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.     

Helical superstructures from charged Poly(styrene)-Poly(isocyanodipeptide) block copolymers

Amphiphilic block copolymers containing a poly(styrene) tail and a charged helical poly(isocyanide) headgroup derived from isocyano-L-alanine-L-alanine and isocyano-L-alanine-L-histidine were prepared. Analogous to low-molecular mass surfactants, these block copolymers self-assembled in aqueous systems to form micelles, vesicles, and bilayer aggregates. The morphology of these aggregates can be controlled by variation of the length of the poly(isocyanide) block, the pH, and the anion-headgroup interactions. The chirality of the macromolecules results in the formation of helical superstructures that have a helical sense opposite to that of the constituent block copolymers. The great variety of morphologies displayed by these block copolymers and the fact that they are easily accessible from poly(styrene) and different types of peptides open new opportunities for applications in the fields of life and materials sciences.     

Hierarchically ordered oxides

Porous silica, niobia, and titania with three-dimensional structures patterned over multiple length scales were prepared by combining micromolding, polystyrene sphere templating, and cooperative assembly of inorganic sol-gel species with amphiphilic triblock copolymers. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from 10 nanometers to several micrometers. The respective ordered structures can be independently modified by choosing different mold patterns, latex spheres, and block copolymers. The examples presented demonstrate the compositional and structural diversities that are possible with this simple approach.     

Self-assembly of ordered microporous materials from rod-coil block copolymers

Rod-coil diblock copolymers in a selective solvent for the coil-like polymer self-organize into hollow spherical micelles having diameters of a few micrometers. Long-range, close-packed self-ordering of the micelles produced highly iridescent periodic microporous materials. Solution-cast micellar films consisted of multilayers of hexagonally ordered arrays of spherical holes whose diameter, periodicity, and wall thickness depended on copolymer molecular weight and composition. Addition of fullerenes into the copolymer solutions also regulated the microstructure and optical properties of the microporous films. These results demonstrate the potential of hierarchical self-assembly of macromolecular components for engineering complex two- and three-dimensional periodic and functional mesostructures.     

On the origins of morphological complexity in block copolymer surfactants

Amphiphilic compounds such as lipids and surfactants are fundamental building blocks of soft matter. We describe experiments with poly(1,2-butadiene-b-ethylene oxide) (PB-PEO) diblock copolymers, which form Y-junctions and three-dimensional networks in water at weight fractions of PEOintermediate to those associated with vesicle and wormlike micelle morphologies. Fragmentation of the network produces a nonergodic array of complex reticulated particles that have been imaged by cryogenic transmission electron microscopy. Data obtained with two sets of PB-PEOcompounds indicate that this type of self-assembly appears above a critical molecular weight. These block copolymers represent versatile amphiphiles, mimicking certain low molecular weight three-component (surfactant/water/oil) microemulsions, without addition of a separate hydrophobe.     

Self-assembled aggregates of rod-coil block copolymers and their solubilization and encapsulation of fullerenes

Amphiphilic poly(phenylquinoline)-block-polystyrene rod-coil diblock copolymers were observed to self-organize into robust, micrometer-scale, spherical, vesicular, cylindrical, and lamellar aggregates from solution. These diverse aggregate morphologies were seen at each composition, but their size scale decreased with a decreasing fraction of the rigid-rod block. Compared to coil-coil block copolymer micelles, the present aggregates are larger by about two orders of magnitude and have aggregation numbers of over 10(8). The spherical and cylindrical aggregates have large hollow cavities. Only spherical aggregates with aggregation numbers in excess of 10(9) were formed in the presence of fullerenes (C60, C70) in solution, resulting in the solubilization and encapsulation of over 10(10) fullerene molecules per aggregate.     

Self-Assembled Smectic Phases in Rod-Coil Block Copolymers

Rod-coil block copolymers are self-assembling polymers that combine the physics of orientational ordering of rodlike polymers and the microphase separation of coil-coil block copolymers. Several new solid-state morphologies were observed in a series of anionically synthesized model poly(hexyl isocyanate-b-styrene) rod-coil diblock copolymers examined by transmission electron microscopy and selected-area electron diffraction. The rod-coils formed smectic C-like and O-like morphologies with domain sizes ranging from tens of nanometers to almost 1 micrometer. Both structural and orientational changes were found for increasing rod volume fractions. In addition, some morphologies exhibited spontaneous long-range orientational order over many tens of micrometers.     

Oil-Water Interface Templating of Mesoporous Macroscale Structures

Ordered mesostructured porous silicas that are also macroscopically structured were created by control of the interface on two different length scales simultaneously. Micellar arrays controlled the nanometer-scale assembly, and at the static boundary between an aqueous phase and an organic phase, control was achieved on the micrometer to centimeter scale. Acid-prepared mesostructures of silica were made with the p6, Pm3n, and the P63/mmc structures in the form of porous fibers 50 to 1000 micrometers in length, hollow spheres with diameters of 1 to 100 micrometers, and thin sheets up to 10 centimeters in diameter and about 10 to 500 micrometers in thickness. These results might have implications for technical applications, such as slow drug-release systems or membranes, and in biomineralization, where many processes are also interface-controlled.     

Chain length recognition: core-shell supramolecular assembly from oppositely charged block copolymers

Molecular recognition based on length was found to occur between oppositely charged pairs of flexible and randomly coiled block copolymers in an aqueous milieu. Matched pairs with the same block lengths of polyanions and polycations exclusively formed even in mixtures with different block lengths. These assemblies of the charged segments with matched chain lengths then formed larger core-shell-type supramolecular assemblies with an extremely narrow size distribution due to the strict phase separation between core- and shell-forming segments.     

Design of Nonionic Surfactants for Supercritical Carbon Dioxide

Interfacially active block copolymer amphiphiles have been synthesized and their self-assembly into micelles in supercritical carbon dioxide (CO2) has been demonstrated with small-angle neutron scattering (SANS). These materials establish the design criteria for molecularly engineered surfactants that can stabilize and disperse otherwise insoluble matter into a CO2 continuous phase. Polystyrene-b-poly(1,1-dihydroperfluorooctyl acrylate) copolymers self-assembled into polydisperse core-shell-type micelles as a result of the disparate solubility characteristics of the different block segments in CO2. These nonionic surfactants for CO2 were shown by SANS to be capable of emulsifying up to 20 percent by weight of a CO2-insoluble hydrocarbon into CO2. This result demonstrates the efficacy of surfactant-modified CO2 in reducing the large volumes of organic and halogenated solvent waste streams released into our environment by solvent-intensive manufacturing and process industries.     

Cylindrical block copolymer micelles and co-micelles of controlled length and architecture

Block copolymers consist of two or more chemically different polymers connected by covalent linkages. In solution, repulsion between the blocks leads to a variety of morphologies, which are thermodynamically driven. Polyferrocenyldimethylsilane block copolymers show an unusual propensity to forming cylindrical micelles in solution. We found that the micelle structure grows epitaxially through the addition of more polymer, producing micelles with a narrow size dispersity, in a process analogous to the growth of living polymer. By adding a different block copolymer, we could form co-micelles. We were also able to selectively functionalize different parts of the micelle. Potential applications for these materials include their use in lithographic etch resists, in redox-active templates, and as catalytically active metal nanoparticle precursors.     

Multiple Morphologies of "Crew-Cut" Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers

The observation by transmission electron microscopy of six different stable aggregate morphologies is reported for the same family of highly asymmetric polystyrene-poly-(acrylic acid) block copolymers prepared in a low molecular weight solvent system. Four of the morphologies consist of spheres, rods, lamellae, and vesicles in aqueous solution, whereas the fifth consists of simple reverse micelle-like aggregates. The sixth consists of up to micrometer-size spheres in aqueous solution that have hydrophilic surfaces and are filled with the reverse micelle-like aggregates. In addition, a needle-like solid, which is highly birefringent, is obtained on drying of aqueous solutions of the spherical micelles. This range of morphologies is believed to be unprecedented for a block copolymer system.     

玉米新品种宁单11号套种密度栽培技术研究

[目的]研究宁单11号的优质高效栽培技术,为该品种的大面积推广提供理论依据。[方法]在玉米和小麦套种模式下,采用单因子随机区组设计,设5个密度处理:45 0005、2 5006、0 0006、7 500和75 000株/hm2,3次重复。采用方差分析、相关分析等方法研究玉米新品种宁单11号套种密度与产量、空秆率、穗粒数、千粒重和植株性状的关系。[结果]宁单11号小区产量与株高、穗位高、倒伏率、秃尖长呈负相关,与穗长、行粒数、百粒重呈正相关。宁单11号随着套种密度的增加,株高和穗位高不断增高,抗倒能力下降,秃尖长增加,穗粒数和千粒重降低。[结论]在套种模式下,宁单11号在栽培密度在52 500~60 000株/hm2,可取得最高的产量。     

牙鲆形态性状对体重的影响效果分析

跟踪测定2032尾牙鲆5月龄与8月龄的体重、全长、体长、头长、吻长、体高、尾柄长、尾柄高8个性状,采用相关分析和通径分析方法,剔除了与体长有共线性的全长,计算了以形态性状为自变量对体重作依变量的相关系数、通径系数和决定系数,定量地分析了形态特征对体重的影响效果。结果表明,牙鲆7个形态性状与体重的相关系数均达到极显著水平（P〈0．01）;体长、体高、尾柄高是直接影响体重的重要指标,头长、吻长、尾柄长对体重直接作用相对较小;决定系数分析结果与通径系数分析结果变化趋势基本相同;不同月龄牙鲆多元分析结果有所差异;最后建立了体长、体高、尾柄高估计体重的多元回归方程,为牙鲆选择育种提供理论依据。     

Particle-stabilized defect gel in cholesteric liquid crystals

Dispersions of colloidal particles in cholesteric liquid crystals form an unusual solid by stabilizing a network of linear defects under tension in the ideal layered structure of the cholesteric. The large length scales of the cholesteric liquid crystals allowed direct observation of the network structure, and its properties were correlated with rheological measurements of elasticity. This system serves as a model for a class of solids formed when particles are mixed with layered materials such as thermotropic and lyotropic smectic liquid crystals and block copolymers.     

Discovery of a Frank-Kasper sigma phase in sphere-forming block copolymer melts

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma (σ) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the σ phase in undiluted linear block copolymers (and certain branched dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.     

晋南盆地夏播玉米种植密度对产量及其相关性状变异系数的影响

为确定‘郑单958’玉米品种在晋南盆地夏播的合理种植密度,充分发挥该品种的增产效能,在山西临汾采用随机区组设计方法研究了种植密度对产量及其相关性状变异系数的影响。结果表明：在降雨正常年份,籽粒产量、千粒重、穗长、穗粗和单稳重在不同种植密度间存在差异,而出粒率、稳行数和收获指数不存在差异;种植密度对相关性状的变异系数影响序列为单稳重〉籽粒产量〉千粒重〉穗长〉穗粗〉穗行数〉出粒率〉收获指数;穗长、穗粗和穗轴重对单穗重（籽粒）的贡献大小为：穗长〉穗粗〉穗轴重。晋南盆地夏播玉米增加种植密度可显著提高籽粒产量,其籽粒产量是随干物质积累的增加而协同提高,对收获指数性状影响较小。该项研究为晋南盆地夏播玉米增加种植密度提供了理论和技术支撑。     

Block copolymer assembly via kinetic control

Block copolymers consist of two or more chemically different polymer segments, or blocks, connected by a covalent linkage. In solution, amphiphilic blocks can self-assemble as a result of energetic repulsion effects between blocks. The degree of repulsion, the lengths of the block segments, and the selectivity of the solvent primarily control the resultant assembled morphology. In an ideal situation, one would like to be able to alter the morphology that forms without having to change the chemistry of the block copolymer. Through the kinetic manipulation of charged, amphiphilic block copolymers in solution, we are able to generate different nanoscale structures with simple block copolymer chemistry. The technique relies on divalent organic counter ions and solvent mixtures to drive the organization of the block copolymers down specific pathways into complex one-dimensional structures. Block copolymers are increasingly used as templating materials; thus, the ability to control the formation of specific patterns and structures is of growing interest and applicability.     

Density multiplication and improved lithography by directed block copolymer assembly

Self-assembling materials spontaneously form structures at length scales of interest in nanotechnology. In the particular case of block copolymers, the thermodynamic driving forces for self-assembly are small, and low-energy defects can get easily trapped. We directed the assembly of defect-free arrays of isolated block copolymer domains at densities up to 1 terabit per square inch on chemically patterned surfaces. In comparing the assembled structures to the chemical pattern, the density is increased by a factor of four, the size is reduced by a factor of two, and the dimensional uniformity is vastly improved.     

玉米主要穗部性状的变异及相关性分析

为了明确玉米主要穗部性状的遗传变异规律,分析重要穗部性状间的相关性。以组合HN4*QN17 自交衍生形成的包括287 个家系的F2：3群体及其相应的亲本作为试验材料,按照随机区组排列进行田间试验。应用Excel2003 和DPS2000 对9 个主要穗部性状数据资料进行变异特性和相关性分析。结果表明,穗部性状呈双向超亲分离,9个穗部性状变异系数的大小两试验点（海南三亚和山东青岛）具有较好一致性,性状变异系数的大小顺序为秃尖长>穗粒重>行粒数>穗长>百粒重>穗行数>穗轴粗>穗粗>出籽率;除秃尖长外,穗粒重与其他7个性状均达到极显著的正相关关系,穗粒重与各性状的相关性大小顺序依次为行粒数>穗长>穗粗>百粒重>穗轴粗>出籽率>穗行数。说明秃尖长、穗粒重、行粒数、尧穗长性状变异系数大,在分离世代中有较广泛的选择空间;秃尖长与穗长、穗轴粗与穗粗性状间呈显著正相关性,在育种实践中同步改良这些性状有一定难度;穗行数与行粒数、穗行数与穗粗性状间的显著正相关性,在育种中同步提高这些有利性状是可行的。穗部性状间的变异规律和关联性可为该组合二环系选育中性状的取舍提供一定理论参考。