Soft Matter Science Research Articles

Template mediated protein self-assembly as a valuable tool in regenerative therapy

The assembly of natural proteinaceous biopolymers into macro-scale architectures is of great importance in synthetic biology, soft-material science and regenerative therapy. The self-assembly of protein tends to be limited due to anisotropic interactions among protein molecules, poor solubility and stability. Here, we introduce a unique platform to self-immobilize diverse proteins (fibrous and globular, positively and negatively charged, low and high molecular weight) using silicon surfaces with pendant –NH2 groups via a facile one step diffusion limited aggregation (DLA) method. All the experimental proteins (type I collagen, bovine serum albumin and cytochrome C) self-assemble into seaweed-like branched dendritic architectures via classical DLA in the absence of any electrolytes. The notable differences in branching architectures are due to dissimilarities in protein colloidal sub-units, which is typical for each protein type, along with the heterogeneous distribution of surface –NH2 groups. Fractal analysis of assembled structures is used to explain the underlying route of fractal deposition; which concludes how proteins with different functionality can yield similar assembly. Further, the nano-micro-structured surfaces can be used to provide functional topographical cues to study cellular responses, as demonstrated using rat bone marrow stem cells. The results indicate that the immobilization of proteins via DLA does not affect functionality, instead serving as topographical cues to guide cell morphology. This indicates a promising design strategy at the tissue-material interface and is anticipated to guide future surface modifications. A cost-effective standard templating strategy is therefore proposed for fundamental and applied particle aggregation studies, which can be used at multiple length scales for biomaterial design and surface reformation.

Crowding, Entropic Forces, and Confinement: Crucial Factors for Structures and Functions in the Cell Nucleus.

The view of the cell nucleus as a crowded system of colloid particles and that chromosomes are giant self-avoiding polymers is stimulating rapid advances in our understanding of its structure and activities, thanks to concepts and experimental methods from colloid, polymer, soft matter, and nano sciences and to increased computational power for simulating macromolecules and polymers. This review summarizes current understanding of some characteristics of the molecular environment in the nucleus, of how intranuclear compartments are formed, and of how the genome is highly but precisely compacted, and underlines the crucial, subtle, and sometimes unintuitive effects on structures and reactions of entropic forces caused by the high concentration of macromolecules in the nucleus.

Microemulsions, Micelles, and Functional Gels: How Colloids and Soft Matter Preserve Works of Art.

Colloid science provides fundamental knowledge to fields such as the pharmaceutical, detergency, paint, and food industry. An exciting application is art conservation, which poses a challenge owing to the complex range of interfacial interactions involved in restoring artefacts. Currently, the majority of the most performing and environmentally safe cleaning and consolidation agents for artworks belong to soft matter and colloids. The development and application of increasingly complex systems, from microemulsions to semi-interpenetrating hydrogels containing such fluids, is presented. These systems have been used on diverse artefacts, from Renaissance frescos to works by Picasso and Pollock. Chemical design can be implemented to meet the requirements of curators, and knowledge of the colloid structure and dynamics can overcome serendipitous approaches of traditional conservation practice. Future perspectives for soft matter and colloid science in the field of cultural heritage preservation are also summarized.

Reversible modulation of the redox activity in conducting polymer nanofilms induced by hydrophobic collapse of a surface-grafted polyelectrolyte

We present the covalent modification of a Pani-like conducting polymer (polyaminobenzylamine, PABA) by grafting of a polyelectrolyte brush (poly [2-(methacryloyloxy)-ethyl-trimethylammonium chloride], PMETAC). As PABA has extra pendant amino moieties, the grafting procedure does not affect the backbone nitrogen atoms that are implicated in the electronic structure of the conducting polymers. Moreover, perchlorate anions interact very strongly with the quaternary ammonium pendant groups of PMETAC through ion pairing. Therefore, the grafting does not only keep the electroactivity of PABA in aqueous solutions but it adds the ion-actuation properties of the PMETAC brush to the modified electrode as demonstrated by contact angle measurements and electrochemical methods. In this way, the conjugation of the electron transfer properties of the conducting polymer with the anion responsiveness of the integrated brush renders perchlorate actuation of the electrochemical response. These results constitute a rational integration of nanometer-sized polymer building blocks that yields synergism of functionalities and illustrate the potentialities of nanoarchitectonics for pushing the limits of soft material science into the nanoworld.

Structuring of Fluid Adlayers upon Ongoing Unimolecular Adsorption.

Fluids with spatial density variations of single or mixed molecules play a key role in biophysics, soft matter, and materials science. The fluid structures usually form via spinodal decomposition or nucleation following an instantaneous destabilization of the initially disordered fluid. However, in practice, an instantaneous quench is often not viable, and the rate of destabilization may be gradual rather than instantaneous. In this work we show that the commonly used phenomenological descriptions of fluid structuring are inadequate under these conditions. We come to that conclusion in the context of surface catalysis, where we employ kinetic MonteCarlo simulations to describe the unimolecular adsorption of gaseous molecules onto a metal surface. The adsorbates diffuse at the surface and, as a consequence of lateral interactions and due to an ongoing increase of the surface coverage, phase separate into coexisting low- and high-density regions. The typical size of these regions turns out to depend much more strongly on the rate of adsorption than predicted from recently reported phenomenological models. We discuss how this finding contributes to the fundamental understanding of the crossover from liquid-liquid to liquid-solid demixing of solution-cast polymer blends.

Introduction to soft matter and neutron scattering

As an opening lecture to the French-Swedish neutron scattering school held in Uppsala (6th to 9th of December 2016), the basic concepts of both soft matter science and neutron scattering are introduced. Typical soft matter systems like self-assembled surfactants in water, microemulsions, (co-)polymers, and colloids are presented. It will be shown that widely different systems have a common underlying physics dominated by the thermal energy, with astonishing consequences on their statistical thermodynamics, and ultimately rheological properties – namely softness. In the second part, the fundamentals of neutron scattering techniques and in particular small-angle neutron scattering as a powerful method to characterize soft matter systems will be outlined.

Special topic on soft matter science and technology

Special topic on soft matter science and technology

Frequency-dependent hydrodynamic interaction between two solid spheres

Hydrodynamic interactions play an important role in many areas of soft matter science. In simulations with implicit solvent, various techniques such as Brownian or Stokesian dynamics explicitly include hydrodynamic interactions a posteriori by using hydrodynamic diffusion tensors derived from the Stokes equation. However, this equation assumes the interaction to be instantaneous which is an idealized approximation and only valid on long time scales. In the present paper, we go one step further and analyze the time-dependence of hydrodynamic interactions between finite-sized particles in a compressible fluid on the basis of the linearized Navier-Stokes equation. The theoretical results show that at high frequencies, the compressibility of the fluid has a significant impact on the frequency-dependent pair interactions. The predictions of hydrodynamic theory are compared to molecular dynamics simulations of two nanocolloids in a Lennard-Jones fluid. For this system, we reconstruct memory functions by extending the inverse Volterra technique. The simulation data agree very well with the theory, therefore, the theory can be used to implement dynamically consistent hydrodynamic interactions in the increasingly popular field of non-Markovian modeling.

Tunable two-dimensional assembly of colloidal particles in rotating electric fields

Tunable interparticle interactions in colloidal suspensions are of great interest because of their fundamental and practical significance. In this paper we present a new experimental setup for self-assembly of colloidal particles in two-dimensional systems, where the interactions are controlled by external rotating electric fields. The maximal magnitude of the field in a suspension is 25 V/mm, the field homogeneity is better than 1% over the horizontal distance of 250 μm, and the rotation frequency is in the range of 40 Hz to 30 kHz. Based on numerical electrostatic calculations for the developed setup with eight planar electrodes, we found optimal experimental conditions and performed demonstration experiments with a suspension of 2.12 μm silica particles in water. Thanks to its technological flexibility, the setup is well suited for particle-resolved studies of fundamental generic phenomena occurring in classical liquids and solids, and therefore it should be of interest for a broad community of soft matter, photonics, and material science.

In vivo analysis of the Escherichia coli ultrastructure by small-angle scattering.

The flagellated Gram-negative bacterium Escherichia coli is one of the most studied microorganisms. Despite extensive studies as a model prokaryotic cell, the ultrastructure of the cell envelope at the nanometre scale has not been fully elucidated. Here, a detailed structural analysis of the bacterium using a combination of small-angle X-ray and neutron scattering (SAXS and SANS, respectively) and ultra-SAXS (USAXS) methods is presented. A multiscale structural model has been derived by incorporating well established concepts in soft-matter science such as a core-shell colloid for the cell body, a multilayer membrane for the cell wall and self-avoiding polymer chains for the flagella. The structure of the cell envelope was resolved by constraining the model by five different contrasts from SAXS, and SANS at three contrast match points and full contrast. This allowed the determination of the membrane electron-density profile and the inter-membrane distances on a quantitative scale. The combination of USAXS and SAXS covers size scales from micrometres down to nanometres, enabling the structural elucidation of cells from the overall geometry down to organelles, thereby providing a powerful method for a non-invasive investigation of the ultrastructure. This approach may be applied for probing in vivo the effect of detergents, antibiotics and antimicrobial peptides on the bacterial cell wall.

Help from a Hindrance: Using Astigmatism in Round Capillaries To Study Contact Angles and Wetting Layers.

Round glass capillaries are a basic tool in soft-matter science, but often are shunned due to the astigmatism they introduce in micrographs. Here, we show how refraction in a capillary can be a help instead of a hindrance to obtain precise and sensitive information on two important interfacial properties: the contact angle of two immiscible fluids and the presence of thin films on the capillary wall. Understanding optical cusps due to refraction allows direct mesurement of the inner diameter of a capillary at the meniscus, which, with the height of the meniscus cap, determines the contact angle. The meniscus can thus be measured without intrusive additives to enhance visibility, such as dyes or calibrated particles, in uniform, curved, or even tapered capillaries or under demanding conditions not accessible by conventional methods, such as small volumes (μL), high temperatures, or high pressures. We further elicit the conditions for strong internal reflection on the inner capillary wall, involving the wall and fluid refractive indices and the wall thickness, and show how to choose the capillary section to detect thin (submicron) layers on the wall, by the contribution of total internal reflection to the cusps. As examples, we report the following: (i) CO2-water or -brine contact angles at glass interfaces, measured at temperatures and pressures up to 200 °C and 600 bar, revealing an effect apparently so far unreported-the decrease in the water-wet character of glass, due to dissolved salts in brine, is strongly reduced at high temperatures, where contact angles converge toward the values in pure water; (ii) A tenuous gas hydrate layer growing from the water-guest contact line on glass, invisible in transmission microscopy but prominent in the cusps due to total internal reflection.

Experimental soft-matter science

Soft condensed matter refers to materials where the constituent building blocks are larger than atoms but smaller than the system itself. The large size of the constituent particles makes these soft materials distinctive from hard condensed matter systems. Soft matter is easily deformable, dissipative, disordered, nonlinear, far from equilibrium, thermal and entropic, slow, observable, susceptible to external fields, patterned, nonlocal, interfacial elastic, memory retaining, and active. This article surveys soft-matter science and discusses different classes of systems including colloids; emulsions; foams; glassy, granular, and jammed matter; liquid crystals; polymers; adaptive mechanical metamaterials; and active matter.

Periodic assembly of nanoparticle arrays in disclinations of cholesteric liquid crystals

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

Further expanding versatility of surface-enhanced Raman spectroscopy: from non-traditional SERS-active to SERS-inactive substrates and single shell-isolated nanoparticle.

After surface-enhanced Raman spectroscopy (SERS) was initiated over four decades ago, its practical application seems to be far behind the fundamental research that has made tremendous progress. SERS as a highly sensitive technique has not been widely adopted by the materials science and surface science communities or in the market of analytical instruments. In this discussion, we first classify the previous approaches along this direction over the past four decades and divide them into three strategies. Based on our recent theoretical and experimental approaches, we discuss in more detail the third strategy related to shell-isolated nanostructures. It can significantly expand the SERS study on nontraditional SERS-active (i.e. weakly SERS-active) materials (e.g. Pt, Ni, Fe, etc.) and even SERS-inactive materials (e.g. Si and Al2O3). We then focus on a single shell-isolated nanoparticle and how to controllably locate the strong electromagnetic field just at the probe surface of various materials. The use of side illumination at a high incident angle and/or nanocubes can further enhance the Raman signal by one to two orders of magnitude, which could be helpful for quantitative studies for surface science, heterogeneous catalysis, and soft matter science.

James Fergason and His Role in the Basic and Applied Science of Liquid Crystals

James Lee Fergason (1934-2008) focused his research on the liquid crystals. His studies and works correspond to a relevant part of the history of soft matter science and technology of liquid crystals. Besides contributing to the basic studies on cholesteric and smectic materials, he developed the twisted-nematic cell, which led to the fist liquid crystal displays. Here we are proposing a discussion of some of his main researches.

Editorial

This special topics issue offers a broad perspective on recent theoretical and computational soft matter science, providing state of the art advances in many of its sub-fields. As is befitting for a discipline as diverse as soft matter, the papers collected here span a considerable range of subjects and questions, but they also illustrate numerous connections into both fundamental science and technological/industrial applications, which have accompanied the field since its earliest days. This issue is dedicated to Kurt Kremer, on the occasion of his 60th birthday, honouring his role in establishing this exciting field and consolidating its standing in the frame of current science and technology.

Filamentous Phages As a Model System in Soft Matter Physics.

Filamentous phages have unique physical properties, such as uniform particle lengths, that are not found in other model systems of rod-like colloidal particles. Consequently, suspensions of such phages provided powerful model systems that have advanced our understanding of soft matter physics in general and liquid crystals in particular. We described some of these advances. In particular we briefly summarize how suspensions of filamentous phages have provided valuable insight into the field of colloidal liquid crystals. We also describe recent experiments on filamentous phages that have elucidated a robust pathway for assembly of 2D membrane-like materials. Finally, we outline unique structural properties of filamentous phages that have so far remained largely unexplored yet have the potential to further advance soft matter physics and material science.

Note: An iterative algorithm to improve colloidal particle locating.

Confocal microscopy of colloids combined with digital image processing has become a powerful tool in soft matter physics and materials science. Together, these techniques enable locating and tracking of more than half a million individual colloidal particles at once. However, despite improvements in locating algorithms that improve position accuracy, it remains challenging to locate all particles in a densely packed, three dimensional colloid without erroneously identifying the same particle more than once. We present a simple iterative algorithm that mitigates both the "missed particle" and "double counting" problems while simultaneously reducing sensitivity to the specific choice of input parameters. It is also useful for analyzing images with spatially varying brightness in which a single set of input parameters is not appropriate for all particles. The algorithm is easy to implement and compatible with existing particle locating software.

Experimental GVD engineering in slow light slot photonic crystal waveguides.

The use in silicon photonics of the new optical materials developed in soft matter science (e.g. polymers, liquids) is delicate because their low refractive index weakens the confinement of light and prevents an efficient control of the dispersion properties through the geometry. We experimentally demonstrate that such materials can be incorporated in 700 μm long slot photonic crystal waveguides, and hence can benefit from both slow-light field enhancement effect and slot-induced ultra-small effective areas. Additionally, we show that their dispersion can be engineered from anomalous to normal regions, along with the presence of multiple zero group velocity dispersion (ZGVD) points exhibiting Normalized Delay Bandwidth Product as high as 0.156. The reported results provide experimental evidence for an accurate control of the dispersion properties of fillable periodical slotted structures in silicon photonics, which is of direct interest for on-chip all-optical data treatment using nonlinear optical effects in hybrid-on-silicon technologies.

Soft matters from nano-atoms to giant molecules

In this brief review, we look back on the conception of nano-atoms and their gradual evolutions into a new class of giant molecules in the context of soft matter science. The structural features and the characteristics about giant molecular self-assembly are summarized. It is found that these giant molecules with high conformational rigidities and precisely-defined shapes and symmetries can exhibit unusual phase structures and phase transition behaviors which are not commonly observed in conventional polymers. Their self-assembly is robust due to collective and cooperative interactions among nano-atoms, forming hierarchical structures that are sensitive to their primary structures. This modular feature is reminiscent to the domain concept in protein science. It is thus proposed that nano-atoms can serve as unique elements for macromolecular science.