Hierarchically structured microfibers of "single stack" perylene bisimide and quaterthiophene nanowires.

Organic nanowires and microfibers are excellent model systems for charge transport in organic semiconductors under nanoscopic confinement and may be relevant for future nanoelectronic devices. For this purpose, however, the preparation of well-ordered organic nanowires with uniform lateral dimensions remains a challenge to achieve. Here, we used the self-assembly of oligopeptide-substituted perylene bisimides and quaterthiophenes to obtain well-ordered nanofibrils.

Structure and enzymatic properties of molecular dendronized polymer-enzyme conjugates and their entrapment inside giant vesicles.

Macromolecular hybrid structures were prepared in which two types of enzymes, horseradish peroxidase (HRP) and bovine erythrocytes Cu,Zn-superoxide dismutase (SOD), were linked to a fluorescently labeled, polycationic, dendronized polymer (denpol). Two homologous denpols of first and second generation were used and compared, and the activities of HRP and SOD of the conjugates were measured in aqueous solution separately and in combination. In the latter case the efficiency of the two enzymes in catalyzing a two-step cascade reaction was evaluated.

Reversible aggregation of DNA-decorated gold nanoparticles controlled by molecular recognition.

The programmable assembly of functional nanomaterials has been extensively addressed; however, their selective reversible assembly in response to an external stimulus has been more difficult to realize. The specificity and programmable interactions of DNA have been exploited for the rational self-assembly of DNA-conjugated nanoparticles, and here we demonstrate the sequence-controlled disaggregation of DNA-modified gold nanoparticles simply by employing two complementary oligonucleotides. Target oligonucleotides with perfectly matching sequence enabled dissociation of aggregated nanoparticles, whereas oligonucleotides differing by one nucleotide did not cause disassembly of the aggregated nanoparticles.

Five-fold symmetric penta-substituted corannulene with gelation properties and a liquid-crystalline phase.

Five-fold symmetric substituted corannulene derivatives that display liquid-crystalline behavior and organogelation properties were prepared by coupling of N-azidoethyl long-chain fatty acid amides to sym-pentabutynyl corannulenes via dipolar cycloaddition chemistry.

Towards lysozyme nanotube and 3D hybrid self-assembly.

We report lysozyme self-assembly into nanotubes, under the effect of hydrolysis at pH 2 and 90 °C. We resolve the final steps of the fibrillation pathway, entailing the closure of multi-stranded helical ribbons into nanotubes, and we provide evidence of β-sheet arrangement within the nanotubes, demonstrating amyloid-like aggregation. Addition of chloroauric acid to the self-assembled structures can lead to generation of either gold single crystal nanoplatelets or gold nanoparticles (when a reducing agent is added) decorating the nanotube and ribbon surfaces.

Magnetic-responsive hybrids of Fe3O4 nanoparticles with β-lactoglobulin amyloid fibrils and nanoclusters.

We report on the synthesis and magnetic-responsive behavior of hybrids formed by dispersing negatively charged iron oxide (Fe3O4) magnetic nanoparticles in positively charged β-lactoglobulin protein solutions at acidic pH, followed by heating at high temperatures. Depending on the pH used, different hybrid aggregates can be obtained, such as nanoparticle-modified amyloid fibrils (pH 3) and spherical nanoclusters (pH 4.5).

The interplay between carbon nanomaterials and amyloid fibrils in bio-nanotechnology.

Recent advances in bio-nanotechnology have not only rapidly broadened the applications and scope of hybrid nanomaterials in biological fields, but also greatly enriched the examples of ordered materials based on supramolecular self-assembly. Among eminent examples of functional nanostructured materials of undisputed impact in nanotechnology and biological environments, carbon nanomaterials (such as fullerenes, carbon nanotubes and graphene) and amyloid fibrils have attracted great attention because of their unique architectures and exceptional physical properties. Nonetheless, combination of these two classes of nanomaterials into functional hybrids is far from trivial.

Non-equilibrium nature of two-dimensional isotropic and nematic coexistence in amyloid fibrils at liquid interfaces.

Two-dimensional alignment of shape-anisotropic colloids is ubiquitous in nature, ranging from interfacial virus assembly to amyloid plaque formation. The principles governing two-dimensional self-assembly have therefore long been studied, both theoretically and experimentally, leading, however, to diverging fundamental interpretations on the nature of the two-dimensional isotropic-nematic phase transition. Here we employ single-molecule atomic force microscopy, cryogenic scanning electron microscopy and passive probe particle tracking to study the adsorption and liquid crystalline ordering of semiflexible β-lactoglobulin fibrils at liquid interfaces.

Hybrid nanocomposites of gold single-crystal platelets and amyloid fibrils with tunable fluorescence, conductivity, and sensing properties.

Gold single-crystal platelets with high aspect ratio are combined with amyloid fibrils to design a new class of hybrid nanocomposites. The films gather physical properties from both constituents, for example, plasmon resonance, fluorescence, and water-dependent conductivities ranging from insulating to metallic levels, yet mirroring gold within a broad range of composition, and can serve multiple purposes such as sensors, diagnostic, printed electronics, micromechanical, and biological devices.

Growth and alignment of thin film organic single crystals from dewetting patterns.

Studying and understanding the conditions under which organic semiconductors can be engineered to form aligned single crystals in thin films is of primary importance owing to their unique orientation-dependent optoelectronic properties. Efforts to reach this goal by self-assembly from solution-processed films have been rewarded only with limited success. In this article we present a new method to grow single crystalline thin films via solvent annealing.

Nanotopographic surfaces with defined surface chemistries from amyloid fibril networks can control cell attachment.

We show for the first time the possibility of using networks of amyloid fibrils, adsorbed to solid supports and with plasma polymer coatings, for the fabrication of chemically homogeneous surfaces with well-defined nanoscale surface features reminiscent of the topography of the extracellular matrix. The robust nature of the fibrils allows them to withstand the plasma polymer deposition conditions used with no obvious deleterious effect, thus enabling the underlying fibril topography to be replicated at the polymer surface. This effect was seen despite the polymer coating thickness being an order of magnitude greater than the fibril network.

Perforated bicontinuous cubic phases with pH-responsive topological channel interconnectivity.

Lipidic lyotropic liquid crystals are at the frontline of current research for release of target therapeutic molecules due to their unique structural complexity and the possibility of engineering stimuli-triggered release of both hydrophilic and hydrophobic molecules. One of the most suitable lipidic mesophases for the encapsulation and delivery of drugs is the reversed double diamond bicontinuous cubic phase, in which two distinct and parallel networks of ∼4 nm water channels percolate independently through the lipid bilayers, following a Pn3m space group symmetry. In the unperturbed Pn3m structure, the two sets of channels act as autonomous and non-communicating 3D transport pathways.

Strain-induced macroscopic magnetic anisotropy from smectic liquid-crystalline elastomer-maghemite nanoparticle hybrid nanocomposites.

We combine tensile strength analysis and X-ray scattering experiments to establish a detailed understanding of the microstructural coupling between liquid-crystalline elastomer (LCE) networks and embedded magnetic core-shell ellipsoidal nanoparticles (NPs). We study the structural and magnetic re-organization at different deformations and NP loadings, and the associated shape and magnetic memory features. In the quantitative analysis of a stretching process, the effect of the incorporated NPs on the smectic LCE is found to be prominent during the reorientation of the smectic domains and the softening of the nanocomposite.

The self-assembly, aggregation and phase transitions of food protein systems in one, two and three dimensions.

The aggregation of proteins is of fundamental relevance in a number of daily phenomena, as important and diverse as blood coagulation, medical diseases, or cooking an egg in the kitchen. Colloidal food systems, in particular, are examples that have great significance for protein aggregation, not only for their importance and implications, which touches on everyday life, but also because they allow the limits of the colloidal science analogy to be tested in a much broader window of conditions, such as pH, ionic strength, concentration and temperature. Thus, studying the aggregation and self-assembly of proteins in foods challenges our understanding of these complex systems from both the molecular and statistical physics perspectives.

Novel mechanistic insight into the molecular basis of amyloid polymorphism and secondary nucleation during amyloid formation.

The formation of amyloid β (Aβ) fibrils is crucial in initiating the cascade of pathological events that culminates in Alzheimer's disease. In this study, we investigated the mechanism of Aβ fibril formation from hydrodynamically well defined species under controlled aggregation conditions. We present a detailed mechanistic model that furnishes a novel insight into the process of Aβ42 fibril formation and the molecular basis for the different structural transitions in the amyloid pathway.

Liquid-crystalline elastomer-nanoparticle hybrids with reversible switch of magnetic memory.

A stimuli-responsive material is synthesized that combines the actuation potential of liquid-crystalline elastomers with the anisotropic magnetic properties of ellipsoidal iron oxide nanoparticles. The resulting nanocomposite exhibits unique shape-memory features with magnetic information, which can be reversibly stored and erased via parameters typical of soft materials, such as high deformations, low stresses, and liquid-crystalline smectic-isotropic transition temperatures.

Controlling anisotropic drug diffusion in lipid-Fe3O4 nanoparticle hybrid mesophases by magnetic alignment.

We present a new strategy to control the anisotropic diffusion of hydrophilic drugs in lyotropic liquid crystals via the dispersion of magnetic nanoparticles in the mesophase, followed by reorientation of the mesophase domains via an external magnetic field. We select a lipid reverse hexagonal phase doped with magnetic iron oxide nanoparticles and glucose and caffeine as model hybrid mesophase and hydrophilic drugs, respectively. Upon cooling through the disorder-order phase transition of the hexagonal phase and under exposure to an external moderate magnetic field (1.

Polymorphism in bovine serum albumin fibrils: morphology and statistical analysis.

We investigate the self-assembly process of the globular protein bovine serum albumin (BSA) into fibrillar structures upon incubating the protein solution at high temperature (90 degreeC) and in an acidic environment (pH 2) for several days. The investigation is performed by atomic force microscopy (AFM) on the self-assembled fibrillar structures, adsorbed on mica substrates from a solution at different fibrillation time snapshots. A rigorous study of structural morphology reveals a sophisticated hierarchy of the BSA fibrils, where two major classes can be identified: flexible and rigid fibrils, with an order of magnitude of difference in their stiffness.

Thermally sensitive block copolymer particles prepared via aerosol flow reactor method: Morphological characterization and behavior in water.

This work describes properties of thermo-sensitive submicron sized particles having the same chemical composition but different morphologies. These particles have been prepared with an aerosol technique using dimethylformamide solutions of linear polystyrene-block-poly(N-isopropylacrylamide-block-polystyrene, PS-b-PNIPAM-b-PS. The particles were characterized by cryo-electron microscopy, microcalorimetry, and light scattering.

Tunable carbon nanotube/protein core-shell nanoparticles with NIR- and enzymatic-responsive cytotoxicity.

A unique procedure is developed to capture carbon nanotubes into closed virus-like protein cages with a controllable shell. The cross-linked shell varies in thickness within ≈10(0) -10(2) nm, and can be entirely removed by enzyme degradation. The cytotoxicity is entirely suppressed, but can be promoted again by enzymes and near-infrared light.

Diffusion, molecular separation, and drug delivery from lipid mesophases with tunable water channels.

Lyotropic liquid crystals characterized by a bicontinuous cubic phase (BCP) have a structure characterized by interpenetrated water channels following triply periodic minimal surfaces, which can be stable in excess water conditions and thus suitable in a multitude of applications. The control of the water channels size in these systems has a direct impact on their use for drug delivery, crystallization, and membrane separation processes. In this work we carry out systematic diffusion studies to show how the control on the water channel dimensions directly correlates with the release and separation performance of bicontinuous cubic phases.

Self-assembly of ovalbumin into amyloid and non-amyloid fibrils.

We study the fibrillation pathway of ovalbumin protein and report the simultaneous formation of several types of fibrils, with clear structural and physical differences. We compare the fibrillation mechanisms at low pH with and without salt, and follow the kinetics of fibrils growth by atomic force microscopy (AFM), static and dynamic light scattering (SLS, DLS), and small-angle X-ray scattering (SAXS). We show that, among the morphologies identified, long semiflexible amyloid fibrils (type I), with persistence length Lp∼3 μm, Young's modulus E∼2.

Gelation, phase behavior, and dynamics of β-lactoglobulin amyloid fibrils at varying concentrations and ionic strengths.

We have investigated the thermodynamic and dynamic behavior of multistranded β-lactoglobulin protein fibrils in water, by combining static, dynamic, and depolarized dynamic light scattering (SLS, DLS, DDLS), small angle neutron scattering (SANS), rheology, and cryogenic transmission electron microscopy (cryo-TEM). We focus on the region of the phase diagram at which ionic strength and concentration changes induce transitions in gelation and lyotropic liquid crystalline behavior. An increase in ionic strength, induced by NaCl salt, progressively causes the phase transitions from nematic (N) to gel (G) phases; a further increase causes the transition to a translucent phase and to a macroscopic phase separation, respectively.

Simultaneous control of pH and ionic strength during interfacial rheology of β-lactoglobulin fibrils adsorbed at liquid/liquid Interfaces.

Proteins can aggregate as amyloid fibrils under denaturing and destabilizing conditions such as low pH (2) and high temperature (90 °C). Fibrils of β-lactoglobulin are surface active and form adsorption layers at fluid-fluid interfaces. In this study, β-lactoglobulin fibrils were adsorbed at the oil-water interface at pH 2.

Functionalization of multiwalled carbon nanotubes and their pH-responsive hydrogels with amyloid fibrils.

New biocompatible, pH-responsive, and fully fibrous hydrogels have been prepared based on amyloid fibrils hybridized and gelled by functionalized multiwalled carbon nanotubes (MWNTs) far below the gelling concentration of amyloid fibrils. Sulfonic functional groups were introduced on the surfaces of MWNTs either by a covalent diazonium reaction or by physical π-π interactions. The presence of the isoelectric point of amyloid fibrils allows a reversible gelling behavior through ionic interactions with functionalized MWNTs.