Marcin Fialkowski

Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice

Self-assembly of charged, equally sized metal nanoparticles of two types (gold and silver) leads to the formation of large, sphalerite (diamond-like) crystals, in which each nanoparticle has four oppositely charged neighbors. Formation of these non–close-packed structures is a consequence of electrostatic effects specific to the nanoscale, where the thickness of the screening layer is commensurate with the dimensions of the assembling objects. Because of electrostatic stabilization of larger crystallizing particles by smaller ones, better-quality crystals can be obtained from more polydisperse nanoparticle solutions.

Micro- and nanotechnology via reaction–diffusion

Reaction–diffusion (RD) processes are common throughout nature, which uses them routinely to build and control structures on length scales from molecular to macroscopic. At the same time, despite a long history of scientific research and a significant level of understanding of the basic aspects of RD, reaction–diffusion has remained an unrealized technological opportunity. This review suggests that RD systems can provide a versatile basis for applications in micro- and nanotechnology. Straightforward experimental methods are described that allow precise control of RD processes in complex microgeometries and enable fabrication of small-scale structures, devices, and functional systems. Uses of RD in sensory applications are also discussed.

Evaluation of Ligand-Selector Interaction from Effective Diffusion Coefficient

We present an analytical technique for determination of ligand-selector equilibrium binding constants. The method is based on the measurements of effective molecular diffusion coefficient of the ligand during Poiseuille flow through a long (approximately 25 m), thin (0.254 mm +/- 0.05 mm ID) capillary with and without the selector. The data are analyzed using the Taylor dispersion theory. Bovine Serum Albumin (BSA) and cyclodextrin (CD) were taken as model selectors. We have tested our method on the following selector-ligand complexes: BSA with warfarin, propranolol, noscapine, salicylic acid, and riboflavin, and cyclodextrin with 4-nitrophenol. The results are in good agreement with data from the literature and with our own results obtained within classical chromatography. This method works equally well for uncharged and charged compounds.

Crossover regime for the diffusion of nanoparticles in polyethylene glycol solutions: influence of the depletion layer

The viscosity in soft matter systems is a scale dependent quantity. In polymer solutions the viscosity of nanoprobes of size R approaches the macroscopic viscosity when R exceeds the radius of gyration of the polymer, Rg. The nano to macroviscosity crossover occurs for R ∼ Rg. Here we analyze diffusion in a polymer (polyethylene glycol) solution of nanoparticles in the crossover regime. We report a scale dependent diffusion coefficient in this regime due to non-uniform viscosity in the depletion layer around particles. The phenomenological scaling of the slow diffusion coefficient as a function of probe size is compared to the same scaling for macroscopic viscosity as a function of polymer size.

Single-walled carbon nanotube/lyotropic liquid crystal hybrid materials fabricated by a phase separation method in the presence of polyelectrolyte.

We present a detailed study on the incorporation of single-walled carbon nanotubes (SWNTs) into lyotropic liquid crystals (LLC) by phase separation in the presence of polyelectrolytes. Two cases were studied in this work: (i) incorporation of SWNTs into the LLC phase formed by an anionic surfactant sodium dodecyl sulfate (SDS) in the presence of an anionic polyelectrolyte poly(sodium styrenesulfonate) (PSS); (ii) incorporation of SWNTs into the LLC phase formed by a cationic surfactant cetyltrimethylammonium bromide (CTAB) in the presence of a cationic polyelectrolyte poly(diallydimethylammonium chloride) (PDADMAC). The SWNTs/LLC composites were characterized by polarized optical microscopy (POM) observations and small-angle X-ray scattering (SAXS) measurements. In both systems, the surfactant phase was condensed into a hexagonal lattice by the polyelectrolyte within the investigated concentration range. Several factors that can influence the property of SWNTs/LLC composite were examined, including concentration of surfactants and polyelectrolytes and temperature. Aggregated SWNTs were not observed, indicating that SWNTs were well dispersed in the LLC phases. SAXS measurements showed the lattice parameter of the host LLC phase changed upon varying the mixing ratio of polyelectrolyte to ionic surfactant. The SWNTs/LLC hybrids showed considerable stability against temperature rise in both systems, and desorption of surfactant from SWNTs was not observed at higher temperature.

Arrays of microlenses of complex shapes prepared by reaction-diffusion in thin films of ionically doped gels

This letter describes a wet-stamping technique for the fabrication of highly regular arrays of microlenses through reaction-diffusion-swelling processes occurring in a thin film of ionically doped gelatin. Geometrical parameters of the lenses depend on and can be controlled by the geometries of the stamped features and the concentrations of chemicals diffusing and reacting in the gelatin matrix. Surface topographies of the lenses are studied experimentally, and are reproduced by a lattice gas reaction-diffusion model.

Aggregation and Layering Transitions in Thin Films of X-, T-, and Anchor-Shaped Bolaamphiphiles at the Air–Water Interface

Aggregation in Langmuir films is usually understood as being a disorderly grouping of molecules turning into chaotic three-dimensional aggregates and is considered an unwanted phenomenon causing irreversible changes. In this work we present the studies of 11 compounds from the group of specific surfactants, known as bolaamphiphiles, that exhibit reversible aggregation and, in many cases, transition to well-defined multilayers, which can be considered as a layering transition. These bolaamphiphiles incorporate rigid π-conjugated aromatics as hydrophobic cores, glycerol-based polar groups and hydrophobic lateral chains. Molecules of different shapes (X-, T-, and anchor) were studied and compared. The key property of these compounds is the partial fluorination of the lateral chains linked to the rigid cores of the molecules. The most interesting feature of the compounds is that, depending on their shape and degree of fluorination, they are able to resist aggregation and preserve a monolayer structure up to relatively high surface pressures (T-shaped and some X-shaped molecules), or create well-defined trilayers (X- and anchor-shaped molecules). Experimental studies were performed using Langmuir balance, surface potential and X-ray reflectivity measurements.

Gold–Oxoborate Nanocomposites and Their Biomedical Applications

A novel inorganic nanocomposite material, called BOA, which has the form of small building blocks composed of gold nanoparticles embedded in a polyoxoborate matrix, is presented. It is demonstrated that cotton wool decorated with the BOA nanocomposite displays strong antibacterial activity toward both Gram-positive and -negative bacteria strains. Importantly, the modified cotton does not release any toxic substances, and the bacteria are killed upon contact with the fibers coated with the BOA. Toxicity tests show that the nanocomposite--in spite of its antiseptic properties--is harmless for mammalian cells. The presented method of surface modification utilizes mild, environmentally friendly fabrication conditions. Thus, it offers a facile approach to obtain durable nontoxic antiseptic coatings for biomedical applications.

Mechanism of reactive wetting and direct visual determination of the kinetics of self-assembled monolayer formation.

Reactive wetting (RW) of alkane thiols and disulfides on gold is studied experimentally using the wet stamping technique. Theoretical description based on Langevin dynamics is developed to explain the experimental results and to clarify the physical processes underlying RW. In this description, thermal fluctuations of the three-phase contact line combine with the surface reaction to gradually build a low-energy self-assembled monolayer (SAM) onto which the front propagates. The results of the model match the experiments and allow determination of the kinetic rate constants of SAM formation.

Quench-jump sequence in phase separation in polymer blends

A two-step process of phase separation–mixing is analyzed for binary mixtures. The system is first quenched into the thermodynamical instability region (temperature T), where the mixture undergoes a process of spinodal decomposition, characterized for short times by the growth of the Cahn peak of a scattered intensity at fixed scattering wave vector. Next we heat up a system (make a temperature jump to temperature T1) above the spinodal line (temperature Ts) and compute the decay of this peak. The peak intensity decreases and the peak position moves toward short wave vectors. The integrated peak intensity decreases exponentially at short times with a characteristic decay time that depends on T, T1, and Ts. The increase of the Euler characteristic from large negative values toward zero suggests that the shift of the peak toward short wave vectors is associated with the disappearance of small connections in a bicontinuous structure formed in the early stages of spinodal decomposition. Slow decay of the surf...