Jason M. Spruell

Monofunctionalized Pillar[5]arene as a Host for Alkanediamines

Alkanediamines serve as neutral guests for the recently discovered host pillar[5]arene. The proposed [2]pseudorotaxane nature of the superstructure of the 1:1 host-guest complexes is supported by the template-directed synthesis of a related [2]rotaxane. A synthetic route to monofunctional pillar[5]arenes has also been developed, allowing for the creation of a fluorescent sensor for alkylamine binding. The precursors to this host could act as starting points for a large library of monofunctional pillar[5]arene macrocycles.

Tunable, High Modulus Hydrogels Driven by Ionic Coacervation

The need for robust and responsive hydrogels in numerous pharmaceutical, biomedical, and industrial applications has motivated intense research efforts in these important polymeric materials. [ 1–6 ] The defi ning feature of hydrogels is that the vast majority of their mass consists of water, yet they still exhibit solid-like mechanical properties due to the presence of a three-dimensional network structure that, classically, is created through in situ covalent bond formation between multifunctional, reactive precursors. [ 6 , 7 ] A wide variety of chemistries have been utilized for covalent crosslinking of hydrogel-forming materials, e.g. free radical polymerization, Michael addition, and thiol-ene coupling, with the resulting hydrogels having good mechanical properties arising from the strong covalently bonded framework. [ 1 , 6–10 ] Limitations of the covalent approach are that the hydrogels are not re-moldable once formed, have limited responsiveness to external stimuli, and may require organic co-solvents/reagents during their formation. To overcome these limitations, hydrogels formed through non-covalent, physical associations arising from intermolecular interactions, in lieu of covalent crosslinks, have attracted signifi cant interest recently, particularly as responsive materials and injectable gels. [ 5 , 6 ] Typically, a drawback of such physically-associated hydrogels is their poor mechanical properties due to generally weak intermolecular interactions. [ 11 , 12 ] However, recent work by Gong et al. [ 13 ] and Yasuda et al . [ 14 ] on double network gels and Wang et al . [ 15 ] on the development of “aquamaterials” has demonstrated that signifi cant improvement in hydrogel mechanical properties is possible through careful design of the intermolecular interactions and length-scales between crosslinks or physical associations. In addressing new strategies to yield high performance, physically associated hydrogels, the role of dynamic materials formed via electrostatic interactions serves as a powerful model. While block copolyelectrolytes are widely used in the construction of hydrogel materials, the majority of these systems are based on block copolymers where the ionic blocks serve as the water soluble component and neutral, hydrophobic blocks

High hopes: can molecular electronics realise its potential?

Manipulating and controlling the self-organisation of small collections of molecules, as an alternative to investigating individual molecules, has motivated researchers bent on processing and storing information in molecular electronic devices (MEDs). Although numerous ingenious examples of single-molecule devices have provided fundamental insights into their molecular electronic properties, MEDs incorporating hundreds to thousands of molecules trapped between wires in two-dimensional arrays within crossbar architectures offer a glimmer of hope for molecular memory applications. In this critical review, we focus attention on the collective behaviour of switchable mechanically interlocked molecules (MIMs)--specifically, bistable rotaxanes and catenanes--which exhibit reset lifetimes between their ON and OFF states ranging from seconds in solution to hours in crossbar devices. When these switchable MIMs are introduced into high viscosity polymer matrices, or self-assembled as monolayers onto metal surfaces, both in the form of nanoparticles and flat electrodes, or organised as tightly packed islands of hundreds and thousands of molecules sandwiched between two electrodes, the thermodynamics which characterise their switching remain approximately constant while the kinetics associated with their reset follow an intuitively predictable trend--that is, fast when they are free in solution and sluggish when they are constrained within closely packed monolayers. The importance of seamless interactions and constant feedback between the makers, the measurers and the modellers in establishing the structure-property relationships in these integrated functioning systems cannot be stressed enough as rationalising the many different factors that impact device performance becomes more and more demanding. The choice of electrodes, as well as the self-organised superstructures of the monolayers of switchable MIMs employed in the molecular switch tunnel junctions (MSTJs) associated with the crossbars of these MEDs, have a profound influence on device operation and performance. It is now clear, after much investigation, that a distinction should be drawn between two types of switching that can be elicited from MSTJs. One affords small ON/OFF ratios and is a direct consequence of the switching in bistable MIMs that leads to a relatively small remnant molecular signature--an activated chemical process. The other leads to a very much larger signature and ON/OFF ratios resulting from physical or chemical changes in the electrodes themselves. Control experiments with various compounds, including degenerate catenanes and free dumbbells, which cannot and do not switch, are crucial in establishing the authenticity of the small ON/OFF ratios and remnant molecular signatures produced by bistable MIMs. Moreover, experiments conducted on monolayers in MSTJs of molecules designed to switch and molecules designed not to switch have been probed directly by spectroscopic and other means in support of MEDs that store information through switching collections of bistable MIMs contained in arrays of MSTJs. In the quest for the next generation of MEDs, it is likely that monolayers of bistable MIMs will be replaced by robust crystalline extended structures wherein the switchable components, derived from bistable MIMs, are organised precisely in a periodic manner.

Acid−Base Actuation of [c2]Daisy Chains

A versatile synthetic strategy, which was conceived and employed to prepare doubly threaded, bistable [c2]daisy chain compounds, is described. Propargyl and 1-pentenyl groups have been grafted onto the stoppers of [c2]daisy chain molecules obtained using a template-directed synthetic protocol. Such [c2]daisy chain molecules undergo reversible extension and contraction upon treatment with acid and base, respectively. The dialkyne-functionalized [c2]daisy chain (AA) was subjected to an [AA+BB] type polymerization with an appropriate diazide (BB) to afford a linear, mechanically interlocked, main-chain polymer. The macromolecular properties of this polymer were characterized by chronocoulometry, size exclusion chromatography, and static light-scattering analysis. The acid-base switching properties of both the monomers and the polymer have been studied in solution, using (1)H NMR spectroscopy, UV/vis absorption spectroscopy, and cyclic voltammetry. The experimental results demonstrate that the functionalized [c2]daisy chains, along with their polymeric derivatives, undergo quantitative, efficient, and fully reversible switching processes in solution. Kinetics measurements demonstrate that the acid/base-promoted extension/contraction movements of the polymeric [c2]daisy chain are actually faster than those of its monomeric counterpart. These observations open the door to correlated molecular motions and to changes in material properties.

Kinetic and Thermodynamic Approaches for the Efficient Formation of Mechanical Bonds

Among the growing collection of molecular systems under consideration for nanoscale device applications, mechanically interlocked compounds derived from electrochemically switchable bistable [2]rotaxanes and [2]catenanes show great promise. These systems demonstrate dynamic, relative movements between their components, such as shuttling and circumrotation, enabling them to serve as stimuli-responsive switches operated via reversible, electrochemical oxidation-reduction rather than through the addition of chemical reagents. Investigations into these systems have been intense for a number of years, yet limitations associated with their synthesis have hindered incorporation of their mechanical bonds into more complex architectures and functional materials. We have recently addressed this challenge by developing new template-directed synthetic protocols, operating under both kinetic and thermodynamic control, for the preparation of bistable rotaxanes and catenanes. These methodologies are compatible with the molecular recognition between the pi-electron-accepting cyclobis(paraquat-p-phenylene) (CBPQT(4+)) host and complementary pi-electron-donating guests. The procedures that operate under kinetic control rely on mild chemical transformations to attach bulky stoppering groups or perform macrocyclizations without disrupting the host-guest binding of the rotaxane or catenane precursors. Alternatively, the protocols that operate under thermodynamic control utilize a reversible ring-opening reaction of the CBPQT(4+) ring, providing a pathway for two cyclic starting materials to thread one another to form more thermodynamically stable catenaned products. These complementary pathways generate bistable rotaxanes and catenanes in high yields, simplify mechanical bond formation in these systems, and eliminate the requirement that the mechanical bonds be introduced into the molecular structure in the final step of the synthesis. These new methods have already been put into practice to prepare previously unavailable rotaxane architectures and novel complex materials. Furthermore, the potential for utilizing mechanically interlocked architectures as device components capable of information storage, the delivery of therapeutic agents, or other desirable functions has increased significantly as a result of the development of these improved synthetic protocols.

Reactive, Multifunctional Polymer Films through Thermal Cross-linking of Orthogonal Click Groups

The ability to produce robust and functional cross-linked materials from soluble and processable organic polymers is dependent upon facile chemistries for both reinforcing the structure through cross-linking and for subsequent decoration with active functional groups. Generally, covalent cross-linking of polymeric assemblies is brought about by the application of heat or light to generate highly reactive groups from stable precursors placed along the chains that undergo coupling or grafting reactions. Typically, these strategies suffer from a general lack of control of the cross-linking chemistry as well as the fleeting nature of the reactive species that precludes secondary chemistry. We have addressed both of these issues using orthogonal chemistries to effect both cross-linking and subsequent functionalization of polymer films by mild heating, which results in exacting control of the cross-link density as well as the density of the residual stable functional groups available for subsequent, stepwise functionalization. This methodology is exploited to develop a strategy for the independent and orthogonal triple-functionalization of cross-linked polymer thin-films through microcontact printing.

Linear versus Dendritic Molecular Binders for Hydrogel Network Formation with Clay Nanosheets: Studies with ABA Triblock Copolyethers Carrying Guanidinium Ion Pendants

ABA-triblock copolyethers 1a-1c as linear polymeric binders, in combination with clay nanosheets (CNSs), afford high-water-content moldable supramolecular hydrogels with excellent mechanical properties by constructing a well-developed crosslinked network in water. The linear binders carry in their terminal A blocks guanidinium ion (Gu(+)) pendants for adhesion to the CNS surface, while their central B block comprises poly(ethylene oxide) (PEO) that serves as a flexible linker for adhered CNSs. Although previously reported dendritic binder 2 requires multistep synthesis and purification, the linear binders can be obtained in sizable quantities from readily available starting materials by controlled polymerization. Together with dendritic reference 2, the modular nature of compounds 1a-1c with different numbers of Gu(+) pendants and PEO linker lengths allowed for investigating how their structural parameters affect the gel network formation and hydrogel properties. The newly obtained hydrogels are mechanically as tough as that with 2, although the hydrogelation takes place more slowly. Irrespective of which binder is used, the supramolecular gel network has a shape memory feature upon drying followed by rewetting, and the gelling water can be freely replaced with ionic liquids and organic fluids, affording novel clay-reinforced iono- and organogels, respectively.

Triggered structural and property changes in polymeric nanomaterials

The combination of ordered macromolecular structures and well-defined responsive molecular triggers is enabling precise and amplified structural and property switching in synthetic architectures leading to useful functions. These features are reminiscent of the most sought after designs in nature, specifically the ability of superstructures to form on-demand, store information, perform actuation, and store/release molecular payloads. Such macromolecular systems arise through the precise placement of environmentally responsive elements within polymer chains, an ability only recently possible for synthetic systems. The drivers behind such progress are described and future possibilities for functional macromolecular superstructures discussed.

Heterogeneous catalysis of a copper-coated atomic force microscopy tip for direct-write click chemistry

We report a constructive scanning probe lithography method that uses heterogeneous copper-coated atomic force microscopy tips to catalyze azide-alkyne cycloadditions (CuAAC) between solvated terminal alkyne molecules and azide-terminated self-assembled monolayers on silicon surfaces. Spatially controlled surface functionalization was carried out successfully with 50 mM ethanolic solutions of small molecules bearing terminal alkyne groups--propargylamine, 4-pentynoic acid, and an alkynyl-oligoethyleneoxide. We observed that reaction occurs only where the copper tip is in contact with an azide-terminated surface resulting in features with linewidths on the order of 50 nm. The extent of surface functionalization, as measured by changes in surface topography and lateral force microscopy, depends on the scanning force (31-350 nN) and scanning speed, with significant surface patterning observed even at speeds as high as 64 microm/s. In contrast with related SPL techniques, this approach affords a direct-write lithographic approach to constructively modifying and patterning surfaces at the nanoscale without the need for auxiliary reagents. All that is required is (1) an azide surface, (2) a solution of a terminal alkyne, and (3) a copper-coated AFM tip. These advantages allow the direct attachment of a potentially limitless library of molecules that bear terminal alkyne functionalities, including biomolecules, under relatively mild conditions, with sub-100 nm spatial resolution.

Improved Performance of Protected Catecholic Polysiloxanes for Bioinspired Wet Adhesion to Surface Oxides

A facile synthetic strategy for introducing catecholic moieties into polymeric materials based on a readily available precursor (eugenol) and efficient chemistries [tris(pentafluorophenyl)borane-catalyzed silation and thiol-ene coupling] is reported. Silyl protection is shown to be critical for the oxidative stability of catecholic moieties during synthesis and processing, which allows functionalized polysiloxane derivatives to be fabricated into 3D microstructures as well as 2D patterned surfaces. Deprotection gives stable catechol surfaces whose adhesion to a variety of oxide surfaces can be precisely tuned by the level of catechol incorporation. The advantage of silyl protection for catechol-functionalized polysiloxanes is demonstrated and represents a promising and versatile new platform for underwater surface treatments.