Multilayer films of organic compounds on solid surfaces have been studied for more than 60 years because they allow fabrication of multicomposite molecular assemblies of tailored architecture. However, both the Langmuir-Blodgett technique and chemisorption from solution can be used only with certain classes of molecules. An alternative approach—fabrication of multilayers by consecutive adsorption of polyanions and polycations—is far more general and has been extended to other materials such as proteins or colloids. Because polymers are typically flexible molecules, the resulting superlattice architectures are somewhat fuzzy structures, but the absence of crystallinity in these films is expected to be beneficial for many potential applications.

https://science.sciencemag.org/content/sci/277/5330/1232.full.pdf

Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites

Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.

Emerging applications of stimuli-responsive polymer materials

Hollow silica and silica-polymer spheres with diameters between 720 and 1000 nanometers were fabricated by consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either by calcination or decomposition upon exposure to solvents. Scanning and transmission electron microscopy images demonstrate that the wall thickness of the hollow spheres can be readily controlled by varying the number of nanoparticle-polymer deposition cycles, and the size and shape are determined by the morphology of the templating colloid. The hollow spheres produced are envisioned to have applications in areas ranging from medicine to pharmaceutics to materials science.

http://science.sciencemag.org/content/sci/282/5391/1111.full.pdf

Nanoengineering of Inorganic and Hybrid Hollow Spheres by Colloidal Templating

We have derived the general solution of a wave equation describing the dynamics of two-layer viscoelastic polymer materials of arbitrary thickness deposited on solid (quartz) surfaces in a fluid environment. Within the Voight model of viscoelastic element, we calculate the acoustic response of the system to an applied shear stress, i.e. we find the shift of the quartz generator resonance frequency and of the dissipation factor, and show that it strongly depends on the viscous loading of the adsorbed layers and on the shear storage and loss moduli of the overlayers. These results can readily be applied to quartz crystal acoustical measurements of the viscoelasticity of polymers which conserve their shape under the shear deformations and do not flow, and layered structures such as protein films adsorbed from solution onto the surface of self-assembled monolayers.

https://iopscience.iop.org/article/10.1238/Physica.Regular.059a00391/pdf

Viscoelastic Acoustic Response of Layered Polymer Films at Fluid-Solid Interfaces: Continuum Mechanics Approach

The design of advanced, nanostructured materials at the molecular level is of tremendous interest for the scientific and engineering communities because of the broad application of these materials in the biomedical field. Among the available techniques, the layer-by-layer assembly method introduced by Decher and co-workers in 1992 has attracted extensive attention because it possesses extraordinary advantages for biomedical applications: ease of preparation, versatility, capability of incorporating high loadings of different types of biomolecules in the films, fine control over the materials’ structure, and robustness of the products under ambient and physiological conditions. In this context, a systematic review of current research on biomedical applications of layer-by-layer assembly is presented. The structure and bioactivity of biomolecules in thin films fabricated by layer-by-layer assembly are introduced. The applications of layer-bylayer assembly in biomimetics, biosensors, drug delivery, protein and cell adhesion, mediation of cellular functions, and implantable materials are addressed. Future developments in the field of biomedical applications of layer-by-layer assembly are also discussed.

/pdf/biomedical-applications-of-layer-by-layer-assembly-from-1i20r8iian.pdf

Biomedical Applications of Layer‐by‐Layer Assembly: From Biomimetics to Tissue Engineering

Multilayer films which contain ordered layers of more than one protein species were assembled by means of altemate electrostatic adsorption mostly with positively charged poly(ethy1enimine) (PEI) or with negatively charged poly(styrenesu1fonate) (PSS). Water-soluble proteins used are cytochrome c (Cyt), myoglobin (Mb), lysozyme (Lys), histone f3, hemoglobin (Hb), glucoamylase (GA), and glucose oxidase (GOD). Charged protein layers formed multilayers with linear polymers acting as glue or filler. The assembly was monitored by a quartz crystal microbalance and W spectroscopy. Linear film growth was observed up to at least 25 molecular layers. The assembly of Mb and Lys, both positively-charged, was realized in altemation with PSS in the form of {PEI/PSS + (Mb/PSS)2 + (MbPSS/Lys/PSS)d}. The assembly of oppositely-charged (at pH 6.5) Lys and GOD consists from Lys and GOD layers separated by a polycatiodpolyanion bilayer: {PEYPSSPEI f (PSS/Lys)2 + PSSPEI f (GOD/PEI)6}. Hb was assembled as “positive” unit at pH 4.5 (in alternation with PSS) and as “negative” unit at pH 9.2 (in altemation with PEI). A multilayer consisting of alternating montmorillonite, PEI, and GOD layers was also assembled. These biomolecular architecture open a way to construct artificially orchestrated protein systems that can carry out complex enzymic reactions.

Assembly of multicomponent protein films by means of electrostatic layer-by-layer adsorption

Alternate layer-by-layer assembly of colloidal SiO2 particles with polycations has been investigated by quartz crystal microbalance (QCM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). QCM measurement confirmed the high regularity and reproducibility of the assembling process that depends on particle concentration, particle size, and ionic strength. The individual adsorption step was completed within 15 s. The thickness of adsorbed layers increased with increasing SiO2 concentrations at the three particle sizes used (45, 25, and 78 nm in diameter), unlike the case for other polyion assemblies. It also increased with increasing ionic strength of aqueous SiO2 dispersions. According to SEM observation, the assembled film possessed surprisingly flat surfaces at optimized ionic strengths. AFM observation revealed that SiO2 particles were not closely packed. The neutralization ratio of SiO2 and PDDA was estimated by turbidity measurement. Comparison of turbidity and QCM data indicated t...

Alternate Assembly of Ordered Multilayers of SiO2 and Other Nanoparticles and Polyions

A careful examination of the adsorption step in the alternate layer-by-layer assembly of linear polyanion and polycation

Fabrication of metal oxide thin films with thickness control of nanometer precision is an important technology that leads to wide practical applications. The present study demonstrates that a surfa...

A Surface Sol−Gel Process of TiO2 and Other Metal Oxide Films with Molecular Precision

Multilayer films of molybdenum oxide were prepared by means of alternate adsorption of ammonium octamolybdate ((NH4)4[Mo8O26]) and poly(allylamine hydrochloride) (PAH). The films were reproducibly grown at each adsorption cycle, as monitored by a quartz crystal microbalance. Adsorption of PAH on the surface of a molybdenum oxide layer was saturated with a constant thickness of 32 ± 21 A. On the other hand, adsorption of octamolybdate on the PAH layer did not show saturation. The thickness of the oxide layer in the individual adsorption step increased with the adsorption time at a rate of ca. 5.7 A/min due to condensation of the adsorbed octamolybdate and the resulting loss of negative charges. The surface of the resulted films was relatively flat with height difference of less than 10 nm, and the film thickness was constant over a large area, as confirmed by scanning electron microscopy.

/pdf/formation-process-of-ultrathin-multilayer-films-of-9mx1e5s21i.pdf

Izumi Ichinose

Papers

Assembly of multicomponent protein films by means of electrostatic layer-by-layer adsorption

Alternate Assembly of Ordered Multilayers of SiO2 and Other Nanoparticles and Polyions

A careful examination of the adsorption step in the alternate layer-by-layer assembly of linear polyanion and polycation

A Surface Sol−Gel Process of TiO2 and Other Metal Oxide Films with Molecular Precision

Formation Process of Ultrathin Multilayer Films of Molybdenum Oxide by Alternate Adsorption of Octamolybdate and Linear Polycations