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.     

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.     

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.     

Toroidal triblock copolymer assemblies

A stable phase of toroidal, or ringlike, supramolecular assemblies was formed by combining dilute solution characteristics critical for both bundling of like-charged biopolymers and block copolymer micelle formation. The key to toroid versus classic cylinder micelle formation is the interaction of the negatively charged hydrophilic block of an amphiphilic triblock copolymer with a positively charged divalent organic counterion. This produces a self-attraction of cylindrical micelles that leads to toroid formation, a mechanism akin to the toroidal bundling of semiflexible charged biopolymers such as DNA. The toroids can be kinetically trapped or chemically cross-linked. Insight into the mechanism of toroid formation can be gained by observation of intermediate structures kinetically trapped during film casting.     

Micellar nanocontainers distribute to defined cytoplasmic organelles

Block copolymer micelles are water-soluble biocompatible nanocontainers with great potential for delivering hydrophobic drugs. An understanding of their cellular distribution is essential to achieving selective delivery of drugs at the subcellular level. Triple-labeling confocal microscopy in live cells revealed the localization of micelles in several cytoplasmic organelles, including mitochondria, but not in the nucleus. Moreover, micelles change the cellular distribution of and increase the amount of the agent delivered to the cells. These micelles may thus be worth exploring for their potential to selectively deliver drugs to specified subcellular targets.     

Mesoporous silicates prepared using preorganized templates in supercritical fluids

Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.     

Giant wormlike rubber micelles

A low molecular weight poly(ethyleneoxide)-poly(butadiene) (PEO-PB) diblock copolymer containing 50 weight percent PEO forms gigantic wormlike micelles at low concentrations (<5 percent by weight) in water. Subsequent generation of free radicals with a conventional water-based redox reaction leads to chemical cross-linking of the PB cores without disruption of the cylindrical morphology, as evidenced by cryotransmission electron microscopy and small-angle neutron scattering experiments. These wormlike rubber micelles exhibit unusual viscoelastic properties in water.     

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.     

Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields

Local control of the domain orientation in diblock copolymer thin films can be obtained by the application of electric fields on micrometer-length scales. Thin films of an asymmetric polystyrene-polymethylmethacrylate diblock copolymer, with cylindrical polymethylmethacrylate microdomains, were spin-coated onto substrates previously patterned with planar electrodes. The substrates, 100-nanometer-thick silicon nitride membranes, allow direct observation of the electrodes and the copolymer domain structure by transmission electron microscopy. The cylinders aligned parallel to the electric field lines for fields exceeding 30 kilovolts per centimeter, after annealing at 250°C in an inert atmosphere for 24 hours. This technique could find application in nanostructure fabrication.     

Phospholipid nonwoven electrospun membranes

Nonwoven fibrous membranes were formed from electrospinning lecithin solutions in a single processing step. As the concentration of lecithin increased, the micellar morphology evolved from spherical to cylindrical, and at higher concentrations the cylindrical micelles overlapped and entangled in a fashion similar to polymers in semi-dilute or concentrated solutions. At concentrations above the onset of entanglements of the wormlike micelles, electrospun fibers were fabricated with diameters on the order of 1 to 5 micrometers. The electrospun phospholipid fibers offer the potential for direct fabrication of biologically based, high-surface-area membranes without the use of multiple synthetic steps, complicated electrospinning designs, or postprocessing surface treatments.     

Spreading of liquids on highly curved surfaces

Because of surface tension, liquid films coating fibers or the insides of capillary tubes are usually unstable and break up into a periodic array of droplets. However, if these films are very thin (of thickness in the range of tens of angstroms), they can be stabilized by long-range van der Waals forces. A simple method for making such wetting films consists of slowly drawing the fiber out of a bath of liquid; the thickness of the film is then measured using a method based on gas chromatography. If these liquid films are thick, and are forced to flow, they may then not break up: the instability becomes "saturated."     

Graphoepitaxy of self-assembled block copolymers on two-dimensional periodic patterned templates

Self-assembling materials are the building blocks of bottom-up nanofabrication processes, but they need to be templated to impose long-range order and eliminate defects. In this work, the self-assembly of a thin film of a spherical-morphology block copolymer is templated using an array of nanoscale topographical elements that act as surrogates for the minority domains of the block copolymer. The orientation and periodicity of the resulting array of spherical microdomains are governed by the commensurability between the block copolymer period and the template period and is accurately described by a free-energy model. This method, which forms high-spatial-frequency arrays using a lower-spatial-frequency template, will be useful in nanolithography applications such as the formation of high-density microelectronic structures.     

Synthesis of reverse osmosis membranes by plasma polymerization of allylamine

The polymerization of allylamine in a radio-frequency electrodeless plasma to form thin polymer films on microporous filter media provides very effective dry composite membranes for reverse osmosis. Salt and urea rejections as high as 98 percent and 46 percent, respectively, have been achieved from a solution containing 10 grams of sodium chloride per liter and 10 grams of urea per liter. The plasma conditions and polymerization technique are discussed.     

Oriented 2D covalent organic framework thin films on single-layer graphene

Covalent organic frameworks (COFs), in which molecular building blocks form robust microporous networks, are usually synthesized as insoluble and unprocessable powders. We have grown two-dimensional (2D) COF films on single-layer graphene (SLG) under operationally simple solvothermal conditions. The layered films stack normal to the SLG surface and show improved crystallinity compared with COF powders. We used SLG surfaces supported on copper, silicon carbide, and transparent fused silica (SiO(2)) substrates, enabling optical spectroscopy of COFs in transmission mode. Three chemically distinct COF films grown on SLG exhibit similar vertical alignment and long-range order, and two of these are of interest for organic electronic devices for which thin-film formation is a prerequisite for characterizing their optoelectronic properties.     

Simulating the self-assembly of gemini (dimeric) surfactants

The morphologies and dynamics of aggregates formed by surfactant molecules are known to influence strongly performance properties spanning biology, household cleaning, and soil cleanup. Molecular dynamics simulations were used to investigate the morphology and dynamics of a class of surfactants, the gemini or dimeric surfactants, that are of potential importance in several industrial applications. Simulation results show that these surfactants form structures and have dynamic properties that are drastically different from those of single-chain surfactants. At the same weight fraction, single-chain surfactants form spherical micelles whereas gemini surfactants, whose two head groups are coupled by a short hydrophobic spacer, form thread-like micelles. Simulations at different surfactant concentrations indicate the formation of various structures, suggesting an alternative explanation for the unexpected viscosity behavior of gemini surfactants.     

不同地膜与覆盖方式土壤水温与作物增产效应

通过大田试验研究了不同地膜(宽幅普通地膜、窄幅普通地膜、宽幅微孔地膜与窄幅微孔地膜)与不同覆盖方式(平铺覆盖和起垄覆盖)下土壤水分和温度的动态变化规律以及对玉米生长发育、产量和水分利用效率的影响。结果表明,不同地膜与覆盖方式都具有明显的增温保水作用,且增温作用强于保水作用,增温作用主要表现在玉米生育前期,显著促进了玉米前期生长,为后期生殖生长奠定了良好的基础。玉米产量均显著高于CK,增产原因主要是显著增加了玉米百粒重,水分利用效率也显著高于CK。在试验区低温干旱并存的气候条件下,宽幅普通地膜平铺覆盖是一种简单、低成本、高效的覆盖栽培方式,能有效提高水分利用率,增加表层土壤温度,显著提高玉米产量,实现最大的经济效益。     

Ion-Induced Morphological Changes in "Crew-Cut" Aggregates of Amphiphilic Block Copolymers

The addition of ions in micromolar (CaCl2 or HCl) or millimolar (NaCl) concentrations can change the morphology of "crew-cut" aggregates of amphiphilic block copolymers in dilute solutions. In addition to spherical, rodlike, and univesicular or lamellar aggregates, an unusual large compound vesicle morphology can be obtained from a single block copolymer. Some features of the spontaneously formed large compound vesicles may make them especially useful as vehicles for delivering drugs and as models of biological cells. Gelation of a dilute spherical micelle solution can also be induced by ions as the result of the formation of a cross-linked "pearl necklace" morphology.     

Electrochemical principles for active control of liquids on submillimeter scales

Electrochemical methods were combined with redox-active surfactants to actively control the motions and positions of aqueous and organic liquids on millimeter and smaller scales. Surfactant species generated at one electrode and consumed at another were used to manipulate the magnitude and direction of spatial gradients in surface tension and guide droplets of organic liquids through simple fluidic networks. Solid microparticles could be transported across unconfined surfaces. Electrochemical control of the position of surface-active species within aqueous films of liquid supported on homogeneous surfaces was used to direct these films into periodic arrays of droplets with deterministic shapes and sizes.     

酶法制备微孔淀粉的研究进展

微孔淀粉吸附能力强,兼有无毒、环保、可食等优点,目前已在食品、医药等包装上有较广泛的应用。为进一步扩大微孔淀粉在食品中的应用范围,对微孔淀粉的微孔形成机理、性能以及制备进行深入的了解就显得尤为重要。本文对微孔淀粉原料的选取、预处理,微孔淀粉的制备方法和微孔淀粉的微孔形成机理进行了较详细的综述,并对目前我国微孔淀粉存在的不足进行了简要的总结及微孔淀粉的发展提出了展望。     

仿生改性水基共聚物包膜氮肥的制备及其性能研究

【目的】 为了提高水基共聚物膜材料的耐水性,依据仿生学原理,采用疏水效果好的纳米二氧化硅和1H,1H,2H,2H-全氟癸基三甲氧基硅烷对其进行疏水改性,明确最佳改性配比及机理,进而制备出缓释效果好的环境友好型包膜氮肥。【方法】 采用三因素三水平L₉(3³)正交试验设计,探究添加不同比例的壳聚糖（0.5%、1.0%、1.5%）、淀粉（0.5%、1.0%、1.5%）和聚乙烯醇（PVA）（2%、3%、4%）对水基共聚物膜材料性能的影响,通过水基共聚物膜材料的吸水率及极差分析筛选出疏水效果好的最优配比。在优选的水基共聚物包膜材料中分别加入0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%和4.0%的纳米二氧化硅进行疏水改性,通过测定纳米改性水基共聚物膜材料的吸水率和渗透率明确最佳纳米二氧化硅用量。随后,将优选的纳米改性水基共聚物膜材料分别置于含0.5%、1.0%、1.5%和2.0%的1H,1H,2H,2H-全氟癸基三甲氧基硅烷（FAS）的正己烷溶液中进行自组装改性,探究组装浓度对膜材料性能的影响。通过对改性前后水基共聚物膜材料疏水性及透性等变化明确其改性效果,通过改性前后膜材料红外光谱特征、表面微观结构变化探讨其疏水改性机理。并通过土壤培养试验探究所制备的仿生改性水基共聚物包膜尿素的养分释放特性。【结果】 当壳聚糖含量为0.5%、淀粉含量为1.5%、PVA含量为4.0%时所制备的水基共聚物膜材料吸水率最低,为42.50%。与水基共聚物膜材料相比,纳米二氧化硅改性水基共聚物膜材料、纳米二氧化硅和FAS双重改性水基共聚物膜材料的吸水率分别降低了38.54%和55.98%,铵离子的渗透率分别降低了24.14%和44.58%,水分子渗透率分别降低了36.14%和60.98%。红外光谱结果表明,纳米二氧化硅改性水基共聚物膜材料的-OH数量减少,并且观察到了Si-O-Si摇摆振动和反对称伸缩振动,纳米二氧化硅和FAS双重改性后水基共聚物材料表面观察到了C-F键。扫描电镜和能谱分析结果表明,在纳米二氧化硅改性水基共聚物膜材料表面发现Si元素,纳米二氧化硅和FAS双重改性水基共聚物膜材料表面发现F元素,并且观察到粗糙的表面结构,其水接触角由62.5°提升到118.6°,表现出良好的疏水效果。此外,土壤培养试验结果表明,纳米二氧化硅改性水基共聚物包膜尿素（NWCU）、纳米二氧化硅和FAS双重改性水基共聚物包膜尿素（SNWCU）的养分缓释期明显延长,SNWCU养分累积释放80%所需时间由改性前的10 d左右提升了28 d左右。【结论】 采用纳米二氧化硅和FAS对水基共聚物膜材料进行联合改性可以显著改善水基共聚物膜材料的耐水性及透性,所制备的仿生改性水基共聚物包膜氮肥具有良好的缓释效果。