One-Pot Synthesis of a Linear [4]Catenate Using Orthogonal Metal Templation and Ring-Closing Metathesis.

The efficient synthesis of well-defined, linear oligocatenanes possessing multiple mechanical bonds remains a formidable challenge in the field of mechanically interlocked molecules. Here, a one-pot synthetic strategy is described to prepare a linear [4]catenate using orthogonal metal templation between a macrocycle precursor, composed of terpyridine and phenanthroline ligands spaced by flexible glycol linkers, and a closed phenanthroline-based molecular ring. Implementation of two simultaneous ring-closing metathesis reactions after metal complexation resulted in the formation of three mechanical bonds. The linear [4]catenate product was isolated in 55% yield as a mixture of topological diastereomers. The intermediate metal complexes and corresponding interlocked products (with and without metals) were characterized by nuclear magnetic resonance, mass spectrometry, gel permeation chromatography, and UV-vis absorption spectroscopy. We envision that this general synthetic strategy may pave the way for the synthesis of higher order linear oligocatenates/catenanes with precise molecular weights and four or more interlocking molecular rings.

Sequence Control of Macromers via Iterative Sequential and Exponential Growth.

A general strategy through the use of direct azidation of alcohols allowed the sequence control of macromers via both the iterative sequential growth and iterative exponential growth methods. The chemistry was highly efficient in building polymers from a sequence of compositionally different macromers tethered together in close proximity. Using the DPPA/DBU method for near quantitative azidation of the benzyl alcohol moiety, sequence controlled polymers were made via a direct and one-step procedure for CuAAC activation. With four different macromers, spherical miktoarm star-like polymers of 50 000 molecular weight were prepared with a low dispersity, and the polymer coil size depended on the type of added macromer. Polymers made via the iterative methods opens the way for the design of advanced materials with predictable properties.

Dynamic, multimodal hydrogel actuators using porphyrin-based visible light photoredox catalysis in a thermoresponsive polymer network.

Hydrogels that can respond to multiple external stimuli represent the next generation of advanced functional biomaterials. Here, a series of multimodal hydrogels were synthesized that can contract and expand reversibly over several cycles while changing their mechanical properties in response to blue and red light, as well as heat (∼50 °C). The light-responsive behavior was achieved through a photoredox-based mechanism consisting of photoinduced electron transfer from a zinc porphyrin photocatalyst in its excited state to oligoviologen-based macrocrosslinkers, both of which were integrated into the hydrogel polymer network during gel formation. Orthogonal thermoresponsive properties were also realized by introducing N-isopropyl acrylamide (NIPAM) monomer simultaneously with hydroxyethyl acrylate (HEA) in the pre-gel mixture to produce a statistical 60 : 40 HEA : NIPAM polymer network. The resultant hydrogel actuators - crosslinked with either a styrenated viologen dimer (2V4+-St) or hexamer (6V12+-St) - were exposed to red or blue light, or heat, for up to 5 h, and their rate of contraction, as well as the corresponding changes in their physical properties (i.e., stiffness, tensile strength, Young's modulus, etc.), were measured. The combined application of blue light and heat to the 6V12+-St-based hydrogels was also demonstrated, resulting in hydrogels with more than two-fold faster contraction kinetics and dramatically enhanced mechanical robustness when fully contracted. We envision that the reported materials and the corresponding methods of remotely manipulating the dynamic hydrogels may serve as a useful blueprint for future adaptive materials used in biomedical applications.

Reversible Hydrogel Photopatterning: Spatial and Temporal Control over Gel Mechanical Properties Using Visible Light Photoredox Catalysis.

There is a growing interest in being able to control the mechanical properties of hydrogels for applications in materials, medicine, and biology. Primarily, changes in the hydrogel's physical properties, i.e., stiffness, toughness, etc., are achieved by modulating the network cross-linking chemistry. Common cross-linking strategies rely on (i) irreversible network bond degradation and reformation in response to an external stimulus, (ii) using dynamic covalent chemistry, or (iii) isomerization of integrated functional groups (e.g., azobenzene or spiropyran). Many of these strategies are executed using ultraviolet or visible light since the incident photons serve as an external stimulus that affords spatial and temporal control over the mechanical adaptation process. Here, we describe a different type of hydrogel cross-linking strategy that uses a redox-responsive cross-linker, incorporated in poly(hydroxyethyl acrylate)-based hydrogels at three different weight percent loadings, which consists of two viologen subunits tethered by hexaethylene glycol and capped with styrene groups at each terminus. These dicationic viologen subunits (V2+) can be reduced to their monoradical cations (V•+) through a photoinduced electron transfer (PET) process using a visible light-absorbing photocatalyst (tris(bipyridine)ruthenium(II) dichloride) embedded in the hydrogel, resulting in the intramolecular stacking of viologen radical cations, through radical-radical pairing interactions, while losing two positive charges and the corresponding counteranions from the hydrogel. It is shown how this concerted process ultimately leads to collapse of the hydrogel network and significantly (p < 0.05) increases (by nearly a factor of 2) the soft material's stiffness, tensile strength, and percent elongation at break, all of which is easily reversed via oxidation of the viologen subunits and swelling in water. Application of this reversible PET process was demonstrated by photopatterning the same hydrogel multiple times, where the pattern was "erased" each time by turning off the blue light (∼450 nm) source and allowing for oxidation and reswelling in between patterning steps. The areas of the hydrogel that were masked exhibited lower (by 1-2 kPa) shear storage moduli (G') than the areas that were irradiated for 1.5 h. Moreover, because the viologen subunits in the functional cross-linker are electrochromic, it is possible to visualize the regions of the hydrogel that undergo changes in mechanical properties. This visualization process was illustrated by photopatterning a larger hydrogel (∼9.5 cm on its longest side) with a photomask in the design of an array of stars.

Densely Packed Multicyclic Polymers.

Highly dense polymer chains were formed through coupling cyclic polymeric units in a sequence controlled manner. It was found that as the number of cyclic units increased the compactness substantially increased in a good solvent to a limiting value after only 12 units. This limiting value was close to that of a linear polymer chain in a θ solvent, in which polymer segment interactions with solvent are minimized. This remarkable result suggests that the unique architecture of the cyclic structure plays an important role to significantly change the polymer conformation and remain soluble in solution, which circumvents the need for cross-linking. The insight found in this work provides a physical mechanism as to why Nature uses cyclic structures in proteins to confer stability and the compacting of DNA strands to induce chromosome territories.

Thermoresponsive Polymer-Supported l-Proline Micelle Catalysts for the Direct Asymmetric Aldol Reaction in Water.

l-Proline moieties bound to a thermoresponsive polymer nanoreactor efficiently directed the asymmetric aldol reaction in water with excellent yields and enantioselectivity (ee). The reactions were efficient at higher temperatures in direct contrast to the low yields and ee values found when the reaction was carried out in a DMF/water mixture due to the location of the l-proline moieties within the hydrophobic pocket inside the core of the nanoreactors. This ideal environment formed for catalysis allows control over the water content as well as enhancing interactions between the carboxylic acid of l-proline and the aldehyde substrate. The nanoreactors were disassembled to fully water-soluble polymers by lowering the temperature to below the lower critical solution temperature (LCST) of the polymer, resulting in precipitation of the product in near pure form. The product was isolated by centrifugation and the polymer/water solution reused in additional catalytic cycles by heating the polymer above its LCST and thus reforming the nanoreactors. Although a small decrease in yield after five cycles was observed, the selectivity (anti/syn ratio and ee) remained high.

Chemical constituents and biological activities of the genus Subergorgia.

The genus Subergorgia (coelenterata, Gorgonacea, Subergorgiidae) is distributed in the Indo-pacific region. Previous investigations on the various species of the genus have revealed the presence of a number of new compounds including alkaloids, sesquiterpenes, diterpenes, and steroids. Certain biological activities particularly cytotoxic activity have been observed for the isolated constituents and compositions derived from the coral. This review covers the secondary metabolites reported from the genus Subergorgia and their biological properties.