Dave J. Adams

Porous organic cages

Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer-Emmett-Teller surface areas of 550 and 23 m2 g(-1), respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

Chemical tuning of CO2 sorption in robust nanoporous organic polymers

We report here the carbon dioxide sorption properties for a series of conjugated microporous polymer (CMP) networks. These CMP materials incorporate a range of chemical functionalities including carboxylic acids, amines, hydroxyl groups, and methyl groups. The carboxylic acid functionalised network, rather than its amine analogue, shows the highest isosteric heat of sorption for CO2. This supports recent computational predictions for metal–organic frameworks and suggests that acid-functionalised frameworks could outperform more widely studied amine sorbents in CO2 capture and separation application.

Microporous organic polymers for carbon dioxide capture

Anthropogenic carbon dioxide emissions are thought to be one cause of global warming. Current methods for CO2 capture result in large energy penalties. Solid adsorbents are a potential method to capture CO2, but the sorbent-sorbate affinity is critical in determining the energetic viability of such processes. In this study, the adsorption of CO2 in a range of microporous organic polymers was tested. These materials adsorb up to 2.20 mmol/g CO2 at 298 K and 1 bar, and thus performance is compared with related porous solids in the literature. The relationship between CO2 uptake and apparent surface area and pore size is described, and this showed that heats of adsorption were important in the low pressure regime. The chemical tuning of gas-sorbent affinity provides a blueprint for the development of improved materials in this area.

Rational design and application of responsive |[alpha]|-helical peptide hydrogels

Biocompatible hydrogels have a wide variety of potential applications in biotechnology and medicine, such as the controlled delivery and release of cells, cosmetics and drugs; and as supports for cell growth and tissue engineering1. Rational peptide design and engineering are emerging as promising new routes to such functional biomaterials2-4. Here we present the first examples of rationally designed and fully characterized self-assembling hydrogels based on standard linear peptides with purely α-helical structures, which we call hydrogelating self-assembling fibres (hSAFs). These form spanning networks of α-helical fibrils that interact to give self-supporting physical hydrogels of >99% water content. The peptide sequences can be engineered to alter the underlying mechanism of gelation and, consequently, the hydrogel properties. Interestingly, for example, those with hydrogen-bonded networks melt upon heating, whereas those formed via hydrophobic interactions strengthen when warmed. The hSAFs are dual-peptide systems that only gel on mixing, which gives tight control over assembly5. These properties raise possibilities for using the hSAFs as substrates in cell culture. We have tested this in comparison with the widely used Matrigel substrate, and demonstrate that, like Matrigel, hSAFs support both growth and differentiation of rat adrenal pheochromocytoma cells for sustained periods in culture.

Modular and predictable assembly of porous organic molecular crystals

Nanoporous molecular frameworks are important in applications such as separation, storage and catalysis. Empirical rules exist for their assembly but it is still challenging to place and segregate functionality in three-dimensional porous solids in a predictable way. Indeed, recent studies of mixed crystalline frameworks suggest a preference for the statistical distribution of functionalities throughout the pores rather than, for example, the functional group localization found in the reactive sites of enzymes. This is a potential limitation for ‘one-pot’ chemical syntheses of porous frameworks from simple starting materials. An alternative strategy is to prepare porous solids from synthetically preorganized molecular pores. In principle, functional organic pore modules could be covalently prefabricated and then assembled to produce materials with specific properties. However, this vision of mix-and-match assembly is far from being realized, not least because of the challenge in reliably predicting three-dimensional structures for molecular crystals, which lack the strong directional bonding found in networks. Here we show that highly porous crystalline solids can be produced by mixing different organic cage modules that self-assemble by means of chiral recognition. The structures of the resulting materials can be predicted computationally, allowing in silico materials design strategies. The constituent pore modules are synthesized in high yields on gram scales in a one-step reaction. Assembly of the porous co-crystals is as simple as combining the modules in solution and removing the solvent. In some cases, the chiral recognition between modules can be exploited to produce porous organic nanoparticles. We show that the method is valid for four different cage modules and can in principle be generalized in a computationally predictable manner based on a lock-and-key assembly between modules.

Porous, Fluorescent, Covalent Triazine-Based Frameworks Via Room-Temperature and Microwave-Assisted Synthesis

Porous, fluorescent, covalent triazine-based frameworks (CTFs) are obtained in an unprecedentedly mild reaction, opening up a scalable pathway for molecular building blocks previously thought incompatible with this chemistry. Choice of monomers and synthetic conditions determines the optical properties and nano-scale ordering of these highly microporous materials with BET surface areas exceeding 1100 m(2) g(-1) and exceptional CO(2) capacities (up to 4.17 mmol g(-1)).

Tunable Organic Photocatalysts for Visible-Light-Driven Hydrogen Evolution

Photocatalytic hydrogen production from water offers an abundant, clean fuel source, but it is challenging to produce photocatalysts that use the solar spectrum effectively. Many hydrogen-evolving photocatalysts are active in the ultraviolet range, but ultraviolet light accounts for only 3% of the energy available in the solar spectrum at ground level. Solid-state crystalline photocatalysts have light absorption profiles that are a discrete function of their crystalline phase and that are not always tunable. Here, we prepare a series of amorphous, microporous organic polymers with exquisite synthetic control over the optical gap in the range 1.94-2.95 eV. Specific monomer compositions give polymers that are robust and effective photocatalysts for the evolution of hydrogen from water in the presence of a sacrificial electron donor, without the apparent need for an added metal cocatalyst. Remarkably, unlike other organic systems, the best performing polymer is only photoactive under visible rather than ultraviolet irradiation.

Metal–Organic Conjugated Microporous Polymers

Zwei vielseitige Strategien fur die Herstellung von Metall-organischen konjugierten mikroporosen Polymeren (MO-CMPs) mit Metallen wie Rhenium, Rhodium und Iridium werden beschrieben (siehe Beispiel). Diese Materialien vereinen in sich zwei Merkmale: eine ausgedehnte, unterbrechungsfreie elektronische Konjugation und das Vorhandensein katalytisch aktiver Metallzentren

A new method for maintaining homogeneity during liquid–hydrogel transitions using low molecular weight hydrogelators

We demonstrate a generic new approach to produce homogeneous and reproducible hydrogels from low molecular weight hydrogelators using the controlled hydrolysis of glucono-δ-lactone (GdL). GdL slowly hydrolyses in water to give gluconic acid, which controllably lowers the pH. This hydrolysis is slower than the rate of dissolution; hence uniform pH change throughout the sample is possible. This results in homogeneous hydrogels that are unaffected by their shear or mixing history. A further advantage of this method is that it allows the gelation process to be monitored, giving further insight into the mechanism by which gelation occurs.

Hypercrosslinked organic polymer networks as potential adsorbents for pre-combustion CO2 capture

Hypercrosslinked polymers (HCPs) synthesized by copolymerisation of p-dichloroxylene (p-DCX) and 4,4′-bis(chloromethyl)-1,1′-biphenyl (BCMBP) constitute a family of low density porous materials with excellent textural development. Such polymers show microporosity and mesoporosity and exhibit Brunauer–Emmett–Teller (BET) surface areas of up to 1970 m2 g−1. The CO2 adsorption capacity of these polymers was evaluated using a thermogravimetric analyser (atmospheric pressure tests) and a high-pressure magnetic suspension balance (high pressure tests). CO2 capture capacities were related to the textural properties of the HCPs. The performance of these materials to adsorb CO2 at atmospheric pressure was characterized by maximum CO2 uptakes of 1.7 mmol g−1 (7.4 wt%) at 298 K. At higher pressures (30 bar), the polymers show CO2 uptakes of up to 13.4 mmol g−1 (59 wt%), superior to zeolite-based materials (zeolite 13X, zeolite NaX) and commercial activated carbons (BPL, Norit R). In addition, these polymers showed low isosteric heats of CO2 adsorption and good selectivity towards CO2. Hypercrosslinked polymers have potential to be applied as CO2 adsorbents in pre-combustion capture processes where high CO2 partial pressures are involved.