Chain pullout and mobility effects in friction and lubrication

The interfacial shear stress that occurs when a network of a polymer that is highly mobile at the segment level (an elastomer) is slid over a smooth surface of an immobile (glassy) polymer has been measured. The glassy material is covered by a thin layer of end-attached chains of the mobile material. The experiment was designed so that there were no free chains at the interface; the slip occurred between network chains on the one side and rigid material plus end-attached mobile chains on the other side. Two main results were obtained. (i) The interfacial shear stress is strongly affected by the segment mobility of the materials on both sides of the slip plane, and considerably lower stress is observed when the materials on both sides of the interface are highly mobile. (ii) Very thin layers of tethered chains can increase the interfacial friction. Both results are relevant to the understanding of a number of practical situations that range from the operation of thin layers of lubricants, such as those found in magnetic storage devices, to the problem of wall slip and melt fracture in polymer processing.     

Large-area three-dimensional molecular ordering of a polymer brush by one-step processing

Rational molecular design and processing, enabling large-area molecular ordering, are important for creating high-performance organic materials and devices. We show that, upon one-step hot-pressing with uniaxially stretched Teflon sheets, a polymer brush carrying azobenzene-containing mesogenic side chains self-assembles into a freestanding film, where the polymer backbone aligns homeotropically to the film plane and the side chains align horizontally. Such an ordered structure forms through translation of a one-dimensional molecular order of the Teflon sheet and propagates from the interface macroscopically on both sides of the film. The resultant wide-area bimorph configuration allows the polymer film to bend rapidly and reversibly when the azobenzene units are photoisomerized. The combination of polymer brushes with hot-pressing and Teflon sheets provides many possibilities in designing functional soft materials.     

Evolution of a protein fold in vitro

A "switch" mutant of the Arc repressor homodimer was constructed by interchanging the sequence positions of a hydrophobic core residue, leucine 12, and an adjacent surface polar residue, asparagine 11, in each strand of an intersubunit beta sheet. The mutant protein adopts a fold in which each beta strand is replaced by a right-handed helix and side chains in this region undergo significant repacking. The observed structural changes allow the protein to maintain solvent exposure of polar side chains and optimal burial of hydrophobic side chains. These results suggest that new protein folds can evolve from existing folds without drastic or large-scale mutagenesis.     

Curving and frustrating flatland

Two polymer chains that occupy equal volumes when covalently linked together at one end self-assemble into an alternating lamellar morphology that has a characteristic period dictated by the molecular weight. When such copolymers are confined within alumina membranes that have cylindrical pores with diameters comparable to the repeat period, the interaction of the blocks with the confining walls and the imposed curvature induces a morphological transformation to relieve the constraints. Here, we show a lamella-to-toroid transition, captured through the dissolution of the surrounding membrane.     

Gas-phase polymerization: ultraslow chemistry

The mechanism of formation of polymer molecules in the gas phase is difficult to study because the involatile polymers tend to condense out of that phase. However, new techniques, involving the use of cloud chambers, have enabled workers to use the nucleation of liquid drops in supersaturated monomer vapors to detect single polymer molecules and therefore to work with so few simultaneously growing polymers that aggregation and condensation are avoided. Chain polymerization in which the chain carriers are either radicals or ions can therefore be studied in the vapor. Furthermore, the ability to work with such small concentrations of growing polymeric radicals, for example, makes it possible to avoid encounters between them that lead to recombination and the formation of "dead" polymers that are incapable of further growth. Many aspects of gas-phase polymerization can be studied including, besides radical and ion chains, ring-opening polymerization, initiation, radiation-induced polymerization, and especially "ultraslow" chemistry.     

Templating organic semiconductors via self-assembly of polymer colloids

A route for producing semiconducting polymer blends is demonstrated in which a doped pi-conjugated polymer is forced into a three-dimensionally continuous minor phase by the self-assembly of colloidal particles and block copolymers. The resulting cellular morphology can be viewed as a high-internal phase polymeric emulsion. Compared with traditional blending procedures, this process reduces the percolation threshold for electrical conductivity by a factor of 10, increases the conductivity by several orders of magnitude, and simultaneously improves thermal stability. Following this route, new applications can be envisaged for semiconducting polymer blends that require only minimal concentrations of doped pi-conjugated polymer.     

Molecular basis of the shish-kebab morphology in polymer crystallization

In the rich and long-standing literature on the flow-induced formation of oriented precursors to polymer crystallization, it is often asserted that the longest, most extended chains are the dominant molecular species in the "shish" of the "shish-kebab" formation. We performed a critical examination of this widely held view, using deuterium labeling to distinguish different chain lengths within an overall distribution. Small-angle neutron-scattering patterns of the differently labeled materials showed that long chains are not overrepresented in the shish relative to their concentration in the material as a whole. We observed that the longest chains play a catalytic role, recruiting other chains adjacent to them into formation of the shish.     

Antigenicity of polypeptides: immunological unresponsiveness to copolymers of gamma-amino acids

Immunological tolerance toward three synthetic random copolymers of the alpha-amino acids, glutamic, lysine, alanine, and tyrosine, was produced by a single injection of the polymers into newborn rabbits. The tolerant state could be extended by an additional intravenous injection of antigen. Repeated injections of the polymer in adjuvant mixture could "break" the tolerant state.     

分子结构与偶氮化合物吸收光谱的关系

设计合成了12种含偶氮苯光学活性侧基的乙烯基单体,利用分光光度计测定测定了它们在乙醇溶液中的吸收峰的变化.结果表明,偶氮乙烯基单体的吸收波长受结构因素的影响很大,共轭体系与吸电子基的存在均会导致其波长向长波长方向移动.     

Topology and formation of triple-stranded H-DNA

Repeating copolymers of (dT-dC)n.(dA-dG)n sequences (TC.AGn) can assume a hinged DNA structure (H-DNA) which is composed of triple-stranded and single-stranded regions. A model for the formation of H-DNA is proposed, based on two-dimensional gel electrophoretic analysis of DNA's with different lengths of (TC.AG)n copolymers. In this model, H-DNA formation is initiated at a small denaturation bubble in the interior of the copolymer, which allows the duplexes on either side to rotate slightly and to fold back, in order to make the first base triplet. This nucleation establishes which of several nonequivalent H-DNA conformations is to be assumed by any DNA molecule, thereby trapping each molecule in one of several metastable conformers that are not freely interconvertible. Subsequently, the acceptor region spools up single-stranded polypyrimidines as they are released by progressive denaturation of the donor region; both the spooling and the denaturation result in relaxation of negative supercoils in the rest of the DNA molecule. From the model, it can be predicted that the levels of supercoiling of the DNA determine which half of the (dT-dC)n repeat is to become the donated third strand.     

New mechanism of nonequilibrium polymer adsorption

Nonequilibrium states of surface composition can be extremely long-lived when polymer chains adsorb competitively. In a model system (polymethylmethacrylate adsorbed from CCl(4) onto oxidized silicon previously saturated with polystyrene), it is shown that a weakly adsorbing polymer was sterically pinned to a surface by a more strongly adsorbing polymer. The dynamical evolution of the surface composition was strongly nonexponential in time and non-Arrhenius in temperature; the phenomenology is analogous to bulk glasses. This interpretation offers a new mechanism to explain why weakly adsorbing chains may bind to surfaces, as well as a direction in which to look for a method to release them.     

Living polymerization methods

Living polymerization techniques can be used to achieve a high degree of control over polymer chain architecture. Examples of the type of polymers that can be synthesized include block copolymers, comb-shaped polymers, multiarmed polymers, ladder polymers, and cyclic polymers. This control of structure, in turn, results in polymers with widely diverse physical properties, even though they are made from readily available low-cost monomers.     

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.     

Polymer brushes

Polymers attached by one end to an interface at relatively high coverage stretch away from the interface to avoid overlapping, forming a polymer "brush." This simple picture may serve as the basis for models in diverse interfacial systems in polymer science, such as polymeric surfactants, stabilized suspensions of colloidal particles, and structures formed by block copolymers. The structure and dynamics of polymer brushes have been the subject of considerable theoretical and experimental activity in recent years. An account is given of recent advances in theoretical understanding of stretched polymers at interfaces, and the diverse experimental probes of systems modeled by brushes are briefly reviewed.     

Total alignment of calcite at acidic polydiacetylene films: cooperativity at the organic-inorganic interface

Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymer's conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.     

Polymer vesicles

Vesicles are microscopic sacs that enclose a volume with a molecularly thin membrane. The membranes are generally self-directed assemblies of amphiphilic molecules with a dual hydrophilic-hydrophobic character. Biological amphiphiles form vesicles central to cell function and are principally lipids of molecular weight less than 1 kilodalton. Block copolymers that mimic lipid amphiphilicity can also self-assemble into vesicles in dilute solution, but polymer molecular weights can be orders of magnitude greater than those of lipids. Structural features of vesicles, as well as properties including stability, fluidity, and intermembrane dynamics, are greatly influenced by characteristics of the polymers. Future applications of polymer vesicles will rely on exploiting unique property-performance relations, but results to date already underscore the fact that biologically derived vesicles are but a small subset of what is physically and chemically possible.     

利用反应挤出技术改善淀粉基聚合物性能的研究

淀粉基聚合物的开发利用很大程度地减轻了环境污染,具有广阔的应用前景。鉴于反应挤出技术在改变产品的结构和化学性质方面极具优势,综述了反应挤出技术在淀粉基接枝共聚物和纳米复合材料等多相复合体系中的发展应用。     

Studies of synthetic polymers by nonradiative energy transfer

Nonradiative energy transfer between fluorescent labels attached to polymers has been used to characterize polymer miscibility, the interpenetration of chain molecules in solution, micelle formation in graft copolymers, the unfolding of collapsed chain molecules in polymer melts, and the transfer of energy absorbed by a large number of donor labels to a small number of acceptors by an "antenna effect." The change in the emission spectrum after ionomer solutions with different fluorescent counterions were mixed provided rate constants for counterion interchange. The fluorescence behavior of dispersions of donor-labeled polymers stabilized by a graft copolymer with acceptor fluorophores in the solution phase led to inferences about the morphology of the dispersed particles.     

Polymerization-induced epitaxy: scanning tunneling microscopy of a hydrogen-bonded sheet of polyamide on graphite

A molecularly thin film of a two-dimensional polymer network formed by hydrogen bonding was synthesized and investigated with scanning tunneling microscopy. Poly(in-caprolactam) (nylon 6) was epitaxially grown on the basal plane of graphite and an ultrathin film of the polymer was obtained after the bulk materials had been washed away with solvents. The polymer chain has a planar, all-trans conformation and adjacent chains run in the antiparallel direction. This produces complete pairing of hydrogen bonding groups, with each amide group lying on a straight line perpendicular to the polymer backbone. This hydrogen-bonded sheet is oriented so that each polymer backbone lies in the (1010) direction on the graphite hexagonal lattice, as opposed to the (1120) direction taken by other paraffinic molecules studied so far. This experiment shows that hydrogen bonding can be used to control the orientation of macromolecules in two dimensions.     

Transfectomas provide novel chimeric antibodies

Methods have been developed to transfect immunoglobulin genes into lymphoid cells. The transfected genes are faithfully expressed, and assembly can occur both between the transfected and endogenous chains and between two transfected chains. Gene transfection can be used to reconstitute immunoglobulin molecules and to produce novel immunoglobulin molecules. These novel molecules can represent unique combinations of heavy and light chains; alternatively, by means of recombinant DNA technology, genes can be assembled in vitro, transfected, and expressed. The end products of such manipulations include chimeric molecules with variable regions joined to different isotypic constant regions; this is possible both within and between species. It is also possible to synthesize altered immunoglobulin molecules, as well as molecules having immunoglobulin sequences fused with nonimmunoglobulin sequences (for example, enzyme sequences).