of the polymer, is small compared to other folded helices, indicating the conformational flexibility of polypeptoid chains. With a firmer understanding of how monomer sequence and composition influence polypeptoid bulk properties, we designed block copolymer systems for self-assembly. Because the governing parameters of block copolymer self-assembly are well understood, this architecture provides a convenient starting point for probing the effect of changing polymer sequence. We found that polystyrene-polypeptoid block copolymers readily self-assemble into hexagonally-packed and lamellar morphologies with long range order, and furthermore, sequence control of the polypeptoid block enables us to tune the strength of segregation (and therefore the order-disorder transition) of the block copolymer. Polypeptoid chain shape also affects self-assembly. In classical synthetic block copolymers, it has typically been difficult to change chain shape without also changing polymer chemistry and therefore other factors affecting self-assembly. The advantage of the polypeptoid system is that it is modular, as the side chain chemistry (and therefore polymer properties) can easily be changed without changing the backbone chemistry. Thus, we have decoupled conformational effects from chemical composition by comparing the self-assembly of block copolymers containing either a helical peptoid block or its racemic, non-helical analog. The increase in the persistence length of the peptoid block due to helicity translates to an increase in the morphological domain spacing. In this work, we further the understanding of the effect of monomer sequence on bulk polypeptoid properties and self-assembly. Our findings pave the way for the rational design of structured synthetic polymers with tunable, sequence-specific properties.
Supramolecular ribbons from amphiphilic trisamides self-assembly.

PubMed

García, Fátima; Buendía, Julia; Sánchez, Luis

2011-08-05

Two amphiphilic C(3)-symmetric OPE-based trisamides have been synthesized and their self-assembling features investigated in solution and on surface. Variable-temperature UV-vis experiments demonstrate the cooperative supramolecular polymerization of these trisamides that self-assemble by the operation of triple C═O···H-N H-bonding arrays between the amide functional groups and π-π stacking between the aromatic units. The helical organization of the aggregates has been demonstrated by circular dichroism at a concentration as low as 1 × 10(-4) M in acetonitrile. In the reported trisamides, the large hydrophobic aromatic core acts as a solvophobic module impeding the interaction between the polar TEG chains and the amide H-bonds. This strategy makes unnecessary the separation of the amide functional groups to the polar tri(ethylene glycol) chains by paraffinic fragments. Achiral trisamide 1 self-assembles into flat ribbon-like structures that experience an amplification of chirality by the addition of a small amount of chiral 2 that generates twisted stripes.
STM study of C60F18 high dipole moment molecules on Au(111)

NASA Astrophysics Data System (ADS)

Bairagi, K.; Bellec, A.; Chumakov, R. G.; Menshikov, K. A.; Lagoute, J.; Chacon, C.; Girard, Y.; Rousset, S.; Repain, V.; Lebedev, A. M.; Sukhanov, L. P.; Svechnikov, N. Yu.; Stankevich, V. G.

2015-11-01

Scanning tunneling microscopy and spectroscopy studies of C60F18 molecules deposited on Au(111) are reported and compared to C60 molecules both at liquid helium temperature and room temperature (RT). Whereas adsorption and electronic properties of C60F18 single molecules were studied at low temperature (LT), self-assemblies were investigated at RT. In both cases, the fluorine atoms of the C60F18 molecules are pointed towards the surface. Individual C60F18 molecules on Au(111) have a HOMO-LUMO gap of 2.9 eV. The self-assembled islands exhibit a close-packed hexagonal lattice with amorphous borders. The comparison with C60 molecules clearly demonstrates the influence of the C60F18 electric dipole moment (EDM) on the electronic properties of single molecules and on the thermodynamics of self-assembled islands. Besides, the apparent height value of a separate molecule increases in a self-assembly environment as a result of a depolarization phenomenon.

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

PubMed

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

2018-04-24

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

PubMed

Janasz, Lukasz; Luczak, Adam; Marszalek, Tomasz; Dupont, Bertrand G R; Jung, Jaroslaw; Ulanski, Jacek; Pisula, Wojciech

2017-06-21

Ambipolar organic field-effect transistors (OFETs) based on heterojunction active films still suffer from an imbalance in the transport of electrons and holes. This problem is related to an uncontrolled phase separation between the donor and acceptor organic semiconductors in the thin films. In this work, we have developed a concept to improve the phase separation in heterojunction transistors to enhance their ambipolar performance. This concept is based on preaggregation of the donor polymer, in this case poly(3-hexylthiophene) (P3HT), before solution mixing with the small-molecular-weight acceptor, phenyl-C61-butyric acid methyl ester (PCBM). The resulting heterojunction transistor morphology consists of self-assembled P3HT fibers embedded in a PCBM matrix, ensuring balanced mobilities reaching 0.01 cm 2 /V s for both holes and electrons. These are the highest mobility values reported so far for ambipolar OFETs based on P3HT/PCBM blends. Preaggregation of the conjugated polymer before fabricating binary blends can be regarded as a general concept for a wider range of semiconducting systems applicable in organic electronic devices.
Development of Self-Assembled Nanoscale Templates via Microphase Separation Induced by Polymer Brushes

NASA Astrophysics Data System (ADS)

Chu, Elza

Phase separation in soft matter has been the crucial element in generating hybrid materials, such as polymer blends and mixed polymer brushes. This dissertation discusses two methods of developing self-assembled nanoscale templates via microphase separation induced by polymer brush synthesis. This work introduces a novel soft substrate approach with renewable grafting sites where polyacrylamide is "grafted through" chitosan soft substrates. The mechanism of grafting leads to ordered arrays of filament-like nanostructures spanning the chitosan-air interface. Additionally, the chemical composition of the filaments allows for post-chemical modification to change the physical properties of the filaments, and subsequently tailor surfaces for specific application. Unlike traditional materials, multi-functional or "smart" materials, such as binary polymer brushes (BPB) are capable of spontaneously changing the spatial distribution of functional groups and morphology at the surface upon external stimuli. Although promising in principle, the limited range of available complementary polymers with common non-selective solvents confines the diversity of usable materials and restricts any further advancement in the field. This dissertation also covers the fabrication and characterization of responsive nanoscale polystyrene templates or "mosaic" brushes that are capable of changing interfacial composition upon exposure to varying solvent qualities. Using a "mosaic" brush template is a unique approach that allows the fabrication of strongly immiscible polymer BPB without the need for a common solvent. The synthesis of such BPB is exemplified by two strongly immiscible polymers, i.e. polystyrene (polar) and polyacrylamide (non-polar), where polyacrylamide brush is "graft through" a Si-substrate modified with the polystyrene collapsed "mosaic" brush. The surface exhibits solvent-triggered responses, as well as application potential for anti-biofouling.
Selective directed self-assembly of coexisting morphologies using block copolymer blends

PubMed Central

Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

2016-01-01

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist. PMID:27480327
Selective directed self-assembly of coexisting morphologies using block copolymer blends

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

Stein, A.; Wright, G.; Yager, K. G.

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. We expand on traditional DSA chemical patterning. Moreover, a blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This contrastsmore » with typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.« less
Selective directed self-assembly of coexisting morphologies using block copolymer blends

DOE PAGES

Stein, A.; Wright, G.; Yager, K. G.; ...

2016-08-02

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. We expand on traditional DSA chemical patterning. Moreover, a blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This contrastsmore » with typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.« less
Self-replicating machines in continuous space with virtual physics.

PubMed

Smith, Arnold; Turney, Peter; Ewaschuk, Robert

2003-01-01

JohnnyVon is an implementation of self-replicating machines in continuous two-dimensional space. Two types of particles drift about in a virtual liquid. The particles are automata with discrete internal states but continuous external relationships. Their internal states are governed by finite state machines, but their external relationships are governed by a simulated physics that includes Brownian motion, viscosity, and springlike attractive and repulsive forces. The particles can be assembled into patterns that can encode arbitrary strings of bits. We demonstrate that, if an arbitrary seed pattern is put in a soup of separate individual particles, the pattern will replicate by assembling the individual particles into copies of itself. We also show that, given sufficient time, a soup of separate individual particles will eventually spontaneously form self-replicating patterns. We discuss the implications of JohnnyVon for research in nanotechnology, theoretical biology, and artificial life.
Proline-poor hydrophobic domains modulate the assembly and material properties of polymeric elastin.

PubMed

Muiznieks, Lisa D; Reichheld, Sean E; Sitarz, Eva E; Miao, Ming; Keeley, Fred W

2015-10-01

Elastin is a self-assembling extracellular matrix protein that provides elasticity to tissues. For entropic elastomers such as elastin, conformational disorder of the monomer building block, even in the polymeric form, is essential for elastomeric recoil. The highly hydrophobic monomer employs a range of strategies for maintaining disorder and flexibility within hydrophobic domains, particularly involving a minimum compositional threshold of proline and glycine residues. However, the native sequence of hydrophobic elastin domain 30 is uncharacteristically proline-poor and, as an isolated polypeptide, is susceptible to formation of amyloid-like structures comprised of stacked β-sheet. Here we investigated the biophysical and mechanical properties of multiple sets of elastin-like polypeptides designed with different numbers of proline-poor domain 30 from human or rat tropoelastins. We compared the contributions of these proline-poor hydrophobic sequences to self-assembly through characterization of phase separation, and to the tensile properties of cross-linked, polymeric materials. We demonstrate that length of hydrophobic domains and propensity to form β-structure, both affecting polypeptide chain flexibility and cross-link density, play key roles in modulating elastin mechanical properties. This study advances the understanding of elastin sequence-structure-function relationships, and provides new insights that will directly support rational approaches to the design of biomaterials with defined suites of mechanical properties. © 2015 Wiley Periodicals, Inc.
Photoinduced Thiol-ene Chemistry Applied to the Synthesis of Self-Assembling Elastin-Inspired Glycopeptides.

PubMed

Piccirillo, Germano; Pepe, Antonietta; Bedini, Emiliano; Bochicchio, Brigida

2017-02-21

Synthetic (glyco)peptides inspired by proteins able to self-assemble are appealing biomaterials in the field of tissue engineering and regenerative medicine. Herein, for the first time, taking advantage of thiol-ene chemistry coupled to solid-phase peptide synthesis, a self-assembling peptide inspired by elastin protein was bioconjugated to three carbohydrates in order to obtain the corresponding glycopeptides. They were studied at the molecular and supramolecular level. The results show that the carbohydrate influences the molecular conformation of the glycopeptide and its self-aggregation properties as well. As future perspective, the results could enable us to tune the final self-aggregation properties of the glycopeptide by changing the sugar moiety. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Gries, K. I.; Vogel, S.; Straubinger, R.

The self-assembled formation of ordered, vertically stacked rocksalt/wurtzite Mg{sub x}Zn{sub 1−x}O heterostructures by planar phase separation is shown. These heterostructures form quasi “natural” two-dimensional hetero-interfaces between the different phases upon annealing of MgO-oversaturated wurtzite Mg{sub x}Zn{sub 1−x}O layers grown by plasma-assisted molecular beam epitaxy on c-plane sapphire substrates. The optical absorption spectra show a red shift simultaneous with the appearance of a cubic phase upon annealing at temperatures between 900 °C and 1000 °C. Transmission electron microscopy reveals that these effects are caused by phase separation leading to the formation of a vertically ordered rock salt/wurtzite heterostructures. To explain these observations, wemore » suggest a phase separation epitaxy model that considers this process being initiated by the formation of a cubic (Mg,Zn)Al{sub 2}O{sub 4} spinel layer at the interface to the sapphire substrate, acting as a planar seed for the epitaxial precipitation of rock salt Mg{sub x}Zn{sub 1−x}O. The equilibrium fraction x of magnesium in the resulting wurtzite (rock salt) layers is approximately 0.15 (0.85), independent of the MgO content of the as-grown layer and determined by the annealing temperature. This model is confirmed by photoluminescence analysis of the resulting layer systems after different annealing temperatures. In addition, we show that the thermal annealing process results in a significant reduction in the density of edge- and screw-type dislocations, providing the possibility to fabricate high quality templates for quasi-homoepitaxial growth.« less
An Active Approach to Engineering the Microscopic

NASA Astrophysics Data System (ADS)

Mallory, Stewart A.

Active colloids, which can be thought of as the synthetic analog of swimming bacteria, exhibit remarkable collective behavior. Using a combination of computer simulations and analytical theory, I have looked to provide quantitative answers to fundamental questions concerning the phase behavior and material properties of active suspensions. A primary focus of my Ph.D work has been devoted to developing novel techniques to exploit the active nature of these particles to manipulate and self-assemble matter at the colloidal scale. In the introductory chapter, I discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field. The remaining chapters are each self-contained and focus on a particular topic within active colloidal self-assembly. These chapters are ordered in terms of system complexity, and begins with characterizing the thermomechanical properties of an ideal active fluid. The next three chapters are centered around characterizing the effective interactions induced by an active suspension. The last two chapters focus on using self-propulsion as a tool to improve colloidal self-assembly, and understanding the interplay between self-propulsion and anisotropic pair interaction.
An investigation of Hebbian phase sequences as assembly graphs

PubMed Central

Almeida-Filho, Daniel G.; Lopes-dos-Santos, Vitor; Vasconcelos, Nivaldo A. P.; Miranda, José G. V.; Tort, Adriano B. L.; Ribeiro, Sidarta

2014-01-01

Hebb proposed that synapses between neurons that fire synchronously are strengthened, forming cell assemblies and phase sequences. The former, on a shorter scale, are ensembles of synchronized cells that function transiently as a closed processing system; the latter, on a larger scale, correspond to the sequential activation of cell assemblies able to represent percepts and behaviors. Nowadays, the recording of large neuronal populations allows for the detection of multiple cell assemblies. Within Hebb's theory, the next logical step is the analysis of phase sequences. Here we detected phase sequences as consecutive assembly activation patterns, and then analyzed their graph attributes in relation to behavior. We investigated action potentials recorded from the adult rat hippocampus and neocortex before, during and after novel object exploration (experimental periods). Within assembly graphs, each assembly corresponded to a node, and each edge corresponded to the temporal sequence of consecutive node activations. The sum of all assembly activations was proportional to firing rates, but the activity of individual assemblies was not. Assembly repertoire was stable across experimental periods, suggesting that novel experience does not create new assemblies in the adult rat. Assembly graph attributes, on the other hand, varied significantly across behavioral states and experimental periods, and were separable enough to correctly classify experimental periods (Naïve Bayes classifier; maximum AUROCs ranging from 0.55 to 0.99) and behavioral states (waking, slow wave sleep, and rapid eye movement sleep; maximum AUROCs ranging from 0.64 to 0.98). Our findings agree with Hebb's view that assemblies correspond to primitive building blocks of representation, nearly unchanged in the adult, while phase sequences are labile across behavioral states and change after novel experience. The results are compatible with a role for phase sequences in behavior and cognition. PMID:24782715
Motility-Induced Phase Separation

NASA Astrophysics Data System (ADS)

Cates, Michael E.; Tailleur, Julien

2015-03-01

Self-propelled particles include both self-phoretic synthetic colloids and various microorganisms. By continually consuming energy, they bypass the laws of equilibrium thermodynamics. These laws enforce the Boltzmann distribution in thermal equilibrium: The steady state is then independent of kinetic parameters. In contrast, self-propelled particles tend to accumulate where they move more slowly. They may also slow down at high density for either biochemical or steric reasons. This creates positive feedback, which can lead to motility-induced phase separation (MIPS) between dense and dilute fluid phases. At leading order in gradients, a mapping relates variable-speed, self-propelled particles to passive particles with attractions. This deep link to equilibrium phase separation is confirmed by simulations but generally breaks down at higher order in gradients: New effects, with no equilibrium counterpart, then emerge. We give a selective overview of the fast-developing field of MIPS, focusing on theory and simulation but including a brief speculative survey of its experimental implications.
Complex coacervation of supercharged proteins with polyelectrolytes.

PubMed

Obermeyer, Allie C; Mills, Carolyn E; Dong, Xue-Hui; Flores, Romeo J; Olsen, Bradley D

2016-04-21

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.
Stress-Triggered Phase Separation Is an Adaptive, Evolutionarily Tuned Response

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

Riback, Joshua A.; Katanski, Christopher D.; Kear-Scott, Jamie L.

In eukaryotic cells, diverse stresses trigger coalescence of RNA-binding proteins into stress granules. In vitro, stress-granule-associated proteins can demix to form liquids, hydrogels, and other assemblies lacking fixed stoichiometry. Observing these phenomena has generally required conditions far removed from physiological stresses. We show that poly(A)-binding protein (Pab1 in yeast), a defining marker of stress granules, phase separates and forms hydrogels in vitro upon exposure to physiological stress conditions. Other RNA-binding proteins depend upon low-complexity regions (LCRs) or RNA for phase separation, whereas Pab1’s LCR is not required for demixing, and RNA inhibits it. Based on unique evolutionary patterns, we createmore » LCR mutations, which systematically tune its biophysical properties and Pab1 phase separation in vitro and in vivo. Mutations that impede phase separation reduce organism fitness during prolonged stress. Poly(A)-binding protein thus acts as a physiological stress sensor, exploiting phase separation to precisely mark stress onset, a broadly generalizable mechanism.« less
Colour-producing β-keratin nanofibres in blue penguin (Eudyptula minor) feathers

PubMed Central

D'Alba, Liliana; Saranathan, Vinodkumar; Clarke, Julia A.; Vinther, Jakob A.; Prum, Richard O.; Shawkey, Matthew D.

2011-01-01

The colours of living organisms are produced by the differential absorption of light by pigments (e.g. carotenoids, melanins) and/or by the physical interactions of light with biological nanostructures, referred to as structural colours. Only two fundamental morphologies of non-iridescent nanostructures are known in feathers, and recent work has proposed that they self-assemble by intracellular phase separation processes. Here, we report a new biophotonic nanostructure in the non-iridescent blue feather barbs of blue penguins (Eudyptula minor) composed of parallel β-keratin nanofibres organized into densely packed bundles. Synchrotron small angle X-ray scattering and two-dimensional Fourier analysis of electron micrographs of the barb nanostructure revealed short-range order in the organization of fibres at the appropriate size scale needed to produce the observed colour by coherent scattering. These two-dimensional quasi-ordered penguin nanostructures are convergent with similar arrays of parallel collagen fibres in avian and mammalian skin, but constitute a novel morphology for feathers. The identification of a new class of β-keratin nanostructures adds significantly to the known mechanisms of colour production in birds and suggests additional complexity in their self-assembly. PMID:21307042
Colour-producing [beta]-keratin nanofibres in blue penguin (Eudyptula minor) feathers

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

D; Alba, Liliana; Saranathan, Vinodkumar

2012-03-26

The colours of living organisms are produced by the differential absorption of light by pigments (e.g. carotenoids, melanins) and/or by the physical interactions of light with biological nanostructures, referred to as structural colours. Only two fundamental morphologies of non-iridescent nanostructures are known in feathers, and recent work has proposed that they self-assemble by intracellular phase separation processes. Here, we report a new biophotonic nanostructure in the non-iridescent blue feather barbs of blue penguins (Eudyptula minor) composed of parallel {beta}-keratin nanofibres organized into densely packed bundles. Synchrotron small angle X-ray scattering and two-dimensional Fourier analysis of electron micrographs of the barbmore » nanostructure revealed short-range order in the organization of fibres at the appropriate size scale needed to produce the observed colour by coherent scattering. These two-dimensional quasi-ordered penguin nanostructures are convergent with similar arrays of parallel collagen fibres in avian and mammalian skin, but constitute a novel morphology for feathers. The identification of a new class of {beta}-keratin nanostructures adds significantly to the known mechanisms of colour production in birds and suggests additional complexity in their self-assembly.« less
Numerical approach on dynamic self-assembly of colloidal particles

NASA Astrophysics Data System (ADS)

Ibrahimi, Muhamet; Ilday, Serim; Makey, Ghaith; Pavlov, Ihor; Yavuz, Özgàn; Gulseren, Oguz; Ilday, Fatih Omer

Far from equilibrium systems of artificial ensembles are crucial for understanding many intelligent features in self-organized natural systems. However, the lack of established theory underlies a need for numerical implementations. Inspired by a novel work, we simulate a solution-suspended colloidal system that dynamically self assembles due to convective forces generated in the solvent when heated by a laser. In order to incorporate with random fluctuations of particles and continuously changing flow, we exploit a random-walk based Brownian motion model and a fluid dynamics solver prepared for games, respectively. Simulation results manage to fit to experiments and show many quantitative features of a non equilibrium dynamic self assembly, including phase space compression and an ensemble-energy input feedback loop.
Nanocomposites based on hierarchical porous carbon fiber@vanadium nitride nanoparticles as supercapacitor electrodes.

PubMed

Ran, Fen; Wu, Yage; Jiang, Minghuan; Tan, Yongtao; Liu, Ying; Kong, Lingbin; Kang, Long; Chen, Shaowei

2018-03-28

In this study, a hybrid electrode material for supercapacitors based on hierarchical porous carbon fiber@vanadium nitride nanoparticles is fabricated using the method of phase-separation mediated by the PAA-b-PAN-b-PAA tri-block copolymer. In the phase-separation procedure, the ionic block copolymer self-assembled on the surface of carbon nanofibers, and is used to adsorb NH 4 VO 3 . Thermal treatment at controlled temperatures under an NH 3 : N 2 atmosphere led to the formation of vanadium nitride nanoparticles that are distributed uniformly on the nanofiber surface. By changing the PAN to PAA-b-PAN-b-PAA ratio in the casting solution, a maximum specific capacitance of 240.5 F g -1 is achieved at the current density of 0.5 A g -1 with good rate capability at a capacitance retention of 72.1% at 5.0 A g -1 in an aqueous electrolyte of 6 mol L -1 KOH within the potential range of -1.10 to 0 V (rN/A = 1.5/1.0). Moreover, an asymmetric supercapacitor is assembled by using the hierarchical porous carbon fiber@vanadium nitride as the negative electrode and Ni(OH) 2 as the positive electrode. Remarkably, at the power density of 400 W kg -1 , the supercapacitor device delivers a better energy density of 39.3 W h kg -1 . It also shows excellent electrochemical stability, and thus might be used as a promising energy-storage device.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Ackerman, P. J.; van de Lagemaat, J.; Smalyukh, I. I.

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains thatmore » exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields.« less

Particle self-assembly at ionic liquid-based interfaces.

PubMed

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

2014-04-01

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

DOEpatents

Scheinberg, David A.; McDevitt, Michael R.; Villa, Carlos H.; Mulvey, J. Justin

2018-05-22

Provided herein are methods for delivering a molecule in situ to a cell and for treating a cancer via the in situ delivery. The methods comprise contacting or administering to the cell, as two separate components, a morpholino oligonucleotide comprising a targeting moiety followed by a single wall nanotube construct comprising second morpholino oligonucleotides complementary to the first morpholino oligonucleotides and one or both of a therapeutic or diagnostic payload molecule linked to the single wall nanotube construct. Upon self-assembly of a single wall nanotube complex via hybridization of the first morpholino and second complementary morpholino oligonucleotides at the cell, the payload molecule is delivered. Also provided is the two component self-assembly single wall nanotube system and the single wall nanotube construct comprising the second component.
Control of Nanomaterial Self-Assembly in Ultrasonically Levitated Droplets.

PubMed

Seddon, Annela M; Richardson, Sam J; Rastogi, Kunal; Plivelic, Tomás S; Squires, Adam M; Pfrang, Christian

2016-04-07

We demonstrate that acoustic trapping can be used to levitate and manipulate droplets of soft matter, in particular, lyotropic mesophases formed from self-assembly of different surfactants and lipids, which can be analyzed in a contact-less manner by X-ray scattering in a controlled gas-phase environment. On the macroscopic length scale, the dimensions and the orientation of the particle are shaped by the ultrasonic field, while on the microscopic length scale the nanostructure can be controlled by varying the humidity of the atmosphere around the droplet. We demonstrate levitation and in situ phase transitions of micellar, hexagonal, bicontinuous cubic, and lamellar phases. The technique opens up a wide range of new experimental approaches of fundamental importance for environmental, biological, and chemical research.
Design and preparation of polymeric scaffolds for tissue engineering.

PubMed

Weigel, Thomas; Schinkel, Gregor; Lendlein, Andreas

2006-11-01

Polymeric scaffolds for tissue engineering can be prepared with a multitude of different techniques. Many diverse approaches have recently been under development. The adaptation of conventional preparation methods, such as electrospinning, induced phase separation of polymer solutions or porogen leaching, which were developed originally for other research areas, are described. In addition, the utilization of novel fabrication techniques, such as rapid prototyping or solid free-form procedures, with their many different methods to generate or to embody scaffold structures or the usage of self-assembly systems that mimic the properties of the extracellular matrix are also described. These methods are reviewed and evaluated with specific regard to their utility in the area of tissue engineering.
Electrical Switching in Semiconductor-Metal Self-Assembled VO2 Disordered Metamaterial Coatings

PubMed Central

Kumar, Sunil; Maury, Francis; Bahlawane, Naoufal

2016-01-01

As a strongly correlated metal oxide, VO2 inspires several highly technological applications. The challenging reliable wafer-scale synthesis of high quality polycrystalline VO2 coatings is demonstrated on 4” Si taking advantage of the oxidative sintering of chemically vapor deposited VO2 films. This approach results in films with a semiconductor-metal transition (SMT) quality approaching that of the epitaxial counterpart. SMT occurs with an abrupt electrical resistivity change exceeding three orders of magnitude with a narrow hysteresis width. Spatially resolved infrared and Raman analyses evidence the self-assembly of VO2 disordered metamaterial, compresing monoclinic (M1 and M2) and rutile (R) domains, at the transition temperature region. The M2 mediation of the M1-R transition is spatially confined and related to the localized strain-stabilization of the M2 phase. The presence of the M2 phase is supposed to play a role as a minor semiconducting phase far above the SMT temperature. In terms of application, we show that the VO2 disordered self-assembly of M and R phases is highly stable and can be thermally triggered with high precision using short heating or cooling pulses with adjusted strengths. Such a control enables an accurate and tunable thermal control of the electrical switching. PMID:27883052
Probing the amphiphile micellar to hexagonal phase transition using Positron Annihilation Lifetime Spectroscopy.

PubMed

Dong, Aurelia W; Fong, Celesta; Hill, Anita J; Boyd, Ben J; Drummond, Calum J

2013-07-15

Positron Annihilation Lifetime Spectroscopy (PALS) has been utilised only sparingly for structural characterisation in self assembled materials. Inconsistencies in approaches to experimental configuration and data analysis between studies has complicated comparisons between studies, meaning that the technique has not provided a cohesive data set across the study of different self assembled systems that advance the technique towards an important tool in soft matter research. In the current work a systematic study was conducted using ionic and non-ionic micellar systems with increasing surfactant concentration to probe positron behaviour on changes between micellar phase structures, and data analysed using contemporary approaches to fit four component spectra. A characteristic orthopositronium lifetime (in the organic regions) of 3.5±0.2 ns was obtained for the hexagonal phase for surfactants with C12 alkyl chains. Chemical quenching of the positron species was also observed for systems with ionic amphiphiles. The application of PALS has also highlighted an inconsistency in the published phase diagram for the octa(ethylene oxide) monododecyl ether (C12EO8) system. These results provide new insight into how the physical properties of micellar systems can be related to PALS parameters and means that the PALS technique can be applied to other more complex self-assembled amphiphile systems. Copyright © 2013 Elsevier Inc. All rights reserved.
FAST TRACK COMMUNICATION Temperature-driven phase transformation in self-assembled diphenylalanine peptide nanotubes

NASA Astrophysics Data System (ADS)

Heredia, A.; Bdikin, I.; Kopyl, S.; Mishina, E.; Semin, S.; Sigov, A.; German, K.; Bystrov, V.; Gracio, J.; Kholkin, A. L.

2010-11-01

Diphenylalanine (FF) peptide nanotubes (PNTs) represent a unique class of self-assembled functional biomaterials owing to a wide range of useful properties including nanostructural variability, mechanical rigidity and chemical stability. In addition, strong piezoelectric activity has recently been observed paving the way to their use as nanoscale sensors and actuators. In this work, we fabricated both horizontal and vertical FF PNTs and examined their optical second harmonic generation and local piezoresponse as a function of temperature. The measurements show a gradual decrease in polarization with increasing temperature accompanied by an irreversible phase transition into another crystalline phase at about 140-150 °C. The results are corroborated by the molecular dynamic simulations predicting an order-disorder phase transition into a centrosymmetric (possibly, orthorhombic) phase with antiparallel polarization orientation in neighbouring FF rings. Partial piezoresponse hysteresis indicates incomplete polarization switching due to the high coercive field in FF PNTs.
Study on the kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin using the fluorescence probe thioflavin T.

PubMed

Yan, Mingyan; Wang, Xinping

2018-05-27

The kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin was characterized by the fluorescence method based on thioflavin T (ThT). The fluorescence probe could bind to the active monomeric collagen with a higher ordered degree of molecule, which displayed the pH and ionic strength dependence, the binding constant higher at neutral pH and proportional to the NaCl concentration. Compared to the turbidity method, ThT was more suitable to characterize the nucleation phase of collagen self-assembly. The nucleus size was determined through the ThT fluorescence and linear-polymerization model. At various pH and ionic strength, the nucleus size was nearly identical, either one or two monomers, demonstrating that one or two active monomeric collagen formed into the nucleus and different pH and ionic strength didn't alter the self-assembly mechanism of collagen. This approach was beneficial to advance the understanding of the kinetic self-assembly of the fish-sourced collagen in vitro. Copyright © 2018 Elsevier B.V. All rights reserved.
Self-assembled nanocages based on the coiled coil bundle motif

NASA Astrophysics Data System (ADS)

Sinha, Nairiti; Villegas, Jose; Saven, Jeffery; Kiick, Kristi; Pochan, Darrin

Computational design of coiled coil peptide bundles that undergo solution phase self-assembly presents a diverse toolbox for engineering new materials with tunable and pre-determined nanostructures that can have various end applications such as in drug delivery, biomineralization and electronics. Self-assembled cages are especially advantageous as the cage geometry provides three distinct functional sites: the interior, the exterior and the solvent-cage interface. In this poster, syntheses and characterization of a peptide cage based on computationally designed homotetrameric coiled coil bundles as building blocks is discussed. Techniques such as Transmission Electron Microscopy (TEM), Small-Angle Neutron Scattering (SANS) and Analytical Ultracentrifugation (AUC) are employed to characterize the size, shape and molecular weight of the self-assembled peptide cages under different pH and temperature conditions. Various self-assembly pathways such as dialysis and thermal quenching are shown to have a significant impact on the final structure of these peptides in solution. Comparison of results with the target cage design can be used to iteratively improve the peptide design and provide greater understanding of its interactions and folding.
Periodic assembly of nanoparticle arrays in disclinations of cholesteric liquid crystals.

PubMed

Li, Yunfeng; Prince, Elisabeth; Cho, Sangho; Salari, Alinaghi; Mosaddeghian Golestani, Youssef; Lavrentovich, Oleg D; Kumacheva, Eugenia

2017-02-28

An important goal of the modern soft matter science is to discover new self-assembly modalities to precisely control the placement of small particles in space. Spatial inhomogeneity of liquid crystals offers the capability to organize colloids in certain regions such as the cores of the topological defects. Here we report two self-assembly modes of nanoparticles in linear defects-disclinations in a lyotropic colloidal cholesteric liquid crystal: a continuous helicoidal thread and a periodic array of discrete beads. The beads form one-dimensional arrays with a periodicity that matches half a pitch of the cholesteric phase. The periodic assembly is governed by the anisotropic surface tension and elasticity at the interface of beads with the liquid crystal. This mode of self-assembly of nanoparticles in disclinations expands our ability to use topological defects in liquid crystals as templates for the organization of nanocolloids.
A self-cleaning underwater superoleophobic mesh for oil-water separation.

PubMed

Zhang, Lianbin; Zhong, Yujiang; Cha, Dongkyu; Wang, Peng

2013-01-01

Oil-water separation has recently become a global challenging task because of the frequent occurrence of oil spill accidents due to the offshore oil production and transportation, and there is an increasing demand for the development of effective and inexpensive approaches for the cleaning-up of the oily pollution in water system. In this study, a self-cleaning underwater superoleophobic mesh that can be used for oil-water separation is prepared by the layer-by-layer (LbL) assembly of sodium silicate and TiO2 nanoparticles on the stainless steel mesh. The integration of the self-cleaning property into the all-inorganic separation mesh by using TiO2 enables the convenient removal of the contaminants by ultraviolet (UV) illumination, and allows for the facile recovery of the separation ability of the contaminated mesh, making it promising for practial oil-water separation applications.
A self-cleaning underwater superoleophobic mesh for oil-water separation

PubMed Central

Zhang, Lianbin; Zhong, Yujiang; Cha, Dongkyu; Wang, Peng

2013-01-01

Oil–water separation has recently become a global challenging task because of the frequent occurrence of oil spill accidents due to the offshore oil production and transportation, and there is an increasing demand for the development of effective and inexpensive approaches for the cleaning-up of the oily pollution in water system. In this study, a self-cleaning underwater superoleophobic mesh that can be used for oil-water separation is prepared by the layer-by-layer (LbL) assembly of sodium silicate and TiO2 nanoparticles on the stainless steel mesh. The integration of the self-cleaning property into the all-inorganic separation mesh by using TiO2 enables the convenient removal of the contaminants by ultraviolet (UV) illumination, and allows for the facile recovery of the separation ability of the contaminated mesh, making it promising for practial oil-water separation applications. PMID:23900109
John H. Dillon Medal Lecture: Magnetic Field Directed Self-Assembly of Block Copolymers and Surfactant Mesophases

NASA Astrophysics Data System (ADS)

Osuji, Chinedum

2015-03-01

Molecular self-assembly of block copolymers and small molecule surfactants gives rise to a rich phase behavior as a function of temperature, composition, and other variables. We consider the directed self-assembly of such soft mesophases using magnetic fields, principally through the use of in situ x-ray scattering studies. Field alignment is predicated on a sufficiently large product of magnetic anisotropy and grain size to produce magnetostatic interactions which are substantive relative to thermal forces. We examine the role of field strength on the phase behavior and alignment dynamics of a series of soft mesophases, outlining the possibility to readily create highly ordered functional materials over macroscopic length scales. We show that magnetic fields as large as 10 T have little discernable impact on the stability of block copolymer systems considered, with shifts in order-disorder transition temperatures of roughly 5 mK or smaller. Consequently, directed self-assembly in these systems proceeds by nucleation of randomly aligned grains which thereafter rotate into registry with the field. We highlight the tradeoff between decreasing mobility and increasing anisotropic field interaction that dictates alignment kinetics while transiting from a high temperature disordered state to an ordered system at lower temperatures. NSF support through DMR-0847534 is gratefully acknowledged.
Kinetics of Surface-Driven Self-Assembly and Fatigue-Induced Disassembly of a Virus-Based Nanocoating.

PubMed

Valbuena, Alejandro; Mateu, Mauricio G

2017-02-28

Self-assembling protein layers provide a "bottom-up" approach for precisely organizing functional elements at the nanoscale over a large solid surface area. The design of protein sheets with architecture and physical properties suitable for nanotechnological applications may be greatly facilitated by a thorough understanding of the principles that underlie their self-assembly and disassembly. In a previous study, the hexagonal lattice formed by the capsid protein (CA) of human immunodeficiency virus (HIV) was self-assembled as a monomolecular layer directly onto a solid substrate, and its mechanical properties and dynamics at equilibrium were analyzed by atomic force microscopy. Here, we use atomic force microscopy to analyze the kinetics of self-assembly of the planar CA lattice on a substrate and of its disassembly, either spontaneous or induced by materials fatigue. Both self-assembly and disassembly of the CA layer are cooperative reactions that proceed until a phase equilibrium is reached. Self-assembly requires a critical protein concentration and is initiated by formation of nucleation points on the substrate, followed by lattice growth and eventual merging of CA patches into a continuous monolayer. Disassembly of the CA layer showed hysteresis and appears to proceed only after large enough defects (nucleation points) are formed in the lattice, whose number is largely increased by inducing materials fatigue that depends on mechanical load and its frequency. Implications of the kinetic results obtained for a better understanding of self-assembly and disassembly of the HIV capsid and protein-based two-dimensional nanomaterials and the design of anti-HIV drugs targeting (dis)assembly and biocompatible nanocoatings are discussed. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.
Self-assembled microstructures of confined rod-coil diblock copolymers by self-consistent field theory.

PubMed

Yang, Guang; Tang, Ping; Yang, Yuliang; Wang, Qiang

2010-11-25

We employ the self-consistent field theory (SCFT) incorporating Maier-Saupe orientational interactions between rods to investigate the self-assembly of rod-coil diblock copolymers (RC DBC) in bulk and especially confined into two flat surfaces in 2D space. A unit vector defined on a spherical surface for describing the orientation of rigid blocks in 3D Euclidean space is discretized with an icosahedron triangular mesh to numerically integrate over rod orientation, which is confirmed to have numerical accuracy and stability higher than that of the normal Gaussian quadrature. For the hockey puck-shaped phases in bulk, geometrical confinement, i.e., the film thickness, plays an important role in the self-assembled structures' transitions for the neutral walls. However, for the lamellar phase (monolayer smectic-C) in bulk, the perpendicular lamellae are always stable, less dependent on the film thicknesses because they can relax to the bulk spacing with less-paid coil-stretching in thin films. In particular, a very thin rod layer near the surfaces is formed even in a very thin film. When the walls prefer rods, parallel lamellae are obtained, strongly dependent on the competition between the degree of the surface fields and film geometrical confinement, and the effect of surface field on lamellar structure as a function of film thickness is investigated. Our simulation results provide a guide to understanding the self-assembly of the rod-coil films with desirable application prospects in the fabrication of organic light emitting devices.
Wafer Scale Fabrication of Dense and High Aspect Ratio Sub-50 nm Nanopillars from Phase Separation of Cross-Linkable Polysiloxane/Polystyrene Blend.

PubMed

Li, Yang; Hao, Yuli; Huang, Chunyu; Chen, Xingyao; Chen, Xinyu; Cui, Yushuang; Yuan, Changsheng; Qiu, Kai; Ge, Haixiong; Chen, Yanfeng

2017-04-19

We demonstrated a simple and effective approach to fabricate dense and high aspect ratio sub-50 nm pillars based on phase separation of a polymer blend composed of a cross-linkable polysiloxane and polystyrene (PS). In order to obtain the phase-separated domains with nanoscale size, a liquid prepolymer of cross-linkable polysiloxane was employed as one moiety for increasing the miscibility of the polymer blend. After phase separation via spin-coating, the dispersed domains of liquid polysiloxane with sub-50 nm size could be solidified by UV exposure. The solidified polysiloxane domains took the role of etching mask for formation of high aspect ratio nanopillars by O 2 reactive ion etching (RIE). The aspect ratio of the nanopillars could be further amplified by introduction of a polymer transfer layer underneath the polymer blend film. The effects of spin speeds, the weight ratio of the polysiloxane/PS blend, and the concentration of polysiloxane/PS blend in toluene on the characters of the nanopillars were investigated. The gold-coated nanopillar arrays exhibited a high Raman scattering enhancement factor in the range of 10 8 -10 9 with high uniformity across over the wafer scale sample. A superhydrophobic surface could be realized by coating a self-assembled monolayers (SAM) of fluoroalkyltrichlorosilane on the nanopillar arrays. Sub-50 nm silicon nanowires (SiNWs) with high aspect ratio of about 1000 were achieved by using the nanopillars as etching mask through a metal-assisted chemical etching process. They showed an ultralow reflectance of approximately 0.1% for wavelengths ranging from 200 to 800 nm.
Manipulating the ABCs of self-assembly via low-χ block polymer design

PubMed Central

Chang, Alice B.; Lee, Byeongdu; Garland, Carol M.; Jones, Simon C.; Matsen, Mark W.

2017-01-01

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAMP. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials. PMID:28588139
New analytical spiral tube assembly for separation of proteins by counter-current chromatography.

PubMed

Ma, Xiaofeng; Ito, Yoichiro

2015-07-31

A new spiral column assembly for analytical separation by counter-current chromatography is described. The column is made from a plastic spiral tube support which has 12 interwoven spiral grooves. The PTFE tubing of 1.6mm ID was first flattened by extruding through a narrow slit and inserted into the grooves to make 5 spiral layers with about 60ml capacity. The performance of the spiral column assembly was tested with separation of three stable protein samples including cytochrome C, myoglobin and lysozyme in a polymer phase system composed of polyethylene glycol 1000 and dibasic potassium phosphate each at 12.5% (w/w) in water. At 2ml/min, three protein samples were well resolved in 1h. The separation time may be further shortened by application of higher revolution speed and flow rate by improving the strength of the spiral tube support in the future. Published by Elsevier B.V.
Hierarchical assembly of Sm2Co7/Co magnetic nanoparticles into highly stable and uniform nanospheres.

PubMed

Saravanan, P; Sreedhar, B; Mishra, D; Perumal, A; Chandrasekaran, V

2011-04-01

Hierarchical assembly of colloidal Sm2Co7/Co clusters in the form of nanospheres has been processed through a polyol process. The SmCo nanospheres are found to be robust, uniform ( 100 nm) and tend to self-assemble in the form of ordered superstructures. Each nanosphere consists of large number of discrete fine particles ( 6.0 nm), having two-phase structure of both Sm2Co7 and Co-phases. Upon annealing, these phases transform into Sm2Co17 phase with very high magnetization (169 emu/g). A possible mechanism on the formation of nanospheres from the individual Sm2Co2o7 and Co nanoparticles is also discussed.
Potential role of gold nanoparticles for improved analytical methods: an introduction to characterizations and applications.

PubMed

Wu, Chung-Shu; Liu, Fu-Ken; Ko, Fu-Hsiang

2011-01-01

Nanoparticle-based material is a revolutionary scientific and engineering venture that will invariably impact the existing analytical separation and preconcentration for a variety of analytes. Nanoparticles can be regarded as a hybrid between small molecule and bulk material. A material on the nanoscale produces considerable changes on various properties, making them size- and shape-dependent. Gold nanoparticles (Au NPs), one of the wide variety of core materials available, coupled with tunable surface properties in the form of inorganic or inorganic-organic hybrid have been reported as an excellent platform for a broad range of analytical methods. This review aims to introduce the basic principles, examples, and descriptions of methods for the characterization of Au NPs by using chromatography, electrophoresis, and self-assembly strategies for separation science. Some of the latest important applications of using Au NPs as stationary phases toward open-tubular capillary electrochromatography, gas chromatography, and liquid chromatography as well as roles of run buffer additive to enhance separation and preconcentration in the field of chromatographic, electrophoretic and in chip-based systems are reviewed. Additionally, we review Au NPs-assisted state-of-the-art techniques involving the use of micellar electrokinetic chromatography, an online diode array detector, solid-phase extraction, and mass spectrometry for the preconcentration of some chemical compounds and biomolecules.

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.
The Lipid domain Phase diagram in a Dipalmitoyl-PC/Docosahaexnoic Acid-PE/Cholesterol System

NASA Astrophysics Data System (ADS)

Lor, Chai; Hirst, Linda

2011-03-01

Lipid domains in bilayer membrane and polyunsaturated fatty acids (PUFAs) are thought to play an important role in cellular activities. In particular, lipids containing docosahaexnoic acid are an interesting class of PUFAs due to their health benefits. In this project, we perform oxidation measurements of DHA-PE to determine the rate of oxidation in combination with antioxidants. A ternary diagram of DPPC/DHA-PE/cholesterol is mapped out to identify phase separation phenomena using atomic force microscope (AFM). Fluorescence microscopy is also used to image lipid domains in a flat bilayer with fluorescent labels. As expected, we observe the phase, shape, and size of lipid domains changes with varying composition. Moreover, we find that the roughness of the domains changes possibly due to overpacking of cholesterol in domains. This model study provides further understanding of the role of cholesterol in the bilayer membrane leading towards a better understanding of cell membranes. NSF award # DMR 0852791, ``CAREER: Self-Assembly of Polyunsaturated Lipids and Cholesterol In The Cell Membrane.''
Phases and Dynamics of Self-Assembled DNA Programmed Nanocubes

NASA Astrophysics Data System (ADS)

Knorowski, Christopher; Travesset, Alex

2013-03-01

Systems of Nanoparticles grafted with complementary DNA strands have been shown to self-assemble into an array of superlattices. In this talk, we extend our previous model, which successfully predicted equilibrium phases and dynamics of assembly for spherical Nanoparticles without fitting parameters, to the case of nanocubes. We show that the phase diagram consists of bcc and sc lattices, depending on DNA length. The bcc lattices are either rotator and orientational glass or cubatic. For temperatures above the DNA melting temperature, the system is equivalent to f-star polymer systems, and consist of bcc, also with rotator, orientational glass or cubatic orientational order as well as sc. We also provide a characterization of the dynamics, including the role of topological defects in crystal nucleation and growth. This work is funded by DOE through the Ames Lab under Contract DE-AC02-07CH11358. Most simulations are performed on the Exalted GPU cluster, which is funded by a grant from Iowa State University and Nvidia Corp.
Halogen-Adatom Mediated Phase Transition of Two-Dimensional Molecular Self-Assembly on a Metal Surface.

PubMed

Niu, Tianchao; Wu, Jinge; Ling, Faling; Jin, Shuo; Lu, Guanghong; Zhou, Miao

2018-01-09

Construction of tunable and robust two-dimensional (2D) molecular arrays with desirable lattices and functionalities over a macroscopic scale relies on spontaneous and reversible noncovalent interactions between suitable molecules as building blocks. Halogen bonding, with active tunability of direction, strength, and length, is ideal for tailoring supramolecular structures. Herein, by combining low-temperature scanning tunneling microscopy and systematic first-principles calculations, we demonstrate novel halogen bonding involving single halogen atoms and phase engineering in 2D molecular self-assembly. On the Au(111) surface, we observed catalyzed dehalogenation of hexabromobenzene (HBB) molecules, during which negatively charged bromine adatoms (Br δ- ) were generated and participated in assembly via unique C-Br δ+ ···Br δ- interaction, drastically different from HBB assembly on a chemically inert graphene substrate. We successfully mapped out different phases of the assembled superstructure, including densely packed hexagonal, tetragonal, dimer chain, and expanded hexagonal lattices at room temperature, 60 °C, 90 °C, and 110 °C, respectively, and the critical role of Br δ- in regulating lattice characteristics was highlighted. Our results show promise for manipulating the interplay between noncovalent interactions and catalytic reactions for future development of molecular nanoelectronics and 2D crystal engineering.
Molecular transport through nanoporous silicon nitride membranes produced from self-assembling block copolymers.

PubMed

Montagne, Franck; Blondiaux, Nicolas; Bojko, Alexandre; Pugin, Raphaël

2012-09-28

To achieve fast and selective molecular filtration, membrane materials must ideally exhibit a thin porous skin and a high density of pores with a narrow size distribution. Here, we report the fabrication of nanoporous silicon nitride membranes (NSiMs) at the full wafer scale using a versatile process combining block copolymer (BCP) self-assembly and conventional photolithography/etching techniques. In our method, self-assembled BCP micelles are used as templates for creating sub-100 nm nanopores in a thin low-stress silicon nitride layer, which is then released from the underlying silicon wafer by etching. The process yields 100 nm thick free-standing NSiMs of various lateral dimensions (up to a few mm(2)). We show that the membranes exhibit a high pore density, while still retaining excellent mechanical strength. Permeation experiments reveal that the molecular transport rate across NSiMs is up to 16-fold faster than that of commercial polymeric membranes. Moreover, using dextran molecules of various molecular weights, we also demonstrate that size-based separation can be achieved with a very good selectivity. These new silicon nanosieves offer a relevant technological alternative to commercially available ultra- and microfiltration membranes for conducting high resolution biomolecular separations at small scales.
Patterning layer-by-layer self-assembled multilayer by lithography and its applications to thin film devices

NASA Astrophysics Data System (ADS)

Hua, Feng

Nanoparticles are exciting materials because they exhibit unique electronic, catalytic, and optical properties. As a novel and promising nanobuilding block, it attracts considerable research efforts in its integration into a wide variety of thin film devices. Nanoparticles were adsorbed onto the substrate with layer-by-layer self-assembly which becomes of great interest due to its suitability in colloid particle assembly. Without extremely high temperatures and sophisticated equipment, molecularly organized films in an exactly pre-designed order can grow on almost all the substrates in nature. Two approaches generating spatially separated patterns comprised of nanoparticles are demonstrated, as well as two approaches patterning more than one type of nonoparticle on a silicon wafer. The structure of the thin film patterned by these approaches are analyzed and considered suitable to the thin film device. Finally, the combination of lithography and layer-by-layer (lbl) self-assembly is utilized to realize the microelectronic device with functional nonoparticles. The lbl self-assembly is the way to coat the nonoparticles and the lighography to pattern them. Based on the coating and patterning technique, a MOS-capacitor, a MOS field-effect-transistor and magnetic thin film cantilever are fabricated.
Self-Assembling Molecular Logic Gates Based on DNA Crossover Tiles.

PubMed

Campbell, Eleanor A; Peterson, Evan; Kolpashchikov, Dmitry M

2017-07-05

DNA-based computational hardware has attracted ever-growing attention due to its potential to be useful in the analysis of complex mixtures of biological markers. Here we report the design of self-assembling logic gates that recognize DNA inputs and assemble into crossover tiles when the output signal is high; the crossover structures disassemble to form separate DNA stands when the output is low. The output signal can be conveniently detected by fluorescence using a molecular beacon probe as a reporter. AND, NOT, and OR logic gates were designed. We demonstrate that the gates can connect to each other to produce other logic functions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fabrication of fuel pin assemblies, phase 3

NASA Technical Reports Server (NTRS)

Keeton, A. R.; Stemann, L. G.

1972-01-01

Five full size and eight reduced length fuel pins were fabricated for irradiation testing to evaluate design concepts for a fast spectrum lithium cooled compact space power reactor. These assemblies consisted of uranium mononitride fuel pellets encased in a T-111 (Ta-8W-2Hf) clad with a tungsten barrier separating fuel and clad. Fabrication procedures were fully qualified by process development and assembly qualification tests. Detailed specifications and procedures were written for the fabrication and assembly of prototype fuel pins.
Communication: Theoretical prediction of free-energy landscapes for complex self-assembly

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

Jacobs, William M.; Reinhardt, Aleks; Frenkel, Daan

2015-01-14

We present a technique for calculating free-energy profiles for the nucleation of multicomponent structures that contain as many species as building blocks. We find that a key factor is the topology of the graph describing the connectivity of the target assembly. By considering the designed interactions separately from weaker, incidental interactions, our approach yields predictions for the equilibrium yield and nucleation barriers. These predictions are in good agreement with corresponding Monte Carlo simulations. We show that a few fundamental properties of the connectivity graph determine the most prominent features of the assembly thermodynamics. Surprisingly, we find that polydispersity in themore » strengths of the designed interactions stabilizes intermediate structures and can be used to sculpt the free-energy landscape for self-assembly. Finally, we demonstrate that weak incidental interactions can preclude assembly at equilibrium due to the combinatorial possibilities for incorrect association.« less
Challenges and advances in the field of self-assembled membranes.

PubMed

van Rijn, Patrick; Tutus, Murat; Kathrein, Christine; Zhu, Leilei; Wessling, Matthias; Schwaneberg, Ulrich; Böker, Alexander

2013-08-21

Self-assembled membranes are of vital importance in biological systems e.g. cellular and organelle membranes, however, more focus is being put on synthetic self-assembled membranes not only as an alternative for lipid membranes but also as an alternative for lithographic methods. More investigations move towards self-assembly processes because of the low-cost preparations, structural self-regulation and the ease of creating composite materials and tunable properties. The fabrication of new smart membrane materials via self-assembly is of interest for delivery vessels, size selective separation and purification, controlled-release materials, sensors and catalysts, scaffolds for tissue engineering, low dielectric constant materials for microelectronic devices, antireflective coatings and proton exchange membranes for polymer electrolyte membrane fuel cells. Polymers and nanoparticles offer the most straightforward approaches to create membrane structures. However, alternative approaches using small molecules or composite materials offer novel ultra-thin membranes or multi-functional membranes, respectively. Especially, the composite material membranes are regarded as highly promising since they offer the possibility to combine properties of different systems. The advantages of polymers which provide elastic and flexible yet stable matrices can be combined with nanoparticles being either inorganic, organic or even protein-based which offers pore-size control, catalytic activity or permeation regulation. It is therefore believed that at the interface of different disciplines with each offering different materials or approaches, the most novel and interesting membrane structures are going to be produced. The combinations and approaches presented in this review offer non-conventional self-assembled membrane materials which exhibit a high potential to advance membrane science and find more practical applications.
A promising routine to fabricate GeSi nanowires via self-assembly on miscut Si (001) substrates.

PubMed

Zhong, Zhenyang; Gong, Hua; Ma, Yingjie; Fan, Yongliang; Jiang, Zuimin

2011-04-11

: Very small and compactly arranged GeSi nanowires could self-assembled on vicinal Si (001) substrates with ~8° off toward ⟨110⟩ during Ge deposition. The nanowires were all oriented along the miscut direction. The small ration of height over width of the nanowire indicated that the nanowires were bordered partly with {1 0 5} facets. These self-assembled small nanowires were remarkably influenced by the growth conditions and the miscut angle of substrates in comparison with large dome-like islands obtained after sufficient Ge deposition. These results proposed that the formation of the nanowire was energetically driven under growth kinetic assistance. Three-dimensionally self-assembled GeSi nanowires were first realized via multilayer Ge growth separated with Si spacers. These GeSi nanowires were readily embedded in Si matrix and compatible with the sophisticated Si technology, which suggested a feasible strategy to fabricate nanowires for fundamental studies and a wide variety of applications.PACS: 81.07.Gf, 81.16.Dn, 68.65.-k, 68.37.Ps.
Team assembly mechanisms determine collaboration network structure and team performance.

PubMed

Guimerà, Roger; Uzzi, Brian; Spiro, Jarrett; Amaral, Luís A Nunes

2005-04-29

Agents in creative enterprises are embedded in networks that inspire, support, and evaluate their work. Here, we investigate how the mechanisms by which creative teams self-assemble determine the structure of these collaboration networks. We propose a model for the self-assembly of creative teams that has its basis in three parameters: team size, the fraction of newcomers in new productions, and the tendency of incumbents to repeat previous collaborations. The model suggests that the emergence of a large connected community of practitioners can be described as a phase transition. We find that team assembly mechanisms determine both the structure of the collaboration network and team performance for teams derived from both artistic and scientific fields.
Performance comparison of three types of high-speed counter-current chromatographs for the separation of components of hydrophilic and hydrophobic color additives.

PubMed

Weisz, Adrian; Ito, Yoichiro

2011-09-09

The performance of three types of high-speed counter-current chromatography (HSCCC) instruments was assessed for their use in separating components in hydrophilic and hydrophobic dye mixtures. The HSCCC instruments compared were: (i) a J-type coil planet centrifuge (CPC) system with a conventional multilayer-coil column, (ii) a J-type CPC system with a spiral-tube assembly-coil column, and (iii) a cross-axis CPC system with a multilayer-coil column. The hydrophilic dye mixture consisted of a sample of FD&C Blue No. 2 that contained mainly two isomeric components, 5,5'- and 5,7'-disulfonated indigo, in the ratio of ∼7:1. The hydrophobic dye mixture consisted of a sample of D&C Red No. 17 (mainly Sudan III) and Sudan II in the ratio of ∼4:1. The two-phase solvent systems used for these separations were 1-butanol/1.3M HCl and hexane/acetonitrile. Each of the three instruments was used in two experiments for the hydrophilic dye mixture and two for the hydrophobic dye mixture, for a total of 12 experiments. In one set of experiments, the lower phase was used as the mobile phase, and in the second set of experiments, the upper phase was used as the mobile phase. The results suggest that: (a) use of a J-type instrument with either a multilayer-coil column or a spiral-tube assembly column, applying the lower phase as the mobile phase, is preferable for separating the hydrophilic components of FD&C Blue No. 2; and (b) use of a J-type instrument with multilayer-coil column, while applying either the upper phase or the lower phase as the mobile phase, is preferable for separating the hydrophobic dye mixture of D&C Red No. 17 and Sudan II. Published by Elsevier B.V.
Directed self-assembly into low-density colloidal liquid crystal phases

NASA Astrophysics Data System (ADS)

Gao, Yongxiang; Romano, Flavio; Dullens, Roel P. A.; Doye, Jonathan K.; Aarts, Dirk G. A. L.

2018-01-01

Alignment of anisometric particles into liquid crystals (LCs) often results from an entropic competition between their rotational and translational degrees of freedom at dense packings. Here we show that by selectively functionalizing the heads of colloidal rods with magnetic nanoparticles this tendency can be broken to direct the particles into novel, low-density LC phases. Under an external magnetic field, the magnetic heads line up in columns whereas the nonmagnetic tails point out randomly in a plane perpendicular to the columns, forming bottle-brush-like objects; laterally, the bottle brushes are entropically stabilized against coalescence. Experiments and simulations show that upon increasing the particle density the system goes from a dilute gas to a dense two-dimensional liquid of bottle brushes with a density well below the zero-field nematic phase. Our findings offer a strategy for self-assembly into three-dimensional open phases that may find applications in switchable photonics, filtration, and light-weight materials.
Design of a single-chain polypeptide tetrahedron assembled from coiled-coil segments.

PubMed

Gradišar, Helena; Božič, Sabina; Doles, Tibor; Vengust, Damjan; Hafner-Bratkovič, Iva; Mertelj, Alenka; Webb, Ben; Šali, Andrej; Klavžar, Sandi; Jerala, Roman

2013-06-01

Protein structures evolved through a complex interplay of cooperative interactions, and it is still very challenging to design new protein folds de novo. Here we present a strategy to design self-assembling polypeptide nanostructured polyhedra based on modularization using orthogonal dimerizing segments. We designed and experimentally demonstrated the formation of the tetrahedron that self-assembles from a single polypeptide chain comprising 12 concatenated coiled coil-forming segments separated by flexible peptide hinges. The path of the polypeptide chain is guided by a defined order of segments that traverse each of the six edges of the tetrahedron exactly twice, forming coiled-coil dimers with their corresponding partners. The coincidence of the polypeptide termini in the same vertex is demonstrated by reconstituting a split fluorescent protein in the polypeptide with the correct tetrahedral topology. Polypeptides with a deleted or scrambled segment order fail to self-assemble correctly. This design platform provides a foundation for constructing new topological polypeptide folds based on the set of orthogonal interacting polypeptide segments.
Dissipative and Autonomous Square-Wave Self-Oscillation of a Macroscopic Hybrid Self-Assembly under Continuous Light Irradiation.

PubMed

Ikegami, Tomonori; Kageyama, Yoshiyuki; Obara, Kazuma; Takeda, Sadamu

2016-07-11

Building a bottom-up supramolecular system to perform continuously autonomous motions will pave the way for the next generation of biomimetic mechanical systems. In biological systems, hierarchical molecular synchronization underlies the generation of spatio-temporal patterns with dissipative structures. However, it remains difficult to build such self-organized working objects via artificial techniques. Herein, we show the first example of a square-wave limit-cycle self-oscillatory motion of a noncovalent assembly of oleic acid and an azobenzene derivative. The assembly steadily flips under continuous blue-light irradiation. Mechanical self-oscillation is established by successively alternating photoisomerization processes and multi-stable phase transitions. These results offer a fundamental strategy for creating a supramolecular motor that works progressively under the operation of molecule-based machines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
A new strategy to engineer polymer bulk heterojunction solar cells with thick active layers via self-assembly of the tertiary columnar phase

DOE PAGES

Li, Hongfei; Yang, Zhenhua; Pan, Cheng; ...

2017-07-14

Here, we report that the addition of a non-photoactive tertiary polymer phase in the binary bulk heterojunction (BHJ) polymer solar cell leads to a self-assembled columnar nanostructure, enhancing the charge mobilities and photovoltaic efficiency with surprisingly increased optimal active blend thicknesses over 300 nm, 3–4 times larger than that of the binary counterpart. Using the prototypical poly(3-hexylthiophene) (P3HT):fullerene blend as a model BHJ system, we discover that the inert poly(methyl methacrylate) (PMMA) added in the binary BHJ blend self-assembles into vertical columns, which not only template the phase segregation of electron acceptor fullerenes but also induce the out-of-plane rotation ofmore » the edge-on-orientated crystalline P3HT phase. Using complementary interrogation methods including neutron reflectivity, X-ray scattering, atomic force microscopy, transmission electron microscopy, and molecular dynamics simulations, we show that the enhanced charge transport originates from the more randomized molecular stacking of the P3HT phase and the spontaneous segregation of fullerenes at the P3HT/PMMA interface, driven by the high surface tension between the two polymeric components. The results demonstrate a potential method for increasing the thicknesses of high-performance polymer BHJ solar cells with improved photovoltaic efficiency, alleviating the burden of stringently controlling the ultrathin blend thickness during the roll-to-roll-type large-area manufacturing environment.« less
Thermal and athermal three-dimensional swarms of self-propelled particles

NASA Astrophysics Data System (ADS)

Nguyen, Nguyen H. P.; Jankowski, Eric; Glotzer, Sharon C.

2012-07-01

Swarms of self-propelled particles exhibit complex behavior that can arise from simple models, with large changes in swarm behavior resulting from small changes in model parameters. We investigate the steady-state swarms formed by self-propelled Morse particles in three dimensions using molecular dynamics simulations optimized for graphics processing units. We find a variety of swarms of different overall shape assemble spontaneously and that for certain Morse potential parameters at most two competing structures are observed. We report a rich “phase diagram” of athermal swarm structures observed across a broad range of interaction parameters. Unlike the structures formed in equilibrium self-assembly, we find that the probability of forming a self-propelled swarm can be biased by the choice of initial conditions. We investigate how thermal noise influences swarm formation and demonstrate ways it can be exploited to reconfigure one swarm into another. Our findings validate and extend previous observations of self-propelled Morse swarms and highlight open questions for predictive theories of nonequilibrium self-assembly.
Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System

PubMed Central

Yang, Guang; Hallinan, Daniel T.

2016-01-01

Using a three-phase system, centimeter-scale monolayer gold nanoparticle (Au NP) films have been prepared that have long-range order and hydrophobic ligands. The system contains an interface between an aqueous phase containing Au NPs and an oil phase containing one of various types of amine ligands, and a water/air interface. As the Au NPs diffuse to the water/oil interface, ligand exchange takes place which temporarily traps them at the water/oil interface. The ligand-exchanged particles then spontaneously migrate to the air/water interface, where they self-assemble, forming a monolayer under certain conditions. The spontaneous formation of the NP film at the air/water interface was due to the minimization of the system Helmholtz free energy. However, the extent of surface functionalization was dictated by kinetics. This decouples interfacial ligand exchange from interfacial self-assembly, while maintaining the simplicity of a single system. The interparticle center-to-center distance was dictated by the amine ligand length. The Au NP monolayers exhibit tunable surface plasma resonance and excellent spatial homogeneity, which is useful for surface-enhanced Raman scattering. The “air/water/oil” self-assembly method developed here not only benefits the fundamental understanding of NP ligand conformations, but is also applicable to the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. PMID:27762394
Manipulating the Ordered Nanostructure of Self-Assembled Monoolein and Phytantriol Nanoparticles with Unsaturated Fatty Acids.

PubMed

Tran, Nhiem; Mulet, Xavier; Hawley, Adrian M; Fong, Celesta; Zhai, Jiali; Le, Tu C; Ratcliffe, Julian; Drummond, Calum J

2018-02-27

Mesophase structures of self-assembled lyotropic liquid crystalline nanoparticles are important factors that directly influence their ability to encapsulate and release drugs and their biological activities. However, it is difficult to predict and precisely control the mesophase behavior of these materials, especially in complex systems with several components. In this study, we report the controlled manipulation of mesophase structures of monoolein (MO) and phytantriol (PHYT) nanoparticles by adding unsaturated fatty acids (FAs). By using high throughput formulation and small-angle X-ray scattering characterization methods, the effects of FAs chain length, cis-trans isomerism, double bond location, and level of chain unsaturation on self-assembled systems are determined. Additionally, the influence of temperature on the phase behavior of these nanoparticles is analyzed. We found that in general, the addition of unsaturated FAs to MO and PHYT induces the formation of mesophases with higher Gaussian surface curvatures. As a result, a rich variety of lipid polymorphs are found to correspond with the increasing amounts of FAs. These phases include inverse bicontinuous cubic, inverse hexagonal, and discrete micellar cubic phases and microemulsion. However, there are substantial differences between the phase behavior of nanoparticles with trans FA, cis FAs with one double bond, and cis FAs with multiple double bonds. Therefore, the material library produced in this study will assist the selection and development of nanoparticle-based drug delivery systems with desired mesophase.

Self-assembling semiconducting polymers--rods and gels from electronic materials.

PubMed

Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

2013-02-26

In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.
The self-assembly of redox active peptides: Synthesis and electrochemical capacitive behavior.

PubMed

Piccoli, Julia P; Santos, Adriano; Santos-Filho, Norival A; Lorenzón, Esteban N; Cilli, Eduardo M; Bueno, Paulo R

2016-05-01

The present work reports on the synthesis of a redox-tagged peptide with self-assembling capability aiming applications in electrochemically active capacitive surfaces (associated with the presence of the redox centers) generally useful in electroanalytical applications. Peptide containing ferrocene (fc) molecular (redox) group (Ac-Cys-Ile-Ile-Lys(fc)-Ile-Ile-COOH) was thus synthesized by solid phase peptide synthesis (SPPS). To obtain the electrochemically active capacitive interface, the side chain of the cysteine was covalently bound to the gold electrode (sulfur group) and the side chain of Lys was used to attach the ferrocene in the peptide chain. After obtaining the purified redox-tagged peptide, the self-assembly and redox capability was characterized by cyclic voltammetry (CV) and electrochemical impedance-based capacitance spectroscopy techniques. The obtained results confirmed that the redox-tagged peptide was successfully attached by forming an electroactive self-assembled monolayer onto gold electrode. The design of redox active self-assembly ferrocene-tagged peptide is predictably useful in the development of biosensor devices precisely to detect, in a label-free platform, those biomarkers of clinical relevance. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 357-367, 2016. © 2016 Wiley Periodicals, Inc.
Water Ordering Controls the Dynamic Equilibrium of Micelle-Fiber Formation in Self-Assembly of Peptide Amphiphiles

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

Deshmukh, Sanket; Solomon, Lee A.; Kamath, Ganesh

Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides has still remained elusive. Here, using a multi-stage atomistic-coarse-grained approach, complemented by circular dichroism/infra-red spectroscopy and dynamic light scattering experiments, we highlight the dual nature of water in dictating the mechanism and dynamics of self-assembly of peptide amphiphiles (PAs). Our computational study shows that (i) Water cage formation and breakage near the hydrophobic groups controls the fusion dynamics and aggregation of PAs in the micellar stage, and (ii) Enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards themore » fiber phase and stimulates structure and order in the PAs when they assemble into a hexagonal nanofiber architecture. Finally, spectroscopy and microscopy studies authenticate our computational observation that water ordering near the PAs increases with increase in time. The measured infra-red O-H bond stretch frequency reminiscent of ice-like suggests that the solvated water becomes increasingly solid-like with increased structural order in the assembled peptide network – thus shedding light on the role of water in a self-assembly process.« less
Water Ordering Controls the Dynamic Equilibrium of Micelle-Fiber Formation in Self-Assembly of Peptide Amphiphiles

DOE PAGES

Deshmukh, Sanket; Solomon, Lee A.; Kamath, Ganesh; ...

2016-08-24

Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides has still remained elusive. Here, using a multi-stage atomistic-coarse-grained approach, complemented by circular dichroism/infra-red spectroscopy and dynamic light scattering experiments, we highlight the dual nature of water in dictating the mechanism and dynamics of self-assembly of peptide amphiphiles (PAs). Our computational study shows that (i) Water cage formation and breakage near the hydrophobic groups controls the fusion dynamics and aggregation of PAs in the micellar stage, and (ii) Enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards themore » fiber phase and stimulates structure and order in the PAs when they assemble into a hexagonal nanofiber architecture. Finally, spectroscopy and microscopy studies authenticate our computational observation that water ordering near the PAs increases with increase in time. The measured infra-red O-H bond stretch frequency reminiscent of ice-like suggests that the solvated water becomes increasingly solid-like with increased structural order in the assembled peptide network – thus shedding light on the role of water in a self-assembly process.« less
Electrostatic Interactions and Self-Assembly in Polymeric Systems

NASA Astrophysics Data System (ADS)

Dobrynin, Andrey

Electrostatic interactions between macroions play an important role in different areas ranging from materials science to biophysics. They are main driving forces behind layer-by-layer assembly technique that allows self-assembly of multilayer films from synthetic polyelectrolytes, DNA, proteins and nanoparticles. They are responsible for complexation and reversible gelation between polyelectrolytes and proteins. In this talk, using results of the molecular dynamics simulations and analytical calculations, I will demonstrate what effect electrostatic interactions, counterion condensation and polymer solvent affinity have on a collapse of polyelectrolyte chain in a poor solvent conditions for the polymer backbone, on complexations and reversible gelation between polyelectrolytes and polyamholytes (unstructured proteins), on microphase separation transitions in spherical and planar charged brushes, and on a layer-by-layer assembly of charged nanoparticles and linear polyelectrolytes on charged surfaces. NSF DMR-1004576 DMR-1409710.
Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities

NASA Astrophysics Data System (ADS)

Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B.; Pink, David A.

2014-11-01

Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid componentt, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness Δ. We modelled three cases: (i) liquid-liquid nano-phase separation, (ii) solid-liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ \\lt 0.0701 u (b) transition regime, 0.0701 u≤slant Δ ≤slant 0.0916 u and (c) thick coating regime, Δ \\gt 0.0916 u . (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0\\lt Δ \\lt 7.0 \\text{nm} transition regime, 7.0\\ltΔ \\lt 9.2 \\text{nm} and thick coating, Δ \\gt 9.2 \\text{nm} (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin coatings) and 0.94% (thick coatings). Minority components can have substantial effects upon aggregation for concentrations less than 1%.
Selective oxoanion separation using a tripodal ligand

DOEpatents

Custelcean, Radu; Moyer, Bruce A.; Rajbanshi, Arbin

2016-02-16

The present invention relates to urea-functionalized crystalline capsules self-assembled by sodium or potassium cation coordination and by hydrogen-bonding water bridges to selectively encapsulate tetrahedral divalent oxoanions from highly competitive aqueous alkaline solutions and methods using this system for selective anion separations from industrial solutions. The method involves competitive crystallizations using a tripodal tris(urea) functionalized ligand and, in particular, provides a viable approach to sulfate separation from nuclear wastes.
Paramaterization of a coarse-grained model for linear alkylbenzene sulfonate surfactants and molecular dynamics studies of their self-assembly in aqueous solution

NASA Astrophysics Data System (ADS)

He, Xibing; Shinoda, Wataru; DeVane, Russell; Anderson, Kelly L.; Klein, Michael L.

2010-02-01

A coarse-grained (CG) forcefield for linear alkylbenzene sulfonates (LAS) was systematically parameterized. Thermodynamic data from experiments and structural data obtained from all-atom molecular dynamics were used as targets to parameterize CG potentials for the bonded and non-bonded interactions. The added computational efficiency permits one to employ computer simulation to probe the self-assembly of LAS aqueous solutions into different morphologies starting from a random configuration. The present CG model is shown to accurately reproduce the phase behavior of solutions of pure isomers of sodium dodecylbenzene sulfonate, despite the fact that phase behavior was not directly taken into account in the forcefield parameterization.
Microstructure and Rheology of a Flow-Induced Structured Phase in Wormlike Micellar Solutions

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

Cardiel Rivera, Joshua J.; Dohnalkova, Alice; Dubash, Neville

2013-04-30

Surfactant molecules found in soaps and detergents can self-assemble into a great variety of morphologies (e.g., spherical micelles, cylindrical micelles, and lamellar phases). The resulting morphology is highly affected by ionic strength, temperature, and flow conditions. In particular, cylindrical micelles in the presence of inorganic or organic salts can self-assemble into large flexible and elongated wormlike micelles. In equilibrium, the wormlike micelles transition from slightly entangled to branched and, finally, to multi-connected structures with increasing salt concentration. In our work, by introducing external flow conditions via microfluidics, these micellar structures can follow very different trajectories on the phase map andmore » new nanoporous structures can be created. This flow induced approach offers great potential to create novel materials and nanoporous scaffolds from wormlike micelles under ambient temperature and pressure, without any chemical and thermal means (1). As a result, this work provides attractive solutions for synthesizing new biocompatible materials under ambient conditions with biosensing, encapsulation, catalysis, photonics, and self-healing applications.« less
Emerging chitin and chitosan nanofibrous materials for biomedical applications

NASA Astrophysics Data System (ADS)

Ding, Fuyuan; Deng, Hongbing; Du, Yumin; Shi, Xiaowen; Wang, Qun

2014-07-01

Over the past several decades, we have witnessed significant progress in chitosan and chitin based nanostructured materials. The nanofibers from chitin and chitosan with appealing physical and biological features have attracted intense attention due to their excellent biological properties related to biodegradability, biocompatibility, antibacterial activity, low immunogenicity and wound healing capacity. Various methods, such as electrospinning, self-assembly, phase separation, mechanical treatment, printing, ultrasonication and chemical treatment were employed to prepare chitin and chitosan nanofibers. These nanofibrous materials have tremendous potential to be used as drug delivery systems, tissue engineering scaffolds, wound dressing materials, antimicrobial agents, and biosensors. This review article discusses the most recent progress in the preparation and application of chitin and chitosan based nanofibrous materials in biomedical fields.
Polymeric Nanofibers in Tissue Engineering

PubMed Central

Dahlin, Rebecca L.; Kasper, F. Kurtis

2011-01-01

Polymeric nanofibers can be produced using methods such as electrospinning, phase separation, and self-assembly, and the fiber composition, diameter, alignment, degradation, and mechanical properties can be tailored to the intended application. Nanofibers possess unique advantages for tissue engineering. The small diameter closely matches that of extracellular matrix fibers, and the relatively large surface area is beneficial for cell attachment and bioactive factor loading. This review will update the reader on the aspects of nanofiber fabrication and characterization important to tissue engineering, including control of porous structure, cell infiltration, and fiber degradation. Bioactive factor loading will be discussed with specific relevance to tissue engineering. Finally, applications of polymeric nanofibers in the fields of bone, cartilage, ligament and tendon, cardiovascular, and neural tissue engineering will be reviewed. PMID:21699434
Creating Quasi Two-Dimensional Cluster-Assembled Materials through Self-Assembly of a Janus Polyoxometalate-Silsesquioxane Co-Cluster.

PubMed

Wu, Han; Zhang, Yu-Qi; Hu, Min-Biao; Ren, Li-Jun; Lin, Yue; Wang, Wei

2017-05-30

Clusters are an important class of nanoscale molecules or superatoms that exhibit an amazing diversity in structure, chemical composition, shape, and functionality. Assembling two types of clusters is creating emerging cluster-assembled materials (CAMs). In this paper, we report an effective approach to produce quasi two-dimensional (2D) CAMs of two types of spherelike clusters, polyhedral oligomeric silsesquioxanes (POSS), and polyoxometalates (POM). To avoid macrophase separation between the two clusters, they are covalently linked to form a POM-POSS cocluster with Janus characteristics and a dumbbell shape. This Janus characteristics enables the cocluster to self-assemble into diverse nanoaggregates, as conventional amphiphilic molecules and macromolecules do, in selective solvents. In our study, we obtained micelles, vesicles, nanosheets, and nanoribbons by tuning the n-hexane content in mixed solvents of acetone and n-hexane. Ordered packing of clusters in the nanosheets and nanoribbons were directly visualized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) technique. We infer that the increase of packing order results in the vesicle-to-sheet transition and the change in packing mode causes the sheet-to-ribbon transitions. Our findings have verified the effectivity of creating quasi 2D cluster-assembled materials though the cocluster self-assembly as a new approach to produce novel CAMs.
Beyond native block copolymer morphologies

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

Doerk, Gregory S.; Yager, Kevin G.

Block copolymers self-assemble into a range of canonical morphologies. Here, we review a broad range of techniques for inducing these materials to form structures beyond the ‘native’ morphologies seen in the bulk equilibrium phase diagram. Methods that exploit intrinsic encoding (molecular design) and external enforcement (directed assembly) are compared.
Beyond native block copolymer morphologies

DOE PAGES

Doerk, Gregory S.; Yager, Kevin G.

2017-09-20

Block copolymers self-assemble into a range of canonical morphologies. Here, we review a broad range of techniques for inducing these materials to form structures beyond the ‘native’ morphologies seen in the bulk equilibrium phase diagram. Methods that exploit intrinsic encoding (molecular design) and external enforcement (directed assembly) are compared.
Depletion forces drive polymer-like self-assembly in vibrofluidized granular materials†

PubMed Central

Nossal, Ralph

2011-01-01

Ranging from nano- to granular-scales, control of particle assembly can be achieved by limiting the available free space, for example by increasing the concentration of particles (“crowding”) or through their restriction to 2D environments. It is unclear, however, if self-assembly principles governing thermally-equilibrated molecules can also apply to mechanically-excited macroscopic particles in non-equilibrium steady-state. Here we show that low densities of vibrofluidized steel rods, when crowded by high densities of spheres and confined to quasi-2D planes, can self-assemble into linear polymer-like structures. Our 2D Monte Carlo simulations show similar finite sized aggregates in thermally equilibrated binary mixtures. Using theory and simulations, we demonstrate how depletion interactions create oriented “binding” forces between rigid rods to form these “living polymers.” Unlike rod-sphere mixtures in 3D that can demonstrate well-defined equilibrium phases, our mixtures confined to 2D lack these transitions because lower dimensionality favors the formation of linear aggregates, thus suppressing a true phase transition. The qualitative and quantitative agreement between equilibrium and granular patterning for these mixtures suggests that entropy maximization is the determining driving force for bundling. Furthermore, this study uncovers a previously unknown patterning behavior at both the granular and nanoscales, and may provide insights into the role of crowding at interfaces in molecular assembly. PMID:22039392
Investigating the Modification of Spontaneous Emission using Layer-by-Layer Self-Assembly

NASA Astrophysics Data System (ADS)

Ashry, Islam Ahmed Ibrahim Youssef

The process of spontaneous emission can be dramatically modified by optical micro- and nanostructures. We studied the modification of fluorescence dynamics using a polymer spacer layer fabricated through layer-by-layer (LbL) self-assembly. The advantages of this method are numerous: The self-assembled spacers can possess exceptional smooth surface morphology; The thickness of the spacer can be controlled with nanometer accuracy; And depending on fabrication conditions, the spacer layer is stimuli responsive and its thickness can be dynamically tuned. This thesis contains three interlinked components. First, we vary LbL spacer layer thickness and explore the change in fluorescence lifetime induced by the modified photonic density of states (PDOS), i.e., Purcell effects. Our experimental results agree well with theoretical predictions based on a classical dipole model, which also yields consistent values for the fluorophores' intrinsic fluorescence lifetime and quantum yield near a dielectric as well as a plasmonic interface. Based on this observation, we further demonstrate that self-assembled fluorophores can be used to probe the modified PDOS near optical micro- and nano-structures. These results naturally lead to the second component of our research. In particularly, based on the PDOS-induced changes in fluorescent lifetime, we develop a non-contact method that can measure morphological changes with nanoscale resolution. Our method relies on quantitatively linking fluorophore position with PDOS, and is validated through direct comparison with ellipsometry and atomic force microscopy (AFM) measurements. To demonstrate the potential application of this method, we investigated the swelling/deswelling of LbL films induced by pH changes. Our results indicate significant difference between a LbL film composed of a single polymer monolayer and a LbL film with 3 monolayers. Such stimuli-responsive polymers can be used to construct active and tunable plasmonic nano-devices. As a proof-of-principle demonstration, we experimentally confirm that it is possible to utilize the swelling/deswelling behavior of stimuli-responsive films to dynamically control the separation between Au nanoparticles and Texas Red (TR) dyes. This result is based on the strong correlation of TR fluorescence lifetime and nanoparticles-TR separation. Finally, we investigate the impact of different lithography processes on the fluorescence properties of self-assembled fluorophores. We consider three methods: direct fluorophore patterning through ultraviolet (UV) ablation, focused ion beam (FIB) milling of self-assembled fluorophores, and self-assembly of fluorescent materials over plasmonic nano-patterns.
Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers

PubMed Central

Pal, Antara; Kamal, Md. Arif; Raghunathan, V. A.

2016-01-01

We report the discovery of a thermodynamically stable line hexatic (N + 6) phase in a three-dimensional (3D) system made up of self-assembled polymer-like micelles of amphiphilic molecules. The experimentally observed phase transition sequence nematic (N) N + 6 two-dimensional hexagonal (2D-H) is in good agreement with the theoretical predictions. Further, the present study also brings to light the effect of chirality on the N + 6 phase. In the chiral N + 6 phase the bond-orientational order within each “polymer” bundle is found to be twisted about an axis parallel to the average polymer direction. This structure is consistent with the theoretically envisaged Moiré state, thereby providing the first experimental demonstration of the Moiré structure. In addition to confirming the predictions of fundamental theories of two-dimensional melting, these results are relevant in a variety of situations in chemistry, physics and biology, where parallel packing of polymer-like objects are encountered. PMID:27577927
Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

DOE PAGES

Misichronis, Konstantinos; Chen, Jihua; Imel, Adam; ...

2017-03-15

A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined in this paper by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (T ODT), for the first time formore » PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χ eff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. Finally, these copolymers exhibit well-ordered structures even at high temperatures (~260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.« less
Chromatographic evaluation of self-immobilized stationary phases for reversed-phase liquid chromatography.

PubMed

Bottoli, Carla B G; Collins, Kenneth E; Collins, Carol H

2003-02-14

The preparation of stationary phases for HPLC using polymers deposited on silica usually includes an immobilization step involving cross-linking by free radicals induced by ionizing radiation or by other radical initiators. The present paper reports changes which occur at ambient temperature in the character of poly(methyloctylsiloxane) deposited on porous silica particles as a function of the time interval between particle loading and column packing. Column performance and retention factors increase with time and these changes are attributed to rearrangement (self-assembly) which result in "self-immobilization" of the polymer molecules on the silica surface.
Manipulating the ABCs of self-assembly via low-χ block polymer design

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

Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAM P. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations andmore » predicts that LAM P is thermodynamically stable below a critical χ AC, above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.« less

Manipulating the ABCs of self-assembly via low-χ block polymer design

DOE PAGES

Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu; ...

2017-06-06

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAM P. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations andmore » predicts that LAM P is thermodynamically stable below a critical χ AC, above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.« less
Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers.

PubMed

Huang, Cheng; Moosmann, Markus; Jin, Jiehong; Heiler, Tobias; Walheim, Stefan; Schimmel, Thomas

2012-01-01

A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This "monolayer copy" of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiO(x). The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1].
Estimated phase transition and melting temperature of APTES self-assembled monolayer using surface-enhanced anti-stokes and stokes Raman scattering

NASA Astrophysics Data System (ADS)

Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki

2016-02-01

A structure's temperature can be determined from the Raman spectrum using the frequency and the ratio of the intensities of the anti-Stokes and Stokes signals (the Ias/Is ratio). In this study, we apply this approach and an equation relating the temperature, Raman frequency, and Ias/Is ratio to in-situ estimation of the phase change point of a (3-aminopropyl)triethoxysilane self-assembled monolayer (APTES SAM). Ag nanoparticles were deposited on APTES to enhance the Raman signals. A time-resolved measurement mode was used to monitor the variation in the Raman spectra in situ. Moreover, the structural change in APTES SAM (from ordered to disordered structure) under heating was discussed in detail, and the phase change point (around 118 °C) was calculated.
Stability of DNA Origami Nanoarrays in Cell Lysate

PubMed Central

Mei, Qian; Wei, Xixi; Su, Fengyu; Liu, Yan; Youngbull, Cody; Johnson, Roger; Lindsay, Stuart; Yan, Hao; Meldrum, Deirdre

2012-01-01

Scaffolded DNA origami, a method to create self-assembled nanostructures with spatially addressable features, has recently been used to develop water-soluble molecular chips for label-free RNA detection, platforms for deterministic protein positioning, and single molecule reaction observatories. These applications highlight the possibility of exploiting the unique properties and biocompatibility of DNA nanostructures in live, cellular systems. Herein, we assembled several DNA origami nanostructures of differing shape, size and probes, and investigated their interaction with lysate obtained from various normal and cancerous cell lines. We separated and analyzed the origami–lysate mixtures using agarose gel electrophoresis and recovered the DNA structures for functional assay and subsequent microscopic examination. Our results demonstrate that DNA origami nanostructures are stable in cell lysate and can be easily separated from lysate mixtures, in contrast to natural, single- and double-stranded DNA. Atomic force microscope (AFM) and transmission electron microscope (TEM) images show that the DNA origami structures are fully intact after separation from cell lysates and hybridize to their targets, verifying the superior structural integrity and functionality of self-assembled DNA origami nanostructures relative to conventional oligonucleotides. The stability and functionality of DNA origami structures in cell lysate validate their use for biological applications, for example, as programmable molecular rafts or disease detection platforms. PMID:21366226
Role of indium tin oxide electrode on the microstructure of self-assembled WO3-BiVO4 hetero nanostructures

NASA Astrophysics Data System (ADS)

Song, Haili; Li, Chao; Van, Chien Nguyen; Dong, Wenxia; Qi, Ruijuan; Zhang, Yuanyuan; Huang, Rong; Chu, Ying-Hao; Duan, Chun-Gang

2017-11-01

Self-assembled WO3-BiVO4 nanostructured thin films were grown on a (001) yttrium stabilized zirconia (YSZ) substrate by the pulsed laser deposition method with and without the indium tin oxide (ITO) bottom electrode. Their microstructures including surface morphologies, crystalline phases, epitaxial relationships, interface structures, and composition distributions were investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray energy dispersive spectroscopy. In both samples, WO3 formed nanopillars embedded into the monoclinic BiVO4 matrix with specific orientation relationships. In the sample with the ITO bottom electrode, an atomically sharp BiVO4/ITO interface was formed and the orthorhombic WO3 nanopillars were grown on a relaxed BiVO4 buffer layer with a mixed orthorhombic and hexagonal WO3 transition layer. In contrast, a thin amorphous layer appears at the interfaces between the thin film and the YSZ substrate in the sample without the ITO electrode. In addition, orthorhombic Bi2WO6 lamellar nanopillars were formed between WO3 and BiVO4 due to interdiffusion. Such a WO3-Bi2WO6-BiVO4 double heterojunction photoanode may promote the photo-generated charge separation and further improve the photoelectrochemical water splitting properties.
New self-assembly strategies for next generation lithography

NASA Astrophysics Data System (ADS)

Schwartz, Evan L.; Bosworth, Joan K.; Paik, Marvin Y.; Ober, Christopher K.

2010-04-01

Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.
Dewetting-mediated pattern formation in nanoparticle assemblies

NASA Astrophysics Data System (ADS)

Stannard, Andrew

2011-03-01

The deposition of nanoparticles from solution onto solid substrates is a diverse subfield of current nanoscience research. Complex physical and chemical processes underpin the self-assembly and self-organization of colloidal nanoparticles at two-phase (solid-liquid, liquid-air) interfaces and three-phase (solid-liquid-air) contact lines. This review discusses key recent advances made in the understanding of nonequilibrium dewetting processes of nanoparticle-containing solutions, detailing how such an apparently simple experimental system can give rise to such a strikingly varied palette of two-dimensional self-organized nanoparticle array morphologies. Patterns discussed include worm-like domains, cellular networks, microscale rings, and fractal-like fingering structures. There remain many unresolved issues regarding the role of the solvent dewetting dynamics in assembly processes of this type, with a significant focus on how dewetting can be coerced to produce nanoparticle arrays with desirable characteristics such as long-range order. In addition to these topics, methods developed to control nanofluid dewetting through routes such as confining the geometries of drying solutions, depositing onto pre-patterned heterogeneous substrates, and post-dewetting pattern evolution via local or global manipulation are covered.
Dewetting-mediated pattern formation in nanoparticle assemblies.

PubMed

Stannard, Andrew

2011-03-02

The deposition of nanoparticles from solution onto solid substrates is a diverse subfield of current nanoscience research. Complex physical and chemical processes underpin the self-assembly and self-organization of colloidal nanoparticles at two-phase (solid-liquid, liquid-air) interfaces and three-phase (solid-liquid-air) contact lines. This review discusses key recent advances made in the understanding of nonequilibrium dewetting processes of nanoparticle-containing solutions, detailing how such an apparently simple experimental system can give rise to such a strikingly varied palette of two-dimensional self-organized nanoparticle array morphologies. Patterns discussed include worm-like domains, cellular networks, microscale rings, and fractal-like fingering structures. There remain many unresolved issues regarding the role of the solvent dewetting dynamics in assembly processes of this type, with a significant focus on how dewetting can be coerced to produce nanoparticle arrays with desirable characteristics such as long-range order. In addition to these topics, methods developed to control nanofluid dewetting through routes such as confining the geometries of drying solutions, depositing onto pre-patterned heterogeneous substrates, and post-dewetting pattern evolution via local or global manipulation are covered.
Fabrication of Polyhedral Particles from Spherical Colloids and Their Self-Assembly into Rotator Phases**

PubMed Central

Vutukuri, Hanumantha Rao; Imhof, Arnout; van Blaaderen, Alfons

2014-01-01

Particle shape is a critical parameter that plays an important role in self-assembly, for example, in designing targeted complex structures with desired properties. Over the last decades, an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micrometer-sized colloidal building blocks of particles with flat facets, that is, particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that in contrast to nanoparticles, the larger colloids are significantly harder to synthesize as single crystals. It is now shown that a very simple building block, such as a micrometer-sized polymeric spherical colloidal particle, is already enough to fabricate particles with regularly placed flat facets, including completely polygonal shapes with sharp edges. As an illustration that the yields are high enough for further self-assembly studies, the formation of three-dimensional rotator phases of fluorescently labelled, micrometer-sized, and charged rhombic dodecahedron particles was demonstrated. This method for fabricating polyhedral particles opens a new avenue for designing new materials. PMID:25366869
A Study on the Rectification Property of Self-Assembled Viologen Single Molecules Using a Scanning Tunneling Microscopy.

PubMed

Lee, Nam-Suk; Shin, Hoon-Kyu; Kwon, Young-Soo

2015-02-01

An ultrahigh vacuum scanning tunneling microscopy (UHV-STM) and a scanning tunneling spectroscopy (STS) are used measure the rectification property of self-assembled viologen single molecules (VC8SH, VC10SH, HSC8VC8SH, and HSC10VC10SH) in the previous study. Using STM we observe viologen single molecules in the self-assembled octanethiol (OT) SAM matrix. In the OT matrix a mixed phase that includes a c(4 x 2) superlattice of high-density standing up-phase is observed. We indicate high peak current-like rectifications at + 1.68 V(VC8SH), + 1.56 V(VC10SH), + 1.14 V(HSC8VC8SH), and + 1.04 V(HSC10VC10SH) based on the experiment implemented in this study. In addition, transition voltages (Vtrans) from direct tunneling to the Fowler-Nordheim tunneling are presented at 1.08 V(VC8SH), 0.97 V(VC10SH), 0.99 V(HSC8VC8SH), and 0.89 V(HSC1VC1SH).
Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

PubMed

Gao, Yu-Ji; Yang, Yichen; Li, Xu-Bing; Wu, Hao-Lin; Meng, Shu-Lin; Wang, Yang; Guo, Qing; Huang, Mao-Yong; Tung, Chen-Ho; Wu, Li-Zhu

2018-05-08

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 μmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.
Self-assembly of silk fibroin under osmotic stress

NASA Astrophysics Data System (ADS)

Sohn, Sungkyun

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

PubMed Central

Xiao, Xin-Ju; Tsai, Wen-Chieh; Hsiao, Yu-Yun; Huang, Jie; Liu, Zhong-Jian

2012-01-01

Background Due to the spatial separation between male and female pollen grains from the anther of most flowering plants, including orchids, pollens are transported by wind or animals and deposited onto the receptive surface of the stigma of a different plant. However, self-pollination is common in pollinating animal-scarce habitats. In such habitats, self-pollinations require the assistance of a pollinating agent (e.g., wind, gravity, or floral assembly) to transport the pollen grains from the anther onto its own stigma. Methodology/Principal Findings Based on observations on floral morphology and flowering phenology, tests of the breeding system, and a comparison of pollination mechanisms, a new self-pollination process was discovered in the hermaphroditic (i.e., possessing spatially separated male and female organs) flower of a slipper orchid, Paphiopedilum parishii. The anther changes from a solid to a liquid state and directly steps onto the stigma surface without the aid of any pollinating agent or floral assembly. Conclusions The mode of self-pollination discussed here is a new addition to the broad range of genetic and morphological mechanisms that have evolved in flowering plants to ensure their reproductive success. The present self-contained pollination mechanism is a possible adaptation to the insect-scarce habitat of the orchid. PMID:22649529
Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

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

Determan, Michael Duane

The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated.more » This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi-responsive properties of the pentablock copolymer. Demonstrate potential biomedical applications of these materials with in vitro drug release studies from pentablock copolymer hydrogels. The intent of this work is to contribute to the knowledge necessary for further tailoring of these, and other functional block copolymer materials for biomedical applications.« less
Far-from-equilibrium magnetic granular layers: dynamic patterns, magnetic order and self-assembled swimmers

NASA Astrophysics Data System (ADS)

Snezhko, Alexey

2010-03-01

Ensembles of interacting particles subject to an external periodic forcing often develop nontrivial collective behavior and self-assembled dynamic patterns. We study emergent phenomena in magnetic granular ensembles suspended at a liquid-air and liquid-liquid interfaces and subjected to a transversal alternating magnetic field. Experiments reveal a new type of nontrivially ordered dynamic self-assembled structures (in particular, ``magnetic snakes'', ``asters'', ``clams'') emerging in such systems in a certain range of excitation parameters. These non-equilibrium dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex magnetic ordering. Transition between different self-assembled phases with parameters of external driving magnetic field is observed. I will show that above some frequency threshold magnetic snakes spontaneously break the symmetry of the self-induced surface flows (symmetry breaking instability) and turn into swimmers. Self-induced surface flows symmetry can be also broken in a controlled fashion by introduction of a large bead to a magnetic snake (bead-snake hybrid), that transforms it into a robust self-locomoting entity. Some features of the self-localized structures can be understood in the framework of an amplitude equation for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows.
Self-Assembled Multilayer Structure and Enhanced Thermochromic Performance of Spinodally Decomposed TiO2-VO2 Thin Film.

PubMed

Sun, Guangyao; Zhou, Huaijuan; Cao, Xun; Li, Rong; Tazawa, Masato; Okada, Masahisa; Jin, Ping

2016-03-23

Composite films of VO2-TiO2 were deposited on sapphire (11-20) substrate by cosputtering method. Self-assembled well-ordered multilayer structure with alternating Ti- and V-rich epitaxial thin layer was obtained by thermal annealing via a spinodal decomposition mechanism. The structured thermochromic films demonstrate superior optical modulation upon phase transition, with significantly reduced transition temperature. The results provide a facile and novel approach to fabricate smart structures with excellent performance.
Self-referenced locking of optical coherence by single-detector electronic-frequency tagging

NASA Astrophysics Data System (ADS)

Shay, T. M.; Benham, Vincent; Spring, Justin; Ward, Benjamin; Ghebremichael, F.; Culpepper, Mark A.; Sanchez, Anthony D.; Baker, J. T.; Pilkington, D.; Berdine, Richard

2006-02-01

We report a novel coherent beam combining technique. This is the first actively phase locked optical fiber array that eliminates the need for a separate reference beam. In addition, only a single photodetector is required. The far-field central spot of the array is imaged onto the photodetector to produce the phase control loop signals. Each leg of the fiber array is phase modulated with a separate RF frequency, thus tagging the optical phase shift for each leg by a separate RF frequency. The optical phase errors for the individual array legs are separated in the electronic domain. In contrast with the previous active phase locking techniques, in our system the reference beam is spatially overlapped with all the RF modulated fiber leg beams onto a single detector. The phase shift between the optical wave in the reference leg and in the RF modulated legs is measured separately in the electronic domain and the phase error signal is feedback to the LiNbO 3 phase modulator for that leg to minimize the phase error for that leg relative to the reference leg. The advantages of this technique are 1) the elimination of the reference beam and beam combination optics and 2) the electronic separation of the phase error signals without any degradation of the phase locking accuracy. We will present the first theoretical model for self-referenced LOCSET and describe experimental results for a 3 x 3 array.
Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly.

PubMed

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

2015-08-14

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

PubMed Central

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

2015-01-01

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

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered (aggregated) phases is shown to exist when liquid vapor is confined in capillaries (condensation-liquefaction-evaporation and flux). This pheno-menon can be experimentally illustrated with suspended nano-sized particles (flocculation-coagulation-peptisation of colloidal sols) being confined in sample holders of varying size. The self-assembled aggregates represent critical self-similar equilibrium structures corres-ponding to rate determining complexes in kinetics. Overall, a self-consistent thermodynamic framework is established for the characterization of two- and three-dimensional phase separations in one-, two- and three-component systems. Copyright © 2018 Elsevier B.V. All rights reserved.

High-Performance Lithium-Sulfur Batteries with a Self-Assembled Multiwall Carbon Nanotube Interlayer and a Robust Electrode-Electrolyte Interface.

PubMed

Kim, Hee Min; Hwang, Jang-Yeon; Manthiram, Arumugam; Sun, Yang-Kook

2016-01-13

Elemental sulfur electrode has a huge advantage in terms of charge-storage capacity. However, the lack of electrical conductivity results in poor electrochemical utilization of sulfur and performance. This problem has been overcome to some extent previously by using a bare multiwall carbon nanotube (MWCNT) paper interlayer between the sulfur cathode and the polymeric separator, resulting in good electron transport and adsorption of dissolved polysulfides. To advance the interlayer concept further, we present here a self-assembled MWCNT interlayer fabricated by a facile, low-cost process. The Li-S cells fabricated with the self-assembled MWCNT interlayer and a high loading of 3 mg cm(-2) sulfur exhibit a first discharge specific capacity of 1112 mAh g(-1) at 0.1 C rate and retain 95.8% of the capacity at 0.5 C rate after 100 cycles as the self-assembled MWCNT interlayer facilitates good interfacial contact between the interlayer and the sulfur cathode and fast electron and lithium-ion transport while trapping and reutilizing the migrating polysulfides. The approach presented here has the potential to advance the commercialization feasibility of the Li-S batteries.
Beyond the continuum: a multi-dimensional phase space for neutral-niche community assembly.

PubMed

Latombe, Guillaume; Hui, Cang; McGeoch, Melodie A

2015-12-22

Neutral and niche processes are generally considered to interact in natural communities along a continuum, exhibiting community patterns bounded by pure neutral and pure niche processes. The continuum concept uses niche separation, an attribute of the community, to test the hypothesis that communities are bounded by pure niche or pure neutral conditions. It does not accommodate interactions via feedback between processes and the environment. By contrast, we introduce the Community Assembly Phase Space (CAPS), a multi-dimensional space that uses community processes (such as dispersal and niche selection) to define the limiting neutral and niche conditions and to test the continuum hypothesis. We compare the outputs of modelled communities in a heterogeneous landscape, assembled by pure neutral, pure niche and composite processes. Differences in patterns under different combinations of processes in CAPS reveal hidden complexity in neutral-niche community dynamics. The neutral-niche continuum only holds for strong dispersal limitation and niche separation. For weaker dispersal limitation and niche separation, neutral and niche processes amplify each other via feedback with the environment. This generates patterns that lie well beyond those predicted by a continuum. Inferences drawn from patterns about community assembly processes can therefore be misguided when based on the continuum perspective. CAPS also demonstrates the complementary information value of different patterns for inferring community processes and captures the complexity of community assembly. It provides a general tool for studying the processes structuring communities and can be applied to address a range of questions in community and metacommunity ecology. © 2015 The Author(s).
Beyond the continuum: a multi-dimensional phase space for neutral–niche community assembly

PubMed Central

Latombe, Guillaume; McGeoch, Melodie A.

2015-01-01

Neutral and niche processes are generally considered to interact in natural communities along a continuum, exhibiting community patterns bounded by pure neutral and pure niche processes. The continuum concept uses niche separation, an attribute of the community, to test the hypothesis that communities are bounded by pure niche or pure neutral conditions. It does not accommodate interactions via feedback between processes and the environment. By contrast, we introduce the Community Assembly Phase Space (CAPS), a multi-dimensional space that uses community processes (such as dispersal and niche selection) to define the limiting neutral and niche conditions and to test the continuum hypothesis. We compare the outputs of modelled communities in a heterogeneous landscape, assembled by pure neutral, pure niche and composite processes. Differences in patterns under different combinations of processes in CAPS reveal hidden complexity in neutral–niche community dynamics. The neutral–niche continuum only holds for strong dispersal limitation and niche separation. For weaker dispersal limitation and niche separation, neutral and niche processes amplify each other via feedback with the environment. This generates patterns that lie well beyond those predicted by a continuum. Inferences drawn from patterns about community assembly processes can therefore be misguided when based on the continuum perspective. CAPS also demonstrates the complementary information value of different patterns for inferring community processes and captures the complexity of community assembly. It provides a general tool for studying the processes structuring communities and can be applied to address a range of questions in community and metacommunity ecology. PMID:26702047
Self-Assembled Heteroepitaxial Oxide Nanocomposite for Photoelectrochemical Solar Water Oxidation

PubMed Central

2016-01-01

We report on spontaneously phase ordered heteroepitaxial SrTiO3 (STO):ZnFe2O4 (ZFO) nanocomposite films that give rise to strongly enhanced photoelectrochemical solar water oxidation, consistent with enhanced photoinduced charge separation. The STO:ZFO nanocomposite yielded an enhanced photocurrent density of 0.188 mA/cm2 at 1.23 V vs a reversible hydrogen electrode, which was 7.9- and 2.6-fold higher than that of the plain STO film and ZFO film cases under 1-sun illumination, respectively. The photoelectrode also produced stable photocurrent and Faradaic efficiencies of H2 and O2 formation that were more than 90%. Incident-photon-to-current-conversion efficiency measurements, Tauc plots, Mott–Schottky plots, and electrochemical impedance spectroscopy measurements proved that the strongly enhanced photogenerated charge separation resulted from vertically aligned pseudosingle crystalline components, epitaxial heterojunctions, and a staggered band alignment of the components of the nanocomposite films. This study presents a completely new avenue for efficient solar energy conversion applications. PMID:27212792
Evidence of an inverted hexagonal phase in self-assembled phospholipid-DNA-metal complexes

NASA Astrophysics Data System (ADS)

Francescangeli, O.; Pisani, M.; Stanic, V.; Bruni, P.; Weiss, T. M.

2004-08-01

We report the first observation of an inverted hexagonal phase of phospholipid-DNA-metal complexes. These ternary complexes are formed in a self-assembled manner when water solutions of neutral lipid dioleoylphosphatidylethanolamine (DOPE), DNA and divalent metal cations (Me2+; Me=Fe, Co, Mg, Mn) are mixed, which represents a striking example of supramolecular chemistry. The structure, derived from synchrotron X-ray diffraction, consists of cylindrical DNA strands coated by neutral lipid monolayers and arranged on a two-dimensional hexagonal lattice (HIIc). Besides the fundamental aspects, DOPE-DNA-Me2+ complexes may be of great interest as efficient nonviral delivery systems in gene therapy applications because of the low inherent cytotoxicity and the potential high transfection efficiency.
Chemical Interactions and Their Role in the Microphase Separation of Block Copolymer Thin Films

PubMed Central

Farrell, Richard A.; Fitzgerald, Thomas G.; Borah, Dipu; Holmes, Justin D.; Morris, Michael A.

2009-01-01

The thermodynamics of self-assembling systems are discussed in terms of the chemical interactions and the intermolecular forces between species. It is clear that there are both theoretical and practical limitations on the dimensions and the structural regularity of these systems. These considerations are made with reference to the microphase separation that occurs in block copolymer (BCP) systems. BCP systems self-assemble via a thermodynamic driven process where chemical dis-affinity between the blocks driving them part is balanced by a restorative force deriving from the chemical bond between the blocks. These systems are attracting much interest because of their possible role in nanoelectronic fabrication. This form of self-assembly can obtain highly regular nanopatterns in certain circumstances where the orientation and alignment of chemically distinct blocks can be guided through molecular interactions between the polymer and the surrounding interfaces. However, for this to be possible, great care must be taken to properly engineer the interactions between the surfaces and the polymer blocks. The optimum methods of structure directing are chemical pre-patterning (defining regions on the substrate of different chemistry) and graphoepitaxy (topographical alignment) but both centre on generating alignment through favourable chemical interactions. As in all self-assembling systems, the problems of defect formation must be considered and the origin of defects in these systems is explored. It is argued that in these nanostructures equilibrium defects are relatively few and largely originate from kinetic effects arising during film growth. Many defects also arise from the confinement of the systems when they are ‘directed’ by topography. The potential applications of these materials in electronics are discussed. PMID:19865513
Diversity oriented high-throughput screening of 1,3,4-oxadiazole modified chlorophenylureas and halogenobenzamides by HPLC with peptidomimetic calixarene-bonded stationary phases.

PubMed

Bazylak, Grzegorz; Malak, Anna; Ali, Imran; Borowiak, Teresa; Dutkiewicz, Grzegorz

2008-06-01

Retention profiles in series of the neutral and highly hydrophobic 1,3,4-oxadiazoles containing chlorophenylurea and halogenobenzamide moiety and indicating analgesic activity were determined in the isocratic standard- and narrow-bore HPLC systems employing, respectively, various octadecylsilica and different calixarene bonded stationary phases. When acetonitrile - 2.65 mM phosphoric acid (55 : 45, %, v/v), pH* 3.25, mobile phase was applied retention of these compounds increased with decline of their overall hydrophobicity according to the general preference of more polar compounds by calixarene cavity in time of its non-specific host-guest supramolecular interactions with halogenated substances. The size of calixarene nanocavity and its upper-rim substitution did not change the observed retention order, resolution and selectivity of separation for oxadiazoles. Compared to the retention on the non-end-capped and the highly-end-capped octadecylsilica HPLC column a most improved separation of some regioisomers of halogenated 1,3,4-oxadiazoles were observed on both used calixarene-type HPLC supports. In addition, preliminary data on the self-assembled supramolecular crystal structure of exemplary 1,3,4-oxadiazolchlorophenylurea with cis-elongated conformation was reported and formation of the monovalent inclusion host-guest complexes between 1,3,4-oxadiazoles and each calixarene-type stationary phase was studied with molecular modelling MM+ and AM1 methods. The structural, isomeric and energetic factors leading to the hydrogen bond stabilized inclusion complexes between these species were considered and used for explanation of observed retention sequence and selectivity of 1,3,4-oxadiazoles separation in applied calixarene-based HPLC systems. All these data would be useful in future development of optimized procedures enabling encapsulation of 1,3,4-oxadiazolurea-type drugs with calixarenes.
Self-degrading niosomes for encapsulation of hydrophilic and hydrophobic drugs: An efficient carrier for cancer multi-drug delivery.

PubMed

Sharma, Varsha; Anandhakumar, Sundaramurthy; Sasidharan, Manickam

2015-11-01

In this study, we have examined the encapsulation and release of hydrophilic and hydrophobic drugs in self-degrading niosomes as a unique method for anticancer therapy. Niosomes were prepared by amphiphilic self-assembly of Tween 80 and cholesterol through film hydration method. Encapsulation studies with two active molecules curcumin and doxorubicin hydrochloride (Dox) showed that curcumin is supposed to accumulate in the shell whereas Dox accumulates in the inner aqueous core of the niosome. Confocal studies indicated that nile red adsorbs preferentially to the head group of the Tween 80 and forms two separate layers in the shell. It was also seen that the niosomes undergo self-degradation in PBS through a sequential process, forming interconnected pores followed by complete collapse after 1week. The release profile shows two phases: i) initial Dox release in the first two days, followed by ii) curcumin release over 7days. Enhanced (synergistic) cytotoxicity was observed for dual-drug loaded niosomes against HeLa cell lines. Thus these niosomes are shown to offer a promising delivery system for hydrophobic and hydrophilic drugs collectively. Copyright © 2015 Elsevier B.V. All rights reserved.
Advanced Colloids Experiment (ACE) Science Overview

NASA Technical Reports Server (NTRS)

Meyer, William V.; Sicker, Ronald J.; Chiaramonte, Francis P.; Luna, Unique J.; Chaiken, Paul M.; Hollingsworth, Andrew; Secanna, Stefano; Weitz, David; Lu, Peter; Yodh, Arjun;

2013-01-01

The Advanced Colloids Experiment is being conducted on the International Space Station (ISS) using the Light Microscopy Module (LMM) in the Fluids Integrated Rack (FIR). Work to date will be discussed and future plans and opportunities will be highlighted. The LMM is a microscope facility designed to allow scientists to process, manipulate, and characterize colloidal samples in micro-gravity where the absence of gravitational settling and particle jamming enables scientists to study such things as:a.The role that disordered and ordered-packing of spheres play in the phase diagram and equation of state of hard sphere systems,b.crystal nucleation and growth, growth instabilities, and the glass transition, c.gelation and phase separation of colloid polymer mixtures,d.crystallization of colloidal binary alloys,e.competition between crystallization and phase separation,f.effects of anisotropy and specific interactions on packing, aggregation, frustration and crystallization,g.effects of specific reversible and irreversible interactions mediated in the first case by hybridization of complementary DNA strands attached to separate colloidal particles,h.Lock and key interactions between colloids with dimples and spheres which match the size and shape of the dimples,i.finding the phase diagrams of isotropic and interacting particles,j.new techniques for complex self-assembly including scenarios for self-replication, k.critical Casimir forces,l.biology (real and model systems) in microgravity,m.etc. By adding additional microscopy capabilities to the existing LMM, NASA will increase the tools available for scientists that fly experiments on the ISS enabling scientists to observe directly what is happening at the particle level. Presently, theories are needed to bridge the gap between what is being observed (at a macroscopic level when photographing samples) with what is happening at a particle (or microscopic) level. What is happening at a microscopic level will be directly accessible with the availability of the Light Microscopy Module (LMM) on ISS. To meet these goals, the ACE experiment is being built-up in stages, with the availability of confocal microscopy being the ultimate objective. Supported by NASAs Physical Sciences Research Program, ESAESTEC, and the authors respective governments.

Self-assembling Gold Nanoparticle Monolayers in a Three-phase System - Overcoming Ligand Size Limitations

NASA Astrophysics Data System (ADS)

Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T., Jr.

An effective self-assembly technique was developed to prepare centimeter-scale monolayer gold nanoparticle (Au NP) films of long-range order with hydrophobic ligands. Aqueous Au NPs were entrapped in the organic/aqueous interface where the Au NP surface was in situ modified with different types of amine ligands, including amine-terminated polystyrene. The Au NPs then spontaneously relocated to the air/water interface to form an NP monolayer. The spontaneous formation of an Au NP film at the organic/water interface was due to the minimization of the system Helmholtz free energy. Self-assembled Au NP films has a hexagonal close packed structure. The interparticle spacing was dictated by the amine ligand length. Thus-assembled Au NP monolayers exhibit tunable surface plasma resonance and excellent spacial homogeneity of surface-enhanced Raman-scattering. The ``air/water/oil'' self-assembly method developed in this study not only benefits the fundamental understanding of NP ligand conformations, but is also promising to scale up the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. This study was financially supported by start-up funding supplied by the Florida State University and the FAMU-FSU College of Engineering.
Phase Transitions in the Nucleus: the functional implications of concentration-dependent assembly of a Liquid-like RNA/Protein Body

NASA Astrophysics Data System (ADS)

Zhu, Lian; Weber, Stephanie; Berry, Joel; Vaidya, Nilesh; Haataja, Mikko; Brangwynne, Clifford

2015-03-01

The nucleolus is a liquid-like membrane-less nuclear body which plays an important role in cell growth and size control. By modulating nucleolar component concentration through RNAi conditions that change C. elegans cell size, we find that nucleoli only assemble above a threshold concentration; moreover, the ripening dynamics of nucleated droplets are consistent with the hypothesis that the assembly of the nucleolus represents an intracellular liquid-liquid phase transition. A key question is how this phase-transition is linked to the primary function of the nucleolus, in transcribing and processing ribosomal RNA. To address this, we characterize the localization of RNA Polymerase I, a key transcriptional enzyme, into nucleolar foci as a function of nucleolar component concentration. Our results suggest that there are a small number of key disordered phosphoproteins that may serve as a link between transcription and assembly. Finally, we present preliminary results using a reduced model system consisting of purified nucleolar proteins to assess the ability of nucleolar proteins to drive liquid-liquid phase separation in vitro. These results lay the foundation for a quantitative understanding of intracellular phase transitions and their impact on biomedically-critical RNA-processing steps.
Microrheological Characterization of Collagen Systems: From Molecular Solutions to Fibrillar Gels

PubMed Central

Shayegan, Marjan; Forde, Nancy R.

2013-01-01

Collagen is the most abundant protein in the extracellular matrix (ECM), where its structural organization conveys mechanical information to cells. Using optical-tweezers-based microrheology, we investigated mechanical properties both of collagen molecules at a range of concentrations in acidic solution where fibrils cannot form and of gels of collagen fibrils formed at neutral pH, as well as the development of microscale mechanical heterogeneity during the self-assembly process. The frequency scaling of the complex shear modulus even at frequencies of ∼10 kHz was not able to resolve the flexibility of collagen molecules in acidic solution. In these solutions, molecular interactions cause significant transient elasticity, as we observed for 5 mg/ml solutions at frequencies above ∼200 Hz. We found the viscoelasticity of solutions of collagen molecules to be spatially homogeneous, in sharp contrast to the heterogeneity of self-assembled fibrillar collagen systems, whose elasticity varied by more than an order of magnitude and in power-law behavior at different locations within the sample. By probing changes in the complex shear modulus over 100-minute timescales as collagen self-assembled into fibrils, we conclude that microscale heterogeneity appears during early phases of fibrillar growth and continues to develop further during this growth phase. Experiments in which growing fibrils dislodge microspheres from an optical trap suggest that fibril growth is a force-generating process. These data contribute to understanding how heterogeneities develop during self-assembly, which in turn can help synthesis of new materials for cellular engineering. PMID:23936454
Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.
Synthesis and Self-Assembly of fcc Phase FePt Nanorods

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

Chen, Min; Pica, Timothy; Jiang, Ying-Bing

2007-05-01

In this paper, we report a synthesis of FePt nanorods by confining decomposition of Fe(CO) 5 and reduction of Pt(caca) 2 in surfactant reverse cylindrical micelles. The controlled nucleation and growth kinetics in confined environment allows easy control over Fe/Pt composition, nanorod uniformity, and nanorod aspect ratio. The FePt nanorods tend to self-assemble into ordered arrays along three-dimensions. Directed assembly under external magnetic field leads to two-dimensional ordered arrays, parallel to the substrate magnetic field. We expect that with optimized external magnetic fields, we should be able to assemble these nanorods into orientated one or two-dimensional arrays, providing a uniformmore » anisotropic magnetic platform for varied applications in enhanced data storage, magneto-electron transport, etc.« less
Rigid open-cell polyurethane foam for cryogenic insulation

NASA Technical Reports Server (NTRS)

Faddoul, J. R.; Lindquist, C. R.; Niendorf, L. R.; Nies, G. E.; Perkins, P. J., Jr.

1971-01-01

Lightweight polyurethane foam assembled in panels is effective spacer material for construction of self-evacuating multilayer insulation panels for cryogenic liquid tanks. Spacer material separates radiation shields with barrier that minimizes conductive and convective heat transfer between shields.
Patterning technology for solution-processed organic crystal field-effect transistors

PubMed Central

Li, Yun; Sun, Huabin; Shi, Yi; Tsukagoshi, Kazuhito

2014-01-01

Organic field-effect transistors (OFETs) are fundamental building blocks for various state-of-the-art electronic devices. Solution-processed organic crystals are appreciable materials for these applications because they facilitate large-scale, low-cost fabrication of devices with high performance. Patterning organic crystal transistors into well-defined geometric features is necessary to develop these crystals into practical semiconductors. This review provides an update on recentdevelopment in patterning technology for solution-processed organic crystals and their applications in field-effect transistors. Typical demonstrations are discussed and examined. In particular, our latest research progress on the spin-coating technique from mixture solutions is presented as a promising method to efficiently produce large organic semiconducting crystals on various substrates for high-performance OFETs. This solution-based process also has other excellent advantages, such as phase separation for self-assembled interfaces via one-step spin-coating, self-flattening of rough interfaces, and in situ purification that eliminates the impurity influences. Furthermore, recommendations for future perspectives are presented, and key issues for further development are discussed. PMID:27877656
Stochastic dynamics of virus capsid formation: direct versus hierarchical self-assembly

PubMed Central

2012-01-01

Background In order to replicate within their cellular host, many viruses have developed self-assembly strategies for their capsids which are sufficiently robust as to be reconstituted in vitro. Mathematical models for virus self-assembly usually assume that the bonds leading to cluster formation have constant reactivity over the time course of assembly (direct assembly). In some cases, however, binding sites between the capsomers have been reported to be activated during the self-assembly process (hierarchical assembly). Results In order to study possible advantages of such hierarchical schemes for icosahedral virus capsid assembly, we use Brownian dynamics simulations of a patchy particle model that allows us to switch binding sites on and off during assembly. For T1 viruses, we implement a hierarchical assembly scheme where inter-capsomer bonds become active only if a complete pentamer has been assembled. We find direct assembly to be favorable for reversible bonds allowing for repeated structural reorganizations, while hierarchical assembly is favorable for strong bonds with small dissociation rate, as this situation is less prone to kinetic trapping. However, at the same time it is more vulnerable to monomer starvation during the final phase. Increasing the number of initial monomers does have only a weak effect on these general features. The differences between the two assembly schemes become more pronounced for more complex virus geometries, as shown here for T3 viruses, which assemble through homogeneous pentamers and heterogeneous hexamers in the hierarchical scheme. In order to complement the simulations for this more complicated case, we introduce a master equation approach that agrees well with the simulation results. Conclusions Our analysis shows for which molecular parameters hierarchical assembly schemes can outperform direct ones and suggests that viruses with high bond stability might prefer hierarchical assembly schemes. These insights increase our physical understanding of an essential biological process, with many interesting potential applications in medicine and materials science. PMID:23244740
In situ synthesis of metal-organic frameworks in a porous polymer monolith as the stationary phase for capillary liquid chromatography.

PubMed

Yang, Shengchao; Ye, Fanggui; Zhang, Cong; Shen, Shufen; Zhao, Shulin

2015-04-21

In this study, HKUST-1 was synthesized in situ on the porous polymer monolith as the stationary phase for capillary liquid chromatography (cLC). The unique carboxyl functionalized poly(methacrylic acid-co-ethylene dimethacrylate) (poly(MAA-co-EDMA)) monolith was used as a support to directly grow HKUST-1 by a controlled layer-by-layer self-assembly strategy. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, and Fourier transform infrared spectroscopy of the resulting HKUST-1-poly(MAA-co-EDMA) monoliths indicated that HKUST-1 was successfully grafted onto the pore surface of the poly(MAA-co-EDMA) monolith. The column performance of HKUST-1-poly(MAA-co-EDMA) monoliths for the separation of various small molecules, such as benzenediols, xylenes, ethylbenzenes, and styrenes, was evaluated. The chromatographic performance was found to improve with increasing HKUST-1 density, and the column efficiencies and resolutions of HKUST-1-poly(MAA-co-EDMA) monoliths were 18 320-19 890 plates m(-1) and 1.62-6.42, respectively, for benzenediols. The HKUST-1-poly(MAA-co-EDMA) monolith displayed enhanced resolution for the separation of positional isomers when compared to the traditional C18 and HKUST-1 incorporated polymer monoliths. Hydrophobic, π-π, and hydrogen bonding interactions within the HKUST-1-poly(MAA-co-EDMA) monolith were observed in the separation of small molecules. The results showed that the HKUST-1-poly(MAA-co-EDMA) monoliths are promising stationary phases for cLC.
Two-Dimensional Layered Oxide Structures Tailored by Self-Assembled Layer Stacking via Interfacial Strain.

PubMed

Zhang, Wenrui; Li, Mingtao; Chen, Aiping; Li, Leigang; Zhu, Yuanyuan; Xia, Zhenhai; Lu, Ping; Boullay, Philippe; Wu, Lijun; Zhu, Yimei; MacManus-Driscoll, Judith L; Jia, Quanxi; Zhou, Honghui; Narayan, Jagdish; Zhang, Xinghang; Wang, Haiyan

2016-07-06

Study of layered complex oxides emerge as one of leading topics in fundamental materials science because of the strong interplay among intrinsic charge, spin, orbital, and lattice. As a fundamental basis of heteroepitaxial thin film growth, interfacial strain can be used to design materials that exhibit new phenomena beyond their conventional forms. Here, we report a strain-driven self-assembly of bismuth-based supercell (SC) with a two-dimensional (2D) layered structure. With combined experimental analysis and first-principles calculations, we investigated the full SC structure and elucidated the fundamental growth mechanism achieved by the strain-enabled self-assembled atomic layer stacking. The unique SC structure exhibits room-temperature ferroelectricity, enhanced magnetic responses, and a distinct optical bandgap from the conventional double perovskite structure. This study reveals the important role of interfacial strain modulation and atomic rearrangement in self-assembling a layered singe-phase multiferroic thin film, which opens up a promising avenue in the search for and design of novel 2D layered complex oxides with enormous promise.
Positron annihilation lifetime spectroscopy (PALS) as a characterization technique for nanostructured self-assembled amphiphile systems.

PubMed

Dong, Aurelia W; Pascual-Izarra, Carlos; Pas, Steven J; Hill, Anita J; Boyd, Ben J; Drummond, Calum J

2009-01-08

Positron annihilation lifetime spectroscopy (PALS) has potential as a novel rapid characterization method for self-assembly amphiphile systems; however, a lack of systematic correlation of PALS parameters with structural attributes has limited its more widespread application. In this study, using the well-characterized phytantriol/water and the phytantriol/vitamin E acetate/water self-assembly amphiphile systems, the impact of systematic structural changes controlled by changes in composition and temperature on PALS parameters has been studied. The PALS parameters (orthopositronium (oPs) lifetime and intensity signatures) were shown to be sensitive to the molecular packing and mobility of the self-assembled lipid molecules in various lyotropic liquid crystalline phases, enabling differentiation between liquid crystalline structures. The oPs lifetime, related to the molecular packing and mobility, is correlated with rheological properties of the individual mesophases. The oPs lifetime links the lipid chain packing and mobility in the various mesophases to resultant macroscopic properties, such as permeability, which is critical for the use of these mesophase structures as diffusion-controlled release matrices for active liposoluble compounds.

Rapid Growth of Acetylated Aβ(16-20) into Macroscopic Crystals.

PubMed

Bortolini, Christian; Klausen, Lasse Hyldgaard; Hoffmann, Søren Vrønning; Jones, Nykola C; Saadeh, Daniela; Wang, Zegao; Knowles, Tuomas P J; Dong, Mingdong

2018-05-22

Aberrant assembly of the amyloid-β (Aβ) is responsible for the development of Alzheimer's disease, but can also be exploited to obtain highly functional biomaterials. The short Aβ fragment, KLVFF (Aβ 16-20 ), is crucial for Aβ assembly and considered to be an Aβ aggregation inhibitor. Here, we show that acetylation of KLVFF turns it into an extremely fast self-assembling molecule, reaching macroscopic ( i.e., mm) size in seconds. We show that KLVFF is metastable and that the self-assembly can be directed toward a crystalline or fibrillar phase simply through chemical modification, via acetylation or amidation of the peptide. Amidated KLVFF can form amyloid fibrils; we observed folding events of such fibrils occurring in as little as 60 ms. The ability of single KLVFF molecules to rapidly assemble as highly ordered macroscopic structures makes it a promising candidate for applications as a rapid-forming templating material.
Contributions of experimental protobiogenesis to the theory of evolution

NASA Technical Reports Server (NTRS)

Fox, S. W.

1976-01-01

Inferences from experiments in protobiogenesis are examined as a forward extension of the theory of evolutionary biology. A nondiscontinuous, intraconsistent theory of general evolution embracing both protobiology and biology is outlined. This overview emphasizes Darwinian selection in the later stages of evolution, and stereochemical molecular selection in some of its earlier stages. It incorporates the concept of limitation of the scope of evolution by internal constraints on variation, based on the argument that internally limiting constraints observed in experiments with molecules are operative in organisms, if chemical processes occur within biological processes and biological processes are assumed to be exponentializations of chemical processes. Major evolutionary events might have occurred by rapid self-assembly processes analogous to those observed in the formation of phase-separated microspheres from amorphous powder or supersaturated solutions.
Biocatalytic Stimuli-Responsive Asymmetric Triblock Terpolymer Membranes for Localized Permeability Gating.

PubMed

Poole, Jennifer L; Donahue, Scott; Wilson, David; Li, Yuk Mun; Zhang, Qi; Gu, Yibei; Ferebee, Rachel; Lu, Zhao; Dorin, Rachel Mika; Hancock, Lawrence F; Takiff, Larry; Hakem, Ilhem F; Bockstaller, Michael R; Wiesner, Ulrich; Walker, Jeremy

2017-10-01

The functionalization with phosphotriesterase of poly(isoprene-b-styrene-b-4-vinylpyridine)-based nanoporous membranes fabricated by self-assembly and nonsolvent induced phase separation (SNIPS) is shown to enable dynamically responsive membranes capable of substrate-specific and localized gating response. Integration of the SNIPS process with macroporous nylon support layers yields mechanically robust textile-type films with high moisture vapor transport rates that display rapid and local order-of-magnitude modulation of permeability. The simplicity of the fabrication process that is compatible with large-area fabrication along with the versatility and efficacy of enzyme reactivity offers intriguing opportunities for engineered biomimetic materials that are tailored to respond to a complex range of external parameters, providing sensing, protection, and remediation capabilities. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Directed Self-Assembly of Poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template.

PubMed

Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Choi, Jaewon; Huang, Caili; Jeong, Gajin; Coughlin, E Bryan; Hsu, Yautzong; Yang, XiaoMin; Lee, Kim Y; Kuo, David S; Xiao, Shuaigang; Russell, Thomas P

2015-08-05

Low molecular weight P2VP-b-PS-b-P2VP triblock copolymer (poly(2-vinlypyridine)-block-polystyrene-block-poly(2-vinylpyridine)] is doped with copper chloride and microphase separated into lamellar line patterns with ultrahigh area density. Salt-doped P2VP-b-PS-b-P2VP triblock copolymer is self-assembled on the top of the nanoimprinted photoresist template, and metallic nanowires with long-range ordering are prepared with platinum-salt infiltration and plasma etching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Controlled self-assembly of conjugated rod-coil block copolymers for applications in organic optoelectronics

NASA Astrophysics Data System (ADS)

Tao, Yuefei

Organic electronics are of great interest in manufacturing light weight, mechanical flexible, and inexpensive large area devices. While significant improvements have been made over the last several years and it is now clear that morphology on the lengthscale of exciton diffusion (10nm) is of crucial importance, a clear relationship between structure and device properties has not emerged. This lack of understanding largely emerges from an inability to control morphology on this lengthscale. This thesis will center around an approach, based on block copolymer self-assembly, to generate equilibrium nanostructures on the 10 nm lengthscale of exciton diffusion and study their effects on device performance. Self-assembly of semiconducting block copolymers is complicated by the non-classical chain shape of conjugated polymers. Unlike classical polymers, the chains do not assume a Gaussian coil shape which is stretched near block copolymer interfaces, instead the chains are elongated and liquid crystalline. Previous work has demonstrated how these new molecular interactions and shapes control the phase diagram of so-called rod-coil block copolymers. Here, we will focus on controlling domain size, orientation, and chemical structure. While domain size can be controlled directly through molecular weight, this requires significant additional synthesis of domain size is to be varied. Here, the domain size is controlled by blending homopolymers into a self-assembling rod-coil block copolymer. When coil-like blocks are incorporated, the domains swell, as expected. When rod-like blocks are incorporated, they interdigitate with the rods of the block copolymers. This results in an increase in interfacial area which forces the coils to rearrange and an overall decrease in domain size with increasing rod content. Control over lamellar orientation is crucial in order to design and control charge transport pathways and exciton recombination or separation interfaces. While numerous techniques have been demonstrated for classical block copolymers, the pi conjugation in the rod blocks allow for additional control mechanisms. Liquid crystals are traditionally aligned in magnetic fields. Here, it is demonstrated that if the rod-like blocks are aligned unidirectionally, the block copolymer interfaces follow to create macroscopic alignment of the nanostructures. Organic Light Emitting Diodes (OLEDs) are generally composed of electron transporting and hole transporting moieties to balance charge recombination. Here, a new multifunctional bipolar rod-coil block copolymer containing the hole transporting and electron transporting materials is synthesized. Self-assembly of this new block copolymer results in 15nm lamellae oriented in grains both parallel and perpendicula to the anode. The self-assembled block copolymer shows superior device performance to controls consisting of a luminescent, analogous homopolymer, and a blend of the two component homopolymers. The effects of the morphologies and chemical structure on photovoltaics is explored with a rod-coil block copolymer, (poly(3-hexylthiophene-b-acrylic perylene)). By varying the kinetics of self-assembly through processing, the block copolymer can be disordered, ordered with only short range registry between the nanodomains, or with long-range order. The short range ordered samples showed the best device performance suggesting that the connectivity that is a biproduct of poor order is beneficial for device performance.
Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids

DOE PAGES

Jin, Haibao; Jiao, Fang; Daily, Michael D.; ...

2016-07-12

Two-dimensional (2D) materials with molecular-scale thickness have attracted increasing interest for separation, electronic, catalytic, optical, energy and biomedical applications. Although extensive research on 2D materials, such as graphene and graphene oxide, has been performed in recent years, progress is limited on self-assembly of 2D materials from sequence-specific macromolecules, especially from synthetic sequences that could exhibit lipid-like self-assembly of bilayer sheets and mimic membrane proteins for functions. The creation of such new class of materials could enable development of highly stable biomimetic membranes that exhibit cell-membrane-like molecular transport with exceptional selectively and high transport rates. Here we demonstrate self-assembly of lipid-likemore » 12-mer peptoids into extremely stable, crystalline, flexible and free-standing 2D membrane materials. As with cell membranes, upon exposure to external stimuli, these materials exhibit changes in thickness, varying from 3.5 nm to 5.6 nm. We find that self-assembly occurs through a facile crystallization process, in which inter-peptoid hydrogen bonds and enhanced hydrophobic interactions drive the formation of a highly-ordered structure. Molecular simulation confirms this is the energetically favored structure. Displaying functional groups at arbitrary locations of membrane-forming peptoids produces membranes with similar structures. This research further shows that single-layer membranes can be coated onto substrate surfaces. Moreover, membranes with mechanically-induced defects can self-repair. Given that peptoids are sequence-specific and exhibit protein-like molecular recognition with enhanced stability, we anticipate our membranes to be a robust platform tailored to specific applications.« less
Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids

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

Jin, Haibao; Jiao, Fang; Daily, Michael D.

Two-dimensional (2D) materials with molecular-scale thickness have attracted increasing interest for separation, electronic, catalytic, optical, energy and biomedical applications. Although extensive research on 2D materials, such as graphene and graphene oxide, has been performed in recent years, progress is limited on self-assembly of 2D materials from sequence-specific macromolecules, especially from synthetic sequences that could exhibit lipid-like self-assembly of bilayer sheets and mimic membrane proteins for functions. The creation of such new class of materials could enable development of highly stable biomimetic membranes that exhibit cell-membrane-like molecular transport with exceptional selectively and high transport rates. Here we demonstrate self-assembly of lipid-likemore » 12-mer peptoids into extremely stable, crystalline, flexible and free-standing 2D membrane materials. As with cell membranes, upon exposure to external stimuli, these materials exhibit changes in thickness, varying from 3.5 nm to 5.6 nm. We find that self-assembly occurs through a facile crystallization process, in which inter-peptoid hydrogen bonds and enhanced hydrophobic interactions drive the formation of a highly-ordered structure. Molecular simulation confirms this is the energetically favored structure. Displaying functional groups at arbitrary locations of membrane-forming peptoids produces membranes with similar structures. This research further shows that single-layer membranes can be coated onto substrate surfaces. Moreover, membranes with mechanically-induced defects can self-repair. Given that peptoids are sequence-specific and exhibit protein-like molecular recognition with enhanced stability, we anticipate our membranes to be a robust platform tailored to specific applications.« less
Molecular dynamics study of intermediate phase of long chain alkyl sulfonate/water systems.

PubMed

Poghosyan, Armen H; Arsenyan, Levon H; Shahinyan, Aram A

2013-01-08

Using atomic level simulation we aimed to investigate various intermediate phases of the long chain alkyl sulfonate/water system. Overall, about 800 ns parallel molecular dynamics simulation study was conducted for a surfactant/water system consisting of 128 sodium pentadecyl sulfonate and 2251 water molecules. The GROMACS software code with united atom force field was applied. Despite some differences, the analysis of main structural parameters is in agreement with X-ray experimental findings. The mechanism of self-assembly of SPDS molecules was also examined. At T = 323 K we obtained both tilted fully interdigitated and liquid crystalline-like disordered hydrocarbon chains; hence, the presence of either gel phase that coexists with a lamellar phase or metastable gel phase with fraction of gauche configuration can be assumed. Further increase of temperature revealed that the system underwent a transition to a lamellar phase, which was clearly identified by the presence of fully disordered hydrocarbon chains. The transition from gel-to-fluid phase was implemented by simulated annealing treatment, and the phase transition point at T = 335 K was identified. The surfactant force field in its presented set is surely enabled to fully demonstrate the mechanism of self-assembly and the behavior of phase transition making it possible to get important information around the phase transition point.
Electron-transfer dynamics of photosynthetic reaction centers in thermoresponsive soft materials.

PubMed

Laible, Philip D; Kelley, Richard F; Wasielewski, Michael R; Firestone, Millicent A

2005-12-15

Poly(ethylene glycol)-grafted, lipid-based, thermoresponsive, soft nanostructures are shown to serve as scaffolding into which reconstituted integral membrane proteins, such as the bacterial photosynthetic reaction centers (RCs) can be stabilized, and their packing arrangement, and hence photophysical properties, can be controlled. The self-assembled nanostructures exist in two distinct states: a liquid-crystalline gel phase at temperatures above 21 degrees C and a non-birefringent, reduced viscosity state at lower temperatures. Characterization of the effect of protein introduction on the mesoscopic structure of the materials by 31P NMR and small-angle X-ray scattering shows that the expanded lamellar structure of the protein-free material is retained. At reduced temperatures, however, the aggregate structure is found to convert from a two-dimensional normal hexagonal structure to a three-dimensional cubic phase upon introduction of the RCs. Structural and functional characteristics of the RCs were determined by ground-state and femtosecond transient absorption spectroscopy. Time-resolved results indicate that the kinetics of primary electron transfer for the RCs in the low-viscosity cold phase of the self-assembled nanostructures are identical to those observed in a detergent-solubilized state in buffered aqueous solutions (approximately 4 ps) over a wide range of protein concentrations and experimental conditions. This is also true for RCs held within the lamellar gel phase at low protein concentrations and at short sample storage times. In contrast are kinetics from samples that are prepared with high RC concentrations and stored for several hours, which display additional kinetic components with extended electron-transfer times (approximately 10-12 ps). This observation is tentatively attributed to energy transfer between RCs that have laterally (in-plane) organized within the lipid bilayers of the lamellar gel phase prior to charge separation. These results not only demonstrate the use of soft nanostructures as a matrix in which to stabilize and organize membrane proteins but also suggest the possibility of using them to control the interactions between proteins and thus to tune their collective optical/electronic properties.
Extension of the charge separated-state lifetime by supramolecular association of a tetrathiafulvalene electron donor to a zinc/gold bisporphyrin.

PubMed

Boixel, Julien; Fortage, Jérôme; Blart, Errol; Pellegrin, Yann; Hammarström, Leif; Becker, Hans-Christian; Odobel, Fabrice

2010-02-14

Supramolecular triads were prepared by self-assembly of 4'-pyridyl-2-tetrathiafulvalene axially bound on ZnP-spacer-AuP(+) dyads; the lifetime of the charge separated state ((+)TTF-ZnP-Spacer-AuP ) formed upon light excitation of the triad is greatly increased with respect to that found in the parent dyad.
Amphiastral Mitotic Spindle Assembly in Vertebrate Cells Lacking Centrosomes

PubMed Central

Hornick, Jessica E.; Mader, Christopher C.; Tribble, Emily K.; Bagne, Cydney C.; Vaughan, Kevin T.; Shaw, Sidney L.; Hinchcliffe, Edward H.

2011-01-01

Summary The role of centrosomes/centrioles during mitotic spindle assembly in vertebrates remains controversial. In cell-free extracts and experimentally derived acentrosomal cells, randomly oriented microtubules (MTs) self-organize around mitotic chromosomes and assemble anastral spindles [1, 2, 3]. However, vertebrate somatic cells normally assemble a connected pair of polarized, astral MT arrays – termed an amphiaster (“a star on both sides” [4]) – that is formed by the splitting and separation of the microtubule-organizing center (MTOC) well before nuclear envelope breakdown (NEB) [5]. Whether amphiaster formation requires splitting of duplicated centrosomes is not known. We found that when centrosomes were removed from living vertebrate cells early in their cell cycle, an acentriolar MTOC re-assembled, and prior to NEB, a functional amphiastral spindle formed. Cytoplasmic dynein, dynactin, and pericentrin are all recruited to the interphase aMTOC, and the activity of kinesin-5 is needed for amphiaster formation. Mitosis proceeded on time and these karyoplasts divided in two. However, ~35% of aMTOCs failed to split/separate before NEB, and these entered mitosis with persistent monastral spindles. The chromatin-mediated RAN-GTP pathway could not restore bipolarity to monastral spindles, and these cells exited mitosis as single daughters. Our data reveal the novel finding that MTOC separation and amphiaster formation does not absolutely require the centrosome, but in its absence, the fidelity of bipolar spindle assembly is highly compromised. PMID:21439826
Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC.

PubMed

Huang, Lili; Lu, Juan; Di, Bin; Feng, Fang; Su, Mengxiang; Yan, Fang

2011-09-01

Monodisperse spherical periodic mesoporous organosilicas (PMOs) with ethane integrated in the framework were synthesized and their application as stationary phase for chromatographic separation is demonstrated. The ethane-PMOs were prepared by condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) in basic condition using octadecyltrimethylammonium chloride (C(18)TMACl) as template and ethanol as co-solvent. The morphology and mesoporous structure of ethane-PMOs were controlled under different concentrations of sodium hydroxide (NaOH) and EtOH. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis showed that ethane-PMOs have spherical morphology, uniform particle distribution, highly ordered pore structure, high surface area and narrow pore-size distribution. The column packed with these materials exhibits good permeability, high chemical stability and good selectivity of mixtures of aromatic hydrocarbons in normal phase high-performance liquid chromatography (HPLC). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Enhancing the Efficiency of Bulk Heterojunction Solar Cells via Templated Self Assembly

NASA Astrophysics Data System (ADS)

Pan, Cheng; Li, Hongfei; Akgun, Bulent; Satijia, Sushil; Gersappe, Dilip; Zhu, Yimei; Rafailovich, Miriam

2013-03-01

Bulk Heterojunction (BHJ) polymer solar cells are an area of intense interest due to their flexibility and relatively low cost. The mixture of polythiophene derivatives (donor) and fullerenes (acceptor) is spin coated on substrate as the active layer, and are phase-separated into interconnected domains. However, due to the disordered inner structures in the active layer, donor or acceptor domains isolated from electrodes and long path conduction, the power conversion efficiency (PCE) of BHJ solar cell is low. Therefore, morphology control in bulk heterojunction (BHJ) solar cell is considered to be critical for the power conversion efficiency (PCE). Here, we present a novel approach that introduces non-photoactive polymer that organizes the poly(3-hexylthiophene) (P3HT) into columnar phases decorated by [6,6]-phenyl C61-butyric acid methyl ester (PCBM) at the interface. This structure represents a realization of an idealized morphology of an organic solar cell, in which, both exiciton dissociation and the carrier transport are optimized leading to increased power conversion efficiency.
Scalable and cleavable polysaccharide nanocarriers for the delivery of chemotherapy drugs.

PubMed

Wang, Hao; Dai, Tingting; Li, Shengli; Zhou, Shuyan; Yuan, Xiaojing; You, Jiayi; Wang, Chenglong; Mukwaya, Vincent; Zhou, Guangdong; Liu, Guojun; Wei, Xiaohui; Dou, Hongjing

2018-05-01

While polysaccharide-based nanocarriers have been recognized for their crucial roles in tumor theranostics, the industrial-scale production of nanotherapeutics still remains a significant challenge. Most current approaches adopt a postpolymerization self-assembly strategy that follows a separate synthetic step and thus suffers from subgram scale yields and a limited range of application. In this study, we demonstrate the kilogram-scale formation of polysaccharide-polyacrylate nanocarriers at concentrations of up to 5 wt% through a one-pot approach - starting from various acrylate monomers and polysaccharides - that combines aspects of hydrophobicity-induced self-assembly with the free radical graft copolymerization of acrylate monomers from polysaccharide backbones into a single process that is thus denoted as a graft copolymerization induced self-assembly. We also demonstrate that this novel approach is applicable to a broad range of polysaccharides and acrylates. Notably, by choosing a crosslinker that bears a disulfide group and two vinyl capping groups to structurally lock the nanocarriers, the products are rendered cleavable in the reducing environments encountered at tumor sites and thus provide ideal candidates for the construction of anticancer nanotherapeutic systems. In vitro and in vivo studies demonstrated that the use of this nanocarrier for the delivery of doxorubicin hydrochloride (DOX) significantly decreased the side effects of DOX and improved the bio-safety of the chemotherapy accordingly. While polysaccharide-based nanocarriers have been recognized for their crucial roles in tumor theranostics, the industrial-scale production of these nanotherapeutics still remains a significant challenge. Most current approaches adopt a post-polymerization self-assembly strategy which that follows a separate synthetic step, and thus suffers from sub-gram scale yields and a limited range of application. In this study, the hydrophobic effect was combined with free radical polymerization to facilitate the graft copolymerization-induced self-assembly (GISA) of acrylate monomers with various hydrophobicities to construct cleavable polysaccharide-polyacrylate nanocarriers at a high efficiency with excellent potential for industrial-scale production. We envision that these nanocarriers will contribute to the development of tumor nanotheranostics that combine the biological functionalities of polysaccharides with the unmatched application-specific flexibility of nanocarriers. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
M13 bacteriophage-activated superparamagnetic beads for affinity separation.

PubMed

Muzard, Julien; Platt, Mark; Lee, Gil U

2012-08-06

The growth of the biopharmaceutical industry has created a demand for new technologies for the purification of genetically engineered proteins.The efficiency of large-scale, high-gradient magnetic fishing could be improved if magnetic particles offering higher binding capacity and magnetization were available. This article describes several strategies for synthesizing microbeads that are composed of a M13 bacteriophage layer assembled on a superparamagnetic core. Chemical cross-linking of the pVIII proteins to a carboxyl-functionalized bead produces highly responsive superparamagnetic particles (SPM) with a side-on oriented, adherent virus monolayer. Also, the genetic manipulation of the pIII proteins with a His(6) peptide sequence allows reversible assembly of the bacteriophage on a nitrilotriacetic-acid-functionalized core in an end-on configuration. These phage-magnetic particles are successfully used to separate antibodies from high-protein concentration solutions in a single step with a >90% purity. The dense magnetic core of these particles makes them five times more responsive to magnetic fields than commercial materials composed of polymer-(iron oxide) composites and a monolayer of phage could produce a 1000 fold higher antibody binding capacity. These new bionanomaterials appear to be well-suited to large-scale high-gradient magnetic fishing separation and promise to be cost effective as a result of the self-assembling and self-replicating properties of genetically engineered M13 bacteriophage. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Tunable PhoXonic Band Gap Materials from Self-Assembly of Block Copoliymers and Colloidal Nanocrystals (NBIT Phase II)

DTIC Science & Technology

2011-05-06

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

PubMed

Meng, Xin; Pan, Hui; Lu, Tao; Chen, Zhixin; Chen, Yanru; Zhang, Di; Zhu, Shenmin

2018-08-10

Fibers with self-assembled photonic structures are of special interest due to their unique photonic properties and potential applications in the smart textile industry. Inspired by nature, the photonic-structured fibers were fabricated through the self-assembly of chiral nematic cellulose nanocrystals (CNCs) and the fibers showed tunably brilliant and selectively reflected colors under crossed-polarization. A simple wet-spinning method was applied to prepare composite fibers of the mixed CNC matrix and polyvinyl alcohol (PVA) additions. During the processing, a cholesteric CNC phase formed photonic fibers through a self-assembly process. The selective color reflection of the composite fibers in the polarized condition showed a typical red-shift tendency with an increase in the PVA content, which was attributed to the increased helical pitch of the CNC. Furthermore, the polarized angle could also alter the reflected colors. Owing to their excellent selective reflection properties under the polarized condition, CNC-based photonic fibers are promising as the next-generation of smart fibers, applied in the fields of specific display and sensing.
Pressure effect on micellization of non-ionic surfactant Triton X-100

NASA Astrophysics Data System (ADS)

Espinosa, Yanis R.; Caffarena, Ernesto R.; Martínez, Yanina Berrueta; Grigera, J. Raúl

2018-02-01

Micellar aggregates can be arranged in new types of conformational assemblies when they are isotropically compressed. Thus, the pressure effects in the underlying fundamental interactions leading to self-assembly of micellar aggregates can be represented by changes in the phase boundaries with increasing pressure. In this paper, we have employed molecular dynamics simulations to study the self-assembly of micelles composed of the non-ionic surfactant Triton X-100 at the atomic scale, monitoring the changes in the solvation dynamics when the micelles are subjected to a wide range of hydrostatic pressures. The computational molecular model was capable of self-assembling and forming a non-ionic micelle, which subsequently was coupled to a high-pressure barostat producing a geometric transition of the micelle due to changes in the solvation dynamics. Accordingly, under a high pressure regime, the hydrogen bonds are redistributed, the water density is modified, and water acts as an unstructured liquid, capable of penetrating into the micelle.
Self-assembly strategies for the synthesis of functional nanostructured materials

NASA Astrophysics Data System (ADS)

Perego, M.; Seguini, G.

2016-06-01

Self-assembly is the autonomous organization of components into patterns or structures without human intervention. This is the approach followed by nature to generate living cells and represents one of the practical strategies to fabricate ensembles of nanostructures. In static self-assembly the formation of ordered structures could require energy but once formed the structures are stable. The introduction of additional regular features in the environment could be used to template the self-assembly guiding the organization of the components and determining the final structure they form. In this regard self-assembly of block copolymers represents a potent platform for fundamental studies at the nanoscale and for application-driven investigation as a tool to fabricate functional nanostructured materials. Block copolymers can hierarchically assemble into chemically distinct domains with size and periodicity on the order of 10nm or below, offering a potentially inexpensive route to generate large-area nanostructured materials. The final structure characteristics of these materials are dictated by the properties of the elementary block copolymers, like chain length, volume fraction or degree of block incompatibility. Modern synthetic chemistry offers the possibility to design these macromolecules with very specific length scales and geometries, directly embodying in the block copolymers the code that drives their self- assembling process. The understanding of the kinetics and thermodynamics of the block copolymer self-assembly process in the bulk phase as well as in thin films represents a fundamental prerequisite toward the exploitation of these materials. Incorporating block copolymer into device fabrication procedures or directly into devices, as active elements, will lead to the development of a new generation of devices fabricated using the fundamental law of nature to our advantage in order to minimize cost and power consumption in the fabrication process. Moreover the capability to precisely organize these nano-objects on appropriate substrates is the key point to support the technological development of new device concepts with predictable characteristics based on these nano-materials. In the next coming years this area of research, at the intersection between fundamental science and technology, is expected to disclose additional insights in the physics of the self-assembly process and to delineate unforeseen applications for these exciting materials.
Traffic model for commercial payloads in the Materials Experiment Assembly (MEA). [market research in commercial space processing

NASA Technical Reports Server (NTRS)

Tietzel, F. A.

1979-01-01

One hundred individuals representing universities, technical institutes, government agencies, and industrial facilities were surveyed to determine potential commercial use of a self-contained, automated assembly for the space processing of materials during frequent shuttle flights for the 1981 to 1987 period. The approach used and the results of the study are summarized. A time time-phased projection (traffic model) of commercial usage of the materials experiment assembly is provided.

Self-assembly behavior of β-cyclodextrin and imipramine. A Free energy perturbation study

NASA Astrophysics Data System (ADS)

Sun, Tingting; Shao, Xueguang; Cai, Wensheng

2010-05-01

The self-assembly behavior of β-cyclodextrin (β-CD) and imipramine (IMI), an antidepressant drug, was investigated by molecular dynamics simulations in the gas phase and in an aqueous solution. The binding free energies for 10 possible arrangements of β-CD/IMI complexes with stoichiometries of 1:1, 2:1, and 1:2 were determined using free energy perturbation calculations. The calculations suggest that the 2:1 inclusion mode is the most energetically favored in both phases, in good agreement with experiment. The environment and the neutral and charged IMI influence the stability of the aggregates. The electrostatic interactions constitute the main contribution to the stability. The results reported in this contribution shed new light on the mechanism of association of β-CD with IMI.
Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

NASA Astrophysics Data System (ADS)

Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

2016-05-01

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.
Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H 2 production

DOE PAGES

Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; ...

2016-05-10

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy) 3 ] 2+ -based precursor and cucurbit[8] uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-'Dawson-type polyoxometalatesmore » (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy) 3 ] 2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.« less
Self Assembled Bi-functional Peptide Hydrogels with Biomineralization-Directing Peptides

PubMed Central

Gungormus, Mustafa; Branco, Monica; Fong, Hanson; Schneider, Joel P.; Tamerler, Candan; Sarikaya, Mehmet

2014-01-01

A peptide-based hydrogel has been designed that directs the formation of hydroxyapatite. MDG1, a twenty-seven residue peptide, undergoes triggered folding to form an unsymmetrical β-hairpin that self-assembles in response to an increase in solution ionic strength to yield a mechanically rigid, self supporting hydrogel. The C-terminal portion of MDG1 contains a heptapeptide (MLPHHGA) capable of directing the mineralization process. Circular dichroism spectroscopy indicates that the peptide folds and assembles to form a hydrogel network rich in β-sheet secondary structure. Oscillatory rheology indicates that the hydrogel is mechanical rigid (G′ ∼ 2500 Pa) before mineralization. In separate experiments, mineralization was induced both biochemically and with cementoblast cells. Mineralization-domain had little effect on the mechanical rigidity of the gel. SEM and EDS show that MDG1 gels are capable of directing the formation of hydroxapatite. Control hydrogels, prepared by peptides either lacking the mineral-directing portion or reversing its sequence, indicated that the heptapeptide is necessary and its actions are sequence specific. PMID:20591477
The Kinetics of the as Grown and Annealed Self-Assembled Monolayer Studied by Force Spectroscopy

NASA Astrophysics Data System (ADS)

Habib, Huma; Yasar, M.; Mehmood, S.; Rafique, Saima; Bhatti, A. S.; Naeem, Aisha

The growth of biological systems like DNA, peptides and proteins are accredited to the self-assembly processes from the molecular level to the nanoscale. The flawless immobilization of DNA on any surface is quite an important step to the development of DNA-based biosensors. The present paper reports the use of atomic force microscopy to determine the mechanical properties of the as grown and annealed self-assembled monolayer (SAM) as well as the mutated DNA immobilized on the SAM. The SAM of alkane thiol (16-mercapto-1-hexadecanol) was developed on Au surface, which was then annealed and analyzed for its structural and mechanical properties. The surface coverage, height and monolayer’s order was studied as a function of incubation time and annealing time. Excessive annealing led to the defragmentation and desorption of SAM structures due to breaking of hydrocarbon bonds. AFM was employed to determine the detach separation, pull-off and work of adhesion of the as grown and annealed SAM.
Ultra-fast self-assembly and stabilization of reactive nanoparticles in reduced graphene oxide films

PubMed Central

Chen, Yanan; Egan, Garth C.; Wan, Jiayu; Zhu, Shuze; Jacob, Rohit Jiji; Zhou, Wenbo; Dai, Jiaqi; Wang, Yanbin; Danner, Valencia A.; Yao, Yonggang; Fu, Kun; Wang, Yibo; Bao, Wenzhong; Li, Teng; Zachariah, Michael R.; Hu, Liangbing

2016-01-01

Nanoparticles hosted in conductive matrices are ubiquitous in electrochemical energy storage, catalysis and energetic devices. However, agglomeration and surface oxidation remain as two major challenges towards their ultimate utility, especially for highly reactive materials. Here we report uniformly distributed nanoparticles with diameters around 10 nm can be self-assembled within a reduced graphene oxide matrix in 10 ms. Microsized particles in reduced graphene oxide are Joule heated to high temperature (∼1,700 K) and rapidly quenched to preserve the resultant nano-architecture. A possible formation mechanism is that microsized particles melt under high temperature, are separated by defects in reduced graphene oxide and self-assemble into nanoparticles on cooling. The ultra-fast manufacturing approach can be applied to a wide range of materials, including aluminium, silicon, tin and so on. One unique application of this technique is the stabilization of aluminium nanoparticles in reduced graphene oxide film, which we demonstrate to have excellent performance as a switchable energetic material. PMID:27515900
Titanium Surface Priming with Phase-Transited Lysozyme to Establish a Silver Nanoparticle-Loaded Chitosan/Hyaluronic Acid Antibacterial Multilayer via Layer-by-Layer Self-Assembly.

PubMed

Zhong, Xue; Song, Yunjia; Yang, Peng; Wang, Yao; Jiang, Shaoyun; Zhang, Xu; Li, Changyi

2016-01-01

The formation of biofilm around implants, which is induced by immediate bacterial colonization after installation, is the primary cause of post-operation infection. Initial surface modification is usually required to incorporate antibacterial agents on titanium (Ti) surfaces to inhibit biofilm formation. However, simple and effective priming methods are still lacking for the development of an initial functional layer as a base for subsequent coatings on titanium surfaces. The purpose of our work was to establish a novel initial layer on Ti surfaces using phase-transited lysozyme (PTL), on which multilayer coatings can incorporate silver nanoparticles (AgNP) using chitosan (CS) and hyaluronic acid (HA) via a layer-by-layer (LbL) self-assembly technique. In this study, the surfaces of Ti substrates were primed by dipping into a mixture of lysozyme and tris(2-carboxyethyl)phosphine (TCEP) to obtain PTL-functionalized Ti substrates. The subsequent alternating coatings of HA and chitosan loaded with AgNP onto the precursor layer of PTL were carried out via LbL self-assembly to construct multilayer coatings on Ti substrates. The results of SEM and XPS indicated that the necklace-like PTL and self-assembled multilayer were successfully immobilized on the Ti substrates. The multilayer coatings loaded with AgNP can kill planktonic and adherent bacteria to 100% during the first 4 days. The antibacterial efficacy of the samples against planktonic and adherent bacteria achieved 65%-90% after 14 days. The sustained release of Ag over 14 days can prevent bacterial invasion until mucosa healing. Although the AgNP-containing structure showed some cytotoxicity, the toxicity can be reduced by controlling the Ag release rate and concentration. The PTL priming method provides a promising strategy for fabricating long-term antibacterial multilayer coatings on titanium surfaces via the LbL self-assembly technique, which is effective in preventing implant-associated infections in the early stage.
Bi-continuous Multi-component Nanocrystal Superlattices for Solar Energy Conversion

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

Kagan, Cherie; Murray, Christopher; Kikkawa, James

2017-06-14

Our SISGR program studied an emerging class of nanomaterials wherein different combinations of semiconductor or semiconductor and plasmonic nanocrystals (NCs) are self-assembled into three-dimensional multi-component superlattices. The NC assemblies were designed to form bicontinuous semiconductor NC sublattices with type-II energy offsets to drive charge separation onto electron and hole transporting sublattices for collection and introduce plasmonic NCs to increase solar absorption and charge separation. Our group is expert in synthesizing and assembling an extraordinary variety of artificial systems by tailoring the NC building blocks and the superlattice unit cell geometry. Under this DOE BES Materials Chemistry program, we introduced chemicalmore » methods to control inter-particle distance and to dope NC assemblies, which enabled our demonstration of strong electronic communication between NCs and the use of NC thin films as electronic materials. We synthesized, assembled and structurally, spectroscopically, and electrically probed NC superlattices to understand and manipulate the flow of energy and charge toward discovering the design rules and optimizing these complex architectures to create materials that efficiently convert solar radiation into electricity.« less
Spatial patterning of P granules by RNA-induced phase separation of the intrinsically-disordered protein MEG-3

PubMed Central

Smith, Jarrett; Calidas, Deepika; Schmidt, Helen; Lu, Tu; Rasoloson, Dominique; Seydoux, Geraldine

2016-01-01

RNA granules are non-membrane bound cellular compartments that contain RNA and RNA binding proteins. The molecular mechanisms that regulate the spatial distribution of RNA granules in cells are poorly understood. During polarization of the C. elegans zygote, germline RNA granules, called P granules, assemble preferentially in the posterior cytoplasm. We present evidence that P granule asymmetry depends on RNA-induced phase separation of the granule scaffold MEG-3. MEG-3 is an intrinsically disordered protein that binds and phase separates with RNA in vitro. In vivo, MEG-3 forms a posterior-rich concentration gradient that is anti-correlated with a gradient in the RNA-binding protein MEX-5. MEX-5 is necessary and sufficient to suppress MEG-3 granule formation in vivo, and suppresses RNA-induced MEG-3 phase separation in vitro. Our findings suggest that MEX-5 interferes with MEG-3’s access to RNA, thus locally suppressing MEG-3 phase separation to drive P granule asymmetry. Regulated access to RNA, combined with RNA-induced phase separation of key scaffolding proteins, may be a general mechanism for controlling the formation of RNA granules in space and time. DOI: http://dx.doi.org/10.7554/eLife.21337.001 PMID:27914198
How Langmuir-Blodgett trilayers act as templates for directed self-assembly of nanoparticles

NASA Astrophysics Data System (ADS)

Mukherjee, Smita; Datta, Alokmay; Biswas, Nupur; Giglia, Angelo; Nannarone, Stefano

2014-04-01

Atomic force microscopy (AFM) shows that Langmuir-Blodgett (LB) deposition of dissimilar metal stearates (MSt, M = Co, Zn, Cd) on templates of Co-stearate (Co-T) and Cd-stearate (Cd-T) results in self-assembly of MSts into nanocrystalline grains having clear and consistent morphological habits. The grains are better formed and well separated on Cd-T than on Co-T. Fourier transform infrared spectroscopy (FTIR) results show that the headgroup coordination of the overlayer is tuned by the coordination of the Cd-T template and remains unaffected by that of the Co-T template. They also indicate co-existence of a different kind of headgroup structure that is close to the undissociated fatty acid headgroup but differing more in the two types of carbon-oxygen bonds, suggesting an inter-headgroup bonding such as hydrogen bond that may exist on a nanocrystal surface. Results of synchrotron x-ray diffraction at C K-edge, of ZnSt on Cd-T (ZnSt/Cd-T) and Co-T (ZnSt/Co-T), point to a non-closed packed structure for ZnSt/Cd-T and a closed-packed structure for ZnSt/Co-T, with significant superlattice order in the former. The presence of crystalline phases of ZnSt in the nanometer scale, on LB templates, in contrast to the the presence of lamellar phase in bulk ZnSt, is attributed to the the presence of unidentate metal-carboxylate coordination in the former and absence of it in the latter, creating different gradients of dipolar forces at template overlayer interface. Relative strength of this long-range force over short-range intermolecular forces in the templates qualitatively explains better crystallinity and higher ordering in ZnSt/Cd-T compared to ZnSt/Co-T. We propose that the role of dipole moment gradient between template and overlayer in tuning of these metal-organic nanoparticles may be somewhat similar to structural and optical tunability of semiconductor nanocrystals by thermal and self-equilibrium strain.
Using Symmetry to Design Self-Assembling Protein Cages and Nanomaterials on the Mid-Nanometer Scale

NASA Astrophysics Data System (ADS)

Yeates, Todd

Self-assembling molecular structures having diverse cellular functions are widespread in nature. Some of the largest and most sophisticated types are built from many copies of the same or similar protein molecules arranged following principles of symmetry. A long-standing engineering goal has been to design novel protein molecules to self-assemble into geometrically specific structures similar to the extraordinary structures that have evolved in Nature. Practical routes to this goal have been developed by using ideas in symmetry to articulate the minimum design requirements for achieving various types of symmetric architectures, including cages, extended two-dimensional layers, and three-dimensional crystalline materials. The key requirement is that two distinct self-associating interfaces, each conferring one element of rotational symmetry, have to be engineered into the protein molecule (or molecules), following particular geometric specifications. The main principle is that combining two separate symmetry elements into a single molecular entity produces a molecule that necessarily assembles into an architecture dictated by a symmetry group that is the product of the two simpler contributing symmetries. Recent experiments have demonstrated success using a variety of symmetry-based strategies. Strategic variations are emerging that differ from each other with respect to biophysical features such as flexibility vs rigidity in the assembled structures, and with respect to design aspects such as whether the protein interfaces are inherited from natural oligomeric proteins or are designed de novo by advanced computational methods. The success of these strategies has been proven by determining crystal structures of several giant, self-assembling protein cages and clusters (10-25 nm in diameter), created by design. The ability to create sophisticated supramolecular structures from designed protein subunits opens the way to broad applications in synthetic biology and nanotechnology.
Thermo-triggerable self-assembly comprising cinnamoyl polymeric β cyclodextrin and cinnamoyl Pluronic F127.

PubMed

Wang, Min Hui; Jeong, Jae Hyun; Kim, Jin-Chul

2016-06-01

Thermo-triggerable self-assembly was prepared by co-dissolving cinnamoyl Pluronic F127 (CinPlu) and cinnamoyl polymeric β cyclodextrin (CinPβCD) in an aqueous phase. On TEM photo, the CinPlu/CinPβCD self-assembly was 100-200nm in diameter. The specific loading of Nile red (NR) in the assembly was calculated to be 5.5% (wt NR/wt polymer), and the molar ratio of NR to βCD residue in the assembly was about 0.89:1. No significant release of NR from the assembly was observed at 10°C and 20°C. However, when the temperature was raised to 30°C, 40°C, 50°C, and 60°C, the cumulative release amount in 5min was 17%, 25%, 32%, and 52%, respectively. The specific loading of doxorubicin (DOX) in the assembly was about 6.8% (wt DOX/wt polymer) (corresponding to the molar ratio of DOX to βCD residue was about 0.41:1). The DOX release from the assembly was proportional to the temperature of release medium. NR and DOX were likely to be expelled out of the cavity of βCD residue by the interaction of the thermally hydrophobicized Pluronic F127 chain (molecular piston) and the cavity of βCD residue (cylinder). After 4h-incubation with KB cell, DOX loaded in CinPlu/CinPβCD self-assembly was found to be internalized into the cancer cell more than free DOX, observed on a confocal laser scanning microscope and a fluorescence activated cell sorter. CinPlu/CinPβCD self-assembly enhanced the in vitro anti-cancer activity of DOX against KB cell without increasing significantly the in vitro toxicity of DOX against Raw264.7 cell. Copyright © 2016 Elsevier B.V. All rights reserved.
Laser induced hierarchical calcium phosphate structures.

PubMed

Kurella, Anil; Dahotre, Narendra B

2006-11-01

The surface properties of biomedical implant materials control the dynamic interactions at tissue-implant interfaces. At such interfaces, if the nanoscale features influence protein interactions, those of the microscale and mesoscale aid cell orientation and provide tissue integration, respectively. It seems imperative that the synthetic materials expected to replace natural hard tissues are engineered to mimic the complexity of their hierarchical assembly. However, the current surface engineering approaches are single scaled. It is demonstrated that using laser surface engineering a controlled multiscale surface can be synthesized for bioactive functions. A systematic organization of bioactive calcium phosphate coating with multiphase composition on Ti-alloy substrate ranging from nano- to mesoscale has been achieved by effectively controlling the thermo physical interactions during laser processing. The morphology of the coating consisted of a periodic arrangement of Ti-rich and Ca-P-deficient star-like phases uniformly distributed inside a Ca-P-rich self-assembled cellular structure with the presence of CaO, alpha-tricalcium phosphate, CaTiO(3), TiO(2) and Ti phase in the coating matrix. The cellular structures ranged in diameter from 2.5 microm to 10 microm as an assembly of cuboid shaped particles of dimensions of approximately 200 nm x 1 microm. The multiscale texture also included nanoscale particles that are the precursors for many of these phases. The rapid cooling associated with the laser processing resulted in formation, organization and controlling dimensions of the Ca-P-rich glassy phase into a micron scale cellular morphology and submicron scale clusters of CaTiO(3) phase inside the cellular structures. The self-assembly of the coating into multiscale structure was influenced by chemical and physical interactions among the multiphases that evolved during laser processing.
Order from the disorder: hierarchical nanostructures self-assembled from the gas phase (Conference Presentation)

NASA Astrophysics Data System (ADS)

Di Fonzo, Fabio

2017-02-01

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

PubMed

Chen, Xiao-Wei; Chen, Ya-Jun; Wang, Jin-Mei; Guo, Jian; Yin, Shou-Wei; Yang, Xiao-Quan

2017-04-15

A current challenge in the area of food emulsion is the design of microstructure that provides controlled release of volatile compounds during storage and consumption. Here, a new strategy addressed this problem at the fundamental level by describing the design of organogel-based emulsion from the self-assembly of β-sitosterol and γ-oryzanol that are capable of tuning volatile release. The results showed that the release rate (v 0 ), maximum headspace concentrations (C max ) and partition coefficients (k a / e ) above structured emulsions were significantly lower than unstructured emulsions and controlled release doing undergo tunable though the self-assembled interface and core fine microstructure from internal phase under dynamic and static condition. This result provides an understanding of how emulsions can behave as delivery system to better design novel food products with enhanced sensorial and nutritional attributes. Copyright © 2016 Elsevier Ltd. All rights reserved.
Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

PubMed

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Thermoelectric performance of SrTiO3 enhanced by nanostructuring-self-assembled particulate film of nanocubes.

PubMed

Dang, Feng; Wan, Chunlei; Park, Nam-Hee; Tsuruta, Kazuki; Seo, Won-Seon; Koumoto, Kunihito

2013-11-13

Self-assembled particulate films with a uniform structure over a large area were prepared from La-SrTiO3 nanocubes for thermoelectric applications. UV irradiation was used to assist the formation of particulate film for decomposition of the organic phase in situ to obtain a mechanically robust structure at high temperature. The thermoelectric properties of the particulate film were measured after calcination at 1000 °C under a reductive atmosphere (Ar/H2 = 60/40). A Seebeck coefficient of S = -239 ± 24 μV/K, electrical conductivity of σ = 160 ± 5 S/cm, and thermal conductivity of κ ≈ 1.5 W/mK were obtained for a self-assembled particulate film (La: 5%) corresponding to a ZT value of 0.2 at room temperature, which exceeded that of a La-SrTiO3 single crystal with similar composition.
Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions

NASA Astrophysics Data System (ADS)

Hudson, Zachary M.; Boott, Charlotte E.; Robinson, Matthew E.; Rupar, Paul A.; Winnik, Mitchell A.; Manners, Ian

2014-10-01

Recent advances in the self-assembly of block copolymers have enabled the precise fabrication of hierarchical nanostructures using low-cost solution-phase protocols. However, the preparation of well-defined and complex planar nanostructures in which the size is controlled in two dimensions (2D) has remained a challenge. Using a series of platelet-forming block copolymers, we have demonstrated through quantitative experiments that the living crystallization-driven self-assembly (CDSA) approach can be extended to growth in 2D. We used 2D CDSA to prepare uniform lenticular platelet micelles of controlled size and to construct precisely concentric lenticular micelles composed of spatially distinct functional regions, as well as complex structures analogous to nanoscale single- and double-headed arrows and spears. These methods represent a route to hierarchical nanostructures that can be tailored in 2D, with potential applications as diverse as liquid crystals, diagnostic technology and composite reinforcement.
High-Definition Self-Assemblies driven by the Hydrophobic Effect: Synthesis and Properties of a Supramolecular Nano-Capsule

PubMed Central

Liu, Simin

2008-01-01

High definition self-assemblies, those that possess order at the molecular level, are most commonly made from subunits possessing metals and metal coordination sites, or groups capable of partaking in hydrogen bonding. In other words, enthalpy is the driving force behind the free energy of assembly. The hydrophobic effect engenders the possibility of (nominally) relying not on enthalpy but entropy to drive assembly. Towards this idea, we describe how template molecules can trigger the dimerization of a cavitand in aqueous solution, and in doing so are encapsulated within the resulting capsule. Although not held together by (enthalpically) strong and directional non-covalent forces, these capsules possess considerable thermodynamic and kinetic stability. As a result, they display unusual and even unique properties. We discuss some of these, including the use of the capsule as a nano-scale reaction chamber and how they can bring about the separation of hydrocarbon gases. PMID:18685753
Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

PubMed Central

Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

2010-01-01

FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

Drug delivery by water-soluble organometallic cages.

PubMed

Therrien, Bruno

2012-01-01

Until recently, organometallic derivatives were generally viewed as moisture- and air-sensitive compounds, and consequently very challenging to synthesise and very demanding in terms of laboratory requirements (Schlenk techniques, dried solvent, glove box). However, an increasing number of stable, water-soluble organometallic compounds are now available, and organometallic chemistry in aqueous phase is a flourishing area of research. As such, coordination-driven self-assemblies using organometallic building blocks are compatible with water, thus opening new perspectives in bio-organometallic chemistry.This chapter gives a short history of coordination-driven self-assembly, with a special attention to organometallic metalla-cycles, especially those composed of half-sandwich complexes. These metalla-assemblies have been used as sensors, as anticancer agents, as well as drug carriers.
Phases, line tension and pattern formation in molecularly thin films at the air-water interface

NASA Astrophysics Data System (ADS)

Mandal, Pritam

A Langmuir film, which is a molecularly thin insoluble film on a liquid substrate, is one practical realization of a quasi-two dimensional matter. The major advantages of this system for the study of phase separation and phase co-existence are (a) it allows accurate control of the components and molecular area of the film and (b) it can be studied by various methods that require very flat films. Phase separation in molecularly thin films plays an important role in a range of systems from biomembranes to biosensors. For example, phase-separated lipid nano-domains in biomembranes are thought to play crucial roles in membrane function. I use Brewster Angel Microscopy (BAM) coupled with Fluorescence Microscopy (FM) and static Light Scattering Microscopy (LSM) to image phases and patterns within Langmuir films. The three microscopic techniques --- BAM, FM and LSM --- are complimentary to each other, providing distinct sets of information. They allow direct comparison with literature results in lipid systems. I have quantitatively validated the use of detailed hydrodynamic simulations to determine line tension in monolayers. Line tension decreases as temperature rises. This decrease gives us information on the entropy associated with the line, and thus about line structure. I carefully consider the thermodynamics of line energy and entropy to make this connection. In the longer run, LSM will be exploited to give us further information about line structure. I have also extended the technique by testing it on domains within the curved surface of a bilayer vesicle. I also note that in the same way that the presence of surface-active agents, known as surfactants, affects surface energy, the addiction of line active agents alters the inter-phase line energy. Thus my results set to stage to systematically study the influence of line active agents ---'linactants' --- on the inter-phase line energy. Hierarchal self-assembled chiral patterns were observed as a function of temperature. I found that the appearance of these domains could be explained with a simple uniaxial optical axis in the underlying structure, which is the first critical step to understanding the origin of these patterns.
Modulating the forces between self-assembling molecules to control the shape of vesicles and the mechanics and alignment of nanofiber networks

NASA Astrophysics Data System (ADS)

Greenfield, Megan Ann

One of the great challenges in supramolecular chemistry is the design of molecules that can self-assemble into functional aggregates with well-defined three-dimensional structures and bulk material properties. Since the self-assembly of nanostructures is greatly influenced by both the nature of the self-assembling components and the environmental conditions in which the components assemble, this work explores how changes in the molecular design and the environment affect the properties of self-assembled structures. We first explore how to control the mechanical properties of self-assembled fibrillar networks by changing environmental conditions. We report here on how changing pH, screening ions, and solution temperature affect the gelation, stiffness, and response to deformation of peptide amphiphile gels. Although the morphology of PA gels formed by charge neutralization and salt-mediated charge screening are similar by electron microscopy, rheological measurements indicate that the calcium-mediated ionic bridges in CaCl2-PA gels form stronger intra- and inter-fiber crosslinks than the hydrogen bonds formed by the protonated carboxylic acid residues in HCl-PA gels. In contrast, the structure of PA gels changes drastically when the PA solution is annealed prior to gel formation. Annealed PA solutions are birefringent and can form viscoelastic strings of aligned nanofibers when manually dragged across a thin film of CaCl2. These aligned arrays of PA nanofibers hold great promise in controlling the orientation of cells in three-dimensions. Separately, we applied the principles of molecular design to create buckled membrane nanostructures that mimic the shape of viruses. When oppositely charged amphiphilic molecules are mixed they can form vesicles with a periodic two-dimensional ionic lattice that opposes the membrane's natural curvature and can result in vesicle buckling. Our results demonstrate that a large +3 to -1 charge imbalance between the cationic and anionic head groups of amphiphiles enables their co-assembly into small buckled vesicles. In contrast to previous reports, the structures described here form without the rigorous exclusion of salt and are tolerant to physiological salt concentrations. Our work opens a new path for exploring how ionic laterally correlated domains can influence the morphology of self-assembled nanostructures.
Spontaneous Self-Organization Enables Dielectrophoresis of Small Nanoparticles and Formation of Photoconductive Microbridges

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

Jung, Seung-Ho; Chen, Chen; Cha, Sang-Ho

Detailed understanding of the mechanism of dielectrophoresis (DEP) and the drastic improvement of its efficiency for small size-quantized nanoparticles (NPs) open the door for the convergence of microscale and nanoscale technologies. It is hindered, however, by the severe reduction of DEP force in particles with volumes below a few hundred cubic nanometers. We report here DEP assembly of size-quantized CdTe nanoparticles (NPs) with a diameter of 4.2 nm under AC voltage of 4–10 V. Calculations of the nominal DEP force for these NPs indicate that it is several orders of magnitude smaller than the force of the Brownian motion destroyingmore » the assemblies even for the maximum applied AC voltage. Despite this, very efficient formation of NP bridges between electrodes separated by a gap of 2 μm was observed even for AC voltages of 6 V and highly diluted NP dispersions. The resolution of this conundrum was found in the intrinsic ability of CdTe NPs to self-assemble. The species being assembled by DEP are substantially bigger than the individual NPs. DEP assembly should be treated as a process taking place for NP chains with a length of ~140 nm. The self-assembled chains increase the nominal volume where the polarization of the particles takes place, while retaining the size-quantized nature of the material. The produced NP bridges were found to be photoactive, producing photocurrent upon illumination. DEP bridges of quantum confined NPs can be used in fast parallel manufacturing of novel MEMS components, sensors, and optical and optoelectronic devices. Purposeful engineering of self-assembling properties of NPs makes possible further facilitation of the DEP and increase of complexity of the produced nano- and microscale structures.« less
Synthesis and liquid crystalline properties of mono-, di- and tri-O-alkyl pentaerythritol derivatives bearing tri-, di- or monogalactosyl heads: the effects of curvature of molecular packing on mesophase formation.

PubMed

Dumoulin, Fabienne; Lafont, Dominique; Huynh, Thai-Lê; Boullanger, Paul; Mackenzie, Grahame; West, Jon J; Goodby, John W

2007-01-01

Self-organisation and self-assembly are critical to the stability of synthetic and biological membranes. Of particular importance is consideration of the packing arrangements of the various molecular species. Both phospho- and glycolipids can pack in ways in which curvature can be introduced into self-organised or self-assembled systems. For instance, it is known that the degree of curvature can affect the structures of any condensed phases that are formed. In this article we report on a systematic study in which we have varied the shapes of glycolipids and examined the condensed phases that they form. In doing so, we have also unified the shape dependency of lyotropic liquid crystals with those of thermotropic liquid crystals. In order to undertake this systematic study a range of different pentaerythritol derivatives was synthesized, which covers combinations of one to three alkyl chains of different lengths (6,7,9,10,11,12,14,16 carbon atoms) and three to one galactosyl heads. Mono- and di-O-galactosyl derivatives were prepared directly by glycosylation of the corresponding alcohols using 2,3,4,6-tetra-O-benzoyl or acetyl-alpha-D-galactopyranosyl trichloroacetimidate or bromide as the donors; the tri-O-galactosyl derivatives were synthesized from O-alkyl-O-benzyl di-O-galactosyl pentaerythritol intermediates, followed by de-O-benzylation and glycosylation steps. All of the fully deprotected products were obtained by standard methods, and their self-organising and self-assembling properties examined.
Bioengineered-inorganic nanosystems for nanophotonics and bio-nanotechnology

NASA Astrophysics Data System (ADS)

Leong, Kirsty; Zin, Melvin T.; Ma, Hong; Huang, Fei; Sarikaya, Mehmet; Jen, Alex K.

2008-08-01

Here we nanoengineered tunable quantum dot and cationic conjugated polymer nanoarrays based on surface plasmon enhanced fluorescence where we achieved a 15-fold and 25-fold increase in their emission intensities, respectively. These peptide mediated hybrid systems were fabricated by horizontally tuning the localized surface plasmon resonance of gold nanoarrays and laterally tuning the distance of the fluorophore from the metal surface. This approach permits a comprehensive control both laterally (i.e., lithographically defined gold nanoarrays) and vertically (i.e., QD/CCP-metal distance) of the collectively behaving QD-NP and CP-NP assemblies by way of biomolecular recognition. The highest photoluminescence was achieved when the quantum dots and cationic conjugated polymers were self-assembled at a distance of 16.00 nm and 18.50 nm from the metal surface, respectively. Specifically, we demonstrated the spectral tuning of plasmon resonant metal nanoarrays and the self-assembly of protein-functionalized QDs/CCPs in a step-wise fashion with a concomitant incremental increase in separation from the metal surface through biotin-streptavidin spacer units. These well-controlled self-assembled patterned arrays provide highly organized architectures for improving optoelectronic devices and/or increasing the sensitivity of bio-chemical sensors.
Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) technology of mercury removal and stabilization

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

Feng, Xiangdong; Liu, Jun; Fryxell, G.E.

1997-09-01

This paper explains the technology developed to produce Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) for mercury removal from aqueous wastewater and from organic wastes. The characteristics of SAMMS materials, including physical characteristics and mercury loading, and its application for mercury removal and stabilization are discussed. Binding kinetics and binding speciations are reported. Preliminary cost estimates are provided for producing SAMMS materials and for mercury removal from wastewater. The characteristics of SAMMS in mercury separation were studied at PNNL using simulated aqueous tank wastes and actual tritiated pump oil wastes from Savannah River Site; preliminary results are outlined. 47 refs., 16more » figs., 16 tabs.« less
Size quantization patterns in self-assembled InAs/GaAs quantum dots

NASA Astrophysics Data System (ADS)

Colocci, M.; Bogani, F.; Carraresi, L.; Mattolini, R.; Bosacchi, A.; Franchi, S.; Frigeri, P.; Taddei, S.; Rosa-Clot, M.

1997-07-01

Molecular beam epitaxy has been used for growing self-assembled InAs quantum dots. A continuous variation of the InAs average coverage across the sample has been obtained by properly aligning the (001) GaAs substrate with respect to the molecular beam. Excitation of a large number of dots (laser spot diameter ≈ 100 μm) results in structured photoluminescence spectra; a clear quantization of the dot sizes is deduced from the distinct luminescence bands separated in energy by an average spacing of 20-30 meV. We ascribe the individual bands of the photoluminescence spectrum after low excitation to families of dots with roughly the same diameter and heights differing by one monolayer.
Particle-based simulations of bilayer membranes: self-assembly, structural analysis, and shock-wave damage

NASA Astrophysics Data System (ADS)

Steinhauser, Martin O.; Schindler, Tanja

2017-01-01

We report on the results of particle-based, coarse-grained molecular dynamics simulations of amphiphilic lipid molecules in aqueous environment where the membrane structures at equilibrium are subsequently exposed to strong shock waves, and their damage is analyzed. The lipid molecules self-assemble from unbiased random initial configurations to form stable bilayer membranes, including closed vesicles. During self-assembly of lipid molecules, we observe several stages of clustering, starting with many small clusters of lipids, gradually merging together to finally form one single bilayer membrane. We find that the clustering of lipids sensitively depends on the hydrophobic interaction h_c of the lipid tails in our model and on temperature T of the system. The self-assembled bilayer membranes are quantitatively analyzed at equilibrium with respect to their degree of order and their local structure. We also show that—by analyzing the membrane fluctuations and using a linearized theory— we obtain area compression moduli K_A and bending stiffnesses κ _B for our bilayer membranes which are within the experimental range of in vivo and in vitro measurements of biological membranes. We also discuss the density profile and the pair correlation function of our model membranes at equilibrium which has not been done in previous studies of particle-based membrane models. Furthermore, we present a detailed phase diagram of our lipid model that exhibits a sol-gel transition between quasi-solid and fluid domains, and domains where no self-assembly of lipids occurs. In addition, we present in the phase diagram the conditions for temperature T and hydrophobicity h_c of the lipid tails of our model to form closed vesicles. The stable bilayer membranes obtained at equilibrium are then subjected to strong shock waves in a shock tube setup, and we investigate the damage in the membranes due to their interaction with shock waves. Here, we find a transition from self-repairing membranes (reducing their damage after impact) and permanent (irreversible) damage, depending on the shock front speed. The here presented idea of using coarse-grained (CG) particle models for soft matter systems in combination with the investigation of shock-wave effects in these systems is a quite new approach.
Rational synthesis of low-polydispersity block copolymer vesicles in concentrated solution via polymerization-induced self-assembly.

PubMed

Gonzato, Carlo; Semsarilar, Mona; Jones, Elizabeth R; Li, Feng; Krooshof, Gerard J P; Wyman, Paul; Mykhaylyk, Oleksandr O; Tuinier, Remco; Armes, Steven P

2014-08-06

Block copolymer self-assembly is normally conducted via post-polymerization processing at high dilution. In the case of block copolymer vesicles (or "polymersomes"), this approach normally leads to relatively broad size distributions, which is problematic for many potential applications. Herein we report the rational synthesis of low-polydispersity diblock copolymer vesicles in concentrated solution via polymerization-induced self-assembly using reversible addition-fragmentation chain transfer (RAFT) polymerization of benzyl methacrylate. Our strategy utilizes a binary mixture of a relatively long and a relatively short poly(methacrylic acid) stabilizer block, which become preferentially expressed at the outer and inner poly(benzyl methacrylate) membrane surface, respectively. Dynamic light scattering was utilized to construct phase diagrams to identify suitable conditions for the synthesis of relatively small, low-polydispersity vesicles. Small-angle X-ray scattering (SAXS) was used to verify that this binary mixture approach produced vesicles with significantly narrower size distributions compared to conventional vesicles prepared using a single (short) stabilizer block. Calculations performed using self-consistent mean field theory (SCMFT) account for the preferred self-assembled structures of the block copolymer binary mixtures and are in reasonable agreement with experiment. Finally, both SAXS and SCMFT indicate a significant degree of solvent plasticization for the membrane-forming poly(benzyl methacrylate) chains.
Isomeric effects on the self-assembly of a plausible prebiotic nucleoside analogue: A theoretical study

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

Vallejo, Emmanuel; Fuentes-Cabrera, Miguel; Sumpter, Bobby G.

For this study, the self-assembly properties of N(9)-(2,3-dihydroxypropyl adenine) (DHPA), a plausible prebiotic nucleoside analogue of adenosine, were investigated using density functional theory. Two different isomers were considered, and it is found that while both isomers can form a variety of structures, including chains, one of them is also able to form cages and helixes. When these results were put in the context of substrate supported molecular self-assembly, it is concluded that gas-phase self-assembly studies that consider isomer identity and composition not only can aid interpreting the experimental results, but also reveal structures that might be overlooked otherwise. In particular,more » this study suggest that a double-helical structure made of DHPA molecules which could have implications in prebiotic chemistry and nanotechnology, is stable even at room temperature. For example electrical properties (energy gap of 4.52eV) and a giant permanent electrical dipole moment (49.22 Debye) were found in our larger double-helical structure (3.7 nm) formed by 14 DHPA molecules. Lastly, the former properties could be convenient for construction of organic dielectric-based devices.« less
Isomeric effects on the self-assembly of a plausible prebiotic nucleoside analogue: A theoretical study

DOE PAGES

Vallejo, Emmanuel; Fuentes-Cabrera, Miguel; Sumpter, Bobby G.; ...

2016-10-22

For this study, the self-assembly properties of N(9)-(2,3-dihydroxypropyl adenine) (DHPA), a plausible prebiotic nucleoside analogue of adenosine, were investigated using density functional theory. Two different isomers were considered, and it is found that while both isomers can form a variety of structures, including chains, one of them is also able to form cages and helixes. When these results were put in the context of substrate supported molecular self-assembly, it is concluded that gas-phase self-assembly studies that consider isomer identity and composition not only can aid interpreting the experimental results, but also reveal structures that might be overlooked otherwise. In particular,more » this study suggest that a double-helical structure made of DHPA molecules which could have implications in prebiotic chemistry and nanotechnology, is stable even at room temperature. For example electrical properties (energy gap of 4.52eV) and a giant permanent electrical dipole moment (49.22 Debye) were found in our larger double-helical structure (3.7 nm) formed by 14 DHPA molecules. Lastly, the former properties could be convenient for construction of organic dielectric-based devices.« less
Small Angle Neutron Scattering (SANS) Studies on the Structural Evolution of Pyromellitamide Self-assembled Gels

DOE PAGES

Scott, Jamieson; Tong, Katie; William, Hamilton; ...

2014-10-31

The kinetics of aggregation of two pyromellitamide gelators; tetrabutyl- (C4) and tetrahexylpyromellitamide (C6), in deuterated cyclohexane has been investigated by small angle neutron scattering (SANS) for up to six days. The purpose of this study was to improve our understanding of how self-assembled gels are formed. Short-term (< 3 hour) time scales revealed multiple phases with the data for the tetrabutylpyromellitamide C4 indicating one dimensional stacking and aggregation corresponding to a multi-fiber braided cluster arrangement that is about 35 Å in diameter. The corresponding tetrahexylpyromellitamide C6 data suggests that the C6 also forms one-dimensional stacks but that these aggregate tomore » a thicker multi-fiber braided cluster that have a diameter of 61.8 Å. Over a longer period of time, the radius, persistence length and contour length all continue to increase in 6 days after cooling. This data suggests that structural changes in self-assembled gels occur over a period exceeding several days and that fairly subtle changes in the structure (e.g. tail-length) can influence the packing of molecules in self-assembled gels on the single-to-few fiber bundle stage.« less
Small angle neutron scattering (SANS) studies on the structural evolution of pyromellitamide self-assembled gels.

PubMed

Jamieson, Scott A; Tong, Katie W K; Hamilton, William A; He, Lilin; James, Michael; Thordarson, Pall

2014-11-25

The kinetics of aggregation of two pyromellitamide gelators, tetrabutyl- (C4) and tetrahexyl-pyromellitamide (C6), in deuterated cyclohexane has been investigated by small angle neutron scattering (SANS) for up to 6 days. The purpose of this study was to improve our understanding of how self-assembled gels are formed. Short-term (< 3 h) time scales revealed multiple phases with the data for the tetrabutylpyromellitamide C4, indicating one-dimensional stacking and aggregation corresponding to a multifiber braided cluster arrangement that is about 35 Å in diameter. The corresponding tetrahexylpyromellitamide C6 data suggest that the C6 also forms one-dimensional stacks but that these aggregate to a thicker multifiber braided cluster that has a diameter of about 62 Å. Over a longer period of time, the radius, persistence length, and contour length all continue to increase in 6 days after cooling. These data suggest that structural changes in self-assembled gels occur over a period exceeding several days and that fairly subtle changes in the structure (e.g., tail-length) can influence the packing of molecules in self-assembled gels on the single-to-few fiber bundle stage.
Small Angle Neutron Scattering (SANS) Studies on the Structural Evolution of Pyromellitamide Self-assembled Gels

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

Scott, Jamieson; Tong, Katie; William, Hamilton

The kinetics of aggregation of two pyromellitamide gelators; tetrabutyl- (C4) and tetrahexylpyromellitamide (C6), in deuterated cyclohexane has been investigated by small angle neutron scattering (SANS) for up to six days. The purpose of this study was to improve our understanding of how self-assembled gels are formed. Short-term (< 3 hour) time scales revealed multiple phases with the data for the tetrabutylpyromellitamide C4 indicating one dimensional stacking and aggregation corresponding to a multi-fiber braided cluster arrangement that is about 35 Å in diameter. The corresponding tetrahexylpyromellitamide C6 data suggests that the C6 also forms one-dimensional stacks but that these aggregate tomore » a thicker multi-fiber braided cluster that have a diameter of 61.8 Å. Over a longer period of time, the radius, persistence length and contour length all continue to increase in 6 days after cooling. This data suggests that structural changes in self-assembled gels occur over a period exceeding several days and that fairly subtle changes in the structure (e.g. tail-length) can influence the packing of molecules in self-assembled gels on the single-to-few fiber bundle stage.« less
Fatigue crack propagation in self-assembling nanocomposites

NASA Astrophysics Data System (ADS)

Klingler, Andreas; Wetzel, Bernd

2016-05-01

Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite. To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.
Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides. Polypeptide vesicles by conformation-specific assembly. Ordered chiral macroporous hybrid silica-polypeptide composites

NASA Astrophysics Data System (ADS)

Bellomo, Enrico Giuseppe

2005-07-01

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides . The aqueous, lyotropic liquid-crystalline phase behavior of an alpha helical polypeptide, has been studied using optical microscopy and X-ray scattering. Solutions of optically pure polypeptide were found to form cholesteric liquid crystals at volume fractions that decreased with increasing average chain length. At very high volume fractions, the formation of a hexagonal mesophase was observed. The pitch of the cholesteric phase could be varied by a mixture of enantiomeric samples, where the pitch increased as the mixture approached equimolar. The cholesteric phases could be untwisted, using either magnetic field or shear flow, into nematic phases, which relaxed into cholesterics upon removal of field or shear. We have found that the phase diagram of this polypeptide in aqueous solution parallels that of poly(gamma-benzyl glutamate) in organic solvents, thus providing a useful system for liquid-crystal applications requiring water as solvent. Polypeptide vesicles by conformation-specific assembly. We have found that block copolymers composed of polypeptide segments provide significant advantages in controlling both the function and supramolecular structure of bioinspired self-assemblies. Incorporation of the stable chain conformations found in proteins into block copolymers was found to provide an additional element of control, beyond amphiphilicity and composition that defines self-assembled architecture. The abundance of functionality present in amino acids, and the ease by which they can be incorporated into these materials, also provides a powerful mechanism to impart block copolypeptides with function. This combination of structure and function work synergistically to enable significant advantages in the preparation of therapeutic agents as well as provide insight into design of self-assemblies beginning to approach the complexity of natural structures such as virus capsids. Ordered chiral macroporous hybrid silica-polypeptide composites. The mineralization of organic templates has been investigated as an effective way to control the size and structure of inorganic frameworks. Hybrid structures incorporating polypeptide with silica have been prepared and characterized using X-ray scattering, TGA, SEM and TEM. The results support the interaction between silica and polymer to form ordered chiral macroporous structures that can be easily controlled by polymer molecular weight and volume fraction.
Enrichment of dynamic chromosomal crosslinks drive phase separation of the nucleolus

PubMed Central

Hult, Caitlin; Adalsteinsson, David; Vasquez, Paula A.; Lawrimore, Josh; Bennett, Maggie; York, Alyssa; Cook, Diana; Yeh, Elaine; Forest, Mark Gregory

2017-01-01

Abstract Regions of highly repetitive DNA, such as those found in the nucleolus, show a self-organization that is marked by spatial segregation and frequent self-interaction. The mechanisms that underlie the sequestration of these sub-domains are largely unknown. Using a stochastic, bead-spring representation of chromatin in budding yeast, we find enrichment of protein-mediated, dynamic chromosomal cross-links recapitulates the segregation, morphology and self-interaction of the nucleolus. Rates and enrichment of dynamic crosslinking have profound consequences on domain morphology. Our model demonstrates the nucleolus is phase separated from other chromatin in the nucleus and predicts that multiple rDNA loci will form a single nucleolus independent of their location within the genome. Fluorescent labeling of budding yeast nucleoli with CDC14-GFP revealed that a split rDNA locus indeed forms a single nucleolus. We propose that nuclear sub-domains, such as the nucleolus, result from phase separations within the nucleus, which are driven by the enrichment of protein-mediated, dynamic chromosomal crosslinks. PMID:28977453
Structural Diversity of Arthropod Biophotonic Nanostructures Spans Amphiphilic Phase-Space

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

Saranathan, Vinod Kumar; Seago, Ainsley E.; Sandy, Alec

2015-05-04

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, precise structural knowledge of many biophotonic nanostructures and the mechanisms controlling their development remain tentative, when such knowledge can open novel biomimetic routes to facilely self-assemble tunable, multifunctional materials. Here, we use synchrotron small-angle X-ray scattering and electron microscopy to characterize the photonic nanostructure of 140 integumentary scales and setae from ~127 species of terrestrial arthropods in 85 genera from 5 orders. We report a rich nanostructural diversity, including triply periodicmore » bicontinuous networks, close-packed spheres, inverse columnar, perforated lamellar, and disordered spongelike 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 lipid-bilayer membranes to develop biophotonic nanostructures that span the phase-space of amphiphilic morphologies, but at optical length scales.« less
Lasing in a three-dimensional photonic crystal of the liquid crystal blue phase II.

PubMed

Cao, Wenyi; Muñoz, Antonio; Palffy-Muhoray, Peter; Taheri, Bahman

2002-10-01

Photonic-bandgap materials, with periodicity in one, two or three dimensions, offer control of spontaneous emission and photon localization. Low-threshold lasing has been demonstrated in two-dimensional photonic-bandgap materials, both with distributed feedback and defect modes. Liquid crystals with chiral constituents exhibit mesophases with modulated ground states. Helical cholesterics are one-dimensional, whereas blue phases are three-dimensional self-assembled photonic-bandgap structures. Although mirrorless lasing was predicted and observed in one-dimensional helical cholesteric materials and chiral ferroelectric smectic materials, it is of great interest to probe light confinement in three dimensions. Here, we report the first observations of lasing in three-dimensional photonic crystals, in the cholesteric blue phase II. Our results show that distributed feedback is realized in three dimensions, resulting in almost diffraction-limited lasing with significantly lower thresholds than in one dimension. In addition to mirrorless lasing, these self-assembled soft photonic-bandgap materials may also be useful for waveguiding, switching and sensing applications.

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

Hsu, Chih-Hao; Yue, Kan; Wang, Jing

Controlling self-assembled nanostructures in thin films allows the bottom-up fabrication of ordered nanoscale patterns. Here we report the unique thickness-dependent phase behavior in thin films of a bolaform-like giant surfactant, which consists of butyl- and hydroxyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS and DPOSS) cages telechelically located at the chain ends of a polystyrene (PS) chain with 28 repeating monomers on average. In the bulk, BPOSS-PS28-DPOSS forms a double gyroid (DG) phase. Both grazing incidence small angle X-ray scattering and transmission electron microscopy techniques are combined to elucidate the thin film structures. Interestingly, films with thicknesses thinner than 200 nm exhibit anmore » irreversible phase transition from hexagonal perforated layer (HPL) to compressed hexagonally packed cylinders (c-HEX) at 130 °C, while films with thickness larger than 200 nm show an irreversible transition from HPL to DG at 200 °C. The thickness-controlled transition pathway suggests possibilities to obtain diverse patterns via thin film self-assembly.« less
The Testing Phase for the Small Unit Decision Making (SUDM) Assessment Battery

DTIC Science & Technology

2014-07-28

on findings from the testing phase, several changes are recommended for the battery. First, it is recommended that self -report measures be separated...of a decision-making assessment battery. The five cognitive competencies are sensemaking, problem solving, adaptability, metacognition , and...flexibility, ambiguity tolerance, resilience, self -regulation, and self - awareness. We added the overarching construct of decision making and developed
Size separation of analytes using monomeric surfactants

DOEpatents

Yeung, Edward S.; Wei, Wei

2005-04-12

A sieving medium for use in the separation of analytes in a sample containing at least one such analyte comprises a monomeric non-ionic surfactant of the of the general formula, B-A, wherein A is a hydrophilic moiety and B is a hydrophobic moiety, present in a solvent at a concentration forming a self-assembled micelle configuration under selected conditions and having an aggregation number providing an equivalent weight capable of effecting the size separation of the sample solution so as to resolve a target analyte(s) in a solution containing the same, the size separation taking place in a chromatography or electrophoresis separation system.
Mixed-Halide Perovskites with Stabilized Bandgaps.

PubMed

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

2017-11-08

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (V OC ) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned V OC from 1.05 to 1.45 V in solar cells.
Thermoelectric properties of SrTiO3 nano-particles dispersed indium selenide bulk composites

NASA Astrophysics Data System (ADS)

Lee, Min Ho; Rhyee, Jong-Soo; Vaseem, Mohammad; Hahn, Yoon-Bong; Park, Su-Dong; Jin Kim, Hee; Kim, Sung-Jin; Lee, Hyeung Jin; Kim, Chilsung

2013-06-01

We investigated the thermoelectric properties of the InSe, InSe/In4Se3 composite, and SrTiO3 (STO) nano-particles dispersed InSe/In4Se3 bulk composites. The electrical conductivity of the InSe/In4Se3 composite with self-assembled phase separation is significantly increased compared with those of InSe and In4Se3-δ implying the enhancement of surface conductivity between grain boundaries. The thermal conductivity of InSe/In4Se3 composite is decreased compared to those of InSe. When the STO nano-particle dispersion was employed in the InSe/In4Se3 composite, a coherent interface was observed between nano-particle precipitates and the InSe bulk matrix with a reduction of the thermal conductivity.
Deciphering the kinetic mechanism of spontaneous self-assembly of icosahedral capsids.

PubMed

Nguyen, Hung D; Reddy, Vijay S; Brooks, Charles L

2007-02-01

Self-assembly of viral proteins into icosahedral capsids is an interesting yet poorly understood phenomenon of which elucidation may aid the exploration of beneficial applications of capsids in materials science and medicine. Using molecular dynamics simulations of coarse-grained models for capsid proteins, we show that the competition between the formation of full capsids and nonidealized structures is strongly dependent upon the protein concentration and temperature, occurring kinetically as a cascade of elementary reactions in which free monomers are added to the growing oligomers on a downhill free-energy landscape. However, the insertion of the final subunits is the rate-limiting, energetically unfavorable step in viral capsid assembly. A phase diagram has been constructed to show the regions where capsids or nonidealized structures are stable at each concentration and temperature. We anticipate that our findings will provide guidance in identifying suitable conditions required for in vitro viral capsid assembly experiments.
Phase behavior of casein micelles/exocellular polysaccharide mixtures: Experiment and theory

NASA Astrophysics Data System (ADS)

Tuinier, R.; de Kruif, C. G.

1999-05-01

Dispersions of casein micelles and an exocellular polysaccharide (EPS), obtained from Lactococcus lactis subsp. cremoris NIZO B40 EPS, show a phase separation. The phase separation is of the colloidal gas-liquid type. We have determined a phase diagram that describes the separation of skim milk with EPS into a casein-micelle rich phase and an EPS rich phase. We compare the phase diagram with those calculated from theories developed by Vrij, and by Lekkerkerker and co-workers, showing that the experimental phase boundary can be predicted quite well. From dynamic light scattering measurements of the self-diffusion of the casein micelles in the presence of EPS the spinodal could be located and it corresponds with the experimental phase boundary.
Hierarchical self-assembly of hexagonal single-crystal nanosheets into 3D layered superlattices with high conductivity

NASA Astrophysics Data System (ADS)

Tao, Yulun; Shen, Yuhua; Yang, Liangbao; Han, Bin; Huang, Fangzhi; Li, Shikuo; Chu, Zhuwang; Xie, Anjian

2012-05-01

While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (Mw/Mn = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm-1, which is even higher than that of the highest previously reported value (16 S cm-1). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost.While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (Mw/Mn = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm-1, which is even higher than that of the highest previously reported value (16 S cm-1). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost. Electronic supplementary information (ESI) available: SEM, and TEM images. See DOI: 10.1039/c2nr30743j
RNA buffers the phase separation behavior of prion-like RNA binding proteins.

PubMed

Maharana, Shovamayee; Wang, Jie; Papadopoulos, Dimitrios K; Richter, Doris; Pozniakovsky, Andrey; Poser, Ina; Bickle, Marc; Rizk, Sandra; Guillén-Boixet, Jordina; Franzmann, Titus M; Jahnel, Marcus; Marrone, Lara; Chang, Young-Tae; Sterneckert, Jared; Tomancak, Pavel; Hyman, Anthony A; Alberti, Simon

2018-05-25

Prion-like RNA binding proteins (RBPs) such as TDP43 and FUS are largely soluble in the nucleus but form solid pathological aggregates when mislocalized to the cytoplasm. What keeps these proteins soluble in the nucleus and promotes aggregation in the cytoplasm is still unknown. We report here that RNA critically regulates the phase behavior of prion-like RBPs. Low RNA/protein ratios promote phase separation into liquid droplets, whereas high ratios prevent droplet formation in vitro. Reduction of nuclear RNA levels or genetic ablation of RNA binding causes excessive phase separation and the formation of cytotoxic solid-like assemblies in cells. We propose that the nucleus is a buffered system in which high RNA concentrations keep RBPs soluble. Changes in RNA levels or RNA binding abilities of RBPs cause aberrant phase transitions. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.
Functional group selective STM Imaging in self-assembled monolayers: Benzeneselenol on Au(111)

NASA Astrophysics Data System (ADS)

Azzam, Waleed; Zharnikov, Michael; Rohwerde, Michael; Bashir, Asif

2018-01-01

Benzeneselenol (PSe) self-assembled monolayers (SAMs) formed on Au(111) substrate by the immersion procedure with an immersion time of 24 h and 4 weeks were studied by high-resolution scanning tunneling microscopy (STM). The short molecular rows, which have been previously attributed to irregular translational domains, were found to be regularly repeated within a single domain in the SAMs fabricated upon the immersion for 4 weeks, forming adlayer structure with a very large unit cell. This structure could be assigned as a (27 × 5) superlattice (α phase) containing 36 molecules in the oblique unit cell. This phase coexisted with a different phase having a commensurate (8√{ 3 } × 4) superstructure (β phase) containing 28 protrusions per rectangular unit cell. Analysis of the STM images suggested that each PSe molecule in the β phase was imaged not as one but as a pair of protrusions, which were attributed to the benzene ring and the selenium headgroup of the PSe molecule. At the given molecular length, the spacing between the protrusions defined the molecular tilt, allowing us to derive the orientation of the SAM constituents directly from the STM image.
Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles

DOE PAGES

Sun, Jing; Jiang, Xi; Lund, Reidar; ...

2016-03-28

The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here,more » we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.« less
Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles

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

Sun, Jing; Jiang, Xi; Lund, Reidar

The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here,more » we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.« less
The assembly and properties of protobiological structures - The beginnings of cellular peptide synthesis

NASA Technical Reports Server (NTRS)

Fox, S. W.; Nakashima, T.

1980-01-01

New data indicate that lysine-rich proteinoids have the ability to catalyze the synthesis of peptide bonds from a variety of amino acids and ATP. This capacity is evident in aqueous solution, in suspension of phase-separated complexes of lysine-rich proteinoid with acidic proteinoids, and in suspension of phase-separated particles composed of lysine-rich proteinoids with polynucleotides. Since the proteinoid complexes can contain other catalytic activities, including ability to catalyze internucleotide bond formation, it is inferred that the first protocells on earth already had a number of biological types of activity.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Misichronis, Konstantinos; Chen, Jihua; Imel, Adam

A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined in this paper by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (T ODT), for the first time formore » PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χ eff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. Finally, these copolymers exhibit well-ordered structures even at high temperatures (~260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.« less
Solvent mediated hybrid 2D materials: black phosphorus - graphene heterostructured building blocks assembled for sodium ion batteries.

PubMed

Li, Mengya; Muralidharan, Nitin; Moyer, Kathleen; Pint, Cary L

2018-06-07

Here we demonstrate the broad capability to exploit interactions at different length scales in 2D materials to prepare macroscopic functional materials containing hybrid black phosphorus/graphene (BP/G) heterostructured building blocks. First, heterostructured 2D building blocks are self-assembled during co-exfoliation in the solution phase based on electrostatic attraction of different 2D materials. Second, electrophoretic deposition is used as a tool to assemble these building blocks into macroscopic films containing these self-assembled 2D heterostructures. Characterization of deposits formed using this technique elucidates the presence of stacked and sandwiched 2D heterostructures, and zeta potential measurements confirm the mechanistic interactions driving this assembly. Building on the exceptional sodium alloying capacity of BP, these materials were demonstrated as superior binder-free and additive-free anodes for sodium batteries with specific discharge capacity of 2365 mA h gP-1 and long stable cycling duration. This study demonstrates how controllable co-processing of 2D materials can enable material control for stacking and building block assembly relevant to broad future applications of 2D materials.
One-step assembly of Fe(III)-CMC chelate hydrogel onto nanoneedle-like CuO@Cu membrane with superhydrophilicity for oil-water separation

NASA Astrophysics Data System (ADS)

Dai, Jiangdong; Chang, Zhongshuai; Xie, Atian; Zhang, Ruilong; Tian, Sujun; Ge, Wenna; Yan, Yongsheng; Li, Chunxiang; Xu, Wei; Shao, Rong

2018-05-01

The research of superhydrophilic interface is developing rapidly, but the preparations of superhydrophilic surfaces through simple methods are still challenging. Herein, we reported a facile, rapid and environmentally-friendly approach for preparing a novel superhydrophilic and underwater superoleophobic membrane via the thermal oxidation of Cu mesh and one-step coordinated assembly of Fe(III)-CMC chelate hydrogel. Superhydrophilicity was attributed to the hydrophilicity of Fe(III)-CMC chelate hydrogel and nanoneedle-like rough structure of CuO@Cu membrane. The membrane was used to separate a variety of oil/water mixtures and exhibited excellent separation performance. Moreover, the membrane exhibited the excellent durability and superior stability against corrosion conditions. We envision that the Fe(III)-CMC@CuO@Cu membrane with good underwater superoleophobicity could provide a candidate not only for oil/water separation but also many other potential applications such as underwater oil manipulation, self-clean, and bio-adhesion control.
The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations.

PubMed

Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata

2018-01-01

Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc) 2 , depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na + cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na + cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. Graphical Abstract ᅟ.
The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations

NASA Astrophysics Data System (ADS)

Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata

2018-01-01

Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc)2, depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na+ cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na+ cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. [Figure not available: see fulltext.
Highly luminescent colloidal nanoplates of perovskite cesium lead halide and their oriented assemblies

DOE PAGES

Bekenstein, Yehonadav; Koscher, Brent A.; Eaton, Samuel W.; ...

2015-12-15

Anisotropic colloidal quasi-two-dimensional nanoplates (NPLs) hold great promise as functional materials due to their combination of low dimensional optoelectronic properties and versatility through colloidal synthesis. Recently, lead-halide perovskites have emerged as important optoelectronic materials with excellent efficiencies in photovoltaic and light-emitting applications. Here we report the synthesis of quantum confined all inorganic cesium lead halide nanoplates in the perovskite crystal structure that are also highly luminescent (PLQY 84%). The controllable self-assembly of nanoplates either into stacked columnar phases or crystallographic-oriented thin-sheet structures is demonstrated. Furthermore, the broad accessible emission range, high native quantum yields, and ease of self-assembly make perovskitemore » NPLs an ideal platform for fundamental optoelectronic studies and the investigation of future devices.« less
Hierarchical self-assembly of hexagonal single-crystal nanosheets into 3D layered superlattices with high conductivity.

PubMed

Tao, Yulun; Shen, Yuhua; Yang, Liangbao; Han, Bin; Huang, Fangzhi; Li, Shikuo; Chu, Zhuwang; Xie, Anjian

2012-06-21

While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (M(w)/M(n) = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm(-1), which is even higher than that of the highest previously reported value (16 S cm(-1)). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost.

Glycerol derivatives of cutin and suberin monomers: synthesis and self-assembly.

PubMed

Douliez, Jean-Paul; Barrault, Joël; Jerome, François; Heredia, Antonio; Navailles, Laurence; Nallet, Frédéric

2005-01-01

Glycerol derivatives of cutin and suberin monomers were synthesized by acid catalysis. Their dispersion in an aqueous solution was examined by phase contrast microscopy, neutron scattering, and solid state NMR. It is shown that the phase behavior strongly depends on the nature of the derivatives forming either lumps of aggregated membranes or well dispersed membranes.
Analysis of a spacecraft instrument ball bearing assembly lubricated by a perfluoroalkylether

NASA Technical Reports Server (NTRS)

Morales, W.; Jones, W. R., Jr.; Buckley, D. H.

1986-01-01

An analysis of a spacecraft instrument ball bearing assembly, subjected to a scanning life test, was performed to determine the possible case of rotational problems involving these units aboard several satellites. The analysis indicated an ineffective transfer of a fluorinated liquid lubricant from a phenolic retainer to the bearing balls. Part of the analysis led to a novel HPLC separation method employing a fluorinated mobile phase in conjunction with silica based size exclusion columns.
Controlled growth of hexagonal gold nanostructures during thermally induced self-assembling on Ge(001) surface

PubMed Central

Jany, B. R.; Gauquelin, N.; Willhammar, T.; Nikiel, M.; van den Bos, K. H. W.; Janas, A.; Szajna, K.; Verbeeck, J.; Van Aert, S.; Van Tendeloo, G.; Krok, F.

2017-01-01

Nano-sized gold has become an important material in various fields of science and technology, where control over the size and crystallography is desired to tailor the functionality. Gold crystallizes in the face-centered cubic (fcc) phase, and its hexagonal closed packed (hcp) structure is a very unusual and rare phase. Stable Au hcp phase has been reported to form in nanoparticles at the tips of some Ge nanowires. It has also recently been synthesized in the form of thin graphene-supported sheets which are unstable under electron beam irradiation. Here, we show that stable hcp Au 3D nanostructures with well-defined crystallographic orientation and size can be systematically created in a process of thermally induced self-assembly of thin Au layer on Ge(001) monocrystal. The Au hcp crystallite is present in each Au nanostructure and has been characterized by different electron microscopy techniques. We report that a careful heat treatment above the eutectic melting temperature and a controlled cooling is required to form the hcp phase of Au on a Ge single crystal. This new method gives scientific prospects to obtain stable Au hcp phase for future applications in a rather simple manner as well as redefine the phase diagram of Gold with Germanium. PMID:28195226
Controlled growth of hexagonal gold nanostructures during thermally induced self-assembling on Ge(001) surface

NASA Astrophysics Data System (ADS)

Jany, B. R.; Gauquelin, N.; Willhammar, T.; Nikiel, M.; van den Bos, K. H. W.; Janas, A.; Szajna, K.; Verbeeck, J.; van Aert, S.; van Tendeloo, G.; Krok, F.

2017-02-01

Nano-sized gold has become an important material in various fields of science and technology, where control over the size and crystallography is desired to tailor the functionality. Gold crystallizes in the face-centered cubic (fcc) phase, and its hexagonal closed packed (hcp) structure is a very unusual and rare phase. Stable Au hcp phase has been reported to form in nanoparticles at the tips of some Ge nanowires. It has also recently been synthesized in the form of thin graphene-supported sheets which are unstable under electron beam irradiation. Here, we show that stable hcp Au 3D nanostructures with well-defined crystallographic orientation and size can be systematically created in a process of thermally induced self-assembly of thin Au layer on Ge(001) monocrystal. The Au hcp crystallite is present in each Au nanostructure and has been characterized by different electron microscopy techniques. We report that a careful heat treatment above the eutectic melting temperature and a controlled cooling is required to form the hcp phase of Au on a Ge single crystal. This new method gives scientific prospects to obtain stable Au hcp phase for future applications in a rather simple manner as well as redefine the phase diagram of Gold with Germanium.
Transport of organic anions and cations in murine embryonic kidney development and in serially-reaggregated engineered kidneys

PubMed Central

Lawrence, Melanie L.; Chang, C-Hong; Davies, Jamie A.

2015-01-01

Recent advances in renal tissue engineering have shown that dissociated, early renogenic tissue from the developing embryo can self-assemble into morphologically accurate kidney-like organs arranged around a central collecting duct tree. In order for such self-assembled kidneys to be useful therapeutically or as models for drug screening, it is necessary to demonstrate that they are functional. One of the main functional characteristics of mature kidneys is transport of organic anions and cations into and out of the proximal tubule. Here, we show that the transport function of embryonic kidneys allowed to develop in culture follows a developmental time-course that is comparable to embryonic kidney development in vivo. We also demonstrate that serially-reaggregated engineered kidneys can transport organic anions and cations through specific uptake and efflux channels. These results support the physiological relevance of kidneys grown in culture, a commonly used model for kidney development and research, and suggest that serially-reaggregated kidneys self-assembled from separated cells have some functional characteristics of intact kidneys. PMID:25766625
Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

NASA Astrophysics Data System (ADS)

Boott, Charlotte E.; Gwyther, Jessica; Harniman, Robert L.; Hayward, Dominic W.; Manners, Ian

2017-08-01

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles—which are promising for many applications—are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach—starting from monomers—that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.
Closed compact Taylor's droplets in a phase-separated lamellar-sponge mixture under shear flow

NASA Astrophysics Data System (ADS)

Courbin, L.; Cristobal, G.; Rouch, J.; Panizza, P.

2001-09-01

We have studied by optical microscopy, small-angle light scattering, and rheology, the behavior under shear flow of a phase-separated lamellar-sponge (Lα - L3) ternary mixture. We observe in the Lα-rich region (ΦLα > 80%) the existence of a Newtonian assembly made of closed compact monodisperse lamellar droplets immersed in the sponge phase. Contrary to the classical onion glassy texture obtained upon shearing Lα phases, the droplet size scales herein as dot gamma-1, the inverse of the shear rate. This result is in good agreement with Taylor's picture. Above a critical shear rate, dot gammac, the droplets organize to form a single colloidal crystal whose lattice size varies as dot gamma-1/3. To the memory of Tess Melissa P.
Carrier-separating demodulation of phase shifting self-mixing interferometry

NASA Astrophysics Data System (ADS)

Tao, Yufeng; Wang, Ming; Xia, Wei

2017-03-01

A carrier separating method associated with noise-elimination had been introduced into a sinusoidal phase-shifting self-mixing interferometer. The conventional sinusoidal phase shifting self-mixing interferometry was developed into a more competitive instrument with high computing efficiency and nanometer accuracy of λ / 100 in dynamical vibration measurement. The high slew rate electro-optic modulator induced a sinusoidal phase carrier with ultralow insertion loss in this paper. In order to extract phase-shift quickly and precisely, this paper employed the carrier-separating to directly generate quadrature signals without complicated frequency domain transforms. Moreover, most noises were evaluated and suppressed by a noise-elimination technology synthesizing empirical mode decomposition with wavelet transform. The overall laser system was described and inherent advantages such as high computational efficiency and decreased nonlinear errors of the established system were demonstrated. The experiment implemented on a high precision PZT (positioning accuracy was better than 1 nm) and compared with laser Doppler velocity meter. The good agreement of two instruments shown that the short-term resolution had improved from 10 nm to 1.5 nm in dynamic vibration measurement with reduced time expense. This was useful in precision measurement to improve the SMI with same sampling rate. The proposed signal processing was performed in pure time-domain requiring no preprocessing electronic circuits.
A novel octadecylsilane functionalized graphene oxide/silica composite stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Wang, Shuai; Liu, Shujuan; Liu, Xia; Jiang, Shengxiang

2012-08-01

An octadecylsilane functionalized graphene oxide/silica stationary phase was fabricated by assembling graphene oxide onto the silica particles through an amide bond and subsequent immobilization of octadecylsilane. The chromatographic properties of the stationary phase were investigated by reversed-phase chromatography with alkylbenzenes, polycyclic aromatic hydrocarbons, amines, and phenolic compounds as the analytes. All the compounds achieved good separation on the column. The comparison between a C18 commercial column and the new stationary phase indicated that the existence of π-electron system of graphene oxide allows π-π interaction between analyte and octadecylsilane functionalized graphene oxide/silica stationary phase except for hydrophobic interaction, while only hydrophobic interaction presented between analyte and C18 commercial column. This suggests that some analytes can be better separated on the octadecylsilane functionalized graphene oxide/silica column. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Bio-Organic Nanotechnology: Using Proteins and Synthetic Polymers for Nanoscale Devices

NASA Technical Reports Server (NTRS)

Molnar, Linda K.; Xu, Ting; Trent, Jonathan D.; Russell, Thomas P.

2003-01-01

While the ability of proteins to self-assemble makes them powerful tools in nanotechnology, in biological systems protein-based structures ultimately depend on the context in which they form. We combine the self-assembling properties of synthetic diblock copolymers and proteins to construct intricately ordered, three-dimensional polymer protein structures with the ultimate goal of forming nano-scale devices. This hybrid approach takes advantage of the capabilities of organic polymer chemistry to build ordered structures and the capabilities of genetic engineering to create proteins that are selective for inorganic or organic substrates. Here, microphase-separated block copolymers coupled with genetically engineered heat shock proteins are used to produce nano-scale patterning that maximizes the potential for both increased structural complexity and integrity.
Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

PubMed

Zou, Shan; Hong, Rui; Emrick, Todd; Walker, Gilbert C

2007-02-13

Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.
Ultrafast frequency-selective optical switching based on thin self-assembled organic chromophoric films with a large second-order nonlinear response

NASA Astrophysics Data System (ADS)

Wang, Gang; Zhu, Peiwang; Marks, Tobin J.; Ketterson, J. B.

2002-09-01

Thin films consisting of self-assembled chromophoric superlattices exhibit very large second-order nonlinear responses [chi](2). Using such films, a "static" diffraction grating is created by the interference of two coherent infrared beams from a pulsed yttritium-aluminum-garnet laser. This grating is used to switch the second-harmonic and third-harmonic "signal" beams (generated from the fundamental "pump" beam or mixed within the chromophoric superlattice) into different channels (directions). Ultrafast switching response as a function of the time overlap of the pumping beams is demonstrated. It is suggested that such devices can be used to spatially and temporally separate signal trains consisting of pulses having different frequencies and arrival times.
Growth patterns of self-assembled InAs quantum dots near the two-dimensional to three-dimensional transition

NASA Astrophysics Data System (ADS)

Colocci, M.; Bogani, F.; Carraresi, L.; Mattolini, R.; Bosacchi, A.; Franchi, S.; Frigeri, P.; Rosa-Clot, M.; Taddei, S.

1997-06-01

Self-assembled InAs quantum dots have been grown by molecular beam epitaxy in such a way as to obtain a continuous variation of InAs coverages across the wafer. Structured photoluminescence spectra are observed after excitation of a large number of dots; deconvolution into Gaussian components yields narrow emission bands (full width at half-maximum 20-30 meV) separated in energy by an average spacing of 30-40 meV. We ascribe the individual bands of the photoluminescence spectra after low excitation to families of dots with similar shapes and with heights differing by one monolayer, as strongly supported by numerical calculations of the fundamental electronic transitions in quantum dot structures.
Controlling water evaporation through self-assembly

PubMed Central

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

2016-01-01

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

NASA Astrophysics Data System (ADS)

Oh, Dongyeop X.; Cha, Yun Jeong; Nguyen, Hoang-Linh; Je, Hwa Heon; Jho, Yong Seok; Hwang, Dong Soo; Yoon, Dong Ki

2016-03-01

Chitin is one of the most abundant biomaterials in nature, with 1010 tons produced annually as hierarchically organized nanofibril fillers to reinforce the exoskeletons of arthropods. This green and cheap biomaterial has attracted great attention due to its potential application to reinforce biomedical materials. Despite that, its practical use is limited since the extraction of chitin nanofibrils requires surface modification involving harsh chemical treatments, leading to difficulties in reproducing their natural prototypal hierarchical structure, i.e. chiral nematic phase. Here, we develop a chemical etching-free approach using calcium ions, called “natural way”, to disintegrate the chitin nanofibrils while keeping the essential moiety for the self-assembly, ultimately resulting in the reproduction of chitin’s natural chiral structure in a polymeric matrix. This chiral chitin nanostructure exceptionally toughens the composite. Our resultant chiral nematic phase of chitin materials can contribute to the understanding and use of the reinforcing strategy in nature.
Electron-beam patterned self-assembled monolayers as templates for Cu electrodeposition and lift-off.

PubMed

She, Zhe; Difalco, Andrea; Hähner, Georg; Buck, Manfred

2012-01-01

Self-assembled monolayers (SAMs) of 4'-methylbiphenyl-4-thiol (MBP0) adsorbed on polycrystalline gold substrates served as templates to control electrochemical deposition of Cu structures from acidic solution, and enabled the subsequent lift-off of the metal structures by attachment to epoxy glue. By exploiting the negative-resist behaviour of MBP0, the SAM was patterned by means of electron-beam lithography. For high deposition contrast a two-step procedure was employed involving a nucleation phase around -0.7 V versus Cu(2+)/Cu and a growth phase at around -0.35 V versus Cu(2+)/Cu. Structures with features down to 100 nm were deposited and transferred with high fidelity. By using substrates with different surface morphologies, AFM measurements revealed that the roughness of the substrate is a crucial factor but not the only one determining the roughness of the copper surface that is exposed after lift-off.
Controlling water evaporation through self-assembly.

PubMed

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

2016-09-13

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

NASA Astrophysics Data System (ADS)

Poonia, Monika; Agarwal, Hitesh; Manjuladevi, V.; Gupta, R. K.

2016-05-01

Detection of proteins and other biomolecules in liquid phase is the essence for the design of a biosensor. The sensitivity of a sensor can be enhanced by the appropriate functionalization of the sensing area so as to establish the molecular specific interaction. In the present work, we have studied the interaction of bovine serum albumin (BSA) protein with a chemically functionalized surface using a quartz crystal microbalance (QCM). The gold-coated quartz crystals (AT-cut/5 MHz) were functionalized by forming self-assembled monolayer (SAM) of 11-Mercaptoundecanoic acid (MUA). The adsorption characteristics of BSA onto SAM of MUA on quartz crystal are reported. BSA showed the highest affinity for SAM of MUA as compared to pure gold surface. The SAM of MUA provides carboxylated surface which enhances not only the adsorption of the BSA protein but also a very stable BSA-MUA complex in the liquid phase.
Measurements of the thickness compressibility of an n-octadecyltriethoxysilane monolayer self-assembled on mica.

PubMed

Kim, Sungsoo; Cho, Kilwon; Curry, Joan E

2005-08-30

The surface forces apparatus technique and the Johnson-Kendall-Roberts theory were used to study the elastic properties of an n-octadecyltriethoxysilane self-assembled monolayer (OTE-SAM) on both untreated and plasma-treated mica. Our aim was to measure the thickness compressibilities of OTE monolayers on untreated and plasma-treated mica and to estimate their surface densities and phase-states from the film compressibility. The compressibility moduli of OTE are (0.96 +/- 0.02) x 10(8) N/m(2) on untreated mica and (1.24 +/- 0.06) x 10(8) N/m(2) on plasma-treated mica. This work suggests that the OTE phase-state is pseudocrystalline. In addition, the results from the compressibility measurements in water vapor suggest that the OTE-SAM on both untreated and plasma-treated mica is not homogeneous but rather contains both crystalline polymerized OTE domains and somewhat hydrophilic gaseous regions.
Self-assembly of nematic liquid crystal elastomer filaments

NASA Astrophysics Data System (ADS)

Wei, Wei-Shao; Xia, Yu; Yang, Shu; Yodh, A. G.

In this work we investigate the self-assembly of nematic liquid crystal polymer (NLCP) filaments and their corresponding cross-linked elastomer structures. Specifically, by fine-tuning surfactant concentration, prepolymer chain length, and temperature within a background aqueous phase we can generate filaments composed of oligomerized LC monomers. Filaments with narrowly dispersed diameters ranging from one hundred nanometers to a few micrometers can be obtained. Using polarization optical microscopy, we show that the nematic LCs within the filaments have an escaped radial structure. After photo-cross-linking, nematic liquid crystal elastomer filaments are obtained with well-maintained directors and smooth surface structure. Since these materials are elastomers, the size and mechanical and optical response of the filaments can be ''tuned'' near the nematic to isotropic phase transition temperature. This work is supported by NSF DMR16-07378, PENN MRSEC Grant DMR11-20901, and NASA Grant NNX08AO0G.

Water outlet control mechanism for fuel cell system operation in variable gravity environments

NASA Technical Reports Server (NTRS)

Vasquez, Arturo (Inventor); McCurdy, Kerri L. (Inventor); Bradley, Karla F. (Inventor)

2007-01-01

A self-regulated water separator provides centrifugal separation of fuel cell product water from oxidant gas. The system uses the flow energy of the fuel cell's two-phase water and oxidant flow stream and a regulated ejector or other reactant circulation pump providing the two-phase fluid flow. The system further uses a means of controlling the water outlet flow rate away from the water separator that uses both the ejector's or reactant pump's supply pressure and a compressibility sensor to provide overall control of separated water flow either back to the separator or away from the separator.
H-Bonding Assisted Self-Assembly of Anionic and Neutral Ligand on Metal: A Comprehensive Strategy To Mimic Ditopic Ligands in Olefin Polymerization.

PubMed

Mote, Nilesh R; Patel, Ketan; Shinde, Dinesh R; Gaikwad, Shahaji R; Koshti, Vijay S; Gonnade, Rajesh G; Chikkali, Samir H

2017-10-16

Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC 6 H 4 NH(CO)NH 2 }{Ph 2 PC 6 H 4 NH(CO)NH 2 }PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC 6 H 4 NH(CO)NHPh}{Ph 2 PC 6 H 4 NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 °C.
Integrity of the Pericentriolar Material Is Essential for Maintaining Centriole Association during M Phase

PubMed Central

Rhee, Kunsoo

2015-01-01

A procentriole is assembled next to the mother centriole during S phase and remains associated until M phase. After functioning as a spindle pole during mitosis, the mother centriole and procentriole are separated at the end of mitosis. A close association of the centriole pair is regarded as an intrinsic block to the centriole reduplication. Therefore, deregulation of this process may cause a problem in the centriole number control, resulting in increased genomic instability. Despite its importance for faithful centriole duplication, the mechanism of centriole separation is not fully understood yet. Here, we report that centriole pairs are prematurely separated in cells whose cell cycle is arrested at M phase by STLC. Dispersal of the pericentriolar material (PCM) was accompanied. This phenomenon was independent of the separase activity but needed the PLK1 activity. Nocodazole effectively inhibited centriole scattering in STLC-treated cells, possibly by reducing the microtubule pulling force around centrosomes. Inhibition of PLK1 also reduced the premature separation of centrioles and the PCM dispersal as well. These results revealed the importance of PCM integrity in centriole association. Therefore, we propose that PCM disassembly is one of the driving forces for centriole separation during mitotic exit. PMID:26407333
System Regulates the Water Contents of Fuel-Cell Streams

NASA Technical Reports Server (NTRS)

Vasquez, Arturo; Lazaroff, Scott

2005-01-01

An assembly of devices provides for both humidification of the reactant gas streams of a fuel cell and removal of the product water (the water generated by operation of the fuel cell). The assembly includes externally-sensing forward-pressure regulators that supply reactant gases (fuel and oxygen) at variable pressures to ejector reactant pumps. The ejector supply pressures depend on the consumption flows. The ejectors develop differential pressures approximately proportional to the consumption flow rates at constant system pressure and with constant flow restriction between the mixer-outlet and suction ports of the ejectors. For removal of product water from the circulating oxygen stream, the assembly includes a water/gas separator that contains hydrophobic and hydrophilic membranes. The water separator imposes an approximately constant flow restriction, regardless of the quality of the two-phase flow that enters it from the fuel cell. The gas leaving the water separator is nearly 100 percent humid. This gas is returned to the inlet of the fuel cell along with a quantity of dry incoming oxygen, via the oxygen ejector, thereby providing some humidification.
From MIPS to Vicsek: A comprehensive phase diagram for self-propelled rods

NASA Astrophysics Data System (ADS)

Shi, Xiaqing

Self-propelled rods interacting by volume exclusion is one of the simplest active matter systems. Despite years of effort, no comprehensive picture of their phase diagram is available. Furthermore, results on explicit rods are so far largely disconnected from those obtained on the relatively better understood cases of motility induced phase separation (MIPS) of (usually) isotropic active particles, and from our current knowledge of Vicsek-style aligning point particles. In this talk, I will present a complete phase diagram of a generic model of self-propelled rods and show how it is connected to both MIPS and Vicsek worlds.
Technical Report: Understanding Functional Lyotropic Liquid Crystal Network Phase Self-Assembly and the Properties of Nanoconfined Water

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

Mahanthappa, Mahesh K; Yethiraj, Arun

Through the synergistic interplay of molecular dynamics (MD) simulations, chemical synthesis, and materials characterization by X-ray and neutron scattering techniques, this project investigated the phase behaviors of new classes of aqueous lyotropic liquid crystals (LLCs) and the properties of water nanoconfined within their pores. A portion of our studies focused on the synthesis of new classes of alkylsulfonic acid and alkylphosphonate amphiphiles, which were shown to undergo water-induced self-assembly to form a wide variety of nanostructured morphologies with unusually high degrees of long-range translational order observed by small- angle X-ray scattering (SAXS). Sample LLC morphologies that were observed include themore » lamellar (L!), tricontinuous double gyroid (G), hexagonally-packed cylinders (H), and low symmetry discontinuous micellar (I) Frank-Kasper phases. Since the G and H phases are the most promising for the development of selective ion transporting membranes for energy applications, we sought the characterize the structure and dynamics of water confined within the sub-3 nm pores of these LLCs using wide-angle neutron diffraction (WAND) and quasielastic neutron scattering (QENS) experiments performed at the Spallation Neutron Source at Oak Ridge National Laboratory. Using molecular dynamics (MD) simulations, we validated models for analyzing this QENS data to obtain water self-diffusion coefficients in LLC G and H phases of carboxylate and sulfonate surfactant LLCs as a function of the identities of their charge compensating counterions.« less
Method for selective immobilization of macromolecules on self assembled monolayer surfaces

DOEpatents

Laskin, Julia [Richland, WA; Wang, Peng [Billerica, MA

2011-11-29

Disclosed is a method for selective chemical binding and immobilization of macromolecules on solid supports in conjunction with self-assembled monolayer (SAM) surfaces. Immobilization involves selective binding of peptides and other macromolecules to SAM surfaces using reactive landing (RL) of mass-selected, gas phase ions. SAM surfaces provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. The invention finds applications in biochemistry ranging from characterization of molecular recognition events at the amino acid level and identification of biologically active motifs in proteins, to development of novel biosensors and substrates for stimulated protein and cell adhesion.
pH-dependent and pH-independent self-assembling behavior of surfactant-like peptides

NASA Astrophysics Data System (ADS)

Gurevich, Leonid; Fojan, Peter

2012-02-01

Self-assembly of amphiphilic peptides designed during the last years by several research groups leads to a large variety of 3D-structures that already found applications in stabilization of large protein complexes, cell culturing systems etc. In this report, we present synthesis and characterization of two novel families of amphiphilic peptides KAn and KAnW (n=6,5,4) that exhibits clear charge separation controllable by pH of the environment. As the pH changes from acidic to basic, the charge on the ends of the peptide molecule varies eventually leading to reorganization of KAn micelles and even micellar inversion. On contrary, the bulky geometry of the tryptophan residue in KAnW limits the variation of the surfactant parameter and hence largely prevents assembly into spherical or cylindrical micelles while favouring flatter geometries. The studied short peptide families demonstrate formation of ordered aggregates with well-defined secondary structure from short unstructured peptides and provide a simple system where factors responsible for self-assembly can be singled out and studied one by one. The ability to control the shape and structure of peptide aggregates can provide basis for novel designer pH sensitive materials including drug delivery and controlled release systems.
Supra-dendron Gelator Based on Azobenzene-Cyclodextrin Host-Guest Interactions: Photoswitched Optical and Chiroptical Reversibility.

PubMed

Xie, Fan; Ouyang, Guanghui; Qin, Long; Liu, Minghua

2016-12-12

A novel amphiphilic dendron (AZOC 8 GAc) with three l-glutamic acid units and an azobenzene moiety covalently linked by an alkyl spacer has been designed. The compound formed hydrogels with water at very low concentration and self-assembled into chiral-twist structures. The gel showed a reversible macroscopic volume phase transition in response to pH variations and photo-irradiation. During the photo-triggered changes, although the gel showed complete reversibility in its optical absorptions, only an incomplete chiroptical property change was achieved. On the other hand, the dendron could form a 1:1 inclusion complex through a host-guest interaction with α-cyclodextrin (α-CD), designated as supra-dendron gelator AZOC 8 GAc/α-CD. The supra-dendron showed similar gelation behavior to that of AZOC 8 GAc, but with enhanced photoisomerization-transition efficiency and chiroptical switching capacity, which was completely reversible in terms of both optical and chiroptical performances. The self-assembly of the supra-dendron is a hierarchical or multi-supramolecular self-assembling process. This work has clearly illustrated that the hierarchical and multi-supramolecular self-assembling system endows the supramolecular nanostructures or materials with superior reversible optical and chiroptical switching. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Surface charge dependent separation of modified and hybrid ferritin in native PAGE: Impact of lysine 104.

PubMed

Subhadarshanee, Biswamaitree; Mohanty, Abhinav; Jagdev, Manas Kumar; Vasudevan, Dileep; Behera, Rabindra K

2017-10-01

Preparation of modified and hybrid ferritin provides a great opportunity to understand the mechanisms of iron loading/unloading, protein self-assembly, size constrained nanomaterial synthesis and targeted drug delivery. However, the large size (M.W.=490kDa) has been limiting the separation of different modified and/or hybrid ferritin nanocages from each other in their intact assembled form and further characterization. Native polyacrylamide gel electrophoresis (PAGE) separates proteins on the basis of both charge and mass, while maintaining their overall native structure and activity. Altering surface charge distribution by substitution of amino acid residues located at the external surface of ferritin (K104E & D40A) affected the migration rate in native PAGE while internal modification had little effect. Crystal structures confirmed that ferritin nanocages made up of subunits with single amino acid substitutions retain the overall structure of ferritin nanocage. Taking advantage of K104E migration behavior, formation of hybrid ferritins with subunits of wild type (WT) and K104E were confirmed and separated in native PAGE. Cage integrity and iron loading ability (ferritin activity) were also tested. The migration pattern of hybrid ferritins in native PAGE depends on the subunit ratio (WT: K104E) in the ferritin cage. Our work shows that native PAGE can be exploited in nanobiotechnology, by analyzing modifications of large proteins like ferritin. Native PAGE, a simple, straight-forward technique, can be used to analyze small modification (by altering external surface charge) in large proteins like ferritin, without disintegrating its self-assembled nanocage structure. In doing so, native PAGE can complement the information obtained from mass spectrometry. The confirmation and separation of modified and hybrid ferritin protein nanocages in native PAGE, opens up various prospects of bio-conjugation, which can be useful in targeted drug delivery, nanobiotechnology and in understanding nature's idea of synthesizing hybrid ferritins in different human tissues. Copyright © 2017 Elsevier B.V. All rights reserved.
Microfluidic techniques for the study of self-assembly of soft materials

NASA Astrophysics Data System (ADS)

Aguade Cabanas, Rafael

This research is an approach to the study of soft condensed matter where the use of new microfluidic technology plays a central role. Often, in the study of soft matter, the sample volumes are very small, of the order of nanoliters. Therefore to quantitatively measure the equilibrium or non-equilibrium phase behavior requires microfluidics. Presented here are (1) a new way of producing aqueous drops of order 1 nl volume, in oil, (2) a new fabrication protocol to make microfluidic devices out of epoxy glue, and (3) a new microfluidic flow cell to study colloidal self-assembly. Also presented here is a new kind of colloidal particle, consisting of single strands of DNA linked to the surface of fd virus. This new particle may serve as a liquid crystalline colloid with a temperature dependent tunable potential. The fabrication process is the first step in the study of the self-assembly of rod-like particles with a temperature dependent potential.
Better Organic Ternary Memory Performance through Self-Assembled Alkyltrichlorosilane Monolayers on Indium Tin Oxide (ITO) Surfaces.

PubMed

Hou, Xiang; Cheng, Xue-Feng; Zhou, Jin; He, Jing-Hui; Xu, Qing-Feng; Li, Hua; Li, Na-Jun; Chen, Dong-Yun; Lu, Jian-Mei

2017-11-16

Recently, surface engineering of the indium tin oxide (ITO) electrode of sandwich-like organic electric memory devices was found to effectively improve their memory performances. However, there are few methods to modify the ITO substrates. In this paper, we have successfully prepared alkyltrichlorosilane self-assembled monolayers (SAMs) on ITO substrates, and resistive random access memory devices are fabricated on these surfaces. Compared to the unmodified ITO substrates, organic molecules (i.e., 2-((4-butylphenyl)amino)-4-((4-butylphenyl)iminio)-3-oxocyclobut-1-en-1-olate, SA-Bu) grown on these SAM-modified ITO substrates have rougher surface morphologies but a smaller mosaicity. The organic layer on the SAM-modified ITO further aged to eliminate the crystalline phase diversity. In consequence, the ternary memory yields are effectively improved to approximately 40-47 %. Our results suggest that the insertion of alkyltrichlorosilane self-assembled monolayers could be an efficient method to improve the performance of organic memory devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Self-assembly of dodecaphenyl POSS thin films

NASA Astrophysics Data System (ADS)

Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor

2017-12-01

The self-assembly abilities of Dodecaphenyl Polyhedral Oligomeric Silsesquioxane thin films on Si(1 0 0) surfaces were studied. Due to their thermal properties - relatively low sublimation temperature and preservation of molecular structure - cage type silsesquioxanes are ideal material for the preparation of a thin films by Physical Vapor Deposition. The Ultra-High Vacuum environment and the deposition precision of the PVD method enable the study of early stages of thin film growth and its molecular organization. X-ray Reflectivity and Atomic Force Microscopy measurements allow to pursuit size-effects in the structure of thin films with thickness ranges from less than a single molecular layer up to several tens of layers. Thermal treatment of the thin films triggered phase change: from a poorly ordered polycrystalline film into a well-ordered multilayer structure. Self-assembly of the layers is the effect of the π-stacking of phenyl rings, which force molecules to arrange in a superlattice, forming stacks of alternating organic-inorganic layers.
Hybrid gels assembled from Fmoc-amino acid and graphene oxide with controllable properties.

PubMed

Xing, Pengyao; Chu, Xiaoxiao; Li, Shangyang; Ma, Mingfang; Hao, Aiyou

2014-08-04

A supramolecular gel is obtained from the self-assembly of an ultralow-molecular-weight gelator (N-fluorenyl-9-methoxycarbonyl glutamic acid) in good and poor solvents. The gelators can self-assemble into a lamellar structure, which can further form twisted fibers and nanotubes in the gel phase. Rheological studies show that the gels are robust and rigid, and are able to rapidly self-recover to a gel after being destroyed by shear force. Fluorescence experiments reveal the aggregation-induced emission effects of the gel system; the fluorescence intensity is significantly enhanced by gel formation. Graphene oxide (GO) is introduced into the system efficiently to give a hybrid material, and the interaction between gelators-GO sheets is studied. Rheological and fluorescent studies imply that the mechanical properties and the fluorescent emission of the hybrid materials can be fine-tuned by controlling the addition of GO. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

PubMed

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; Brennan, Michael C; Morozov, Yurii V; Manser, Joseph S; Kamat, Prashant V; Schneider, William F; Kuno, Masaru

2017-08-04

Mixed halide hybrid perovskites, CH 3 NH 3 Pb(I 1-x Br x ) 3 , represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.
Demonstration of a Variable Phase Turbine Power System for Low Temperature Geothermal Resources

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

Hays, Lance G

2014-07-07

A variable phase turbine assembly will be designed and manufactured having a turbine, operable with transcritical, two-phase or vapor flow, and a generator – on the same shaft supported by process lubricated bearings. The assembly will be hermetically sealed and the generator cooled by the refrigerant. A compact plate-fin heat exchanger or tube and shell heat exchanger will be used to transfer heat from the geothermal fluid to the refrigerant. The demonstration turbine will be operated separately with two-phase flow and with vapor flow to demonstrate performance and applicability to the entire range of low temperature geothermal resources. The vapormore » leaving the turbine is condensed in a plate-fin refrigerant condenser. The heat exchanger, variable phase turbine assembly and condenser are all mounted on single skids to enable factory assembly and checkout and minimize installation costs. The system will be demonstrated using low temperature (237F) well flow from an existing large geothermal field. The net power generated, 1 megawatt, will be fed into the existing power system at the demonstration site. The system will demonstrate reliable generation of inexpensive power from low temperature resources. The system will be designed for mass manufacturing and factory assembly and should cost less than $1,200/kWe installed, when manufactured in large quantities. The estimated cost of power for 300F resources is predicted to be less than 5 cents/kWh. This should enable a substantial increase in power generated from low temperature geothermal resources.« less
Enrichment of dynamic chromosomal crosslinks drive phase separation of the nucleolus.

PubMed

Hult, Caitlin; Adalsteinsson, David; Vasquez, Paula A; Lawrimore, Josh; Bennett, Maggie; York, Alyssa; Cook, Diana; Yeh, Elaine; Forest, Mark Gregory; Bloom, Kerry

2017-11-02

Regions of highly repetitive DNA, such as those found in the nucleolus, show a self-organization that is marked by spatial segregation and frequent self-interaction. The mechanisms that underlie the sequestration of these sub-domains are largely unknown. Using a stochastic, bead-spring representation of chromatin in budding yeast, we find enrichment of protein-mediated, dynamic chromosomal cross-links recapitulates the segregation, morphology and self-interaction of the nucleolus. Rates and enrichment of dynamic crosslinking have profound consequences on domain morphology. Our model demonstrates the nucleolus is phase separated from other chromatin in the nucleus and predicts that multiple rDNA loci will form a single nucleolus independent of their location within the genome. Fluorescent labeling of budding yeast nucleoli with CDC14-GFP revealed that a split rDNA locus indeed forms a single nucleolus. We propose that nuclear sub-domains, such as the nucleolus, result from phase separations within the nucleus, which are driven by the enrichment of protein-mediated, dynamic chromosomal crosslinks. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.
On theoretical and experimental modeling of metabolism forming in prebiotic systems

NASA Astrophysics Data System (ADS)

Bartsev, S. I.; Mezhevikin, V. V.

Recently searching for extraterrestrial life attracts more and more attention However the searching hardly can be effective without sufficiently universal concept of life origin which incidentally tackles a problem of origin of life on the Earth A concept of initial stages of life origin including origin of prebiotic metabolism is stated in the paper Suggested concept eliminates key difficulties in the problem of life origin and allows experimental verification of it According to the concept the predecessor of living beings has to be sufficiently simple to provide non-zero probability of self-assembling during short in geological or cosmic scale time In addition the predecessor has to be capable of autocatalysis and further complication evolution A possible scenario of initial stage of life origin which can be realized both on other planets and inside experimental facility is considered In the scope of the scenario a theoretical model of multivariate oligomeric autocatalyst coupled with phase-separated particle is presented Results of computer simulation of possible initial stage of chemical evolution are shown Conducted estimations show the origin of autocatalytic oligomeric phase-separated system is possible at reasonable values of kinetic parameters of involved chemical reactions in a small-scale flow reactor Accepted statements allowing to eliminate key problems of life origin imply important consequence -- organisms emerged out of the Earth or inside a reactor have to be based on another different from terrestrial biochemical
Effect of solvent and subsequent thermal annealing on the performance of phenylenevinylene copolymer: PCBM solar cells.

PubMed

Sharma, G D; Suresh, P; Sharma, S S; Vijay, Y K; Mikroyannidis, John A

2010-02-01

The morphology of the photoactive layer used in the bulk heterojunction photovoltaic devices is crucial for efficient charge generation and their collection at the electrodes. We investigated the solvent vapor annealing and thermal annealing effect of an alternating phenylenevinylene copolymer P:PCBM blend on its morphology and optical properties. The UV-visible absorption spectroscopy shows that both solvent and thermal annealing can result in self-assembling of copolymer P to form an ordered structure, leading to enhanced absorption in the red region and hole transport enhancement. By combining the solvent and thermal annealing of the devices, the power conversion efficiency is improved. This feature was attributed to the fact that the PCBM molecules begin to diffuse into aggregates and together with the ordered copolymer P phase form bicontinuous pathways in the entire layer for efficient charge separation and transport. Furthermore, the measured photocurrent also suggests that the space charges no longer limit the values of the short circuit current (J(sc)) and fill factor (FF) for solvent-treated and thermally annealed devices. These results indicate that the higher J(sc) and PCE for the solvent-treated and thermally annealed devices can be attributed to the phase separation of active layers, which leads to a balanced carrier mobility. The overall PCE of the device based on the combination of solvent annealing and thermal annealing is about 3.7 %.
Comparison in partition efficiency of protein separation between four different tubing modifications in spiral high-speed countercurrent chromatography

PubMed Central

Ito, Yoichiro; Clary, Robert

2016-01-01

High-speed countercurrent chromatography with a spiral tube assembly can retain a satisfactory amount of stationary phase of polymer phase systems used for protein separation. In order to improve the partition efficiency a simple tool to modify the tubing shapes was fabricated, and the following four different tubing modifications were made: intermittently pressed at 10 mm width, flat, flat-wave, and flat-twist. Partition efficiencies of the separation column made from these modified tubing were examined in protein separation with an aqueous-aqueous polymer phase system at flow rates of 1–2 ml/min under 800 rpm. The results indicated that the column with all modified tubing improved the partition efficiency at a flow rate of 1 ml/min, but at a higher flow rate of 2 ml/min the columns made of flattened tubing showed lowered partition efficiency apparently due to the loss of the retained stationary phase. Among all the modified columns, the column with intermittently pressed tubing gave the best peak resolution. It may be concluded that the intermittently pressed and flat-twist improve the partition efficiency in a semi-preparative separation while other modified tubing of flat and flat-wave configurations may be used for analytical separations with a low flow rate. PMID:27790621

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