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Sample records for functional self-assembling bolaamphiphilic

  1. Functional self-assembling bolaamphiphilic polydiacetylenes as colorimetric sensor scaffolds

    SciTech Connect

    Song, Jie; Cisar, Justin S.; Bertozzi, Carolyn R.

    2004-05-28

    Conjugated polymers capable of responding to external stimuli by changes in optical, electrical or electrochemical properties can be used for the construction of direct sensing devices. Polydiacetylene-based systems are attractive for sensing applications due to their colorimetric response to changes in the local environment. Here we present the design, preparation and characterization of self-assembling functional bolaamphiphilic polydiacetylenes (BPDAs) inspired by Nature's strategy for membrane stabilization. We show that by placing polar headgroups on both ends of the diacetylene lipids in a transmembranic fashion, and altering the chemical nature of the polar surface residues, the conjugated polymers can be engineered to display a range of radiation-, thermal- and pH-induced colorimetric responses. We observed dramatic nanoscopic morphological transformations accompanying charge-induced chromatic transitions, suggesting that both side chain disordering and main chain rearrangement play important roles in altering the effective conjugation lengths of the poly(ene-yne). These results establish the foundation for further development of BPDA-based colorimetric sensors.

  2. Biomimetic Catalytic and Sensing Cascades Built with Two Designer Bolaamphiphilic Self-Assemblies.

    PubMed

    Kwak, Jinyoung; Kim, Min-Chul; Lee, Sang-Yup

    2015-07-01

    A system performing both a catalytic hydrolysis reaction and the direct optical monitoring of the product was created by the combination of two bolaamphiphile self-assemblies. Two bolaamphiphilic self-assemblies were applied as a biomimetic catalyst of p-nitrophenyl acetate (p-NPA) hydrolysis and an optical sensor probe that detects p-NPA hydrolysis through photoluminescence quenching by p-nitrophenol (p-NP), the product of p-NPA hydrolysis. One bolaamphiphilic self-assembly with a histidine moiety catalytically hydrolyzed the p-NPA substrate, and the other self-assembly of tyrosyl bolaamphiphile monitored the product of p-NP by photoluminescence quenching. The progression of the reaction and quenching degree were adjusted by controlling the quantity of histidyl and tyrosyl self-assemblies, respectively. The reaction and subsequent sensing cascade could be interrupted by a reducing agent. The addition of NaBH4 induced the chemical conversion of p-NP to p-aminophenol, which retarded photoluminescence quenching. Thus, it was demonstrated that hydrolysis of an organic substrate and subsequent monitoring of the hydrolysis reaction could be achieved through a combination of independent bolaamphiphilic self-assemblies. This study demonstrated the construction of a catalytic reaction and detection system incorporating designer biomimetic self-assemblies whose functionalities were devised to realize deliberate functions. PMID:26052625

  3. Hemoglobin-mimetic oxygen adsorbent prepared via self-assembly of cysteinyl bolaamphiphiles.

    PubMed

    Lee, Chaemyeong; Kim, Min-Chul; Lee, Sang-Yup

    2016-06-01

    In this study, a novel cysteinyl bolaamphiphilic molecule was synthesized and its self-assembled planar suprastructure was applied as a biomimetic matrix to create a hemoglobin-mimetic oxygen adsorbent that exploits the ability of cysteine thiols to bind hemin. Self-assembly of the cysteinyl bolaamphiphilic molecule exposed cysteine thiols on its surface in the presence of β-mercaptoethanol, known to reduce disulfide bonds, without which, helically coiled structures were generated. The self-assembled planar structure was used as a soft matrix to create a hemoglobin-mimetic oxygen adsorbent. The surface-exposed cysteine thiols were used to attach hemin, producing a hemin-bound, planar structure mimicking hemoglobin. This hemoglobin mimic strongly adsorbed oxygen and remained stable up to 50°C. The cysteinyl bolaamphiphile self-assembled structure provided a biomimetic platform that allowed for the association of biological substances in a manner similar to natural proteins. PMID:26970824

  4. Mussel-inspired bolaamphiphile sticky self-assemblies for the preparation of magnetic nanoparticles.

    PubMed

    Lee, Chaemyeong; Lee, Sang-Yup

    2015-03-01

    Adopting the strong metal binding moiety of a mussel protein, a novel bolaamphiphile molecule was prepared and applied to the fabrication of magnetic core-shell nanoparticles. The novel bolaamphiphile molecule with 3,4-dihydroxyphenylalanine (DOPA) end groups was synthesized and its self-assembly was used as a template to adsorb metal ions and subsequently to produce magnetic nanoparticles. The DOPA bolaamphiphile molecule self-assembled in aqueous solution to produce nanospherical structures that exposed the catechol moiety of DOPA to the outer surface. The catechol groups adsorbed cobalt and iron ions to create magnetic metal oxide clusters on the self-assembly. Spectroscopic analysis showed that the cobalt and iron ions were coordinated with quinone, an oxidized form of the catechol. Exploiting the strong metal-adsorbing and binding properties of DOPA, dense cobalt oxide and iron oxide shell layers were created on the nanospherical self-assembly to produce magnetic core-shell nanoparticles. This study demonstrated a simple method for creating magnetic metal oxide nanoparticles that exploits the molecular binding forces and self-assembly property of DOPA. PMID:25658196

  5. Self-assembly pathway of peptide nanotubes formed by a glutamatic acid-based bolaamphiphile.

    PubMed

    da Silva, Emerson Rodrigo; Alves, Wendel Andrade; Castelletto, Valeria; Reza, Mehedi; Ruokolainen, Janne; Hussain, Rohanah; Hamley, Ian William

    2015-07-25

    The self-assembly of peptide nanotubes formed by an L-glutamic acid-based bolaamphiphile is shown to proceed via a remarkable mechanism where the peptide conformation changes from β-sheet to unordered. The kinetics of this process are elucidated via X-ray scattering and UV circular dichroism methods. The reverse transition from "unordered" to β-sheet structures is triggered by UV radiation. PMID:26094619

  6. Peroxidase-like oxidative activity of a manganese-coordinated histidyl bolaamphiphile self-assembly

    NASA Astrophysics Data System (ADS)

    Kim, Min-Chul; Lee, Sang-Yup

    2015-10-01

    A peroxidase-like catalyst was constructed through the self-assembly of histidyl bolaamphiphiles coordinated to Mn2+ ions. The prepared catalyst exhibited oxidation activity for the organic substrate o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H2O2). The histidyl bolaamphiphiles of bis(N-alpha-amido-histidine)-1,7-heptane dicarboxylates self-assembled to make spherical structures in an aqueous solution. Subsequent association of Mn2+ ions with the histidyl imidazoles in the self-assembly produced catalytic active sites. The optimal Mn2+ ion concentration was determined and coordination of the Mn2+ ion with multiple histidine imidazoles was investigated using spectroscopy analysis. The activation energy of the produced catalysts was 55.0 kJ mol-1, which was comparable to other peroxidase-mimetic catalysts. A detailed kinetics study revealed that the prepared catalyst followed a ping-pong mechanism and that the turnover reaction was promoted by increasing the substrate concentration. Finally, application of the prepared catalyst for glucose detection was demonstrated through cascade enzyme catalysis. This study demonstrated a facile way to prepare an enzyme-mimetic catalyst through the self-assembly of an amphiphilic molecule containing amino acid segments.A peroxidase-like catalyst was constructed through the self-assembly of histidyl bolaamphiphiles coordinated to Mn2+ ions. The prepared catalyst exhibited oxidation activity for the organic substrate o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H2O2). The histidyl bolaamphiphiles of bis(N-alpha-amido-histidine)-1,7-heptane dicarboxylates self-assembled to make spherical structures in an aqueous solution. Subsequent association of Mn2+ ions with the histidyl imidazoles in the self-assembly produced catalytic active sites. The optimal Mn2+ ion concentration was determined and coordination of the Mn2+ ion with multiple histidine imidazoles was investigated using spectroscopy

  7. Entropically Driven Self-Assembly of Bolaamphiphilic Perylene Dyes in Water.

    PubMed

    Görl, Daniel; Würthner, Frank

    2016-09-19

    The specific hydrophobic effect involved in the self-assembly of a bolaamphiphilic perylene bisimide (PBI) dye bearing oligoethylene glycol (OEG) chains has been identified. In pure water, the self-assembly is entropically driven and enthalpically disfavored, as explored by optical spectroscopy and isothermal titration calorimetry studies. Besides strong π-π interactions between the PBI units that are primarily of enthalpic nature, the major contribution to the self-assembly is the gain of entropy by release of confined water molecules from the hydration shell of the hydrophilic OEG moieties. Both contributions favor self-assembly, but their countervailing thermodynamic parameters are reflected in an uncommon temperature dependence, which can be inverted upon gradual addition of an organic cosolvent that makes the π-π interaction increasingly dominant. PMID:27558471

  8. Self-assembling oligothiophene-bolaamphiphiles for loading and controlled release of doxorubicin into living cells.

    PubMed

    Schmid, S; Ng, D Y W; Mena-Osteritz, E; Wu, Y; Weil, T; Bäuerle, P

    2016-02-21

    Design and synthesis of symmetric mannose-functionalized oligothiophenes is reported. Self-organization of these bolaamphiphiles in solution and in the solid state was investigated by optical and AFM experiments. Fluorescence measurements revealed efficient loading and pH-dependent release of the anti-cancer drug doxorubicin. Delivery and release of the active drug into viable A549 cells as well as chirality-dependent cellular toxicity of the bolaamphiphilic transporter were evident from in vitro experiments. PMID:26812468

  9. An enzyme-coupled artificial photosynthesis system prepared from antenna protein-mimetic tyrosyl bolaamphiphile self-assembly.

    PubMed

    Kwak, Jinyoung; Kim, Min-Chul; Lee, Sang-Yup

    2016-08-11

    An artificial photosynthesis system coupled with an enzyme was constructed using the nanospherical self-assembly of tyrosyl bolaamphiphiles, which worked as a host matrix exhibiting an antenna effect that allowed enhanced energy transfer to the ZnDPEG photosensitizer. The excited electrons from the photosensitizer were transferred to NAD+ to produce NADH, which subsequently initiated the conversion of an aldehyde to ethanol by alcohol dehydrogenase. Production of NADH and ethanol was enhanced by increasing the concentration of tyrosyl bolaamphiphiles. Spectroscopic investigations proved that the photosensitizer closely associated with the surface of the bolaamphiphile assembly through hydrogen bonds that allowed energy transfer between the host matrix and the photosensitizer. This study demonstrates that the self-assembly of bolaamphiphiles could be applicable to the construction of biomimetic energy systems exploiting biochemical activity. PMID:27480074

  10. Tubular Structures Self-Assembled from a Bola-Amphiphilic Pillar[5]arene in Water and Applied as a Microreactor.

    PubMed

    Chen, Rener; Jiang, Huajiang; Gu, Haining; Zhou, Qizhong; Zhang, Zhen; Wu, Jiashou; Jin, Zhengneng

    2015-09-01

    Various nanomorphologies were obtained by simply changing the fabrication conditions, such as the pH of the system, different solvent, or different concentration, of bola-amphiphilic pillar[5]arene Bola-AP5. Importantly, hybrid microtubules as a microreactor were successfully prepared by directly reducing AuCl4(-) on the surface of Bola-AP5-based tubular structures in water. PMID:26275020

  11. Functional Self-Assembled Nanofibers by Electrospinning

    NASA Astrophysics Data System (ADS)

    Greiner, A.; Wendorff, J. H.

    Electrospinning constitutes a unique technique for the production of nanofibers with diameters down to the range of a few nanometers. In strong contrast to conventional fiber producing techniques, it relies on self-assembly processes driven by the Coulomb interactions between charged elements of the fluids to be spun to nanofibers. The transition from a macroscopic fluid object such as a droplet emerging from a die to solid nanofibers is controlled by a set of complex physical instability processes. They give rise to extremely high extensional deformations and strain rates during fiber formation causing among others a high orientational order in the nanofibers as well as enhanced mechanical properties. Electrospinning is predominantly applied to polymer based materials including natural and synthetic polymers, but, more recently, its use has been extended towards the production of metal, ceramic and glass nanofibers exploiting precursor routes. The nanofibers can be functionalized during electrospinning by introducing pores, fractal surfaces, by incorporating functional elements such as catalysts, quantum dots, drugs, enzymes or even bacteria. The production of individual fibers, random nonwovens, or orientationally highly ordered nonwovens is achieved by an appropriate selection of electrode configurations. Broad areas of application exist in Material and Life Sciences for such nanofibers, including not only optoelectronics, sensorics, catalysis, textiles, high efficiency filters, fiber reinforcement but also tissue engineering, drug delivery, and wound healing. The basic electrospinning process has more recently been extended towards compound co-electrospinning and precision deposition electrospinning to further broaden accessible fiber architectures and potential areas of application.

  12. Bolaamphiphiles: A Pharmaceutical Review

    PubMed Central

    Fariya, Mayur; Jain, Ankitkumar; Dhawan, Vivek; Shah, Sanket; Nagarsenker, Mangal S.

    2014-01-01

    The field of drug discovery is ever growing and excipients play a major role in it. A novel class of amphiphiles has been discussed in the review. The review focuses on natural as well as synthetic bolaamphiphiles, their chemical structures and importantly, their ability to self assemble rendering them of great use to pharmaceutical industry. Recent reports on their ability to be used in fabrication of suitable nanosized carriers for drug as well as genes to target site, has been discussed substantially to understand the potential of bolaamphiphiles in field of drug delivery. PMID:25671179

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

    PubMed Central

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

    2015-01-01

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

  14. Self-Assembly for the Synthesis of Functional Biomaterials

    PubMed Central

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

    2012-01-01

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

  15. Self-assembled peptide nanostructures for functional materials.

    PubMed

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

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies. PMID:27578525

  16. Next generation high density self assembling functional protein arrays

    PubMed Central

    Ramachandran, Niroshan; Raphael, Jacob V.; Hainsworth, Eugenie; Demirkan, Gokhan; Fuentes, Manuel G.; Rolfs, Andreas; Hu, Yanhui; LaBaer, Joshua

    2009-01-01

    We report a high-density self assembling protein microarray that displays thousands of proteins, produced and captured in situ from immobilized cDNA templates. Over 1500 unique cDNAs were tested with > 90% success with nearly all proteins displaying yields within 2 fold of the mean, minimal sample variation and good day to day reproducibility. The displayed proteins revealed selective protein interactions. This method will enable various experimental approaches to study protein function in high throughput. PMID:18469824

  17. Molecular Motions in Functional Self-Assembled Nanostructures

    PubMed Central

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

    2013-01-01

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

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

    PubMed

    Faul, Charl F J

    2014-12-16

    CONSPECTUS: The challenge of constructing soft functional materials over multiple length scales can be addressed by a number of different routes based on the principles of self-assembly, with the judicious use of various noncovalent interactions providing the tools to control such self-assembly processes. It is within the context of this challenge that we have extensively explored the use of an important approach for materials construction over the past decade: exploiting electrostatic interactions in our ionic self-assembly (ISA) method. In this approach, cooperative assembly of carefully chosen charged surfactants and oppositely charged building blocks (or tectons) provides a facile noncovalent route for the rational design and production of functional nanostructured materials. Generally, our research efforts have developed with an initial focus on establishing rules for the construction of novel noncovalent liquid-crystalline (LC) materials. We found that the use of double-tailed surfactant species (especially branched double-tailed surfactants) led to the facile formation of thermotropic (and, in certain cases, lyotropic) phases, as demonstrated by extensive temperature-dependent X-ray and light microscopy investigations. From this core area of activity, research expanded to cover issues beyond simple construction of anisotropic materials, turning to the challenge of inclusion and exploitation of switchable functionality. The use of photoactive azobenzene-containing ISA materials afforded opportunities to exploit both photo-orientation and surface relief grating formation. The preparation of these anisotropic LC materials was of interest, as the aim was the facile production of disposable and low-cost optical components for display applications and data storage. However, the prohibitive cost of the photo-orientation processes hampered further exploitation of these materials. We also expanded our activities to explore ISA of biologically relevant tectons

  19. Self-assembly of active colloidal molecules with dynamic function

    NASA Astrophysics Data System (ADS)

    Soto, Rodrigo; Golestanian, Ramin

    Catalytically active colloids maintain non-equilibrium conditions in which they produce and deplete chemicals at their surface. While individual colloids that are symmetrically coated do not exhibit dynamical activity, the concentration fields resulting from their chemical activity decay as 1/r and produce gradients that attract or repel other colloids depending on their surface chemistry and ambient variables. This results in a non-equilibrium analogue of ionic systems, but with the remarkable novel feature of action-reaction symmetry breaking. In dilute conditions these active colloids join up to form molecules via generalized ionic bonds. Colloids are found to join up to form self-assembled molecules that could be inert or have spontaneous activity in the form of net translational velocity and spin depending on their symmetry properties and their constituents. As the interactions do not satisfy detailed-balance, it is possible to achieve structures with time dependent functionality. We study a molecule that adopts spontaneous oscillations and another that exhibits a run-and-tumble dynamics similar to bacteria. Our study shows that catalytically active colloids could be used for designing self-assembled structures that posses dynamical functionalities.

  20. Soft materials design via self assembly of functionalized icosahedral particles

    NASA Astrophysics Data System (ADS)

    Muthukumar, Vidyalakshmi Chockalingam

    In this work we simulate self assembly of icosahedral building blocks using a coarse grained model of the icosahedral capsid of virus 1m1c. With significant advancements in site-directed functionalization of these macromolecules [1], we propose possible application of such self-assembled materials for drug delivery. While there have been some reports on organization of viral particles in solution through functionalization, exploiting this behaviour for obtaining well-ordered stoichiometric structures has not yet been explored. Our work is in well agreement with the earlier simulation studies of icosahedral gold nanocrystals, giving chain like patterns [5] and also broadly in agreement with the wet lab works of Finn, M.G. et al., who have shown small predominantly chain-like aggregates with mannose-decorated Cowpea Mosaic Virus (CPMV) [22] and small two dimensional aggregates with oligonucleotide functionalization on the CPMV capsid [1]. To quantify the results of our Coarse Grained Molecular Dynamics Simulations I developed analysis routines in MATLAB using which we found the most preferable nearest neighbour distances (from the radial distribution function (RDF) calculations) for different lengths of the functional groups and under different implicit solvent conditions, and the most frequent coordination number for a virus particle (histogram plots further using the information from RDF). Visual inspection suggests that our results most likely span the low temperature limits explored in the works of Finn, M.G. et al., and show a good degree of agreement with the experimental results in [1] at an annealing temperature of 4°C. Our work also reveals the possibility of novel stoichiometric N-mer type aggregates which could be synthesized using these capsids with appropriate functionalization and solvent conditions.

  1. Self-assembling Functionalized Single-walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Gao, Yan

    Single-walled carbon nanotubes (SWCNTs) are promising bottom-up building materials due to their superior properties. However, the lack of an effective method to arrange large quantities of SWCNTs poses an obstacle toward their applications. Existing studies to functionalize, disperse, position, and assemble SWCNTs provide a broad understandings regarding SWCNTs behavior, especially in aqueous electrolyte solution. Inspired by ionic polymer metal composite (IPMC) materials, this dissertation envisions fabrication of orderly SWCNTs network structure via their ionic clustering-mediated self-assembly. SWCNTs tend to bundle together due to inter-nanotube VDW attractions, which increase with nanotube length. The author seeks short SWCNTs with long chain molecules bearing ionic termini to facilitate debundling and self-assembly in aqueous electrolyte solution through end-clustering. First, a simple model was applied based on essential physical factors. The results indicated that SWCNTs must be shorter than ˜100 nm to achieve stable network structures. Experiments were then carried out based upon the results. Short SWCNTs (50-100 nm) were end-functionalized with hexaethylene glycol (HEG) linkers bearing terminal carboxylate anions. Both 2D and 3D network structures were observed after placing the functionalized SWCNTs in aqueous electrolyte (sodium ion). The network structures were characterized by microscopic and spectroscopic methods. A novel approach was applied via electron tomography to study the 3D structures of SWCNTs structure in aqueous electrolyte. Free energy analysis of the SWCNTs network structure was implemented with the assistance of both analytical tools and molecular simulations. The results indicate that, when a cluster is formed by three functionalized SWCNTs ends, the resulting network structure is most stable. Indeed, 72% of the clusters/joints were formed by three nanotubes, as observed in experiments. Finally, Monte Carlo simulations of coarse

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

    SciTech Connect

    Li, W.; Malinsky, J.E.; Chou, H.

    1998-07-01

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

  3. Self-assembled diatom substrates with plasmonic functionality

    NASA Astrophysics Data System (ADS)

    Kwon, Sun Yong; Park, Sehyun; Nichols, William T.

    2014-04-01

    Marine diatoms have an exquisitely complex exoskeleton that is promising for engineered surfaces such as sensors and catalysts. For such applications, creating uniform arrays of diatom frustules across centimeter scales will be necessary. Here, we present a simple, low-cost floating interface technique to self-assemble the diatom frustules. We show that well-prepared diatoms form floating hexagonal close-packed arrays at the air-water interface that can be transferred directly to a substrate. We functionalize the assembled diatom surfaces with gold and characterize the plasmonic functionality by using surface enhanced Raman scattering (SERS). Thin gold films conform to the complex, hierarchical diatom structure and produce a SERS enhancement factor of 2 × 104. Small gold nanoparticles attached to the diatom's surface produce a higher enhancement of 7 × 104 due to stronger localization of the surface plasmons. Taken together, the large-scale assembly and plasmonic functionalization represent a promising platform to control the energy and the material flows at a complex surface for applications such as sensors and plasmonic enhanced catalysts.

  4. Sequence, structure, and function of peptide self-assembled monolayers.

    PubMed

    Nowinski, Ann K; Sun, Fang; White, Andrew D; Keefe, Andrew J; Jiang, Shaoyi

    2012-04-01

    Cysteine is commonly used to attach peptides onto gold surfaces. Here we show that the inclusion of an additional linker with a length of four residues (-PPPPC) and a rigid, hydrophobic nature is a better choice for forming peptide self-assembled monolayers (SAMs) with a well-ordered structure and high surface density. We compared the structure and function of the nonfouling peptide EKEKEKE-PPPPC-Am with EKEKEKE-C-Am. Circular dichroism, attenuated total internal reflection Fourier transform IR spectroscopy, and molecular dynamics results showed that EKEKEKE-PPPPC-Am forms a secondary structure while EKEKEKE-C-Am has a random structure. Surface plasmon resonance sensor results showed that protein adsorption on EKEKEKE-PPPPC-Am/gold is very low with small variation while protein adsorption on EKEKEKE-C-Am/gold is high with large variation. X-ray photoelectron spectroscopy results showed that both peptides have strong gold-thiol binding with the gold surface, indicating that their difference in protein adsorption is due to their assembled structures. Further experimental and simulation studies were performed to show that -PPPPC is a better linker than -PC, -PPC, and -PPPC. Finally, we extended EKEKEKE-PPPPC-Am with the cell-binding sequence RGD and demonstrated control over specific versus nonspecific cell adhesion without using poly(ethylene glycol). Adding a functional peptide to the nonfouling EK sequence avoids complex chemistries that are used for its connection to synthetic materials. PMID:22401132

  5. Investigation of functionalized silicon nanowires by self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hemed, Nofar Mintz; Convertino, Annalisa; Shacham-Diamand, Yosi

    2016-03-01

    The functionalization using self assembled monolayer (SAM) of silicon nanowires (SiNW) fabricated by plasma enhanced chemical vapor deposition (PECVD) is reported here. The SAM is being utilized as the first building block in the functionalization process. The morphology of the SiNW comprises a polycrystalline core wrapped by an hydrogenated amorphous silicon (α-Si:H) shell. Since most of the available methods for SAM verification and characterization are suitable only for flat substrates; therefore, in addition to the SiNW α-Si:H on flat samples were produced in the same system as the SiNWs. First we confirmed the SAM's presence on the flat α-Si:H samples using the following methods: contact angle measurement to determine the change in surface energy; atomic force microscopy (AFM) to determine uniformity and molecular coverage. Spectroscopic ellipsometry and X-ray reflectivity (XRR) were performed to measure SAM layer thickness and density. X-ray photoelectron spectroscopy (XPS) was applied to study the chemical states of the surface. Next, SiNW/SAM were tested by electrochemical impedance spectroscopy (EIS), and the results were compared to α-Si:H/SAM. The SAM electrical coverage on SiNW and α-Si:H was found to be ∼37% and ∼65 ± 3%, respectively. A model, based on transmission line theory for the nanowires is presented to explain the disparity in results between the nanowires and flat surface of the same materials.

  6. Self-assembly of active colloidal molecules with dynamic function

    NASA Astrophysics Data System (ADS)

    Soto, Rodrigo; Golestanian, Ramin

    2015-05-01

    Catalytically active colloids maintain nonequilibrium conditions in which they produce and deplete chemicals and hence effectively act as sources and sinks of molecules. While individual colloids that are symmetrically coated do not exhibit any form of dynamical activity, the concentration fields resulting from their chemical activity decay as 1 /r and produce gradients that attract or repel other colloids depending on their surface chemistry and ambient variables. This results in a nonequilibrium analog of ionic systems, but with the remarkable novel feature of action-reaction symmetry breaking. We study solutions of such chemically active colloids in dilute conditions when they join up to form molecules via generalized ionic bonds and discuss how we can achieve structures with time-dependent functionality. In particular, we study a molecule that adopts a spontaneous oscillatory pattern of conformations and another that exhibits a run-and-tumble dynamics similar to bacteria. Our study shows that catalytically active colloids could be used for designing self-assembled structures that possess dynamical functionalities that are determined by their prescribed three-dimensional structures, a strategy that follows the design principle of proteins.

  7. Nucleobase-functionalized ABC triblock copolymers: self-assembly of supramolecular architectures.

    PubMed

    Zhang, Keren; Fahs, Gregory B; Aiba, Motohiro; Moore, Robert B; Long, Timothy E

    2014-08-21

    RAFT polymerization afforded acrylic ABC triblock copolymers with self-complementary nucleobase-functionalized external blocks and a low-Tg soft central block. ABC triblock copolymers self-assembled into well-defined lamellar microphase-separated morphologies for potential applications as thermoplastic elastomers. Complementary hydrogen bonding within the hard phase facilitated self-assembly and enhanced mechanical performance. PMID:24984613

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

    PubMed Central

    Wei, Alexander

    2007-01-01

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

  9. Manipulation of graphene work function using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Seo, Jung-Tak; Bong, Jihye; Cha, Janghwan; Lim, Taekyung; Son, Junyoung; Park, Sung Ha; Hwang, Jungseek; Hong, Suklyun; Ju, Sanghyun

    2014-08-01

    We report an effective and reliable method to increase the work function of graphene to as high as 5.50 eV by applying a self-assembled monolayer on its surface. The work function of pristine graphene (4.56 eV) was increased by approximately +0.94 eV following trichlorosilane (HDF-S) self-assembly. This increase in the work function was confirmed by ab initio calculations. HDF-S self-assembled graphene exhibited no significant changes in structural, optical, or electrical characteristics compared with pristine graphene. In addition, we verified that the modified work function of HDF-S self-assembled graphene was not affected by the underlying substrates.

  10. Self-assembled supramolecular nanotube yarn.

    PubMed

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

    2013-11-01

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

  11. Sustained delivery of VEGF from designer self-assembling peptides improves cardiac function after myocardial infarction

    SciTech Connect

    Guo, Hai-dong; Cui, Guo-hong; Yang, Jia-jun; Wang, Cun; Zhu, Jing; Zhang, Li-sheng; Jiang, Jun; Shao, Shui-jin

    2012-07-20

    Highlights: Black-Right-Pointing-Pointer The designer peptide LRKKLGKA could self-assemble into nanofibers. Black-Right-Pointing-Pointer Injection of LRKKLGKA peptides could promote the sustained delivery of VEGF. Black-Right-Pointing-Pointer Injection of VEGF with LRKKLGKA peptides lead to sufficient angiogenesis. Black-Right-Pointing-Pointer Injection of VEGF with LRKKLGKA peptides improves heart function. -- Abstract: Poor vascularization and insufficient oxygen supply are detrimental to the survival of residual cardiomyocytes or transplanted stem cells after myocardial infarction. To prolong and slow the release of angiogenic factors, which stimulate both angiogenesis and vasculogenesis, we constructed a novel self-assembling peptide by attaching the heparin-binding domain sequence LRKKLGKA to the self-assembling peptide RADA16. This designer self-assembling peptide self-assembled into nanofiber scaffolds under physiological conditions, as observed by atomic force microscopy. The injection of designer self-assembling peptides can efficiently provide the sustained delivery of VEGF for at least 1 month. At 4 weeks after transplantation, cardiac function was improved, and scar size and collagen deposition were markedly reduced in the group receiving VEGF with the LRKKLGKA scaffolds compared with groups receiving VEGF alone, LRKKLGKA scaffolds alone or VEGF with RADA16 scaffolds. The microvessel density in the VEGF with LRKKLGKA group was higher than that in the VEGF with RADA16 group. TUNEL and cleaved caspase-3 expression assays showed that the transplantation of VEGF with LRKKLGKA enhanced cell survival in the infarcted heart. These results present the tailor-made peptide scaffolds as a new generation of sustained-release biomimetic biomaterials and suggest that the use of angiogenic factors along with designer self-assembling peptides can lead to myocardial protection, sufficient angiogenesis, and improvement in cardiac function.

  12. Twins, quadruplexes, and more: functional aspects of native and engineered RNA self-assembly in vivo.

    PubMed

    Lease, Richard A; Arluison, Véronique; Lavelle, Christophe

    2012-03-01

    The primacy and power of RNA in governing many processes of life has begun to be more fully appreciated in both the discovery and inventive sciences. A variety of RNA interactions regulate gene expression, and structural self-assembly underlies many of these processes. The understanding sparked by these discoveries has inspired and informed the engineering of novel RNA structures, control elements, and genetic circuits in cells. Many of these engineered systems are built up fundamentally from RNA-RNA interactions, often combining modular, rational design with functional selection and screening. It is therefore useful to review the particular class of RNA-based regulatory mechanisms that rely on RNA self-assembly either through homomeric (self-self) or heteromeric (self-nonself) RNA-RNA interactions. Structures and sequence elements within individual RNAs create a basis for the pairing interactions, and in some instances can even lead to the formation of RNA polymers. Example systems of dimers, multimers, and polymers are reviewed in this article in the context of natural systems, wherein the function and impact of self-assemblies are understood. Following this, a brief overview is presented of specific engineered RNA self-assembly systems implemented in vivo, with lessons learned from both discovery and engineering approaches to RNA-RNA self-assembly. PMID:23914307

  13. Twins, quadruplexes, and more: functional aspects of native and engineered RNA self-assembly in vivo

    PubMed Central

    Lease, Richard A.; Arluison, Véronique; Lavelle, Christophe

    2013-01-01

    The primacy and power of RNA in governing many processes of life has begun to be more fully appreciated in both the discovery and inventive sciences. A variety of RNA interactions regulate gene expression, and structural self-assembly underlies many of these processes. The understanding sparked by these discoveries has inspired and informed the engineering of novel RNA structures, control elements, and genetic circuits in cells. Many of these engineered systems are built up fundamentally from RNA–RNA interactions, often combining modular, rational design with functional selection and screening. It is therefore useful to review the particular class of RNA-based regulatory mechanisms that rely on RNA self-assembly either through homomeric (self–self) or heteromeric (self–nonself) RNA–RNA interactions. Structures and sequence elements within individual RNAs create a basis for the pairing interactions, and in some instances can even lead to the formation of RNA polymers. Example systems of dimers, multimers, and polymers are reviewed in this article in the context of natural systems, wherein the function and impact of self-assemblies are understood. Following this, a brief overview is presented of specific engineered RNA self-assembly systems implemented in vivo, with lessons learned from both discovery and engineering approaches to RNA–RNA self-assembly. PMID:23914307

  14. Biological colloid engineering: Self-assembly of dipolar ferromagnetic chains in a functionalized biogenic ferrofluid

    NASA Astrophysics Data System (ADS)

    Ruder, Warren C.; Hsu, Chia-Pei D.; Edelman, Brent D.; Schwartz, Russell; LeDuc, Philip R.

    2012-08-01

    We have studied the dynamic behavior of nanoparticles in ferrofluids consisting of single-domain, biogenic magnetite (Fe3O4) isolated from Magnetospirillum magnetotacticum (MS-1). Although dipolar chains form in magnetic colloids in zero applied field, when dried upon substrates, the solvent front disorders nanoparticle aggregation. Using avidin-biotin functionalization of the particles and substrate, we generated self-assembled, linear chain motifs that resist solvent front disruption in zero-field. The engineered self-assembly process we describe here provides an approach for the creation of ordered magnetic structures that could impact fields ranging from micro-electro-mechanical systems development to magnetic imaging of biological structures.

  15. Modeling the self-assembly of functionalized fullerenes on solid surfaces using Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Bubnis, Gregory J.

    Since their discovery 25 years ago, carbon fullerenes have been widely studied for their unique physicochemical properties and for applications including organic electronics and photovoltaics. For these applications it is highly desirable for crystalline fullerene thin films to spontaneously self-assemble on surfaces. Accordingly, many studies have functionalized fullerenes with the aim of tailoring their intermolecular interactions and controlling interactions with the solid substrate. The success of these rational design approaches hinges on the subtle interplay of intermolecular forces and molecule-substrate interactions. Molecular modeling is well-suited to studying these interactions by directly simulating self-assembly. In this work, we consider three different fullerene functionalization approaches and for each approach we carry out Monte Carlo simulations of the self-assembly process. In all cases, we use a "coarse-grained" molecular representation that preserves the dominant physical interactions between molecules and maximizes computational efficiency. The first approach we consider is the traditional gold-thiolate SAM (self-assembled monolayer) strategy which tethers molecules to a gold substrate via covalent sulfur-gold bonds. For this we study an asymmetric fullerene thiolate bridged by a phenyl group. Clusters of 40 molecules are simulated on the Au(111) substrate at different temperatures and surface coverage densities. Fullerenes and S atoms are found to compete for Au(111) surface sites, and this competition prevents self-assembly of highly ordered monolayers. Next, we investigate self-assembled monolayers formed by fullerenes with hydrogen-bonding carboxylic acid substituents. We consider five molecules with different dimensions and symmetries. Monte Carlo cooling simulations are used to find the most stable solid structures of clusters adsorbed to Au(111). The results show cases where fullerene-Au(111) attraction, fullerene close-packing, and

  16. Class I Hydrophobin Vmh2 Adopts Atypical Mechanisms to Self-Assemble into Functional Amyloid Fibrils.

    PubMed

    Gravagnuolo, Alfredo Maria; Longobardi, Sara; Luchini, Alessandra; Appavou, Marie-Sousai; De Stefano, Luca; Notomista, Eugenio; Paduano, Luigi; Giardina, Paola

    2016-03-14

    Hydrophobins are fungal proteins whose functions are mainly based on their capability to self-assemble into amphiphilic films at hydrophobic-hydrophilic interfaces (HHI). It is widely accepted that class I hydrophobins form amyloid-like structures, named rodlets, which are hundreds of nanometers long, packed into ordered lateral assemblies and do not exhibit an overall helical structure. We studied the self-assembly of the Class I hydrophobin Vmh2 from Pleurotus ostreatus in aqueous solutions by dynamic light scattering (DLS), thioflavin T (ThT), fluorescence assay, circular dichroism (CD), cryogenic trasmission electron microscopy (cryo-TEM), and TEM. Vmh2 does not form fibrillar aggregates at HHI. It exhibits spherical and fibrillar assemblies whose ratio depends on the protein concentration when freshly solubilized at pH ≥ 7. Moreover, it spontaneously self-assembles into isolated, micrometer long, and twisted amyloid fibrils, observed for the first time in fungal hydrophobins. This process is promoted by acidic pH, temperature, and Ca(2+) ions. A model of self-assembly into amyloid-like structures has been proposed. PMID:26828412

  17. Rational peptide design for functional materials via molecular self-assembly

    NASA Astrophysics Data System (ADS)

    Rajagopal, Karthikan

    Supra-molecular self-assembly of rationally designed peptides is a promising approach to construct functional materials. This thesis specifically focuses on hydrogels, an important class of materials with potential for applications in tissue engineering, drug delivery and micro-fluidic systems. The objective is to design short peptides that would specifically adopt a stimulus dependent conformation that is strongly amenable to self-assembly resulting in material formation. With this concept the rational design of a 20 amino acid peptide (MAX1) that folds into an amphiphilic beta-hairpin structure and then self-assembles to form a rigid hydrogel under alkaline conditions is presented. The molecular level conformation of MAX1 was characterized using circular dichroism and FTIR spectroscopies. The mesoscale structure of the hydrogel assessed using confocal and transmission electron micron microscopies and neutron scattering techniques shows that peptide self-assembly results in the formation of fibrils that are homogeneously 3 nm in diameter. The mechanical properties of the hydrogel probed using oscillatory rheology shows that MAX1 forms a stiff hydrogel. Since the self-assembly process is coupled to the intra-molecularly folded state of the peptide, stimulus responsiveness can be specifically engineered into the sequence by rational design. This was demonstrated in the design of peptides that form hydrogels in response to a specific stimulus such as temperature, pH or ionic strength. The significance of peptide design in the context of self-assembly and its relationship to the nanostructure was studied by designing a series of peptides derived from MAX1. Evolving from these studies is an understanding of the relationship between molecular level peptide structure and the nanoscale supra-molecular morphology. Based on this, it has been shown that alternate morphologies distinct from those observed with the gel forming peptides, such as non-twisting laminates or tube

  18. 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

  19. Functional metal-bipyridinium frameworks: self-assembly and applications.

    PubMed

    Sun, Jian-Ke; Zhang, Jie

    2015-11-28

    Metal-organic frameworks (MOFs) as newly emerged materials have experienced rapid development in the last few years. The modular synthesis procedure allows integrating functional groups in their frameworks with varied applications. Due to the easy modification of the backbone and highly charged characteristics with interesting electron-active properties, the use of bipyridinium derivatives as synthons for the fabrication of functional metal-bipyridinium frameworks (MBPFs) has attracted increased interest over the past few years. Various bipyridinium-bearing ligands have been designed for the construction of functional MBPFs, and some of them present intriguing properties for potential applications including photochromism and photoswitching, sensing, molecule adsorption and separation. This perspective aims to highlight the recent progress in this area, and seeks to uncover promising ideas that will underscore future advancements at both the fundamental and applied levels. PMID:26477671

  20. An adaptive biointerface from self-assembled functional peptides for tissue engineering.

    PubMed

    Li, Li-Li; Qi, Guo-Bin; Yu, Faquan; Liu, Shi-Jie; Wang, Hao

    2015-05-27

    A self-assembled peptide-based biointerface is demonstrated with triple functional layers that can significantly improve the tissue self-healing process or prevent biofilm-mediated chronic inflammation. This smart biointerface is composed of three functional moieties (i.e., a cell-adhesive peptide, an infectious environment-responsive peptide, and an antifouling hexaethylene glycol (HEG) layer), and the resulting interface coated onto prosthetic replacements can smartly respond to the surrounding physiological or pathological microenvironment. PMID:25874994

  1. Self-Assembled Functionalized Graphene Nanoribbons from Carbon Nanotubes

    PubMed Central

    Cunha, Eunice; Proença, Maria Fernanda; Costa, Florinda; Fernandes, António J; Ferro, Marta A C; Lopes, Paulo E; González-Debs, Mariam; Melle-Franco, Manuel; Deepak, Francis Leonard; Paiva, Maria C

    2015-01-01

    Graphene nanoribbons (GNR) were generated in ethanol solution by unzipping pyrrolidine-functionalized carbon nanotubes under mild conditions. Evaporation of the solvent resulted in regular few-layer stacks of graphene nanoribbons observed by transmission electron microscopy (TEM) and X-ray diffraction. The experimental interlayer distance (0.49–0.56 nm) was confirmed by computer modelling (0.51 nm). Computer modelling showed that the large interlayer spacing (compared with graphite) is due to the presence of the functional groups and depends on their concentration. Stacked nanoribbons were observed to redissolve upon solvent addition. This preparation method could allow the fine-tuning of the interlayer distances by controlling the number and/or the nature of the chemical groups in between the graphene layers. PMID:25969808

  2. Self-assembly of intramolecular charge-transfer compounds into functional molecular systems.

    PubMed

    Li, Yongjun; Liu, Taifeng; Liu, Huibiao; Tian, Mao-Zhong; Li, Yuliang

    2014-04-15

    Highly polarized compounds exhibiting intramolecular charge transfer (ICT) are used widely as nonlinear optical (NLO) materials and red emitters and in organic light emitting diodes. Low-molecular-weight donor/acceptor (D/A)-substituted ICT compounds are ideal candidates for use as the building blocks of hierarchically structured, multifunctional self-assembled supramolecular systems. This Account describes our recent studies into the development of functional molecular systems with well-defined self-assembled structures based on charge-transfer (CT) interactions. From solution (sensors) to the solid state (assembled structures), we have fully utilized intrinsic and stimulus-induced CT interactions to construct these functional molecular systems. We have designed some organic molecules capable of ICT, with diversity and tailorability, that can be used to develop novel self-assembled materials. These ICT organic molecules are based on a variety of simple structures such as perylene bisimide, benzothiadiazole, tetracyanobutadiene, fluorenone, isoxazolone, BODIPY, and their derivatives. The degree of ICT is influenced by the nature of both the bridge and the substituents. We have developed new methods to synthesize ICT compounds through the introduction of heterocycles or heteroatoms to the π-conjugated systems or through extending the conjugation of diverse aromatic systems via another aromatic ring. Combining these ICT compounds featuring different D/A units and different degrees of conjugation with phase transfer methodologies and solvent-vapor techniques, we have self-assembled various organic nanostructures, including hollow nanospheres, wires, tubes, and ribbonlike architectures, with controllable morphologies and sizes. For example, we obtained a noncentrosymmetric microfiber structure that possessed a permanent dipole along its fibers' long axis and a transition dipole perpendicular to it; the independent NLO responses of this material can be separated and

  3. Self-assembling functionalized nanopeptides for immediate hemostasis and accelerative liver tissue regeneration

    NASA Astrophysics Data System (ADS)

    Cheng, Tzu-Yun; Wu, Hsi-Chin; Huang, Ming-Yuan; Chang, Wen-Han; Lee, Chao-Hsiung; Wang, Tzu-Wei

    2013-03-01

    Traumatic injury or surgery may trigger extensive bleeding. However, conventional hemostatic methods have limited efficacy and may cause surrounding tissue damage. In this study, we use self-assembling peptides (SAPs) and specifically extend fragments of functional motifs derived from fibronectin and laminin to evaluate the capability of these functionalized SAPs in the effect of hemostasis and liver tissue regeneration. From the results, these peptides can self-assemble into nanofibrous network structure and gelate into hydrogel with pH adjustment. In animal studies, the efficacy of hemostasis is achieved immediately within seconds in a rat liver model. The histological analyses by hematoxylin-eosin stain and immunohistochemistry reveal that SAPs with these functionalized motifs significantly enhance liver tissue regeneration. In brief, these SAPs may have potential as pharmacological tools to extensively advance clinical therapeutic applications in hemostasis and tissue regeneration in the field of regenerative medicine.Traumatic injury or surgery may trigger extensive bleeding. However, conventional hemostatic methods have limited efficacy and may cause surrounding tissue damage. In this study, we use self-assembling peptides (SAPs) and specifically extend fragments of functional motifs derived from fibronectin and laminin to evaluate the capability of these functionalized SAPs in the effect of hemostasis and liver tissue regeneration. From the results, these peptides can self-assemble into nanofibrous network structure and gelate into hydrogel with pH adjustment. In animal studies, the efficacy of hemostasis is achieved immediately within seconds in a rat liver model. The histological analyses by hematoxylin-eosin stain and immunohistochemistry reveal that SAPs with these functionalized motifs significantly enhance liver tissue regeneration. In brief, these SAPs may have potential as pharmacological tools to extensively advance clinical therapeutic applications

  4. CO2-responsive polymeric materials: synthesis, self-assembly, and functional applications.

    PubMed

    Darabi, Ali; Jessop, Philip G; Cunningham, Michael F

    2016-08-01

    CO2 is an ideal trigger for switchable or stimuli-responsive materials because it is benign, inexpensive, green, abundant, and does not accumulate in the system. Many different CO2-responsive materials including polymers, latexes, solvents, solutes, gels, surfactants, and catalysts have been prepared. This review focuses on the preparation, self-assembly, and functional applications of CO2-responsive polymers. Detailed discussion is provided on the synthesis of CO2-responsive polymers, in particular using reversible deactivation radical polymerization (RDRP), formerly known as controlled/living radical polymerization (CLRP), a powerful technique for the preparation of well-defined (co)polymers with precise control over molecular weight distribution, chain-end functional groups, and polymer architectural design. Self-assembly in aqueous dispersed media is highlighted as well as emerging potential applications. PMID:27284587

  5. M13 Bacteriophage-Based Self-Assembly Structures and Their Functional Capabilities

    PubMed Central

    Moon, Jong-Sik; Kim, Won-Geun; Kim, Chuntae; Park, Geun-Tae; Heo, Jeong; Yoo, So Y; Oh, Jin-Woo

    2015-01-01

    Controlling the assembly of basic structural building blocks in a systematic and orderly fashion is an emerging issue in various areas of science and engineering such as physics, chemistry, material science, biological engineering, and electrical engineering. The self-assembly technique, among many other kinds of ordering techniques, has several unique advantages and the M13 bacteriophage can be utilized as part of this technique. The M13 bacteriophage (Phage) can easily be modified genetically and chemically to demonstrate specific functions. This allows for its use as a template to determine the homogeneous distribution and percolated network structures of inorganic nanostructures under ambient conditions. Inexpensive and environmentally friendly synthesis can be achieved by using the M13 bacteriophage as a novel functional building block. Here, we discuss recent advances in the application of M13 bacteriophage self-assembly structures and the future of this technology. PMID:26146494

  6. Self-assembly of diphenylalanine backbone homologues and their combination with functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Dinesh, Bhimareddy; Squillaci, Marco A.; Ménard-Moyon, Cécilia; Samorì, Paolo; Bianco, Alberto

    2015-09-01

    The integration of carbon nanotubes (CNTs) into organized nanostructures is of great interest for applications in materials science and biomedicine. In this work we studied the self-assembly of β and γ homologues of diphenylalanine peptides under different solvent and pH conditions. We aimed to investigate the role of peptide backbone in tuning the formation of different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, β and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on the self-assembly. The variation of the pH allowed to transform the nanofibers into spherical structures. Moreover, the co-assembly of β and γ peptides with carbon nanotubes covalently functionalized with the same peptide generated unique dendritic assemblies. This comparative study on self-assembly using diphenylalanine backbone homologues and of the co-assembly with CNT covalent conjugates is the first example exploring the capacity of β and γ peptides to adopt precise nanostructures, particularly in combination with carbon nanotubes. The dendritic organization obtained by mixing carbon nanotubes and peptides might find interesting applications in tissue engineering and neuronal interfacing.The integration of carbon nanotubes (CNTs) into organized nanostructures is of great interest for applications in materials science and biomedicine. In this work we studied the self-assembly of β and γ homologues of diphenylalanine peptides under different solvent and pH conditions. We aimed to investigate the role of peptide backbone in tuning the formation of different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, β and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on the self-assembly. The variation of the pH allowed to

  7. Steric environment around acetylcholine head groups of bolaamphiphilic nanovesicles influences the release rate of encapsulated compounds

    PubMed Central

    Stern, Avital; Guidotti, Matteo; Shaubi, Eleonora; Popov, Mary; Linder, Charles; Heldman, Eliahu; Grinberg, Sarina

    2014-01-01

    Two bolaamphiphilic compounds with identical acetylcholine (ACh) head groups, but with different lengths of an alkyl chain pendant adjacent to the head group, as well as differences between their hydrophobic skeleton, were investigated for their ability to self-assemble into vesicles that release their encapsulated content upon hydrolysis of their head groups by acetylcholinesterase (AChE). One of these bolaamphiphiles, synthesized from vernolic acid, has an alkyl chain pendant of five methylene groups, while the other, synthesized from oleic acid, has an alkyl chain pendant of eight methylene groups. Both bolaamphiphiles formed stable spherical vesicles with a diameter of about 130 nm. The ACh head groups of both bolaamphiphiles were hydrolyzed by AChE, but the hydrolysis rate was significantly faster for the bolaamphiphile with the shorter aliphatic chain pendant. Likewise, upon exposure to AChE, vesicles made from the bolaamphiphile with the shorter alkyl chain pendant released their encapsulated content faster than vesicles made from the bolaamphiphile with the longer alkyl chain pendant. Our results suggest that the steric environment around the ACh head group of bolaamphiphiles is a major factor affecting the hydrolysis rate of the head groups by AChE. Attaching an alkyl chain to the bolaamphiphile near the ACh head group allows self-assembled vesicles to form with a controlled release rate of the encapsulated materials, whereas shorter alkyl chains enable a faster head group hydrolysis, and consequently faster release, than longer alkyl chains. This principle may be implemented in the design of bolaamphiphiles for the formation of vesicles for drug delivery with desired controlled release rates. PMID:24531296

  8. Self-assembly of functional molecules into 1D crystalline nanostructures.

    PubMed

    Guo, Yanbing; Xu, Liang; Liu, Huibiao; Li, Yongjun; Che, Chi-Ming; Li, Yuliang

    2015-02-01

    Self-assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high-performance devices. One-dimensional (1D) crystalline nanostructures, especially molecule-composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self-assembled nanostructures of functional molecules, which include both a small molecule-derived and a polymer-based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self-assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors. PMID:25523368

  9. Biological colloid engineering: Self-assembly of dipolar ferromagnetic chains in a functionalized biogenic ferrofluid.

    PubMed

    Ruder, Warren C; Hsu, Chia-Pei D; Edelman, Brent D; Schwartz, Russell; Leduc, Philip R

    2012-08-01

    We have studied the dynamic behavior of nanoparticles in ferrofluids consisting of single-domain, biogenic magnetite (Fe(3)O(4)) isolated from Magnetospirillum magnetotacticum (MS-1). Although dipolar chains form in magnetic colloids in zero applied field, when dried upon substrates, the solvent front disorders nanoparticle aggregation. Using avidin-biotin functionalization of the particles and substrate, we generated self-assembled, linear chain motifs that resist solvent front disruption in zero-field. The engineered self-assembly process we describe here provides an approach for the creation of ordered magnetic structures that could impact fields ranging from micro-electro-mechanical systems development to magnetic imaging of biological structures. PMID:22952408

  10. Self-Assembly of a Functional Oligo(Aniline)-Based Amphiphile into Helical Conductive Nanowires

    PubMed Central

    2015-01-01

    A tetra(aniline)-based cationic amphiphile, TANI-NHC(O)C5H10N(CH3)3+Br– (TANI-PTAB) was synthesized, and its emeraldine base (EB) state was found to self-assemble into nanowires in aqueous solution. The observed self-assembly is described by an isodesmic model, as shown by temperature-dependent UV–vis investigations. Linear dichroism (LD) studies, combined with computational modeling using time-dependent density functional theory (TD-DFT), suggests that TANI-PTAB molecules are ordered in an antiparallel arrangement within nanowires, with the long axis of TANI-PTAB arranged perpendicular to the nanowire long axis. Addition of either S- or R- camphorsulfonic acid (CSA) to TANI-PTAB converted TANI to the emeraldine salt (ES), which retained the ability to form nanowires. Acid doping of TANI-PTAB had a profound effect on the nanowire morphology, as the CSA counterions’ chirality translated into helical twisting of the nanowires, as observed by circular dichroism (CD). Finally, the electrical conductivity of CSA-doped helical nanowire thin films processed from aqueous solution was 2.7 mS cm–1. The conductivity, control over self-assembled 1D structure and water-solubility demonstrate these materials’ promise as processable and addressable functional materials for molecular electronics, redox-controlled materials and sensing. PMID:26496508

  11. Pathway Complexity in the Enantioselective Self-Assembly of Functional Carbonyl-Bridged Triarylamine Trisamides.

    PubMed

    Haedler, Andreas T; Meskers, Stefan C J; Zha, R Helen; Kivala, Milan; Schmidt, Hans-Werner; Meijer, E W

    2016-08-24

    Functional supramolecular systems like carbonyl-bridged triarylamine (CBT) trisamides are known for their long-range energy transport at room temperature. Understanding the complex self-assembly processes of this system allows for control over generated structures using controlled supramolecular polymerization. Here, we present two novel CBT trisamides with (S)- or (R)-chiral side chains which show a two-pathway self-assembly behavior in solution. Depending on the thermal profile during the self-assembly process, two different stable states are obtained under otherwise identical conditions. A kinetically trapped state A is reached upon cooling to 7 °C, via a proposed isodesmic process. In addition, there is a thermodynamically stable state B at 7 °C that is induced by first undercooling to -5 °C, via a nucleation-elongation mechanism. In both cases, helical supramolecular aggregates comprising H-aggregated CBTs are formed. Additionally, controlled supramolecular polymerization was achieved by mixing the two different states (A and B) from the same enantiomer, leading to a conversion of the kinetically trapped state to the thermodynamically stable state. This process is highly enantioselective, as no conversion is observed if the two states consist of opposite enantiomers. We thus show the importance and opportunities emerging from understanding the pathway complexity of functional supramolecular systems. PMID:27462007

  12. Surface functional modification of self-assembled insulin nanospheres for improving intestinal absorption.

    PubMed

    Shi, Kai; Fang, Yan; Kan, Qiming; Zhao, Jian; Gan, Yanqiu; Liu, Zheng

    2015-03-01

    In this work we fabricated therapeutic protein drugs such as insulin as free-carrier delivery system to improve their oral absorption efficiency. The formulation involved self-assembly of insulin into nanospheres (INS) by a novel thermal induced phase separation method. In consideration of harsh environment in gastrointestinal tract, surface functional modification of INS with ɛ-poly-L-lysine (EPL) was employed to form a core-shell structure (INS@EPL) and protect them from too fast dissociation before their arriving at target uptake sites. Both INS and INS@EPL were characterized as uniformly spherical particles with mean diameter size of 150-300 nm. The process of transient thermal treatment did not change their biological potency retention significantly. In vitro dissolution studies showed that shell cross-linked of INS with EPL improved the release profiles of insulin from the self-assembled nanospheres at intestinal pH. Confocal microscopy visualization and transport experiments proved the enhanced paracellular permeability of INS@EPL in Caco-2 cells. Compared to that of INS, enteral administration of INS@EPL at 20 IU/kg resulted in more significant hypoglycemic effects in diabetic rats up to 12 h. Accordingly, the results indicated that surface functional modification of self-assembled insulin nanospheres with shell cross-linked polycationic peptide could be a promising candidate for oral therapeutic protein delivery. PMID:25433129

  13. Molecular Dynamics Studies of Self-Assembling Biomolecules and DNA-functionalized Gold Nanoparticles

    NASA Astrophysics Data System (ADS)

    Cho, Vince Y.

    This thesis is organized as following. In Chapter 2, we use fully atomistic MD simulations to study the conformation of DNA molecules that link gold nanoparticles to form nanoparticle superlattice crystals. In Chapter 3, we study the self-assembly of peptide amphiphiles (PAs) into a cylindrical micelle fiber by using CGMD simulations. Compared to fully atomistic MD simulations, CGMD simulations prove to be computationally cost-efficient and reasonably accurate for exploring self-assembly, and are used in all subsequent chapters. In Chapter 4, we apply CGMD methods to study the self-assembly of small molecule-DNA hybrid (SMDH) building blocks into well-defined cage-like dimers, and reveal the role of kinetics and thermodynamics in this process. In Chapter 5, we extend the CGMD model for this system and find that the assembly of SMDHs can be fine-tuned by changing parameters. In Chapter 6, we explore superlattice crystal structures of DNA-functionalized gold nanoparticles (DNA-AuNP) with the CGMD model and compare the hybridization.

  14. Self-assembly of diphenylalanine backbone homologues and their combination with functionalized carbon nanotubes.

    PubMed

    Dinesh, Bhimareddy; Squillaci, Marco A; Ménard-Moyon, Cécilia; Samorì, Paolo; Bianco, Alberto

    2015-10-14

    The integration of carbon nanotubes (CNTs) into organized nanostructures is of great interest for applications in materials science and biomedicine. In this work we studied the self-assembly of β and γ homologues of diphenylalanine peptides under different solvent and pH conditions. We aimed to investigate the role of peptide backbone in tuning the formation of different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, β and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on the self-assembly. The variation of the pH allowed to transform the nanofibers into spherical structures. Moreover, the co-assembly of β and γ peptides with carbon nanotubes covalently functionalized with the same peptide generated unique dendritic assemblies. This comparative study on self-assembly using diphenylalanine backbone homologues and of the co-assembly with CNT covalent conjugates is the first example exploring the capacity of β and γ peptides to adopt precise nanostructures, particularly in combination with carbon nanotubes. The dendritic organization obtained by mixing carbon nanotubes and peptides might find interesting applications in tissue engineering and neuronal interfacing. PMID:26359907

  15. Active colloids at liquid-liquid interfaces: dynamic self-assembly and functionality

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor

    2012-02-01

    Self-assembled materials must actively consume energy and remain out of equilibrium in order to support structural complexity and functional diversity. Colloids of interacting particles suspended at liquid-liquid interfaces and maintained out of equilibrium by external alternating electromagnetic fields develop nontrivial collective dynamics and self-assembly. We use ferromagnetic colloidal micro-particles (so the magnetic moment is fixed in each particle and interactions between colloids is highly anisotropic and directional) suspended over an interface of two immiscible liquids and energized by vertical alternating magnetic fields to demonstrate novel dynamic and active self-assembled structures (``asters'') which are not accessible through thermodynamic assembly. Structures are attributed to the interplay between surface waves, generated at the liquid/liquid interface by the collective response of magnetic microparticles to the alternating magnetic field, and hydrodynamic fields induced in the boundary layers of both liquids forming the interface. Two types of magnetic order are reported. We demonstrate that asters develop self-propulsion in the presence of a small in-plane dc magnetic field. We show that asters can capture, transport, and position target microparticles.

  16. Cationic Bolaamphiphiles for Gene Delivery

    NASA Astrophysics Data System (ADS)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  17. Synthesis of Functionalized Mono-, Bis-, and Trisethynyltriptycenes for One-Dimensional Self-Assembly on Surfaces.

    PubMed

    Sirven, Agnès M; Garbage, Romain; Qiao, Yun; Kammerer, Claire; Rapenne, Gwénaël

    2015-10-12

    This paper describes the synthesis of triptycene-based building blocks that are able to interact through hydrogen bonds to form one-dimensional self-assembled motifs on surfaces. We designed 9,10-diethynyltriptycene derivatives functionalized at the ethynyl end groups by a variety of hydrogen-bonding groups for homomolecular recognition and complementary building blocks for heteromolecular recognition. We also present the synthesis of bis- and trisethynyltriptycenes with terminal alkyne functional groups available for on-surface azide-alkyne cycloaddition reaction to expand the potential of the triptycene building block. PMID:26334027

  18. Self-assemblies of cationic porphyrins with functionalized water-soluble single-walled carbon nanotubes.

    PubMed

    Kubát, Pavel; Lang, Kamil; Jandal, Pavel; Frank, Ota; Matulková, Irena; Sýkora, Jan; Civis, Svatopluk; Hof, Martin; Kavan, Ladislav

    2009-10-01

    5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin, 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrin, and 5,10,15,20-tetrakis(4-trimethylammoniophenyl)porphyrin form self-assemblies with single-walled carbon nanotubes (SWNT) functionalized by polyaminobenzene sulfonic acid. Both steady-state and time-resolved emission studies revealed efficient quenching of the excited singlet states of the porphyrins. Atomic force microscopy, fluorescence confocal microscopy, and fluorescence lifetime imaging allowed the visualization of individual bundles of SWNTs and the differentiation of porphyrin molecules at specific binding sites of SWNT. PMID:19908455

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    Smart gating membranes, inspired by the gating function of ion channels across cell membranes, are artificial membranes composed of non-responsive porous membrane substrates and responsive gates in the membrane pores that are able to dramatically regulate the trans-membrane transport of substances in response to environmental stimuli. Easy fabrication, high flux, significant response and strong mechanical strength are critical for the versatility of such smart gating membranes. Here we show a novel and simple strategy for one-step fabrication of smart gating membranes with three-dimensionally interconnected networks of functional gates, by self-assembling responsive nanogels on membrane pore surfaces in situ during a vapor-induced phase separation process for membrane formation. The smart gating membranes with in situ self-assembled responsive nanogels as functional gates show large flux, significant response and excellent mechanical property simultaneously. Because of the easy fabrication method as well as the concurrent enhancement of flux, response and mechanical property, the proposed smart gating membranes will expand the scope of membrane applications, and provide ever better performances in their applications.

  20. Self-Assembly and Molecular Dynamics of Peptide-Functionalized Polyphenylene Dendrimers

    SciTech Connect

    Mondeshki,M.; Milhov, G.; Graf, R.; Spiess, H.; Mullen, K.; Papadopoulos, P.; Gitsas, A.; Floudas, G.

    2006-01-01

    The self-assembly mechanism and the associated molecular dynamics are studied for a series of poly-L-lysine-functionalized polyphenylene dendrimer melts as a function of the core size (generation), functionality, and polypeptide length using X-rays, solid-state NMR, calorimetry, and dielectric spectroscopy. A striking dependence of the polyphenylene self-assembly on the poly-L-lysine length is shown. In addition, the type ({alpha}helix/{beta}-sheet) of peptide secondary structure is controlled by the packing restrictions imposed by the polyphenylene core. We show that constrained poly-L-lysines can adopt different secondary structures from their linear analogues. The dynamic investigation revealed significant mobility associated solely with the polypeptide through three processes: a glass transition, a slower process associated with the relaxation of {alpha}-helical segments, and a glassy mode whose origin could be resolved by site-specific solid-state NMR techniques. Solid-state NMR studies further indicated a mobility gradient in going from the rigid peptide backbone to the side chains.

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

    PubMed Central

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

    2015-01-01

    Smart gating membranes, inspired by the gating function of ion channels across cell membranes, are artificial membranes composed of non-responsive porous membrane substrates and responsive gates in the membrane pores that are able to dramatically regulate the trans-membrane transport of substances in response to environmental stimuli. Easy fabrication, high flux, significant response and strong mechanical strength are critical for the versatility of such smart gating membranes. Here we show a novel and simple strategy for one-step fabrication of smart gating membranes with three-dimensionally interconnected networks of functional gates, by self-assembling responsive nanogels on membrane pore surfaces in situ during a vapor-induced phase separation process for membrane formation. The smart gating membranes with in situ self-assembled responsive nanogels as functional gates show large flux, significant response and excellent mechanical property simultaneously. Because of the easy fabrication method as well as the concurrent enhancement of flux, response and mechanical property, the proposed smart gating membranes will expand the scope of membrane applications, and provide ever better performances in their applications. PMID:26434387

  2. Chemical Functionalization, Self-Assembly, and Applications of Nanomaterials and Nanocomposites

    SciTech Connect

    Jiao, Tifeng; Yan, Xingbin; Balan, Lavinia; Stepanov, Andrey; Chen, Xinqing; Hu, Michael Z.

    2014-01-01

    This special issue addresses the research studies on chemical functionalization, self-assembly, and applications of nanomaterials and nanocomposites. It contains twentyfour articles including two reviews and twenty-two research articles. It is used to create new functional nanomaterials and nanocomposites with a variety of sizes and morphologies such as Zn/Al layered double hydroxide, tin oxide nanowires, FeOOH-modified anion resin, Au nanoclusters silica composite nanospheres, Ti-doped ZnO sol-composite films, TiO2/ZnO composite, graphene oxide nanocomposites, LiFePO4/C nanocomposites, and chitosan nanoparticles. These nanomaterials and nanocomposites have widespread applications in tissue engineering, antitumor, sensors, photoluminescence, electrochemical, and catalytic properties. In addition, this themed issue includes some research articles about self-assembly systems covering organogels and Langmuir films. Furthermore, B. Blasiak et al. performed a literature survey on the recent advances in production, functionalization, toxicity reduction, and application of nanoparticles in cancer diagnosis, treatment, and treatment monitoring. P. Colson et al. performed a literature survey on the recent advances in nanosphere lithography due to its compatibility with wafer-scale processes as well as its potential to manufacture a wide variety of homogeneous one-, two-, or three-dimensional nanostructures.

  3. Hierarchical Self-Assembly of Peptide Amphiphiles: Form and Function at Multiple Length Scales

    NASA Astrophysics Data System (ADS)

    Zha, Runye Helen

    assembled with HA into membranes that may be used as PA delivery vehicles in adjuvant cancer therapy. Membranes exhibiting non-fibrous microstructure can act as sustained release materials triggered by enzymatic degradation, while membranes exhibiting aligned-fiber microstructure may act as materials with only surface-localized cytotoxicity. Ultimately, these functions are directed by PA chemical structure with nanoscale self-assembly as an intermediate step, thus further demonstrating that material structure and properties can be tailored using molecular design by considering the interplay of supramolecular interactions.

  4. Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

    PubMed

    Xia, Zhenyuan; Leonardi, Francesca; Gobbi, Marco; Liu, Yi; Bellani, Vittorio; Liscio, Andrea; Kovtun, Alessandro; Li, Rongjin; Feng, Xinliang; Orgiu, Emanuele; Samorì, Paolo; Treossi, Emanuele; Palermo, Vincenzo

    2016-07-26

    We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite. PMID:27299370

  5. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  6. Controlled release of functional proteins through designer self-assembling peptide nanofiber hydrogel scaffold

    PubMed Central

    Koutsopoulos, Sotirios; Unsworth, Larry D.; Nagai, Yusuke; Zhang, Shuguang

    2009-01-01

    The release kinetics for a variety of proteins of a wide range of molecular mass, hydrodynamic radii, and isoelectric points through a nanofiber hydrogel scaffold consisting of designer self-assembling peptides were studied by using single-molecule fluorescence correlation spectroscopy (FCS). In contrast to classical diffusion experiments, the single-molecule approach allowed for the direct determination of diffusion coefficients for lysozyme, trypsin inhibitor, BSA, and IgG both inside the hydrogel and after being released into the solution. The results of the FCS analyses and the calculated pristine in-gel diffusion coefficients were compared with the values obtained from the Stokes–Einstein equation, Fickian diffusion models, and the literature. The release kinetics suggested that protein diffusion through nanofiber hydrogels depended primarily on the size of the protein. Protein diffusivities decreased, with increasing hydrogel nanofiber density providing a means of controlling the release kinetics. Secondary and tertiary structure analyses and biological assays of the released proteins showed that encapsulation and release did not affect the protein conformation and functionality. Our results show that this biocompatible and injectable designer self-assembling peptide hydrogel system may be useful as a carrier for therapeutic proteins for sustained release applications. PMID:19273853

  7. Self-assembled insect muscle bioactuators with long term function under a range of environmental conditions

    PubMed Central

    Baryshyan, A.L.; Domigan, L.J.; Hunt, B.; Trimmer, B.A.; Kaplan, D. L.

    2014-01-01

    The use of mammalian muscles as device actuators is severely limited by their sensitivity to environmental conditions and short lifetime. To overcome these limitations insect muscle stem cells were used to generate organized 3D muscle constructs with significant enhancements in environmental tolerance and long term function. These tissues self-assembled, self-repaired, survived for months in culture without media replenishment and produced stresses of up to 2 kPa, all under ambient conditions. The muscle tissues continued to function for days even under biologically extreme temperature and pH. Furthermore, the dimensions and geometry of these tissues can be easily scaled to MEMS or meso-scale devices. The versatility, environmental hardiness and long term function provide a new path forward for biological actuators for device needs. PMID:25285210

  8. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets.

    PubMed

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. PMID:27102889

  9. Amphiphilic invertible polymers: Self-assembly into functional materials driven by environment polarity

    NASA Astrophysics Data System (ADS)

    Hevus, Ivan

    Stimuli-responsive polymers adapt to environmental changes by adjusting their chain conformation in a fast and reversible way. Responsive polymeric materials have already found use in electronics, coatings industry, personal care, and bio-related areas. The current work aims at the development of novel responsive functional polymeric materials by manipulating environment-dependent self-assembly of a new class of responsive macromolecules strategically designed in this study,—amphiphilic invertible polymers (AIPs). Environment-dependent micellization and self-assembly of three different synthesized AIP types based on poly(ethylene glycol) as a hydrophilic fragment and varying hydrophobic constituents was demonstrated in polar and nonpolar solvents, as well as on the surfaces and interfaces. With increasing concentration, AIP micelles self-assemble into invertible micellar assemblies composed of hydrophilic and hydrophobic domains. Polarity-responsive properties of AIPs make invertible micellar assemblies functional in polar and nonpolar media including at interfaces. Thus, invertible micellar assemblies solubilize poorly soluble substances in their interior in polar and nonpolar solvents. In a polar aqueous medium, a novel stimuli-responsive mechanism of drug release based on response of AIP-based drug delivery system to polarity change upon contact with the target cell has been established using invertible micellar assemblies loaded with curcumin, a phytochemical drug. In a nonpolar medium, invertible micellar assemblies were applied simultaneously as nanoreactors and stabilizers for size-controlled synthesis of silver nanoparticles stable in both polar and nonpolar media. The developed amphiphilic nanosilver was subsequently used as seeds to promote anisotropic growth of CdSe semiconductor nanoparticles that have potential in different applications ranging from physics to medicine. Amphiphilic invertible polymers were shown to adsorb on the surface of silica

  10. A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111).

    PubMed

    Mete, Ersen; Yılmaz, Ayşen; Danışman, Mehmet Fatih

    2016-05-14

    Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, (5 × 5) was found to be more stable than . PMID:27108565

  11. Bioengineering mini functional thymic units with EAK16-II/EAKIIH6 self-assembling hydrogel.

    PubMed

    Tajima, Asako; Liu, Wen; Pradhan, Isha; Bertera, Suzanne; Bagia, Christina; Trucco, Massimo; Meng, Wilson S; Fan, Yong

    2015-09-01

    Herein, we highlight the technical feasibility of generating a functional mini thymus with a novel hydrogel system, based on a peptide-based self-assembly platform that can induce the formation of 3-D thymic epithelial cell (TEC) clusters. Amphiphilic peptide EAK16-II co-assembled with its histidinylated analogue EAKIIH6 into beta-sheet fibrils. When adaptor complexes (recombinant protein A/G molecules loaded with both anti-His and anti-EpCAM IgGs) were added to the mix, TECs were tethered to the hydrogel and formed 3-D mini clusters. TECs bound to the hydrogel composites retained their molecular properties; and when transplanted into athymic nude mice, they supported the development of functional T-cells. These mini thymic units of TECs can be useful in clinical applications to reconstitute T-cell adaptive immunity. PMID:25805654

  12. Construction of supramolecular organogels and hydrogels from crown ether based unsymmetric bolaamphiphiles.

    PubMed

    Gao, Lingyan; Xu, Donghua; Zheng, Bo

    2014-10-18

    A bolaamphiphilic low-molecular-weight gelator based on crown ether, which could self-assemble into organogels and hydrogels, was prepared. The contribution of each part of the structure to the gelation property was investigated by designing a series of analogues. A simple framework (crown ether-hydrophobic linkage-ammonium salt) was proposed. PMID:25174940

  13. Advantages and limitations of density functional theory in block copolymer directed self-assembly

    NASA Astrophysics Data System (ADS)

    Liu, Jimmy; Laachi, Nabil; Delaney, Kris T.; Fredrickson, Glenn H.

    2015-03-01

    A major challenge in the application of block copolymer directed self-assembly (DSA) to advanced lithography is the exploration of large design spaces, including the selection of confinement shape and size, surface chemistry to affect wetting conditions, copolymer chain length and block fraction. To sweep such large spaces, a computational model is ideally both fast and accurate. In this study, we investigate various incarnations of the density functional theory (DFT) approach and evaluate their suitability to DSA applications. We introduce a new optimization scheme to capitalize on the speed advantages of DFT, while minimizing loss of accuracy relative to the benchmark of self-consistent field theory (SCFT). Although current DFT models afford a 100-fold reduction in computational complexity over SCFT, even the best optimized models fail to match SCFT density profiles and make extremely poor predictions of commensurability windows and defect energetics. These limitations suggest that SCFT will remain the gold standard for DSA simulations in the near future.

  14. Self-Assembly of Amphiphilic Anthracene-Functionalized β-Cyclodextrin (CD-AN) through Multi-Micelle Aggregation.

    PubMed

    Zhang, Yuannan; Xu, Hongjie; Ma, Xiaodong; Shi, Zixing; Yin, Jie; Jiang, Xuesong

    2016-06-01

    Multi-micelle aggregation (MMA) mechanism is widely acknowledged to explicate large spherical micelles self-assembly, but the process of MMA during self-assembly is hard to observe. Herein, a novel kind of strong, regular microspheres fabricated from self-assembly of amphiphilic anthracene-functionalized β-cyclodextrin (CD-AN) via Cu(I)-catalyzed azide-alkyne click reactions is reported. The obtained CD-AN amphiphiles can self-assemble in water from primary core-shell micelles to secondary aggregates with the diameter changing from several tens nm to around 600-700 nm via MMA process according to the images of scanning electron microscopy, transmission electron microscopy, and atomic force microscopy as well as the dynamic light scattering measurements, followed by further crosslinking through photo-dimerization of anthracene. What merits special attention is that such photo-crosslinked self-assemblies are able to disaggregate reversibly into primary nanoparticles when changing the solution conditions, which is benefited from the designed regular structure of CD-AN and the rigid ranging of anthracene during assembly, thus confirming the process of MMA. PMID:27145434

  15. Functional Materials for Microsystems: Smart Self-Assembled Photochromic Films: Final Report

    SciTech Connect

    BURNS, ALAN R.; SASAKI, DARRYL Y.; CARPICK, R.W.; SHELNUTT, JOHN A.; BRINKER, C. JEFFREY

    2001-11-01

    This project set out to scientifically-tailor ''smart'' interfacial films and 3-D composite nanostructures to exhibit photochromic responses to specific, highly-localized chemical and/or mechanical stimuli, and to integrate them into optical microsystems. The project involved the design of functionalized chromophoric self-assembled materials that possessed intense and environmentally-sensitive optical properties (absorbance, fluorescence) enabling their use as detectors of specific stimuli and transducers when interfaced with optical probes. The conjugated polymer polydiacetylene (PDA) proved to be the most promising material in many respects, although it had some drawbacks concerning reversibility. Throughout his work we used multi-task scanning probes (AFM, NSOM), offering simultaneous optical and interfacial force capabilities, to actuate and characterize the PDA with localized and specific interactions for detailed characterization of physical mechanisms and parameters. In addition to forming high quality mono-, bi-, and tri-layers of PDA via Langmuir-Blodgett deposition, we were successful in using the diacetylene monomer precursor as a surfactant that directed the self-assembly of an ordered, mesostructured inorganic host matrix. Remarkably, the diacetylene was polymerized in the matrix, thus providing a PDA-silica composite. The inorganic matrix serves as a perm-selective barrier to chemical and biological agents and provides structural support for improved material durability in microsystems. Our original goal was to use the composite films as a direct interface with microscale devices as optical elements (e.g., intracavity mirrors, diffraction gratings), taking advantage of the very high sensitivity of device performance to real-time dielectric changes in the films. However, our optical physics colleagues (M. Crawford and S. Kemme) were unsuccessful in these efforts, mainly due to the poor optical quality of the composite films.

  16. Self-assembled monolayers based spintronics: from ferromagnetic surface functionalization to spin-dependent transport

    NASA Astrophysics Data System (ADS)

    Tatay, Sergio; Galbiati, Marta; Delprat, Sophie; Barraud, Clément; Bouzehouane, Karim; Collin, Sophie; Deranlot, Cyrile; Jacquet, Eric; Seneor, Pierre; Mattana, Richard; Petroff, Frédéric

    2016-03-01

    Chemically functionalized surfaces are studied for a wide range of applications going from medicine to electronics. Whereas non-magnetic surfaces have been widely studied, functionalization of magnetic surfaces is much less common and has almost never been used for spintronics applications. In this article we present the functionalization of La2/3Sr1/3MnO3, a ferromagnetic oxide, with self-assembled monolayers for spintronics. La2/3Sr1/3MnO3 is the prototypical half-metallic manganite used in spintronics studies. First, we show that La2/3Sr1/3MnO3 can be functionalized by alkylphosphonic acid molecules. We then emphasize the use of these functionalized surfaces in spintronics devices such as magnetic tunnel junctions fabricated using a nano-indentation based lithography technique. The observed exponential increase of tunnel resistance as a function of alkyl chain length is a direct proof of the successful connection of molecules to ferromagnetic electrodes. For all alkyl chains studied we obtain stable and robust tunnel magnetoresistance, with effects ranging from a few tens to 10 000%. These results show that functionalized electrodes can be integrated in spintronics devices and open the door to a molecular engineering of spintronics.

  17. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets

    NASA Astrophysics Data System (ADS)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M.; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. Electronic supplementary information (ESI) available: SEM, AFM and TEM characterization of PAA-MoS2 and PAM-MoS2 nanocomposites. More characterization and electrochemical properties of LBL films

  18. Noncovalent functionalization of solid-state nanopores via self-assembly of amphipols

    NASA Astrophysics Data System (ADS)

    Pérez-Mitta, Gonzalo; Burr, Loïc; Tuninetti, Jimena S.; Trautmann, Christina; Toimil-Molares, María Eugenia; Azzaroni, Omar

    2016-01-01

    In recent years there has been increasing interest in the development of new methods for conferring functional features to nanopore-based fluidic devices. In this work, we describe for the first time the noncovalent integration of amphoteric-amphipathic polymers, also known as ``amphipols'', into single conical nanopores in order to obtain signal-responsive chemical nanodevices. Highly-tapered conical nanopores were fabricated by single-sided chemical etching of polycarbonate foils. After etching, the surface of the conical nanopores was chemically modified, by first metallizing the surface via gold sputtering and then by amphiphilic self-assembly of the amphipol. The net charge of adsorbed amphipols was regulated via pH changes under the environmental conditions. The pH-dependent chemical equilibrium of the weak acidic and basic monomers facilitates the regulation of the ionic transport through the nanopore by adjusting the pH of the electrolyte solution. Our results demonstrate that functional amphipathic polymers are powerful building blocks for the surface modification of nanopores and might ultimately pave the way to a new means of integrating functional and/or responsive units within nanofluidic structures.In recent years there has been increasing interest in the development of new methods for conferring functional features to nanopore-based fluidic devices. In this work, we describe for the first time the noncovalent integration of amphoteric-amphipathic polymers, also known as ``amphipols'', into single conical nanopores in order to obtain signal-responsive chemical nanodevices. Highly-tapered conical nanopores were fabricated by single-sided chemical etching of polycarbonate foils. After etching, the surface of the conical nanopores was chemically modified, by first metallizing the surface via gold sputtering and then by amphiphilic self-assembly of the amphipol. The net charge of adsorbed amphipols was regulated via pH changes under the environmental

  19. Functionalized self-assembled monolayers on mesoporous silica nanoparticles with high surface coverage

    PubMed Central

    2012-01-01

    Mesoporous silica nanoparticles (MSNs) containing vinyl-, propyl-, isobutyl- and phenyl functionalized monolayers were reported. These functionalized MSNs were prepared via molecular self-assembly of organosilanes on the mesoporous supports. The relative surface coverage of the organic monolayers can reach up to 100% (about 5.06 silanes/nm2). These monolayer functionalize MSNs were analyzed by a number of techniques including transmission electron microscope, fourier transform infrared spectroscopy, X-ray diffraction pattern, cross-polarized Si29 MAS NMR spectroscopy, and nitrogen sorption measurement. The main elements (i.e., the number of absorbed water, the reactivity of organosilanes, and the stereochemistry of organosilane) that greatly affected the surface coverage and the quality of the organic functionalized monolayers on MSNs were fully discussed. The results show that the proper amount of physically absorbed water, the use of high active trichlorosilanes, and the functional groups with less steric hindrance are essential to generate MSNs with high surface coverage of monolayers. PMID:22720819

  20. End Groups of Functionalized Siloxane Oligomers Direct Block-Copolymeric or Liquid-Crystalline Self-Assembly Behavior.

    PubMed

    Zha, R Helen; de Waal, Bas F M; Lutz, Martin; Teunissen, Abraham J P; Meijer, E W

    2016-05-01

    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

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

    PubMed

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

    2015-11-01

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

  2. 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

  3. Self-Assembly Synthesis and Functionalization of Mesoporous Carbon Materials for Energy-Related Applications

    SciTech Connect

    Dai, Sheng

    2009-01-01

    Self-Assembly Synthesis and Functionalization of Mesoporous Carbon Materials for Energy-Related Applications Sheng Dai Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6201 Porous carbon materials are ubiquitous in separation, catalysis, and energy storage/conversion. Well-defined mesoporous carbon materials are essential for a number of the aforementioned applications. Ordered porous carbon materials have previously been synthesized using colloidal crystals and presynthesized mesoporous silicas as hard templates. The mesostructures of these carbon materials are connected via ultrathin carbon filaments and can readily collapse under high-temperature conditions. Furthermore, these hard-template methodologies are extremely difficult to adapt to the fabrication of large-scale ordered nanoporous films or monoliths with controlled pore orientations. More recently, my research group at the Oak Ridge National Laboratory and several others around the world have developed alternative methods for synthesis of highly ordered mesoporous carbons via self-assembly. Unlike the mesoporous carbons synthesized via hard-template methods, these mesoporous carbons are highly stable and can be graphitized at high temperature (>2800ᵒC) without significant loss of mesopores. The surface properties of these materials can be further tailored via surface functionalization. This seminar will provide an overview and perspective of the mesoporous carbon materials derived from soft-template synthesis and surface functionalization and their fascinating applications in catalysis, separation, and energy storage devices. Dr. Sheng Dai got his B.S. and M.S. degrees from Zhejiang University in 1984 and 1986, respectively. He subsequently obtained a PhD degree from the University of Tennessee, Knoxville in 1990. He is currently a Senior Staff Scientist and Group Leader of Nanomaterials Group and Center for Nanophase Materials Science of Oak Ridge National Laboratory and

  4. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Zheng, Yijun; Cui, Jiaxi; Ikeda, Taichi

    2015-11-01

    We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N3-SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N3-SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10-10 mol cm-2 and 4.6 ± 0.3 × 10-10 mol cm-2, respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N3-SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

  5. Noncovalent functionalization of solid-state nanopores via self-assembly of amphipols.

    PubMed

    Pérez-Mitta, Gonzalo; Burr, Loïc; Tuninetti, Jimena S; Trautmann, Christina; Toimil-Molares, María Eugenia; Azzaroni, Omar

    2016-01-21

    In recent years there has been increasing interest in the development of new methods for conferring functional features to nanopore-based fluidic devices. In this work, we describe for the first time the noncovalent integration of amphoteric-amphipathic polymers, also known as "amphipols", into single conical nanopores in order to obtain signal-responsive chemical nanodevices. Highly-tapered conical nanopores were fabricated by single-sided chemical etching of polycarbonate foils. After etching, the surface of the conical nanopores was chemically modified, by first metallizing the surface via gold sputtering and then by amphiphilic self-assembly of the amphipol. The net charge of adsorbed amphipols was regulated via pH changes under the environmental conditions. The pH-dependent chemical equilibrium of the weak acidic and basic monomers facilitates the regulation of the ionic transport through the nanopore by adjusting the pH of the electrolyte solution. Our results demonstrate that functional amphipathic polymers are powerful building blocks for the surface modification of nanopores and might ultimately pave the way to a new means of integrating functional and/or responsive units within nanofluidic structures. PMID:26676314

  6. Self-assembly and modular functionalization of three-dimensional crystals from oppositely charged proteins

    PubMed Central

    Liljeström, Ville; Mikkilä, Joona; Kostiainen, Mauri A.

    2014-01-01

    Multicomponent crystals and nanoparticle superlattices are a powerful approach to integrate different materials into ordered nanostructures. Well-developed, especially DNA-based, methods for their preparation exist, yet most techniques concentrate on molecular and synthetic nanoparticle systems in non-biocompatible environment. Here we describe the self-assembly and characterization of binary solids that consist of crystalline arrays of native biomacromolecules. We electrostatically assembled cowpea chlorotic mottle virus particles and avidin proteins into heterogeneous crystals, where the virus particles adopt a non-close-packed body-centred cubic arrangement held together by avidin. Importantly, the whole preparation process takes place at room temperature in a mild aqueous medium allowing the processing of delicate biological building blocks into ordered structures with lattice constants in the nanometre range. Furthermore, the use of avidin–biotin interaction allows highly selective pre- or post-functionalization of the protein crystals in a modular way with different types of functional units, such as fluorescent dyes, enzymes and plasmonic nanoparticles. PMID:25033911

  7. Self-assembly and modular functionalization of three-dimensional crystals from oppositely charged proteins

    NASA Astrophysics Data System (ADS)

    Liljeström, Ville; Mikkilä, Joona; Kostiainen, Mauri A.

    2014-07-01

    Multicomponent crystals and nanoparticle superlattices are a powerful approach to integrate different materials into ordered nanostructures. Well-developed, especially DNA-based, methods for their preparation exist, yet most techniques concentrate on molecular and synthetic nanoparticle systems in non-biocompatible environment. Here we describe the self-assembly and characterization of binary solids that consist of crystalline arrays of native biomacromolecules. We electrostatically assembled cowpea chlorotic mottle virus particles and avidin proteins into heterogeneous crystals, where the virus particles adopt a non-close-packed body-centred cubic arrangement held together by avidin. Importantly, the whole preparation process takes place at room temperature in a mild aqueous medium allowing the processing of delicate biological building blocks into ordered structures with lattice constants in the nanometre range. Furthermore, the use of avidin-biotin interaction allows highly selective pre- or post-functionalization of the protein crystals in a modular way with different types of functional units, such as fluorescent dyes, enzymes and plasmonic nanoparticles.

  8. Diphenylalanine peptide nanotubes self-assembled on functionalized metal surfaces for potential application in drug-eluting stent.

    PubMed

    Zohrabi, Tayebeh; Habibi, Neda; Zarrabi, Ali; Fanaei, Maryam; Lee, Lai Yeng

    2016-09-01

    This study focuses on the potential of diphenylalanine self-assembled peptide nanotubes (FF Nts) for delivery of flufenamic acid (FA) from metal implants. Self-assembly of FF Nts was studied in solution and on surfaces of glass, silicone and gold substrates. FA was loaded inside the shell of FF Nts and subsequently FF/FA Nts were attached to gold surfaces. The substrate were characterized by Field Emission Scanning Electron Microscopy (FESEM), fluorescence microscopy, confocal microscopy, and UV-vis spectroscopy. Release of FA from FF Nts were investigated by immersing coated metal substrates in phosphate-buffered saline for 12 days. Self-assembly of FF in water and solvent resulted in formation of nanotubes, which efficiently loaded 98% of FA with concentration of 20 µg/mL. FESEM images confirmed successful attachment of FF/FA Nts to functionalized gold substrates. In vitro release studies indicated using FF Nts has prolonged the release rate of FA for several days. Biocompatibility studied confirmed more than 50% of the cells were alive in concentration of 250-1000 µg/mL of FF Nts thus suggesting the potential of peptide based self-assemble nanostructures as an alternate system for polymer coating in drugs eluting stents. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2280-2290, 2016. PMID:27119433

  9. Peptide-directed self-assembly of functionalized polymeric nanoparticles part I: design and self-assembly of peptide-copolymer conjugates into nanoparticle fibers and 3D scaffolds.

    PubMed

    Ding, Xiaochu; Janjanam, Jagadeesh; Tiwari, Ashutosh; Thompson, Martin; Heiden, Patricia A

    2014-06-01

    A robust self-assembly of nanoparticles into fibers and 3D scaffolds is designed and fabricated by functionalizing a RAFT-polymerized amphiphilic triblock copolymer with designer ionic complementary peptides so that the assembled core-shell polymeric nanoparticles are directed by peptide assembly into continuous "nanoparticle fibers," ultimately leading to 3D fiber scaffolds. The assembled nanostructure is confirmed by FESEM and optical microscopy. The assembly is not hindered when a protein (insulin) is incorporated within the nanoparticles as an active ingredient. MTS cytotoxicity tests on SW-620 cell lines show that the peptides, copolymers, and peptide-copolymer conjugates are biocompatible. The methodology of self-assembled nanoparticle fibers and 3D scaffolds is intended to combine the advantages of a flexible hydrogel scaffold with the versatility of controlled release nanoparticles to offer unprecedented ability to incorporate desired drug(s) within a self-assembled scaffold system with individual control over the release of each drug. PMID:24610743

  10. Synthetic self-assembling clostridial chimera for modulation of sensory functions.

    PubMed

    Ferrari, Enrico; Gu, Chunjing; Niranjan, Dhevahi; Restani, Laura; Rasetti-Escargueil, Christine; Obara, Ilona; Geranton, Sandrine M; Arsenault, Jason; Goetze, Tom A; Harper, Callista B; Nguyen, Tam H; Maywood, Elizabeth; O'Brien, John; Schiavo, Giampietro; Wheeler, Daniel W; Meunier, Frederic A; Hastings, Michael; Edwardson, J Michael; Sesardic, Dorothea; Caleo, Matteo; Hunt, Stephen P; Davletov, Bazbek

    2013-10-16

    Clostridial neurotoxins reversibly block neuronal communication for weeks and months. While these proteolytic neurotoxins hold great promise for clinical applications and the investigation of brain function, their paralytic activity at neuromuscular junctions is a stumbling block. To redirect the clostridial activity to neuronal populations other than motor neurons, we used a new self-assembling method to combine the botulinum type A protease with the tetanus binding domain, which natively targets central neurons. The two parts were produced separately and then assembled in a site-specific way using a newly introduced 'protein stapling' technology. Atomic force microscopy imaging revealed dumbbell shaped particles which measure ∼23 nm. The stapled chimera inhibited mechanical hypersensitivity in a rat model of inflammatory pain without causing either flaccid or spastic paralysis. Moreover, the synthetic clostridial molecule was able to block neuronal activity in a defined area of visual cortex. Overall, we provide the first evidence that the protein stapling technology allows assembly of distinct proteins yielding new biomedical properties. PMID:24011174

  11. Controlled hydrophobic functionalization of natural fibers through self-assembly of amphiphilic diblock copolymer micelles.

    PubMed

    Aarne, Niko; Laine, Janne; Hänninen, Tuomas; Rantanen, Ville; Seitsonen, Jani; Ruokolainen, Janne; Kontturi, Eero

    2013-07-01

    The functionalization of natural fibers is an important task that has recently received considerable attention. We investigated the formation of a hydrophobic layer from amphiphilic diblock copolymer micelles [polystyrene-block-poly(N-methyl-4-vinyl pyridinium iodide)] on natural fibers and on a model surface (mica). A series of micelles were prepared. The micelles were characterized by using cryoscopic TEM and light scattering, and their hydrophobization capability was studied through contact angle measurements, water adsorption, and Raman imaging. Mild heat treatment (130 °C) was used to increase the hydrophobization capability of the micelles. The results showed that the micelles could not hydrophobize a model surface, but could render the natural fibers water repellent both with and without heat treatment. This effect was systematically studied by varying the composition of the constituent blocks. The results showed that the micelle size (and the molecular weight of the constituent diblock copolymers) was the most important parameter, whereas the cationic (hydrophilic) part played only a minor role. We hypothesized that the hydrophobization effect could be attributed to a combination of the micelle size and the shrinkage of the natural fibers upon drying. The shrinking caused the roughness to increase on the fiber surface, which resulted in a rearrangement of the self- assembled layer in the wet state. Consequently, the fibers became hydrophobic through the roughness effects at multiple length scales. Mild heat treatment melted the micelle core and decreased the minimum size necessary for hydrophobization. PMID:23687082

  12. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers.

    PubMed

    Kruszewski, Kristen M; Nistico, Laura; Longwell, Mark J; Hynes, Matthew J; Maurer, Joshua A; Hall-Stoodley, Luanne; Gawalt, Ellen S

    2013-05-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (-CH3) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an "active" antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. PMID:23498233

  13. Dynamic Covalent Functionalization as a route to Controlling Self Assembly of Organic Molecules

    NASA Astrophysics Data System (ADS)

    Pentzer, Emily

    Efforts to optimize the optoelectronic properties of conjugated organic materials are ongoing across many fields of science and engineering. For example, in bulk heterojunction polymer solar cells, researchers seek to optimize absorption of the solar spectrum by the active materials, form interpenetrating domains of p-type and n-type materials to facilitate exciton dissociation, and improve interactions between electrode, charge blocking layers, and active layers to ensure rapid charge transport. One advantage of organic polymers compared to inorganic materials (e.g., silicon), is the low cost and ability process the materials in solution. Moreover, assembly of conjugated organic materials in solution or in the solid state (i.e., films) can be used to optimize both a material's optoelectronic properties and its interface with surfaces and other materials, addressing many of the concerns listed above. Unfortunately, such solution processability requires appendage of insulating alkyl chains to the conjugated frameworks, which don solubility, but are also insulating and thus can hurt device performance. This presentation will report recent results from the Pentzer Lab from Case Western Reserve University on using functional alkyl chains that serve to control self-assembly, control interfaces with other materials, or can be removed by an external stimulus as a route to optimizing the materials for solar cell applications.

  14. Modeling Protein Self Assembly

    ERIC Educational Resources Information Center

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

    2004-01-01

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

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

    PubMed

    Garab, Győző

    2016-01-01

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

  16. Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

    NASA Technical Reports Server (NTRS)

    Yang, Yi; Lu, Yunfeng; Lu, Mengcheng; Huang, Jinman; Haddad, Raid; Xomeritakis, George; Liu, Nanguo; Malanoski, Anthony P.; Sturmayr, Dietmar; Fan, Hongyou; Sasaki, Darryl Y.; Assink, Roger A.; Shelnutt, John A.; van Swol, Frank; Lopez, Gabriel P.; Burns, Alan R.; Brinker, C. Jeffrey

    2003-01-01

    Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.

  17. Spatially Modulating Interfacial Properties of Transparent Conductive Oxides: Patterning Work Function with Phosphonic Acid Self-Assembled Monolayers

    SciTech Connect

    Knesting, Kristina M.; Hotchkiss, Peter J.; MacLeod, Bradley A.; Marder, Seth R.; Ginger, David S.

    2011-09-29

    The interface between an organic semiconductor and a transparent conducting oxide is crucial to the performance of organic optoelectronics. We use microcontact printing to pattern pentafluorobenzyl phosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO). We obtain high-fidelity patterns with sharply defined edges and with large work function contrast (comparable to that obtained from phosphonic acid SAMs deposited from solution).

  18. Self-assembled lecithin/chitosan nanoparticles for oral insulin delivery: preparation and functional evaluation

    PubMed Central

    Liu, Liyao; Zhou, Cuiping; Xia, Xuejun; Liu, Yuling

    2016-01-01

    Purpose Here, we investigated the formation and functional properties of self-assembled lecithin/chitosan nanoparticles (L/C NPs) loaded with insulin following insulin–phospholipid complex preparation, with the aim of developing a method for oral insulin delivery. Methods Using a modified solvent-injection method, insulin-loaded L/C NPs were obtained by combining insulin–phospholipid complexes with L/C NPs. The nanoparticle size distribution was determined by dynamic light scattering, and morphologies were analyzed by cryogenic transmission electron microscopy. Fourier transform infrared spectroscopy analysis was used to disclose the molecular mechanism of prepared insulin-loaded L/C NPs. Fast ultrafiltration and a reversed-phase high-performance liquid chromatography assay were used to separate free insulin from insulin entrapped in the L/C NPs, as well as to measure the insulin-entrapment and drug-loading efficiencies. The in vitro release profile was obtained, and in vivo hypoglycemic effects were evaluated in streptozotocin-induced diabetic rats. Results Our results indicated that insulin-containing L/C NPs had a mean size of 180 nm, an insulin-entrapment efficiency of 94%, and an insulin-loading efficiency of 4.5%. Cryogenic transmission electron microscopy observations of insulin-loaded L/C NPs revealed multilamellar structures with a hollow core, encircled by several bilayers. In vitro analysis revealed that insulin release from L/C NPs depended on the L/C ratio. Insulin-loaded L/C NPs orally administered to streptozotocin-induced diabetic rats exerted a significant hypoglycemic effect. The relative pharmacological bioavailability following oral administration of L/C NPs was 6.01%. Conclusion With the aid of phospholipid-complexation techniques, some hydrophilic peptides, such as insulin, can be successfully entrapped into L/C NPs, which could improve oral bioavailability, time-dependent release, and therapeutic activity. PMID:26966360

  19. Self-Assembling Organic Nanopores as Synthetic Transmembrane Channels with Tunable Functions

    NASA Astrophysics Data System (ADS)

    Wei, Xiaoxi

    nanotubular assembly, rather than the individual molecules of 3, is required to partition into the lipid bilayer in order for these macrocycles to act as channels. Further structural modification has led to fourth-generation macrocycles 4 having readily-tunable cavities (Chapter 4). Macrocycles 4 , with a hybrid backbone composed half of the oligoamide and half of the phenylene ethynylene moieties, exhibits similar self-assembling behavior by forming nanotubular stacks. The results of a preliminary study based on LUVs-assays and BLM single channel recording experiments are summarized and clearly indicate that ion channels formed by this fourth-generation exhibit high stability and differing ion selectivity largely consistent with the corresponding structural modification of the interior cavity. Especially, the increased anion conductance observed for 4d indicates that our strategy of tuning supramolecular function based on synthetic modification of the backbone and pore is effective. In Chapter 5, our four-residue tetraurea macrocycles 5 have shown significant potency to selectively interact with the G-quadruplex, leading to a strong stabilization effect for G-quadruplex without binding to duplex DNA as observed by UV-melt assays. The ready synthetic availability of these macrocycles makes them amenable to future chemical modification, which allows systematic improvement of binding affinity and specificity. Moreover, it has been discovered that these macrocycles can partition into lipid bilayers and form very stable transmembrane ion channels with a pore size of ˜5 A. Preliminary data shows that this smaller ion channel may lead to exceptional ion conducting selectivity, which is rarely seen in the field of synthetic ion pores. These molecules may serve as a unique platform for the rational development of potent and versatile therapeutic agents. The exceptional ion conducting properties of these channels place aromatic oligoamide macrocycles 3 and 4 at a unique position with

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

    PubMed

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

    2013-07-01

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

  1. Proteolysis Triggers Self-Assembly and Unmasks Innate Immune Function of a Human α-Defensin Peptide

    PubMed Central

    Chairatana, Phoom; Shen, Bo; Bevins, Charles L.; Nolan, Elizabeth M.

    2015-01-01

    Human α-defensin 6 (HD6) is a unique peptide of the defensin family that provides innate immunity in the intestine by self-assembling to form high-order oligomers that entrap bacteria and prevent host cell invasion. Here, we report critical steps in the self-assembly pathway of HD6. We demonstrate that HD6 is localized in secretory granules of small intestinal Paneth cells. HD6 is stored in these granules as an 81-residue propeptide (proHD6), and is recovered from ileal lumen as a 32-residue mature peptide. The propeptide neither forms higher-order oligomers, nor agglutinates bacteria, nor prevents Listeria monocytogenes invasion into epithelial cells. The Paneth cell granules also contain the protease trypsin, and trypsin-catalyzed hydrolysis of proHD6 liberates mature HD6, unmasking its latent activities. This work illustrates a remarkable example of how nature utilizes a propeptide strategy to spatially and temporally control peptide self-assembly, and thereby initiates innate immune function in the human intestine. PMID:27076903

  2. Photoresponsive Toroidal Nanostructure Formed by Self-Assembly of Azobenzene-Functionalized Tris(phenylisoxazolyl)benzene.

    PubMed

    Adachi, Hiroaki; Hirai, Yuko; Ikeda, Toshiaki; Maeda, Makoto; Hori, Ryo; Kutsumizu, Shoichi; Haino, Takeharu

    2016-03-01

    The self-assembly of tris(phenylisoxazolyl)benzene 1b with photochemically addressable azobenzene moieties produced toroidal nanostructures, the formation and dissociation of which were reversibly regulated upon photoirradiation. 1b displayed a mesogenic behavior. In the solution, the stacked assemblies along with their C3 axes were formed. In the mesophase, two molecules of 1b most likely adopted the antiparallel arrangement to stabilize the columnar organization. This assembling behavior most likely triggered the development of the supramolecular toroidal nanostructures. PMID:26910789

  3. Polymerization-Induced Self-Assembly of Galactose-Functionalized Biocompatible Diblock Copolymers for Intracellular Delivery

    PubMed Central

    2013-01-01

    Recent advances in polymer science are enabling substantial progress in nanobiotechnology, particularly in the design of new tools for enhanced understanding of cell biology and for smart drug delivery formulations. Herein, a range of novel galactosylated diblock copolymer nano-objects is prepared directly in concentrated aqueous solution via reversible addition–fragmentation chain transfer polymerization using polymerization-induced self-assembly. The resulting nanospheres, worm-like micelles, or vesicles interact in vitro with galectins as judged by a turbidity assay. In addition, galactosylated vesicles are highly biocompatible and allow intracellular delivery of an encapsulated molecular cargo. PMID:23941545

  4. Polymerization-induced self-assembly of galactose-functionalized biocompatible diblock copolymers for intracellular delivery.

    PubMed

    Ladmiral, Vincent; Semsarilar, Mona; Canton, Irene; Armes, Steven P

    2013-09-11

    Recent advances in polymer science are enabling substantial progress in nanobiotechnology, particularly in the design of new tools for enhanced understanding of cell biology and for smart drug delivery formulations. Herein, a range of novel galactosylated diblock copolymer nano-objects is prepared directly in concentrated aqueous solution via reversible addition-fragmentation chain transfer polymerization using polymerization-induced self-assembly. The resulting nanospheres, worm-like micelles, or vesicles interact in vitro with galectins as judged by a turbidity assay. In addition, galactosylated vesicles are highly biocompatible and allow intracellular delivery of an encapsulated molecular cargo. PMID:23941545

  5. Characterization of liver-specific structure and function during hepatocyte spheroid self-assembly: Implications for a bioartificial liver device

    NASA Astrophysics Data System (ADS)

    Friend, Julie Renee

    A hollow fiber bioreactor containing collagen-entrapped hepatocytes has been developed as a bioartificial liver device. For clinical application, further scale-up of the device is desirable. This may be achieved through the use of hepatocyte spheroids, which are compacted aggregates that exhibit prolonged viability, higher liver-specific function and a more tissue-like ultrastructure compared to hepatocytes cultured as monolayers. In order to gain a better understanding of structural changes in spheroids over the course of their self-assembly, confocal microscopy was used to optically section spheroids and monitor changes in situ. Channels within spheroids hypothesized to be bile canaliculi were first evaluated by monitoring the diffusion of a fluorescent tracer, FITC-dextran, into spheroids. Three-dimensional reconstruction of spheroids showed that a continuous network of channels was forming within spheroids. Functionality of these channels as bile canaliculi was demonstrated by monitoring secretion of a fluorescently tagged bile acid, FITC-glycocholate, by hepatocytes in spheroids. Secretion of FITC-glycocholate could be seen in both rat and porcine hepatocyte spheroids. To elucidate changes in metabolism occurring during spheroid self-assembly, metabolic flux analysis was applied to hepatocyte spinner cultures. Glucose, lactate, amino acid, albumin and urea concentration in culture medium were measured and used to estimate intracellular fluxes within hepatocytes. Metabolism before and after spheroid formation was compared. Overall, little difference was seen in metabolism before and after spheroid self-assembly. As the BAL approaches clinical trials, methods of bioreactor storage for shipping and inventory purposed need to be developed. Storage conditions were tested in various hepatocyte culture systems. A protocol for storing reactors for 24 hours without significant loss in function was developed. Further optimization will be necessary for storage for longer

  6. Construction of Endo-Functionalized Two Dimensional Metallacycles via Coordination-Driven Self-Assembly

    PubMed Central

    Ghosh, Koushik; Zheng, Yao-Rong

    2009-01-01

    The synthesis of three endofunctionalized two-dimensional supramolecular metallacycles including two [2 + 2] rhomboids (5 and 6) and a [3 + 3] hexagon (7) is reported. The resulting self-assembled supramolecular structures, containing several nitrobenzyl moieties at their interior surface, have been fully characterized by multinuclear NMR (31P and 1H) and electrospray ionization mass spectrometry. A significant C–H…O hydrogen bonding between the nitrobenzyl acceptor and the edge molecules of the supramolecular architecture is observed in the small rhomboid 5 and this interaction gradually decreases upon the enlargement of the resulting polygonal structures from a small rhomboid 5 through a large rhomboid 6 to a hexagon 7. Molecular modeling with the MMFF force field gives a possible conformation of each self-assembly in different solvents and shows that the hydrophilic nitrobenzyl moiety prefers to be buried in the cavity of the resulting polygonal structures in nonpolar solvents, thus forming hydrogen bonds with the peripheral component building units. PMID:19835395

  7. Directed self-assembly of end-functionalized nanofibers: from percolated networks to liquid crystal-like phases

    NASA Astrophysics Data System (ADS)

    Xie, Bo; Buehler, Markus J.; Xu, Zhiping

    2015-05-01

    We explore the directed self-assembly (DSA) process of end-functionalized nanofibers (NFs) by performing coarse-grained molecular dynamics simulations. We find that by tuning their interactions, NFs aggregate and self-organize into networks with specific topologies ranging from percolated networks to liquid crystal-like long-chain phases. The underlying mechanism is explained through an analytical model from a minimum energy perspective. In addition to offering microscopic understandings of the DSA process, the findings reported here can also guide robust target-specified design of nanofibrous materials into organized network structures.

  8. The Effect of Small Molecule Additives on the Self-Assembly and Functionality of Protein-Polymer Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Thomas, Carla; Xu, Liza; Olsen, Bradley

    2013-03-01

    Self-assembly of globular protein-polymer block copolymers into well-defined nanostructures provides a route towards the manufacture of protein-based materials which maintains protein fold and function. The model material mCherry-b-poly(N-isopropyl acrylamide) forms self-assembled nanostructures from aqueous solutions via solvent evaporation. To improve retention of protein functionality when dehydrated, small molecules such as trehalose and glycerol are added in solution prior to solvent removal. With as little as 10 wt% additive, improvements in retained functionality of 20-60% are observed in the solid-state as compared to samples in which no additive is present. Higher additive levels (up to 50%) continue to show improvement until approximately 100% of the protein function is retained. These large gains are hypothesized to originate from the ability of the additives to replace hydrogen bonds normally fulfilled by water. The addition of trehalose in the bulk material also improves the thermal stability of the protein by 15-20 °C, while glycerol decreases the thermal stability. Materials containing up to 50% additives remain microphase separated, and, upon incorporation of additives, nanostructure domain spacing tends to increase, accompanied by order-order transitions.

  9. Self-Assembly of Topological Solitons and Functional Nanoparticles in Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Ackerman, Paul Jeffrey

    As a result of their intrinsic orientational order, soft elasticity, and facile response to external stimuli, liquid crystals (LCs) provide a rich environment for both fundamental science and viable technological applications. In this thesis I explore the emergent properties of confinement-frustrated chiral nematic LCs and nanoparticle-LC composites. Due to a complex free energy landscape, con- fined LCs exhibit a large number of local and global energy minima and can facilitate self-assembly of many types of topological solitons. These localized configurations of molecular orientation field are useful for technological applications, have properties that are enhanced by colloidal inclusions and enable the fundamental studies of nanoparticle interactions. Experimental and numerical ex- ploration of these topologically nontrivial solitons may influence the experimental realization of their analogs in physical systems ranging from elementary particles to cosmology. The delicate interplay of topology, chirality and confinement of LCs can enable spontaneous or optical vortex initiated self-assembly of solitons. In turn, the optical generation and patterning of reconfigurable LC solitons can enable the production of optical vortices in laser beams, demon- strating hierarchical control of defects in matter and light with potential technological applications. The elasticity and facile response of LCs to applied fields facilitates the self-assembly of crystals and chains of solitons, giant electrostriction, as well as electrically driven nonequilibrium dynamics in the form of reversible directional motion of stable defect pairs. Concepts of chirality and topo- logical invariants, such as Hopf index and Skyrmion number, are invoked to examine and classify a variety of spatial solitons, including Skyrmions, Hopfions, and torons, as well as to analyze the role of chirality and the unexpected observation of twist handedness reversal that enables soliton stability. By

  10. Chiral nematic self-assembly of minimally surface damaged chitin nanofibrils and its load bearing functions

    PubMed Central

    Oh, Dongyeop X.; Cha, Yun Jeong; Nguyen, Hoang-Linh; Je, Hwa Heon; Jho, Yong Seok; Hwang, Dong Soo; Yoon, Dong Ki

    2016-01-01

    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. PMID:26988392

  11. 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.

  12. Chiral nematic self-assembly of minimally surface damaged chitin nanofibrils and its load bearing functions.

    PubMed

    Oh, Dongyeop X; Cha, Yun Jeong; Nguyen, Hoang-Linh; Je, Hwa Heon; Jho, Yong Seok; Hwang, Dong Soo; Yoon, Dong Ki

    2016-01-01

    Chitin is one of the most abundant biomaterials in nature, with 10(10) 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. PMID:26988392

  13. Self-assembly, redox activity, and charge transport of functional surface nano-architectures by molecular design

    NASA Astrophysics Data System (ADS)

    Skomski, Daniel

    Surface-assisted molecular self-assembly is a promising strategy to program the structure and chemical state of atoms and molecules in nano-architectures to achieve a specific function. The experiments described in this thesis demonstrate that the design and programming of basic organic components leads to desired characteristics by self-assembly. The fabrication of uniform single-site metal centers at surfaces, important for high selectivity in next-generation catalysts, was accomplished by coordination to redox non-innocent phenanthroline and tetrazine-based ligands. These examples were the first demonstrating tuning of the metal oxidation state in surface coordination architectures through rational ligand design. The molecular-scale coordination architectures were the first formed from chromium and vanadium, and the first from platinum in a non-porphyrin system. The first mixed valence metal-ligand surface structure was fabricated that attained the same ligand coordination number for all metal sites. A new surface reaction method was demonstrated between an inexpensive sodium chloride reagent and carboxylate ligands. High-temperature, molecular-resolution microscopy and spectroscopy of the ordered metal-organic structures demonstrated thermal stability up to 300 °C, the highest molecular-level thermal stability in organic surface nanostructures yet achieved, making such systems potential candidates for moderate-temperature catalytic reactions. Molecular self-assembly was expanded into organic semiconductor thin films. In a two-component, bi-layered system, hydrogen bonding between carboxylates and carboxylic acid-substituted thiophenes was utilized, yielding the first real-space images of phenyl-thiophene stacking. In a one-component system, multiple donor-acceptor pi-pi contacts between phenyltriazole building blocks accomplished assembly of flat-lying molecules from a surface with molecular-scale precision through more than twenty molecular layers. Sufficient

  14. Highlighting functional groups in self-assembled overlayers with specific functionalized scanning tunnelling microscopy tips

    NASA Astrophysics Data System (ADS)

    Volcke, Cedric; Simonis, Priscilla; Thiry, Paul A.; Lambin, Philippe; Culot, Christine; Humbert, Christophe

    2005-11-01

    Overlayers of a fatty acid (palmitic and lauric acid) formed at the interface between a solution of this molecule in phenyloctane and the basal plane of graphite are studied by in situ scanning tunnelling microscopy. The layers organize into lamellae, which are formed by a close packing arrangement of molecules parallel to the graphite surface. Chemical modification of the STM tips used allowed identification of the functional group. Indeed, the gold tips used are functionalized with 4-mercaptobenzoic acid (4-MBA) and 4-mercaptotoluene (4-MT). The same functional group on a sample is then 'seen' as a dark and a bright spot when imaged with 4-MBA and 4-MT modified tips, respectively. This contrast distinction is related to interactions (or a lack of them) between the carboxyl group on the sample and molecules on the tip, which can facilitate (or hinder) the electron tunnelling.

  15. Surface-enhanced Raman spectroscopy of functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Ye, Qi

    1997-09-01

    The central theme of this research is to study Self-Assembled Monolayers (SAMs) with Surface-Enhanced Raman Spectroscopy (SERS). SERS is a relatively new surface characterization technique, but it is very promising because of its submonolayer sensitivity and in-situ applicability in aqueous systems. In this thesis, we have assessed the potential of this technique by presenting our studies in SERS enhancement mechanisms and in applications of SERS to SAM electrochemistry, stability, polymerization, and molecular interactions. Studying SERS-active substrate provides the bases for any quantitative study involving SERS. Based on examination of various substrates, we have developed a new type of SERS-active substrate that supports a reproducible, stable, and large enhancement factor. This best substrate is further characterized with a scanning probe microscope. Useful probe range of SERS has been established by studying the distance dependence of SERS from an azobenzene Raman label covalently attached to the end of a self-assembling molecule. The distance dependence curves have been analyzed using a previously reported electromagnetic enhancement theory. Electrochamical properties of azobenzene SAMs have been investigated by a combined methodology of cyclic voltammetry and Raman spectroscopy. Electron transfer through the alkyl spacer is a tunneling process that is chain length dependent. We propose that electron transfer to and from the azobenzene redox center is a two-electron, two proton redox process, based on our in-situ SERS spectroscopic data. Stability of SAMs under various chemical and electrochemical conditions has been studied by an experimental technique which we named "cyclic voltarammetry". By monitoring the in-situ Raman spectra during potential cycling, we can study the desorption of SAMs in various media. In order to improve SAM stability, topochemical polymerization of SAMs containing diacetylene groups has been designed and explored. Our results

  16. Design and self-assembly of siRNA-functionalized RNA nanoparticles for use in automated nanomedicine

    PubMed Central

    Afonin, Kirill A; Grabow, Wade W; Walker, Faye M; Bindewald, Eckart; Dobrovolskaia, Marina A; Shapiro, Bruce A; Jaeger, Luc

    2012-01-01

    Individual genes can be targeted with siRNAs. The use of nucleic acid nanoparticles (NPs) is a convenient method for delivering combinations of specific siRNAs in an organized and programmable manner. We present three assembly protocols to produce two different types of RNA self-assembling functional NPs using processes that are fully automatable. These NPs are engineered based on two complementary nanoscaffold designs (nanoring and nanocube), which serve as carriers of multiple siRNAs. The NPs are functionalized by the extension of up to six scaffold strands with siRNA duplexes. The assembly protocols yield functionalized RNA NPs, and we show that they interact in vitro with human recombinant Dicer to produce siRNAs. Our design strategies allow for fast, economical and easily controlled production of endotoxin-free therapeutic RNA NPs that are suitable for preclinical development. PMID:22134126

  17. Electrowetting of nitro-functionalized oligoarylene thiols self-assembled on polycrystalline gold.

    PubMed

    Casalini, Stefano; Berto, Marcello; Bortolotti, Carlo A; Foschi, Giulia; Operamolla, Alessandra; Di Lauro, Michele; Omar, Omar Hassan; Liscio, Andrea; Pasquali, Luca; Montecchi, Monica; Farinola, Gianluca M; Borsari, Marco

    2015-02-25

    Four linear terarylene molecules (i) 4-nitro-terphenyl-4″-methanethiol (NTM), (ii) 4-nitro-terphenyl-3″,5″-dimethanethiol (NTD), (iii) ([1,1';4',1″] terphenyl-3,5-diyl)methanethiol (TM), and (iv) ([1,1';4',1″] terphenyl-3,5-diyl)dimethanethiol (TD) have been synthesized and their self-assembled monolayers (SAMs) have been obtained on polycrystalline gold. NTM and NTD SAMs have been characterized by X-ray photoelectron spectroscopy, Kelvin probe measurements, electrochemistry, and contact angle measurements. The terminal nitro group (-NO2) is irreversibly reduced to hydroxylamine (-NHOH), which can be reversibly turned into nitroso group (-NO). The direct comparison between NTM/NTD and TM/TD SAMs unambiguously shows the crucial influence of the nitro group on electrowetting properties of polycrystalline Au. The higher grade of surface tension related to NHOH has been successfully exploited for basic operations of digital μ-fluidics, such as droplets motion and merging. PMID:25646868

  18. Functionalized d-form self-assembling peptide hydrogels for bone regeneration

    PubMed Central

    He, Bin; Ou, Yunsheng; Zhou, Ao; Chen, Shuo; Zhao, Weikang; Zhao, Jinqiu; Li, Hong; Zhu, Yong; Zhao, Zenghui; Jiang, Dianming

    2016-01-01

    Bone defects are very common in orthopedics, and there is great need to develop suitable bone grafts for transplantation in vivo. However, current bone grafts still encounter some limitations, including limited availability, immune rejection, poor osteoinduction and osteoconduction, poor biocompatibility and degradation properties, etc. Self-assembling peptide nanofiber scaffolds have emerged as an important substrate for cell culture and bone regeneration. We report on the structural features (eg, Congo red staining, circular dichroism spectroscopy, transmission electron microscopy, and rheometry assays) and osteogenic ability of d-RADA16-RGD peptide hydrogels (with or without basic fibroblast growth factor) due to the better stability of peptide bonds formed by these peptides compared with those formed by l-form peptides, and use them to fill the femoral condyle defect of Sprague Dawley rat model. The bone morphology change, two-dimensional reconstructions using microcomputed tomography, quantification of the microcomputed tomography analyses as well as histological analyses have demonstrated that RGD-modified d-form peptide scaffolds are able to enhance extensive bone regeneration. PMID:27114701

  19. Reversible work function changes induced by photoisomerization of asymmetric azobenzene dithiol self-assembled monolayers on gold

    SciTech Connect

    Ah Qune, Lloyd F. N.; Wee, Andrew T. S.; Akiyama, H.; Nagahiro, T.; Tamada, K.

    2008-08-25

    We measured reversible changes in the work function ({delta}{phi}{sub Au}) of gold substrates modified by asymmetric azobenzene dithiol self-assembled monolayers (SAMs) following photoisomerization and thermal recovery of the azo unit. The azobenzene derivative SAMs were photoisomerized to cis form by UV irradiation. {delta}{phi}{sub Au} was monitored in real time during thermal recovery to trans form by ultraviolet photoelectron spectroscopy using a synchrotron light source. Changing the substituted functional group in the p{sup '} position of the azobenzene from electron donating to electron withdrawing resulted in opposite responses of {delta}{phi}{sub Au} against photoisomerization. Hence, a direct correlation between {delta}{phi}{sub Au} and changes in molecular dipole moments was obtained.

  20. Bionanotechnology application of polypeptides in a hair color product: self-assembly enables expression, processing, and functionality.

    PubMed

    Rouvière, Pierre E; Li, Jing; Brill, Donald J; Reiss, Lisa D; Schwartz, Timothy R; Butterick, Lisa A; Fahnestock, Stephen R; Gruber, Tanja

    2013-02-01

    Bionanotechnology aims to impart new properties to materials from unique functionalities present in biomolecules. However, the promise of bionanotechnology has not materialized beyond the biomedical field due in large part to issues of scalability, purity, and cost of manufacturing. In this work we demonstrate an approach to co-engineer production and system functionality into a single polypeptide. We designed a system to anchor particles onto hair via a multifunctional polypeptide composed of two domains, one with affinity to hair and the other capable of strong interactions with the particle surface. These strong interactions, exemplified by resistance to anionic surfactants, stem from the ability to self-assemble into higher order structures, which were observed by atomic force microscopy. At the same time, the controlled solubility properties of the particle binding domain permit the scalable production in Escherichia coli via inclusion bodies and cost effective purification. We believe this is a significant advance toward the development of bionanotechnology for industrial applications. PMID:22777899

  1. Synergistic effect of self-assembled carboxylic acid-functionalized carbon nanotubes and carbon fiber for improved electro-activated polymeric shape-memory nanocomposite

    NASA Astrophysics Data System (ADS)

    Lu, Haibao; Min Huang, Wei

    2013-06-01

    The present work studies the synergistic effect of self-assembled carboxylic acid-functionalized carbon nanotube (CNT) and carbon fiber on the electrical property and electro-activated recovery behavior of shape memory polymer (SMP) nanocomposites. The combination of CNT and carbon fiber results in improved electrical conductivity in the SMP nanocomposites. Carboxylic acid-functionalized CNTs are grafted onto the carbon fibers and then self-assembled by deposition to significantly enhance the reliability of the bonding between carbon fiber and SMP via van der Waals and covalent crosslink. Furthermore, the self-assembled carboxylic acid-functionalized CNTs and carbon fibers enable the SMP nanocomposites for Joule heating triggered shape recovery.

  2. Directing Hybrid Structures by Combining Self-Assembly of Functional Block Copolymers and Atomic Layer Deposition: A Demonstration on Hybrid Photovoltaics.

    PubMed

    Moshonov, Moshe; Frey, Gitti L

    2015-11-24

    The simplicity and versatility of block copolymer self-assembly offers their use as templates for nano- and meso-structured materials. However, in most cases, the material processing requires multiple steps, and the block copolymer is a sacrificial building block. Here, we combine a self-assembled block copolymer template and atomic layer deposition (ALD) of a metal oxide to generate functional hybrid films in a simple process with no etching or burning steps. This approach is demonstrated by using the crystallization-induced self-assembly of a rod-coil block copolymer, P3HT-b-PEO, and the ALD of ZnO. The block copolymer self-assembles into fibrils, ∼ 20 nm in diameter and microns long, with crystalline P3HT cores and amorphous PEO corona. The affinity of the ALD precursors to the PEO corona directs the exclusive deposition of crystalline ZnO within the PEO domains. The obtained hybrid structure possesses the properties desired for photovoltaic films: donor-acceptor continuous nanoscale interpenetrated networks. Therefore, we integrated the films into single-layer hybrid photovoltaics devices, thus demonstrating that combining self-assembly of functional block copolymers and ALD is a simple approach to direct desired complex hybrid morphologies. PMID:26523422

  3. Glycine-Spacers Influence Functional Motifs Exposure and Self-Assembling Propensity of Functionalized Substrates Tailored for Neural Stem Cell Cultures

    PubMed Central

    Taraballi, Francesca; Natalello, Antonino; Campione, Marcello; Villa, Omar; Doglia, Silvia M.; Paleari, Alberto; Gelain, Fabrizio

    2009-01-01

    The understanding of phenomena involved in the self-assembling of bio-inspired biomaterials acting as three-dimensional scaffolds for regenerative medicine applications is a necessary step to develop effective therapies in neural tissue engineering. We investigated the self-assembled nanostructures of functionalized peptides featuring four, two or no glycine-spacers between the self-assembly sequence RADA16-I and the functional biological motif PFSSTKT. The effectiveness of their biological functionalization was assessed via in vitro experiments with neural stem cells (NSCs) and their molecular assembly was elucidated via atomic force microscopy, Raman and Fourier Transform Infrared spectroscopy. We demonstrated that glycine-spacers play a crucial role in the scaffold stability and in the exposure of the functional motifs. In particular, a glycine-spacer of four residues leads to a more stable nanostructure and to an improved exposure of the functional motif. Accordingly, the longer spacer of glycines, the more effective is the functional motif in both eliciting NSCs adhesion, improving their viability and increasing their differentiation. Therefore, optimized designing strategies of functionalized biomaterials may open, in the near future, new therapies in tissue engineering and regenerative medicine. PMID:20162033

  4. Chemical Reactions Directed Peptide Self-Assembly

    PubMed Central

    Rasale, Dnyaneshwar B.; Das, Apurba K.

    2015-01-01

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

  5. Self-Assembly of a Functional Triple Protein: Hemoglobin-Avidin-Hemoglobin via Biotin-Avidin Interactions.

    PubMed

    Singh, Serena; Kluger, Ronald

    2016-05-24

    Hypertension resulting from vasoconstriction in clinical trials of cross-linked tetrameric (α2β2) human hemoglobins implicates the extravasation of the hemoglobins into endothelia where they scavenge nitric oxide (NO), which is the signal for relaxation of the surrounding smooth muscle. Thus, we sought an efficient route to create a larger species that avoids extravasation while maintaining the oxygenation function of hemoglobin. Selectively formed cysteine-linked biotin conjugates of hemoglobin undergo self-assembly with avidin into a stable triple protein, hemoglobin-avidin-hemoglobin (HbAvHb), which binds and releases oxygen with moderate affinity and cooperativity. The triple protein is likely to be stabilized by interactions of each constituent hemoglobin (pI 6.9) with the oppositely charged avidin (pI 10.5) as well as the strong association of the biotin moieties on hemoglobin with avidin. PMID:27126305

  6. Urea-Functionalized M4L6 Cage Receptors: Self-Assembly, Dynamics, and Anion Recognition in Aqueous Solutions

    SciTech Connect

    Custelcean, Radu; Bonnesen, Peter V; Duncan, Nathan C; Van Berkel, Gary J; Hay, Benjamin

    2012-01-01

    We present an extensive study of a novel class of de novo designed tetrahedral M{sub 4}L{sub 6} (M = Ni, Zn) cage receptors, wherein internal decoration of the cage cavities with urea anion-binding groups, via functionalization of the organic components L, led to selective encapsulation of tetrahedral oxoanions EO{sub 4}{sup -} (E = S, Se, Cr, Mo, W, n = 2; E = P, n = 3) from aqueous solutions, based on shape, size, and charge recognition. External functionalization with tBu groups led to enhanced solubility of the cages in aqueous methanol solutions, thereby allowing for their thorough characterization by multinuclear ({sup 1}H, {sup 13}C, {sup 77}Se) and diffusion NMR spectroscopies. Additional experimental characterization by electrospray ionization mass spectrometry, UV-vis spectroscopy, and single-crystal X-ray diffraction, as well as theoretical calculations, led to a detailed understanding of the cage structures, self-assembly, and anion encapsulation. We found that the cage self-assembly is templated by EO{sub 4}{sup -} oxoanions (n {ge} 2), and upon removal of the templating anion the tetrahedral M{sub 4}L{sub 6} cages rearrange into different coordination assemblies. The exchange selectivity among EO{sub 4}{sup -} oxoanions has been investigated with {sup 77}Se NMR spectroscopy using {sup 77}SeO{sub 4}{sup 2-} as an anionic probe, which found the following selectivity trend: PO{sub 4}{sup 3-} CrO{sub 4}{sup 2-} > SO{sub 4}{sup 2-} > SeO{sub 4}{sup 2-} > MoO{sub 4}{sup 2-} > WO{sub 4}{sup 2-}. In addition to the complementarity and flexibility of the cage receptor, a combination of factors have been found to contribute to the observed anion selectivity, including the anions charge, size, hydration, basicity, and hydrogen-bond acceptor abilities.

  7. Ordered self-assembled monolayers terminated with different chemical functional groups direct neural stem cell linage behaviours.

    PubMed

    Yao, Shenglian; Liu, Xi; He, Jin; Wang, Xiumei; Wang, Ying; Cui, Fu-Zhai

    2016-02-01

    Neural stem cells (NSCs) have been a promising candidate for stem cell-based nerve tissue regeneration. Therefore, the design of idea biomaterials that deliver precise regulatory signals to control stem cell fate is currently a crucial issue that depends on a profound understanding of the interactions between NSCs with the surrounding micro-environment. In this work, self-assembled monolayers of alkanethiols on gold with different chemical groups, including hydroxyl (-OH), amino (-NH2), carboxyl (-COOH) and methyl (-CH3), were used as a simple model to study the effects of surface chemistry on NSC fate decisions. Contact angle measurement and x-ray photoelectron spectroscopy (XPS) examination implied that all types of alkanethiols self-assembled on gold into a close-packed phase structure with similar molecular densities. In this study, we evaluated NSC adhesion, migration and differentiation in response to different chemical functional groups cultured under serum-free conditions. Our studies showed that NSCs exhibited certain phenotypes with extreme sensitivity to surface chemical groups. Compared with other functional groups, the SAMs with hydroxyl end-groups provided the best micro-environment in promoting NSC migration and maintaining an undifferentiated or neuronal differentiation state.  -NH2 surfaces directed neural stem cells into astrocytic lineages, while NSCs on  -COOH and  -CH3 surfaces had a similar potency to differentiate into three nerve lineages. To further investigate the possible signaling pathway, the gene expression of integrin β1 and β4 were examined. The results indicated that a high expression of β1 integrin would probably have a tight correlation with the expression of nestin, which implied the stemness of NSCs, while β4 integrin seemed to correspond to the differentiated NSCs. The results presented here give useful information for the future design of biomaterials to regulate the preservation, proliferation and

  8. Onset of self-assembly

    SciTech Connect

    Chitanvis, S.M.

    1998-02-01

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

  9. Self-assembly via microfluidics

    PubMed Central

    Wang, Lei

    2015-01-01

    The self-assembly of amphiphilic building blocks has attracted extensive interest in myriad fields in recent years, due to their great potential in the nanoscale design of functional hybrid materials. Microfluidic techniques provide an intriguing method to control kinetic aspects of the self-assembly of molecular amphiphiles by the facile adjustment of the hydrodynamics of the fluids. Up to now, there have been several reports about one-step direct self-assembly of different building blocks with versatile and multi-shape products without templates, which demonstrated the advantages of microfluidics. These assemblies with different morphologies have great applications in various areas such as cancer therapy, micromotor fabrication, and controlled drug delivery. PMID:26486277

  10. The functionalization of nanodiamonds (diamondoids) as a key parameter of their easily controlled self-assembly in micro- and nanocrystals from the vapor phase

    NASA Astrophysics Data System (ADS)

    Gunawan, Maria A.; Poinsot, Didier; Domenichini, Bruno; Dirand, Céline; Chevalier, Sébastien; Fokin, Andrey A.; Schreiner, Peter R.; Hierso, Jean-Cyrille

    2015-01-01

    We detail herein readily accessible processes to control previously unobserved robust self-assemblies of nanodiamonds (diamondoids) in micro- and nanocrystals from their mild vapor deposition. The chemical functionalization of uniform and discernible nanodiamonds was found to be a key parameter, and depending on the type of functional group (hydroxy, fluorine, etc.) and its position on the diamondoid, the structure of the discrete deposits can vary dramatically. Thus, well-defined anisotropic structures such as rod, needle, triangle or truncated octahedron shapes can be obtained, and self-assembled edifices of sizes ranging from 20 nm to several hundred micrometers formed with conservation of a similar structure for a given diamondoid. Key thermodynamic data including sublimation enthalpy of diamondoid derivatives are reported, and the SEM of the self-assemblies coupled with EDX analyses and XRD attest the nature and purity of nanodiamond crystal deposits. This attractive method is simple and outperforms in terms of deposit quality dip-coating methods we used. This vapor phase deposition approach is expected to allow for an easy formation of diamondoid nanoobjects on different types of substrates.We detail herein readily accessible processes to control previously unobserved robust self-assemblies of nanodiamonds (diamondoids) in micro- and nanocrystals from their mild vapor deposition. The chemical functionalization of uniform and discernible nanodiamonds was found to be a key parameter, and depending on the type of functional group (hydroxy, fluorine, etc.) and its position on the diamondoid, the structure of the discrete deposits can vary dramatically. Thus, well-defined anisotropic structures such as rod, needle, triangle or truncated octahedron shapes can be obtained, and self-assembled edifices of sizes ranging from 20 nm to several hundred micrometers formed with conservation of a similar structure for a given diamondoid. Key thermodynamic data including

  11. Effect of Small Molecule Osmolytes on the Self-Assembly and Functionality of Globular Protein-Polymer Diblock Copolymers

    SciTech Connect

    Thomas, Carla S.; Xu, Liza; Olsen, Bradley D.

    2013-12-05

    Blending the small molecule osmolytes glycerol and trehalose with the model globular protein–polymer block copolymer mCherry-b-poly(N-isopropyl acrylamide) (mCherry-b-PNIPAM) is demonstrated to improve protein functionality in self-assembled nanostructures. The incorporation of either additive into block copolymers results in functionality retention in the solid state of 80 and 100% for PNIPAM volume fractions of 40 and 55%, respectively. This represents a large improvement over the 50–60% functionality observed in the absence of any additive. Furthermore, glycerol decreases the thermal stability of block copolymer films by 15–20 °C, while trehalose results in an improvement in the thermal stability by 15–20 °C. These results suggest that hydrogen bond replacement is responsible for the retention of protein function but suppression or enhancement of thermal motion based on the glass transition of the osmolyte primarily determines thermal stability. While both osmolytes are observed to have a disordering effect on the nanostructure morphology with increasing concentration, this effect is less pronounced in materials with a larger polymer volume fraction. Glycerol preferentially localizes in the protein domains and swells the nanostructures, inducing disordering or a change in morphology depending on the PNIPAM coil fraction. In contrast, trehalose is observed to macrophase separate from the block copolymer, which results in nanodomains becoming more disordered without changing significantly in size.

  12. Self-assembly with orthogonal-imposed stimuli to impart structure and confer magnetic function to electrodeposited hydrogels.

    PubMed

    Li, Ying; Liu, Yi; Gao, Tieren; Zhang, Boce; Song, Yingying; Terrell, Jessica L; Barber, Nathan; Bentley, William E; Takeuchi, Ichiro; Payne, Gregory F; Wang, Qin

    2015-05-20

    A magnetic nanocomposite film with the capability of reversibly collecting functionalized magnetic particles was fabricated by simultaneously imposing two orthogonal stimuli (electrical and magnetic). We demonstrate that cathodic codeposition of chitosan and Fe3O4 nanoparticles while simultaneously applying a magnetic field during codeposition can (i) organize structure, (ii) confer magnetic properties, and (iii) yield magnetic films that can perform reversible collection/assembly functions. The magnetic field triggered the self-assembly of Fe3O4 nanoparticles into hierarchical "chains" and "fibers" in the chitosan film. For controlled magnetic properties, the Fe3O4-chitosan film was electrodeposited in the presence of various strength magnetic fields and different deposition times. The magnetic properties of the resulting films should enable broad applications in complex devices. As a proof of concept, we demonstrate the reversible capture and release of green fluorescent protein (EGFP)-conjugated magnetic microparticles by the magnetic chitosan film. Moreover, antibody-functionalized magnetic microparticles were applied to capture cells from a sample, and these cells were collected, analyzed, and released by the magnetic chitosan film, paving the way for applications such as reusable biosensor interfaces (e.g., for pathogen detection). To our knowledge, this is the first report to apply a magnetic field during the electrodeposition of a hydrogel to generate magnetic soft matter. Importantly, the simple, rapid, and reagentless fabrication methodologies demonstrated here are valuable features for creating a magnetic device interface. PMID:25923335

  13. Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies

    NASA Astrophysics Data System (ADS)

    Patil, Avinash J.; Li, Mei; Mann, Stephen

    2013-07-01

    Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of ``inorganic molecular wrapping'' of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as ``armour-plated'' enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

  14. 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.

  15. Self-assembled nanomaterials for photoacoustic imaging.

    PubMed

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

    2016-02-01

    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. PMID:26757620

  16. Self-assembled anchor layers/polysaccharide coatings on titanium surfaces: a study of functionalization and stability

    PubMed Central

    Zemek, Josef; Neykova, Neda; Demianchuk, Roman; Chánová, Eliška Mázl; Šlouf, Miroslav; Houska, Milan; Rypáček, František

    2015-01-01

    Summary Composite materials based on a titanium support and a thin, alginate hydrogel could be used in bone tissue engineering as a scaffold material that provides biologically active molecules. The main objective of this contribution is to characterize the activation and the functionalization of titanium surfaces by the covalent immobilization of anchoring layers of self-assembled bisphosphonate neridronate monolayers and polymer films of 3-aminopropyltriethoxysilane and biomimetic poly(dopamine). These were further used to bind a bio-functional alginate coating. The success of the titanium surface activation, anchoring layer formation and alginate immobilization, as well as the stability upon immersion under physiological-like conditions, are demonstrated by different surface sensitive techniques such as spectroscopic ellipsometry, infrared reflection–absorption spectroscopy and X-ray photoelectron spectroscopy. The changes in morphology and the established continuity of the layers are examined by scanning electron microscopy, surface profilometry and atomic force microscopy. The changes in hydrophilicity after each modification step are further examined by contact angle goniometry. PMID:25821702

  17. Hydrogen bonding strength of diblock copolymers affects the self-assembled structures with octa-functionalized phenol POSS nanoparticles.

    PubMed

    Lu, Yi-Syuan; Yu, Chia-Yu; Lin, Yung-Chih; Kuo, Shiao-Wei

    2016-02-28

    In this study, the influence of the functional groups by the diblock copolymers of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), poly(styrene-b-2-vinylpyridine) (PS-b-P2VP), and poly(styrene-b-methyl methacrylate) (PS-b-PMMA) on their blends with octa-functionalized phenol polyhedral oligomeric silsesquioxane (OP-POSS) nanoparticles (NPs) was investigated. The relative hydrogen bonding strengths in these blends follow the order PS-b-P4VP/OP-POSS > PS-b-P2VP/OP-POSS > PS-b-PMMA/OP-POSS based on the Kwei equation from differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopic analyses. Small-angle X-ray scattering and transmission electron microscopic analyses show that the morphologies of the self-assembly structures are strongly dependent on the hydrogen bonding strength at relatively higher OP-POSS content. The PS-b-P4VP/OP-POSS hybrid complex system with the strongest hydrogen bonds shows the order-order transition from lamellae to cylinders and finally to body-centered cubic spheres upon increasing OP-POSS content. However, PS-b-P2VP/OP-POSS and PS-b-PMMA/OP-POSS hybrid complex systems, having relatively weaker hydrogen bonds, transformed from lamellae to cylinder structures at lower OP-POSS content (<50 wt%), but formed disordered structures at relatively high OP-POSS contents (>50 wt%). PMID:26781581

  18. Fibronectin Binding to the Treponema pallidum Adhesin Protein Fragment rTp0483 on Functionalized Self-Assembled Monolayers

    PubMed Central

    Dickerson, Matthew T.; Abney, Morgan B.; Cameron, Caroline E.; Knecht, Marc; Bachas, Leonidas G.; Anderson, Kimberly W.

    2012-01-01

    Past work has shown that Treponema pallidum, the causative agent of syphilis, binds host fibronectin (FN). FN and other host proteins are believed to bind to rare outer membrane proteins (OMPs) of T. pallidum, and it is postulated that this interaction may facilitate cell attachment and mask antigenic targets on the surface. This research seeks to prepare a surface capable of mimicking the FN binding ability of T. pallidum in order to investigate the impact of FN binding with adsorbed Tp0483 on the host response to the surface. By understanding this interaction it may be possible to develop more effective treatments for infection and possibly mimic the stealth properties of the bacteria. Functionalized self-assembled monolayers (SAMs) on0 gold were used to investigate rTp0483 and FN adsorption. Using a quartz crystal microbalance (QCM) rTp0483 adsorption and subsequent FN adsorption onto rTp0483 was determined to be higher on negatively charged carboxylate-terminated self-assembled monolayers (−COO− SAMs) compared to the other surfaces analyzed. Kinetic analysis of rTp0483 adsorption using surface plasmon resonance (SPR) supported this finding. Kinetic analysis of FN adsorption using SPR revealed a multi-step event, where the concentration of immobilized rTp0483 plays a role in FN binding. An examination of relative QCM dissipation energy compared to the shift in frequency showed a correlation between the physical properties of adsorbed rTp0483 and SAM surface chemistry. In addition, AFM images of rTp0483 on selected SAMs illustrated a preference of rTp0483 to bind as aggregates. Adsorption on −COO− SAMs was more uniform across the surface, which may help further explain why FN bound more strongly. rTp0483 antibody studies suggested the involvement of amino acids 274–289 and 316–333 in binding between rTp0483 to FN, while a peptide blocking study only showed inhibition of binding with amino acids 316–333. Finally, surface adsorbed rTp0483 with FN

  19. New bioactive motifs and their use in functionalized self-assembling peptides for NSC differentiation and neural tissue engineering

    NASA Astrophysics Data System (ADS)

    Gelain, F.; Cigognini, D.; Caprini, A.; Silva, D.; Colleoni, B.; Donegá, M.; Antonini, S.; Cohen, B. E.; Vescovi, A.

    2012-04-01

    Developing functionalized biomaterials for enhancing transplanted cell engraftment in vivo and stimulating the regeneration of injured tissues requires a multi-disciplinary approach customized for the tissue to be regenerated. In particular, nervous tissue engineering may take a great advantage from the discovery of novel functional motifs fostering transplanted stem cell engraftment and nervous fiber regeneration. Using phage display technology we have discovered new peptide sequences that bind to murine neural stem cell (NSC)-derived neural precursor cells (NPCs), and promote their viability and differentiation in vitro when linked to LDLK12 self-assembling peptide (SAPeptide). We characterized the newly functionalized LDLK12 SAPeptides via atomic force microscopy, circular dichroism and rheology, obtaining nanostructured hydrogels that support human and murine NSC proliferation and differentiation in vitro. One functionalized SAPeptide (Ac-FAQ), showing the highest stem cell viability and neural differentiation in vitro, was finally tested in acute contusive spinal cord injury in rats, where it fostered nervous tissue regrowth and improved locomotor recovery. Interestingly, animals treated with the non-functionalized LDLK12 had an axon sprouting/regeneration intermediate between Ac-FAQ-treated animals and controls. These results suggest that hydrogels functionalized with phage-derived peptides may constitute promising biomimetic scaffolds for in vitro NSC differentiation, as well as regenerative therapy of the injured nervous system. Moreover, this multi-disciplinary approach can be used to customize SAPeptides for other specific tissue engineering applications.Developing functionalized biomaterials for enhancing transplanted cell engraftment in vivo and stimulating the regeneration of injured tissues requires a multi-disciplinary approach customized for the tissue to be regenerated. In particular, nervous tissue engineering may take a great advantage from the

  20. Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals.

    PubMed

    Meyer, Dominik; Schäfer, Tobias; Schulz, Philip; Jung, Sebastian; Rittich, Julia; Mokros, Daniel; Segger, Ingolf; Maercks, Franziska; Effertz, Christian; Mazzarello, Riccardo; Wuttig, Matthias

    2016-09-01

    Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics. PMID:27504721

  1. Self-assembled monolayers of pyridylthio-functionalized carbon nanotubes used as a support to immobilize cytochrome c

    PubMed Central

    2013-01-01

    Self-assembled monolayers (SAMs) of pyridylthio-functionalized multiwalled carbon nanotubes (pythio-MWNTs) have been constructed on the gold substrate surface, which were used as a support to immobilize cytochrome c (Cyt c). The assembly processes of the SAMs and adsorption of Cyt c were monitored by using quartz crystal microbalance (QCM). Based on the frequency change of the QCM resonator, the surface coverage for the SAMs of pythio-MWNTs was estimated to be about 5.2 μg/cm2, and that of the Cyt c adsorbed was about 0.29 μg/cm2. For the gold electrode modified by the SAMs of pythio-MWNTs-Cyt c, a quasi-reversible redox wave was recorded with the cathodic and anodic potentials at about −0.55 and −0.28 V vs Ag/AgCl, respectively. Compositions and morphologies of the SAMs before and after immobilization of Cyt c were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. PMID:23391460

  2. Morphological control of PbS grown on functionalized self-assembled monolayers by chemical bath deposition.

    PubMed

    Yang, Jing; Walker, Amy V

    2014-06-17

    We have investigated the chemical bath deposition (CBD) of PbS on functionalized alkanethiolate self-assembled monolayers (SAMs) using time-of-flight secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The deposition mechanism involves both cluster-by-cluster and ion-by-ion growth. The dominant reaction pathway and the chemical composition and morphology of the deposited layer are dependent on both the SAM terminal group and the experimental conditions. On -COOH-terminated SAMs, three types of crystallites are observed: nanocrystals formed by heterogeneous ion-by-ion growth, larger needle-like particles, and ~2 μm particles deposited by homogeneous cluster-by-cluster deposition. The nanocrystals nucleate at Pb(2+)-carboxylate surface complexes, and so strongly adhere to the substrate. On -OH- and -CH3-terminated SAMs, only the micrometer-sized particles are formed by a cluster-by-cluster deposition mechanism. These particles do not adhere strongly to the SAM surface and can be easily removed. SIMS and XPS analyses indicate that the larger needle-like crystals and micrometer-sized particles are composed of oxidized lead sulfide and lead oxides, while the nanocrystals are composed of ≥85% PbS. Using sonication-assisted CBD, we demonstrate that PbS is deposited by ion-by-ion growth alone on -COOH-terminated SAMs. The deposited film is more compact with a smaller grain size and is >90% PbS. PMID:24854067

  3. Self-assembly of palladium nanoparticles on functional TiO2 nanotubes for a nonenzymatic glucose sensor.

    PubMed

    Chen, Xianlan; Li, Gang; Zhang, Guowei; Hou, Keyu; Pan, Haibo; Du, Min

    2016-05-01

    Polydiallyldimethylammonium chloride, PDDA, was used as a stabilizer and linker for functionalized TiO2 nanotubes (TiO2 NTs). Self-assembled process with palladium nanoparticles (NPs) was successfully synthesized and used for the oxidation of glucose on glassy carbon electrodes. Based on the voltammetric and amperometric results, Pd NPs efficiently catalyzed the oxidation of glucose at -0.05 V in the presence of 0.1 M NaCl and showed excellent resistance toward interference poisoning from such interfering species as ascorbic acid, uric acid and urea. To further increase sensitivity, the Pd NPs-PDDA-TiO2 NTs/GCE was electrochemically treated with H2SO4 and NaOH, the glucose oxidation current was magnified 2.5 times than that before pretreatments due to greatly enhancing the electron transport property of the sensor based on the increased defect sites and surface oxide species. In view of the physiological level of glucose, the wide linear concentration range of glucose (4×10(-7)-8×10(-4)M) with a detection limit of 8×10(-8)M (S/N=3) was obviously good enough for clinical application. PMID:26952430

  4. Functionalized SPIONs: the surfactant nature modulates the self-assembly and cluster formation.

    PubMed

    Luchini, Alessandra; Heenan, Richard K; Paduano, Luigi; Vitiello, Giuseppe

    2016-07-21

    SuperParamagnetic Iron Oxide Nanoparticles (SPIONs) represent a suitable system for several applications especially in nanomedicine. Great efforts have been made to design stable and biocompatible functionalized SPIONs suitable for diagnostics and drug delivery. In particular, zwitterionic-surfactant functionalized SPIONs, obtained through a coating strategy based on hydrophobic interaction, are promising systems for biomedical applications. The size of functionalized SPIONs has emerged as a crucial parameter determining their fate in living organisms. However, not all the proposed functionalization strategies lead to monodispersed systems and SPION clustering often occurs. In this study, we report a systematic investigation on different surfactant-functionalized SPIONs in order to explore the possibility of tuning the particle size by choosing an appropriate amphiphilic molecule. By combining Small-Angle Neutron Scattering (SANS) and Dynamic Light Scattering (DLS) analysis, we have provided a detailed description of the functionalized SPION structure. Furthermore, we have also related the surfactant aggregation properties, i.e. the Critical Micelle Concentration (CMC), to their efficiency in coating the SPION surface. A lack in the formation of a compact shell leads to a clusters formation. On this basis, the present study contributes to furnishing decisive information to define synthetic strategies able to tune functionalized-SPION design. PMID:27338137

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

    PubMed Central

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

    2015-01-01

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

  6. Insights into the surface topology of polyhydroxyalkanoate synthase: self-assembly of functionalized inclusions.

    PubMed

    Hooks, David O; Rehm, Bernd H A

    2015-10-01

    The polyhydroxyalkanoate (PHA) synthase catalyzes the synthesis of PHA and remains attached to the hydrophobic PHA inclusions it creates. Although this feature is actively exploited to generate functionalized biobeads via protein engineering, little is known about the structure of the PHA synthase. Here, the surface topology of Ralstonia eutropha PHA synthase was probed to inform rational protein engineering toward the production of functionalized PHA beads. Surface-exposed residues were detected by conjugating biotin to inclusion-bound PHA synthase and identifying the biotin-conjugated lysine and cysteine residues using peptide fingerprinting analysis. The identified sites (K77, K90, K139, C382, C459, and K518) were investigated as insertion sites for the generation of new protein fusions. Insertions of FLAG epitopes into exposed sites K77, K90, K139, and K518 were tolerated, retaining >65 % of in vivo activity. Sites K90, K139, and K518 were also tested by insertion of the immunoglobulin G (IgG)-binding domain (ZZ), successfully producing PHA inclusions able to bind human IgG in vitro. Although simultaneous insertions of the ZZ domain into two sites was permissive, insertion at all three lysine sites inactivated the synthase. The K90/K139 double ZZ insertion had the optimum IgG-binding capacity of 16 mg IgG/g wet PHA beads and could selectively purify the IgG fraction from human serum. Overall, this study identified surface-exposed flexible regions of the PHA synthase which either tolerate protein/peptide insertions or are critical for protein function. This further elucidates the structure and function of PHA synthase and provides new opportunities for generating functionalized PHA biobeads. PMID:26048474

  7. Orientation and Mg Incorporation of Calcite Grown on Functionalized Self-Assembled Monolayers: A Synchrotron X-ray Study

    SciTech Connect

    Kwak,S.; DiMasi, E.; Han, Y.; Aizenberg, J.; Kuzmenko, I.

    2005-01-01

    Calcite crystals were nucleated from MgCl2/CaCl2 solutions onto functionalized self-assembled monolayers adsorbed onto E-beam evaporated Au films. Synchrotron X-ray scattering studies of the crystals reveal new information about preferred orientation and Mg incorporation. The Au [111] axis is distributed within 2.6 degrees of the film surface normal, but the oriented crystals may be tilted up to 6 degrees away from this axis. For low Mg{sup 2+} content, SO{sub 3}--functionalized films nucleated primarily near the (106) calcite face, odd-chain-length carboxylic acid terminated alkanethiol films nucleated near the (012) face, and even-chain-length carboxylic acid terminated alkanethiol films nucleated near the (113) face. [Mg{sup 2+}]/[Ca{sup 2+}] concentration ratios (n) of 2 and greater defeated this preferred orientation and created a powder texture. Diffraction patterns within the layer plane from the coarse calcite powders indicated a shift to higher 2 accompanied by peak broadening with increasing n. For 0.5 < n < 3.5, a double set of calcite peaks is observed, showing that two distinct Mg calcite phases form: one of comparatively lower Mg content, derived from the templated crystals, and a Mg-rich phase derived from amorphous precursor particles. According to the refinement of lattice parameters, Mg incorporation of up to 18 mol % occurs for n = 4, independent of film functionality. We discuss the differences between the differently functionalized monolayers and also introduce the hypothesis that two separate routes to Mg calcite formation occur in this system.

  8. Controlling Self-Assembly Kinetics of DNA-Functionalized Liposomes Using Toehold Exchange Mechanism.

    PubMed

    Parolini, Lucia; Kotar, Jurij; Di Michele, Lorenzo; Mognetti, Bortolo M

    2016-02-23

    The selectivity of Watson-Crick base pairing has allowed the design of DNA-based functional materials bearing an unprecedented level of accuracy. Examples include DNA origami, made of tiles assembling into arbitrarily complex shapes, and DNA coated particles featuring rich phase behaviors. Frequently, the realization of conceptual DNA-nanotechnology designs has been hampered by the lack of strategies for effectively controlling relaxations. In this article, we address the problem of kinetic control on DNA-mediated interactions between Brownian objects. We design a kinetic pathway based on toehold-exchange mechanisms that enables rearrangement of DNA bonds without the need for thermal denaturation, and test it on suspensions of DNA-functionalized liposomes, demonstrating tunability of aggregation rates over more than 1 order of magnitude. While the possibility to design complex phase behaviors using DNA as a glue is already well recognized, our results demonstrate control also over the kinetics of such systems. PMID:26845414

  9. A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

    PubMed Central

    Du, Ping; Bléger, David; Charra, Fabrice; Bouchiat, Vincent; Kreher, David; Mathevet, Fabrice

    2015-01-01

    Summary Two-dimensional (2D), supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D) building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2)-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications. PMID:25821703

  10. Adamantane-Based Tripodal Thioether Ligands Functionalized with a Redox-Active Ferrocenyl Moiety for Self-Assembled Monolayers

    PubMed Central

    Weidner, Tobias; Zharnikov, Michael; Hoβbach, Jens; Castner, David G.; Siemeling, Ulrich

    2010-01-01

    Self-assembled monolayers (SAMs) can decorate surfaces with `smart´ functional units possessing reversible stimulus–response behavior for optical, thermal, magnetic or redox-chemical stimuli. An independent performance of individual functional groups in such a film is desirable, which can be, in particular, ensured by fairly large lateral separations between tailgroups in the SAM. Adsorbate molecules with multiple attachment points are very promising in this context owing to their large surface footprint, which covers a surface area exceeding the lateral dimensions of the functional groups. To address these design constraints, novel tridentate long-chain tripodal thioether ligands with central adamantine units and a redox-active ferrocenyl tailgroup, 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-octylsulfanyl)phenyl]adamantine (T8) and 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-dodecylsulfanyl)phenyl]adamantine (T12), were synthesized and used as tripodal adsorbate molecules for the fabrication of redox-active ferrocenyl-terminated SAMs on Au(111). These SAMs were characterized by X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and sum frequency generation spectroscopy. The data suggest that T8 and T12 form almost contamination-free, well-aligned and fairly densely-packed SAMs on Au(111) with laterally separated ferrocenyl units. The SAMs show a homogeneous binding chemistry, an important requirement for high fidelity SAMs. SFG results indicate lateral interactions between neighboring molecules via the long-chain binding units. PMID:21399702

  11. Implantation of cardiac progenitor cells using self-assembling peptide improves cardiac function after myocardial infarction.

    PubMed

    Tokunaga, Masakuni; Liu, Mei-Lan; Nagai, Toshio; Iwanaga, Koji; Matsuura, Katsuhisa; Takahashi, Toshinao; Kanda, Masato; Kondo, Naomichi; Wang, Pin; Naito, Atsuhiko T; Komuro, Issei

    2010-12-01

    Implantation of various types of cells into the heart has been reported to be effective for heart failure, however, it is unknown what kinds of cells are most suitable for myocardial repair. To examine which types of cells are most effective, we injected cell-Puramatrix™ (PM) complex into the border area and overlaid the cell-PM patch on the myocardial infarction (MI) area. We compared cardiac morphology and function at 2 weeks after transplantation. Among clonal stem cell antigen-1 positive cardiac progenitors with PM (cSca-1/PM), bone marrow mononuclear cells with PM (BM/PM), skeletal myoblasts with PM (SM/PM), adipose tissue-derived mesenchymal cells with PM (AMC/PM), PM alone (PM), and non-treated MI group (MI), the infarct area of cSca-1/PM was smaller than that of BM/PM, SM/PM, PM and MI. cSca-1/PM and AMC/PM attenuated ventricular enlargement and restored cardiac function in comparison with MI. Capillary density in the infarct area of cSca-1/PM was higher than that of other five groups. The percentage of TUNEL positive cardiomyocytes in the infarct area of cSca-1/PM was lower than that of MI and PM. cSca-1 secreted VEGF and some of them differentiated into cardiomyocytes and vascular smooth muscle cells. These results suggest that transplantation of cSca-1/PM most effectively prevents cardiac remodeling and dysfunction through angiogenesis, inhibition of apoptosis and myocardial regeneration. PMID:20869968

  12. Protein self-assembly via supramolecular strategies.

    PubMed

    Bai, Yushi; Luo, Quan; Liu, Junqiu

    2016-05-21

    Proteins, as the elemental basis of living organisms, mostly execute their biological tasks in the form of supramolecular self-assemblies with subtle architectures, dynamic interactions and versatile functionalities. Inspired by the structural harmony and functional beauty of natural protein self-assemblies to fabricate sophisticated yet highly ordered protein superstructures represents an adventure in the pursuit of nature's supreme wisdom. In this review, we focus on building protein self-assembly systems based on supramolecular strategies and classify recent progress by the types of utilized supramolecular driving forces. Especially, the design strategy, structure control and the thermodynamic/kinetic regulation of the self-assemblies, which will in turn provide insights into the natural biological self-assembly mechanism, are highlighted. In addition, recently, this research field is starting to extend its interest beyond constructing complex morphologies towards the potential applications of the self-assembly systems; several attempts to design functional protein complexes are also discussed. As such, we hope that this review will provide a panoramic sketch of the field and draw a roadmap towards the ultimate construction of advanced protein self-assemblies that even can serve as analogues of their natural counterparts. PMID:27080059

  13. Structure, Function, Self-Assembly and Origin of Simple Membrane Proteins

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew

    2003-01-01

    Integral membrane proteins perform such essential cellular functions as transport of ions, nutrients and waste products across cell walls, transduction of environmental signals, regulation of cell fusion, recognition of other cells, energy capture and its conversion into high-energy compounds. In fact, 30-40% of genes in modem organisms codes for membrane proteins. Although contemporary membrane proteins or their functional assemblies can be quite complex, their transmembrane fragments are usually remarkably simple. The most common structural motif for these fragments is a bundle of alpha-helices, but occasionally it could be a beta-barrel. In a series of molecular dynamics computer simulations we investigated self-organizing properties of simple membrane proteins based on these structural motifs. Specifically, we studied folding and insertion into membranes of short, nonpolar or amphiphatic peptides. We also investigated glycophorin A, a peptide that forms sequence-specific dimers, and a transmembrane aggregate of four identical alpha-helices that forms an efficient and selective voltage-gated proton channel was investigated. Many peptides are attracted to water-membrane interfaces. Once at the interface, nonpolar peptides spontaneously fold to a-helices. Whenever the sequence permits, peptides that contain both polar and nonpolar amino also adopt helical structures, in which polar and nonpolar amino acid side chains are immersed in water and membrane, respectively. Specific identity of side chains is less important. Helical peptides at the interface could insert into the membrane and adopt a transmembrane conformation. However, insertion of a single helix is unfavorable because polar groups in the peptide become completely dehydrated upon insertion. The unfavorable free energy of insertion can be regained by spontaneous association of peptides in the membrane. The first step in this process is the formation of dimers, although the most common are aggregates of 4

  14. Self-assembly of copper(II) ion-mediated nanotube and its supramolecular chiral catalytic behavior.

    PubMed

    Jin, Qingxian; Zhang, Li; Cao, Hai; Wang, Tianyu; Zhu, Xuefeng; Jiang, Jian; Liu, Minghua

    2011-11-15

    Self-assembly of several low-molecular-weight L-glutamic acid-based gelators, which individually formed helical nanotube or nanofiber structures, was investigated in the presence of Cu(2+) ion. It was found that, when Cu(2+) was added into the system, the self-assembly manner changed significantly. Only in the case of bolaamphiphilic glutamic acid, N,N'-hexadecanedioyl-di-L-glutamic acid (L-HDGA), were the hydrogel formation as well as the nanotube structures maintained. The addition of Cu(2+) ion caused a transition from monolayer nanotube of L-HDGA to a multilayer nanotube with the thickness of the tubular wall about 10 nm. For the other amphiphiles, the gel was destroyed and nanofiber structures were mainly formed. The formed Cu(2+)-containing nanostructures can function as an asymmetric catalyst for Diels-Alder cycloaddition between cyclopentadiene and aza-chalcone. In comparison with the other Cu(2+)-containing nanostructures, the Cu(2+)-mediated nanotube structure showed not only accelerated reaction rate, but enhanced enantiomeric selectivity. It was suggested that, through the Cu(2+) mediated nanotube formation, the substrate molecules could be anchored on the nanotube surfaces and produced a stereochemically favored alignment. When adducts reacted with the substrate, both the enantiomeric selectivity and the reaction rate were increased. Since the Cu(2+)-mediated nanotube can be fabricated easily and in large amount, the work opened a new way to perform efficient chiral catalysis through the supramolecular gel. PMID:21978005

  15. Self assembling proteins

    DOEpatents

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

    2004-06-29

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

  16. Multifunctional self-assembled monolayers

    SciTech Connect

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

    1996-06-01

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

  17. Bolaamphiphiles Promote Phospholipid Translocation Across Vesicle Membranes

    PubMed Central

    Forbes, Christopher C.; DiVittorio, Kristy M.; Smith, Bradley D.

    2008-01-01

    A series of membrane-spanning bolaamphiphiles (molecules with two hydrophilic end-groups connected by a hydrophobic linker) were prepared by a modular synthetic method and evaluated for their abilities to affect the dynamics of a surrounding bilayer membrane. The goal was to determine if the bolaamphiphiles promote the translocation of phospholipids across vesicle membranes. The bolaamphiphiles were incorporated at low levels (up to 5 mol%) in vesicles composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Inward translocation assays were performed using fluorescent, NBD-labeled phospholipid probes with phosphocholine (PC) or phosphoglycerol (PG) head-groups. The membrane-spanning bolaamphiphiles promote the translocation of both phospholipid probes in the order PG > PC, while shorter bolaamphiphiles (structures that must adopt a U-shape and keep both end-groups in the same leaflet of the membrane), and regular amphiphiles with one hydrophilic end-group, are inactive. These results are an exception to the rule-of-thumb that membrane-spanning bolaamphiphiles are inherently membrane stabilizing molecules that inhibit all types of membrane transport. PMID:16834395

  18. Photovoltaic self-assembly.

    SciTech Connect

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

    2010-10-01

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

  19. Adaptive soft molecular self-assemblies.

    PubMed

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

    2016-01-14

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

  20. End-Group-Functionalized Poly(α-olefinates) as Non-Polar Building Blocks: Self-Assembly of Sugar-Polyolefin Hybrid Conjugates.

    PubMed

    Thomas, Tessy S; Hwang, Wonseok; Sita, Lawrence R

    2016-04-01

    Living coordinative chain-transfer polymerization of α-olefins, followed by chemical functionalization of a Zn(polymeryl)2 intermediate, provides entry to end-group functionalized poly(α-olefinates) (x-PAOs) that can serve as a new class of non-polar building block with tailorable occupied volumes. Application of these x-PAOs for the synthesis and self-assembly of sugar-polyolefin hybrid conjugates demonstrate the ability to manipulate the morphology of the ultra-thin film nanostructure through variation in occupied volume of the x-PAO domain. PMID:26961338

  1. Characterization of self-assembled functional polymeric nanostructures: I. magnetic nanostructures from metallopolymers II. Zwitterionic polymer vesicles in ionic liquid

    NASA Astrophysics Data System (ADS)

    Maddikeri, Raghavendra Raj

    matrix is confined between the non-magnetic cylinders, had second highest and lamellar morphology with least confinement among BCPs, exhibited lowest coercivity. The proposed hypothesis was further tested by systematically varying the dipolar interactions between the SPM cobalt nanoparticles by reducing the density of cobalt within the cylindrical domains and varying the dimensions of the cylindrical domains (i.e. diameter). A series of novel ferrocene-cobalt containing block copolymers were developed and cobalt density within the cylindrical domains of BCP was varied by changing the chemical composition of the metal functionalized block. Further, the diameter of the cylindrical domains was varied by varying the molecular weight of the cobalt-containing BCPs. These studies allowed us to understand the fundamental correlations between the self-assembled nanostructures and their macroscopic magnetic properties. In the second part of the thesis, a novel amphiphilic block copolymer (ABC), composed of a hydrophilic zwitterionic block and a hydrophobic PS block, was synthesized by ROMP. The formation of zwitterionic vesicles in an ionic liquid, as well as in PBS buffer, was confirmed by TEM and DLS characterization. The dispersion of vesicles within ionic liquid enabled the usage of conventional, room temperature TEM to visualize them in their solution state. This technique of materials characterization could be extended for the visualization of other hydrophilic soft matter.

  2. Silk Reconstitution Disrupts Fibroin Self-Assembly.

    PubMed

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

    2015-09-14

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

  3. Hierarchical self-assembly of di-, tri- and tetraphenylalanine peptides capped with two fluorenyl functionalities: from polymorphs to dendrites.

    PubMed

    Mayans, Enric; Ballano, Gema; Casanovas, Jordi; Del Valle, Luis J; Pérez-Madrigal, Maria M; Estrany, Francesc; Jiménez, Ana I; Puiggalí, Jordi; Cativiela, Carlos; Alemán, Carlos

    2016-06-28

    Homopeptides with 2, 3 and 4 phenylalanine (Phe) residues and capped with fluorenylmethoxycarbonyl and fluorenylmethyl esters at the N-terminus and C-terminus, respectively, have been synthesized to examine their self-assembly capabilities. Depending on the conditions, the di- and triphenylalanine derivatives self-organize into a wide variety of stable polymorphic structures, which have been characterized: stacked braids, doughnut-like shapes, bundled arrays of nanotubes, corkscrew-like shapes and spherulitic microstructures. These highly aromatic Phe-based peptides also form incipient branched dendritic microstructures, even though they are highly unstable, making their manipulation very difficult. Conversely, the tetraphenylalanine derivative spontaneously self-assembles into stable dendritic microarchitectures made of branches growing from nucleated primary frameworks. The fractal dimension of these microstructures is ∼1.70, which provides evidence for self-similarity and two-dimensional diffusion controlled growth. DFT calculations at the M06L/6-31G(d) level have been carried out on model β-sheets since this is the most elementary building block of Phe-based peptide polymorphs. The results indicate that the antiparallel β-sheet is more stable than the parallel one, with the difference between them growing with the number of Phe residues. Thus, the cooperative effects associated with the antiparallel disposition become more favorable when the number of Phe residues increases from 2 to 4, while those of the parallel disposition remained practically constant. PMID:27220532

  4. Interplay between self-assembled structure of bone morphogenetic protein-2 (BMP-2) and osteoblast functions in three-dimensional titanium alloy scaffolds: Stimulation of osteogenic activity.

    PubMed

    Nune, K C; Kumar, A; Murr, L E; Misra, R D K

    2016-02-01

    Three-dimensional cellular scaffolds are receiving significant attention in bone tissue engineering to treat segmental bone defects. However, there are indications of lack of significant osteoinductive ability of three-dimensional cellular scaffolds. In this regard, the objective of the study is to elucidate the interplay between bone morphogenetic protein (BMP-2) and osteoblast functions on 3D mesh structures with different porosities and pore size that were fabricated by electron beam melting. Self-assembled dendritic microstructure with interconnected cellular-type morphology of BMP-2 on 3D scaffolds stimulated osteoblast functions including adhesion, proliferation, and mineralization, with prominent effect on 2-mm mesh. Furthermore, immunofluorescence studies demonstrated higher density and viability of osteoblasts on lower porosity mesh structure (2 mm) as compared to 3- and 4-mm mesh structures. Enhanced filopodia cellular extensions with extensive cell spreading was observed on BMP-2 treated mesh structures, a behavior that is attributed to the unique self-assembled structure of BMP-2 that effectively communicates with the cells. The study underscores the potential of BMP-2 in imparting osteoinductive capability to the 3D printed scaffolds. PMID:26475990

  5. MicroRNA-triggered, cascaded and catalytic self-assembly of functional ``DNAzyme ferris wheel'' nanostructures for highly sensitive colorimetric detection of cancer cells

    NASA Astrophysics Data System (ADS)

    Zhou, Wenjiao; Liang, Wenbin; Li, Xin; Chai, Yaqin; Yuan, Ruo; Xiang, Yun

    2015-05-01

    The construction of DNA nanostructures with various sizes and shapes has significantly advanced during the past three decades, yet the application of these DNA nanostructures for solving real problems is still in the early stage. On the basis of microRNA-triggered, catalytic self-assembly formation of the functional ``DNAzyme ferris wheel'' nanostructures, we show here a new signal amplification platform for highly sensitive, label-free and non-enzyme colorimetric detection of a small number of human prostate cancer cells. The microRNA (miR-141), which is catalytically recycled and reused, triggers isothermal self-assembly of a pre-designed, G-quadruplex sequence containing hairpin DNAs into ``DNAzyme ferris wheel''-like nanostructures (in association with hemin) with horseradish peroxidase mimicking activity. These DNAzyme nanostructures catalyze an intensified color transition of the probe solution for highly sensitive detection of miR-141 down to 0.5 pM with the naked eye, and the monitoring of as low as 283 human prostate cancer cells can also, theoretically, be achieved in a colorimetric approach. The work demonstrated here thus offers new opportunities for the construction of functional DNA nanostructures and for the application of these DNA nanostructures as an effective signal amplification means in the sensitive detection of nucleic acid biomarkers.

  6. Construction of carbon quantum dots/proton-functionalized graphitic carbon nitride nanocomposite via electrostatic self-assembly strategy and its application

    NASA Astrophysics Data System (ADS)

    Jian, Xuan; Liu, Xian; Yang, Hui-min; Li, Jia-gang; Song, Xiu-li; Dai, Hong-yan; Liang, Zhen-hai

    2016-05-01

    Carbon quantum dots (CQDs) and graphitic carbon nitride (g-C3N4), as advanced metal-free material catalysts have been the focus of considerable attention because of their superior photocatalytic activities. In this study, we developed a novel approach to obtain CQDs/g-C3N4 nanocomposite with effective interfacial contact by incorporating negatively charged CQDs and tailor-made proton-functionalized g-C3N4via the electrostatic self-assembly strategy. Then, the morphology and microstructure of the new nanocomposite were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). The CQDs and proton-functionalized g-C3N4 nanocomposite exhibited excellent electron transfer properties though electrochemical impedance spectroscopy (EIS), significantly enhanced photoactivity in the photoelectrochemical i-t curve test and degradation of methylene blue solution under visible light irradiation. These results demonstrated that the electrostatic self-assembly strategy process is a promising method of fabricating uniform metal-free material catalysts for an extensive range of applications.

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

    DOEpatents

    Bouchard, Ann M.; Osbourn, Gordon C.

    2013-01-08

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

  8. Functionalization of cotton fiber by partial etherification and self-assembly of polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework.

    PubMed

    Lange, Laura E; Obendorf, S Kay

    2015-02-25

    A combination of a Keggin-type polyoxometalate (POM), [CuPW11O39](5-), with a Cu3(BTC)2 metal-organic framework (MOF-199/HKUST-1; where BTC is benzene-1,3,5-tricarboxylate), was successfully self-assembled on a cellulose substrate (cotton) with a room-temperature process. Cotton fibers were functionalized by partial etherification. Cu3(BTC)2 metal-organic framework and polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework were self-assembled on the carboxymethylate ion sites initiated with copper nitrate using ethanol and water as solvents. Octahedral crystals were observed on both MOF-cotton and POM-MOF-cotton; both contained copper while the POM-MOF-cotton also contained tungsten. Occupancy of POM in MOF cages was calculated to be about 13%. Moisture content remained at 3 to 4 wt % similar to that of untreated cotton. Reactivity to both hydrogen sulfide and methyl parathion was higher for POM-MOF-cotton due to the Keggin polyoxometalate and the extra-framework cations Cu(2+) ions compensating the charges of the encapsulated Keggins. The POM-MOF material was found to effectively remove 0.089 mg of methyl parathion per mg of MOF from a hexane solution while MOF-cotton removed only 0.054 mg of methyl parathion per mg of MOF. PMID:25647089

  9. High-efficiency extraction of nucleosides based on the combination of self-assembly ionic liquid layer and boronic acid-functionalized attapulgite.

    PubMed

    Li, Huihui; Cheng, Ting; Wang, Shuxia; Zhu, Xinyue; Zhang, Haixia

    2016-06-01

    Boronate affinity materials have been widely used for selective capture of cis-diol-containing molecules, but most do not have sufficient extraction efficiency. We have prepared boronic acid-functionalized attapulgite, and then it was coated with imidazolium-based ionic liquid, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), via physical self-assembly process. The extraction efficiency of the material increased dramatically after coated with C12mimBr, and its enrichment ratios for nucleosides increased by 9- to 282-fold. Besides, the C12mimBr-coated adsorbent did not lose selectivity and was able to capture cis-diols in the presence of a 100-fold excess of interferences. C12mimBr-coated material was applied to selective enrichment of nucleosides from human urine. The limits of detection and the limits of quantification were in the range of 0.06-0.46ngmL(-1) and 0.20-1.53ngmL(-1), respectively. Reproducibility of the method was determined with relative standard deviations≤9.9%. The recoveries of the target nucleosides from spiked human urine were in the range of 87.8-109.6%. In our preception, self-assembly ionic liquid layer can serve as a promising alternative to improve the extraction efficiency of boronate affinity materials. PMID:27130092

  10. Self-assembled gelators for organic electronics.

    PubMed

    Babu, Sukumaran Santhosh; Prasanthkumar, Seelam; Ajayaghosh, Ayyappanpillai

    2012-02-20

    Nature excels at engineering materials by using the principles of chemical synthesis and molecular self-assembly with the help of noncovalent forces. Learning from these phenomena, scientists have been able to create a variety of self-assembled artificial materials of different size, shapes, and properties for wide ranging applications. An area of great interest in this regard is solvent-assisted gel formation with functional organic molecules, thus leading to one-dimensional fibers. Such fibers have improved electronic properties and are potential soft materials for organic electronic devices, particularly in bulk heterojunction solar cells. Described herein is how molecular self-assembly, which was originally proposed as a simple laboratory curiosity, has helped the evolution of a variety of soft functional materials useful for advanced electronic devices such as organic field-effect transistors and organic solar cells. Highlights on some of the recent developments are discussed. PMID:22278754

  11. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations.

    PubMed

    Yan, Chang; Yuan, Rongfeng; Pfalzgraff, William C; Nishida, Jun; Wang, Lu; Markland, Thomas E; Fayer, Michael D

    2016-05-01

    Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments. PMID:27044113

  12. Covalent functionalized self-assembled lipo-polymerosome bearing amphotericin B for better management of leishmaniasis and its toxicity evaluation.

    PubMed

    Gupta, Pramod K; Jaiswal, Anil K; Kumar, Vivek; Verma, Ashwni; Dwivedi, Pankaj; Dube, Anuradha; Mishra, Prabhat R

    2014-03-01

    Amphotericin B remains the preferred choice for leishmanial infection, but it has limited clinical applications due to substantial dose limiting toxicities. In the present work, AmB has been formulated in lipo-polymerosome (L-Psome) by spontaneous self-assembly of synthesized glycol chitosan-stearic acid copolymer. The optimized L-Psome formulation with vesicle size of 243.5 ± 17.9 nm, PDI of 0.168 ± 0.08 and zeta potential of (+) 27.15 ± 0.46 mV with 25.59 ± 0.87% AmB loading was obtained. The field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM) images suggest nearly spherical morphology of L-Psome. An in vitro study showed comparatively sustained AmB release (66.082 ± 1.73% within 24 h) and high plasma stability compared to commercial Ambisome and Fungizone, where glycol chitosan content was found to be efficient in preventing L-Psome destabilization in the presence of plasma protein. In vitro and in vivo toxicity studies revealed less toxicity of AmB-L-Psome compared to commercialized Fungizone and Ambisome favored by monomeric form of AmB within L-Psome, observed by UV-visible spectroscopy. Experimental results of in vitro (macrophage amastigote system) and in vivo (Leishmania donovani infected hamsters) illustrated the efficacy of AmB-L-Psome to augment effective antileishmanial properties supported by upregulation of Th-1 cytokines (TNF-α, IL-12 and IFN-γ) and inducible nitric oxide synthase, and downregulation of Th-2 cytokines (TGF-β, IL-10 and IL-4), measured by quantitative mRNA analysis by real time PCR (RT-PCR). Conclusively, developed L-Psome system could be a viable alternative to the current less stable, toxic commercial formulations and developed as a highly efficacious drug delivery system. PMID:24495144

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  14. Immunohistochemical characterization and functional identification of mammary gland telocytes in the self-assembly of reconstituted breast cancer tissue in vitro.

    PubMed

    Mou, Yongchao; Wang, Yan; Li, Junjie; Lü, Shuanghong; Duan, Cuimi; Du, Zhiyan; Yang, Guili; Chen, Weizhen; Zhao, Siyang; Zhou, Jin; Wang, Changyong

    2013-01-01

    Telocyte (TC) as a special stromal cell exists in mammary gland and might play an important role in the balance of epithelium-stroma of mammary gland. Considering that different types of breast interstitial cells influence the development and progression of breast cancer, TCs may have its distinct role in this process. We here studied the roles of TCs in the self-assembly of reconstituted breast cancer tissue. We co-cultured primary isolated TCs and other breast stromal cells with breast cancer EMT-6 cells in collagen/Matrigel scaffolds to reconstitute breast cancer tissue in vitro. Using histology methods, we investigated the immunohistochemical characteristics and potential functions of TCs in reconstituted breast cancer tissue. TCs in primary mammary gland stromal cells with long and thin overlapping cytoplasmic processes, expressed c-kit/CD117, CD34 and vimentin in reconstitute breast cancer tissue. The transmission electron microscopy showed that the telocyte-like cells closely communicated with breast cancer cells as well as other stromal cells, and might serve as a bridge that directly linked the adjacent cells through membrane-to-membrane contact. Compared with cancer tissue sheets of EMT-6 alone, PCNA proliferation index analysis and TUNEL assay showed that TCs and other breast stromal cells facilitated the formation of typical nest structure, promoted the proliferation of breast cancer cells, and inhibited their apoptosis. In conclusion, we successfully reconstituted breast cancer tissue in vitro, and it seems to be attractive that TCs had potential functions in self-assembly of EMT-6/stromal cells reconstituted breast cancer tissue. PMID:23206234

  15. Covalent immobilization of native biomolecules onto Au(111) via N-hydroxysuccinimide ester functionalized self-assembled monolayers for scanning probe microscopy.

    PubMed Central

    Wagner, P; Hegner, M; Kernen, P; Zaugg, F; Semenza, G

    1996-01-01

    We have worked out a procedure for covalent binding of native biomacromolecules on flat gold surfaces for scanning probe microscopy in aqueous buffer solutions and for other nanotechnological applications, such as the direct measurement of interaction forces between immobilized macromolecules, of their elastomechanical properties, etc. It is based on the covalent immobilization of amino group-containing biomolecules (e.g., proteins, phospholipids) onto atomically flat gold surfaces via omega-functionalized self-assembled monolayers. We present the synthesis of the parent compound, dithio-bis(succinimidylundecanoate) (DSU), and a detailed study of the chemical and physical properties of the monolayer it forms spontaneously on Au(111). Scanning tunneling microscopy and atomic force microscopy (AFM) revealed a monolayer arrangement with the well-known depressions that are known to stem from an etch process during the self-assembly. The total density of the omega-N-hydroxysuccinimidyl groups on atomically flat gold was 585 pmol/cm(2), as determined by chemisorption of (14)C-labeled DSU. This corresponded to approximately 75% of the maximum density of the omega-unsubstituted alkanethiol. Measurements of the kinetics of monolayer formation showed a very fast initial phase, with total coverage within 30 S. A subsequent slower rearrangement of the chemisorbed molecules, as indicated by AFM, led to a decrease in the number of monolayer depressions in approximately 60 min. The rate of hydrolysis of the omega-N-hydroxysuccinimide groups at the monolayer/water interface was found to be very slow, even at moderately alkaline pH values. Furthermore, the binding of low-molecular-weight amines and of a model protein was investigated in detail. Images FIGURE 1 FIGURE 2 FIGURE 9 PMID:9172730

  16. Structure-Based Design of Dendritic Peptide Bolaamphiphiles for siRNA Delivery

    PubMed Central

    2015-01-01

    Development of safe and effective delivery vectors is a critical challenge for the application of RNA interference (RNAi)-based biotechnologies. In this study we show the rational design of a series of novel dendritic peptide bolaamphiphile vectors that demonstrate high efficiency for the delivery of small interfering RNA (siRNA) while exhibiting low cytotoxicity and hemolytic activity. Systematic investigation into structure–property relationships revealed an important correlation between molecular design, self-assembled nanostructure, and biological activity. The unique bolaamphiphile architecture proved a key factor for improved complex stability and transfection efficiency. The optimal vector contains a fluorocarbon core and exhibited enhanced delivery efficiency to a variety of cell lines and improved serum resistance when compared to hydrocarbon analogues and lipofectamine RNAiMAX. In addition to introducing a promising new vector system for siRNA delivery, the structure–property relationships and “fluorocarbon effect” revealed herein offer critical insight for further development of novel materials for nucleic acid delivery and other biomaterial applications. PMID:26436138

  17. Self-assembled nanolaminate coatings (SV)

    SciTech Connect

    Fan, H.

    2012-03-01

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

  18. Self-assembly of azide containing dipeptides.

    PubMed

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

    2014-07-01

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

  19. Etching of Crystalline ZnO Surfaces upon Phosphonic Acid Adsorption: Guidelines for the Realization of Well-Engineered Functional Self-Assembled Monolayers.

    PubMed

    Ostapenko, Alexandra; Klöffel, Tobias; Eußner, Jens; Harms, Klaus; Dehnen, Stefanie; Meyer, Bernd; Witte, Gregor

    2016-06-01

    Functionalization of metal oxides by means of covalently bound self-assembled monolayers (SAMs) offers a tailoring of surface electronic properties such as their work function and, in combination with its large charge carrier mobility, renders ZnO a promising conductive oxide for use as transparent electrode material in optoelectronic devices. In this study, we show that the formation of phosphonic acid-anchored SAMs on ZnO competes with an unwanted chemical side reaction, leading to the formation of surface precipitates and severe surface damage at prolonged immersion times of several days. Combining atomic force microscopy (AFM), X-ray diffraction (XRD), and thermal desorption spectroscopy (TDS), the stability and structure of the aggregates formed upon immersion of ZnO single crystal surfaces of different orientations [(0001̅), (0001), and (101̅0)] in phenylphosphonic acid (PPA) solution were studied. By intentionally increasing the immersion time to more than 1 week, large crystalline precipitates are formed, which are identified as zinc phosphonate. Moreover, the energetics and the reaction pathway of this transformation have been evaluated using density functional theory (DFT), showing that zinc phosphonate is thermodynamically more favorable than phosphonic acid SAMs on ZnO. Precipitation is also found for phosphonic acids with fluorinated aromatic backbones, while less precipitation occurs upon formation of SAMs with phenylphosphinic anchoring units. By contrast, no precipitates are formed when PPA monolayer films are prepared by sublimation under vacuum conditions, yielding smooth surfaces without noticeable etching. PMID:27159837

  20. Dissipative self-assembly of vesicular nanoreactors.

    PubMed

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

    2016-07-01

    Dissipative self-assembly is exploited by nature to control important biological functions, such as cell division, motility and signal transduction. The ability to construct synthetic supramolecular assemblies that require the continuous consumption of energy to remain in the functional state is an essential premise for the design of synthetic systems with lifelike properties. Here, we show a new strategy for the dissipative self-assembly of functional supramolecular structures with high structural complexity. It relies on the transient stabilization of vesicles through noncovalent interactions between the surfactants and adenosine triphosphate (ATP), which acts as the chemical fuel. It is shown that the lifetime of the vesicles can be regulated by controlling the hydrolysis rate of ATP. The vesicles sustain a chemical reaction but only as long as chemical fuel is present to keep the system in the out-of-equilibrium state. The lifetime of the vesicles determines the amount of reaction product produced by the system. PMID:27325101

  1. Additive, modular functionalization of reactive self-assembled monolayers: toward the fabrication of multilevel optical storage media.

    PubMed

    Gentili, Denis; Barbalinardo, Marianna; Manet, Ilse; Durso, Margherita; Brucale, Marco; Mezzi, Alessio; Melucci, Manuela; Cavallini, Massimiliano

    2015-04-28

    We report a novel strategy based on iterative microcontact printing, which provides additive, modular functionalization of reactive SAMs by different functional molecules. We demonstrate that after printing the molecules form an interpenetrating network at the SAM surface preserving their individual properties. We exploited the process by fabricating new optical storage media that consist of a multilevel TAG. PMID:25824851

  2. Poly(ε-caprolactone) modified with fusion protein containing self-assembled hydrophobin and functional peptide for selective capture of human blood outgrowth endothelial cells.

    PubMed

    Huang, Yujian; Zhang, Suai; Niu, Baolong; Wang, Dandan; Wang, Zefang; Feng, Shuren; Xu, Haijin; Kong, Deling; Qiao, Mingqiang

    2013-01-01

    Human blood outgrowth endothelial cells (HBOECs)-specific binding peptide, TPSLEQRTVYAK (TPS), was proposed to be applied on autologous cell therapy for treating cardiovascular diseases. Hydrophobins, as a family of self-assembly proteins originated from fungi, have demonstrated unique characteristics to modulate surface properties of other materials coated with these amphiphilic proteins in previous studies. In this report, a fusion protein which was composed of class I hydrophobin HGFI originated from Grifola frondosa and functional peptide TPS was expressed by Pichia pastoris expression system. Then, we purified this fusion protein by ultrafiltration and reverse-phase high performance liquid chromatography. Water contact angle, X-ray photoelectron spectroscopy measurements indicated that the surface properties of hydrophobin were greatly preserved by this fusion protein while comparing with wild HGFI. Cell binding assay showed that this fusion protein demonstrated specific binding property to HBOECs while coating on biodegradable poly(ε-caprolactone) (PCL) grafts in the presence of fetal bovine serum, whereas HGFI-coated PCL non-selectively enhanced all types of cells attachments. Methylthiazol tetrazolium assay was employed to verify the cytocompatibility of this fusion protein-based material. This work presented a new perspective to apply hydrophobin in tissue engineering and regenerative medicine and provided an alternative approach to study endothelial progenitor cells. PMID:23010042

  3. Additive, modular functionalization of reactive self-assembled monolayers: toward the fabrication of multilevel optical storage media

    NASA Astrophysics Data System (ADS)

    Gentili, Denis; Barbalinardo, Marianna; Manet, Ilse; Durso, Margherita; Brucale, Marco; Mezzi, Alessio; Melucci, Manuela; Cavallini, Massimiliano

    2015-04-01

    We report a novel strategy based on iterative microcontact printing, which provides additive, modular functionalization of reactive SAMs by different functional molecules. We demonstrate that after printing the molecules form an interpenetrating network at the SAM surface preserving their individual properties. We exploited the process by fabricating new optical storage media that consist of a multilevel TAG.We report a novel strategy based on iterative microcontact printing, which provides additive, modular functionalization of reactive SAMs by different functional molecules. We demonstrate that after printing the molecules form an interpenetrating network at the SAM surface preserving their individual properties. We exploited the process by fabricating new optical storage media that consist of a multilevel TAG. Electronic supplementary information (ESI) available: Experimental details, synthesis and characterization of compounds 1, 2, 1-Sil and 2-Sil, and materials. See DOI: 10.1039/c5nr00346f

  4. Magnetic manipulation of self-assembled colloidal asters

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor S.

    2011-09-01

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

  5. Magnetic manipulation of self-assembled colloidal asters.

    SciTech Connect

    Snezhko, A.; Aranson, I. S.

    2011-09-01

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

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

    PubMed Central

    Stauth, Sean A.; Parviz, Babak A.

    2006-01-01

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

  7. The construction of functional protein nanotubes by small molecule-induced self-assembly of cricoid proteins.

    PubMed

    Miao, Lu; Fan, Qiusheng; Zhao, Linlu; Qiao, Qinglong; Zhang, Xiyu; Hou, Chunxi; Xu, Jiayun; Luo, Quan; Liu, Junqiu

    2016-03-14

    A simple strategy has been developed to construct high-ordered protein nanotubes using electrostatic interactions and "zero-length" crosslinking induced by small molecular ethylenediamine. Furthermore, utilizing covalent crosslinking, we constructed stable nanoenzymes with multi-glutathione peroxidase (GPx) active centers on the surface of the nanotubes, which were anticipated to be ideal functional bionanomaterials. PMID:26899168

  8. Controlling and imaging biomimetic self-assembly

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  9. Harmonic oscillator wave functions of a self-assembled InAs quantum dot measured by scanning tunneling microscopy.

    PubMed

    Teichmann, Karen; Wenderoth, Martin; Prüser, Henning; Pierz, Klaus; Schumacher, Hans W; Ulbrich, Rainer G

    2013-08-14

    InAs quantum dots embedded in an AlAs matrix inside a double barrier resonant tunneling diode are investigated by cross-sectional scanning tunneling spectroscopy. The wave functions of the bound quantum dot states are spatially and energetically resolved. These bound states are known to be responsible for resonant tunneling phenomena in such quantum dot diodes. The wave functions reveal a textbook-like one-dimensional harmonic oscillator behavior showing up to five equidistant energy levels of 80 meV spacing. The derived effective oscillator mass of m* = 0.24m0 is 1 order of magnitude higher than the effective electron mass of bulk InAs that we attribute to the influence of the surrounding AlAs matrix. This underlines the importance of the matrix material for tailored QD devices with well-defined properties. PMID:23777509

  10. Functional and structural insights on self-assembled nanofiber-based novel antibacterial ointment from antimicrobial peptides, bacitracin and gramicidin S.

    PubMed

    Mandal, Santi M; Roy, Anupam; Mahata, Denial; Migliolo, Ludovico; Nolasco, Diego O; Franco, Octavio L

    2014-11-01

    A novel antibacterial ointment using bacitracin, specific for Gram-positive bacteria, and gramicidin S, a highly toxic antibacterial peptide, was here developed showing broad-spectrum antibacterial activities against pathogenic strains with less toxicity after self-assembly into nanofiber structures. Such structures were confirmed with scanning electron microscopy and CD analyses. In addition, in silico studies using docking associated with molecular dynamics were carried out to obtain information about fiber structural oligomerization. Thus, the bacitracin and gramicidin S-based self-assembled nanopeptide ribbon may be a successful ointment formulation for bacterial infection control. PMID:24894183

  11. Functionalized thermoresponsive micelles self-assembled from biotin-PEG-b-P(NIPAAm-co-HMAAm)-b-PMMA for tumor cell target.

    PubMed

    Cheng, Cheng; Wei, Hua; Zhu, Jing-Ling; Chang, Cong; Cheng, Han; Li, Cao; Cheng, Si-Xue; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2008-06-01

    Novel micelles, comprising hydrophilic PEG shells, hydrophobic PMMA cores, and thermosensitive P(NIPAAm-co-HMAAm) segments were self-assembled from the biotin-PEG-b-P(NIPAAm-co-HMAAm)-b-PMMA triblock copolymer. The thermosensitive micelles exhibited superior stability and showed thermotriggered drug release behavior upon temperature alterations. The fluorescence spectroscopy and confocal microscopy studies confirmed that the self-assembled biotinylated micelles can be specifically and efficiently bonded to cancer cells with the administration of biotin-transferrin, suggesting that the multifunctional micelles have great potential as drug carriers for tumor targeting chemotherapy. PMID:18476730

  12. Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets.

    PubMed

    Park, Je Seob; Cho, Sung Min; Kim, Woo-Jae; Park, Juhyun; Yoo, Pil J

    2011-02-01

    In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors. PMID:21207942

  13. The single transmembrane segment drives self-assembly of OutC and the formation of a functional type II secretion system in Erwinia chrysanthemi.

    PubMed

    Login, Frédéric H; Shevchik, Vladimir E

    2006-11-01

    Many pathogenic Gram-negative bacteria secrete toxins and lytic enzymes via a multiprotein complex called the type II secretion system. This system, named Out in Erwinia chrysanthemi, consists of 14 proteins integrated or associated with the two bacterial membranes. OutC, a key player in this process, is probably implicated in the recognition of secreted proteins and signal transduction. OutC possesses a short cytoplasmic sequence, a single transmembrane segment (TMS), and a large periplasmic region carrying a putative PDZ domain. A hydrodynamic study revealed that OutC forms stable dimers of an elongated shape, whereas the PDZ domain adopts a globular shape. Bacterial two-hybrid, cross-linking, and pulldown assays revealed that the self-association of OutC is driven by the TMS, whereas the periplasmic region is dispensable for self-association. Site-directed mutagenesis of the TMS revealed that cooperative interactions between three polar residues located at the same helical face provide adequate stability for OutC self-assembly. An interhelical H-bonding mediated by Gln(29) appears to be the main driving force, and two Arg residues located at the TMS boundaries are essential for the stabilization of OutC oligomers. Stepwise mutagenesis of these residues gradually diminished OutC functionality and self-association ability. The triple OutC mutant R15V/Q29L/R36A became monomeric and nonfunctional. Self-association and functionality of the triple mutant were partially restored by the introduction of a polar residue at an alternative position in the interhelical interface. Thus, the OutC TMS is more than just a membrane anchor; it drives the protein self-association that is essential for formation of a functional secretion system. PMID:16956883

  14. Evaporation-Induced Self-Assembly of Hybrid Bridged Silsesquioxane Film and Particulate Mesophases with Integral Organic Functionality

    SciTech Connect

    LU,YUNFENG; FAN,HONGYOU; DOKE,NILESH; LOY,DOUGLAS A.; ASSINK,ROGER A.; LAVAN,DAVID A.; BRINKER,C. JEFFREY

    2000-06-12

    Since the discovery of surfactant-templated silica mesophases, the development of organic modification schemes to impart functionality to the pore surfaces has received much attention. Most recently, using the general class of compounds referred to as bridged silsesquioxanes (RO){sub 3}Si-R{prime}-Si(OR){sub 3} (Scheme 1), three research groups have reported the formation of a new class of poly(bridgedsilsesquioxane) mesophases BSQMs with integral organic functionality. In contrast to previous hybrid mesophases where organic ligands or molecules are situated on pore surfaces, this class of materials necessarily incorporates the organic constituents into the framework as molecularly dispersed bridging ligands. Although it is anticipated that this new mesostructural organization should result in synergistic properties derived from the molecular scale mixing of the inorganic and organic components, few properties of BSQMs have been measured. In addition samples prepared to date have been in the form of granular precipitates, precluding their use in applications like membranes, fluidics, and low k dielectric films needed for all foreseeable future generations of microelectronics.

  15. Multi-responsive Hydrogels Derived from the Self-assembly of Tethered Allyl-functionalized Racemic Oligopeptides

    PubMed Central

    He, Xun; Fan, Jingwei; Zhang, Fuwu; Li, Richen; Pollack, Kevin A.; Raymond, Jeffery E.; Zou, Jiong; Wooley, Karen L.

    2014-01-01

    A multi-responsive triblock hydrogelator oligo(dl-allylglycine)-block-poly(ethylene glycol)-block-oligo(dl-allylglycine) (ODLAG-b-PEG-b-ODLAG) was synthesized facilely by ring-opening polymerization (ROP) of DLAG N-carboxyanhydride (NCA) with a diamino-terminated PEG as the macroinitiator. This system exhibited heat-induced sol-to-gel transitions and either sonication- or enzyme-induced gel-to-sol transitions. The β-sheeting of the oligopeptide segments was confirmed by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and wide-angle X-ray scattering (WAXS). The β-sheets further displayed tertiary ordering into fibrillar structures that, in turn generated a porous and interconnected hydrogel matrix, as observed via transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The reversible macroscopic sol-to-gel transitions triggered by heat and gel-to-sol transitions triggered by sonication were correlated with the transformation of nanostructural morphologies, with fibrillar structures observed in gel and spherical aggregates in sol, respectively. The enzymatic breakdown of the hydrogels was also investigated. This allyl-functionalized hydrogelator can serve as a platform for the design of smart hydrogels, appropriate for expansion into biological systems as bio-functional and bio-responsive materials. PMID:25485113

  16. Self-assembling amphiphilic peptides†

    PubMed Central

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

    2014-01-01

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

  17. Functional Self-Assembled Peptide Nanofibers for Bone Marrow Mesenchymal Stem Cell Encapsulation and Regeneration in Nucleus Pulposus.

    PubMed

    Wu, Yaohong; Jia, Zhiwei; Liu, Longgang; Zhao, Yachao; Li, Hao; Wang, Chaofeng; Tao, Hui; Tang, Yong; He, Qing; Ruan, Dike

    2016-06-01

    Low back pain (LBP) is mainly caused by intervertebral disc degeneration (IDD). Recent studies have demonstrated that the transplantation of mesenchymal stem cells (MSCs) can regenerate regions that have undergone degeneration, and the regenerative effect can be enhanced by using a hydrogel carrier. This article describes an injectable functional hydrogel system manufactured by combining RADA16-I and RADA-KPSS (RADA-KPSS was manufactured by conjugating a bioactive motif derived from BMP-7 [KPSS] onto the C terminal of RADA16-I) at a volume ratio of 1:1. This hydrogel system can enhance the proliferation, differentiation, and chemotactic migration of BMSCs. In addition, the encapsulation of BMSCs with this system maintains cell viability for a long period after transplantation into an ex vivo cultured disc model. In conclusion, KPSS-conjugated RADKPS is an ideal encapsulation system for BMSCs in intervertebral disc (IVD) regeneration. PMID:27153338

  18. A density functional study of silver clusters on a stepped graphite surface: formation of self-assembled nano-wires.

    PubMed

    Singh, Akansha; Sen, Prasenjit

    2015-05-21

    Adsorption and diffusion of silver adatoms and clusters containing up to eight atoms on an HOPG substrate with an armchair step are studied using density functional methods. Step edges act as attractive sinks for adatoms and clusters. The diffusion barrier of an Ag adatom along the step edge is much larger than that on a clean terrace. At zero temperature, Ag clusters either distort or dissociate by forming covalent bonds with the edge C atoms. At 600 K, Ag5 and Ag8 clusters diffuse to the step edges, and then break up so as to maximize Ag-C bonds. The Ag atoms try to form a nanowire structure along the step edge. At such high temperatures, diffusion of clusters along the step edge involves diffusion of individual Ag atoms not bonded to the edge C atoms. Assumption of complete immobility of clusters trapped at step edges in the Gates-Robins model is not valid at high temperatures in this particular system. PMID:25903308

  19. Photo-Response of Functionalized Self-Assembled Graphene Oxide on Zinc Oxide Heterostructure to UV Illumination.

    PubMed

    Fouda, A N; El Basaty, A B; Eid, E A

    2016-12-01

    Convective assembly technique which is a simple and scalable method was used for coating uniform graphene oxide (GO) nanosheets on zinc oxide (ZnO) thin films. Upon UV irradiation, an enhancement in the on-off ratio was observed after functionalizing ZnO films by GO nanosheets. The calculations of on-off ratio, the device responsivity, and the external quantum efficiency were investigated and implied that the GO layer provides a stable pathway for electron transport. Structural investigations of the assembled GO and the heterostructure of GO on ZnO were performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The covered GO layer has a wide continuous area, with wrinkles and folds at the edges. In addition, the phonon lattice vibrations were investigated by Raman analysis. For GO and the heterostructure, a little change in the ratio between the D-band and G-band was found which means that no additional defects were formed within the heterostructure. PMID:26754939

  20. Heparin as a Bundler in a Self-Assembled Fibrous Network of Functionalized Protein-Based Polymers.

    PubMed

    Włodarczyk-Biegun, Małgorzata K; Slingerland, Cornelis J; Werten, Marc W T; van Hees, Ilse A; de Wolf, Frits A; de Vries, Renko; Stuart, Martien A Cohen; Kamperman, Marleen

    2016-06-13

    Nature shows excellent control over the mechanics of fibrous hydrogels by assembling protein fibers into bundles of well-defined dimensions. Yet, obtaining artificial materials displaying controlled bundling remains a challenge. Here, we developed genetically engineered protein-based polymers functionalized with heparin-binding KRSR domains and show controlled bundling using heparin as a binder. The protein polymer forms fibers upon increasing the pH to physiological values and at higher concentrations fibrous gels. We show that addition of heparin to the protein polymer with incorporated KRSR domains, induces bundling, which results in faster gel formation and stiffer gels. The interactions are expected to be primarily electrostatic and fiber bundling has an optimum when the positive charges of KRSR are approximately in balance with the negative charges of the heparin. Our study suggests that, generally, a straightforward method to control the properties of fibrous gels is to prepare a fiber former with specific binding domains and then simply adding an appropriate amount of binder. PMID:27129090

  1. Photo-Response of Functionalized Self-Assembled Graphene Oxide on Zinc Oxide Heterostructure to UV Illumination

    NASA Astrophysics Data System (ADS)

    Fouda, A. N.; El Basaty, A. B.; Eid, E. A.

    2016-01-01

    Convective assembly technique which is a simple and scalable method was used for coating uniform graphene oxide (GO) nanosheets on zinc oxide (ZnO) thin films. Upon UV irradiation, an enhancement in the on-off ratio was observed after functionalizing ZnO films by GO nanosheets. The calculations of on-off ratio, the device responsivity, and the external quantum efficiency were investigated and implied that the GO layer provides a stable pathway for electron transport. Structural investigations of the assembled GO and the heterostructure of GO on ZnO were performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The covered GO layer has a wide continuous area, with wrinkles and folds at the edges. In addition, the phonon lattice vibrations were investigated by Raman analysis. For GO and the heterostructure, a little change in the ratio between the D-band and G-band was found which means that no additional defects were formed within the heterostructure.

  2. Approaches to nanostructure control and functionalizations of polymer@silica hybrid nanograss generated by biomimetic silica mineralization on a self-assembled polyamine layer

    PubMed Central

    Yuan, Jian-Jun

    2011-01-01

    Summary We report the rational control of the nanostructure and surface morphology of a polyamine@silica nanoribbon-based hybrid nanograss film, which was generated by performing a biomimetic silica mineralization reaction on a nanostructured linear polyethyleneimine (LPEI) layer preorganized on the inner wall of a glass tube. We found that the film thickness, size and density of the nanoribbons and the aggregation/orientation of the nanoribbons in the film were facile to tune by simple adjustment of the biomimetic silicification conditions and LPEI self-assembly on the substrate. Our LPEI-mediated nanograss process allows the facile and programmable generation of a wide range of nanostructures and surface morphologies without the need for complex molecular design or tedious techniques. This ribbon-based nanograss has characteristics of a LPEI@silica hybrid structure, suggesting that LPEI, as a polymeric secondary amine, is available for subsequent chemical reaction. This feature was exploited to functionalize the nanograss film with three representative species, namely porphyrin, Au nanoparticles and titania. Of particular note, the novel silica@titania composite nanograss surface demonstrated the ability to convert its wetting behavior between the extreme states (superhydrophobic–superhydrophilic) by surface hydrophobic treatment and UV irradiation. The anatase titania component in the nanograss film acts as a highly efficient photocatalyst for the decomposition of the low-surface-energy organic components attached to the nanosurface. The ease with which the nanostructure can be controlled and facilely functionalized makes our nanograss potentially important for device-based application in microfluidic, microreactor and biomedical fields. PMID:22259759

  3. Layer-by-layer self-assembly of functionalized graphene nanoplates for glucose sensing in vivo integrated with on-line microdialysis system.

    PubMed

    Gu, Hui; Yu, Yanyan; Liu, Xiaoqian; Ni, Bing; Zhou, Tianshu; Shi, Guoyue

    2012-02-15

    In this work, a novel amperometric biosensor for hydrogen peroxide was fabricated through the layer-by-layer (LBL) self-assembling of amine-terminated ionic liquid (IL-NH(2)), and sulfonic acid (SO(3)(-)) functionalized graphene by covalent bonding. The modification of the two functionalities introduced positive and negative charge onto the surface of graphene respectively, thus facilitating the formation of a multilayer film denoted with {IL-RGO/S-RGO}(n) through electrostatic interaction and further immobilization of glucose oxidase (GOx). The resulting {IL-RGO/S-RGO}(n)/GOx/Nafion biosensor displayed an excellent response to glucose at a potential of -200 mV. Combined with on-line microdialysis system, the glucose biosensor in the on-line system showed good linear range from 10 μM to 500 μM with the detection limit of 3.33 μM (S/N=3). Consequently, the basal level of glucose in the striatum of anesthetic rats was calculated to be 0.376 ± 0.028 mM (mean ± s.d., n=3). The {IL-RGO/S-RGO}(n)/GOx/Nafion biosensor was further applied for in vivo sensing of the glucose level in the striatum when rats received intraperitoneal (i.p.) injection of 30 μL insulin, which resulted in an obvious decrease in the extracellular concentration of glucose within 30 min. The method was proved to be sensitive and reproducible, which enabled its promising application in physiology and pathology. PMID:22209068

  4. The dynamics of gas-surface energy exchange in collisions of Ar atoms with ω-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Day, B. Scott; Shuler, Shelby F.; Ducre, Adonis; Morris, John R.

    2003-10-01

    Atomic-beam scattering experiments using n-alkanethiol and ω-functionalized alkanethiol self-assembled monolayers (SAMs) on gold are employed to explore the dynamics of gas-surface energy exchange in collisions with model organic surfaces. The studies are performed by directing a nearly monoenergetic beam of 80 kJ/mol Ar atoms onto a particular SAM at an incident angle of 30° with respect to the surface normal and recording the time-of-flight distributions for the atoms as they scatter from the surface at a final angle of 30°. Among the monolayers studied, long-chain CH3-terminated SAMs are found to be the most effective at dissipating the translational energy of impinging atoms. For alkanethiols with greater than seven total carbon atoms (HS(CH2)n>6CH3), we find that, for specular scattering conditions, over 80% of the incident energy is transferred to the surface and that over 60% of the impinging atoms approach thermal equilibrium with the surface before scattering back into the gas phase. In contrast to CH3-terminated monolayers, SAMs constructed from hydrogen-bonding alkanethiols: HS(CH2)11OH, HS(CH2)10COOH, and HS(CH2)11NH2, exhibit characteristics of more rigid collision partners. The Ar atoms transfer about 77% of their energy to these surfaces with only 43% of the atoms reaching thermal or near thermal equilibrium before recoiling. Further comparisons of mixed OH- and CH3-terminated SAMs and alkene-terminated SAMs suggest that intramonolayer hydrogen bonding of terminal functional groups may play an important role in determining the extent of energy transfer and thermalization.

  5. Templated Self Assemble of Nano-Structures

    SciTech Connect

    Suo, Zhigang

    2013-04-29

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

  6. Interparticle Forces Underlying Nanoparticle Self-Assemblies.

    PubMed

    Luo, Dan; Yan, Cong; Wang, Tie

    2015-12-01

    Studies on the self-assembly of nanoparticles have been a hot topic in nanotechnology for decades and still remain relevant for the present and future due to their tunable collective properties as well as their remarkable applications to a wide range of fields. The novel properties of nanoparticle assemblies arise from their internal interactions and assemblies with the desired architecture key to constructing novel nanodevices. Therefore, a comprehensive understanding of the interparticle forces of nanoparticle self-assemblies is a pre-requisite to the design and control of the assembly processes, so as to fabricate the ideal nanomaterial and nanoproducts. Here, different categories of interparticle forces are classified and discussed according to their origins, behaviors and functions during the assembly processes, and the induced collective properties of the corresponding nanoparticle assemblies. Common interparticle forces, such as van der Waals forces, electrostatic interactions, electromagnetic dipole-dipole interactions, hydrogen bonds, solvophonic interactions, and depletion interactions are discussed in detail. In addition, new categories of assembly principles are summarized and introduced. These are termed template-mediated interactions and shape-complementary interactions. A deep understanding of the interactions inside self-assembled nanoparticles, and a broader perspective for the future synthesis and fabrication of these promising nanomaterials is provided. PMID:26436692

  7. Meniscus height controlled convective self-assembly

    NASA Astrophysics Data System (ADS)

    Choudhary, Satyan; Crosby, Alfred

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

  8. Fabrication and optoelectronic properties of novel films based on functionalized multiwalled carbon nanotubes and (phthalocyaninato)ruthenium(II) via coordination bonded layer-by-layer self-assembly.

    PubMed

    Zhao, Wei; Tong, Bin; Shi, Jianbing; Pan, Yuexiu; Shen, Jinbo; Zhi, Junge; Chan, Wai Kin; Dong, Yuping

    2010-10-19

    4-(2-(4-pyridinyl)Ethynyl)benzenic diazonium salt (PBD) was used to modify multiwalled carbon nanotubes (MWCNTs) by the self-assembly technique. After the decomposition of the diazonium group in PBD under UV irradiation, the PBD monolayer film covalently anchored on multiwalled carbon nanotubes is very stable. The obtained pyridine-modified MWCNTs (Py(Ar)-MWCNTs) have good solubility in common organic solvents. Furthermore, the layer-by-layer (LBL) self-assembled fully conjugated films of Py(Ar)-MWCNTs and (phthalocyaninato)ruthenium(II) (RuPc) were fabricated on the PBD-modified substrates, and characterized using UV-vis absorption spectroscopy, scanning electron microscopy (SEM), and electrochemistry. The UV-vis analysis results indicate that the LBL RuPc/Py(Ar)-MWCNTs self-assembled multilayer films with axial ligands between the ruthenium atom and pyridine group were successfully fabricated, and the progressive assembly runs regularly with almost equal amounts of deposition in each cycle. A top view SEM image shows a random and homogeneous distribution of Py(Ar)-MWCNTs over the PBD-modified silicon substrate, which indicates well independence between all Py(Ar)-MWCNTs. Moreover, the opto-electronic conversion was also studied by assembling RuPc/Py(Ar)-MWCNTs multilayer films on PBD-modified ITO substrate. Under illumination, the LBL self-assembled films on ITO showed an effective photoinduced charge transfer because of their conjugated structure and the ITO current density changed with the number of bilayer. As the number of bilayers was increased, the photocurrent increases and reaches its maximum value (∼300 nA/cm(2)) at nine bilayers. These results allow us to design novel materials for applications in optoelectronic devices by using LBL self-assembly techniques. PMID:20853832

  9. Structural perturbation of a dipalmitoylphosphatidylcholine (DPPC) bilayer by warfarin and its bolaamphiphilic analogue: A molecular dynamics study.

    PubMed

    Ayee, Manuela Aseye Ayele; Roth, Charles William; Akpa, Belinda Sena

    2016-04-15

    Compounds with nominally similar biological activity may exhibit differential toxicity due to differences in their interactions with cell membranes. Many pharmaceutical compounds are amphiphilic and can be taken up by phospholipid bilayers, interacting strongly with the lipid-aqueous interface whether or not subsequent permeation through the bilayer is possible. Bolaamphiphilic compounds, which possess two hydrophilic ends and a hydrophobic linker, can likewise undergo spontaneous uptake by bilayers. While membrane-spanning bolaamphiphiles can stabilize membranes, small molecules with this characteristic have the potential to create membrane defects via disruption of bilayer structure and dynamics. When compared to the amphiphilic therapeutic anticoagulant, warfarin, the bolaamphiphilic analogue, brodifacoum, exhibits heightened toxicity that goes beyond superior inhibition of the pharmacological target enzyme. We explore, herein, the consequences of anticoagulant accumulation in a dipalmitoylphosphatidylcholine (DPPC) bilayer. Coarse-grained molecular dynamics simulations reveal that permeation of phospholipid bilayers by brodifacoum causes a disruption of membrane barrier function that is driven by the bolaamphiphilic nature and size of this molecule. We find that brodifacoum partitioning into bilayers causes membrane thinning and permeabilization and promotes lipid flip-flop - phenomena that are suspected to play a role in triggering cell death. These phenomena are either absent or less pronounced in the case of the less toxic, amphiphilic compound, warfarin. PMID:26852346

  10. Adsorption of Dissolved Metals in the Berkeley Pit using Thiol-Functionalized Self-Assembled Monolayers on Mesoporous Supports (Thiol-SAMMS)

    SciTech Connect

    Betancourt, Amaury P.; Mattigod, Shas V.; Wellman, Dawn M.

    2010-03-07

    The Berkeley Pit in Butte, Montana, is heavily contaminated with dissolved metals. Adsorption and extraction of these metals can be accomplished through the use of a selective adsorbent. For this research, the adsorbent used was thiol-functionalized Self-Assembled Monolayers on Mesoporous Supports (thiol-SAMMS), which was developed at Pacific Northwest National Laboratory (PNNL). Thiol-SAMMS selectively binds to numerous types of dissolved metals. The objective of this research was to evaluate the loading and kinetics of aluminum, beryllium, copper, and zinc on thiol-SAMMS. For the loading tests, a series of Berkeley Pit water to thiol-SAMMS ratios (mL:g) were tested. These ratios were 1000:1, 500:1, 100:1, and 50:1. Berkeley Pit water is acidic (pH {approx} 2.5). This can affect the performance of SAMMS materials. Therefore, the effect of pH was evaluated by conducting parallel series of loading tests wherein the Berkeley Pit water was neutralized before or after addition of thiol-SAMMS, and a series of kinetics tests wherein the Berkeley Pit water was neutralized before addition of thiol-SAMMS for the first test and was not neutralized for the second test. For the kinetics tests, one Berkeley Pit water to thiol-SAMMS ratio was tested, which was 2000:1. The results of the loading and kinetics tests suggest that a significant decrease in dissolved metal concentration at Berkeley Pit could be realized through neutralization of Berkeley Pit water. Thiol-SAMMS technology has a limited application under the highly acidic conditions posed by the Berkeley Pit. However, thiol-SAMMS could provide a secondary remedial technique which would complete the remedial system and remove dissolved metals from the Berkeley Pit to below drinking water standards.

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

    PubMed Central

    Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

    2013-01-01

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

  12. Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH 3, OH, and CONHCH 3 functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Morales-Cruz, Angel L.; Tremont, Rolando; Martínez, Ramón; Romañach, Rodolfo; Cabrera, Carlos R.

    2005-03-01

    Chemical and mechanical properties of different compounds can be elucidated by measuring fundamental forces such as adhesion, attraction and repulsion, between modified surfaces by means of atomic force microscopy (AFM) in force mode calibration. This work presents a combination of AFM, self-assembled monolayers (SAMs), and crystallization techniques to study the forces of interaction between excipients and active ingredients used in pharmaceutical formulations. SAMs of 16-mercaptohexadecanoate, which represent magnesium stereate, were used to modify the probe tip, whereas CH3-, OH- and CONHCH3-functional SAMs were formed on a gold-coated mica substrate, and used as examples of the surfaces of lactose and theophylline. The crystals of lactose and theophylline were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modification of gold surfaces with 16-mercaptohexadecanoate, 10-mercapto-1-decanol (OH-functional SAM), 1-decanethiol (CH3-functional) and N-methyl-11-mercaptoundecanamide (CONHCH3-functional SAM) was studied by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Fourier transform-infrared spectroscopy (FT-IR) in specular reflectance mode. XPS and AES results of the modified surfaces showed the presence of sulfur binding, and kinetic energies that correspond to the presence of 10-mercapto-1-decanol, 1-decanethiol, N-methyl-11-mercaptoundecanamide and the salt of 16-mercaptohexadecanoic acid. The absorption bands in the IR spectra further confirm the modification of the gold-coated substrates with these compounds. Force versus distance measurements were performed between the modified tip and the modified gold-coated mica substrates. The mean adhesion forces between the COO-Ca2+ functionalized tip and the CH3-, OH-, and CONHCH3-modified substrates were determined to be 4.5, 8.9 and 6.3 nN, respectively. The magnitude of the adhesion force (ion-dipole) interaction between the modified tip and

  13. Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Willey, T; Willey, T

    2004-03-24

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the mechanically attached

  14. Characterization of functionalized self-assembled monolayers and surface-attached interlocking molecules using near-edge X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Willey, Trevor Michael

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a "molecular riveting" step to hold the mechanically attached

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2012-01-25

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

  17. Self-Assembly of MinE on the Membrane Underlies Formation of the MinE Ring to Sustain Function of the Escherichia coli Min System*

    PubMed Central

    Zheng, Min; Chiang, Ya-Ling; Lee, Hsiao-Lin; Kong, Lih-Ren; Hsu, Shang-Te Danny; Hwang, Ing-Shouh; Rothfield, Lawrence I.; Shih, Yu-Ling

    2014-01-01

    The pole-to-pole oscillation of the Min proteins in Escherichia coli results in the inhibition of aberrant polar division, thus facilitating placement of the division septum at the midcell. MinE of the Min system forms a ring-like structure that plays a critical role in triggering the oscillation cycle. However, the mechanism underlying the formation of the MinE ring remains unclear. This study demonstrates that MinE self-assembles into fibrillar structures on the supported lipid bilayer. The MinD-interacting domain of MinE shows amyloidogenic properties, providing a possible mechanism for self-assembly of MinE. Supporting the idea, mutations in residues Ile-24 and Ile-25 of the MinD-interacting domain affect fibril formation, membrane binding ability of MinE and MinD, and subcellular localization of three Min proteins. Additional mutations in residues Ile-72 and Ile-74 suggest a role of the C-terminal domain of MinE in regulating the folding propensity of the MinD-interacting domain for different molecular interactions. The study suggests a self-assembly mechanism that may underlie the ring-like structure formed by MinE-GFP observed in vivo. PMID:24914211

  18. Self-assembly-driven nematization.

    PubMed

    Nguyen, Khanh Thuy; Sciortino, Francesco; De Michele, Cristiano

    2014-04-29

    The anisotropy of attractive interactions between particles can favor, through a self-assembly process, the formation of linear semi-flexible chains. In the appropriate temperatures and concentration ranges, the growing aspect ratio of the aggregates can induce formation of a nematic phase, as recently experimentally observed in several biologically relevant systems. We present here a numerical study of the isotropic-nematic phase boundary for a model of bifunctional polymerizing hard cylinders, to provide an accurate benchmark for recent theoretical approaches and to assess their ability to capture the coupling between self-assembly and orientational ordering. The comparison indicates the importance of properly modeling excluded volume and orientational entropy and provides a quantitative confirmation of some theoretical predictions. PMID:24701976

  19. Harnessing Surface Dislocation Networks for Molecular Self-Assembly

    NASA Astrophysics Data System (ADS)

    Pohl, Karsten

    2009-03-01

    The controlled fabrication of functional wafer-based nano-arrays is one of the ultimate quests in current nanotechnologies. Well-ordered misfit dislocation networks of ultrathin metal films are viable candidates for the growth of two- dimensional ordered cluster arrays in the nanometer regime. Such bottom-up processes can be very complex, involving collective effects from a large number of atoms. Unraveling the fundamental forces that drive these self-assembly processes requires detailed experimental information at the atomic level of large ensembles of hundreds to thousands of atoms. The combination of variable temperature measurements from our home-built STM correlated with 2D Frenkel-Kontorova models based on first-principle interaction parameters is used to explain how uniform arrays can form with the strain in the thin film as the driving force responsible for the surface self-assembly process. This process is generally applicable to assemble many molecular species thus opening avenues towards complex self-assembled structures based on a lock-and-key type approach. Moreover, when increasing the molecular coverage and/or decreasing the strain in the thin film the intermolecular interactions will eventually dominate the elastic effects and dictate the self-assembly process via molecular structure and functionality. We will show that controlling this delicate balance leads to a richness of structures, ranging from disperse ordered arrays of molecular clusters to patterned self-assembled monolayers (SAMs) of functionalized fullerenes and methanethiol.

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

    DOEpatents

    Fryxell, Glen E.; Zemanian, Thomas S.; Addleman, R. Shane; Aardahl, Christopher L.; Zheng, Feng; Busche, Brad; Egorov, Oleg B.

    2009-06-30

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

  1. A self-assembled ionophore

    NASA Astrophysics Data System (ADS)

    Tirumala, Sampath K.

    1997-11-01

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

  2. Self-assembly of tunable protein suprastructures from recombinant oleosin

    PubMed Central

    Vargo, Kevin B.; Parthasarathy, Ranganath; Hammer, Daniel A.

    2012-01-01

    Using recombinant amphiphilic proteins to self-assemble suprastructures would allow precise control over surfactant chemistry and the facile incorporation of biological functionality. We used cryo-TEM to confirm self-assembled structures from recombinantly produced mutants of the naturally occurring sunflower protein, oleosin. We studied the phase behavior of protein self-assembly as a function of solution ionic strength and protein hydrophilic fraction, observing nanometric fibers, sheets, and vesicles. Vesicle membrane thickness correlated with increasing hydrophilic fraction for a fixed hydrophobic domain length. The existence of a bilayer membrane was corroborated in giant vesicles through the localized encapsulation of hydrophobic Nile red and hydrophilic calcein. Circular dichroism revealed that changes in nanostructural morphology in this family of mutants was unrelated to changes in secondary structure. Ultimately, we envision the use of recombinant techniques to introduce novel functionality into these materials for biological applications. PMID:22753512

  3. Chiral self-assembly of helical particles.

    PubMed

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

    2016-04-12

    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. PMID:26767786

  4. Self-assembling magnetic "snakes"

    SciTech Connect

    2010-01-01

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

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

    PubMed

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

    2016-01-26

    Self-assembled peptide nanostructures have unique physical and biological properties and promising applications in electrical devices and functional molecular recognition. Although solution-based peptide molecules can self-assemble into different morphologies, it is challenging to control the self-assembly process. Herein, controllable self-assembly of diphenylalanine (FF) in an evaporative dewetting solution is reported. The fluid mechanical dimensionless numbers, namely Rayleigh, Marangoni, and capillary numbers, are introduced to control the interaction between the solution and FF molecules in the self-assembly process. The difference in the film thickness reflects the effects of Rayleigh and Marangoni convection, and the water vapor flow rate reveals the role of viscous fingering in the emergence of aligned FF flakes. By employing dewetting, various FF self-assembled patterns, like concentric and spokelike, and morphologies, like strips and hexagonal tubes/rods, can be produced, and there are no significant lattice structural changes in the FF nanostructures. PMID:26654935

  6. Bioprinting synthetic self-assembling peptide hydrogels for biomedical applications.

    PubMed

    Loo, Yihua; Hauser, Charlotte A E

    2016-02-01

    Three-dimensional (3D) bioprinting is a disruptive technology for creating organotypic constructs for high-throughput screening and regenerative medicine. One major challenge is the lack of suitable bioinks. Short synthetic self-assembling peptides are ideal candidates. Several classes of peptides self-assemble into nanofibrous hydrogels resembling the native extracellular matrix. This is a conducive microenvironment for maintaining cell survival and physiological function. Many peptides also demonstrate stimuli-responsive gelation and tuneable mechanical properties, which facilitates extrusion before dispensing and maintains the shape fidelity of the printed construct in aqueous media. The inherent biocompatibility and biodegradability bodes well for in vivo applications as implantable tissues and drug delivery matrices, while their short length and ease of functionalization facilitates synthesis and customization. By applying self-assembling peptide inks to bioprinting, the dynamic complexity of biological tissue can be recreated, thereby advancing current biomedical applications of peptide hydrogel scaffolds. PMID:26694103

  7. Self-assembled controllable microswimmers

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  8. Self-assembling RNA square

    SciTech Connect

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

    2011-12-22

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

  9. Self-assembled virus-membrane complexes

    SciTech Connect

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

    2010-11-16

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

  10. Self-Assemblies of novel molecules, VECAR

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Halverson, Jonathan D.; Tkachenko, Alexei V.

    2016-03-01

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

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

    PubMed

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

    2010-11-18

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

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

    PubMed

    De Santis, Emiliana; Ryadnov, Maxim G

    2015-11-21

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

  14. Stereochemistry in subcomponent self-assembly.

    PubMed

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

    2014-07-15

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

  15. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1996-01-01

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

  16. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1999-10-12

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

  17. Self-assembling multimeric nucleic acid constructs

    DOEpatents

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

    1996-10-01

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

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

    PubMed

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

    2005-03-01

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

  19. Self-assembly and application of diphenylalanine-based nanostructures.

    PubMed

    Yan, Xuehai; Zhu, Pengli; Li, Junbai

    2010-06-01

    Micro- and nanostructures fabricated from biological building blocks have attracted tremendous attention owing to their potential for application in biology and in nanotechnology. Many biomolecules, including peptides and proteins, can interact and self-assemble into highly ordered supramolecular architectures with functionality. By imitating the processes where biological peptides or proteins are assembled in nature, one can delicately design and synthesize various peptide building blocks composed of several to dozens of amino acids for the creation of biomimetic or bioinspired nanostructured materials. This tutorial review aims to introduce a new kind of peptide building block, the diphenylalanine motif, extracted with inspiration of a pathogenic process towards molecular self-assembly. We highlight recent and current advances in fabrication and application of diphenylalanine-based peptide nanomaterials. We also highlight the preparation of such peptide-based nanostructures as nanotubes, spherical vesicles, nanofibrils, nanowires and hybrids through self-assembly, the improvement of their properties and the extension of their applications. PMID:20502791

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    2005-03-01

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

  3. Interfacial self-assembled functional nanoparticle array: a facile surface-enhanced Raman scattering sensor for specific detection of trace analytes.

    PubMed

    Zhang, Kun; Ji, Ji; Li, Yixin; Liu, Baohong

    2014-07-01

    Surface-enhanced Raman scattering (SERS) has proven to be promising for the detection of trace analytes; however, the precise nanofabrication of a specific and sensitive plasmonic SERS-active substrate is still a major challenge that limits the scope of its applications. In this work, gold nanoparticles are self-assembled into densely packed two-dimensional arrays at a liquid/liquid interface between dimethyl carbonate and water in the absence of template controller molecules. Both the simulation and experiment results show that the particles within these film-like arrays exhibit strong electromagnetic coupling and enable large amplification of Raman signals. In order to realize the level of sensing specificity, the surface chemistry of gold nanoparticles (Au NPs) is rationally tailored by incorporating an appropriate chemical moiety that specifically captures molecules of interest. The ease of fabrication and good uniformity make this platform ideal for in situ SERS sensing of trace targets in complex samples. PMID:24915488

  4. Inorganic/organic small molecular semiconductor self-assembly to functional core-shell nanoarchitectures for ultrasensitive chemiresistors to aniline vapor.

    PubMed

    Wang, Ke; Yang, Hui; Qian, Xuemin; Xue, Zheng; Li, Yongjun; Liu, Huibiao; Li, Yuliang

    2014-08-14

    We developed a new method combining the in situ liquid-solid phase reaction and self-assembly in solution to synthesize novel inorganic/organic small molecular semiconductor core-shell nanoparticles of ZnS/PTCDA (ZPNPs). This method is a one-step process which can produce stoichiometric inorganic/organic core-shell nanoparticles and does not introduce any impurity. The film of ZPNPs exhibited an ultrasensitive detection of aniline vapor. The film of ZPNPs can highly selectively distinguish aniline vapor from many volatile organic compounds and water due to the strong synergistic interactions of π-π and hydrogen-bonds between electron donor (aniline) and acceptor (PTCDA) molecules, in which the detection limit was lowered to 100 ppb at room temperature. PMID:24915438

  5. Nanotechnology and Quasicrystals: From Self-Assembly to Photonic Applications

    NASA Astrophysics Data System (ADS)

    Lifshitz, R.

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

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

    PubMed

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

    2014-11-01

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

  7. A redox-sensitive, oligopeptide-guided, self-assembling, and efficiency-enhanced (ROSE) system for functional delivery of microRNA therapeutics for treatment of hepatocellular carcinoma.

    PubMed

    Hu, Qida; Wang, Kai; Sun, Xu; Li, Yang; Fu, Qihan; Liang, Tingbo; Tang, Guping

    2016-10-01

    Lack of efficient adjuvant therapy contributes to a high incidence of recurrence and metastasis of hepatocellular carcinoma (HCC). A novel therapeutic is required for adjuvant treatment of HCC. We developed a polymer-based nanosystem (ROSE) for functional gene therapy by synthesizing a supramolecular complex self-assembled from polycations and functional adamantyl modules. The ROSE system condensing tumor suppressor microRNA-34a (miR-34a) therapeutics becomes ROSE/miR-34a nanoparticles that could facilitate gene transfection in HCC cells with satisfied stability and efficiency, possibly due to proton sponge effect by polycations, PEGlyation protection, and controlled release by breakdown of disulfide bonds. Meanwhile, modification with a targeting oligopeptide SP94 in ROSE/miR-34a enables approximately higher affinity for LM3 HCC cells than hepatocytes in vitro and greater HCC specificity in vivo. Furthermore, ROSE/miR-34a nanoparticles significantly inhibits HCC cell proliferation and in vivo tumor growth, representing a notable effect improvement over conventional gene delivery strategies. ROSE/miR-34a, featuring redox-responsiveness, oligopeptide-guided specificity, self-assembly, and enhanced transfection, is therefore a potential therapeutic agent in future adjuvant therapy for HCC treatment. PMID:27459325

  8. Initiation of Chondrocyte Self-Assembly Requires an Intact Cytoskeletal Network.

    PubMed

    Lee, Jennifer K; Hu, Jerry C Y; Yamada, Soichiro; Athanasiou, Kyriacos A

    2016-02-01

    Self-assembly and self-organization have recently emerged as robust scaffold-free tissue engineering methodologies that can be used to generate various tissues, including cartilage, vessel, and liver. Self-assembly, in particular, is a scaffold-free platform for tissue engineering that does not require the input of exogenous energy to the system. Although self-assembly can generate functional tissues, most notably neocartilage, the mechanisms of self-assembly remain unclear. To study the self-assembling process, we used articular chondrocytes as a model to identify parameters that can affect this process. Specifically, the roles of cell-cell and cell-matrix adhesion molecules, surface-bound collagen, and the actin cytoskeletal network were investigated. Using time-lapse imaging, we analyzed the early stages of chondrocyte self-assembly. Within hours, chondrocytes rapidly coalesced into cell clusters before compacting to form tight cellular structures. Chondrocyte self-assembly was found to depend primarily on integrin function and secondarily on cadherin function. In addition, actin or myosin II inhibitors prevented chondrocyte self-assembly, suggesting that cell adhesion alone is not sufficient, but rather the active contractile actin cytoskeleton is essential for proper chondrocyte self-assembly and the formation of neocartilage. Better understanding of the self-assembly mechanisms allows for the rational modulation of this process toward generating neocartilages with improved properties. These findings are germane to understanding self-assembly, an emerging platform for tissue engineering of a plethora of tissues, especially as these neotissues are poised for translation. PMID:26729374

  9. Probing peptide amphiphile self-assembly in blood serum.

    PubMed

    Ghosh, Arijit; Buettner, Christian J; Manos, Aaron A; Wallace, Ashley J; Tweedle, Michael F; Goldberger, Joshua E

    2014-12-01

    There has been recent interest in designing smart diagnostic or therapeutic self-assembling peptide or polymeric materials that can selectively undergo morphological transitions to accumulate at a disease site in response to specific stimuli. Developing approaches to probe these self-assembly transitions in environments that accurately amalgamate the diverse plethora of proteins, biomolecules, and salts of blood is essential for creating systems that function in vivo. Here, we have developed a fluorescence anisotropy approach to probe the pH-dependent self-assembly transition of peptide amphiphile (PA) molecules that transform from spherical micelles at pH 7.4 to nanofibers under more acidic pH's in blood serum. By mixing small concentrations of a Ru(bipy)3(2+)-tagged PA with a Gd(DO3A)-tagged PA having the same lipid-peptide sequence, we showed that the pH dependence of self-assembly is minimally affected and can be monitored in mouse blood serum. These PA vehicles can be designed to transition from spherical micelles to nanofibers in the pH range 7.0-7.4 in pure serum. In contrast to the typical notion of serum albumin absorbing isolated surfactant molecules and disrupting self-assembly, our experiments showed that albumin does not bind these anionic PAs and instead promotes nanofibers due to a molecular crowding effect. Finally, we created a medium that replicates the transition pH in serum to within 0.08 pH units and allows probing self-assembly behavior using conventional spectroscopic techniques without conflicting protein signals, thus simplifying the development pathway from test tube to in vivo experimentation for stimuli-responsive materials. PMID:25347387

  10. 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…

  11. The thermodynamics of the self-assembly of covalently linked oligomeric naphthalenediimides into helical organic nanotubes.

    PubMed

    Tambara, Koujiro; Olsen, John-Carl; Hansen, David E; Pantoş, G Dan

    2014-01-28

    The mechanism and thermodynamic functions of the self-assembly of a family of covalently linked oligomeric naphthalenediimides (NDIs) were investigated through variable-temperature NMR and CD studies. The NDIs were shown to self-assemble into helical supramolecular nanotubes via an isodesmic polymerisation mechanism, and regardless of the oligomer length a surprising entropy-enthalpy compensation was observed. PMID:24287562

  12. Self-assembly of highly luminescent heteronuclear coordination cages.

    PubMed

    Schmidt, Andrea; Hollering, Manuela; Han, Jiaying; Casini, Angela; Kühn, Fritz E

    2016-08-01

    Exo-functionalized Pd2L4 cage compounds with attached Ru(ii) pyridine complexes were prepared via coordination-driven self-assembly. Unlike most of the previously reported palladium(ii) cages, one of these metallocages exhibits an exceptionally high quantum yield of 66%. The presented approach is promising to obtain luminescent coordination complexes for various applications. PMID:27436541

  13. Supramolecular self-assembly of amphiphilic hyperbranched polymers at all scales and dimensions: progress, characteristics and perspectives.

    PubMed

    Zhou, Yongfeng; Yan, Deyue

    2009-03-14

    This feature article describes the supramolecular self-assembly of hyperbranched polymers (HBPs), including the progress, unique characteristics and future perspectives. HBPs are irregular in molecular structure compared with that of linear block copolymers and dendrimers. However, similar to these well-defined polymer tectons, HBPs have displayed great potential to be excellent precursors in solution self-assembly, interfacial self-assembly and hybrid self-assembly. Many impressive supramolecular aggregates and hybrids at all scales and dimensions, such as macroscopic tubes, micro- or nano-vesicles, fibers, spherical micelles and honeycomb films, have been generated. In addition, HBPs also demonstrate unique characteristics or advantages in supramolecular self-assembly behaviours, including controllable morphologies and structures, special properties, characteristic self-assembly mechanism and facile functionalization process. Although still being at the early stage, self-assembly of HBPs has provided a new avenue for the development of supramolecular chemistry. PMID:19240868

  14. Magnetic self-assembly of small parts

    NASA Astrophysics Data System (ADS)

    Shetye, Sheetal B.

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

  15. Self-assembly of amphiphilic homopolymers bearing ferrocene and carboxyl functionalities: effect of polymer concentration, β-cyclodextrin, and length of alkyl linker.

    PubMed

    Feng, Chun; Lu, Guolin; Li, Yongjun; Huang, Xiaoyu

    2013-08-27

    Three new acrylamide monomers containing ferrocene and tert-butyl ester groups were first synthesized via multistep nucleophilic substitution reaction under mild conditions followed by reversible addition-fragmentation chain transfer (RAFT) homopolymerization to give well-defined homopolymers with narrow molecular weight distributions (M(w)/M(n) ≤ 1.36). The target amphiphilic homopolymers were obtained by the acidic hydrolysis of tert-butyoxycarbonyls to carboxyls in every repeating unit using CF3COOH. The self-assembly behaviors of these amphiphilic homopolymers bearing both ferrocene and carboxyl moieties in each repeating unit in aqueous media were investigated by transmission emission microscopy (TEM), dynamic light scattering (DLS), and atomic force microscopy (AFM). Large compound micelles with different morphologies were formed by these amphiphilic homopolymers, which consist of the corona formed by hydrophilic carboxyls and the core containing numerous reverse micelles with hydrophilic islands of carboxyls in continuous hydrophobic phase of ferrocene-based segments. The morphologies of the formed micelles could be tuned by the concentration of amphiphilic homopolymers, pH value of the solution, the length of -CH2 linker between ferrocene group and carboxyl, and the amount of β-cyclodextrin (β-CD). PMID:23977901

  16. Pentadecyl phenol- and cardanol-functionalized fluorescent, room-temperature liquid-crystalline perylene bisimides: effect of pendant chain unsaturation on self-assembly.

    PubMed

    Bhavsar, Ghanashyam A; Asha, S K

    2011-11-01

    A new perylene bisimide (PBI) building block based on pentadecyl phenol (PDP) or cardanol was developed, which upon esterification with 3,4,5-tridodecyloxy gallate resulted in highly emissive, room-temperature liquid-crystalline (LC) molecules. The self assembly in solution was studied in detail by NMR spectroscopy, UV/Vis absorption, and fluorescence spectroscopy. In solution both PDP- and cardanol-based PBI exhibited similar behavior. They were molecularly dissolved in chloroform (CHCl(3)) but formed rotationally displaced H-type aggregates that emitted at 640 nm in methylcyclohexane (MCH). Surface morphology in dropcast films were characterized using microscopic techniques such as SEM, TEM, and atomic force microscopy (AFM). The liquid-crystalline properties were studied using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and variable-temperature X-ray (small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WXRD)) studies. Variable-temperature X-ray studies in the LC phase indicated strong π-π stacking interaction present in the PDP-based PBI derivative, whereas the stacking was absent in the LC phase of the cardanol-based PBI. The latter formed self-organized structures of extremely short length due to the presence of cis double bonds in the C15 alkyl side chain, whereas the saturated alkyl side chain in PDP could pack efficiently, thereby resulting in nanofibers that were several micrometers in length. PMID:21956257

  17. Self-assembly of MPG1, a hydrophobin protein from the rice blast fungus that forms functional amyloid coatings, occurs by a surface-driven mechanism

    PubMed Central

    Pham, Chi L. L.; Rey, Anthony; Lo, Victor; Soulès, Margaux; Ren, Qin; Meisl, Georg; Knowles, Tuomas P. J.; Kwan, Ann H.; Sunde, Margaret

    2016-01-01

    Rice blast is a devastating disease of rice caused by the fungus Magnaporthe oryzae and can result in loss of a third of the annual global rice harvest. Two hydrophobin proteins, MPG1 and MHP1, are highly expressed during rice blast infections. These hydrophobins have been suggested to facilitate fungal spore adhesion and to direct the action of the enzyme cutinase 2, resulting in penetration of the plant host. Therefore a mechanistic understanding of the self-assembly properties of these hydrophobins and their interaction with cutinase 2 is crucial for the development of novel antifungals. Here we report details of a study of the structure, assembly and interactions of these proteins. We demonstrate that, in vitro, MPG1 assembles spontaneously into amyloid structures while MHP1 forms a non-fibrillar film. The assembly of MPG1 only occurs at a hydrophobic:hydrophilic interface and can be modulated by MHP1 and other factors. We further show that MPG1 assemblies can much more effectively retain cutinase 2 activity on a surface after co-incubation and extensive washing compared with other protein coatings. The assembly and interactions of MPG1 and MHP1 at hydrophobic surfaces thereby provide the basis for a possible mechanism by which the fungus can develop appropriately at the infection interface. PMID:27142249

  18. Self-assembly of MPG1, a hydrophobin protein from the rice blast fungus that forms functional amyloid coatings, occurs by a surface-driven mechanism.

    PubMed

    Pham, Chi L L; Rey, Anthony; Lo, Victor; Soulès, Margaux; Ren, Qin; Meisl, Georg; Knowles, Tuomas P J; Kwan, Ann H; Sunde, Margaret

    2016-01-01

    Rice blast is a devastating disease of rice caused by the fungus Magnaporthe oryzae and can result in loss of a third of the annual global rice harvest. Two hydrophobin proteins, MPG1 and MHP1, are highly expressed during rice blast infections. These hydrophobins have been suggested to facilitate fungal spore adhesion and to direct the action of the enzyme cutinase 2, resulting in penetration of the plant host. Therefore a mechanistic understanding of the self-assembly properties of these hydrophobins and their interaction with cutinase 2 is crucial for the development of novel antifungals. Here we report details of a study of the structure, assembly and interactions of these proteins. We demonstrate that, in vitro, MPG1 assembles spontaneously into amyloid structures while MHP1 forms a non-fibrillar film. The assembly of MPG1 only occurs at a hydrophobic:hydrophilic interface and can be modulated by MHP1 and other factors. We further show that MPG1 assemblies can much more effectively retain cutinase 2 activity on a surface after co-incubation and extensive washing compared with other protein coatings. The assembly and interactions of MPG1 and MHP1 at hydrophobic surfaces thereby provide the basis for a possible mechanism by which the fungus can develop appropriately at the infection interface. PMID:27142249

  19. Self assembly properties of primitive organic compounds

    NASA Technical Reports Server (NTRS)

    Deamer, D. W.

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  1. Self-assembling biomolecular catalysts for hydrogen production

    NASA Astrophysics Data System (ADS)

    Jordan, Paul C.; Patterson, Dustin P.; Saboda, Kendall N.; Edwards, Ethan J.; Miettinen, Heini M.; Basu, Gautam; Thielges, Megan C.; Douglas, Trevor

    2016-02-01

    The chemistry of highly evolved protein-based compartments has inspired the design of new catalytically active materials that self-assemble from biological components. A frontier of this biodesign is the potential to contribute new catalytic systems for the production of sustainable fuels, such as hydrogen. Here, we show the encapsulation and protection of an active hydrogen-producing and oxygen-tolerant [NiFe]-hydrogenase, sequestered within the capsid of the bacteriophage P22 through directed self-assembly. We co-opted Escherichia coli for biomolecular synthesis and assembly of this nanomaterial by expressing and maturing the EcHyd-1 hydrogenase prior to expression of the P22 coat protein, which subsequently self assembles. By probing the infrared spectroscopic signatures and catalytic activity of the engineered material, we demonstrate that the capsid provides stability and protection to the hydrogenase cargo. These results illustrate how combining biological function with directed supramolecular self-assembly can be used to create new materials for sustainable catalysis.

  2. Molecular gated transistors: Role of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Shaya, O.; Halpern, E.; Khamaisi, B.; Shaked, M.; Usherenko, Y.; Shalev, G.; Doron, A.; Levy, I.; Rosenwaks, Y.

    2010-07-01

    In order to understand the biosensing mechanism of field-effect based biosensors and optimize their performance, the effect of each of its molecular building block must be understood. In this work the gating effect of self-assembled linker molecules on field-effect transistor was studied in detail. We have combined Kelvin probe force microscopy, current-voltage measurements, capacitance-voltage measurements, equivalent circuit modeling and device simulations in order to trace the mechanism of silicon-on-insulator biological field-effect transistors. The measurements were conducted on the widely used linker molecules (3-aminopropyl)-trimethoxysilane (APTMS) and 11-aminoundecyl-triethoxysilane (AUTES), which were self-assembled on ozone activated silicon oxide surface covering the transistor channel. In a dry environment, the work function of the modified silicon oxide decreased by more than 1.5 eV, and the transistor threshold voltage increased by about 30 V following the self-assembly. A detailed analysis indicates that these changes are due to negative induced charges on the top dielectric layer, and an effective dipole due to the polar monolayer. However, the self-assembly did not change the silicon flat-band voltage when in contact with an electrolyte. This is attributed to electrostatic screening by the electrolyte.

  3. Directed intermixing in multi-component self-assembling biomaterials

    PubMed Central

    Gasiorowski, Joshua Z.; Collier, Joel H.

    2011-01-01

    The non-covalent co-assembly of multiple different peptides can be a useful route for producing multifunctional biomaterials. However, to date such materials have almost exclusively been investigated as homogeneous self-assemblies, having functional components uniformly distributed throughout their supramolecular structures. Here we illustrate control over the intermixing of multiple different self-assembling peptides, in turn providing a simple but powerful means for modulating these materials’ mechanical and biological properties. In beta-sheet fibrillizing hydrogels, significant increases in stiffening could be achieved using heterobifunctional cross-linkers by sequestering peptides bearing different reactive groups into distinct populations of fibrils, thus favoring inter-fibril cross-linking. Further, by specifying the intermixing of RGD-bearing peptides in 2-D and 3-D self-assemblies, the growth of HUVECs and NIH 3T3 cells could be significantly modulated. This approach may be immediately applicable towards a wide variety of self-assembling systems that form stable supramolecular structures. PMID:21863894

  4. Investigation of carboxylic-functionalized and n-alkanethiol self-assembled monolayers on gold and their application as pH-sensitive probes using scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Boldt, Frank-Mario; Baltes, Norman; Borgwarth, Kai; Heinze, Jürgen

    2005-12-01

    We investigated the insulating properties of n-alkanethiol self-assembled monolayers (SAMs) of varying chain lengths [CH 3(CH 2) nSH; n = 7, 9, 11, 15] on polycrystalline gold electrodes using scanning electrochemical microscopy (SECM) and cyclic voltammetry. On the basis of SECM approach curves we examined the local ET through monolayers with increasing chain length in different redox mediators. We were able to distinguish the monolayers because of their different insulating properties and in addition, the status of SAM formation after immersion times of 2 h and 24 h, respectively, could be observed. Cyclic voltammetric measurements confirmed the SECM results and were in good agreement with other experimental data in the literature. High-resolution SECM images of hexadecanethiol SAM micropatterns down to 4 μm in diameter formed by microcontact printing (μCP) were obtained in the feedback mode. Furthermore, we studied the ET and the pH-dependent behavior of mercaptoundecanoic acid monolayers on gold at varying pH and in different redox mediator solutions to test their application as pH-sensors. An additional influence on the ET could be established based on Coulomb/ionic interactions between the charged monolayer and the redox mediator at changing pH. Therefore, we present a new approach for designing pH-sensitive SECM probes using 11-mercaptoundecanoic acid-coated 10 μm-diameter gold ultramicroelectrodes (HOOC-C 11SH/Au UMEs) in aqueous solutions containing hexacyanoferrate. Voltammetric measurements at HOOC-C 11SH/Au UMEs at different pH values enabled us to estimate the degree of dissociation of the carboxylic-terminated monolayers.

  5. PREFACE: IUMRS-ICA 2008 Symposium, Sessions 'X. Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' and 'Y. Frontier of Polymeric Nano-Soft-Materials - Precision Polymer Synthesis, Self-assembling and Their Functionalization'

    NASA Astrophysics Data System (ADS)

    Takahara, Atsushi; Kawahara, Seiichi

    2009-09-01

    Tashiro (Toyota Technological Institute) Professor Kazuo Sakurai(Kitakyushu University) Professor Keiji Tanaka (Kyushu University) Dr Sono Sasaki (JASRI/Spring-8) Professor Naoya Torikai (KENS) Professor Moonhor Ree (POSTECH) Professor Kookheon Char (Seoul National University) Professor Charles C Han (CAS) Professor Atsushi Takahara(Kyushu University) Frontier of Polymeric Nano-Soft-Materials, Precision Polymer Synthesis, Self-assembling and Their Functionalization (Symposium Y of IUMRS-ICA2008) Seiichi Kawahara, Rong-Ming Ho, Hiroshi Jinnai, Masami Kamigaito, Takashi Miyata, Hiroshi Morita, Hideyuki Otsuka, Daewon Sohn, Keiji Tanaka It is our great pleasure and honor to publish peer-reviewed papers, presented in Symposium Y 'Frontier of Polymeric Nano-Soft-Materials Precision Polymer Synthesis, Self-assembling and Their Functionalization' at the International Union of Materials Research Societies International Conference in Asia 2008 (IUMRS-ICA2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. 'Polymeric nano-soft-materials' are novel outcomes based on a recent innovative evolution in polymer science, i.e. precision polymer synthesis, self-assembling and functionalization of multi-component systems. The materials are expected to exhibit specific functions and unique properties due to their hierarchic morphologies brought either by naturally-generated ordering or by artificial manipulation of the systems, e.g., crystallization and phase-separation. The emerging precision synthesis has brought out new types of polymers with well-controlled primary structures. Furthermore, the surface and interface of the material are recognized to play an important role in the outstanding mechanical, electrical and optical properties, which are required for medical and engineering applications. In order to understand structure-property relationships in the nano-soft-materials, it is indispensable to develop novel characterization techniques. Symposium Y

  6. Self-assembly of coordination molecular baskets as inorganic analogues of cyclotriveratrylenes (CTV).

    PubMed

    Li, Sheng-Hui; Huang, Hai-Ping; Yu, Shu-Yan; Li, Yi-Zhi; Huang, Hui; Sei, Yoshihisa; Yamaguchi, Kentaro

    2005-07-21

    A [3 + 3] modular self-assembly gives rise to the formation of basket-shaped, crown ether-functionalized, nano-sized trimetallo-macrocycles, which function as structural analogues of cyclotriveratrylenes (CTV). PMID:15995740

  7. Directed Self-Assembly of Nanodispersions

    SciTech Connect

    Furst, Eric M

    2013-11-15

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

  8. From Solvolysis to Self-Assembly*

    PubMed Central

    Stang, Peter J.

    2009-01-01

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

  9. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly

    PubMed Central

    Moore, Tyler G.; Garzon, Max H.; Deaton, Russell J.

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are “strong” assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly

  10. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly.

    PubMed

    Moore, Tyler G; Garzon, Max H; Deaton, Russell J

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are "strong" assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly systems

  11. Solvent mediated self-assembly of solids

    SciTech Connect

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

    1997-12-12

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

  12. Formation of a Double Diamond Cubic Phase by Thermotropic Liquid Crystalline Self-Assembly of Bundled Bolaamphiphiles.

    PubMed

    Zeng, Xiangbing; Prehm, Marko; Ungar, Goran; Tschierske, Carsten; Liu, Feng

    2016-07-11

    A quaternary amphiphile with swallow-tail side groups displays a new bicontinuous thermotropic cubic phase with symmetry Pn3‾ m and formed by two interpenetrating networks where cylindrical segments are linked by H bonds at tetrahedral junctions. Each network segment contains two bundles, each containing 12 rod-like mesogens, lying along the segment axis. This assembly leads to the first thermotropic structure of the "double diamond" type. A quantitative geometric model is proposed to explain the occurrence of this rare phase. PMID:27270840

  13. Synthesis and self-assembly of poly(3-hexylthiophene)-block-poly(acrylic acid)

    SciTech Connect

    Li, Zicheng; Ono, Robert J.; Wu, Zong-Quan; Bielawski, Christopher W.

    2011-01-01

    A modular and convenient synthesis of ethynyl end functionalized poly(3-hexylthiophene) in high purity is reported; this material facilitated access to poly(3-hexylthiophene)-block-poly(acrylic acid) which self-assembled into hierarchical structures.

  14. Scaffold and scaffold-free self-assembled systems in regenerative medicine.

    PubMed

    Thomas, Dilip; Gaspar, Diana; Sorushanova, Anna; Milcovich, Gesmi; Spanoudes, Kyriakos; Mullen, Anne Maria; O'Brien, Timothy; Pandit, Abhay; Zeugolis, Dimitrios I

    2016-06-01

    Self-assembly in tissue engineering refers to the spontaneous chemical or biological association of components to form a distinct functional construct, reminiscent of native tissue. Such self-assembled systems have been widely used to develop platforms for the delivery of therapeutic and/or bioactive molecules and various cell populations. Tissue morphology and functional characteristics have been recapitulated in several self-assembled constructs, designed to incorporate stimuli responsiveness and controlled architecture through spatial confinement or field manipulation. In parallel, owing to substantial functional properties, scaffold-free cell-assembled devices have aided in the development of functional neotissues for various clinical targets. Herein, we discuss recent advancements and future aspirations in scaffold and scaffold-free self-assembled devices for regenerative medicine purposes. Biotechnol. Bioeng. 2016;113: 1155-1163. © 2015 Wiley Periodicals, Inc. PMID:26498484

  15. Patterning Self-Assembled Monolayers on Gold: Green Materials Chemistry in the Teaching Laboratory

    ERIC Educational Resources Information Center

    McFarland, Adam D.; Huffman, Lauren M.; Parent, Kathryn, E.; Hutchison, James E.; Thompson, John E.

    2004-01-01

    An experiment demonstrating self-assembled monolayer (SAM) chemistry, organic thin-film patterning and the use of molecular functionality to control macroscopic properties is described. Several important green chemistry principles are introduced.

  16. Progress Report on the Generation of Polyfunctional Microscale Particles for Programmed Self-Assembly

    PubMed Central

    2015-01-01

    A process for 3D programmed self-assembly of lithographically printable microscale polymer particles using ssDNA hybridization as the associative force is described. We report our progress in establishing the unit processes required for 3D programmed self-assembly and demonstrate the successful fabrication and sequence-specific self-assembly of covalent ssDNA-functionalized parallelepipeds with dimensions in the sub 10 μm regime characterized by optical microscopy and imaging flow cytometry. This technology has the potential to produce parallelepiped particles with different ssDNA on each facet. PMID:24803723

  17. Directed self-assembly of performance materials

    NASA Astrophysics Data System (ADS)

    Nealey, Paul

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

  18. Host-Guest Binding-Site-Tunable Self-Assembly of Stimuli-Responsive Supramolecular Polymers.

    PubMed

    Yao, Hao; Qi, Miao; Liu, Yuyang; Tian, Wei

    2016-06-13

    Despite the remarkable progress made in controllable self-assembly of stimuli-responsive supramolecular polymers (SSPs), a basic issue that has not been consideration to date is the essential binding site. The noncovalent binding sites, which connect the building blocks and endow supramolecular polymers with their ability to respond to stimuli, are expected to strongly affect the self-assembly of SSPs. Herein, the design and synthesis of a dual-stimuli thermo- and photoresponsive Y-shaped supramolecular polymer (SSP2) with two adjacent β-cyclodextrin/azobenzene (β-CD/Azo) binding sites, and another SSP (SSP1) with similar building blocks, but only one β-CD/Azo binding site as a control, are described. Upon gradually increasing the polymer solution temperature or irradiating with UV light, SSP2 self-assemblies with a higher binding-site distribution density; exhibits a flower-like morphology, smaller size, and more stable dynamic aggregation process; and greater controllability for drug-release behavior than those observed with SSP1 self-assemblies. The host-guest binding-site-tunable self-assembly was attributed to the positive cooperativity generated among adjacent binding sites on the surfaces of SSP2 self-assemblies. This work is beneficial for precisely controlling the structural parameters and controlled release function of SSP self-assemblies. PMID:27167577

  19. Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface

    SciTech Connect

    Maksymovych, P.; Sorescu, D.C.; Yates, J.T., Jr.

    2006-10-06

    Microscopic evidence for Au-adatom-induced self-assembly of alkanethiolate species on the Au(111) surface is presented. Based on STM measurements and density-functional theory calculations, a new model for the low-coverage self-assembled monolayer of alkanethiolate on the Au(111) surface is developed, which involves the adsorbate complexes incorporating Au adatoms. It is also concluded that the Au(111) herringbone reconstruction is lifted by the alkanethiolate self-assembly because the reconstructed surface layer provides reactive Au adatoms that drive self-assembly.

  20. Self-Assembly of Tetraphenylalanine Peptides.

    PubMed

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

    2015-11-16

    Three different tetraphenylalanine (FFFF) based peptides that differ at the N- and C-termini have been synthesized by using standard procedures to study their ability to form different nanoassemblies under a variety of conditions. The FFFF peptide assembles into nanotubes that show more structural imperfections at the surface than those formed by the diphenylalanine (FF) peptide under the same conditions. Periodic DFT calculations (M06L functional) were used to propose a model that consists of three FFFF molecules defining a ring through head-to-tail NH3(+)⋅⋅⋅(-)OOC interactions, which in turn stack to produce deformed channels with internal diameters between 12 and 16 Å. Depending on the experimental conditions used for the peptide incubation, N-fluorenylmethoxycarbonyl (Fmoc) protected FFFF self-assembles into a variety of polymorphs: ultra-thin nanoplates, fibrils, and star-like submicrometric aggregates. DFT calculations indicate that Fmoc-FFFF prefers a parallel rather than an antiparallel β-sheet assembly. Finally, coexisting multiple assemblies (up to three) were observed for Fmoc-FFFF-OBzl (OBzl = benzyl ester), which incorporates aromatic protecting groups at the two peptide terminals. This unusual and noticeable feature is attributed to the fact that the assemblies obtained by combining the Fmoc and OBzl groups contained in the peptide are isoenergetic. PMID:26419936

  1. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

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

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

    PubMed

    Rudchenko, M N; Zamyatnin, A A

    2015-04-01

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

  3. Dynamic self-assembly of microscale rotors and swimmers

    NASA Astrophysics Data System (ADS)

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

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

  4. Dynamic self-assembly of microscale rotors and swimmers.

    PubMed

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

    2016-05-18

    Biological systems often involve the self-assembly of basic components into complex and functioning structures. Artificial systems that mimic such processes can provide a well-controlled setting to explore the principles involved and also synthesize useful micromachines. Our experiments show that immotile, but active, components self-assemble into two types of structure that exhibit the fundamental forms of motility: translation and rotation. Specifically, micron-scale metallic rods are designed to induce extensile surface flows in the presence of a chemical fuel; these rods interact with each other and pair up to form either a swimmer or a rotor. Such pairs can transition reversibly between these two configurations, leading to kinetics reminiscent of bacterial run-and-tumble motion. PMID:27121100

  5. Self-Assembly of Peptides to Nanostructures

    PubMed Central

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

    2014-01-01

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

  6. Self-assembly of nanocomposite materials

    DOEpatents

    Brinker, C. Jeffrey; 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.

  7. From self-assembled vesicles to protocells.

    PubMed

    Chen, Irene A; Walde, Peter

    2010-07-01

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

  8. From Self-Assembled Vesicles to Protocells

    PubMed Central

    Chen, Irene A.; Walde, Peter

    2010-01-01

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

  9. Remote control of self-assembled microswimmers

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  10. Computing by molecular self-assembly

    PubMed Central

    Jonoska, Nataša; Seeman, Nadrian C.

    2012-01-01

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

  11. Self-assembly of chlorophenols in water

    PubMed Central

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

    1999-01-01

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

  12. Remote control of self-assembled microswimmers

    PubMed Central

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

    2015-01-01

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

  13. Nondeterministic self-assembly with asymmetric interactions.

    PubMed

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

    2016-08-01

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

  14. Nondeterministic self-assembly with asymmetric interactions

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  15. GeSi strained nanostructure self-assembly for nano- and opto-electronics.

    SciTech Connect

    Means, Joel L.; Floro, Jerrold Anthony

    2001-07-01

    Strain-induced self-assembly during semiconductor heteroepitaxy offers a promising approach to produce quantum nanostructures for nanologic and optoelectronics applications. Our current research direction aims to move beyond self-assembly of the basic quantum dot towards the fabrication of more complex, potentially functional structures such as quantum dot molecules and quantum wires. This report summarizes the steps taken to improve the growth quality of our GeSi molecular beam epitaxy process, and then highlights the outcomes of this effort.

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

    DOE PAGESBeta

    Jonathan D. Halverson; Tkachenko, Alexei V.

    2016-03-04

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

  17. Self-assembled amyloid fibrils with controllable conformational heterogeneity.

    PubMed

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  18. Self-assembled amyloid fibrils with controllable conformational heterogeneity

    NASA Astrophysics Data System (ADS)

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-11-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled.

  19. Evolutionary dynamics in a simple model of self-assembly

    NASA Astrophysics Data System (ADS)

    Johnston, Iain G.; Ahnert, Sebastian E.; Doye, Jonathan P. K.; Louis, Ard A.

    2011-06-01

    We investigate the evolutionary dynamics of an idealized model for the robust self-assembly of two-dimensional structures called polyominoes. The model includes rules that encode interactions between sets of square tiles that drive the self-assembly process. The relationship between the model’s rule set and its resulting self-assembled structure can be viewed as a genotype-phenotype map and incorporated into a genetic algorithm. The rule sets evolve under selection for specified target structures. The corresponding complex fitness landscape generates rich evolutionary dynamics as a function of parameters such as the population size, search space size, mutation rate, and method of recombination. Furthermore, these systems are simple enough that in some cases the associated model genome space can be completely characterized, shedding light on how the evolutionary dynamics depends on the detailed structure of the fitness landscape. Finally, we apply the model to study the emergence of the preference for dihedral over cyclic symmetry observed for homomeric protein tetramers.

  20. Self-assembled amyloid fibrils with controllable conformational heterogeneity

    PubMed Central

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  1. Materials self-assembly and fabrication in confined spaces

    SciTech Connect

    Ramanathan, Nathan Muruganathan; Kilbey, II, S Michael; Ji, Dr. Qingmin; Hill, Dr. Jonathan P; Ariga, Katsuhiko

    2012-01-01

    Molecular assemblies have been mainly researched in open spaces for long time. However, recent researches have revealed that there are many interesting aspects remained in self-assemblies in confined spaces. Molecular association within nanospaces such as mesoporous materials provide unusual phenomena based on highly restricted molecular motions. Current research endeavors in materials science and technology are focused on developing either new class of materials or materials with novel/multiple functionalities which is often achived via molecular assembly in confined spaces. Template synthesis and guided assemblies are distinguishable examples for molecular assembly in confined spaces. So far, different aspects of molecular confinements are discussed separately. In this review, the focus is specifically to bring some potential developments in various aspects of confined spaces for molecular self-assembly under one roof. We arrange the sections in this review based on the nature of the confinements; accordingly the topological/geometrical confinements, chemical and biological confinements, and confinements within thin film, respectively. Following these sections, molecular confinements for practical applications are shortly described in order to show connections of these scientific aspects with possible practical uses. One of the most important facts is that the self-assembly in confined spaces stands at meeting points of top-down and bottom-up fabrications, which would be an ultimate key to push the limits of nanotechnology and nanoscience.

  2. Chiral Perylene Materials by Ionic Self-Assembly.

    PubMed

    Echue, Geraldine; Hamley, Ian; Lloyd Jones, Guy C; Faul, Charl F J

    2016-09-01

    Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV-vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure-function relationship is easily explored here due to the wide selection and easy availability of common surfactants. PMID:27486788

  3. Quantitative Characterization of Surface Self-Assembly Imaging Using Shapelets

    NASA Astrophysics Data System (ADS)

    Abukhdeir, Nasser Mohieddin; Suderman, Robert; Lizotte, Daniel J.

    Microscopy and imaging of surface self-assembly phenomena have advanced significantly over the past decade. In order to determine structure/property relationships robust automated analysis of the resulting images is required, but has not advanced at an equally rapid pace. Recently, quantitative characterization techniques have been developed and applied, such as using bond-orientational order (BOO) theory. BOO-based methods have significant limitations in that they do not provide pixel-level resolution and are not robust in the presence of measurement noise. In this work, a fundamentally different method for automated quantitative characterization of surface self-assembly imaging is presented which uses a family of localized functions called ``shapelets''. The method is presented and applied to quantitative characterization of stripe and hexagonal patterns which are frequently observed in surface self-assembly. The shapelet-based method is shown to be general, highly accurate, and robust in the presence of measurement noise. It is able to efficiently determine local pattern characteristics such as pattern strength and orientation for the determination of structure/property relationships. This work was made possible by the Natural Sciences and Engineering Research Council of Canada and Compute Ontario.

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

    PubMed Central

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

    2015-01-01

    In nature, sophisticated functional materials are created through hierarchical self-assembly of simple nanoscale motifs1–4. In the laboratory, much progress has been made in the controlled assembly of molecules into one-5–7, two-6,8,9 and three-dimensional10 artificial nanostructures, but bridging from the nanoscale to the macroscale to create useful macroscopic materials remains a challenge. Here we show a scalable self-assembly approach to making free-standing films from amyloid protein fibrils. The films were well ordered and highly rigid, with a Young’s modulus of up to 5–7 GPa, which is comparable to the highest values for proteinaceous materials found in nature. We show that the self-organizing protein scaffolds can align otherwise unstructured components (such as fluorophores) within the macroscopic films. Multiscale self-assembly that relies on highly specific biomolecular interactions is an attractive path for realizing new multifunctional materials built from the bottom up. PMID:20190750

  5. Algorithmic Self-Assembly of DNA Sierpinski Triangles

    PubMed Central

    2004-01-01

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

  6. Nanopropulsion by biocatalytic self-assembly.

    PubMed

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

    2014-09-23

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

  7. Self-assembly micro optical filter

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

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

  8. Self-assembling materials for therapeutic delivery✩

    PubMed Central

    Branco, Monica C.; Schneider, Joel P.

    2009-01-01

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

  9. [INVITED] Self-assembled optical metamaterials

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  10. Self-Assembly and Headgroup Effect in Nanostructured Organogels via Cationic Amphiphile-Graphene Oxide Composites

    PubMed Central

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Yan, Xuehai; Zhao, Xiaoqing; Zhou, Jingxin; Gao, Faming

    2014-01-01

    Self-assembly of hierarchical graphene oxide (GO)-based nanomaterials with novel functions has received a great deal of attentions. In this study, nanostructured organogels based on cationic amphiphile-GO composites were prepared. The gelation behaviors of amphiphile-GO composites in organic solvents can be regulated by changing the headgroups of amphiphiles. Ammonium substituted headgroup in molecular structures in present self-assembled composites is more favorable for the gelation in comparison to pyridinium headgroup. A possible mechanism for headgroup effects on self-assembly and as-prepared nanostructures is proposed. It is believed that the present amphiphile-GO self-assembled system will provide an alternative platform for the design of new GO nanomaterials and soft matters. PMID:24983466

  11. Computational study of trimer self-assembly and fluid phase behavior

    SciTech Connect

    Hatch, Harold W. Shen, Vincent K.; Mittal, Jeetain

    2015-04-28

    The fluid phase diagram of trimer particles composed of one central attractive bead and two repulsive beads was determined as a function of simple geometric parameters using flat-histogram Monte Carlo methods. A variety of self-assembled structures were obtained including spherical micelle-like clusters, elongated clusters, and densely packed cylinders, depending on both the state conditions and shape of the trimer. Advanced simulation techniques were employed to determine transitions between self-assembled structures and macroscopic phases using thermodynamic and structural definitions. Simple changes in particle geometry yield dramatic changes in phase behavior, ranging from macroscopic fluid phase separation to molecular-scale self-assembly. In special cases, both self-assembled, elongated clusters and bulk fluid phase separation occur simultaneously. Our work suggests that tuning particle shape and interactions can yield superstructures with controlled architecture.

  12. Surface-induced self-assembly of dipeptides onto nanotextured surfaces.

    PubMed

    Demirel, Gokhan; Buyukserin, Fatih

    2011-10-18

    There is an increasing interest for the utilization of biomolecules for fabricating novel nanostructures due to their ability for specific molecular recognition, biocompatibility, and ease of availability. Among these molecules, diphenylalanine (Phe-Phe) dipeptide is considered as one of the simplest molecules that can generate a family of self-assembly based nanostructures. The properties of the substrate surface, on which the self-assembly process of these peptides occurs, play a critical role. Herein, we demonstrated the influence of surface texture and functionality on the self-assembly of Phe-Phe dipeptides using smooth silicon surfaces, anodized aluminum oxide (AAO) membranes, and poly(chloro-p-xylylene) (PPX) films having columnar and helical morphologies. We found that helical PPX films, AAO, and silicon surfaces induce similar self-assembly processes and the surface hydrophobicity has a direct influence for the final dipeptide structure whether being in an aggregated tubular form or creating a thin film that covers the substrate surface. Moreover, the dye staining data indicates that the surface charge properties and hence the mechanism of the self-assembly process are different for tubular structures as opposed to the peptidic film. We believe that our results may contribute to the control of surface-induced self-assembly of peptide molecules and this control can potentially allow the fabrication of novel peptide based materials with desired morphologies and unique functionalities for different technological applications. PMID:21879773

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

    DOE PAGESBeta

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

    2016-02-24

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

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

    PubMed

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

    2016-06-28

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

  15. Tightening up the structure, lighting up the pathway: Application of molecular constraints and light to manipulate protein folding, self-assembly and function

    PubMed Central

    Markiewicz, Beatrice N.; Culik, Robert M.; Gai, Feng

    2015-01-01

    Chemical cross-linking provides an effective avenue to reduce the conformational entropy of polypeptide chains and hence has become a popular method to induce or force structural formation in peptides and proteins. Recently, other types of molecular constraints, especially photoresponsive linkers and functional groups, have also found increased use in a wide variety of applications. Herein, we provide a concise review of using various forms of molecular strategies to constrain proteins, thereby stabilizing their native states, gaining insight into their folding mechanisms, and/or providing a handle to trigger a conformational process of interest with light. The applications discussed here cover a wide range of topics, ranging from delineating the details of the protein folding energy landscape to controlling protein assembly and function. PMID:25722715

  16. Simulations of molecular self-assembled monolayers on surfaces: packing structures, formation processes and functions tuned by intermolecular and interfacial interactions.

    PubMed

    Wen, Jin; Li, Wei; Chen, Shuang; Ma, Jing

    2016-08-17

    Surfaces modified with a functional molecular monolayer are essential for the fabrication of nano-scale electronics or machines with novel physical, chemical, and/or biological properties. Theoretical simulation based on advanced quantum chemical and classical models is at present a necessary tool in the development, design, and understanding of the interfacial nanostructure. The nanoscale surface morphology, growth processes, and functions are controlled by not only the electronic structures (molecular energy levels, dipole moments, polarizabilities, and optical properties) of building units but also the subtle balance between intermolecular and interfacial interactions. The switchable surfaces are also constructed by introducing stimuli-responsive units like azobenzene derivatives. To bridge the gap between experiments and theoretical models, opportunities and challenges for future development of modelling of ferroelectricity, entropy, and chemical reactions of surface-supported monolayers are also addressed. Theoretical simulations will allow us to obtain important and detailed information about the structure and dynamics of monolayer modified interfaces, which will guide the rational design and optimization of dynamic interfaces to meet challenges of controlling optical, electrical, and biological functions. PMID:27138016

  17. Molecular Self-Assembly into One-Dimensional Nanostructures

    PubMed Central

    PALMER, LIAM C.; STUPP, SAMUEL I.

    2008-01-01

    CONSPECTUS Self-assembly of small molecules into one-dimensional nanostructures offers many potential applications in electronically and biologically active materials. The recent advances discussed in this Account demonstrate how researchers can use the fundamental principles of supramolecular chemistry to craft the size, shape, and internal structure of nanoscale objects. In each system described here, we used atomic force microscopy (AFM) and transmission electron microscopy (TEM) to study the assembly morphology. Circular dichroism, nuclear magnetic resonance, infrared, and optical spectroscopy provided additional information about the self-assembly behavior in solution at the molecular level. Dendron rod–coil molecules self-assemble into flat or helical ribbons. They can incorporate electronically conductive groups and can be mineralized with inorganic semiconductors. To understand the relative importance of each segment in forming the supramolecular structure, we synthetically modified the dendron, rod, and coil portions. The self-assembly depended on the generation number of the dendron, the number of hydrogen-bonding functions, and the length of the rod and coil segments. We formed chiral helices using a dendron–rod–coil molecule prepared from an enantiomerically enriched coil. Because helical nanostructures are important targets for use in biomaterials, nonlinear optics, and stereoselective catalysis, researchers would like to precisely control their shape and size. Tripeptide-containing peptide lipid molecules assemble into straight or twisted nanofibers in organic solvents. As seen by AFM, the sterics of bulky end groups can tune the helical pitch of these peptide lipid nanofibers in organic solvents. Furthermore, we demonstrated the potential for pitch control using trans-to-cis photoisomerization of a terminal azobenzene group. Other molecules called peptide amphiphiles (PAs) are known to assemble in water into cylindrical nanostructures that

  18. Molecular and supramolecular control of the work function of an inorganic electrode with self-assembled monolayer of umbrella-shaped fullerene derivatives.

    PubMed

    Lacher, Sebastian; Matsuo, Yutaka; Nakamura, Eiichi

    2011-10-26

    The surface properties of inorganic substrates can be altered by coating with organic molecules, which may result in the improvement of the properties suitable for electronic or biological applications. This article reports a systematic experimental study on the influence of the molecular and supramolecular properties of umbrella-shaped penta(organo)[60]fullerene derivatives, and on the work function and the water contact angle of indium-tin oxide (ITO) and gold surfaces. We could relate these macroscopic characteristics to single-molecular level properties, such as ionization potential and molecular dipole. The results led us to conclude that the formation of a SAM of a polar compound generates an electronic field through intermolecular interaction of the molecular charges, and this field makes the overall dipole of the SAM much smaller than the one expected from the simple sum of the dipoles of all molecules in the SAM. This effect, which was called depolarization and previously discussed theoretically, is now quantitatively probed by experiments. The important physical properties in surface science such as work function, ionization potential, and water contact angles have been mutually correlated at the level of molecular structures and molecular orientations on the substrate surface. We also found that the SAMs on ITO and gold operate under the same principle except that the "push-back" effect operates specifically for gold. The study also illustrates the ability of the photoelectron yield spectroscopy technique to rapidly measure the work function of a SAM-covered substrate and the ionization potential value of a molecule on the surface. PMID:21923177

  19. DNA triangles and self-assembled hexagonal tilings.

    PubMed

    Chelyapov, Nickolas; Brun, Yuriy; Gopalkrishnan, Manoj; Reishus, Dustin; Shaw, Bilal; Adleman, Leonard

    2004-11-01

    We have designed and constructed DNA complexes in the form of triangles. We have created hexagonal planar tilings from these triangles via self-assembly. Unlike previously reported structures self-assembled from DNA, our structures appear to involve bending of double helices. Bending helices may be a useful design option in the creation of self-assembled DNA structures. It has been suggested that DNA self-assembly may lead to novel materials and efficient computational devices. PMID:15506744

  20. Self-Assembling Protein Microarrays

    NASA Astrophysics Data System (ADS)

    Ramachandran, Niroshan; Hainsworth, Eugenie; Bhullar, Bhupinder; Eisenstein, Samuel; Rosen, Benjamin; Lau, Albert Y.; C. Walter, Johannes; LaBaer, Joshua

    2004-07-01

    Protein microarrays provide a powerful tool for the study of protein function. However, they are not widely used, in part because of the challenges in producing proteins to spot on the arrays. We generated protein microarrays by printing complementary DNAs onto glass slides and then translating target proteins with mammalian reticulocyte lysate. Epitope tags fused to the proteins allowed them to be immobilized in situ. This obviated the need to purify proteins, avoided protein stability problems during storage, and captured sufficient protein for functional studies. We used the technology to map pairwise interactions among 29 human DNA replication initiation proteins, recapitulate the regulation of Cdt1 binding to select replication proteins, and map its geminin-binding domain.

  1. Self-assembly of microcapsules via colloidal bond hybridization and anisotropy

    NASA Astrophysics Data System (ADS)

    Evers, Chris H. J.; Luiken, Jurriaan A.; Bolhuis, Peter G.; Kegel, Willem K.

    2016-06-01

    Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable owing to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and the colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy and deformability have not yet been realized. Here we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogously to the simplest chemical bond—in which two isotropic orbitals hybridize into the molecular orbital of H2—these flexible groups redistribute on binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, whereas anisotropic snowman-shaped particles self-assemble into hollow monolayer microcapsules. A modest change in the building blocks thus results in much greater complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into markedly more complex structures than do similar particles that are isotropic or non-deformable.

  2. Self-assembly of protein aggregates in ageing disorders: the lens and cataract model

    PubMed Central

    Clark, John I.

    2013-01-01

    Cataract, neurodegenerative disease, macular degeneration and pathologies of ageing are often characterized by the slow progressive destabilization of proteins and their self-assembly to amyloid-like fibrils and aggregates. During normal cell differentiation, protein self-assembly is well established as a dynamic mechanism for cytoskeletal organization. With the increased emphasis on ageing disorders, there is renewed interest in small-molecule regulators of protein self-assembly. Synthetic peptides, mini-chaperones, aptamers, ATP and pantethine reportedly regulate self-assembly mechanisms involving small stress proteins, represented by human αB-crystallin, and their targets. Small molecules are being considered for direct application as molecular therapeutics to protect against amyloid and protein aggregation disorders in ageing cells and tissues in vivo. The identification of specific interactive peptide sites for effective regulation of protein self-assembly is underway using conventional and innovative technologies. The quantification of the functional interactions between small stress proteins and their targets in vivo remains a top research priority. The quantitative parameters controlling protein–protein interactions in vivo need characterization to understand the fundamental biology of self-assembling systems in normal cells and disorders of ageing. PMID:23530262

  3. Self-assembly of protein aggregates in ageing disorders: the lens and cataract model.

    PubMed

    Clark, John I

    2013-05-01

    Cataract, neurodegenerative disease, macular degeneration and pathologies of ageing are often characterized by the slow progressive destabilization of proteins and their self-assembly to amyloid-like fibrils and aggregates. During normal cell differentiation, protein self-assembly is well established as a dynamic mechanism for cytoskeletal organization. With the increased emphasis on ageing disorders, there is renewed interest in small-molecule regulators of protein self-assembly. Synthetic peptides, mini-chaperones, aptamers, ATP and pantethine reportedly regulate self-assembly mechanisms involving small stress proteins, represented by human αB-crystallin, and their targets. Small molecules are being considered for direct application as molecular therapeutics to protect against amyloid and protein aggregation disorders in ageing cells and tissues in vivo. The identification of specific interactive peptide sites for effective regulation of protein self-assembly is underway using conventional and innovative technologies. The quantification of the functional interactions between small stress proteins and their targets in vivo remains a top research priority. The quantitative parameters controlling protein-protein interactions in vivo need characterization to understand the fundamental biology of self-assembling systems in normal cells and disorders of ageing. PMID:23530262

  4. Self-assembly of microcapsules via colloidal bond hybridization and anisotropy.

    PubMed

    Evers, Chris H J; Luiken, Jurriaan A; Bolhuis, Peter G; Kegel, Willem K

    2016-06-16

    Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable owing to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and the colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy and deformability have not yet been realized. Here we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogously to the simplest chemical bond--in which two isotropic orbitals hybridize into the molecular orbital of H2--these flexible groups redistribute on binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, whereas anisotropic snowman-shaped particles self-assemble into hollow monolayer microcapsules. A modest change in the building blocks thus results in much greater complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into markedly more complex structures than do similar particles that are isotropic or non-deformable. PMID:27281213

  5. Programmed two-dimensional self-assembly of multiple DNA origami jigsaw pieces.

    PubMed

    Rajendran, Arivazhagan; Endo, Masayuki; Katsuda, Yousuke; Hidaka, Kumi; Sugiyama, Hiroshi

    2011-01-25

    We demonstrate a novel strategy of self-assembly to scale up origami structures in two-dimensional (2D) space using multiple origami structures, named "2D DNA jigsaw pieces", with a specially designed shape. For execution of 2D self-assembly along the helical axis (horizontal direction), sequence-programmed tenon and mortise were introduced to promote selective connections via π-stacking interaction, sequence-complementarity, and shape-complementarity. For 2D self-assembly along the helical side (vertical direction), the jigsaw shape-complementarity in the top and bottom edges and the sequence-complementarity of single-stranded overhangs were used. We designed and prepared nine different jigsaw pieces and tried to obtain a 3 × 3 assembly. The proof of concept was obtained by performing the assembly in four different ways. Among them, the stepwise self-assembly from the three vertical trimer assemblies gave the target 2D assembly with ∼35% yield. Finally, the surfaces of jigsaw pieces were decorated with hairpin DNAs to display the letters of the alphabet, and the self-assembled 2D structure displayed the word "DNA JIG SAW" in nanoscale. The method can be expanded to create self-assembled modules carrying various functional molecules for practical applications. PMID:21188996

  6. Self-assembling membranes and related methods thereof

    DOEpatents

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

    2013-08-20

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

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

    NASA Astrophysics Data System (ADS)

    Chandran, Harish

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

  8. Scanning tunneling microscopy and density functional theory investigations on molecular self-assembly of graphene on Ru(0 0 0 1)

    NASA Astrophysics Data System (ADS)

    Song, Junjie; Zhang, Han-jie; Zhang, Yuxi; Cai, Yiliang; Bao, Shining; He, Pimo

    2016-03-01

    Investigations on the bottom-up fabrication of graphene with 1,3,5-triphenylbenzene as precursor on Ru(0 0 0 1) was carried out using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Upon annealing 1,3,5-triphenylbenzene overlayer on Ru(0 0 0 1) at 550 °C, the precursors dehydrogenated and coalesced into graphitized flakes, and subsequent annealing up to 600 °C results in complete graphene conversion. The migration behavior and close-packing morphology of precursors were captured during STM measurements, and DFT calculations indicated that the inter-molecular interaction is responsible for the accumulation and close-packing of the precursors. The noticeable increment in the dehydrogenation barrier from 1.27 eV for monomer adsorption to 1.62 eV for dimer adsorption is well consistent with the observed drastic reduction of the graphitization temperature at lower precursor coverage, suggesting the crucial influence of inter-molecular vdW interaction on the dehydrogenation process.

  9. Self-assembled Oniontype Multiferroic Nanostructures

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

  10. Self Assembly of Complex Building Blocks

    NASA Astrophysics Data System (ADS)

    Stucke, David; Crespi, Vincent

    2004-03-01

    A genetic search algorithm for optimizing the packing density of self-assembled multicomponent crystals of nanoparticles applied to complex colloidal building blocks will be presented. The algorithm searches the complex multi-dimensional space to find preferred crystal structures where standard methods fail. Mixtures of colloidal molecules and the structures found to be preferred to phase separation for different species of coloidal molecule mixtures will be shown.

  11. Single photon ionisation of self assembled monolayers

    NASA Astrophysics Data System (ADS)

    King, B. V.; Savina, M. R.; Tripa, C. E.; Calaway, W. F.; Veryovkin, I. V.; Moore, J. F.; Pellin, M. J.

    2002-05-01

    Self assembled monolayers formed from benzenethiol, diphenylsulphide and diphenyldisulphide have been analysed using secondary ion mass spectrometry (SIMS), sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation mass spectrometry (LDPI). The peak corresponding to the parent ion was much stronger in LDPI than with SIMS or SNMS analysis and fragmentation was lower. A useful yield of order 0.5% was obtained for LDPI from diphenyldisulphide.

  12. The dynamics of nacre self-assembly

    PubMed Central

    Cartwright, Julyan H.E; Checa, Antonio G

    2006-01-01

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

  13. Directed Self-assembly for Lithography Applications

    NASA Astrophysics Data System (ADS)

    Cheng, Joy

    2010-03-01

    Economics dictated that semiconductor devices need to be scaled approximately to 70 percent linearly in order to follow the pace of Moore's law and maintain cost effectiveness. Optical lithography has been the driving force for scaling; however, it approaches its physical limit to print patterns beyond 22nm node. Directed self-assembly (DSA), which combines ``bottom-up'' self-assembled polymers and ``top-down'' lithographically defined substrates, has been considered as a potential candidate to extend optical lithography. Benefit from nanometer-scale self-assembly features and the registration precision of advanced lithography, DSA provides precise and programmable nanopatterns beyond the resolution limit of conventional lithography. We have demonstrated DSA concepts including frequency multiplication and pattern rectification using guiding prepattern with proper chemical and topographical information generated by e-beam lithography. In addition, we seek to integrate DSA with 193 nm optical lithography in a straightforward manner in order to move DSA from the research stage to a viable manufacturing technology. Recently, we implemented various integration strategies using photolithography to produce guiding patterns for DSA. This new ability enables DSA to be applied to large areas with state-of-the-art lithography facilities.

  14. Symmetry, Equivalence and Self-Assembly

    NASA Astrophysics Data System (ADS)

    Douglas, Jack

    2006-03-01

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

  15. Self-Assembly of Nanoparticle Surfactants

    NASA Astrophysics Data System (ADS)

    Lombardo, Michael T.

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

  16. Self-assembled plasmonic nanohole arrays.

    PubMed

    Lee, Si Hoon; Bantz, Kyle C; Lindquist, Nathan C; Oh, Sang-Hyun; Haynes, Christy L

    2009-12-01

    We present a simple and massively parallel nanofabrication technique to produce self-assembled periodic nanohole arrays over a millimeter-sized area of metallic film, with a tunable hole shape, diameter, and periodicity. Using this method, 30 x 30 microm(2) defect-free areas of 300 nm diameter or smaller holes were obtained in silver; this area threshold is critical because it is larger than the visible wavelength propagation length of surface plasmon waves ( approximately 27 microm) in the silver film. Measured optical transmission spectra show highly homogeneous characteristics across the millimeter-size patterned area, and they are in good agreement with FDTD simulations. The simulations also reveal intense electric fields concentrated near the air/silver interface, which was used for surface-enhanced Raman spectroscopy (SERS). Enhancement factors (EFs) measured with different hole shape and excitation wavelengths on the self-assembled nanohole arrays were 10(4)-10(6). With an additional Ag electroless plating step, the EF was further increased up to 3 x 10(6). The periodic nanohole arrays produced using this tunable self-assembly method show great promise as inexpensive SERS substrates as well as surface plasmon resonance biosensing platforms. PMID:19831350

  17. Engineered Self-Assembly of Plasmonic Nanomaterials

    NASA Astrophysics Data System (ADS)

    Tao, Andrea

    2013-03-01

    A critical need in nanotechnology is the development of new tools and methods to organize, connect, and integrate solid-state nanocomponents. Self-assembly - where components spontaneously organize themselves - can be carried out on a massively parallel scale to construct large-scale architectures using solid-state nanocrystal building blocks. I will present our recent work on the synthesis and self-assembly of nanocrystals for plasmonics, where light is propagated, manipulated, and confined by solid-state components that are smaller than the wavelength of light itself. We show the organization of polymer-grafted metal nanocrystals into hierarchical nanojunction arrays that possess intense ``hot spots'' due to electromagnetic field localization. We also show that doped semiconductor nanocrystals can serve as a new class of plasmonic building blocks, where shape and carrier density can be actively tuned to engineer plasmon resonances. These examples demonstrate that nanocrystals possess unique electromagnetic properties that rival top-down structures, and the potential of self-assembly for fabricating designer plasmonic materials.

  18. Chemical solution route to self-assembled epitaxial oxide nanostructures.

    PubMed

    Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

    2014-04-01

    Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials. PMID:24418962

  19. Self-assembled biomimetic nanoreactors I: Polymeric template

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  20. Metal nanowires from self-assembled protein fibers

    NASA Astrophysics Data System (ADS)

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

    2002-03-01

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

  1. Spin State As a Probe of Vesicle Self-Assembly.

    PubMed

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

    2016-03-01

    A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution of surfactants between the bilayers and the aqueous bulk. PMID:26859700

  2. A Programmable Transducer Self-Assembled from DNA

    PubMed Central

    Chakraborty, Banani; Jonoska, Natasha; Seeman, Nadrian C.

    2012-01-01

    A transducer consists of an input/output alphabet, a finite set of states, and a transition function. From an input symbol applied to a given state, the transition function determines the next state, and an output symbol. Using DNA, we have constructed a transducer that divides a number by 3. The input consists of a series of individually addressable 2-state DNA nanomechanical devices that control the orientations of a group of flat 6-helix DNA motifs; these motifs have edge domains tailed in sticky ends corresponding to the numbers 0 and 1. Three-domain DNA molecules (TX tiles) act as computational tiles that correspond to the transitions that the transducer can undergo. The output domain of these TX tiles contains sticky ends that also correspond to 0 or 1. Two different DNA tiles can chelate these output domains: A 5 nm gold nanoparticle is attached to the chelating tile that binds to 0-domains and a 10 nm gold nanoparticle is attached to the chelating tile that binds to 1-domains. The answer to the division is represented by the series of gold nanoparticles, which can be interpreted as a binary number. The answers of the computation are read out by examination of the transducer complexes under a transmission electron microscope. The start or end points of the output sequence can be indicated by the presence of a 15 nm gold nanoparticle. This work demonstrates two previously unreported features integrated in a single framework: [1] a system that combines DNA algorithmic self-assembly with DNA nanomechanical devices that control that input, and [2] the arrangement of non-DNA species, here metallic nanoparticles, through DNA algorithmic self-assembly. The nanomechanical devices are controlled by single-stranded DNA strands, allowing multiple input sequences to be applied to the rest of the system, thus guiding the algorithmic self-assembly to a variety of outputs. PMID:23139854

  3. Combustion and self-assembly of nanoenergetic materials

    NASA Astrophysics Data System (ADS)

    Malchi, Jonathan Yaniv

    are easily changed and their effects on the flame spread rate are observed. Overall, spread rates are 2 to 3 orders of magnitude greater than what is demonstrated with typical solid fuels due to the high reactivity of the nAl. This large difference in spread rate brings about a fingering combustion instability in normal gravity conditions that has only been shown to occur in microgravity conditions. Moreover, a stability map is created based on the nondimensional Lewis and Damkohler numbers that predicts when a continuous flame front will transition to a fingering instability. This, along with the various other trends, is predicted using a simple scaling analysis. A nanoscale thermite is created via sonication of nAl and nanocopper-oxide (nCuO) particles. Although the mixture is unorganized and random, these materials boast extremely exothermic reactions with propagation rates on the order of 1 km/s. Experiments are performed to examine the effect of adding a diluent to the system. Two types of materials are added, a stable end product, aluminum-oxide, and long alkyl chain hydrocarbons. Both materials severely hinder the propagation rate, however, experiments suggest that hydrocarbon addition could help with the material's sensitivity to electrostatic discharge. Equilibrium calculations suggest that a dual temperature and gas production criteria must be met to allow for the convective propagation mechanism to take place and fast propagation rates to occur. Because of the hydrocarbons required for self-assembly, these experiments also give an indication of how the self-assembled material will react. To electrostatically self-assemble a nAl/nCuO thermite, the constituents are first coated with an o-functionalized alkyl chain ligand and suspended in a separate solutions. Upon mixing, the opposite electrostatic charges agglomerate the two constituents, which subsequently precipitate out of solution. Analyzing the material with Scanning Electron Microscopy shows that a

  4. Bacterial expression of self-assembling peptide hydrogelators

    NASA Astrophysics Data System (ADS)

    Sonmez, Cem

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

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

    PubMed

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

    2015-08-12

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

  6. Final Report for Grant # DE-FG02-02ER46000 Simulations of Self-Assembly of Tethered Nanoparticle Shape Amphiphiles

    SciTech Connect

    Glotzer, Sharon C.

    2014-08-25

    Self-assembly of nanoparticle building blocks including nanospheres, nanorods, nanocubes, nano plates, nanoprisms, etc., may provide a promising means for manipulating these building blocks into functional and useful materials. One increasingly popular method for self-assembly involves functionalizing nanoparticles and nanostructured molecules with “tethers” of organic polymers or biomolecules with specific or nonspecific interactions to facilitate their assembly. However, there is little theory and little understanding of the general principles underlying self-assembly in these complex materials. Using computer simulation to elucidate the principles of self-assembly and develop a predictive theoretical framework was the central goal of this project.

  7. Fluorine-labeling as a diagnostic for thiol-ligand and gold nanocluster self-assembly.

    PubMed

    Snow, Arthur W; Foos, Edward E; Coble, Melissa M; Jernigan, Glenn G; Ancona, Mario G

    2009-09-01

    An omega-fluorine-labeled oxyethylene thiol ligand, F(CH2CH2O)2CH2CH2SH, was synthesized, characterized and incorporated into mixed self-assembled monolayers with CH3(OCH2CH2)3SH onto a planar gold substrate and onto 2 nm gold nanoclusters. The fluorine-labeled nanocluster was self-assembled onto gold substrates using alkane dithiol (HS(CH2)nSH; n = 5, 8, 11) and oxyethylene dithiol (HS(CH2CH2O)nCH2CH2SH; n = 1, 2, 3) linking agents with equivalent chain lengths for comparative purposes. X-ray photoelectron spectroscopy (XPS) was used to track the fluorine-label in the self-assembly operations and to evaluate the effectiveness of the dithiols. For adequate XPS sensitivity at least 10% of the monolayer-forming molecules should be functionalized with this fluorine-label. In the comparative self-assembly of the fluorine-labeled gold nanoclusters in chloroform solution, the alkane dithiols were observed to be the more effective linking agents. This effectiveness correlates with the XPS analysis of alkane dithiols self-assembling onto the gold substrates with a higher packing density and with a larger fraction of molecules having one thiol group as opposed to two bonded to the gold surface. The oxyethylene dithiols self-assemble with a smaller packing density and a smaller fraction of molecules with an unbonded thiol group available for self-assembly. PMID:19684901

  8. A coarse-grained model of microtubule self-assembly

    NASA Astrophysics Data System (ADS)

    Regmi, Chola; Cheng, Shengfeng

    Microtubules play critical roles in cell structures and functions. They also serve as a model system to stimulate the next-generation smart, dynamic materials. A deep understanding of their self-assembly process and biomechanical properties will not only help elucidate how microtubules perform biological functions, but also lead to exciting insight on how microtubule dynamics can be altered or even controlled for specific purposes such as suppressing the division of cancer cells. Combining all-atom molecular dynamics (MD) simulations and the essential dynamics coarse-graining method, we construct a coarse-grained (CG) model of the tubulin protein, which is the building block of microtubules. In the CG model a tubulin dimer is represented as an elastic network of CG sites, the locations of which are determined by examining the protein dynamics of the tubulin and identifying the essential dynamic domains. Atomistic MD modeling is employed to directly compute the tubulin bond energies in the surface lattice of a microtubule, which are used to parameterize the interactions between CG building blocks. The CG model is then used to study the self-assembly pathways, kinetics, dynamics, and nanomechanics of microtubules.

  9. Self-assembled lipid bilayer materials

    DOEpatents

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

    2005-11-08

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

  10. Ionically self-assembled monolayers (ISAMs)

    NASA Astrophysics Data System (ADS)

    Janik, John

    2001-04-01

    Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

  11. Conceptual, self-assembling graphene nanocontainers

    NASA Astrophysics Data System (ADS)

    Boothroyd, Simon; Anwar, Jamshed

    2015-07-01

    We show that graphene nano-sheets, when appropriately functionalised, can form self-assembling nanocontainers which may be opened or closed using a chemical trigger such as pH or polarity of solvent. Conceptual design rules are presented for different container structures, whose ability to form and encapsulate guest molecules is verified by molecular dynamics simulations. The structural simplicity of the graphene nanocontainers offers considerable scope for scaling the capacity, modulating the nature of the internal environment, and defining the trigger for encapsulation or release of the guest molecule(s). This design study will serve to provide additional impetus to developing synthetic approaches for selective functionalisation of graphene.

  12. Self-assembly of Random Copolymers

    PubMed Central

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

    2014-01-01

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

  13. Self-assembly of colloidal surfactants

    NASA Astrophysics Data System (ADS)

    Kegel, Willem

    2012-02-01

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

  14. Self-assembly of magnetic biofunctional nanoparticles

    SciTech Connect

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

    2005-05-15

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

  15. Self-assembly of information in networks

    NASA Astrophysics Data System (ADS)

    Rosvall, M.; Sneppen, K.

    2006-06-01

    We model self-assembly of information in networks to investigate necessary conditions for building a global perception of a system by local communication. Our approach is to let agents chat in a model system to self-organize distant communication pathways. We demonstrate that simple local rules allow agents to build a perception of the system, that is robust to dynamical changes and mistakes. We find that messages are most effectively forwarded in the presence of hubs, while transmission in hub-free networks is more robust against misinformation and failures.

  16. Self-assembled quantum dot-bioconjugates: characterization and use for sensing proteolytic activity

    NASA Astrophysics Data System (ADS)

    Medintz, Igor L.; Pons, Thomas; Sapsford, Kim E.; Dawson, Philip E.; Mattoussi, Hedi

    2008-04-01

    We present a characterization of the metal-affinity driven self-assembly between luminescent CdSe-ZnS core-shell semiconductor quantum dots (QDs) and either peptides or proteins appended with various length terminal polyhistidine tags. We first monitor the kinetics of self-assembly between surface-immobilized QDs and proteins/peptides under flow conditions (immobilized). To accomplish this, the QDs were immobilized onto functionalized substrates and then exposed to dye-labeled peptides/proteins. By using evanescent wave excitation of the substrate, self-assembly was assessed by monitoring the time-dependent changes in the dye fluorescence. This configuration was complemented with experiments using freely diffusing QDs and proteins/peptides (solution-phase) via energy transfer between QDs and dye-labeled proteins/peptides. Cumulatively, these measurements allowed determination of kinetic parameters, including association and dissociation rates (k on and k off) and the binding constant (K d). We find that self-assembly is rapid with an equilibrium constant K d -1 in the low nM. We next demonstrate the importance of understanding this self-assembly by creating QD-peptide bioconjugates which we employ as substrates to monitor the cleavage activity of proteolytic enzymes. This confirms that metal-affinity interactions can provide QD-bioconjugates that are functional and stable.

  17. Imaging fluorescence correlation spectroscopy studies of dye diffusion in self-assembled organic nanotubes.

    PubMed

    Xu, Hao; Nagasaka, Shinobu; Kameta, Naohiro; Masuda, Mitsutoshi; Ito, Takashi; Higgins, Daniel A

    2016-06-22

    The rate and mechanism of diffusion by anionic sulforhodamine B (SRB) dye molecules within organic nanotubes self-assembled from bolaamphiphile surfactants were investigated by imaging fluorescence correlation spectroscopy (imaging-FCS). The inner and outer surfaces of the nanotubes are terminated with amine and glucose groups, respectively; the former allow for pH-dependent manipulation of nanotube surface charge while the latter enhance their biocompatibility. Wide-field fluorescence video microscopy was used to locate and image dye-doped nanotubes dispersed on a glass surface. Imaging-FCS was then used to spatially resolve the SRB transport dynamics. Mobilization of the dye molecules was achieved by immersion of the nanotubes in buffer solution. Experiments were performed in pH 6.4, 7.4 and 8.4 buffers, at ionic strengths ranging from 1.73 mM to 520 mM. The results show that coulombic interactions between cationic ammonium ions on the inner nanotube surface and the anionic SRB molecules play a critical role in governing mass transport of the dye. The apparent dye diffusion coefficient, D, was found to generally increase with increasing ionic strength and with increasing pH. The D values obtained were found to be invariant along the nanotube length. Mass transport of the SRB molecules within the nanotubes is concluded to occur by a desorption-mediated Fickian diffusion mechanism in which dye motion is slowed by its coulombic interactions with the inner surfaces of the nanotubes. The results of these studies afford information essential to the use of organic nanotubes in controlled drug release applications. PMID:27271313

  18. Celebrating Soft Matter's 10th Anniversary: Approaches to program the time domain of self-assemblies.

    PubMed

    Heinen, Laura; Walther, Andreas

    2015-10-28

    Self-regulating reconfigurable soft matter systems are of great interest for creating adaptive and active material properties. Such complex functionalities emerge from non-linear and interactive behavior in space and time as demonstrated by a plethora of dynamic, self-organizing biological structures (e.g., the cytoskeleton). In man-made self-assemblies, patterning of the spatial domain has advanced to creating hierarchical structures via precise molecular programming. However, orchestration of the time domain of self-assemblies is still in its infancy and lacks universal design principles. In this Emerging Area article we outline major strategies for programming the time domain of self-assemblies following the concepts of regulatory reaction networks, energy dissipation and kinetic control. Such concepts operate outside thermodynamic equilibrium and pave the way for temporally patterned, dynamic, and autonomously acting functional materials. PMID:26314799

  19. Polycatenar Ligand Control of the Synthesis and Self-Assembly of Colloidal Nanocrystals.

    PubMed

    Diroll, Benjamin T; Jishkariani, Davit; Cargnello, Matteo; Murray, Christopher B; Donnio, Bertrand

    2016-08-24

    Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior. PMID:27472457

  20. The dynamin middle domain is critical for tetramerization and higher-order self-assembly

    PubMed Central

    Ramachandran, Rajesh; Surka, Mark; Chappie, Joshua S; Fowler, Douglas M; Foss, Ted R; Song, Byeong Doo; Schmid, Sandra L

    2007-01-01

    The large multidomain GTPase dynamin self-assembles around the necks of deeply invaginated coated pits at the plasma membrane and catalyzes vesicle scission by mechanisms that are not yet completely understood. Although a structural role for the ‘middle' domain in dynamin function has been suggested, it has not been experimentally established. Furthermore, it is not clear whether this putative function pertains to dynamin structure in the unassembled state or to its higher-order self-assembly or both. Here, we demonstrate that two mutations in this domain, R361S and R399A, disrupt the tetrameric structure of dynamin in the unassembled state and impair its ability to stably bind to and nucleate higher-order self-assembly on membranes. Consequently, these mutations also impair dynamin's assembly-dependent stimulated GTPase activity. PMID:17170701

  1. The dynamin middle domain is critical for tetramerization and higher-order self-assembly.

    PubMed

    Ramachandran, Rajesh; Surka, Mark; Chappie, Joshua S; Fowler, Douglas M; Foss, Ted R; Song, Byeong Doo; Schmid, Sandra L

    2007-01-24

    The large multidomain GTPase dynamin self-assembles around the necks of deeply invaginated coated pits at the plasma membrane and catalyzes vesicle scission by mechanisms that are not yet completely understood. Although a structural role for the 'middle' domain in dynamin function has been suggested, it has not been experimentally established. Furthermore, it is not clear whether this putative function pertains to dynamin structure in the unassembled state or to its higher-order self-assembly or both. Here, we demonstrate that two mutations in this domain, R361S and R399A, disrupt the tetrameric structure of dynamin in the unassembled state and impair its ability to stably bind to and nucleate higher-order self-assembly on membranes. Consequently, these mutations also impair dynamin's assembly-dependent stimulated GTPase activity. PMID:17170701

  2. Triggered self-assembly of magnetic nanoparticles.

    PubMed

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

    2016-01-01

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

  3. Triggered self-assembly of magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  4. Self-Assembly of Gemini Surfactants

    NASA Astrophysics Data System (ADS)

    Yethiraj, Arun; Mondal, Jagannath; Mahanthappa, Mahesh

    2013-03-01

    The self-assembly behavior of Gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. This gemini architecture, in which two single tailed surfactants are joined through a flexible hydrophobic linker, has been shown to exhibit concentration-dependent aqueous self-assembly into lyotropic phases including hexagonal, gyroid, and lamellar morphologies. Our simulations reproduce the experimentally observed phases at similar amphiphile concentrations in water, including the unusual ability of these surfactants to form gyroid phases over unprecedentedly large amphiphile concentration windows. We demonstrate quanitative agreement between the predicted and experimentally observed domain spacings of these nanostructured materials. Through careful conformation analyses of the surfactant molecules, we show that the gyroid phase is electrostatically stabilized related to the lamellar phase. By starting with a lamellar phase, we show that decreasing the charge on the surfactant headgroups by carboxylate protonation or use of a bulkier tetramethyl ammonium counterion in place of sodium drives the formation of a gyroid phase.

  5. Self-assembled Nanofibrils for Immunomodulation

    NASA Astrophysics Data System (ADS)

    Zhao, Fan

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

  6. Triggered self-assembly of magnetic nanoparticles

    PubMed Central

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

    2016-01-01

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

  7. Transmetalation of self-assembled, supramolecular complexes.

    PubMed

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

    2014-03-21

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

  8. Quantifying quality in DNA self-assembly

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  9. Directed Self-Assembly: Expectations and Achievements

    PubMed Central

    2010-01-01

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

  10. Stochastic lag time in nucleated linear self-assembly.

    PubMed

    Tiwari, Nitin S; van der Schoot, Paul

    2016-06-21

    Protein aggregation is of great importance in biology, e.g., in amyloid fibrillation. The aggregation processes that occur at the cellular scale must be highly stochastic in nature because of the statistical number fluctuations that arise on account of the small system size at the cellular scale. We study the nucleated reversible self-assembly of monomeric building blocks into polymer-like aggregates using the method of kinetic Monte Carlo. Kinetic Monte Carlo, being inherently stochastic, allows us to study the impact of fluctuations on the polymerization reactions. One of the most important characteristic features in this kind of problem is the existence of a lag phase before self-assembly takes off, which is what we focus attention on. We study the associated lag time as a function of system size and kinetic pathway. We find that the leading order stochastic contribution to the lag time before polymerization commences is inversely proportional to the system volume for large-enough system size for all nine reaction pathways tested. Finite-size corrections to this do depend on the kinetic pathway. PMID:27334194

  11. Control of crystal nucleation by patterned self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Aizenberg, Joanna; Black, Andrew J.; Whitesides, George M.

    1999-04-01

    An important requirement in the fabrication of advanced inorganic materials, such as ceramics and semiconductors, is control over crystallization. In principle, the synthetic growth of crystals can be guided by molecular recognition at interfaces. But it remains a practical challenge to control simultaneously the density and pattern of nucleation events, and the sizes and orientations of the growing crystals. Here we report a route to crystal formation, using micropatterned self-assembled monolayers,, which affords control over all these parameters. We begin with a metal substrate patterned with a self-assembled monolayer having areas of different nucleating activity-in this case, an array of acid-terminated regions separated by methyl-terminated regions. By immersing the patterned substrates in a calcium chloride solution and exposing them to carbon dioxide, we achieve ordered crystallization of calcite in the polar regions, where the rate of nucleation is fastest; crystallization can be completely suppressed elsewhere by a suitable choice of array spacing, which ensures that the solution is undersaturated in the methyl-terminated regions. The nucleation density (the number of crystals formed per active site) may be controlled by varying the area and distribution of the polar regions, and we can manipulate the crystallographic orientation by using different functional groups and substrates.

  12. Simulation of self-assembly of polyzwitterions into vesicles

    DOE PAGESBeta

    Mahalik, Jyoti P.; Muthukumar, Murugappan

    2016-08-19

    Using the Langevin dynamics method and a coarse-grained model, we have researched the formation of vesicles by hydrophobic polymers consisting of periodically placed zwitterion side groups in dilute salt-free aqueous solutions. The zwitterions, being permanent charge dipoles, provide long-range electrostatic correlations which are interfered by the conformational entropy of the polymer. Our simulations are geared towards gaining conceptual understanding in these correlated dipolar systems, where theoretical calculations are at present formidable. A competition between hydrophobic interactions and dipole-dipole interactions leads to a series of self-assembled structures. As the spacing d between the successive zwitterion side groups decreases, single chains undergomore » globule → disk → worm-like structures. We have calculated the Flory-Huggins χ parameter for these systems in terms of d and monitored the radius of gyration, hydrodynamic radius, spatial correlations among hydrophobic and dipole monomers, and dipole-dipole orientational correlation functions. During the subsequent stages of self-assembly, these structures lead to larger globules and vesicles as d is decreased up to a threshold value, below which no large scale morphology forms. Finally the vesicles form via a polynucleation mechanism whereby disk-like structures form first, followed by their subsequent merger.« less

  13. Self-assembly of FKE8 peptides using CHARMM

    NASA Astrophysics Data System (ADS)

    Ouazzani, Abdelillah; Kara, Abdelkader; Bhattacharya, Aniket

    2009-03-01

    We investigate the molecular self-assembly of FKE8 peptides (with a sequence FKFEFKFE) using CHARMM. Previous studies^1,2 of the FKE8 peptides have shown helical ribbon structures during the formation of β-sheets. In order to understand this supra-molecular structure,first we investigate the stable configuration of two FKE8 molecules as a function of the orientation of the long axis of the molecules. We find that stable configuration of these two molecules (based on energy minimization) occurs when the long axes of the two molecules are orientated at an angle ˜51.5^0 with respect to each other. This angle may be relevant to understand the pitch of the helical structure. Next we study the self-assembly of several FKE8 molecules starting with an initial configuration where two successive FKE8 molecules are oriented at an angle ˜51.5^0 with respect to each other. ^1 W. Hwang, D. Marini, R. D. Kamm, and S. Zhang, J. Chem. Phys. 118, 389 (2003).^2 S. Vauthey, S. Santoso, H. Gong, N. Watson, and S. Zhang, Proc. Natl. Acad. Sci. U.S.A. 99, 5355 (2002).

  14. Stochastic lag time in nucleated linear self-assembly

    NASA Astrophysics Data System (ADS)

    Tiwari, Nitin S.; van der Schoot, Paul

    2016-06-01

    Protein aggregation is of great importance in biology, e.g., in amyloid fibrillation. The aggregation processes that occur at the cellular scale must be highly stochastic in nature because of the statistical number fluctuations that arise on account of the small system size at the cellular scale. We study the nucleated reversible self-assembly of monomeric building blocks into polymer-like aggregates using the method of kinetic Monte Carlo. Kinetic Monte Carlo, being inherently stochastic, allows us to study the impact of fluctuations on the polymerization reactions. One of the most important characteristic features in this kind of problem is the existence of a lag phase before self-assembly takes off, which is what we focus attention on. We study the associated lag time as a function of system size and kinetic pathway. We find that the leading order stochastic contribution to the lag time before polymerization commences is inversely proportional to the system volume for large-enough system size for all nine reaction pathways tested. Finite-size corrections to this do depend on the kinetic pathway.

  15. Simulation of self-assembly of polyzwitterions into vesicles.

    PubMed

    Mahalik, J P; Muthukumar, M

    2016-08-21

    Using the Langevin dynamics method and a coarse-grained model, we have studied the formation of vesicles by hydrophobic polymers consisting of periodically placed zwitterion side groups in dilute salt-free aqueous solutions. The zwitterions, being permanent charge dipoles, provide long-range electrostatic correlations which are interfered by the conformational entropy of the polymer. Our simulations are geared towards gaining conceptual understanding in these correlated dipolar systems, where theoretical calculations are at present formidable. A competition between hydrophobic interactions and dipole-dipole interactions leads to a series of self-assembled structures. As the spacing d between the successive zwitterion side groups decreases, single chains undergo globule → disk → worm-like structures. We have calculated the Flory-Huggins χ parameter for these systems in terms of d and monitored the radius of gyration, hydrodynamic radius, spatial correlations among hydrophobic and dipole monomers, and dipole-dipole orientational correlation functions. During the subsequent stages of self-assembly, these structures lead to larger globules and vesicles as d is decreased up to a threshold value, below which no large scale morphology forms. The vesicles form via a polynucleation mechanism whereby disk-like structures form first, followed by their subsequent merger. PMID:27544126

  16. Self-assembly mechanism in colloids: perspectives from statistical physics

    NASA Astrophysics Data System (ADS)

    Giacometti, Achille

    2012-06-01

    Motivated by recent experimental findings in chemical synthesis of colloidal particles, we draw an analogy between self-assembly processes occurring in biological systems (e.g. protein folding) and a new exciting possibility in the field of material science. We consider a self-assembly process whose elementary building blocks are decorated patchy colloids of various types, that spontaneously drive the system toward a unique and predetermined targeted macroscopic structure. To this aim, we discuss a simple theoretical model — the Kern-Frenkel model — describing a fluid of colloidal spherical particles with a pre-defined number and distribution of solvophobic and solvophilic regions on their surface. The solvophobic and solvophilic regions are described via a short-range square-well and a hard-sphere potentials, respectively. Integral equation and perturbation theories are presented to discuss structural and thermodynamical properties, with particular emphasis on the computation of the fluid-fluid (or gas-liquid) transition in the temperaturedensity plane. The model allows the description of both one and two attractive caps, as a function of the fraction of covered attractive surface, thus interpolating between a square-well and a hard-sphere fluid, upon changing the coverage. By comparison with Monte Carlo simulations, we assess the pros and the cons of both integral equation and perturbation theories in the present context of patchy colloids, where the computational effort for numerical simulations is rather demanding.

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

    NASA Astrophysics Data System (ADS)

    Saranathan, Vinod Kumar; Prum, Richard O.

    2015-03-01

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

  18. Block Copolymer Directed Self-Assembly Approaches for Doping Planar and Non-Planar Semiconductors

    NASA Astrophysics Data System (ADS)

    Popere, Bhooshan; Russ, Boris; Heitsch, Andrew; Trefonas, Peter; Segalman, Rachel

    As electronic circuits continue to shrink, reliable nanoscale doping of functional devices presents new challenges. While directed self-assembly (DSA) of block copolymers (BCPs) has enabled excellent pitch control for lithography, controlling the 3D dopant distribution remains a fundamental challenge. To this end, we have developed a BCP self-assembly approach to confine dopants to nanoscopic domains within a semiconductor. This relies on the supramolecular encapsulation of the dopants within the core of the block copolymer (PS- b-P4VP) micelles, self-assembly of these micelles on the substrate, followed by rapid thermal diffusion of the dopants into the underlying substrate. We show that the periodic nature of the BCP domains enables precise control over the dosage and spatial position of dopant atoms on the technologically relevant length scales (10-100 nm). Additionally, as the lateral density of 2D circuit elements approaches the Moore's limit, novel 3D architectures have emerged. We have utilized our BCP self-assembly approach towards understanding the self-assembly our micelles directed by such nanoscale non-planar features. We show that the geometric confinement imposed by the hard feature walls directs the assembly of these micelles.

  19. Charge and Sequence Effects on the Self-assembly and Subsequent Hydrogelation of Fmoc-Depsipeptides

    PubMed Central

    Nguyen, Mary M.; Eckes, Kevin M.

    2014-01-01

    Herein we report on the self-assembly of a family of Fmoc-depsipeptides into nanofibers and hydrogels. We show that fiber formation occurs in depsipeptide structures in which the fluorenyl group is closely associated and that side-chain charge and sequence affect the extent of self-assembly and subsequent gelation. Using fluorescence emission spectroscopy and circular dichroism, we show that self-assembly can be monitored and is observed in these slow-gelling systems prior to hydrogel formation. We also demonstrate that the ionic strength of salt-containing solutions affects the time at which self-assembly results in gelation of the bulk solution. From transmission electron microscopy, we report that morphological changes progress over time and are observed as micelles transitioning to fibers prior to the onset of gelation. Gelled depsipeptides degraded at a slower rate than non-gelled samples in the presence of salt, while hydrolysis in water of both gels and solution samples was minimal even after 14 days. Our work shows that while incorporating ester functionality within a peptide backbone reduces the number of hydrogen bonding sites available for forming and stabilizing supramolecular assemblies, the substitution does not prohibit self-assembly and subsequent gelation. PMID:24647784

  20. Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells.

    PubMed

    Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua

    2015-01-01

    Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process. PMID:26643504

  1. Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells

    NASA Astrophysics Data System (ADS)

    Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua

    2015-12-01

    Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process.

  2. Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells

    PubMed Central

    Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua

    2015-01-01

    Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process. PMID:26643504

  3. Rational Design of Chiral Nanostructures from Self-Assembly of a Ferrocene-Modified Dipeptide.

    PubMed

    Wang, Yuefei; Qi, Wei; Huang, Renliang; Yang, Xuejiao; Wang, Mengfan; Su, Rongxin; He, Zhimin

    2015-06-24

    We report a new paradigm for the rational design of chiral nanostructures that is based on the hierarchical self-assembly of a ferrocene (Fc)-modified dipeptide, ferrocene-L-Phe-L-Phe-OH (Fc-FF). Compared to other chiral self-assembling systems, Fc-FF is unique because of its smaller size, biocompatibility, multiple functions (a redox center), and environmental responsiveness. X-ray and spectroscopic analyses showed that the incorporation of counterions during the hierarchical self-assembly of Fc-FF changed the conformations of the secondary structures from flat β sheets into twisted β sheets. This approach enables chiral self-assembly and the formation of well-defined chiral nanostructures composed of helical twisted β sheets. We identified two elementary forms for the helical twist of the β sheets, which allowed us to create a rich variety of rigid chiral nanostructures over a wide range of scales. Furthermore, through subtle modulations in the counterions, temperature, and solvent, we are able to precisely control the helical pitch, diameter, and handedness of the self-assembled chiral nanostructures. This unprecedented level of control not only offers insights into how rationally designed chiral nanostructures can be formed from simple molecular building blocks but also is of significant practical value for the use in chiroptics, templates, chiral sensing, and separations. PMID:26018930

  4. Self-assembly of Open-Shell-containing Block Polymer Thin Films

    NASA Astrophysics Data System (ADS)

    Boudouris, Bryan; Rostro, Lizbeth; Baradwaj, Aditya; Laster, Jennifer

    Radical polymers, where a stable open-shell group is present on each repeat unit of a non-conjugated macromolecular backbone, are emerging as promising materials in organic electronic and magnetic applications. As such, designing molecular motifs that allow for the self-assemble of these open-shell species into nanostructured domains could be beneficial in a host of next-generation flexible electronic applications. In addition, the relatively flexible nature of their macromolecular backbone and ability to conduct charge in the amorphous state offer distinct advantages regarding their self-assembly relative to block polymers based on conjugated semiconducting polymers. Here, we demonstrate the controlled synthesis and self-assembly of diblock copolymers containing radical polymer moieties. In fact, we show that A-B diblock copolymers, where the A moiety contains nitroxide radical functionalities and the B moiety is a closed-shell, low glass transition temperature polymer, self-assemble into ordered structures with domain spacing values that are consistent with common coil-coil diblock copolymers (d = 30 nm). In this way, we present a means by which to readily generate electronically-active macromolecules that self-assemble into nanostructured thin films with controlled morphologies over long ranges.

  5. Electrochemically Directed Self-Assembly and Conjugated Polymer Semiconductors for Organic Electronic Applications

    NASA Astrophysics Data System (ADS)

    Pillai, Rajesh Gopalakrishna

    2011-07-01

    hybrid materials (PPy0DBS-Li+) with immobile dopant anions and mobile cations have been observed and explained on the basis of movement of the cations in an applied electric field. Based on this principle, functioning polymer resistive memory devices have been demonstrated which can be scalable to lower dimensions for nanoelectronics applications. Finally, proof of concept for using a conducting polymer as a top contact in molecular electronic devices created using electrochemically directed self-assembly is demonstrated.

  6. Multiple interfaces in self-assembled breath figures.

    PubMed

    Wan, Ling-Shu; Zhu, Liang-Wei; Ou, Yang; Xu, Zhi-Kang

    2014-04-21

    This feature article describes the multiple interfaces in the breath figure (BF) method toward functional honeycomb films with ordered pores. If a drop of polymer solution in a volatile solvent such as carbon disulphide is placed in a humid environment, evaporative cooling leads to self-assembled arrays of condensed water droplets. After evaporation of the solvent and water, patterned pores can be formed. During this BF process, the interfaces between the solution and the substrate, the solution and water droplets, and the film surface and air play extremely important roles in determining both the structures and functions of the honeycomb films. Progress in the BF method is reviewed by emphasizing the roles of the interfacial interactions. The applications of hierarchical and functional honeycomb films in separation, biocatalysis, biosensing, templating, stimuli-responsive surfaces and adhesive surfaces are also discussed. PMID:24589741

  7. Synergistic self-assembly of RNA and DNA molecules

    NASA Astrophysics Data System (ADS)

    Ko, Seung Hyeon; Su, Min; Zhang, Chuan; Ribbe, Alexander E.; Jiang, Wen; Mao, Chengde

    2010-12-01

    DNA has recently been used as a programmable 'smart' building block for the assembly of a wide range of nanostructures. It remains difficult, however, to construct DNA assemblies that are also functional. Incorporating RNA is a promising strategy to circumvent this issue as RNA is structurally related to DNA but exhibits rich chemical, structural and functional diversities. However, only a few examples of rationally designed RNA structures have been reported. Herein, we describe a simple, general strategy for the de novo design of nanostructures in which the self-assembly of RNA strands is programmed by DNA strands. To demonstrate the versatility of this approach, we have designed and constructed three different RNA-DNA hybrid branched nanomotifs (tiles), which readily assemble into one-dimensional nanofibres, extended two-dimensional arrays and a discrete three-dimensional object. The current strategy could enable the integration of the precise programmability of DNA with the rich functionality of RNA.

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

    PubMed

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

    2016-06-01

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

  9. Lipid-bilayer-assisted two-dimensional self-assembly of DNA origami nanostructures

    NASA Astrophysics Data System (ADS)

    Suzuki, Yuki; Endo, Masayuki; Sugiyama, Hiroshi

    2015-08-01

    Self-assembly is a ubiquitous approach to the design and fabrication of novel supermolecular architectures. Here we report a strategy termed `lipid-bilayer-assisted self-assembly' that is used to assemble DNA origami nanostructures into two-dimensional lattices. DNA origami structures are electrostatically adsorbed onto a mica-supported zwitterionic lipid bilayer in the presence of divalent cations. We demonstrate that the bilayer-adsorbed origami units are mobile on the surface and self-assembled into large micrometre-sized lattices in their lateral dimensions. Using high-speed atomic force microscopy imaging, a variety of dynamic processes involved in the formation of the lattice, such as fusion, reorganization and defect filling, are successfully visualized. The surface modifiability of the assembled lattice is also demonstrated by in situ decoration with streptavidin molecules. Our approach provides a new strategy for preparing versatile scaffolds for nanofabrication and paves the way for organizing functional nanodevices in a micrometer space.

  10. Hydrotropic salt promotes anionic surfactant self-assembly into vesicles and ultralong fibers.

    PubMed

    Lin, Yiyang; Qiao, Yan; Cheng, Xinhao; Yan, Yun; Li, Zhibo; Huang, Jianbin

    2012-03-01

    Molecular self-assembly has become a versatile approach to create complex and functional nanoarchitectures. In this work, the self-assembly behavior of an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a hydrotropic salt (benzylamine hydrochloride, BzCl) in aqueous solution is investigated. Benzylamine hydrochloride is found to facilitate close packing of surfactants in the aggregates, inducing the structural transformation from SDBS micelles into unilamellar vesicles, and multilamellar vesicles. The multilamellar vesicles can transform into macroscale fibers, which are long enough to be visualized by the naked eye. Particularly, these fibers are robust enough to be conveniently separated from the surfactant solution. The combined effect of non-covalent interactions (e.g., hydrophobic effect, electrostatic attractions, and π-π interactions) is supposed to be responsible for the robustness of these self-assembled aggregates, in which π-π interactions provide the directional driving force for one-dimensional fiber formation. PMID:22209412

  11. Enzyme-mediated self-assembly of highly ordered structures from disordered proteins

    NASA Astrophysics Data System (ADS)

    Athamneh, Ahmad I.; Barone, Justin R.

    2009-10-01

    Wheat gluten is an amorphous storage protein. Trypsin hydrolysis of wheat gluten produced glutamine-rich peptides. Some peptides were able to self-assemble into fibrous structures extrinsic to native wheat gluten. The final material was an in situ formed peptide composite of highly ordered nanometer-sized fibrils and micron-sized fibers embedded in an unassembled peptide matrix. Fourier transform infrared spectroscopic and x-ray diffraction data suggested that the new structures resembled that of cross- β fibrils found in some insect silk and implicated in prion diseases. The largest self-assembled fibers were about 10 µm in diameter with right-handed helicity and appeared to be bundles of smaller nanometer-sized fibrils. Results demonstrated the potential for utilizing natural mechanisms of protein self-assembly to design advanced materials that can provide a wide range of structural and chemical functionality.

  12. Supramolecular cooperative self assembling in statistical copolymers - from two-dimensional to three dimensional assemblies

    SciTech Connect

    Stadler, R.; Hellmann, J.; Schirle, M.; Beckmann, J.

    1993-12-31

    Based on on previous work where it was shown that 4-urazoyl benzoic acid groups (U4A), which were statistically attached to polybutadiene, form ordered supramolecular arrays in the polymer matrix. The present work describes the synthesis of a new molecular building block capable for self assembling in the unpolar matrix. 5-urazoylisophthalic acid groups (U35A) attached to 1,4-polybutadiene chains show an endothermic transition, characteristic for supramolecular self assembling. The melting temperature increases for low levels of modification from 130{degrees}C up to 190{degrees}C. The IR-data indicate than the 5-urazoylisophthalic acid groups are 4-functional with respect to supramolecular self-addressing. Based on the detailed knowledge of the structure of the self-assembled domains in 4-urazoyl benzoic acid groups, a model is developed which describes qualitatively the observed material properties.

  13. Emergence of reconfigurable wires and spinners via dynamic self-assembly

    PubMed Central

    Kokot, Gasper; Piet, David; Whitesides, George M.; Aranson, Igor S.; Snezhko, Alexey

    2015-01-01

    Dissipative colloidal materials use energy to generate and maintain structural complexity. The energy injection rate, and properties of the environment are important control parameters that influence the outcome of dynamic self-assembly. Here we demonstrate that dispersions of magnetic microparticles confined at the air-liquid interface, and energized by a uniaxial in-plane alternating magnetic field, self-assemble into a variety of structures that range from pulsating clusters and single-particle-thick wires to dynamic arrays of spinners (self-assembled short chains) rotating in either direction. The spinners emerge via spontaneous breaking of the uniaxial symmetry of the energizing magnetic field. Demonstration of the formation and disaggregation of particle assemblies suggests strategies to form new meso-scale structures with the potential to perform functions such as mixing and sensing. PMID:25810144

  14. Multiscale simulations of nanoribbon structures from chromophore amphiphile self-assemblies

    NASA Astrophysics Data System (ADS)

    Huang, Dongxu; Yao, Zhenwei; Olvera, Monica; Stupp, Samuel

    Finite-width self-assembled one-dimensional nanostructures have many potential applications as electronically or biologically active materials. Understanding the driving forces for supramolecular self-assembly is essential for the molecular design of new highly functional structures. Here we use multi-scale molecular dynamics simulations to study the self-assembly of chromophore amphiphiles into a nanoribbon previously shown to be useful in photocatalysis. We demonstrate that the nanoribbon structure is a result of the competition between electrostatics and the hydrophobic effect. We incorporate a scaling analysis that correlates the electrostatic strength with the finite width of the ribbon. These results with additional numerical calculations show that anisotropy of the short-range intermolecular interactions and long-range electrostatics can be used to control the dimensionality of these systems.

  15. Self-assembly of mixed lipids into bicelles and vesicles: molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Sharma, Hari; Wang, Zilu; Dormidontova, Elena

    Formation of complex supramolecular nanostructures, such as micelles, bicelles, vesicles (liposomes) etc. via self-assembly of simple molecules has provided a new pathway for the design and development of effective drug carriers. Solid nanoparticles or functional biopolymers, such as RNA, DNA, peptides can be encapsulated into these carriers for controlled delivery or selective targeting. We performed coarse grained molecular dynamics simulation using the MARTINI force field to study the self-assembly of a binary surfactant mixture composed of long and short phospholipids, DPPC and DHPC, in the ratio 3:1. We found that at low temperature lipids self-assemble into a bicelle (nanodisc) with the longer lipid mainly forming the interior and short lipid the rim of the bicelle. At higher temperature the nanodisc transforms into a vesicle with homogeneously distributed lipids. The structural changes of these nanodiscs and vesicles imposed by gold nanoparticle encapsulation and pegylation will be addressed.

  16. Emergence of reconfigurable wires and spinners via dynamic self-assembly

    DOE PAGESBeta

    Kokot, Gasper; Piet, David; Whitesides, George M.; Aranson, Igor S.; Snezhko, Alexey

    2015-03-26

    Dissipative colloidal materials use energy to generate and maintain structural complexity. The energy injection rate, and properties of the environment are important control parameters that influence the outcome of dynamic self-assembly. Here we demonstrate that dispersions of magnetic microparticles confined at the air-liquid interface, and energized by a uniaxial in-plane alternating magnetic field, self-assemble into a variety of structures that range from pulsating clusters and single-particle-thick wires to dynamic arrays of spinners (self-assembled short chains) rotating in either direction. The spinners emerge via spontaneous breaking of the uniaxial symmetry of the energizing magnetic field. Demonstration of the formation and disaggregationmore » of particle assemblies suggests strategies to form new meso-scale structures with the potential to perform functions such as mixing and sensing.« less

  17. Emergence of reconfigurable wires and spinners via dynamic self-assembly

    SciTech Connect

    Kokot, Gasper; Piet, David; Whitesides, George M.; Aranson, Igor S.; Snezhko, Alexey

    2015-03-26

    Dissipative colloidal materials use energy to generate and maintain structural complexity. The energy injection rate, and properties of the environment are important control parameters that influence the outcome of dynamic self-assembly. Here we demonstrate that dispersions of magnetic microparticles confined at the air-liquid interface, and energized by a uniaxial in-plane alternating magnetic field, self-assemble into a variety of structures that range from pulsating clusters and single-particle-thick wires to dynamic arrays of spinners (self-assembled short chains) rotating in either direction. The spinners emerge via spontaneous breaking of the uniaxial symmetry of the energizing magnetic field. Demonstration of the formation and disaggregation of particle assemblies suggests strategies to form new meso-scale structures with the potential to perform functions such as mixing and sensing.

  18. Self-assembly and structural relaxation in a model ionomer melt

    NASA Astrophysics Data System (ADS)

    Goswami, Monojoy; Borreguero, Jose M.; Sumpter, Bobby G.

    2015-02-01

    Molecular dynamics simulations are used to understand the self-assembly and structural relaxation in ionomer melts containing less than 10% degree of ionization on the backbone. The self-assembly of charged sites and counterions shows structural ordering and agglomeration with a range of structures that can be achieved by changing the dielectric constant of the medium. The intermediate scattering function shows a decoupling of charge and counterion relaxation at longer length scales for only high dielectric constant and at shorter length scales for all dielectric constants. Overall, the slow structural decay of counterions in the strongly correlated ionomer system closely resembles transport properties of semi-flexible polymers.

  19. Hierarchical self-assembly of colloidal magnetic particles into reconfigurable spherical structures

    NASA Astrophysics Data System (ADS)

    Morphew, Daniel; Chakrabarti, Dwaipayan

    2015-04-01

    Colloidal self-assembly has enormous potential as a bottom-up means of structure fabrication. Here we demonstrate hierarchical self-assembly of rationally designed charge-stabilised colloidal magnetic particles into ground state structures that are topologically equivalent to a snub cube and a snub dodecahedron, the only two chiral Archimedean solids, for size-selected clusters. These spherical structures open up in response to an external magnetic field and demonstrate controllable porosity. Such features are critical to their applications as functional materials.

  20. Photochemical Reactions in Self-Assembled Organic Monolayers Characterized by using Scanning Tunneling Microscopy.

    PubMed

    Guo, Chao; Li, Min; Kang, ShiZhao

    2016-03-16

    Research on the supramolecular self-assembly behavior at interfaces is of great importance to improving the performance of nanodevices that are based on optical functional materials. In this Minireview, several photoinduced isomerization and polymerization reactions in self-assembled organic monolayers on surfaces are discussed. Typical organic molecules contain azobenzene, alkynyl, or olefins groups. The feature surface base is a highly oriented pyrolytic graphite (HOPG) surface or a gold surface. Scanning tunneling microscopy (STM) is used as a strong tool to characterize new species' structures before and after illumination. PMID:26797865

  1. Biological passivation of porous silicon by a self-assembled nanometric biofilm of proteins

    NASA Astrophysics Data System (ADS)

    de Stefano, Luca; Rea, Ilaria; de Tommasi, Eduardo; Giardina, Paola; Armenante, Annunziata; Longobardi, Sara; Giocondo, Michele; Rendina, Ivo

    2009-10-01

    Self-assembled monolayers are surfaces consisting of a single layer of molecules on a substrate: widespread examples of chemical and biological nature are alkylsiloxane, fatty acids, and alkanethiolate which can be deposited by different techniques on a large variety of substrates ranging from metals to oxides. We have found that a self-assembled biofilm of proteins can passivate porous silicon (PSi) based optical structures without affecting the transducing properties. Moreover, the protein coated PSi layer can also be used as a functionalized surface for proteomic applications.

  2. Self-assembled magnetic surface swimmers.

    SciTech Connect

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

    2009-03-20

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

  3. Capillary self-assembly of floating bodies

    NASA Astrophysics Data System (ADS)

    Jung, Sunghwan; Thompson, Paul; Bush, John

    2007-11-01

    We study the self-assembly of bodies supported on the water surface by surface tension. Attractive and repulsive capillary forces exist between menisci of, respectively, the same and opposite signs. In nature, floating objects (e.g. mosquito larvae) thus interact through capillary forces to form coherent packings on the water surface. We here present the results of an experimental investigation of such capillary pattern formation. Thin elliptical metal sheets were designed to have variable shape, flexibility and mass distribution. On the water surface, mono-, bi-, or tri-polar menisci could thus be achieved. The influence of the form of the menisci on the packings arising from the interaction of multiple floaters is explored. Biological applications are discussed.

  4. Self-assembled magnetic surface swimmers.

    PubMed

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

    2009-03-20

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

  5. Pseudotannins self-assembled into antioxidant complexes.

    PubMed

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

    2015-10-21

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

  6. Self-assembling triblock proteins for biofunctional surface modification

    NASA Astrophysics Data System (ADS)

    Fischer, Stephen E.

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

  7. Enzymatically Active Microgels from Self-Assembling Protein Nanofibrils for Microflow Chemistry

    PubMed Central

    2015-01-01

    Amyloid fibrils represent a generic class of protein structure associated with both pathological states and with naturally occurring functional materials. This class of protein nanostructure has recently also emerged as an excellent foundation for sophisticated functional biocompatible materials including scaffolds and carriers for biologically active molecules. Protein-based materials offer the potential advantage that additional functions can be directly incorporated via gene fusion producing a single chimeric polypeptide that will both self-assemble and display the desired activity. To succeed, a chimeric protein system must self-assemble without the need for harsh triggering conditions which would damage the appended functional protein molecule. However, the micrometer to nanoscale patterning and morphological control of protein-based nanomaterials has remained challenging. This study demonstrates a general approach for overcoming these limitations through the microfluidic generation of enzymatically active microgels that are stabilized by amyloid nanofibrils. The use of scaffolds formed from biomaterials that self-assemble under mild conditions enables the formation of catalytic microgels while maintaining the integrity of the encapsulated enzyme. The enzymatically active microgel particles show robust material properties and their porous architecture allows diffusion in and out of reactants and products. In combination with microfluidic droplet trapping approaches, enzymatically active microgels illustrate the potential of self-assembling materials for enzyme immobilization and recycling, and for biological flow-chemistry. These design principles can be adopted to create countless other bioactive amyloid-based materials with diverse functions. PMID:26030507

  8. Ion-specific control of the self-assembly dynamics of a nanostructured protein lattice.

    PubMed

    Rad, Behzad; Haxton, Thomas K; Shon, Albert; Shin, Seong-Ho; Whitelam, Stephen; Ajo-Franklin, Caroline M

    2015-01-27

    Self-assembling proteins offer a potential means of creating nanostructures with complex structure and function. However, using self-assembly to create nanostructures with long-range order whose size is tunable is challenging, because the kinetics and thermodynamics of protein interactions depend sensitively on solution conditions. Here we systematically investigate the impact of varying solution conditions on the self-assembly of SbpA, a surface-layer protein from Lysinibacillus sphaericus that forms two-dimensional nanosheets. Using high-throughput light scattering measurements, we mapped out diagrams that reveal the relative yield of self-assembly of nanosheets over a wide range of concentrations of SbpA and Ca(2+). These diagrams revealed a localized region of optimum yield of nanosheets at intermediate Ca(2+) concentration. Replacement of Mg(2+) or Ba(2+) for Ca(2+) indicates that Ca(2+) acts both as a specific ion that is required to induce self-assembly and as a general divalent cation. In addition, we use competitive titration experiments to find that 5 Ca(2+) bind to SbpA with an affinity of 67.1 ± 0.3 μM. Finally, we show via modeling that nanosheet assembly occurs by growth from a negligibly small critical nucleus. We also chart the dynamics of nanosheet size over a variety of conditions. Our results demonstrate control of the dynamics and size of the self-assembly of a nanostructured lattice, the constituents of which are one of a class of building blocks able to form novel hybrid nanomaterials. PMID:25494454

  9. Ion-Specific Control of the Self-Assembly Dynamics of a Nanostructured Protein Lattice

    PubMed Central

    2015-01-01

    Self-assembling proteins offer a potential means of creating nanostructures with complex structure and function. However, using self-assembly to create nanostructures with long-range order whose size is tunable is challenging, because the kinetics and thermodynamics of protein interactions depend sensitively on solution conditions. Here we systematically investigate the impact of varying solution conditions on the self-assembly of SbpA, a surface-layer protein from Lysinibacillus sphaericus that forms two-dimensional nanosheets. Using high-throughput light scattering measurements, we mapped out diagrams that reveal the relative yield of self-assembly of nanosheets over a wide range of concentrations of SbpA and Ca2+. These diagrams revealed a localized region of optimum yield of nanosheets at intermediate Ca2+ concentration. Replacement of Mg2+ or Ba2+ for Ca2+ indicates that Ca2+ acts both as a specific ion that is required to induce self-assembly and as a general divalent cation. In addition, we use competitive titration experiments to find that 5 Ca2+ bind to SbpA with an affinity of 67.1 ± 0.3 μM. Finally, we show via modeling that nanosheet assembly occurs by growth from a negligibly small critical nucleus. We also chart the dynamics of nanosheet size over a variety of conditions. Our results demonstrate control of the dynamics and size of the self-assembly of a nanostructured lattice, the constituents of which are one of a class of building blocks able to form novel hybrid nanomaterials. PMID:25494454

  10. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    NASA Astrophysics Data System (ADS)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  11. Computational de novo design of a self-assembling peptide with predefined structure.

    PubMed

    Kaltofen, Sabine; Li, Chenge; Huang, Po-Ssu; Serpell, Louise C; Barth, Andreas; André, Ingemar

    2015-01-30

    Protein and peptide self-assembly is a powerful design principle for engineering of new biomolecules. More sophisticated biomaterials could be built if both the structure of the overall assembly and that of the self-assembling building block could be controlled. To approach this problem, we developed a computational design protocol to enable de novo design of self-assembling peptides with predefined structure. The protocol was used to design a peptide building block with a βαβ fold that self-assembles into fibrillar structures. The peptide associates into a double β-sheet structure with tightly packed α-helices decorating the exterior of the fibrils. Using circular dichroism, Fourier transform infrared spectroscopy, electron microscopy and X-ray fiber diffraction, we demonstrate that the peptide adopts the designed conformation. The results demonstrate that computational protein design can be used to engineer protein and peptide assemblies with predefined three-dimensional structures, which can serve as scaffolds for the development of functional biomaterials. Rationally designed proteins and peptides could also be used to investigate the subtle energetic and entropic tradeoffs in natural self-assembly processes and the relation between assembly structure and assembly mechanism. We demonstrate that the de novo designed peptide self-assembles with a mechanism that is more complicated than expected, in a process where small changes in solution conditions can lead to significant differences in assembly properties and conformation. These results highlight that formation of structured protein/peptide assemblies is often dependent on the formation of weak but highly precise intermolecular interactions. PMID:25498388

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

    NASA Astrophysics Data System (ADS)

    Pan, Sheng

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

  13. Self-assembled levan nanoparticles for targeted breast cancer imaging.

    PubMed

    Kim, Sun-Jung; Bae, Pan Kee; Chung, Bong Hyun

    2015-01-01

    We report on the targeted imaging of breast cancer using self-assembled levan nanoparticles. Indocyanine green (ICG) was encapsulated in levan nanoparticles via self-assembly. Levan-ICG nanoparticles were found to be successfully accumulated in breast cancer via specific interaction between fructose moieties in levan and overexpressed glucose transporter 5 in breast cancer cells. PMID:25383444

  14. Mastering Dendrimer Self-Assembly for Efficient siRNA Delivery: From Conceptual Design to In Vivo Efficient Gene Silencing.

    PubMed

    Chen, Chao; Posocco, Paola; Liu, Xiaoxuan; Cheng, Qiang; Laurini, Erik; Zhou, Jiehua; Liu, Cheng; Wang, Yang; Tang, Jingjie; Col, Valentina Dal; Yu, Tianzhu; Giorgio, Suzanne; Fermeglia, Maurizio; Qu, Fanqi; Liang, Zicai; Rossi, John J; Liu, Minghua; Rocchi, Palma; Pricl, Sabrina; Peng, Ling

    2016-07-01

    Self-assembly is a fundamental concept and a powerful approach in molecular science. However, creating functional materials with the desired properties through self-assembly remains challenging. In this work, through a combination of experimental and computational approaches, the self-assembly of small amphiphilic dendrons into nanosized supramolecular dendrimer micelles with a degree of structural definition similar to traditional covalent high-generation dendrimers is reported. It is demonstrated that, with the optimal balance of hydrophobicity and hydrophilicity, one of the self-assembled nanomicellar systems, totally devoid of toxic side effects, is able to deliver small interfering RNA and achieve effective gene silencing both in cells - including the highly refractory human hematopoietic CD34(+) stem cells - and in vivo, thus paving the way for future biomedical implementation. This work presents a case study of the concept of generating functional supramolecular dendrimers via self-assembly. The ability of carefully designed and gauged building blocks to assemble into supramolecular structures opens new perspectives on the design of self-assembling nanosystems for complex and functional applications. PMID:27244195

  15. Adsorption of Amelogenin onto Self-Assembled and Fluoroapatite Surfaces

    SciTech Connect

    Tarasevich, Barbara J.; Lea, Alan S.; Bernt, William; Engelhard, Mark H.; Shaw, Wendy J.

    2009-02-19

    Abstract. The interactions of proteins at surfaces are of great importance to biomineralizaton processes and to the development and function of biomaterials. Amelogenin is a unique biomineralization protein because it self-assembles to form supramolecular structures called “nanospheres,” spherical aggregates of monomers that are 20-60 nm in diameter. Although the nanosphere quaternary structure has been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is also of great interest because the surface structure is critical to its function. We report studies of the adsorption of the amelogenin onto self-assembled monolayers (SAMs) with COOH and CH3 end group functionality and single crystal fluoroapatite (FAP). Dynamic light scattering (DLS) experiments showed that the solutions contained nanospheres and aggregates of nanospheres. Protein adsorption onto the various substrates was evidenced by null ellipsometry, x-ray photoelectron spectroscopy (XPS), and external reflectance Fourier transform infrared spectroscopy (ERFTIR). Although only nanospheres were observed in solution, ellipsometry and atomic force microscopy (AFM) indicated that the protein adsorbates were much smaller structures than the original nanospheres, from monomers to small oligomers in size. Monomer adsorption was promoted onto the CH3 surfaces and small oligomer adsorption was promoted onto the COOH and FAP substrates. In some cases, remnants of the original nanospheres adsorbed as multilayers on top of the underlying subnanosphere layers. This work suggests that amelogenin can adsorb by the “shedding” or disassembling of substructures from the nanospheres onto substrates and indicates that amelogenin may have a range of possible quaternary structures depending on whether it is in solution or interacting with surfaces.

  16. Nanostructured donor-acceptor self assembly with improved photoconductivity.

    PubMed

    Saibal, B; Ashar, A Z; Devi, R Nandini; Narayan, K S; Asha, S K

    2014-11-12

    Nanostructured supramolecular donor-acceptor assemblies were formed when an unsymmetrical N-substituted pyridine functionalized perylenebisimide (UPBI-Py) was complexed with oligo(p-phenylenevinylene) (OPVM-OH) complementarily functionalized with hydroxyl unit and polymerizable methacrylamide unit at the two termini. The resulting supramolecular complex [UPBI-Py (OPVM-OH)]1.0 upon polymerization by irradiation in the presence of photoinitiator formed well-defined supramolecular polymeric nanostructures. Self-assembly studies using fluorescence emission from thin film samples showed that subtle structural changes occurred on the OPV donor moiety following polymerization. The 1:1 supramolecular complex showed red-shifted aggregate emission from both OPV (∼500 nm) and PBI (∼640 nm) units, whereas the OPV aggregate emission was replaced by intense monomeric emission (∼430 nm) upon polymerizing the methacrylamide units on the OPVM-OH. The bulk structure was studied using wide-angle X-ray diffraction (WXRD). Complex formation resulted in distinct changes in the cell parameters of OPVM-OH. In contrast, a physical mixture of 1 mol each of OPVM-OH and UPBI-Py prepared by mixing the powdered solid samples together showed only a combination of reflections from both parent molecules. Thin film morphology of the 1:1 molecular complex as well as the supramolecular polymer complex showed uniform lamellar structures in the domain range <10 nm. The donor-acceptor supramolecular complex [UPBI-Py (OPVM-OH)]1.0 exhibited space charge limited current (SCLC) with a bulk mobility estimate of an order of magnitude higher accompanied by a higher photoconductivity yield compared to the pristine UPBI-Py. This is a very versatile method to obtain spatially defined organization of n and p-type semiconductor materials based on suitably functionalized donor and acceptor molecules resulting in improved photocurrent response using self-assembly. PMID:25283356

  17. Large-scale superlattices from colloidal TiO2 nanorods: A facile self-assembly approach

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Liu, Fa-Min

    2016-03-01

    Self-assembly of nanoparticles into superlattices allows a bottom-up approach for fabricating functional materials. For the first time, the colloidal TiO2 nanorods were self-assembled into nine arrays, three of these arrays were highly ordered superlattices over large areas. The relationship between the packing types and the concentration of TiO2 nanorods and oleic acid has been established. The self-assembly process is primarily driven by the density-driven phase evolution and entropic depletion attraction. This facile self-assembly procedure can be used to design and fabricate various materials into superlattices. Furthermore, these superlattices of TiO2 nanorods can be easily tailored for wide ranging devices.

  18. A self-assembling lanthanide molecular nanoparticle for optical imaging†

    PubMed Central

    Brown, Katherine A.; Yang, Xiaoping; Schipper, Desmond; Hall, Justin W.; DePue, Lauren J.; Gnanam, Annie J.; Arambula, Jonathan F.; Jones, Jessica N.; Swaminathan, Jagannath; Dieye, Yakhya; Vadivelu, Jamuna; Chandler, Don J.; Marcotte, Edward M.; Sessler, Jonathan L.; Ehrlich, Lauren I. R.; Jones, Richard A.

    2015-01-01

    Chromophores that incorporate f-block elements have considerable potential for use in bioimaging applications because of their advantageous photophysical properties compared to organic dye, which are currently widely used. We are developing new classes of lanthanide-based self-assembling molecular nanoparticles as reporters for imaging and as multi-functional nanoprobes or nanosensors for use with biological samples. One class of these materials, which we call lanthanide “nano-drums”, are homogeneous 4d–4f clusters approximately 25 to 30 Å in diameter. These are capable of emitting from the visible to near-infrared wavelengths. Here, we present the synthesis, crystal structure, photophysical properties and comparative cytotoxicity data for a 32 metal Eu-Cd nano-drum [Eu8Cd24L12(OAc)48] (1). We also explored the imaging capabilities of this nano-drum using epifluorescence, TIRF, and two-photon microscopy platforms. PMID:25512085

  19. Directed Self-Assembly of Colloidal Janus Matchsticks

    NASA Astrophysics Data System (ADS)

    Chaudhary, Kundan; Chen, Qian; Juarez, Jaime; Granick, Steve; Lewis, Jennifer

    2013-03-01

    The ability to assemble anisotropic colloidal building blocks into ordered configurations is scientifically and technologically important for developing new classes of soft materials. We are studying the fabrication and electric field driven assembly of end- and side-coated Janus rods. Specifically, we fabricate silica rods (L/D = 2-4) functionalized with hydrophobic gold (Au) patches using a multistep process involving electric field alignment and crystallization, microcontact printing, and selective metallization. In the absence of an applied electric filed, the Janus matchsticks (end-coated rods) self-assemble into multi pods (e.g., bi-, tri- and tetrapods) of varying coordination number and patch angle in aqueous solution. By contrast, both Janus matchsticks and side-coated Janus rods form complex chains in applied AC electric fields of varying magnitude and frequency, whose configurations vary significantly from those formed by pure silica rods.

  20. Protein machines and self assembly in muscle organization

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  1. Piezoelectric resonators based on self-assembled diphenylalanine microtubes

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  2. Self-assembly of nanoscale lateral segregation profiles

    NASA Astrophysics Data System (ADS)

    Stania, R.; Heckel, W.; Kalichava, I.; Bernard, C.; Kerscher, T. C.; Cun, H. Y.; Willmott, P. R.; Schönfeld, B.; Osterwalder, J.; Müller, S.; Greber, T.

    2016-04-01

    The surface segregation profile of an intermetallic compound becomes vertically and laterally modulated upon epitaxial growth of a single-layer hexagonal boron nitride (h -BN) nanomesh. h -BN on PtRh(111) forms an 11-on-10 superhoneycomb, such as that on Rh(111) [Corso et al., Science 303, 217 (2004), 10.1126/science.1091979], though with a smaller lattice constant of 2.73 nm. X-ray photoelectron diffraction shows that the h -BN layer reduces the Pt enrichment of the first layer by promoting site swapping of about 10 Pt-Rh pairs within the 10 ×10 unit cell between the first and second layers. This segregation profile is confirmed by density-functional-theory-based cluster-expansion calculations. Generally, a strong modulation of the h -BN bonding strength and a higher affinity to one of the constituents leads to self-assembly of top layer patches underneath the nanomesh pores.

  3. Electrostatically Tuned Self-Assembly of Branched Amphiphilic Peptides

    DOE PAGESBeta

    Ting, Christina L.; Frischknecht, Amalie L.; Stevens, Mark J.; Spoerke, Erik D.

    2014-06-19

    Electrostatics plays an important role in the self-assembly of amphiphilic peptides. To develop a molecular understanding of the role of the electrostatic interactions, we develop a coarse-grained model peptide and apply self-consistent field theory to investigate the peptide assembly into a variety of aggregate nanostructures. We find that the presence and distribution of charged groups on the hydrophilic branches of the peptide can modify the molecular configuration from extended to collapsed. This change in molecular configuration influences the packing into spherical micelles, cylindrical micelles (nanofibers), or planar bilayers. The effects of charge distribution therefore has important implications for the designmore » and utility of functional materials based on peptides.« less

  4. Electrostatically Tuned Self-Assembly of Branched Amphiphilic Peptides

    SciTech Connect

    Ting, Christina L.; Frischknecht, Amalie L.; Stevens, Mark J.; Spoerke, Erik D.

    2014-06-19

    Electrostatics plays an important role in the self-assembly of amphiphilic peptides. To develop a molecular understanding of the role of the electrostatic interactions, we develop a coarse-grained model peptide and apply self-consistent field theory to investigate the peptide assembly into a variety of aggregate nanostructures. We find that the presence and distribution of charged groups on the hydrophilic branches of the peptide can modify the molecular configuration from extended to collapsed. This change in molecular configuration influences the packing into spherical micelles, cylindrical micelles (nanofibers), or planar bilayers. The effects of charge distribution therefore has important implications for the design and utility of functional materials based on peptides.

  5. A self assembled monolayer based microfluidic sensor for urea detection

    NASA Astrophysics Data System (ADS)

    Srivastava, Saurabh; Solanki, Pratima R.; Kaushik, Ajeet; Ali, Md. Azahar; Srivastava, Anchal; Malhotra, B. D.

    2011-07-01

    Urease (Urs) and glutamate dehydrogenase (GLDH) have been covalently co-immobilized onto a self-assembled monolayer (SAM) comprising of 10-carboxy-1-decanthiol (CDT) via EDC-NHS chemistry deposited onto one of the two patterned gold (Au) electrodes for estimation of urea using poly(dimethylsiloxane) based microfluidic channels (2 cm × 200 μm × 200 μm). The CDT/Au and Urs-GLDH/CDT/Au electrodes have been characterized using Fourier transform infrared (FTIR) spectroscopy, contact angle (CA), atomic force microscopy (AFM) and electrochemical cyclic voltammetry (CV) techniques. The electrochemical response measurement of a Urs-GLDH/CDT/Au bioelectrode obtained as a function of urea concentration using CV yield linearity as 10 to 100 mg dl-1, detection limit as 9 mg dl-1 and high sensitivity as 7.5 μA mM-1 cm-2.

  6. Modelling the self-assembly of virus capsids

    NASA Astrophysics Data System (ADS)

    Johnston, Iain G.; Louis, Ard A.; Doye, Jonathan P. K.

    2010-03-01

    We use computer simulations to study a model, first proposed by Wales (2005 Phil. Trans. R. Soc. A 363 357), for the reversible and monodisperse self-assembly of simple icosahedral virus capsid structures. The success and efficiency of assembly as a function of thermodynamic and geometric factors can be qualitatively related to the potential energy landscape structure of the assembling system. Even though the model is strongly coarse-grained, it exhibits a number of features also observed in experiments, such as sigmoidal assembly dynamics, hysteresis in capsid formation and numerous kinetic traps. We also investigate the effect of macromolecular crowding on the assembly dynamics. Crowding agents generally reduce capsid yields at optimal conditions for non-crowded assembly, but may increase yields for parameter regimes away from the optimum. Finally, we generalize the model to a larger triangulation number T = 3, and observe assembly dynamics more complex than that seen for the original T = 1 model.

  7. Self-Assembly of Amyloid Fibrils That Display Active Enzymes

    PubMed Central

    Zhou, Xiao-Ming; Entwistle, Aiman; Zhang, Hong; Jackson, Antony P; Mason, Thomas O; Shimanovich, Ulyana; Knowles, Tuomas P J; Smith, Andrew T; Sawyer, Elizabeth B; Perrett, Sarah

    2014-01-01

    Enzyme immobilization is an important strategy to enhance the stability and recoverability of enzymes and to facilitate the separation of enzymes from reaction products. However, enzyme purification followed by separate chemical steps to allow immobilization on a solid support reduces the efficiency and yield of the active enzyme. Here we describe polypeptide constructs that self-assemble spontaneously into nanofibrils with fused active enzyme subunits displayed on the amyloid fibril surface. We measured the steady-state kinetic parameters for the appended enzymes in situ within fibrils and compare these with the identical protein constructs in solution. Finally, we demonstrated that the fibrils can be recycled and reused in functional assays both in conventional batch processes and in a continuous-flow microreactor. PMID:25937845

  8. Self-assembled ultrathin nanotubes on diamond (100) surface

    NASA Astrophysics Data System (ADS)

    Lu, Shaohua; Wang, Yanchao; Liu, Hanyu; Miao, Mao-Sheng; Ma, Yanming

    2014-04-01

    Surfaces of semiconductors are crucially important for electronics, especially when the devices are reduced to the nanoscale. However, surface structures are often elusive, impeding greatly the engineering of devices. Here we develop an efficient method that can automatically explore the surface structures using structure swarm intelligence. Its application to a simple diamond (100) surface reveals an unexpected surface reconstruction featuring self-assembled carbon nanotubes arrays. Such a surface is energetically competitive with the known dimer structure under normal conditions, but it becomes more favourable under a small compressive strain or at high temperatures. The intriguing covalent bonding between neighbouring tubes creates a unique feature of carrier kinetics (that is, one dimensionality of hole states, while two dimensionality of electron states) that could lead to novel design of superior electronics. Our findings highlight that the surface plays vital roles in the fabrication of nanodevices by being a functional part of them.

  9. Self-assembled ordered carbon-nanotube arrays and membranes.

    SciTech Connect

    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 growth 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.

  10. Designed self-assembly of molecular necklaces.

    PubMed

    Park, Ki-Min; Kim, Soo-Young; Heo, Jungseok; Whang, Dongmok; Sakamoto, Shigeru; Yamaguchi, Kentaro; Kim, Kimoon

    2002-03-13

    This paper reports an efficient strategy to synthesize molecular necklaces, in which a number of small rings are threaded onto a large ring, utilizing the principles of self-assembly and coordination chemistry. Our strategy involves (1) threading a molecular "bead" with a short "string" to make a pseudorotaxane and then (2) linking the pseudorotaxanes with a metal complex with two cis labile ligands acting as an "angle connector" to form a cyclic product (molecular necklace). A 4- or 3-pyridylmethyl group is attached to each end of 1,4-diaminobutane or 1,5-diaminopentane to produce the short "strings" (C4N4(2+), C4N3(2+), C5N4(2+), and C5N3(2+)), which then react with a cucurbituril (CB) "bead" to form stable pseudorotaxanes (PR44(2+), PR43(2+), PR54(2+), and PR53(2+), respectively). The reaction of the pseudorotaxanes with Pt(en)(NO(3))(2) (en = ethylenediamine) produces a molecular necklace [4]MN, in which three molecular "beads" are threaded on a triangular framework, and/or a molecular necklace [5]MN, in which four molecular "beads" are threaded on a square framework. Under refluxing conditions, the reaction with PR44(2+) or PR54(2+) yields exclusively [4]MN (MN44T or MN54T, respectively), whereas that with PR43(2+) or PR53(2+) produces exclusively [5]MN (MN43S or MN53S, respectively). The products have been characterized by various methods including X-ray crystallography. At lower temperatures, on the other hand, the reaction with PR44(2+) or PR54(2+) affords both [4]MN and [5]MN. The supermolecules reported here are the first series of molecular necklaces obtained as thermodynamic products. The overall structures of the molecular necklaces are strongly influenced by the structures of pseudorotaxane building blocks, which is discussed in detail on the basis of the X-ray crystal structures. The temperature dependence of the product distribution observed in this self-assembly process is also discussed. PMID:11878967

  11. Multifunctional Nanoparticles Self-Assembled from Small Organic Building Blocks for Biomedicine.

    PubMed

    Xing, Pengyao; Zhao, Yanli

    2016-09-01

    Supramolecular self-assembly shows significant potential to construct responsive materials. By tailoring the structural parameters of organic building blocks, nanosystems can be fabricated, whose performance in catalysis, energy storage and conversion, and biomedicine has been explored. Since small organic building blocks are structurally simple, easily modified, and reproducible, they are frequently employed in supramolecular self-assembly and materials science. The dynamic and adaptive nature of self-assembled nanoarchitectures affords an enhanced sensitivity to the changes in environmental conditions, favoring their applications in controllable drug release and bioimaging. Here, recent significant research advancements of small-organic-molecule self-assembled nanoarchitectures toward biomedical applications are highlighted. Functionalized assemblies, mainly including vesicles, nanoparticles, and micelles are categorized according to their topological morphologies and functions. These nanoarchitectures with different topologies possess distinguishing advantages in biological applications, well incarnating the structure-property relationship. By presenting some important discoveries, three domains of these nanoarchitectures in biomedical research are covered, including biosensors, bioimaging, and controlled release/therapy. The strategies regarding how to design and characterize organic assemblies to exhibit biomedical applications are also discussed. Up-to-date research developments in the field are provided and research challenges to be overcome in future studies are revealed. PMID:27273862

  12. Improving Photocatalytic Activity through Electrostatic Self-Assembly: Polyelectrolytes as Tool for Solar Energy Conversion?

    NASA Astrophysics Data System (ADS)

    Groehn, Franziska

    2015-03-01

    With regard to the world's decreasing energy resources, developing strategies to exploit solar energy become more and more important. One approach is to take advantage of photocatalysis. Inspired by natural systems such as assemblies performing photosynthesis, it is highly promising to self-assemble synthetic functional species to form more effective or tailored supramolecular units. In this contribution, a new type of photocatalytically active self-assembled nanostructures in aqueous solution will be presented: supramolecular nano-objects obtained through self-assembly of macroions and multivalent organic or inorganic counterions. Polyelectrolyte-porphyrin nanoscale assemblies exhibit up to 10-fold higher photocatalytic activity than the corresponding porphyrins without polymeric template. Other self-assembled catalysts based on polyelectrolytes can exhibit expressed selectivity in a photocatalytic model reaction or even allow catalytic reactions in solution that are not possible with the building blocks only. Further, current results on combining different functional units at the polyelectrolyte template represent a next step towards more complex supramolecular structures for solar energy conversion.

  13. Self-assembled biomimetic superhydrophobic hierarchical arrays.

    PubMed

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

    2013-09-01

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

  14. Initial condition of stochastic self-assembly

    NASA Astrophysics Data System (ADS)

    Davis, Jason K.; Sindi, Suzanne S.

    2016-02-01

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

  15. Self-assembling holographic biosensors and biocomputers.

    SciTech Connect

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

    2006-05-01

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

  16. Restricted meniscus convective self-assembly.

    PubMed

    Chen, Kai; Stoianov, Stefan V; Bangerter, Justin; Robinson, Hans D

    2010-04-15

    Convective (or evaporation-induced) self-assembly is a standard technique for depositing uniform, poly-crystalline coatings of nanospheres across multiple square centimeters on the timescale of minutes. In this paper, we present a variation of this technique, where the drying meniscus is restricted by a straight-edge located approximately 100 microm above the substrate adjacent to the drying zone. Surprisingly, we find this technique to yield films at roughly twice the growth rate compared to the standard technique. We attribute this to differing rates of diffusion of vapor from the drying crystal in the two cases. We also investigate the crystal growth rate dependence on ambient relative humidity and find, contrary to some previous reports, that the growth rate depends strongly on the humidity. We introduce a model which indicates that while the length of the drying zone may increase with humidity, this alone cannot compensate for the simultaneous reduction in evaporation rate, so a lower humidity must always lead to a higher growth speed. Comparing the model to our experimental results, we find that the length of the drying zone is constant and mostly independent of parameters such as humidity and surface tension. PMID:20132947

  17. Dissipative adaptation in driven self-assembly.

    PubMed

    England, Jeremy L

    2015-11-01

    In a collection of assembling particles that is allowed to reach thermal equilibrium, the energy of a given microscopic arrangement and the probability of observing the system in that arrangement obey a simple exponential relationship known as the Boltzmann distribution. Once the same thermally fluctuating particles are driven away from equilibrium by forces that do work on the system over time, however, it becomes significantly more challenging to relate the likelihood of a given outcome to familiar thermodynamic quantities. Nonetheless, it has long been appreciated that developing a sound and general understanding of the thermodynamics of such non-equilibrium scenarios could ultimately enable us to control and imitate the marvellous successes that living things achieve in driven self-assembly. Here, I suggest that such a theoretical understanding may at last be emerging, and trace its development from historic first steps to more recent discoveries. Focusing on these newer results, I propose that they imply a general thermodynamic mechanism for self-organization via dissipation of absorbed work that may be applicable in a broad class of driven many-body systems. PMID:26530021

  18. Polymer blends for directed self-assembly

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  19. Surfactant mediated polyelectrolyte self-assembly

    SciTech Connect

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

    2015-11-25

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

  20. Surfactant mediated polyelectrolyte self-assembly

    DOE PAGESBeta

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

    2015-11-25

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

  1. Self-Assembled Epitaxical Nanostructure Arrays

    NASA Astrophysics Data System (ADS)

    Madhukar, Anupam

    2003-03-01

    The past decade has witnessed major strides in the realization of nanostructures with 3-dimensionally confined electronic states, dubbed quantum dots (QDs). Most notable classes are the solution grown colloidal nanocrystals, also called nanoparticles (NPs) and the strain-driven semiconductor epitaxical islands formed spontaneously beyond a critical deposition amount during growth of a film with a high lattice mismatch with the substrate. The latter, though spatially randomly positioned, by virtue of their epitaxical nature, are readily integrable in a variety of test and device structures. Consequently these have led the way in providing platforms for examining QD physics and QD based devices such as lasers, detectors, amplifiers, and transistors. The colloidal nanocrystals are in desperate need of being epitaxically integrated onto appropriate substrates and thus providing the platform for realizing more flexible and varied classes of quantum nanostructures for even wider range of applications. Epitaxy and spatially-selective self-assembly are thus two key features of wide classes of nanostructures essential for future advanced information sensing, processing, communication and computing technologies within the largely current paradigms of chip and system architectures. In this talk I will focus on some fundamental issues of epitaxical growth and ordering, structural and chemical template engineering approaches, and their implementation for realization of epitaxical QDs in regular 2D and 3D ultra-dense arrays.

  2. Self-assembly of smallest magnetic particles

    PubMed Central

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

    2015-01-01

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

  3. Dissipative adaptation in driven self-assembly

    NASA Astrophysics Data System (ADS)

    England, Jeremy L.

    2015-11-01

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

  4. Initial condition of stochastic self-assembly.

    PubMed

    Davis, Jason K; Sindi, Suzanne S

    2016-02-01

    The formation of a stable protein aggregate is regarded as the rate limiting step in the establishment of prion diseases. In these systems, once aggregates reach a critical size the growth process accelerates and thus the waiting time until the appearance of the first critically sized aggregate is a key determinant of disease onset. In addition to prion diseases, aggregation and nucleation is a central step of many physical, chemical, and biological process. Previous studies have examined the first-arrival time at a critical nucleus size during homogeneous self-assembly under the assumption that at time t=0 the system was in the all-monomer state. However, in order to compare to in vivo biological experiments where protein constituents inherited by a newly born cell likely contain intermediate aggregates, other possibilities must be considered. We consider one such possibility by conditioning the unique ergodic size distribution on subcritical aggregate sizes; this least-informed distribution is then used as an initial condition. We make the claim that this initial condition carries fewer assumptions than an all-monomer one and verify that it can yield significantly different averaged waiting times relative to the all-monomer condition under various models of assembly. PMID:26986290

  5. Syntheses and self-assembly of novel asparagine-derived amphiphiles: Applications in the encapsulation of proteins, hydrophobic, and hydrophilic drug models

    NASA Astrophysics Data System (ADS)

    Mfuh, Adelphe Mbufung

    supramolecular assemblies of this lipid were examined for the ability to encapsulate and release chemical entity in response to UV-assisted [2+2]-photodimerization. Chapter 6 presents the fabrication of an organic core/inorganic shell microcapsules from the catanionic self-assemblies of a series of symmetrical asparagine-derived bolaamphiphiles and polyallyl amine, followed by surfacing coating with silica nanoparticles. Unlike layer-by-layer or polymer salt aggregates (PSA) capsules reported in the chemical literature, these particles show encapsulation for wider range of chemical entities with different solubility properties. Studies suggest that these particles efficiently encapsulated protoporphyrin IX. dimethylester, doxorubicin and a fluorescently labeled bovine serum albumin (FITC-BSA).

  6. Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles.

    PubMed

    Liu, Hao; Luo, Jiancheng; Shan, Wenpeng; Guo, Dong; Wang, Jing; Hsu, Chih-Hao; Huang, Mingjun; Zhang, Wei; Lotz, Bernard; Zhang, Wen-Bin; Liu, Tianbo; Yue, Kan; Cheng, Stephen Z D

    2016-07-26

    The ability to manipulate self-assembly of molecular building blocks is the key to achieving precise "bottom-up" fabrications of desired nanostructures. Herein, we report a rational design, facile synthesis, and self-assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking α-Keggin-type polyoxometalate (POM) nanoclusters with functionalized polyhedral oligomeric silsesquioxane (POSS) cages. Diverse nanostructures were obtained by tuning secondary interactions among the building blocks and solvents via three factors: solvent polarity, surface functionality of POSS derivatives, and molecular topology. Self-assembled morphologies of KPOM-BPOSS (B denotes isobutyl groups) were found dependent on solvent polarity. In acetonitrile/water mixtures with a high dielectric constant, colloidal nanoparticles with nanophase-separated internal lamellar structures quickly formed, which gradually turned into one-dimensional nanobelt crystals upon aging, while stacked crystalline lamellae were dominantly observed in less polar methanol/chloroform solutions. When the crystallizable BPOSS was replaced with noncrystallizable cyclohexyl-functionalized CPOSS, the resulting KPOM-CPOSS also formed colloidal spheres; however, it failed to further evolve into crystalline nanobelt structures. In less polar solvents, KPOM-CPOSS crystallized into isolated two-dimensional nanosheets, which were composed of two inner crystalline layers of Keggin POM covered by two monolayers of amorphous CPOSS. In contrast, self-assembly of KPOM-2BPOSS was dominated by crystallization of the BPOSS cages, which was hardly sensitive to solvent polarity. The BPOSS cages formed the crystalline inner bilayer, sandwiched by two outer layers of Keggin POM clusters. These results illustrate a rational strategy to purposely fabricate self-assembled nanostructures with diverse dimensionality from MJPs with controlled molecular composition and topology. PMID:27337531

  7. Intrinsic defect formation in peptide self-assembly

    NASA Astrophysics Data System (ADS)

    Deng, Li; Zhao, Yurong; Xu, Hai; Wang, Yanting

    2015-07-01

    In contrast to extensively studied defects in traditional materials, we report here a systematic investigation of the formation mechanism of intrinsic defects in self-assembled peptide nanostructures. The Monte Carlo simulations with our simplified dynamic hierarchical model revealed that the symmetry breaking of layer bending mode at the two ends during morphological transformation is responsible for intrinsic defect formation, whose microscopic origin is the mismatch between layer stacking along the side-chain direction and layer growth along the hydrogen bond direction. Moreover, defect formation does not affect the chirality of the self-assembled structure, which is determined by the initial steps of the peptide self-assembly process.

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

    DOE PAGESBeta

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

    2016-03-07

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

  9. Examples of Molecular Self-Assembly at Surfaces.

    PubMed

    Whitelam, Stephen

    2015-10-14

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

  10. Peptide-directed self-assembly of hydrogels

    PubMed Central

    Kopeček, Jindřich; Yang, Jiyuan

    2009-01-01

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

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

    PubMed Central

    LIN, Yiyang; MAO, Chuanbin

    2011-01-01

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

  12. Simulation and Numerical Modeling of the Self-assembly of an Optoelectronic Peptide

    NASA Astrophysics Data System (ADS)

    Mansbach, Rachael; Ferguson, Andrew

    We report molecular dynamics simulations of the self-assembly of synthetic π-conjugated oligopeptides into optoelectronic nanostructures. The electronic properties provide the basis for an array of organic electronic devices, such as light-emitting diodes, field-effect transistors, and solar cells. Control of the structure, stability, and kinetics of self-assembled organic electronics by tuning monomer chemistry and environmental conditions presents a powerful route to the fabrication of biocompatible ``designer materials.'' We have performed coarse-grained simulations of the self-assembly of several hundred peptides over microsecond time scales to probe the morphology and kinetics of aggregation with molecular-level detail. We have subsequently used this simulation data to parameterize a kinetic aggregation model based on Smoluchowski coagulation theory to enable prediction of aggregation dynamics on millisecond time scales. These numerical models are now being integrated into a multi-physics model of peptide aggregation in a microfluidic flow cell developed by our experimental collaborators to model the self-assembly of diverse peptide architectures under tailored flow-fields for the fabrication of biocompatible assemblies with defined morphology and optoelectronic function.

  13. In situ microscopy of the self-assembly of branched nanocrystals in solution

    DOE PAGESBeta

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

    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

  14. Solvent-induced structural transition of self-assembled dipeptide: from organogels to microcrystals.

    PubMed

    Zhu, Pengli; Yan, Xuehai; Su, Ying; Yang, Yang; Li, Junbai

    2010-03-01

    Organogels that are self-assembled from simple peptide molecules are an interesting class of nano- and mesoscale soft matter with simplicity and functionality. Investigating the precise roles of the organic solvents and their effects on stabilization of the formed organogel is an important topic for the development of low-molecular-weight gelators. We report the structural transition of an organogel self-assembled from a single dipeptide building block, diphenylalanine (L-Phe-L-Phe, FF), in toluene into a flower-like microcrystal merely by introducing ethanol as a co-solvent; this provides deeper insights into the phase transition between mesostable gels and thermodynamically stable microcrystals. Multiple characterization techniques were used to reveal the transitions. The results indicate that there are different molecular-packing modes formed in the gels and in the microcrystals. Further studies show that the co-solvent, ethanol, which has a higher polarity than toluene, might be involved in the formation of hydrogen bonds during molecular self-assembly of the dipeptide in mixed solvents, thus leading to the transition of organogels into microcrystals. The structural transformation modulated by the co-solvent might have a potential implication in controllable molecular self-assembly. PMID:20119986

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

    PubMed Central

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

    2008-01-01

    Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 31 hydroxyl group and the 131 carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by ≈30 cm−1 to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom. PMID:18755898

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

    PubMed

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

    2008-09-01

    Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3(1) hydroxyl group and the 13(1) carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by approximately 30 cm(-1) to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom. PMID:18755898

  17. Modulating the Mechanical Properties of Self-Assembled Peptide Hydrogels via Native Chemical Ligation

    PubMed Central

    Jung, Jangwook P.; Jones, Julia L.; Cronier, Samantha A.; Collier, Joel H.

    2008-01-01

    Hydrogels produced from self-assembling peptides and peptide derivatives are being investigated as synthetic extracellular matrices for defined cell culture substrates and scaffolds for regenerative medicine. In many cases, however, they are less stiff than the tissues and extracellular matrices they are intended to mimic, and they are prone to cohesive failure. We employed native chemical ligation to produce peptide bonds between the termini of fibrillized β-sheet peptides to increase gel stiffness in a chemically specific manner while maintaining the morphology of the self-assembled fibrils. Polymerization, fibril structure, and mechanical properties were measured by SDS-PAGE, mass spectrometry, TEM, circular dichroism, and oscillating rheometry; and cellular responses to matrix stiffening were investigated in cultures of human umbilical vein endothelial cells (HUVECs). Ligation led to a fivefold increase in storage modulus and a significant enhancement of HUVEC proliferation and expression of CD31 on the surface of the gels. The approach was also orthogonal to the inclusion of unprotected RGD-functionalized self-assembling peptides, which further increased proliferation. This strategy broadens the utility of self-assembled peptide materials for applications that require enhancement or modulation of matrix mechanical properties by providing a chemoselective means for doing so without significantly disrupting the gels’ fibrillar structure. PMID:18261790

  18. Low-voltage p- and n-type organic self-assembled monolayer field effect transistors.

    PubMed

    Novak, Michael; Ebel, Alexander; Meyer-Friedrichsen, Timo; Jedaa, Abdesselam; Vieweg, Benito F; Yang, Guang; Voitchovsky, Kislon; Stellacci, Francesco; Spiecker, Erdmann; Hirsch, Andreas; Halik, Marcus

    2011-01-12

    We report on p- and n-type organic self-assembled monolayer field effect transistors. On the base of quaterthiophene and fullerene units, multifunctional molecules were synthesized, which have the ability to self-assemble and provide multifunctional monolayers. The self-assembly approach, based on phosphonic acids, is very robust and allows the fabrication of functional devices even on larger areas. The p- and n-type transistor devices with only one molecular active layer were demonstrated for transistor channel lengths up to 10 μm. The monolayer composition is proven by electrical experiments and by high-resolution transmission electron microscopy, electron energy loss spectroscopy, XPS, and AFM experiments. Because of the molecular design and the contribution of isolating alkyl chains to the hybrid dielectric, our devices operate at low supply voltages (-4 V to +4 V), which is a key requirement for practical use and simplifies the integration in standard applications. The monolayer devices operate in ambient air and show hole and electron mobilities of 10(-5) cm(2)/(V s) and 10(-4) cm(2)/(V s) respectively. In particular the n-type operation of self-assembled monolayer transistors has not been reported before. Hereby, structure-property relations of the SAMs have been studied. Furthermore an approach to protect the sensitive C(60) from immediate degradation within the molecular design is provided. PMID:21133354

  19. Nondeterministic self-assembly of two tile types on a lattice

    NASA Astrophysics Data System (ADS)

    Tesoro, S.; Ahnert, S. E.

    2016-04-01

    Self-assembly is ubiquitous in nature, particularly in biology, where it underlies the formation of protein quaternary structure and protein aggregation. Quaternary structure assembles deterministically and performs a wide range of important functions in the cell, whereas protein aggregation is the hallmark of a number of diseases and represents a nondeterministic self-assembly process. Here we build on previous work on a lattice model of deterministic self-assembly to investigate nondeterministic self-assembly of single lattice tiles and mixtures of two tiles at varying relative concentrations. Despite limiting the simplicity of the model to two interface types, which results in 13 topologically distinct single tiles and 106 topologically distinct sets of two tiles, we observe a wide variety of concentration-dependent behaviors. Several two-tile sets display critical behaviors in the form of a sharp transition from bound to unbound structures as the relative concentration of one tile to another increases. Other sets exhibit gradual monotonic changes in structural density, or nonmonotonic changes, while again others show no concentration dependence at all. We catalog this extensive range of behaviors and present a model that provides a reasonably good estimate of the critical concentrations for a subset of the critical transitions. In addition, we show that the structures resulting from these tile sets are fractal, with one of two different fractal dimensions.

  20. Synthesis and characterization of self-assembling water-soluble polymers

    SciTech Connect

    Hogen-Esch, T.E.; Amis, E.J.

    1992-05-01

    The synthesis is proposed of water-soluble vinyl and other polymers capable of self-assembly through hydrophobic bonding of pendent fluorocarbon and other hydrophobic groups. The self-assembly process will be studied by viscometry and dynamic viscoelasticity, and by static and dynamic light scattering. These investigations are aimed at identifying the structural features of polymers that are important in enhancing the viscosity of aqueous polymer solutions at very low polymer concentrations (< 1,000 ppm). The authors also initiate small angle neutron scattering (SANS) measurements aimed at the determination of the size of the fluorocarbon-containing hydrophobic aggregates. They will be interested in the degree of self assembly as a function of the type and length of the hydrophobic groups and of the type and length of the flexible spacer group linking the hydrophobic to the polymer backbone. The nature of the hydrophilic chain will also be of interest. Thus, they investigate a number of hydrophilic comonomers such as acrylamide, N-vinylpyrrolidone and anionic or cationic vinyl monomers. Surface interactions of these interesting copolymers will be studied by adsorption onto appropriate modified latex spheres. Finally, they propose to explore the synthesis of water-soluble polymers capable of self assembly through interactions of pendent polyanions and polycations.

  1. Epsilon-poly-L-lysine guided improving pulmonary delivery of supramolecular self-assembled insulin nanospheres.

    PubMed

    Shi, Kai; Liu, Yang; Ke, Liyuan; Fang, Yan; Yang, Rui; Cui, Fude

    2015-01-01

    This work presents new spherical nanoparticles that are fabricated from supramolecular self-assembly of therapeutic proteins for inhalation treatment. The formation involved self-assembly of insulin into nanospheres (INS) by a novel thermal induced phase separation method. Surface functional modification of INS with ɛ-poly-L-lysine (EPL), a homopolymerized cationic peptide, was followed to form a core-shell structure (INS@EPL). Both INS and INS@EPL were characterized as spherical particles with mean diameter size of 150-250 nm. The process of transient thermal treatment did not change their biological potency retention significantly. FTIR and CD characterizations indicated that their secondary structures and biological potencies were not changed significantly after self-assembly. The in vivo investigation after pulmonary administration, including lung deposition, alveoli distribution, pharmacological effects and serum pharmacokinetics were investigated. Compared to that of INS, intratracheal administration of INS@EPL offered a pronounced and prolonged lung distribution, as well as pharmacological effects which were indicated by the 23.4% vs 11.7% of relative bioavailability. Accordingly, the work described here demonstrates the possibility of spherical supramolecular self-assembly of therapeutic proteins in nano-scale for pulmonary delivery application. PMID:25450837

  2. Controlling Peptide Self-Assembly through a Native Chemical Ligation/Desulfurization Strategy.

    PubMed

    Rasale, Dnyaneshwar B; Konda, Maruthi; Biswas, Sagar; Das, Apurba K

    2016-03-18

    Self-assembled peptides were synthesized by using a native chemical ligation (NCL)/desulfurization strategy that maintained the chemical diversity of the self-assembled peptides. Herein, we employed oxo-ester-mediated NCL reactions to incorporate cysteine, a cysteine-based dipeptide, and a sterically hindered unnatural amino acid (penicillamine) into peptides. Self-assembly of the peptides resulted in the formation of self-supporting gels. Microscopy analysis indicated the formation of helical nanofibers, which were responsible for the formation of gel matrices. The self-assembly of the ligated peptides was governed by covalent and non-covalent interactions, as confirmed by FTIR, CD, fluorescence spectroscopy, and MS (ESI) analyses. Peptide disassembly was induced by desulfurization reactions with tris(2-carboxyethyl)phosphine (TCEP) and glutathione at 80 °C. Desulfurization reactions of the ligated peptides converted the Cys and penicillamine functionalities into Ala and Val moieties, respectively. The self-supporting gels showed significant shear-thinning and thixotropic properties. PMID:26808117

  3. In situ microscopy of the self-assembly of branched nanocrystals in solution.

    PubMed

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

    2016-01-01

    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. PMID:27040366

  4. 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.

  5. In situ microscopy of the self-assembly of branched nanocrystals in solution

    PubMed Central

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

    2016-01-01

    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. PMID:27040366

  6. Sequential Block Copolymer Self-Assemblies Controlled by Metal-Ligand Stoichiometry.

    PubMed

    Yin, Liyuan; Wu, Hongwei; Zhu, Mingjie; Zou, Qi; Yan, Qiang; Zhu, Liangliang

    2016-06-28

    While numerous efforts have been devoted to developing easy-to-use probes based on block copolymers for detecting analytes due to their advantages in the fields of self-assembly and sensing, a progressive response on block copolymers in response to a continuing chemical event is not readily achievable. Herein, we report the self-assembly of a 4-piperazinyl-1,8-naphthalimide based functional block copolymer (PS-b-PN), whose self-assembly and photophysics can be controlled by the stoichiometry-dependent metal-ligand interaction upon the side chain. The work takes advantages of (1) stoichiometry-controlled coordination-structural transformation of the piperazinyl moiety on PS-b-PN toward Fe(3+) ions, thereby resulting in a shrinkage-expansion conversion of the self-assembled nanostructures in solution as well as in thin film, and (2) stoichiometry-controlled competition between photoinduced electron transfer and spin-orbital coupling process upon naphthalimide fluorophore leading to a boost-decline emission change of the system. Except Fe(3+) ions, such a stoichiometry-dependent returnable property cannot be observed in the presence of other transition ions. The strategy for realizing the dual-channel sequential response on the basis of the progressively alterable nanomorphologies and emissions might provide deeper insights for the further development of advanced polymeric sensors. PMID:27275516

  7. Expanding the solvent chemical space for self-assembly of dipeptide nanostructures.

    PubMed

    Mason, Thomas O; Chirgadze, Dimitri Y; Levin, Aviad; Adler-Abramovich, Lihi; Gazit, Ehud; Knowles, Tuomas P J; Buell, Alexander K

    2014-02-25

    Nanostructures composed of short, noncyclic peptides represent a growing field of research in nanotechnology due to their ease of production, often remarkable material properties, and biocompatibility. Such structures have so far been almost exclusively obtained through self-assembly from aqueous solution, and their morphologies are determined by the interactions between building blocks as well as interactions between building blocks and water. Using the diphenylalanine system, we demonstrate here that, in order to achieve structural and morphological control, a change in the solvent environment represents a simple and convenient alternative strategy to the chemical modification of the building blocks. Diphenylalanine (FF) is a dipeptide capable of self-assembly in aqueous solution into needle-like hollow micro- and nanocrystals with continuous nanoscale channels that possess advantageous properties such as high stiffness and piezoelectricity and have so emerged as attractive candidates for functional nanomaterials. We investigate systematically the solubility of diphenylalanine in a range of organic solvents and probe the role of the solvent in the kinetics of self-assembly and the structures of the final materials. Finally, we report the crystal structure of the FF peptide in microcrystalline form grown from MeOH solution at 1 Å resolution and discuss the structural changes relative to the conventional materials self-assembled in aqueous solution. These findings provide a significant expansion of the structures and morphologies that are accessible through FF self-assembly for existing and future nanotechnological applications of this peptide. Solvent mediation of molecular recognition and self-association processes represents an important route to the design of new supramolecular architectures deriving their functionality from the nanoscale ordering of their components. PMID:24422499

  8. Self assembly: An approach to terascale integration

    SciTech Connect

    Singer, S.

    1993-09-01

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

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

    Mallory, S A; Cacciuto, A

    2016-08-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

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

  13. Modeling the Kinetics of Open Self-Assembly.

    PubMed

    Verdier, Timothée; Foret, Lionel; Castelnovo, Martin

    2016-07-01

    In this work, we explore theoretically the kinetics of molecular self-assembly in the presence of constant monomer flux as an input, and a maximal size. The proposed model is supposed to reproduce the dynamics of viral self-assembly for enveloped virus. It turns out that the kinetics of open self-assembly is rather quantitatively different from the kinetics of similar closed assembly. In particular, our results show that the convergence toward the stationary state is reached through assembly waves. Interestingly, we show that the production of complete clusters is much more efficient in the presence of a constant input flux, rather than providing all monomers at the beginning of the self-assembly. PMID:27295398

  14. Self-assembled monolayers for studying enzyme immobilization and ion recognition

    NASA Astrophysics Data System (ADS)

    Kang, Jie

    This thesis explores the use of self-assembled monolayers on gold for studying enzyme immobilization and ion recognition. Chapter 1 serves as a general introduction to biosensing, self-assembled monolayers, protein immobilization, and surface characterization techniques. Chapter 2 through Chapter 5 describe the immobilization of a redox enzyme, glucose oxidase, to a variety of functional self-assembled monolayers by either noncovalent adsorption or covalent attachment. The characteristics of different immobilization methods are investigated, and the activity of the immobilized enzyme is assessed electrochemically. Chapter 2 presents detailed procedures for measuring glucose oxidase activity by an electrochemical technique---cyclic voltammetry. Chapter 3 describes the adsorption of glucose oxidase to hydrophobic and hydrophilic self-assembled monolayers (SAMs). Significant glucose oxidase adsorption to hydrophobic, methyl-terminated SAMs was observed, while long chain, hydrophilic SAMs terminated by hydroxyl and carboxyl groups resist enzyme adsorption. Chapter 4 examines the covalent attachment of glucose oxidase to N-hydroxysuccinimide ester (NHS ester)-terminated self-assembled monolayers. The reactivity of the surface NHS ester group is found to increase as its coverage is lowered. This observation is explained by the steric effect. Chapter 5 reports the electrostatic adsorption of glucose oxidase to self-assembled monolayers of cystamine. The adsorbed enzyme shows superior activity to enzyme immobilized by other means. The rate constants of surface enzyme catalysis are determined and compared with those of the enzyme in solution. Chapter 6 is concerned with iron (III) recognition by a self-assembled monolayer terminated with a siderophore group, desferrioxamine (H3DFO). We first demonstrate that the iron coverage of the ferrioxamine (FeDFO)-terminated SAM can be successfully assayed by cyclic voltammetry. We then present results for iron (III) binding to the H3

  15. Self-Assembling Hydrogel Scaffolds for Photocatalytic Hydrogen Production

    PubMed Central

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

    2015-01-01

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

  16. Vortical superlattices in a gold nanorods' self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Xie, Yong; Liang, Yujia; Chen, Dongxue; Wu, Xiaochun; Dai, Luru; Liu, Qian

    2014-02-01

    This paper describes the novel vortical self-assembly of CTAB-capped gold nanorods. Representative left-hand, radial, and right-hand vortices are shown. Micelles formed by CTAB molecules enhance the organized self-assembly process. The drag force of solvent flow and dynamic vortex flow in the thin solvent layer are thought to be responsible for the final vortical superlattices. FDTD simulation suggests these structures have potential applications in nanofocusing and polarized light response.

  17. Formation of Ordered Biomolecular Structures by the Self-assembly of Short Peptides

    PubMed Central

    Yuran, Sivan; Reches, Meital

    2013-01-01

    In nature, complex functional structures are formed by the self-assembly of biomolecules under mild conditions. Understanding the forces that control self-assembly and mimicking this process in vitro will bring about major advances in the areas of materials science and nanotechnology. Among the available biological building blocks, peptides have several advantages as they present substantial diversity, their synthesis in large scale is straightforward, and they can easily be modified with biological and chemical entities1,2. Several classes of designed peptides such as cyclic peptides, amphiphile peptides and peptide-conjugates self-assemble into ordered structures in solution. Homoaromatic dipeptides, are a class of short self-assembled peptides that contain all the molecular information needed to form ordered structures such as nanotubes, spheres and fibrils3-8. A large variety of these peptides is commercially available. This paper presents a procedure that leads to the formation of ordered structures by the self-assembly of homoaromatic peptides. The protocol requires only commercial reagents and basic laboratory equipment. In addition, the paper describes some of the methods available for the characterization of peptide-based assemblies. These methods include electron and atomic force microscopy and Fourier-Transform Infrared Spectroscopy (FT-IR). Moreover, the manuscript demonstrates the blending of peptides (coassembly) and the formation of a "beads on a string"-like structure by this process.9 The protocols presented here can be adapted to other classes of peptides or biological building blocks and can potentially lead to the discovery of new peptide-based structures and to better control of their assembly. PMID:24301009

  18. Formation of ordered biomolecular structures by the self-assembly of short peptides.

    PubMed

    Yuran, Sivan; Reches, Meital

    2013-01-01

    In nature, complex functional structures are formed by the self-assembly of biomolecules under mild conditions. Understanding the forces that control self-assembly and mimicking this process in vitro will bring about major advances in the areas of materials science and nanotechnology. Among the available biological building blocks, peptides have several advantages as they present substantial diversity, their synthesis in large scale is straightforward, and they can easily be modified with biological and chemical entities(1,2). Several classes of designed peptides such as cyclic peptides, amphiphile peptides and peptide-conjugates self-assemble into ordered structures in solution. Homoaromatic dipeptides, are a class of short self-assembled peptides that contain all the molecular information needed to form ordered structures such as nanotubes, spheres and fibrils(3-8). A large variety of these peptides is commercially available. This paper presents a procedure that leads to the formation of ordered structures by the self-assembly of homoaromatic peptides. The protocol requires only commercial reagents and basic laboratory equipment. In addition, the paper describes some of the methods available for the characterization of peptide-based assemblies. These methods include electron and atomic force microscopy and Fourier-Transform Infrared Spectroscopy (FT-IR). Moreover, the manuscript demonstrates the blending of peptides (coassembly) and the formation of a "beads on a string"-like structure by this process.(9) The protocols presented here can be adapted to other classes of peptides or biological building blocks and can potentially lead to the discovery of new peptide-based structures and to better control of their assembly. PMID:24301009

  19. Design strategies for self-assembly of discrete targets

    SciTech Connect

    Madge, Jim; Miller, Mark A.

    2015-07-28

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

  20. Synthetic Self-Assembled Materials in Biological Environments.

    PubMed

    Versluis, Frank; van Esch, Jan H; Eelkema, Rienk

    2016-06-01

    Synthetic self-assembly has long been recognized as an excellent approach for the formation of ordered structures on the nanoscale. Although the development of synthetic self-assembling materials has often been inspired by principles observed in nature (e.g., the assembly of lipids, DNA, proteins), until recently the self-assembly of synthetic molecules has mainly been investigated ex vivo. The past few years however, have witnessed the emergence of a research field in which synthetic, self-assembling systems are used that are capable of operating as bioactive materials in biological environments. Here, this up-and-coming field, which has the potential of becoming a key area in chemical biology and medicine, is reviewed. Two main categories of applications of self-assembly in biological environments are identified and discussed, namely therapeutic and imaging agents. Within these categories key concepts, such as triggers and molecular constraints for in vitro/in vivo self-assembly and the mode of interaction between the assemblies and the biological materials will be discussed. PMID:27042774

  1. Design strategies for self-assembly of discrete targets

    NASA Astrophysics Data System (ADS)

    Madge, Jim; Miller, Mark A.

    2015-07-01

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

  2. Effect of polymerization on hierarchical self-assembly into nanosheets.

    PubMed

    Ikeda, Taichi

    2015-01-20

    The oligomers consisting of phenyl-capped bithiophene and tetra(ethylene glycol)s linked by azide-alkyne Huisgen cycloaddition were synthesized. The relationship between the degree of polymerization and self-assembling ability was investigated in o-dichlorobenzene and dimethyl sulfoxide. From the absorption spectrum, it was confirmed that the critical degree of polymerization (CDP) for thiophene unit aggregation was 4. The morphology of the aggregated product was observed by atomic force microscopy. The oligomers 4mer and 5mer could not self-assemble into well-defined structures due to the weak driving force for the self-assembly. In the cases of 6mer and 7mer, aggregates with nonwell-defined and nanosheet structures coexisted. In the cases of 8mer and 9mer, the nanosheet was the main product. The critical point between 7mer and 8mer could be confirmed by different aggregation behaviors in the cooling process of the solution (nonsigmoidal and sigmoidal). In the cases of 8mer and 9mer, polymer folding prior to intermolecular self-assembly, which was supported by sigmoidal aggregation behavior, leads to the nanosheet formation. On the contrary, shorter oligomers than 8mer experience intermolecular aggregation prior to intramolecular polymer folding, which was supported by the nonsigmoidal aggregation behavior. This is the first report to prove the existence of CDP for folded polymer nanosheet formation which requires hierarchical self-assembly, i.e., polymer folding followed by intermolecular self-assembly. PMID:25526560

  3. Self-Assembling Peptide Amphiphiles for Targeted Drug Delivery

    NASA Astrophysics Data System (ADS)

    Moyer, Tyson

    The systemic delivery of therapeutics is currently limited by off-target side effects and poor drug uptake into the cells that need to be treated. One way to circumvent these issues is to target the delivery and release of therapeutics to the desired location while limiting systemic toxicity. Using self-assembling peptide amphiphiles (PAs), this work has investigated supramolecular nanostructures for the development of targeted therapies. Specifically, the research has focused on the interrelationships between presentation of targeting moeities and the control of nanostructure morphology in the context of systemic delivery for targeting cancer and vascular injuries. The self-assembly region of the PA was systematically altered to achieve control of nanostructure widths, from 100 nm to 10 nm, by the addition of valine-glutamic acid dimers into the chemical structure, subsequently increasing the degree of nanostructure twist. For the targeting of tumors, a homing PA was synthesized to include a dimeric, cyclic peptide sequence known to target the cancer-specific, death receptor 5 (DR5) and initiate apoptosis through the oligomerization of DR5. This PA presented a multivalent display of DR5-binding peptides, resulting in improved binding affinity measured by surface plasmon resonance. The DR5-targeting PA also showed enhanced efficacy in both in vitro and in vivo tumor models relative to non-targeted controls. Alternative modifications to the PA-based antitumor therapies included the use of a cytotoxic, membrane-lytic PA coassembled with a pegylated PA, which showed enhanced biodistribution and in vivo activity after coassembly. The functionalization of the hydrophobic core was also accomplished through the encapsulation of the chemotherapy camptothecin, which was shown to be an effective treatment in vivo. Additionally, a targeted PA nanostructure was designed to bind to the site of vascular intervention by targeting collagen IV. Following balloon angioplasty

  4. Self-assembly and interactions of biomimetic thin films

    NASA Astrophysics Data System (ADS)

    Handa, Hitesh

    Bilayer lipid membranes create the natural environment for the immobilization of functional proteins and have been used as a model for understanding structure and properties of cell membranes. The development of biomimetic surfaces requires in depth knowledge of surface science, self-assembly, immobilization techniques, nanofabrication, biomolecular interactions and analytical techniques. This research is focused on synthesizing and characterizing biomimetic artificial surfaces for fundamental studies in membrane structure and better understanding of specific and non-specific interactions. The other main focus is on surface engineering of self-assembled, nanostructured interfaces that mimic cell membranes. These structures provide a powerful bottom-up approach to the studies of the structure and functionality of cell membranes and their interactions with other molecules. One of the advantages of this approach is that the complexity of the system can be controlled and gradually increased to add functionalities. This dissertation provides a first single molecule force measurement of the specific interactions between Salmonella typhimurium and P22 bacteriophage. This dissertation also provides a novel model system for the confined crystallization of drug molecules such as aspirin using the concept of phospholipid bilayer assembly at surfaces. The results will impact the development of biosensors and drug delivery. The defense will focus on the preparation and bio-recognition interactions between a monolayer of bacteriophage P22, covalently bound to glass substrates through a bifunctional cross linker 3-aminopropyltrimethoxysilane, and the outer membrane of Salmonella, lipopolysaccharides (LPS). The LPS bilayer was deposited on poly (ethylenimine)-modified mica from their sonicated unilamellar vesicle solution. The specific binding of Salmonella typhimurium to the phage monolayer was studied by enzyme-linked immunosorbent assay (ELISA) and atomic force microscopy (AFM

  5. A multi-stimuli responive, self-assembling, boronic acid dipeptide

    DOE PAGESBeta

    Jones, Brad Howard; Martinez, Alina Marissa; Wheeler, Jill S.; McKenzie, Bonnie B.; Miller, Lance Lee; Wheeler, David R.; Spoerke, Erik David

    2015-08-11

    Modification of the dipeptide of phenylalanine, FF, with a boronic acid (BA) functionality imparts unique aqueous self-assembly behavior that responds to multiple stimuli. Changes in pH and ionic strength are used to trigger hydrogelation via the formation of nanoribbon networks. Thus, we show for the first time that the binding of polyols to the BA functionality can modulate a peptide between its assembled and disassembled states.

  6. Molecular self-assembly for biological investigations and nanoscale lithography

    NASA Astrophysics Data System (ADS)

    Cheunkar, Sarawut

    Small, diffusible molecules when recognized by their binding partners, such as proteins and antibodies, trigger enzymatic activity, cell communication, and immune response. Progress in analytical methods enabling detection, characterization, and visualization of biological dynamics at the molecular level will advance our exploration of complex biological systems. In this dissertation, analytical platforms were fabricated to capture membrane-associated receptors, which are essential proteins in cell signaling pathways. The neurotransmitter serotonin and its biological precursor were immobilized on gold substrates coated with self-assembled monolayers (SAMs) of oligo(ethylene glycol)alkanethiols and their reactive derivatives. The SAM-coated substrates present the biologically selective affinity of immobilized molecules to target native membrane-associated receptors. These substrates were also tested for biospecificity using antibodies. In addition, small-molecule-functionalized platforms, expressing neurotransmitter pharmacophores, were employed to examine kinetic interactions between G-protein-coupled receptors and their associated neurotransmitters. The binding interactions were monitored using a quartz crystal microbalance equipped with liquid-flow injection. The interaction kinetics of G-protein-coupled serotonin 1A receptor and 5-hydroxytyptophan-functionalized surfaces were studied in a real-time, label-free environment. Key binding parameters, such as equilibrium dissociation constants, binding rate constants, and dissociative half-life, were extracted. These parameters are critical for understanding and comparing biomolecular interactions in modern biomedical research. By integrating self-assembly, surface functionalization, and nanofabrication, small-molecule microarrays were created for high-throughput screening. A hybrid soft-lithography, called microcontact insertion printing, was used to pattern small molecules at the dilute scales necessary for highly

  7. Structures Self-Assembled Through Directional Solidification

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2005-01-01

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

  8. Polymerization and electrochemical blocking of self-assembled alkylthiol monolayers

    SciTech Connect

    Peanasky, J.S.; Willicut, R.J.; Caston, S.L.

    1996-10-01

    Numerous advantages exist for the use of electroactive alkylthiol self-assembled monolayer modified gold electrodes over other monolayer/substrate systems for use as sensors or biosensors. Among these advantages are a wide electrical potential window, large variety of functionality, extensive order within the monolayer, and a vast amount of literature presently describing this system. One weakness is the facile gold-thiolate bond that results in desorption or displacement of the immobilized species from the surface. This is especially true when the {open_quotes}devices{close_quotes} are exposed to organic solutions. This study discusses the usefulness of photopolymerizing unsaturated functionalities located at internal or external positions on the alkyl chain to enhance immobilization of the electroactive species. Discussion focuses on electrochemical blocking by the monolayer before and after polymerization as determined using cyclic voltammetry. Structural changes within the monolayer, as determined by Fourier transform infrared spectroscopy, are related to changes seen electrochemically. Other parameters such as the type of unsaturated functionality, the alkyl chain length, and the exposure of the devices to oxygen are discussed.

  9. Simple Peptide-Tuned Self-Assembly of Photosensitizers towards Anticancer Photodynamic Therapy.

    PubMed

    Liu, Kai; Xing, Ruirui; Zou, Qianli; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-02-24

    Peptide-tuned self-assembly of functional components offers a strategy towards improved properties and unique functions of materials, but the requirement of many different functions and a lack of understanding of complex structures present a high barrier for applications. Herein, we report a photosensitive drug delivery system for photodynamic therapy (PDT) by a simple dipeptide- or amphiphilic amino-acid-tuned self-assembly of photosensitizers (PSs). The assembled nanodrugs exhibit multiple favorable therapeutic features, including tunable size, high loading efficiency, and on-demand drug release responding to pH, surfactant, and enzyme stimuli, as well as preferable cellular uptake and biodistribution. These features result in greatly enhanced PDT efficacy in vitro and in vivo, leading to almost complete tumor eradication in mice receiving a single drug dose and a single exposure to light. PMID:26804551

  10. A path to designing self-assembling surface patterns on particles for self-assembly of the particles themselves

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    Patchy colloids are promising candidates for self-assembly of metamaterials since directional attraction and high specificity reduces the ambiguity of the low energy state, this simplifies the design of self-assembling building blocks. However, the large scale fabrication of colloids with specific patterns becomes more difficult as the complexity of the surface pattern increases. Self-organiziation of the surface patterns themselves have been suggested as a promising fabrication method due to the new types of patterns it makes accessible. We present a method for designing self-assembling patterns in multiple components system on particle surfaces. The method is based on an analytical treatment of an effective interaction representation of real systems. As an example, we use a simplified model of Alkalethoils-on-gold to show how a limited amount of system parameters can be tuned in order to cause self-assembly of desired surface patterns. We perform in silico self-assembly of surface patterns on spherical colloids, the patterns then causes the colloids themselves to self-assemble into various geometric target structures like strings, membranes, cubic aggregates and lattices. OL and MNJ acknowledge support from the SuMo Biomaterials center of excellence.

  11. Design of nanostructured materials from block copolymer self-assembly

    NASA Astrophysics Data System (ADS)

    Leolukman, Melvina

    We present two classes of nanostructured materials by combining the self assembly of block copolymer (BCP) with suitable small molecule chemistry, which are applicable to organic electro-optics (EO) and as etch-resistant masks for nanofabrication. The underlying principles of designing the specific interactions between BCP host and guest molecules, driving the self-assembly in bulk and thin film, and dictating domain orientation are concepts common to both of these areas. Nanostructured EO materials were created by selectively encapsulating EO chromophores by hydrogen-bonding to the pyridine groups of a linear-diblock copolymer (linear-diBCP) namely polystyrene-block-poly(4-vinyl pyridine) [PS-b-P4VP], or a linear-dendritic-BCP. With the linear-diBCP host, we discovered that poled order in confined domains depends on domain shape, chromophore concentration within the domain, and thermal history. The linear-dendritic-BCP is an excellent host as it efficiently disperses the chromophores into small domains (5-10nm), and keeps the chromophores apart within the domains due to the dendritic architecture. These morphological effects translated into excellent film processability, increased chromophore loading, and two-fold enhancements in the EO coefficient (r 33) when compared to a corresponding homopolymer system. A new class of organic-inorganic nanostructured materials based on polyhedral oligomeric silsesquioxane (POSS) was synthesized as a passive template for pattern transfer. We developed a living anionic polymerization route for methacrylate-functionalized POSS and synthesized two kinds of BCPs, namely PS-b-PMAPOSS and PMMA-b-PMAPOSS. The anionic route allows high degree of polymerization, narrow polydispersity, and tunable POSS block length. These lead to well defined spherical, cylindrical, and lamellar morphologies, as well as formation of hierarchical structures upon thermal annealing. Both POSS-containing BCPs were assembled in thin film and converted to hard

  12. Anandamide and analogous endocannabinoids: a lipid self-assembly study

    SciTech Connect

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Mulet, Xavier; Drummond, Calum J.

    2014-09-24

    Anandamide, the endogenous agonist of the cannabinoid receptors, has been widely studied for its interesting biological and medicinal properties and is recognized as a highly significant lipid signaling molecule within the nervous system. Few studies have, however, examined the effect of the physical conformation of anandamide on its function. The study presented herein has focused on characterizing the self-assembly behaviour of anandamide and four other endocannabinoid analogues of anandamide, viz., 2-arachidonyl glycerol, arachidonyl dopamine, 2-arachidonyl glycerol ether (noladin ether), and o-arachidonyl ethanolamide (virodhamine). Molecular modeling of the five endocannabinoid lipids indicates that the highly unsaturated arachidonyl chain has a preference for a U or J shaped conformation. Thermal phase studies of the neat amphiphiles showed that a glass transition was observed for all of the endocannabinoids at {approx} -110 C with the exception of anandamide, with a second glass transition occurring for 2-arachidonyl glycerol, 2-arachidonyl glycerol ether, and virodhamine (-86 C, -95 C, -46 C respectively). Both anandamide and arachidonyl dopamine displayed a crystal-isotropic melting point (-4.8 and -20.4 C respectively), while a liquid crystal-isotropic melting transition was seen for 2-arachidonyl glycerol (-40.7 C) and 2-arachidonyl glycerol ether (-71.2 C). No additional transitions were observed for virodhamine. Small angle X-ray scattering and cross polarized optical microscopy studies as a function of temperature indicated that in the presence of excess water, both 2-arachidonyl glycerol and anandamide form co-existing Q{sub II}{sup G} (gyroid) and Q{sub II}{sup D} (diamond) bicontinuous cubic phases from 0 C to 20 C, which are kinetically stable over a period of weeks but may not represent true thermodynamic equilibrium. Similarly, 2-arachidonyl glycerol ether acquired an inverse hexagonal (HII) phase in excess water from 0 C to 40 C, while

  13. Photocatalytic nanolithography of self-assembled monolayers and proteins.

    PubMed

    Ul-Haq, Ehtsham; Patole, Samson; Moxey, Mark; Amstad, Esther; Vasilev, Cvetelin; Hunter, C Neil; Leggett, Graham J; Spencer, Nicholas D; Williams, Nicholas H

    2013-09-24

    Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium-cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni(2+), enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope. PMID:23971891

  14. Self-assembled hierarchically structured organic-inorganic composite systems.

    PubMed

    Tritschler, Ulrich; Cölfen, Helmut

    2016-01-01

    Designing bio-inspired, multifunctional organic-inorganic composite materials is one of the most popular current research objectives. Due to the high complexity of biocomposite structures found in nacre and bone, for example, a one-pot scalable and versatile synthesis approach addressing structural key features of biominerals and affording bio-inspired, multifunctional organic-inorganic composites with advanced physical properties is highly challenging. This article reviews recent progress in synthesizing organic-inorganic composite materials via various self-assembly techniques and in this context highlights a recently developed bio-inspired synthesis concept for the fabrication of hierarchically structured, organic-inorganic composite materials. This one-step self-organization concept based on simultaneous liquid crystal formation of anisotropic inorganic nanoparticles and a functional liquid crystalline polymer turned out to be simple, fast, scalable and versatile, leading to various (multi-)functional composite materials, which exhibit hierarchical structuring over several length scales. Consequently, this synthesis approach is relevant for further progress and scientific breakthrough in the research field of bio-inspired and biomimetic materials. PMID:27175790

  15. Photocatalytic Nanolithography of Self-Assembled Monolayers and Proteins

    PubMed Central

    2013-01-01

    Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium–cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni2+, enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope. PMID:23971891

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

    PubMed

    Sherman, Zachary M; Swan, James W

    2016-05-24

    Crystals self-assembled from nanoparticles have useful properties such as optical activity and sensing capability. During fabrication, however, gelation and glassification often leave these materials arrested in defective or disordered metastable states. This is a key difficulty preventing adoption of self-assembled nanoparticle materials at scale. Processes which suppress kinetic arrest and defect formation while accelerating growth of ordered materials are essential for bottom-up approaches to creating nanomaterials. Dynamic, directed self-assembly processes in which the interactions between self-assembling components are actuated temporally offer one promising methodology for accelerating and controlling bottom-up growth of nanostructures. In this article, we show through simulation and theory how time-dependent, periodically toggled interparticle attractions can avoid kinetic barriers and yield well-ordered crystalline domains for a dispersion of nanoparticles interacting via a short-ranged, isotropic potential. The growth mechanism and terminal structure of the dispersion are controlled by parameters of the toggling protocol. This control allows for selection of processes that yield rapid self-assembled, low defect crystals. Although self-assembly via periodically toggled attractions is inherently unsteady and out-of-equilibrium, its outcome is predicted by a first-principles theory of nonequilibrium thermodynamics. The theory necessitates equality of the time average of pressure and chemical potential in coexisting phases of the dispersion. These quantities are evaluated using well known equations of state. The phase behavior predicted by this theory agrees well with measurements made in Brownian dynamics simulations of sedimentation equilibrium and homogeneous nucleation. The theory can easily be extended to model dynamic self-assembly directed by other toggled conservative force fields. PMID:27096705

  17. Fibrin self-assembly is adapted to oxidation.

    PubMed

    Rosenfeld, Mark A; Bychkova, Anna V; Shchegolikhin, Alexander N; Leonova, Vera B; Kostanova, Elizaveta A; Biryukova, Marina I; Sultimova, Natalia B; Konstantinova, Marina L

    2016-06-01

    Fibrinogen is extremely susceptible to attack by reactive oxygen species (ROS). Having been suffered an oxidative modification, the fibrinogen molecules, now with altered spatial structure and function of fibrin network, affect hemostasis differently. However, the potential effects of the oxidative stress on the early stages of the fibrin self-assembly process remain unexplored. To clarify the damaging influence of ROS on the knob 'A': hole 'a' and the D:D interactions, the both are operating on the early stages of the fibrin polymerization, we have used a novel approach based on exploration of FXIIIa-mediated self-assembly of the cross-linked fibrin oligomers dissolved in the moderately concentrated urea solutions. The oligomers were composed of monomeric desA fibrin molecules created by cleaving the fibrinopeptides A off the fibrinogen molecules with a thrombin-like enzyme, reptilase. According to the UV-absorbance and fluorescence measurements data, the employed low ozone/fibrinogen ratios have induced only a slight fibrinogen oxidative modification that was accompanied by modest chemical transformations of the aromatic amino acid residues of the protein. Else, a slight consumption of the accessible tyrosine residues has been observed due to intermolecular dityrosine cross-links formation. The set of experimental data gathered with the aid of electrophoresis, elastic light scattering and analytical centrifugation has clearly witnessed that the oxidation can serve as an effective promoter for the observed enhanced self-assembly of the covalently cross-linked oligomers. At urea concentration of 1.20M, the pristine and oxidized fibrin oligomers were found to comprise a heterogeneous set of the double-stranded protofibrils that are cross-linked only by γ-γ dimers and the fibers consisting on average of four strands that are additionally linked by α polymers. The amounts of the oxidized protofibrils and the fibers accumulated in the system were higher than those

  18. Crops: a green approach toward self-assembled soft materials.

    PubMed

    Vemula, Praveen Kumar; John, George

    2008-06-01

    . Importantly, an enzyme triggered drug-delivery model for hydrophobic drugs was demonstrated by using these supramolecularly assembled hydrogels. Following a similar biocatalytic approach, vitamin C amphiphiles were synthesized with different hydrocarbon chain lengths, and their ability to self-assemble into molecular gels and liquid crystals has been studied in detail. Such biobased soft materials were successfully used to develop novel organic-inorganic hybrid materials by in situ synthesis of metal nanoparticles. The self-assembled soft materials were characterized by several spectroscopic techniques, UV-visible, infrared, and fluorescence spectrophotometers, as well as microscopic methods including polarized optical, confocal, scanning, and transmission electron microscopes, and thermal analysis. The molecular packing of the hierarchically assembled bilayer membranes was fully elucidated by X-ray analysis. We envision that the results summarized in this Account will encourage interdisciplinary collaboration between scientists in the fields of organic synthesis, soft materials research, and green chemistry to develop functional materials from underutilized crop-based renewable feedstock, with innovation driven both by material needs and environmentally benign design principles. PMID:18507403

  19. Nanoparticles of adaptive supramolecular networks self-assembled from nucleotides and lanthanide ions.

    PubMed

    Nishiyabu, Ryuhei; Hashimoto, Nozomi; Cho, Ten; Watanabe, Kazuto; Yasunaga, Takefumi; Endo, Ayataka; Kaneko, Kenji; Niidome, Takuro; Murata, Masaharu; Adachi, Chihaya; Katayama, Yoshiki; Hashizume, Makoto; Kimizuka, Nobuo

    2009-02-18

    Amorphous nanoparticles of supramolecular coordination polymer networks are spontaneously self-assembled from nucleotides and lanthanide ions in water. They show intrinsic functions such as energy transfer from nucleobase to lanthanide ions and excellent performance as contrast enhancing agents for magnetic resonance imaging (MRI). Furthermore, adaptive inclusion properties are observed in the self-assembly process: functional materials such as fluorescent dyes, metal nanoparticles, and proteins are facilely encapsulated. Dyes in these nanoparticles fluoresce in high quantum yields with a single exponential decay, indicating that guest molecules are monomerically wrapped in the network. Gold nanoparticles and ferritin were also wrapped by the supramolecular shells. In addition, these nucleotide/lanthanide nanoparticles also serve as scaffolds for immobilizing enzymes. The adaptive nature of present supramolecular nanoparticles provides a versatile platform that can be utilized in a variety of applications ranging from material to biomedical sciences. As examples, biocompatibility and liver-directing characteristics in in vivo tissue localization experiments are demonstrated. PMID:19166341

  20. Cyclodextrin-covered organic nanotubes derived from self-assembly of dendrons and their supramolecular transformation

    PubMed Central

    Park, Chiyoung; Lee, Im Hae; Lee, Sanghwa; Song, Yumi; Rhue, Mikyo; Kim, Chulhee

    2006-01-01

    The dendritic building blocks with a focal pyrene unit self-organize into vesicles in aqueous phase. The in situ inclusion of the focal pyrene units into the cavity of β- or γ-cyclodextrin (CD) induces self-assembled organic nanotubes with an average outer diameter of ≈45 nm and inner diameter of 22 nm. The surface of the nanotube is covered with CD. Therefore, the functional group on the surface of the nanotube is controlled simply by modifying the functionality of CD. The removal of CD from the nanotube with poly(propylene glycol) reversibly generates vesicles. This work provides an efficient methodology not only to create an additional class of CD-covered organic nanotubes but also to exhibit reversible transformation of nanotubes and vesicles triggered by the motifs of dendron self-assembly, CD inclusion, and pseudorotaxane formation. PMID:16423900