Synthesis, nanocrystalline morphology, lattice dynamics and nonlinear optics of mesoporous SiO&LiNbO nanocomposite.

We demonstrate a hybrid nanocomposite combining mesoporous silica, p , as a host medium and guest lithium niobate nanocrystals embedded into tubular silica nanochannels by calcination of the precursor mixed solution of lithium and niobium salts. High-resolution transmission electron microscopy, X-ray diffraction and Raman scattering techniques reveal trigonal nanocrystals within the p nanochannels, indicating their random texture morphology. Annealing at high temperatures ( 950 C) during calcination also leads to partial crystallization of the p matrix with the formation of trigonal - nanocrystals.

Deformation dynamics of nanopores upon water imbibition.

Capillarity-driven transport in nanoporous solids is widespread in nature and crucial for modern liquid-infused engineering materials. During imbibition, curved menisci driven by high negative Laplace pressures exert an enormous contractile load on the porous matrix. Due to the challenge of simultaneously monitoring imbibition and deformation with high spatial resolution, the resulting coupling of solid elasticity to liquid capillarity has remained largely unexplored.

Self-Assembly of Ionic Superdiscs in Nanopores.

Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs.

Polymeric liquids in mesoporous photonic structures: From precursor film spreading to imbibition dynamics at the nanoscale.

Polymers are known to wet nanopores with high surface energy through an atomically thin precursor film followed by slower capillary filling. We present here light interference spectroscopy using a mesoporous membrane-based chip that allows us to observe the dynamics of these phenomena in situ down to the sub-nanometer scale at milli- to microsecond temporal resolution. The device consists of a mesoporous silicon film (average pore size 6 nm) with an integrated photonic crystal, which permits to simultaneously measure the phase shift of thin film interference and the resonance of the photonic crystal upon imbibition.

Mapping the nanoscale elastic property modulations of polypyrrole thin films in liquid electrolyte with EC-AFM.

Linking structure to mechanical and elastic properties is a major concern for the development of novel electroactive materials. This work reports on the potential-induced changes in thickness and Young modulus of a substrate supported, perchlorate doped polypyrrole thin film (<100 nm) investigated with electrochemical atomic force microscopy (AFM) under conditions. This was accomplished by nanomechanical mapping of potentiodynamically electropolymerized polypyrrole film in electrolyte solution with AFM during redox cycling.

Does thermotropic liquid crystalline self-assembly control biological activity in amphiphilic amino acids? - tyrosine ILCs as a case study.

Amphiphilic amino acids represent promising scaffolds for biologically active soft matter. In order to understand the bulk self-assembly of amphiphilic amino acids into thermotropic liquid crystalline phases and their biological properties a series of tyrosine ionic liquid crystals (ILCs) was synthesized, carrying a benzoate unit with 0-3 alkoxy chains at the tyrosine unit and a cationic guanidinium head group. Investigation of the mesomorphic properties by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (WAXS, SAXS) revealed smectic A bilayers (SmA) for ILCs with 4-alkoxy- and 3,4-dialkoxybenzoates, whereas ILCs with 3,4,5-trisalkoxybenzoates showed hexagonal columnar mesophases (Col), while different counterions had only a minor influence.

Wafer-Scale Fabrication of Hierarchically Porous Silicon and Silica by Active Nanoparticle-Assisted Chemical Etching and Pseudomorphic Thermal Oxidation.

Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here, an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-crystalline silicon with a bimodal pore-size distribution is presented, i.

On the issue of textured crystallization of Ba(NO) in mesoporous SiO: Raman spectroscopy and lattice dynamics analysis.

The lattice dynamics of preferentially aligned nanocrystals formed upon drying of aqueous Ba(NO) solutions in a mesoporous silica glass traversed by tubular pores of approximately 12 nm are explored by Raman scattering. To interpret the experiments on the confined nanocrystals polarized Raman spectra of bulk single crystals and X-ray diffraction experiments are also performed. Since a cubic symmetry is inherent to Ba(NO), a special Raman scattering geometry was utilized to separate the phonon modes of A and E species.

Impact of confinement and polarizability on dynamics of ionic liquids.

Polarizability is a key factor when it comes to an accurate description of different ionic systems. The general importance of including polarizability into molecular dynamics simulations was shown in various recent studies for a wide range of materials, ranging from proteins to water to complex ionic liquids and for solid-liquid interfaces. While most previous studies focused on bulk properties or static structure factors, this study investigates in more detail the importance of polarizable surfaces on the dynamics of a confined ionic liquid in graphitic slit pores, as evident in modern electrochemical capacitors or in catalytic processes.

Assessment of nanoparticle immersion depth at liquid interfaces from chemically equivalent macroscopic surfaces.

Hypothesis: We test whether the wettability of nanoparticles (NPs) straddling at an air/water surface or oil/water interface can be extrapolated from sessile drop-derived macroscopic contact angles (mCAs) on planar substrates, assuming that both the nanoparticles and the macroscopic substrates are chemically equivalent and feature the same electrokinetic potential.

Experiments: Pure silica (SiO) and amino-terminated silica (APTES-SiO) NPs are compared to macroscopic surfaces with extremely low roughness (root mean square [RMS] roughness ≤ 2 nm) or a roughness determined by a close-packed layer of NPs (RMS roughness ∼ 35 nm). Equivalence of the surface chemistry is assessed by comparing the electrokinetic potentials of the NPs via electrophoretic light scattering and of the macroscopic substrates via streaming current analysis.

Dynamic Kerr and Pockels electro-optics of liquid crystals in nanopores for active photonic metamaterials.

Photonic metamaterials with properties unattainable in base materials are already beginning to revolutionize optical component design. However, their exceptional characteristics are often static, as artificially engineered into the material during the fabrication process. This limits their application for in-operando adjustable optical devices and active optics in general.

Wafer-Scale Electroactive Nanoporous Silicon: Large and Fully Reversible Electrochemo-Mechanical Actuation in Aqueous Electrolytes.

Nanoporosity in silicon results in interface-dominated mechanics, fluidics, and photonics that are often superior to the ones of the bulk material. However, their active control, for example, by electronic stimuli, is challenging due to the absence of intrinsic piezoelectricity in the base material. Here, for large-scale nanoporous silicon cantilevers wetted by aqueous electrolytes, electrosorption-induced mechanical stress generation of up to 600 kPa that is reversible and adjustable at will by potential variations of ≈1 V is shown.

How water wets and self-hydrophilizes nanopatterns of physisorbed hydrocarbons.

Hypothesis: Weakly bound, physisorbed hydrocarbons could in principle provide a similar water-repellency as obtained by chemisorption of strongly bound hydrophobic molecules at surfaces.

Experiments: Here we present experiments and computer simulations on the wetting behaviour of water on molecularly thin, self-assembled alkane carpets of dotriacontane (n-CH or C32) physisorbed on the hydrophilic native oxide layer of silicon surfaces during dip-coating from a binary alkane solution. By changing the dip-coating velocity we control the initial C32 surface coverage and achieve distinct film morphologies, encompassing homogeneous coatings with self-organised nanopatterns that range from dendritic nano-islands to stripes.

Synergistic and Competitive Adsorption of Hydrophilic Nanoparticles and Oil-Soluble Surfactants at the Oil-Water Interface.

Fundamental insights into the interplay and self-assembly of nanoparticles and surface-active agents at the liquid-liquid interface play a pivotal role in understanding the ubiquitous colloidal systems present in our natural surroundings, including foods and aquatic life, and in the industry for emulsion stabilization, drug delivery, or enhanced oil recovery. Moreover, well-controlled model systems for mixed interfacial adsorption of nanoparticles and surfactants allow unprecedented insights into nonideal or contaminated particle-stabilized emulsions. Here, we investigate such a model system composed of hydrophilic, negatively, and positively charged silica nanoparticles and the oil-soluble cationic lipid octadecyl amine with in situ synchrotron-based X-ray reflectometry, which is analyzed and discussed jointly with dynamic interfacial tensiometry.