Search

Increased demand for highly selective and energy-efficient separations processes has stimulated substantial interest in emerging two-dimensional (2D) nanomaterials as a potential platform for next-generation membranes. However, persistently poor separation performance continues to hinder the viability of many novel 2D-nanosheet membranes in desalination applications. In this study, we examine the role of the lamellar structure of 2D membranes on their performance. Using self-fabricated molybdenum disulfide (MoS2) membranes as a platform, we show that the separation layer of 2D nanosheet frameworks not only fails to demonstrate water-salt selectivity but also exhibits low rejection toward dye molecules. Moreover, the MoS2 membranes possess a molecular weight cutoff comparable to its underlying porous support, implying negligible selectivity of the MoS2 layer. By tuning the nanochannel size through intercalation with amphiphilic molecules and analyzing mass transport in the lamellar structure using Monte Carlo simulations, we reveal that small imperfections in the stacking of MoS2 nanosheets result in the formation of catastrophic microporous defects. These defects lead to a precipitous reduction in the selectivity of the lamellar structure by negating the interlayer sieving mechanism that prevents the passage of large penetrants. Notably, the imperfect stacking of nanosheets in the MoS2 membrane was further verified using 2D X-ray diffraction measurements. We conclude that developing a well-controlled fabrication process, in which the lamellar structure can be carefully tuned, is critical to achieving defect-free and highly selective 2D desalination membranes.

Organic solvent–stable membranes exhibiting strong selectivity and high permeance have the potential to transform energy utilization in chemical separation processes. A key goal is developing materials with uniform, well-defined pores at the 1-nm scale, with sizes that can be tuned in small increments with high fidelity. Here, we demonstrate a class of organic solvent–stable nanoporous membranes derived from self-assembled liquid crystal mesophases that display such characteristics and elucidate their transport properties. The transport-regulating dimensions are defined by the mesophase geometry and can be controlled in increments of ~0.1 nm by modifying the chemical structure of the mesogen or the composition of the mesophase. The highly ordered nanostructure affords previously unidentified opportunities for the systematic design of organic solvent nanofiltration membranes with tailored selectivity and permeability and for understanding and modeling rejection in nanoscale flows. Hence, these membranes represent progress toward the goal of enabling precise organic solvent nanofiltration.

Creating well-defined single-crystal textures in materials requires the biaxial alignment of all grains into desired orientations, which is challenging to achieve in soft materials. Here we report the formation of single crystals with rigorously controlled texture over macroscopic areas (>1 cm2) in a soft mesophase of a columnar discotic liquid crystal. We use two modes of directed self-assembly, physical confinement and magnetic fields, to achieve control of the orientations of the columnar axes and the hexagonal lattice along orthogonal directions. Field control of the lattice orientation emerges in a low-temperature phase of tilted discogens that breaks the field degeneracy around the columnar axis present in non-tilted states. Conversely, column orientation is controlled by physical confinement and the resulting imposition of homeotropic anchoring at bounding surfaces. These results extend our understanding of molecular organization in tilted systems and may enable the development of a range of new materials for distinct applications. Macroscopic single crystals with controlled texture are formed from a self-assembled columnar discotic liquid crystal.

Nanostructured materials with precisely defined and water-bicontinuous 1-nm-scale pores are highly sought after as advanced materials for next-generation nanofiltration membranes. While several self-assembled systems appear to satisfy this need, straightforward fabrication of such materials as submicron films with high-fidelity retention of their ordered nanostructure represents a nontrivial challenge. We report the development of a lyotropic liquid crystal mesophase that addresses the aforementioned issue. Films as thin as ∼200 nm are prepared on conventional support membranes using solution-based methods. Within these films, the system is composed of a hexagonally ordered array of ∼3 nm diameter cylinders of cross-linked polymer, embedded in an aqueous medium. The cylinders are uniformly oriented in the plane of the film, providing a transport-limiting dimension of ∼1 nm, associated with the space between the outer surfaces of nearest-neighbor cylinders. These membranes exhibit molecular weight cutoffs of ∼300 Da for organic solutes and are effective in rejecting dissolved salts, and in particular, divalent species, while exhibiting water permeabilities that rival or exceed current state-of-the-art commercial nanofiltration membranes. These materials have the ability to address a broad range of nanofiltration applications, while structure-property considerations suggest several avenues for potential performance improvements.

Periodic, nanostructured porous polymer membranes made from the cross-linked inverted hexagonal phase of self-assembled lyotropic liquid crystals (LLCs) are a promising class of materials for selective separations. In this work, we investigate an experimentally characterized LLC polymer membrane using atomistic molecular modeling. In particular, we compare simulated X-ray diffraction (XRD) patterns with experimental XRD data to quantify and understand the differences between simulation and experiment. We find that the nanopores are likely composed of five columns of stacked LLC monomers which surround each hydrophilic core. Evidence suggests that these columns likely move independently of each other over longer time scales than accessible via atomistic simulation. We also find that wide-angle X-ray scattering structural features previously attributed to monomer tail tilt are likely instead due to ordered tail packing. Although this system has been reported as dry, we show that small amounts of water are necessary to reproduce all features from the experimental XRD pattern because of asymmetries introduced by hydrogen bonds between the monomer head groups and water molecules. Finally, we explore the composition and structure of the nanopores and reveal that there exists a composition gradient rather than an abrupt partition between the hydrophilic and hydrophobic regions. A caveat is that the time scales of the dynamics are extremely long for this system, resulting in simulated structures that appear too ordered, thus requiring careful examination of the metastable states observed in order to draw any conclusions. The clear picture of the nanoscopic structure of these membranes provided in this study will enable a better understanding of the mechanisms of small-molecule transport within these nanopores.

Biofouling is a major obstacle for the efficient and reliable operation of membrane-based desalination processes. Innovations in membrane materials and fabrication processes are therefore needed to develop antibiofouling strategies. In this study, we utilize the alignability of an emerging two-dimensional nanomaterial, graphene oxide (GO), to fabricate a desalination membrane with enhanced bacterial resistance. GO nanosheets are dispersed in a polymer solution to form a homogeneous mixture, which undergoes slow solvent evaporation in a magnetic field to create a thin nanocomposite membrane with vertically aligned GO nanosheets. The structural characteristics of the fabricated membranes confirm the enhanced exposure of nanosheet edges on the surface through the vertical alignment of GO. Notably, the addition and alignment of GO do not compromise membrane water permeability and water–salt selectivity. When contacted with bacterial cells, membranes with vertically aligned GO nanosheets exhibit enhanced antim...

The graft-through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self-assembly of GBCPs resulted in ordered nanostructures with ultra-small domain sizes down to 2.8 nm (half-pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self-assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.

Stretchable ionic conductors are appealing for tissue-like soft electronics, yet suffer from a tardy mechanoelectric response due to their poor modulation of ionic conduction arising from intrinsic homogeneous soft chain network. Here, a highly robust ionotronic fiber is designed by synergizing ionic liquid and liquid crystal elastomer with alternate rigid mesogen units and soft chain spacers, which shows an unprecedented strain-induced ionic conductivity boost (≈103 times enhanced as stretched to 2000% strain). Such a surprisingly high enhancement is attributed to the formation of microphase-separated low-tortuosity ion-conducting nanochannels guided by strain-induced emergence of aligned smectic mesophases, thus allowing for ultrafast ion transport that resembles the role of “swimming lanes.” Intriguingly, the boosting conductivity even reverses Pouillet's Law-dictated resistance increase at certain strains, leading to unique waveform-discernible strain sensing. Moreover, the fiber retains thermal actuation properties with a maximum of 70% strain changes upon heating, and enables integrated self-perception and actuation. The findings offer a promising molecular engineering route to mechanically modulate the ion transport behavior of ionic conductors toward advanced ionotronic applications.

We present a strategy for robustly cross-linking self-assembled lamellar mesophases made from plant-derived materials to generate polymer nanosheets decorated with a high density of functional groups. We formulate a supramoleclar complex by hydrogen-bonding conjugated linoleic acid moieties to a structure-directing tribasic aromatic core. The resulting constructs self-assemble into a thermotropic lamellar mesophase. Photo-cross-linking the mesophase with the aid of an acrylate cross-linker yields a polymeric material with high-fidelity retention of the lamellar mesophase structure. Transmission electron microscopy images demonstrate the preservation of the large area, highly ordered layered nanostructures in the polymer. Subsequent extraction of the tribasic core and neutralization of the carboxyl groups by NaOH result in exfoliation of polymer nanosheets with a uniform thickness of ∼3 nm. The nanosheets have a large specific area of ∼800 m2/g, are decorated by negatively charged carboxylate groups at a d...

The development of facile and versatile strategies with low-cost for hydrogel construction is of tremendous scientific interest. Herein, we demonstrate that naturally derived, cost-effective tannic acid (TA) can be an efficient gelation binder for the hydrogel formation with a series of commercially available water-soluble polymers. With a five-polyphenol-arm structure, TA molecules are able to grasp polymer chains through either hydrogen or ionic bonds and cross-link them together by coordinate bonds in the presence of Fe(III) ions. These two interactions can be elegantly balanced by tuning the weight ratios of polymer/TA and TA/Fe3+, which is the key point for the construction of supramolecular hydrogels. The supramolecular hydrogels exhibit multiple functionalities including mechanical tenability, rapid self-healing, pH-stimuli responsiveness, and free radical scavenging abilities. TA as a dynamic and versatile catechol group modifier provides a simple path to the construction of multifunctional hydrog...

We demonstrate precise nanofiltration of molecular solutes in self-assembled membranes derived from a direct lyotropic mesophase., Self-assembled materials are attractive for next-generation membranes. However, the need to align self-assembled nanostructures (e.g. cylinders, lamellae) and the narrow stability windows for ordered bicontinuous systems present serious challenges. We propose and demonstrate a novel approach that circumvents these challenges by exploiting size-selective transport in the water-continuous medium of a nanostructured polymer templated from a self-assembled lyotropic H1 mesophase. Optimization of the mesophase composition enables high-fidelity retention of the H1 structure on photoinduced cross-linking. The resulting material is a mechanically robust nanostructured polymer possessing internally and externally cross-linked nanofibrils surrounded by a continuous aqueous medium. Fabricated membranes show size selectivity at the 1- to 2-nm length scale and water permeabilities of ~10 liters m−2 hour−1 bar−1 μm. Moreover, the membranes display excellent antimicrobial properties due to the quaternary ammonium groups on the nanofibril surfaces. These results represent a breakthrough for the potential use of polymerized lyotropic mesophase membranes in practical water purification applications.

Creating well-defined single-crystal textures in materials requires the biaxial alignment of all grains into desired orientations, which is challenging to achieve in soft materials. Here we report the formation of single crystals with rigorously controlled texture over macroscopic areas (1 cm

Membrane separations are critically important in areas ranging from health care and analytical chemistry to bioprocessing and water purification. An ideal nanoporous membrane would consist of a thin film with physically continuous and vertically aligned nanopores and would display a narrow distribution of pore sizes. However, the current state of the art departs considerably from this ideal and is beset by intrinsic trade-offs between permeability and selectivity. We demonstrate an effective and scalable method to fabricate polymer films with ideal membrane morphologies consisting of submicron thickness films with physically continuous and vertically aligned 1 nm pores. The approach is based on soft confinement to control the orientation of a cross-linkable mesophase in which the pores are produced by self-assembly. The scalability, exceptional ease of fabrication, and potential to create a new class of nanofiltration membranes stand out as compelling aspects.

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles.

The cytotoxicity of 2D graphene-based nanomaterials (GBNs) is highly important for engineered applications and environmental health. However, the isotropic orientation of GBNs, most notably graphene oxide (GO), in previous experimental studies obscured the interpretation of cytotoxic contributions of nanosheet edges. Here, we investigate the orientation-dependent interaction of GBNs with bacteria using GO composite films. To produce the films, GO nanosheets are aligned in a magnetic field, immobilized by cross-linking of the surrounding matrix, and exposed on the surface through oxidative etching. Characterization by small-angle X-ray scattering and atomic force microscopy confirms that GO nanosheets align progressively well with increasing magnetic field strength and that the alignment is effectively preserved by cross-linking. When contacted with the model bacterium Escherichia coli, GO nanosheets with vertical orientation exhibit enhanced antibacterial activity compared with random and horizontal orientations. Further characterization is performed to explain the enhanced antibacterial activity of the film with vertically aligned GO. Using phospholipid vesicles as a model system, we observe that GO nanosheets induce physical disruption of the lipid bilayer. Additionally, we find substantial GO-induced oxidation of glutathione, a model intracellular antioxidant, paired with limited generation of reactive oxygen species, suggesting that oxidation occurs through a direct electron-transfer mechanism. These physical and chemical mechanisms both require nanosheet penetration of the cell membrane, suggesting that the enhanced antibacterial activity of the film with vertically aligned GO stems from an increased density of edges with a preferential orientation for membrane disruption. The importance of nanosheet penetration for cytotoxicity has direct implications for the design of engineering surfaces using GBNs.

Hybrid nanomaterials are molecular or colloidal-level combinations of organic and inorganic materials, or otherwise strongly dissimilar materials. They are often, though not exclusively, anisotropic in shape. A canonical example is an inorganic nanorod or nanosheet sheathed in, or decorated by, a polymeric or other organic material, where both the inorganic and organic components are important for the properties of the system. Hybrid nanomaterials and nanocomposites have generated strong interest for a broad range of applications due to their functional properties. Generating macroscopic assemblies of hybrid nanomaterials and nanomaterials in nanocomposites with controlled orientation and placement by directed assembly is important for realizing such applications. Here, a survey of critical issues and themes in directed assembly of hybrid nanomaterials and nanocomposites is provided, highlighting recent efforts in this field with particular emphasis on scalable methods.

We describe a combination of molecular templating and directed self-assembly to realize highly selective vertically aligned nanopores in polymer membranes using sustainably derived materials. The approach exploits a structure-directing molecule to template the assembly of plant-derived fatty acids into highly ordered columnar mesophases. Directed self-assembly using physical confinement and magnetic fields provides vertical alignment of the columnar nanostructures in large area (several cm2) thin films. Chemically cross-linking the mesophase with added conventional vinyl comonomers and removing the molecular template results in a mechanically robust polymer film with vertically aligned 1.2–1.5 nm diameter nanopores with a large specific surface area of ∼670 m2/g. The nanoporous polymer films display exceptional size and charge selectivity as demonstrated by adsorption experiments using model penetrant molecules. These materials have significant potential to function as high-performance nanofiltration memb...

Magnetic-field-directed assembly of lyotropic surfactant mesophases provides a scalable approach for the fabrication of aligned nanoporous polymers by templated polymerization. We develop and characterize a lyotropic liquid crystalline system containing hexagonally packed cylindrical micelles of a polymerizable surfactant in a polymerizable solvent. The system exhibits negative magnetic anisotropy, resulting in the degenerate alignment of cylindrical micelles perpendicular to the magnetic field. Sample rotation during field alignment is used to effectively break this degeneracy and enable the production of uniformly well-aligned mesophases. High-fidelity retentions of the hexagonal structure and alignment were successfully achieved in polymer films produced upon UV exposure of the reactive system. The success of this effort provides a route for the fabrication of aligned nanoporous membranes suitable for highly selective separations, sensing, and templated nanomaterial synthesis.

Swelling of block copolymers is a complex process in which deformation and microphase separation couple together. Here we demonstrated that nanoparticles of block copolymers and polymer composites which have a large variety of phase separation patterns and different shapes can be generated through swelling process. Particularly, we focused on the swelling process of lamellae-forming diblock copolymer nanoparticles and first observed the formation of terrace edges in diblock copolymer nanoparticles as a metastable microstructure in swelling. Moreover, the trace amount of swelling solvent shows a significant influence on the shape of polymer nanoparticles, leading to block copolymer nanodisks and snowman-like composite nanoparticles.

We report on a new method for the fabrication of polymer nanofibers based on wetting of cylindrical alumina nanopores with solvent vapour swollen polymers. Solvent annealing is used to swell and soften polymers at room temperature, so that they are allowed to infiltrate into cylindrical nanopores by capillary force. The method of swelling assisted infiltration is capable of eliminating the problem of thermal degradation from the widely used “melt wetting”; in addition, the thus formed nanofibers display well aligned one-dimensional structures and controllable aspect ratios, in contrast to those from “solution wetting”, the morphologies of which are difficult to be controlled. By using the proposed method, several homopolymers including thermo-sensitive polyvinyl chloride (PVC) and conducting poly(3-hexylthiophene) (P3HT) were found to form nanofibers with high aspect ratios. In particular, we have studied the microphase separation behaviour of vapour swollen block copolymers (BCPs) under cylindrical confinement, and found that the intrinsic ordered pattern of BCPs (i.e., in the melt state) would transform into a different structure due to solvent swelling under cylindrical confinement.

We apply the concept of wettability transition to manipulate the morphology and entrapment of polymer nanostructures inside cylindrical nanopores of anodic aluminum oxide (AAO) membranes. When AAO/polystyrene (PS) hybrids, i.e., AAO/PS nanorods or AAO/PS nanotubes, are immersed into a polyethylene glycol (PEG) reservoir above the glass transition temperature of PS, a wettability transition from wetting to nonwetting of PS can be triggered due to the invasion of the more wettable PEG melt. The wettability transition enables us to develop a nondestructive method to entrap hemispherically capped nanorods inside nanopores. Moreover, we can obtain single nanorods with the desired aspect ratio by further dissolving the AAO template, in contrast to the drawbacks of nonuniformity or destructiveness from the conventional ultrasonication method. In the case of AAO/PS nanotubes, the wettability transition induced dewetting of PS nanotube walls results in the disconnection and entrapment of nonwetting PS domains (i.e., nanospheres, nanocapsules, or capped nanorods). Moreover, PEG is then washed to recover the pristine wettability of PS on the alumina surface; further annealing of the PS nanospheres inside AAO nanopores under vacuum can generate some unique nanostructures, particularly semicylindrical nanorods.

We report a simple method to produce block copolymer nanospheres by swelling the short rodlike entities generated from Rayleigh instability of polymer nanotubes within the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. Poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) nanotubes were first allowed to form inside the cylindrical nanopores through solution-wetting of an AAO membrane followed by solvent evaporation. Upon thermal annealing, undulations in the nanotube wall occurred due to Rayleigh instability and finally led to the formation of nanorods containing regular encapsulated holes. The structures were susceptible to ultrasonication and could be cut into short rodlike blocks with uniform size. These PS-b-P2VP entities were suspended in water with the help of a nonionic surfactant and then swollen by a good solvent for both PS and P2VP. The swollen PS-b-P2VP entities were deformable and spontaneously evolved into nanospheres so as to minimize the interfacial energy. The characterization of...

In this study, we report for the first time the fabrication of polymer nanospheres, nanocapsules, and hemispherically capped nanorods simply through the wetting of anodic aluminum oxide (AAO) membranes with polymer solutions. For the wetting with polystyrene solutions, we have demonstrated that the formation of nanorods is dependent upon the solvents used (e.g., tetrahydrofuran and methyl ethyl ketone) which have strongly adsorbent nature toward alumina surfaces, displaying no correlation to molecular weight. More importantly, we have shown that there is a coarsening process from spheres to capsules to rods in AAO cylindrical nanopores during solvent evaporation. The coarsening process could serve as the formation mechanism for nanorods which have the similar diameter as the AAO nanopores. Our observation also provides a facile approach for fabricating polymer nanospheres and nanocapsules that can be directed by cylindrical nanopores into ordered arrays.

The fabrication of block copolymer (BCP) thin films is reported with vertically aligned cylindrical domains using continuous electrospray deposition onto bare wafer surfaces. The out-of-plane orientation of hexagonally packed styrene cylinders is achieved in the "fast-wet" deposition regime in which rapid evaporation of the solvent in deposited droplets of polymer solution drives the vertical alignment of the self-assembled structure. Thermally activated crosslinking of the polybutadiene matrix provides kinetic control of the morphology, freezing the vertical alignment and preventing relaxation of the system to its preferred parallel orientation on the nontreated substrate. Physically continuous vertically oriented domains can be achieved over several micrometers of film thickness. The ability of electrospray deposition to fabricate well-ordered and aligned BCP films on nontreated substrates, the low amount of material used relative to spin-coating, and the continuous nature of the deposition may open up new opportunities for BCP thin films.

There is long-standing interest in developing membranes possessing uniform pores with dimensions in the range of 1 nm and physical continuity in the macroscopic transport direction to meet the needs of challenging small molecule and ionic separations. Here we report facile, scalabe fabrication of polymer membranes with vertically (i.e., along the through-plane direction) aligned 1 nm pores by magnetic-field alignment and subsequent cross-linking of a liquid crystalline mesophase. We utilize a wedge-shaped amphiphilic species as the building block of a thermotropic columnar mesophase with 1 nm ionic nanochannels, and leverage the magnetic anisotropy of the amphiphile to control the alignment of these pores with a magnetic field. In situ X-ray scattering and subsequent optical microscopy reveal the formation of highly ordered nanostructured mesophases and cross-linked polymer films with orientational order parameters of ca. 0.95. High-resolution transmission electron microscopy (TEM) imaging provides direct visualization of long-range persistence of vertically aligned, hexagonally packed nanopores in unprecedented detail, demonstrating high-fidelity retention of structure and alignment after photo-cross-linking. Ionic conductivity measurements on the aligned membranes show a remarkable 85-fold enhancement of conductivity over nonaligned samples. These results provide a path to achieving the large area control of morphology and related enhancement of properties required for high-performance membranes and other applications.

Forming micelles: The first in situ AFM study of Gibbs films of semifluorinated alkanes at liquid crystal/air interfaces is presented. The Gibbs films self-organize in a hexagonal close packing of surface micelles with shapes and lateral dimensions that are similar to micelles forming on aqueous and solid surfaces. It is concluded that he formation of surfaces micelles and their self-organization in large-area dense hexagonal arrays are intrinsic properties of semifluorinated alkane molecules.

We present an ellipsometry study of the interface between thermotropic liquid crystals and liquid phases consisting of various binary mixtures of water and glycerol. The liquid-crystal samples contain a small constant amount of a surfactant which induces a homeotropic anchoring at the interface. We determine the smectic or nematic order at the interface in the temperature range above the liquid-crystal--isotropic transition while the water to glycerol ratio is varied, corresponding to a systematic modification of the polarity of the liquid phase. The surface-induced order becomes less pronounced with increasing glycerol concentration in the liquid phase. The observed behavior is compared with previous studies in which the surfactant concentration in the liquid-crystal bulk phase was varied. The results indicate that in both cases the magnitude of the surfactant coverage at the interface is the key quantity which determines the liquid-crystal surface order at the interface.

Surface modification of carbon nanotubes is crucial for the dispersion and interfacial adhesion of carbon nanotubes in polymer composites. Here we present a novel method to construct single-walled carbon nanotube/chitosan composites using phosphotungstic acid as an anchor reagent to modify single-walled carbon nanotubes. The most direct benefit from this method is that this modification is mild but effective: the induced defects on single-walled carbon nanotubes are negligible based on Raman and transmission electron microscopy observations; and homogeneous dispersion of single-walled carbon nanotubes in chitosan matrices and strong binding between single-walled carbon nanotubes and chitosan are achieved. Moreover, according to the results of tetrazolium-based colorimetric assays in vitro, we demonstrate that the produced phosphotungstic-acid-modified single-walled carbon nanotube/chitosan composites have good biocompatibility. Thus, our study provides a feasible route to fabricate biocompatible composites containing single-walled carbon nanotubes for potential application in bone tissue engineering.

Carbon nanotubes loaded with peptides, proteins and drugs can translocate across the cell membrane. This big advantage has attracted increasing attention to design a novel delivery system using nanotubes. Polyoxometalate (POM) is a promising antitumor drug and it shows a very strong interaction with carbon nanotube surfaces. In this paper, a novel complex of POM-modified single-walled carbon nanotubes (SWNTs) and chitosan was fabricated through a layer-by-layer self-assembly process. With the addition of SWNTs, the loading of POM in this thin film was doubled in the high ionic strength. The initial burst release of POMs in the (POM/chitosan)(n) thin film was suppressed in the (POM-SWNT/chitosan)(n) thin film. Also the instability of POMs in a physiologically relevant pH environment was overcome. The strong interaction between POMs and SWNTs was believed to be the determinant factor in the higher loading and prolonged release of POMs in (POM-SWNT/chitosan)(n) thin films.

We study the surface ordering and anchoring behaviour at liquid crystal/air interfaces laden with the semifluorinated alkane C18H37–C12F25. On alkanes, the semifluorinated alkane is known to form Gibbs films exhibiting a sharp transition from a dilute state at higher temperatures to a dense state at lower temperatures. We observe a similar transition in Gibbs films of this compound on the surface of cyanobiphenyl liquid crystals. The transition temperature can be tuned by controlling the C18H37–C12F25 concentration in the liquid crystal bulk phase. Our results show that the transition in the Gibbs film changes the anchoring of the liquid crystal from homeotropic at higher temperatures to planar at lower temperatures. When the transition temperature of the Gibbs film is tuned so that it takes place above the nematic–isotropic or smectic–isotropic transition of the liquid crystals, a pronounced effect on the nematic or smectic surface order is observed. Our study demonstrates for the first time that the ordering and anchoring behaviour of thermotropic liquid crystals can be tuned at a liquid crystal/air interface.