Mesophase structure-mechanical and ionic transport correlations in extended amphiphilic dendrons

We have studied the self-assembly of amphiphilic dendrons extended with linear polyethylene oxide (PEO) chains and their ion complexes. Keeping the dendron core and linear PEO chain compatible allows for the combination of dendritic core-shell and conventional blockcopolymer characteristics for complex mesophase behavior. An unexpected sequence of crystalline lamellar, cubic micellar (Pm3n), hexagonal columnar, continuous cubic (Ia3d), and lamellar mesophases is observed. Multiple phase behavior within single compounds allows for the study of charge transport and mechanical property correlations as a function of structure. The results suggest an advanced molecular design concept for the next generation of nanostructured materials in applications involving charge transport.     

Ordered mesoporous materials from metal nanoparticle-block copolymer self-assembly

The synthesis of ordered mesoporous metal composites and ordered mesoporous metals is a challenge because metals have high surface energies that favor low surface areas. We present results from the self-assembly of block copolymers with ligand-stabilized platinum nanoparticles, leading to lamellar CCM-Pt-4 and inverse hexagonal (CCM-Pt-6) hybrid mesostructures with high nanoparticle loadings. Pyrolysis of the CCM-Pt-6 hybrid produces an ordered mesoporous platinum-carbon nanocomposite with open and large pores (>/=10 nanometers). Removal of the carbon leads to ordered porous platinum mesostructures. The platinum-carbon nanocomposite has very high electrical conductivity (400 siemens per centimeter) for an ordered mesoporous material fabricated from block copolymer self-assembly.     

Hierarchical self-assembly of F-actin and cationic lipid complexes: stacked three-layer tubule networks

We describe a distinct type of spontaneous hierarchical self-assembly of cytoskeletal filamentous actin (F-actin), a highly charged polyelectrolyte, and cationic lipid membranes. On the mesoscopic length scale, confocal microscopy reveals ribbonlike tubule structures that connect to form a network of tubules on the macroscopic scale (more than 100 micrometers). Within the tubules, on the 0.5- to 50-nanometer length scale, x-ray diffraction reveals an unusual structure consisting of osmotically swollen stacks of composite membranes with no direct analog in simple amphiphilic systems. The composite membrane is composed of three layers, a lipid bilayer sandwiched between two layers of actin, and is reminiscent of multilayered bacterial cell walls that exist far from equilibrium. Electron microscopy reveals that the actin layer consists of laterally locked F-actin filaments forming an anisotropic two-dimensional tethered crystal that appears to be the origin of the tubule formation.     

Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures

A model is presented to explain the formation and morphologies of surfactant-silicate mesostructures. Three processes are identified: multidentate binding of silicate oligomers to the cationic surfactant, preferential silicate polymerization in the interface region, and charge density matching between the surfactant and the silicate. The model explains present experimental data, including the transformation between lamellar and hexagonal mesophases, and provides a guide for predicting conditions that favor the formation of lamellar, hexagonal, or cubic mesostructures. Model Q(230) proposed by Mariani and his co-workers satisfactorily fits the x-ray data collected on the cubic mesostructure material. This model suggests that the silicate polymer forms a unique infinite silicate sheet sitting on the gyroid minimal surface and separating the surfactant molecules into two disconnected volumes.     

Molecular borromean rings

The realization of the Borromean link in a wholly synthetic molecular form is reported. The self-assembly of this link, which is topologically achiral, from 18 components by the template-directed formation of 12 imine and 30 dative bonds, associated with the coordination of three interlocked macrocycles, each tetranucleating and decadentate overall, to a total of six zinc(II) ions, is near quantitative. Three macrocycles present diagonally in pairs, six exo-bidentate bipyridyl and six endo-diiminopyridyl ligands to the six zinc(II) ions. The use, in concert, of coordination, supramolecular, and dynamic covalent chemistry allowed the highly efficient construction, by multiple cooperative self-assembly processes, of a nanoscale dodecacation with an approximate diameter of 2.5 nanometers and an inner chamber of volume 250 A(3), lined with 12 oxygen atoms.     

Self-assembly of disk-shaped molecules to coiled-coil aggregates with tunable helicity

A disk-shaped molecule with chiral tails is shown to form long fibers of molecular diameter and micrometer length by self-assembly in chloroform. The molecules are derived from crown ethers and contain a phthalocyanine ring. In the fibers, they have a clockwise, staggered orientation that leads to an overall right-handed helical structure. These structures, in turn, self-assemble to form coiled-coil aggregates with left-handed helicity. Addition of potassium ions to the fibers leaves their structure intact but blocks the transfer of the chirality from the tails to the cores, leading to loss of the helicity of the fibers. These tunable chiral materials have potential in optoelectronic applications and as components in sensor devices.     

Surfactant-mediated two-dimensional crystallization of colloidal crystals

Colloidal particles can form unexpected two-dimensional ordered colloidal crystals when they interact with surfactants of the opposite charge. Coulomb interactions lead to self-limited adsorption of the particles on the surface of vesicles formed by the surfactants. The adsorbed particles form ordered but fluid rafts on the vesicle surfaces, and these ultimately form robust two-dimensional crystals. This use of attractive Coulomb interaction between colloidal particles and surfactant structures offers a potential new route to self-assembly of ordered colloidal structures.     

Mode of Chemical-Degradation of s-Triazines by Montmorillonite

Chemical hydrolysis of the s-triazines after interaction with less than 2-micron (equivalent spherical diameter) montmorillonite clay occurs as a result of protonation at the colloidal surface; protonation occurs even when the exchange sites are occupied by metallic cations. The adsorbed hydrolytic degradation product is not the hydroxy analog, but it is predominantly the keto form of the protonated hydroxy species. This cationic form is held tightly by the clay which may restrict vertical movement and entrance into groundwater. Protonation of the hydroxy analog occurs on the heterocyclic ring nitrogen.     

Colloidosomes: selectively permeable capsules composed of colloidal particles

We present an approach to fabricate solid capsules with precise control of size, permeability, mechanical strength, and compatibility. The capsules are fabricated by the self-assembly of colloidal particles onto the interface of emulsion droplets. After the particles are locked together to form elastic shells, the emulsion droplets are transferred to a fresh continuous-phase fluid that is the same as that inside the droplets. The resultant structures, which we call "colloidosomes," are hollow, elastic shells whose permeability and elasticity can be precisely controlled. The generality and robustness of these structures and their potential for cellular immunoisolation are demonstrated by the use of a variety of solvents, particles, and contents.     

Non-centrosymmetric cylindrical micelles by unidirectional growth

Although solution self-assembly of block copolymers (BCPs) represents one of the most promising approaches to the creation of nanoparticles from soft matter, the formation of non-centrosymmetric nanostructures with shape anisotropy remains a major challenge. Through a combination of crystallization-driven self-assembly of crystalline-coil BCPs in solution and selective micelle corona cross-linking, we have created short (about 130 nanometers), monodisperse cylindrical seed micelles that grow unidirectionally. These nanostructures grow to form long, non-centrosymmetric cylindrical A-B and A-B-C block co-micelles upon the addition of further BCPs. We also illustrate the formation of amphiphilic cylindrical A-B-C block co-micelles, which spontaneously self-assemble into hierarchical star-shaped supermicelle architectures with a diameter of about 3 micrometers. The method described enables the rational creation of non-centrosymmetric, high aspect ratio, colloidally stable core-shell nanoparticles in a manner that until now has been restricted to the biological domain.     

Dephosphorylation of the calcium pump coupled to counterion occlusion

P-type ATPases extract energy by hydrolysis of adenosine triphosphate (ATP) in two steps, formation and breakdown of a covalent phosphoenzyme intermediate. This process drives active transport and countertransport of the cation pumps. We have determined the crystal structure of rabbit sarcoplasmic reticulum Ca2+ adenosine triphosphatase in complex with aluminum fluoride, which mimics the transition state of hydrolysis of the counterion-bound (protonated) phosphoenzyme. On the basis of structural analysis and biochemical data, we find this form to represent an occluded state of the proton counterions. Hydrolysis is catalyzed by the conserved Thr-Gly-Glu-Ser motif, and it exploits an associative nucleophilic reaction mechanism of the same type as phosphoryl transfer from ATP. On this basis, we propose a general mechanism of occluded transition states of Ca2+ transport and H+ countertransport coupled to phosphorylation and dephosphorylation, respectively.     

The role and implications of bassanite as a stable precursor phase to gypsum precipitation

Calcium sulfate minerals such as gypsum play important roles in natural and industrial processes, but their precipitation mechanisms remain largely unexplored. We used time-resolved sample quenching and high-resolution microscopy to demonstrate that gypsum forms via a three-stage process: (i) homogeneous precipitation of nanocrystalline hemihydrate bassanite below its predicted solubility, (ii) self-assembly of bassanite into elongated aggregates co-oriented along their c axis, and (iii) transformation into dihydrate gypsum. These findings indicate that a stable nanocrystalline precursor phase can form below its bulk solubility and that in the CaSO(4) system, the self-assembly of nanoparticles plays a crucial role. Understanding why bassanite forms prior to gypsum can lead to more efficient anti-scaling strategies for water desalination and may help to explain the persistence of CaSO(4) phases in regions of low water activity on Mars.     

Nanoassembly of a fractal polymer: a molecular "Sierpinski hexagonal gasket"

Mathematics and art converge in the fractal forms that also abound in nature. We used molecular self-assembly to create a synthetic, nanometer-scale, Sierpinski hexagonal gasket. This nondendritic, perfectly self-similar fractal macromolecule is composed of bis-terpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.     

Theory of spontaneous vesicle formation in surfactant mixtures

The curvature elastic energy of bilayer vesicles formed by a mixture of two surfactants, which individually form either micelles or lamellar bilayer phases is described theoretically. In the limit of large bending elastic modulus K being much greater than the temperature T, the free energy is minimized by vesicles with different concentrations of the two surfactants in each monolayer of the bilayer. Vesicles are more stable than lameliar structures only when interactions or complexing of the two surfactants is taken into account.     

Conversion of supramolecular clusters to macromolecular objects

In a reaction proceeding within a nanoscopic volume, supramolecular clusters were transformed to polymer objects while retaining their shape and size. Spatial isolation of the cross-linkable blocks of oligobutadiene that were involved in this stitching reaction was achieved by self-assembly of the molecules that made up the clusters. Thermal activation of cross-linking yielded macromolecules (molecular weight of 70,000) with a narrow size distribution that was similar to that of the supramolecular clusters. The macromolecules obtained have an anisotropic shape (2 nanometers by 8 nanometers), as determined by electron microscopy and small-angle x-ray scattering, and form materials that exhibit a liquid crystalline state.     

Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.     

Orthopyroxene exsolution in augite: a two-step, diffusion-transformation process

Orthopyroxene lamellae exsolved from augite on (100) are shown to grow by a two-step process involving (i) the diffusion of calcium and (magnesium, iron) to form clinohypersthene and (ii) the inversion of clinohypersthene to orthopyroxene, probably by glide twinning. If complete inversion is prevented by cooling or steep concentration gradients, the two-step process produces orthopyroxene with narrow margins of clinohypersthene. Measured elemental concentration gradients at (100) lamellar interfaces support this mechanism.     

Ordering of ruthenium cluster carbonyls in mesoporous silica

The anionic ruthenium cluster carbonylates [Ru6C(CO)16]2- or [H2Ru10(CO)25]2- interspersed with bis(triphenylphosphino)iminium counterions (PPN+) are incorporated from solution into the pores of MCM-41 mesoporous silica (3 nanometers in diameter), where they form tightly packed arrays. These arrays were shown by high-resolution transmission electron microscopy, Fourier transform optical diffraction, and computer simulations to be well ordered both along and perpendicular to the axis of the cylindrical pores. In their denuded state produced by gentle thermolysis, the cluster carbonylates yield nanoparticles of ruthenium that are less well ordered than their assimilated precursors but show good activity as hydrogenation catalysts for hexene and cyclooctene. In both their as-prepared and denuded states, these encapsulated clusters are likely to exhibit interesting electronic and other properties.     

Ultraviolet reflection of a male butterfly: interference color caused by thin-layer elaboration of wing scales

Males of the butterfly Eurema lisa, like many other members of the family Pieridae, reflect ultraviolet light. The color is structural rather than pigmentary, and originates from optical interference in a microscopic lamellar system associated with ridges on the outer scales of the wing. The dimensions and angular orientation of the lamellar system conform to predictions based on physical measurement of the spectral characteristics, including "color shifts" with varying angles of incidence, of the reflected ultraviolet light. The female lacks such scales and is consequently nonreflectant. The ultraviolet dimorphism supposedly serves as the basis for sexual recognition in courtship.     

pH对大菱鲆幼鱼平均日增重及鳃显微结构的影响

研究不同pH对大菱鲆（Scophthalmusmaximus）幼鱼平均日增重及鳃显微结构的影响。结果显示：大菱鲆平均日增重随pH升高而降低,pH8．3和8．8组平均日增重显著低于其他处理组（P〈0．05）。pH6．3时鳃小片上皮细胞角质化较为严重;pH6．8和7．8时鳃上皮细胞未见明显变化;pH8.3时上皮细胞出现脱离,部分出现角质化;pH8．8时上皮细胞角质化较为严重。结果表明,水环境pH在6．8～7．8范围内比较适宜于大菱鲆幼鱼的健康生长。