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Intrinsically disordered proteins (IDPs) can display a broad spectrum of binding modes and highly variable binding affinities when interacting with both biological and nonbiological materials. A quantitative model of such behavior is important for the better understanding of the function of IDPs when encountering inorganic nanomaterials with the potential to control their behavior in vivo and in vitro . Depending on their amino acid composition and chain length, binding properties can vary strongly between different IDPs. Moreover, due to differences in the physical chemical properties of clusters of amino acid residues along the IDP primary sequence, individual residues can adopt a wide range of bound state populations. Quantitative experimental binding affinities with synthetic silica nanoparticles (SNPs) at residue-level resolution, which were obtained for a set of IDPs by solution NMR relaxation experiments, are explained here by a first-principle analytical statistical mechanical model termed SILC. SILC quantitatively predicts residue-specific binding affinities to nanoparticles and it expresses binding cooperativity as the cumulative result of pairwise residue effects. The model, which was parametrized for anionic SNPs and applied to experimental data of four IDP systems with distinctive binding behavior, successfully predicts differences in overall binding affinities, fine details of IDP-SNP affinity profiles, and site-directed mutagenesis effects with a spatial resolution at the individual residue level. The SILC model provides an analytical description of such types of fuzzy IDP-SNP complexes and may help advance understanding nanotoxicity and in vivo targeting of IDPs by specifically designed nanomaterials.

Asymmetric mesoporous silica nanoparticles (MSNs) with controllable head-tail structures have been successfully synthesized. The head particle type is tunable (solid or porous), and the tail has dendritic large pores. The tail length and tail coverage on head particles are adjustable. Compared to spherical silica nanoparticles with a solid structure (Stöber spheres) or large-pore symmetrical MSNs with fully covered tails, asymmetrical head-tail MSNs (HTMSNs) show superior hemocompatibility due to reduced membrane deformation of red blood cells and decreased level of reactive oxygen species. Moreover, compared to Stöber spheres, asymmetrical HTMSNs exhibit a higher level of uptake and in vitro maturation of immune cells including dendritic cells and macrophage. This study has provided a new family of nanocarriers with potential applications in vaccine development and immunotherapy.

Asymmetric single-hole mesoporous silica nanocages, which are eccentric hollow structured spheres and consist of mesoporous shell with an open hole on their surface, with uniform particle size (100-240 nm), have successfully been synthesized via a novel anisotropic encapsulation of the mesoporous silica. In this unique nanocarrier, the eccentric hollow cavity and big hole (∼25 nm) can serve as a storage space and passage for large guest molecules. Meanwhile, the uniform mesopores (2-10 nm) with a high surface area (∼500 m(2)/g) in the silica shells of the nanocages can provide storage space for small guest molecules. The obtained single-hole mesoporous nanocages can be endowed upconversion luminescence. The obtained upconversion nanoparticles functionalized eccentric single-hole nanorattles were used to codeliver bovine serum albumin and doxorubicin dual-sized guests. The release of the dual-sized guests can be well controlled independently by heat and near-infrared (NIR) light with the assistance of NIR to ultraviolet/visible (UV/vis) optical properties of upconversion nanoparticles and heat-sensitive phase change materials.

A facile and controllable interface-directed coassembly (IDCA) approach is developed for the first time to synthesize uniform discrete mesoporous silica particles with a large pore size (ca. 8 nm) by using 3-dimensional macroporous carbon (3DOMC) as the nanoreactor for the confined coassembly of template molecules and silica source. By controlling the amount of the precursor solution and using Pluronic templates with different compositions, we can synthesize mesoporous silica particles with diverse morphologies (spheres, hollow spheres, and hemispheres) and different mesostructure (e.g., 2-D hexagonal and 3D face centered cubic symmetry), high surface area of about 790 m(2)/g, and large pore volume (0.98 cm(3)/g). The particle size can be tunable from submicrometer to micrometer regimes by changing the macropore diameter of 3DOMC. Importantly, this synthesis concept can be extended to fabricate multifunctional mesoporous composite spheres with a magnetic core and a mesoporous silica shell, large saturated magnetization (23.5 emu/g), and high surface area (280 m(2)/g). With the use of the magnetic mesoporous silica spheres as a magnetically recyclable absorbent, a fast and efficient removal of microcystin from water is achieved, and they can be recycled for 10 times without a significant decrease of removal efficiency for microcystin.

Organized self-assemblies of Janus catalytic motors, induced by hydrophobic surface interactions involving multiple motor/motor and motor/nonmotor particles, display controlled coordinated self-propulsion. The influence of the self-assembled structures upon the motion behavior is investigated. A dynamic 'on-the-fly' assembly is observed during the continuous movement of the individual components, along with changes in the motion behavior. Organized assemblies of multiple motor/nonmotor particles are also illustrated toward optimal cargo transport and delivery. Such controlled structures and motion of chemically powered Janus micromotor assemblies hold considerable promise for the creation of intelligent nanomachines that perform collective tasks.

Ultrasmall sub-10 nm nanoprobes and carriers are of significant interest due to their favorable biodistribution characteristics in in vivo experiments. Here we describe the one-pot synthesis of PEGylated mesoporous silica nanoparticles with a single pore, tunable sizes around 9 nm and narrow size distributions that can be labeled with near-infrared dye Cy5.5. Particles are characterized by a combination of transmission electron microscopy, dynamic light scattering, fluorescence correlation spectroscopy, optical spectroscopy, nuclear magnetic resonance spectroscopy, and nitrogen sorption/desorption measurements. The possibility to distinguish an "inside" and "outside" may render these particles an interesting subject for further studies in sensing, drug delivery, and theranostics applications.

Azidopropyl functionalized mesoporous silica SBA-15 were prepared with variable azide loadings of 0.03-0.7 mmol g(-1) (~2-50% of maximal surface coverage) through a direct synthesis, co-condensation approach. These materials are functionalized selectively with ethynylated organic moieties through a copper-catalyzed azide alkyne cycloaddition (CuAAC) or "click" reaction. Specific loading within a material can be regulated by either the azide loading or limiting the alkyne reagent relative to the azide loading. The immobilization of ferrocene, pyrene, tris(pyridylmethyl)amine (TPA), and iron porphyrin (FeTPP) demonstrates the robust nature and reproducibility of this two-step synthetic attachment strategy. Loading-sensitive pyrene fluorescence correlates with a theoretically random surface distribution, rather than a uniform one; site-isolation of tethered moieties ~15 Å in length occurs at loadings less than 0.02 mmol g(-1). The effect of surface loading on reactivity is observed in the oxygenation of SBA-15-[Cu(I)(TPA)]. SBA-15-[Mn(II)(TPA)]-catalyzed epoxidation exhibits a systematic dependence on surface loading. A comparison of homogeneous, site-isolated and site-dense complexes provides insight into catalyst speciation and ligand activity.

Hexagonally ordered mesoporous silica coined COK-12 was synthesized in a continuous process by combining streams of sodium silicate and citric acid/sodium citrate buffered solution of (ethylene oxide)(20)-(propylene oxide)(70)-(ethylene oxide)(20) triblock copolymer (Pluronic P123) from separate reservoirs. COK-12 precipitated spontaneously upon combining both streams at nearly neutral pH and ambient temperature. Stable intermediates of the COK-12 formation process could be prepared by limiting sodium silicate addition. Investigation of these intermediates using small-angle X-ray scattering revealed COK-12 formed via an assembly process departing from spherical uncharged core-shell P123-silica micelles. The sterical stabilization of these micelles decreased upon accumulation of silicate oligomers in their shell. Aggregation of the spherical micelles led to cylindrical micelles, which aligned and adopted the final hexagonal organization. This unprecedentedly fast formation of P6m ordered mesoporous silica was caused by two factors in the synthesis medium: the neutral pH favoring uncharged silicate oligomers and the high salt concentration promoting hydrophobic interactions with surfactant micelles leading to silica accumulation in the PEO shell. The easy continuous synthesis process is convenient for large-scale production. The platelet particle morphology with short and identical internal channels will be advantageous for many applications such as pore replication, nanotube or fiber growth, catalytic functionalization, drug delivery, film and sensor development, and in nano dyes as well as for investigation of pore diffusion phenomena.

Cage-type, two-dimensional (2D) cylindrical hexagonal (C), bicontinuous diamond (D), bicontinuous gyroid (G), and one-dimensional (1D) lamellar (L) structures of silica mesoporous crystals (SMCs) were obtained by using the anionic surfactant N-stearoyl-l-glutamic acid (C(18)GluA) as a template in the presence of the nonionic surfactant C(16)(EO)(10) (Brij-56). The mesostructures were controlled by the organic/inorganic interface curvature change induced by Brij-56. A synthesis-field diagram showed that the mesostructure changed in the sequence cage-type → C → intergrowth of C and D → intergrowth of C and G → D → G → L with increase of the amount of Brij-56. Mixed micelles were formed by the anionic and nonionic surfactants, the packing parameter g of which increased with increasing the addition amount of nonionic surfactant and the reaction temperature. The local g parameter was obtained from electron crystallography reconstruction results by calculating mean curvatures and Gaussian curvatures from the equi-electrostatic potential surface. The intergrowth of C and D and two kinds of intergrowth of C and G are also discussed.

There has always been a fascination with "impossible" compounds, ones that do not break any rules of chemical bonding or valence but whose structures are unstable and do not exist. This instability can usually be rationalized in terms of chemical or physical restrictions associated with valence electron shells, multiple bonding, oxidation states, catenation, and the inert pair effect. In the pursuit of these "impossible" materials, appropriate conditions have sometimes been found to overcome these instabilities and synthesize missing compounds, yet for others these tricks have yet to be uncovered and the materials remain elusive. In the scientifically and technologically important field of periodic mesoporous silicas (PMS), one such "impossible" material is periodic mesoporous hydridosilica (meso-HSiO(1.5)). It is the archetype of a completely interrupted silica open framework material: its pore walls are comprised of a three-connected three-dimensional network that should be so thermodynamically unstable that any mesopores present would immediately collapse upon removal of the mesopore template. In this study we show that meso-HSiO(1.5) can be synthesized by template-directed self-assembly of HSi(OEt)(3) under aqueous acid-catalyzed conditions and after template extraction remains stable to 300 °C. Above this temperature, bond redistribution reactions initiate a metamorphic transformation which eventually yields periodic mesoporous nanocrystalline silicon-silica, meso-ncSi/SiO(2), a nanocomposite material in which brightly photoluminescent silicon nanocrystallites are embedded within a silica matrix throughout the mesostructure. The integration of the properties of silicon nanocrystallinity with silica mesoporosity provides a wealth of new opportunities for emerging nanotechnologies., (© 2011 American Chemical Society)

Although the experimental study of spherical colloids has been extensive, similar studies on rodlike particles are rare because suitable model systems are scarcely available. To fulfill this need, we present the synthesis of monodisperse rodlike silica colloids with tunable dimensions. Rods were produced with diameters of 200 nm and greater and lengths up to 10 μm, resulting in aspect ratios from 1 to ∼25. The growth mechanism of these rods involves emulsion droplets inside which silica condensation takes place. Due to an anisotropic supply of reactants, the nucleus grows to one side only, resulting in rod formation. In concentrated dispersions, these rods self-assemble in liquid crystal phases, which can be studied quantitatively on the single particle level in three-dimensional real-space using confocal microscopy. Isotropic, paranematic, and smectic phases were observed for this system.

This paper uses the measure of hemolysis to evaluate the toxicity of nonporous and porous silica nanoparticles with varied sizes and investigates the effects of porous structure and integrity on the nanoparticle-cell interaction. The results show that both nonporous and porous silica cause red blood cell membrane damage in a concentration- and size-dependent manner. In the case of mesoporous silica nanoparticles, the size-dependent hemolysis effect is only present when the nanoparticles have long-range ordered porous structure, revealing that pore structure is critical in cell-nanoparticle interactions. Mesoporous silica nanoparticles show lower hemolytic activity than their nonporous counterparts of similar size, likely due to fewer silanol groups on the cell-contactable surface of the porous silica nanoparticles. The extent of hemolysis by mesoporous silica nanoparticles increases as the pore structure is compromised by mild aging in phosphate-buffered solutions, initiating mesopore collapse. The pore integrity of mesoporous silica nanoparticles is examined by TEM, XRD, N(2) adsorption-desorption isotherms, and quantification of dissolved silica. In these nanoparticles, pore stability is clearly an important factor in determining the hemolytic activity; further work demonstrates that nanoparticle-induced hemolysis can be eliminated by modifying the silanol surface with a poly(ethylene glycol) coating.

Highly versatile nanocomposite nanoparticles were synthesized by decorating the surface of mesoporous dye-doped silica nanoparticles with multiple magnetite nanocrystals. The superparamagnetic property of the magnetite nanocrystals enabled the nanoparticles to be used as a contrast agent in magnetic resonance (MR) imaging, and the dye molecule in the silica framework imparted optical imaging modality. Integrating a multitude of magnetite nanocrystals on the silica surface resulted in remarkable enhancement of MR signal due to the synergistic magnetism. An anticancer drug, doxorubicin (DOX), could be loaded in the pores and induced efficient cell death. In vivo passive targeting and accumulation of the nanoparticles at the tumor sites was confirmed by both T2 MR and fluorescence imaging. Furthermore, apoptotic morphology was clearly detected in tumor tissues of mice treated with DOX loaded nanocomposite nanoparticles, demonstrating that DOX was successfully delivered to the tumor sites and its anticancer activity was retained.

A pair of chiral bola-type enantiomers, ll-12PyBr and dd-12PyBr, was synthesized. They can cause physical gels in pure water. Sol-gel transcriptions were carried out to control mesoporous 1,4-phenylene-silica nanostructures and helicity using the organic self-assemblies of these amphiphiles as templates. Under acidic conditions, left-handed helical 1,4-phenylene-silica bundles were prepared using the self-assemblies of ll-12PyBr as templates. Additionally, right-handed helical silica and 1,4-phenylene-silica bundles were prepared using the self-assemblies of dd-12PyBr as templates. Under basic conditions, 1,4-phenylene-silica bundles were also obtained. However, it is hard to determine the handedness. For all of the 1,4-phenylene-silica bundles, it is interesting to find that the aromatic rings are packing in helix within the wall of the pore channels. Powder X-ray diffraction patterns indicated that the aromatic rings of 1,4-phenylene-silica bundles prepared under basic conditions showed a greater degree of order than those of 1,4-phenylene-silica bundles prepared under acidic conditions. Moreover, helical silica, 1,3-phenylene-silica, ethene-silica, and ethane-silica bundles were also prepared using the self-assemblies ll-12PyBr and dd-12PyBr as templates.

Hoogsteen-bonded tetrads and pentamers are formed by a large variety of organic molecules through H-donor and acceptor groups capable of inducing self-organization to form columnar and hexagonal mesophases. The biological importance of such macromolecular structures is exemplified by the assembly of guanosine-rich groups of telomere units and their implication in chromosomal replication. Folic acid is composed of a pterin group, chemically and structurally similar to guanine, conjugated to an l-glutamate moiety via a p-amino benzoic acid. Our aim has been to develop a delivery vehicle for folic acid and at the same time provide a novel synthetic route for ordered mesoporous materials without the use of amphiphilic surfactants. We present a new nonsurfactant route for the synthesis of highly ordered mesoporous materials, based on the supramolecular templating of stacked arrays of the tetramer-forming pterin groups of folic acid under a variety of synthetic conditions. This method leads to hexagonally ordered mesoporous structures with gyroid, spherical, and chiral morphologies with pores on the order of 25-30 A in diameter and surface areas above 1000 m(2)/g. More importantly circular dichroism studies reveal that the folate template possesses a chiral signature within the pores in the as-synthesized solid and that chirality is transferred from the folate template to the pore surface via the aminopropyl triethoxysilane costructure directing agent used in the supramolecular assembly. This novel templating approach for ordered mesoporous materials breaks the hegemony of surfactant micellar systems for the preparation of these exciting high surface area solids and opens new opportunities for structural control, design of pore geometry, and novel applications.

Mesoporous crystalline silica has attracted the attention of scientists due to its extraordinary functionalities. In particular, substantial progress has been made in the synthesis of mesoporous crystalline silica using biomimetic approaches under ambient conditions. However, the biomimetic synthesis of mesoporous amorphous silica has not been well studied so far. Here we show that amorphous silica can be synthesized in aqueous solution under ambient conditions via biological catalysis. The high purity amorphous silica is obtained as spicules (average diameter: 15.6 microm) that are cemented through junctions, thereby forming the skeleton of the freshwater sponge Cauxi. We discover that such amorphous spicules themselves contain mesopores. This opens a potential avenue to develop highly durable mesoporous membranes at room temperature. We also describe the macro- and microstructural features, the mechanism of biological precipitation, and the properties of the Cauxi skeleton.

The surface of monodisperse silica particles synthesized using the Stober process were coated with a thin layer of polystyrene. Surface charge groups were attached by a grafting polymerization of styrene sulfonate. The resulting highly charged monodisperse silica particles self-assemble into crystalline colloidal arrays (CCA) in deionized water. We polymerized hydroxyethyl methacrylate (HEMA) around the CCA to form a HEMA-polymerized crystalline colloidal array (PCCA). Hydrofluoric acid was utilized to etch out the silica particles to produce a three-dimensional periodic array of voids in the HEMA PCCA. The diffraction from the embedded CCA sensitively monitors the concentration of ethanol in water because the HEMA PCCA shows a large volume dependence on ethanol due to a decreased Flory-Huggins mixing parameter. Between pure water and 40% ethanol the diffraction shifts across the entire visible spectral region. We accurately modeled the dependence of the diffraction wavelength on ethanol concentration using Flory theory. We also fabricated a PCCA (which responds to pH changes in both low and high ionic strength solutions) by utilizing a second polymerization to incorporate carboxyl groups into the HEMA PCCA. We were also able to model the pH dependence of diffraction of the HEMA PCCA by using Flory theory. An unusual feature of the pH response is a hysteresis in response to titration to higher and lower pH. This hysteresis results from the formation of a Donnan potential at high pH which shifts the ionic equilibrium. The kinetics of equilibration is very slow due to the ultralow diffusion constant of protons in the carboxylated PCCA as predicted earlier by the Tanaka group.

Mesoporous silica with squared one-dimensional channels (KSW-2-type mesoporous silica), possessing a molecularly ordered framework arising from a starting layered polysilicate kanemite, was obtained through silylation of a surfactant (hexadecyltrimethylammonium, C16TMA)-containing mesostructured precursor with octoxytrichlorosilane (C8H17OSiCl3) and octylmethyldichlorosilane (C8H17(CH3)SiCl2). The presence of the molecular ordering in the silicate framework was confirmed by XRD and TEM. Octoxy groups grafted on KSW-2 can be eliminated by subsequent hydrolysis under very mild condition, and pure mesoporous silica was obtained with the retention of the kanemite-based framework. The framework is structurally stabilized by the attachment of additional SiO4 units to the framework, and the mesostructural ordering hardly changed under the presence of water vapor. A large number of silanol groups remained at the mesopore surfaces because C16TMA ions and octoxy groups can be removed without calcination. Octylmethylsilyl groups are regularly arranged at the mesopore surface due to the molecular ordering in the silicate framework. The molecularly ordered structural periodicity originating from kanemite is retained even after calcination at 550 degrees C, while that in the precursor without silylation disappeared. The synthetic strategy is quite useful for the design of the silicate framework of mesostructured and mesoporous materials with and without surface functional organic groups.

Water soluble alpha-helical polypeptides were used to prepare silica coated hexagonal single crystal platelets in concentrated solutions. To our knowledge, there is no other instance where polymer single crystals, typically formed under high dilution, can be grown in a bulk material. This unprecedented self-assembly process relies on complex cooperative interactions where silica condensation mediates the growth of polypeptide crystals, which in turn template silica overgrowth. The helices were also used to align samples giving monoliths composed of highly oriented layers of platelets. Overall, this procedure allows preparation of composites with good structural order and complexity via a simple biomimetic process.

Several studies have demonstrated the use of biomimetic approaches in the synthesis of a variety of inorganic materials. Poly-L-lysine (PLL) promotes the precipitation of silica from a silicic acid solution within minutes. The molecular weight of PLL was found to affect the morphology of the resulting silica precipitate. Larger-molecular weight PLL produced hexagonal silica platelets, whereas spherical silica particles were obtained using low-molecular weight PLL. Here we report on the polypeptide secondary-structure transition that occurs during the silicification reaction. The formation of the hexagonal silica platelets is attributed to the PLL helical chains that are formed in the presence of monosilicic acid and phosphate ions. Hexagonal PLL crystals can also serve as templates in directing the growth of the silica in a manner that generates a largely mesoporous silica phase that is oriented with respect to the protein crystal template.

Tubular structure of nanoparticles is highly attractive due to their structural attributes, such as the distinctive inner and outer surfaces, over conventional spherical nanoparticles. Inner voids can be used for capturing, concentrating, and releasing species ranging in size from large proteins to small molecules. Distinctive outer surfaces can be differentially functionalized with environment-friendly and/or probe molecules to a specific target. Magnetic particles have been extensively studied in the field of biomedical and biotechnological applications, including drug delivery, biosensors, chemical and biochemical separation and concentration of trace amounts of specific targets, and contrast enhancement in magnetic resonance imaging (MRI). Therefore, by combining the attractive tubular structure with magnetic property, the magnetic nanotube (MNT) can be an ideal candidate for the multifunctional nanomaterial toward biomedical applications, such as targeting drug delivery with MRI capability. Here, we successfully synthesized magnetic silica-iron oxide composite nanotubes and demonstrated the magnetic-field-assisted chemical and biochemical separations, immunobinding, and drug delivery.

The preparation, characterization, and preliminary biomedical application of various nitric oxide (NO)-releasing fumed silica particles (0.2-0.3 microm) are reported. The tiny NO-releasing particles are synthesized by first tethering alkylamines onto the surface of the silica using amine-containing silylation reagents. These amine groups are then converted to corresponding N-diazeniumdiolate groups via reaction with NO(g) at high pressure in the presence of methoxide bases (e.g., NaOMe). N-Diazeniumdiolate groups were found to form more readily with secondary amino nitrogens than primary amino nitrogens tethered to the silica. Different alkali metal cations of the methoxide bases, however, have little effect on the degree of N-diazeniumdiolate formation. The N-diazeniumdiolate moieties attached on the silica surface undergo a primarily proton-driven dissociation to NO under physiological conditions, with an "apparent" reaction order somewhat greater than 1 owing to local increases in pH at the surface of the particles as free amine groups are generated. The rates of N-diazeniumdiolate dissociation are further related to the parent amine structures and the pH of the soaking buffer. The N-diazeniumdiolate groups also undergo slow thermal dissociation to NO, with zero-order dissociation observed at both -15 and 23 degrees C. It is further shown that the resulting NO-releasing fumed silica particles can be embedded into polymer films to create coatings that are thromboresistant, via the release of NO at fluxes that mimic healthy endothelial cells (EC). For example a polyurethane coating containing 20 wt % of NO-releasing particles prepared with pendant hexane diamine structure (i.e., Sil-2N[6]-N(2)O(2)Na) is shown to exhibit improved surface thromboresistivity (compared to controls) when used to coat the inner walls of extracorporeal circuits (ECC) employed in a rabbit model for extracorporeal blood circulation.

An MCM-41 type mesoporous silica nanosphere-based (MSN) controlled-release delivery system has been synthesized and characterized using surface-derivatized cadmium sulfide (CdS) nanocrystals as chemically removable caps to encapsulate several pharmaceutical drug molecules and neurotransmitters inside the organically functionalized MSN mesoporous framework. We studied the stimuli-responsive release profiles of vancomycin- and adenosine triphosphate (ATP)-loaded MSN delivery systems by using disulfide bond-reducing molecules, such as dithiothreitol (DTT) and mercaptoethanol (ME), as release triggers. The biocompatibility and delivery efficiency of the MSN system with neuroglial cells (astrocytes) in vitro were demonstrated. In contrast to many current delivery systems, the molecules of interest were encapsulated inside the porous framework of the MSN not by adsorption or sol-gel types of entrapment but by capping the openings of the mesoporous channels with size-defined CdS nanoparticles to physically block the drugs/neurotransmitters of certain sizes from leaching out. We envision that this new MSN system could play a significant role in developing new generations of site-selective, controlled-release delivery nanodevices.

Silica molecular sieves with uniform pores on the borderline between micropore (diameter <2 nm) and mesopore (from 2 to 50 nm) ranges were synthesized by a novel method using judiciously chosen mixtures of short double-chain alkylammonium surfactants. These silicas were characterized using X-ray diffraction (XRD), thermogravimetry, and nitrogen and argon adsorption. The calcined materials exhibited either 2-dimensional (2-D) hexagonal or disordered structures with XRD interplanar spacing from 2.51 to 2.93 nm, including the value of as small as 2.69 nm for highly ordered 2-D hexagonal silica. The dependence of the pore size and surfactant content on the surfactant chain length provided strong evidence for supramolecular templating being operative in the formation of small-pore silicas, even for the surfactant chain length of six carbon atoms. Both hexagonally ordered and disordered calcined samples were shown to exhibit narrow pore size distributions with maxima in the range from 1.96 to 2.61 nm (reliably evaluated on the basis of the unit-cell dimension and pore volume for 2-D hexagonal materials, and calculated using a properly calibrated procedure), tailored by the surfactant chain length. The samples exhibited primary pore volumes from 0.28 to 0.54 cm(3) g(-1) and specific surface areas from 730 to 930 m(2) g(-1). Because of their small yet uniform pore size and large specific surface area, the silicas reported herein promise to be useful in applications in adsorption and catalysis. Adsorption studies of these materials provided a unique new insight into the pore-filling mechanism for small-pore materials. Moreover, the approach proposed herein is expected to facilitate the synthesis of not only small-pore silicas but also materials with other framework compositions, thus largely contributing to bridging the gap in attainable pore sizes between micropore and mesopore ranges.