Ilya Zharov

Poly(2-(dimethylamino)ethyl methacrylate)-modified nanoporous Colloidal films with pH and ion response.

Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes were grown using surface-initiated atom transfer radical polymerization on the nanopore surface inside the colloidal films assembled from 255 nm silica spheres. The molecular transport through PDMAEMA-modified colloidal nanopores was studied as a function of pH and ionic strength by measuring the flux of neutral and positively charged redox-active species across the colloidal films using cyclic voltammetry. Nanopores modified with PDMAEMA brushes exhibited pH- and ion-dependent behavior as follows. The diffusion rates decreased with decreasing pH as a result of electrostatic interactions and steric hindrance. At low pH (in the protonated state) the diffusion rates increased with increasing salt concentration because of the charge screening. We also quaternized the surface-grafted PDMAEMA, which led to the formation of strong polyelectrolyte brushes that hindered the diffusion of neutral molecules through the nanopores due to steric effects and the diffusion of positively charged species due to both electrostatic and steric effects.

Ion Transport in Sulfonated Nanoporous Colloidal Films

The surface of self-assembled nanoporous silica colloidal crystalline films comprised of 184-nm-diameter silica spheres has been sulfonated using 1,3-propanesultone. The transport of ions through the sulfonated films has been studied using cyclic voltammetry in water as a function of ion charge, pH, and solution ionic strength. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. This behavior is pH-dependent and is due to electrostatic repulsion/attraction that can be modulated by changing the ionic strength of the contacting solution.

Surface-Modified Silica Colloidal Crystals: Nanoporous Films and Membranes with Controlled Ionic and Molecular Transport

Nanoporous membranes are important for the study of the transport of small molecules and macromolecules through confined spaces and in applications ranging from separation of biomacromolecules and pharmaceuticals to sensing and controlled release of drugs. For many of these applications, chemists need to gate the ionic and molecular flux through the nanopores, which in turn depends on the ability to control the nanopore geometry and surface chemistry. Most commonly used nanoporous membrane materials are based on polymers. However, the nanostructure of polymeric membranes is not well-defined, and their surface is hard to modify. Inorganic nanoporous materials are attractive alternatives for polymers in the preparation of nanoporous membranes. In this Account, we describe the preparation and surface modification of inorganic nanoporous films and membranes self-assembled from silica colloidal spheres. These spheres form colloidal crystals with close-packed face centered cubic lattices upon vertical deposition from colloidal solutions. Silica colloidal crystals contain ordered arrays of interconnected three dimensional voids, which function as nanopores. We can prepare silica colloidal crystals as supported thin films on various flat solid surfaces or obtain free-standing silica colloidal membranes by sintering the colloidal crystals above 1000 °C. Unmodified silica colloidal membranes are capable of size-selective separation of macromolecules, and we can surface-modify them in a well-defined and controlled manner with small molecules and polymers. For the surface modification with small molecules, we use silanol chemistry. We grow polymer brushes with narrow molecular weight distribution and controlled length on the colloidal nanopore surface using atom transfer radical polymerization or ring-opening polymerization. We can control the flux in the resulting surface-modified nanoporous films and membranes by pH and ionic strength, temperature, light, and small molecule binding. When we modify the surface of the colloidal nanopores with ionizable moieties, they can generate an electric field inside the nanopores, which repels ions of the same charge and attracts ions of the opposite charge. This allows us to electrostatically gate the ionic flux through colloidal nanopores, controlled by pH and ionic strength of the solution when surface amines or sulfonic acids are present or by irradiation with light in the case of surface spiropyran moieties. When we modify the surface of the colloidal nanopores with chiral moieties capable of stereoselective binding of enantiomers, we generate colloidal films with chiral permselectivity. By filling the colloidal nanopores with polymer brushes attached to the pore surface, we can control the ionic flux through the corresponding films and membranes electrostatically using reversibly ionizable polymer brushes. By filling the colloidal nanopores with polymer brushes whose conformation reversibly changes in response to pH, ionic strength, temperature, or small molecule binding, we can control the molecular flux sterically. There are various potential applications for surface-modified silica colloidal films and membranes. Due to their ordered nanoporous structure and mechanical durability, they are beneficial in nanofluidics, nanofiltration, separations, and fuel cells and as catalyst supports. Reversible gating of flux by external stimuli may be useful in drug release, in size-, charge-, and structure-selective separations, and in microfluidic and sensing devices.

Biomimetic glass nanopores employing aptamer gates responsive to a small molecule

We report the preparation of 20 and 65 nm radii glass nanopores whose surface is modified with DNA aptamers controlling the molecular transport through the nanopores in response to small molecule binding.

Free-Standing Silica Colloidal Nanoporous Membranes

We prepared robust free-standing 200 microm-thick colloidal membranes (nanofrits) with a relatively large area and no mechanical defects by sintering silica colloidal films. The silica spheres used to prepare the nanofrits were 338, 300, or 251 nm in diameter, leading to 25, 22.5, and 19 nm nanopore sizes, respectively. The room-temperature diffusional flux through these membranes is of the order of 3.6 x 10(-10) mol s(-1) cm(-2) for a Fe(bpy)32+ ion in acetonitrile test solution in the absence of applied pressure and is in good agreement with the calculated diffusional flux for colloidal crystals of the same thickness. To evaluate the feasibility of nanofrit surface modification, we treated them with 3-aminopropyltriethoxysilane after rehydroxylation. We found, by measuring the surface coverage for dansyl amide on the surface, that the number of the amines on the nanofrit surface is lower as compared to that observed for colloidal films not treated with heat. As a result, the selectivity for the transport of Fe(bpy)3(2+) through the aminated nanofrits in the presence of acid is lower than the selectivity observed for amine-modified colloidal films.

p-tert-Butyl thiacalix[4]arenes functionalized at the lower rim by amide, hydroxyl and ester groups as anion receptors

New p-tert-butyl thiacalix[4]arenes differently substituted at the lower rim with amide, hydroxyl and ester groups were synthesized. Binding properties of the compounds toward some tetrabutylammonium salts n-Bu(4)NX (X = F(-), Cl(-), Br(-), I(-), CH(3)CO(2)(-), H(2)PO(4)(-), NO(3)(-)) were studied by UV spectroscopy. It was found that the stoichiometry of the complexes, generally, is 1 : 1, and the association constants are in the range of 10(3)-10(5) M(-1). The p-tert-butyl thiacalix[4]arenes containing secondary amide groups trisubstituted at the lower rim bind the studied anions most effectively. Selective receptors for fluoride and dihydrogen phosphate salts of tetrabutylammonium were found.

Poly(L-alanine)-modified nanoporous colloidal films

The surfaces of nanopores in colloidal films assembled from 255 nm silica spheres were modified with poly(L-alanine) brushes using surface-initiated polycondensation. Polymer length was controlled by the polymerization time. The molecular transport through the colloidal films was studied using cyclic voltammetry as a function of polymer brush thickness, temperature, and pH. Transport rates through the colloidal films were found to be dependent on temperature and pH, with the magnitude of the effect dependent on the length of the polypeptide chain.

Chiral permselectivity in nanoporous opal films surface-modified with chiral selector moieties

The chiral permselectivity in thin opal films modified on the silica surface with chiral selector moieties was studied as a function of opal film geometry, supporting electrolyte concentration, solvent polarity, and chiral selector and linker structure. While opal film thickness, supporting electrolyte concentration and linker length and structure did not have a significant influence on the chiral permselectivity, the nanopore size, solvent polarity and selector structure had a pronounced effect. These observations are in agreement with the chiral selectivity mechanism in the opal films in which the permeating enantiomers are transported with different rates through the surface utilizing non-covalent interactions between the chiral permeant molecules and surface-bound chiral selectors. The chiral selectivity (transport rate ratio for S and R enantiomers) achieved in the present study was 4.5, which is one of the highest reported for chiral membranes.

SiO2@Au Core-Shell Nanospheres Self-Assemble To Form Colloidal Crystals That Can Be Sintered and Surface Modified To Produce pH-Controlled Membranes

We prepared colloidal crystals by self-assembly of gold-coated silica nanospheres, and free-standing nanoporous membranes by sintering these colloidal crystals. We modified the nanopore surface with ionizable functional groups, by forming a monolayer of L-cysteine or by surface-initiated polymerization of methacrylic acid. Diffusion experiments for the cationic dye Rhodamine B through L-cysteine-modified membranes showed a decrease in flux upon addition of an acid due to the nanopore surface becoming positively charged. Diffusion experiments for the neutral dye, ferrocenecarboxaldehyde, through the PMAA-modified membranes showed a 13-fold increase in flux upon addition of an acid resulting from the protonated polymer collapsing onto the nanopore surface leading to larger pore size. Our results demonstrate that SiO2@Au core-shell nanospheres can self-assemble into colloidal crystals and that transport through the corresponding surface-modified Au-coated colloidal membranes can be controlled by pH.

Nanoporous membranes with tunable pore size by pressing/sintering silica colloidal spheres.

We prepared robust nanoporous membranes with controlled area and uniform thickness by pressing silica colloidal spheres into disks followed by sintering. Three different diameters of silica particles, 390, 220, and 70 nm, were used to prepare the membranes with different pore size. In order to evaluate their size-selectivity, we measured the diffusion of polystyrene particles through these membranes. Although pressed silica colloidal membranes do not possess visible order or uniform pore size, they showed size-selective transport. We also demonstrated that pressed silica colloidal membranes can be functionalized via pore-filling. Sulfonated polymer brushes were grown inside the pores via surface-initiated atom transfer radical polymerization, which resulted in a material with high proton conductivity suitable for fuel cell applications.