Controlling the shape and alignment of mesopores by confinement in colloidal crystals: designer pathways to silica monoliths with hierarchical porosity

Monolithic pieces of hierarchically structured silica, containing both periodic macropores and mesopores with well-controlled architecture, are synthesized by dual templating methods. Colloidal crystal templating with close-packed arrays of poly(methyl methacrylate) spheres yields regular, highly interconnected macropores a few hundred nanometers in diameter, and templating with nonionic surfactants produces mesoporosity (2.5-5.1 nm pore diameters) in the macropore walls. Several distinct mesostructures can be achieved within the silica skeleton, depending on the choice of surfactant, co-surfactant, and processing conditions. In the three-dimensional (3D) confinement of the colloidal crystal template, wormlike channels, cubic (Pm3n), or two-dimensional (2D) hexagonal (P6mm) mesostructures are produced with the surfactant Brij 56 (C16H33(OCH2CH2)nOH (n approximately 10) and dodecane as cosurfactant. In the 2D hexagonal structure, channels are oriented perpendicular to the polymer spheres, thereby connecting adjacent macropores through the silica walls. This orientation contrasts with channel alignment parallel to latex spheres when the polymeric surfactant Pluronic P123 (EO20PO70EO20) is used. On the basis of high-resolution 3D transmission electron microscopy, scanning electron microscopy, small-angle X-ray scattering, and nitrogen sorption measurements, structural and textural properties of the monoliths are described in detail as a function of the synthesis parameters. The control over the mesoarchitecture of these silica-surfactant systems in 3D confinement is explained by considering the relative dimensions of the mesostructures with respect to the interstitial space in the latex template, interfacial interactions, entropic effects, and structural frustration.     

Controlling the geometry (Janus balance) of amphiphilic colloidal particles

A simple, generalizable method is described to produce Janus colloidal particles in large quantity with control over their respective hydrophobic and hydrophilic areas (Janus balance) in large quantity. To this end, charged particles adsorb onto the liquid-liquid interface of emulsions of molten wax and water in the presence of surfactants of opposite charge, whose concentration modifies how deeply particles penetrate the oil-water interface, and subsequent surface chemical modification of the resulting colloidosomes is performed after lowering temperature to solidify the wax. Silica particles modified in this way using different amounts of didodecyldimethylammonium bromide (DDAB) display contact angles that vary controllably between 37 degrees and 75 degrees. Janus balance also varies but over a more limited range with control of pH, salt concentration, or the presence of nonionic surfactant (Tween 20 or ethanol). Purity, Janus balance, and colloidosome structure are evaluated by a combination of fluorescence microscopy, flow cytometry, and scanning electron microscopy (SEM). The three-phase contact angle is obtained by observing SEM images of voids left by particles escaped from the surface. Colloidosomes made in the presence of DDAB are markedly improved with respect to the hexagonal close packing, which helps increase the efficiency of the method. Gram-sized quantities of particles are synthesized.     

Growth of mesoporous materials within colloidal crystal films by spin-coating

A combination of colloidal crystal planarization, stabilization, and novel infiltration techniques is used to build a bimodal porous silica film showing order at both the micron and the nanometer length scale. An infiltration method based on the spin-coating of the mesophase precursor onto a three-dimensional polystyrene colloidal crystal film allows a nanometer control tuning of the filling fraction of the mesoporous phase while preserving the optical quality of the template. These materials combine a high specific surface arising from the nanopores with increased mass transport and photonic crystal properties provided by the order of the macropores. Optical Bragg diffraction from these type of hierarchically ordered oxides is observed, allowing performing of optical monitoring of the different processes involved in the formation of the bimodal silica structure.     

Aqueous dispersions of colloidal poly(3-hexylthiophene) gel particles with high internal porosity

This work outlines the development of nano-porous, sub-micron poly(3-hexylthiophene) (P3HT) gel particles as solution-processable inks for applications in polymer solar cells. These dispersions are produced by emulsifying bulk P3HT organogels into water containing surfactant. The optical characteristics and stability of the resulting gel particles are assessed and their structure characterized. The P3HT within the gel particles is shown to retain its crystallinity with no evidence of doping. The gel particles are shown to be stable against aggregation due to the presence of surfactant at the oil/water interface. The fracture of the gel network during emulsification produces a bimodal distribution of particles that increase in size with increasing P3HT concentration in the 'parent' organogel. Small Angle Neutron Scattering measurements show that the particles maintain the structure of the bulk gels with high specific surface area. Spray-coating the gel particle dispersions produces uniform thin-films, which have been used to fabricate polymer/fullerene solar cells with a fully spray-coated active layer.     

Supramolecular Strategies for Controlling Reactivity within Confined Nanospaces

Nanospaces are ubiquitous in the realm of biological systems and are of significant interest among supramolecular chemists. Understanding chemical behavior within nanospaces offers new perspectives on biological phenomena in nature and opens the way to highly unusual and selective forms of catalysis. Supramolecular chemistry exploits weak, yet effective, intermolecular interactions such as hydrogen bonding, metal‐ligand coordination, and the hydrophobic effect to assemble nano‐sized molecular architectures, providing reactions with remarkable rate acceleration, substrate specificity, and product selectivity. In this minireview, the focus is on the strategies that supramolecular chemists use to emulate the efficiency of biological processes, and elucidating how chemical reactivity is efficiently controlled within well‐defined nanospaces. Approaches such as orientation and proximity of substrate, transition‐state stabilization, and active‐site incorporation will be discussed.     

Controlling chemistry with cations: photochemistry within zeolites

The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.     

Dynamics within the exciton fine structure of colloidal CdSe quantum dots

Evidence for an interaction between the quantum dot exciton fine structure states F = +/-1 is obtained by measuring the dynamics of transitions among those states, exciton spin relaxation or flipping. An ultrafast transient grating experiment based on a crossed-linear polarization grating is reported. By using the quantum dot selection rules for absorption of circularly polarized light, it is demonstrated that it is possible to detect transitions between nominally degenerate fine structure states, even in a rotationally isotropic system. The results for colloidal CdSe quantum dots reveal a strong size dependence for the exciton spin relaxation rate from one bright exciton state (F = +/-1) to the other in CdSe colloidal quantum dots at 293 K, on a time scale ranging from femtoseconds to picoseconds, depending on the quantum dot size. The results are consistent with an interaction between those states attributed to a long-range contribution to the electron-hole exchange interaction.     

Control of colloidal particle deposit patterns within picoliter droplets ejected by ink-jet printing

Particle deposit morphologies that resulted from evaporating ink-jetted microdroplets were controlled by varying the ink compositions and concentrations. The ink was a well-dispersed aqueous dispersion of monodisperse silica microspheres. Silica particles suspended in the microdroplet undergo self-assembly upon the evaporation of the solvent. A ringlike deposit of the self-assembled silica particles was produced from the water-based ink, while a uniform two-dimensional monolayer with a well-ordered hexagonal structure was obtained from the mixed-solvent-based inks. Variations in the deposit patterns can be explained in terms of competing effects between the convective and Marangoni flows, which vary with the types of the high-boiling-point solvent added to the ink. The macroscopic shape and microstructure of the silica colloidal deposits were observed by SEM, AFM, and a confocal microscope.     

Controlling the rotation of a complexed guest within a molecular cage

A molecular cage-based complex, in which the complexed guest changes its binding geometry with respect to the macrocyclic host upon the addition and removal of K(+) ions, is reported.     

Controlling cesium cation recognition via cation metathesis within an ion pair receptor

Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO(3), in solution (10% methanol-d(4) in chloroform-d) as inferred from (1)H NMR spectroscopic analyses. The addition of KClO(4) to these cesium salt complexes leads to a novel type of cation metathesis in which the "exchanged" cations occupy different binding sites. Specifically, K(+) becomes bound at the expense of the Cs(+) cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO(3) and CsCl from an aqueous D(2)O layer into nitrobenzene-d(5) as inferred from (1)H NMR spectroscopic analyses and radiotracer measurements. The Cs(+) cation of the CsNO(3) extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO(4) solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.     

Radiation-induced synthesis of gold nanoparticles within lamellar phases. Formation of aligned colloidal gold by radiolysis

A sheared lamellar phase has been used as a nanoreactor for the synthesis of gold nanoparticles by radiolysis and by a photochemical approach. A gold salt solution (KAuCl4, 10(-2) M) is introduced into the aqueous compartments between the lipid-based bilayers. Gold nanoparticles grow within the lamellar phase as shown by TEM analysis and X-ray diffraction, limiting the particle size. Homodisperse, 2.4- and 5.9-nm-sized, spherical nanoparticles are produced by gamma irradiation and UV irradiation, respectively. When produced by radiolysis, they are perfectly aligned along the lamellae. Their UV-vis spectra display a maximum at 565 nm suggesting that nanoparticles are coupled by dipole-dipole interactions within the lamellar phase.     

Design and analysis of the homogeneous and heterogeneous distribution of water confined within colloidal polymer particles

Water is known to distribute within polymeric films in multiple states differentiable by the energy of association. Potentiometric swelling of carboxylated latex samples and subsequent differential scanning calorimetry (DSC) and thermogravimetric analysis verified this distribution of water, specifically confined within colloidal nanoparticle dimensions. DSC cooling curves can delineate between the freezable bound and freezable unbound water at low total water content but become difficult to distinguish the freezable bound contribution at high total water content. Of note is that the ratio of weakly bound water in the secondary layer to the water strongly hydrogen-bound to the polymer is approximately constant regardless of carboxylic acid type and, in fact, is greater for the case of the hydrophobic base polymer. Aside from its distribution within the particles, the total water content also appeared to be more related to the hydroplasticized glass point of the polymer colloid as opposed to the polarity of the polymer.     

Controlling Topology within Halogen-Bonded Networks by Varying the Regiochemistry of the Cyclobutane-Based Nodes

The formation of a pair of extended networks sustained by halogen bonds based upon two regioisomers of a photoproduct, namely rctt-1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (ht-PP) and rctt-1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (hh-PP), that have varied topology is reported. These networks are held together via I⋯N halogen bonds between the photoproduct and the halogen-bond donor 1,4-diiodoperchlorobenzene (C₆I₂Cl₄). The observed topology in each solid is controlled by the regiochemical position of the halogen-bond accepting 4-pyridyl group. This paper demonstrates the ability to vary the topology of molecular networks by altering the position of the halogen bond acceptor within the cyclobutane-based node.     

Video microscopy of colloidal suspensions and colloidal crystals

Colloidal suspensions are simple model systems for the study of phase transitions. Video microscopy is capable of directly imaging the structure and dynamics of colloidal suspensions in different phases. Recent results related to crystallization, glasses, and 2D systems complement and extend previous theoretical and experimental studies. Moreover, new techniques allow the details of interactions between individual colloidal particles to be carefully measured. Understanding these details will be crucial for designing novel colloidal phases and new materials, and for manipulating colloidal suspensions for industrial uses.     

A dielectric study on the relaxation and switching behaviour of liquid crystals confined within a colloidal network

The molecular ordering and dynamics of a liquid crystal (LC E7) in the presence of a three-dimensional network of submicron particles have been studied by dielectric relaxation spectroscopy. The field-dependent orientation of the LC was quantified by the director order parameter and modelled by use of a three-phase model. The influence of the colloidal network on the molecular dynamics was assessed from the dielectric spectra, e.g. from the position of relaxation peaks as well as from the strength of the two principal relaxations (α and γ). The spectra changed noticeably upon application of an increasing d.c. bias. A reduction of the threshold field was observed upon addition of colloidal particles to the LC. This was associated with a switching between two metastable states induced by anchoring on the filler particles. Modelled spectra were found to be in good agreement with the experimental data. The modelling showed that the confined LC phase is composed of two fractions, viz. an ordered and a disordered one with different molecular mobilities. Furthermore, switching experiments were conducted at various temperatures in order to evaluate the impact of the colloidal network on the (temperature-dependent) orientational behaviour of the LC molecules. For the colloid-filled LC higher conductivities were found, which gave rise to longer switch-off times.     

Nitrocellulose porosity - thermoporometry

Nitrocellulose porosity was investigated by thermoporometry, based on melting point depression of liquid in limited space. Strange behaviour of water-saturated nitrocellulose was observed, which consisted of melting peak shifting of some of liquid. Thermal resistance, connected with limited contact area of nitrocellulose walls and water, is supposed as the source of phenomenon. Water is unable to completely penetrate into pores as nitrocellulose is a hydrophobic material, though prolonged stirring or boiling of mixture improves saturation. Thus total pore volume cannot be estimated correctly. In spite of this pore radius was calculated from obtained DSC curves. The results show good consistency for the same nitrocellulose materials, which proves that thermoporometry is a useful method of nitrocellulose characterisation. This revised version was published online in July 2006 with corrections to the Cover Date.