Two types (imine and boronate) of covalent organic frameworks (COFs) having a porphyrin unit have been synthesized. The two highly crystalline porphyrin COFs (COF-366 and COF-66) display excellent chemical and thermal stability and are permanently porous. Two-dimensional extended layered structures of the two COFs demonstrate very high charge carrier mobility values (8.1 cm2 V−1 s−1).

Conspectus Nanotechnology has been cited as a response to the most challenging issues facing society as a whole today. With nanoscale assemblies promising to improve on previously established therapeutic and diagnostic motifs, medicine stands to benefit significantly from advances in nanotechnology. To this end, the use of delivery platforms has attracted attention during the past decade, with researchers shifting their focus towards devising ways to deliver therapeutic and / or diagnostic agents, and away from developing new drug candidates. Metaphorically, the use of delivery platforms in medicine can be viewed as the “bow-and-arrow” approach, where the drugs are the arrows and the delivery vehicles are the bows. Even if one possesses the best arrows that money can buy, the arrows are not going to be useful if one does not have the appropriate bow to deliver the arrows to a desired location. The same can be said of drugs. Currently, a variety of strategies for delivering bioactive agents within living tissue exists. Dendrimers, polymers, micelles, vesicles, and nanoparticles have all been investigated for their use as possible delivery vehicles. With the growth of nanomedicine, one can then envisage the possibility in theranostic medicine of fabricating a vector that is capable of releasing simultaneously powerful therapeutics and diagnostic markers selectively to diseased tissue. In our design of new theranostic delivery systems, we have focused our attention on using mesoporous silica nanoparticles (SNPs). It is possible to store a payload of “cargo” molecules within such a robust platform that is stable to a wide range of chemical conditions. This stability allows SNPs to be functionalized with responsive mechanically interlocked molecules (MIMs) in the shape of bistable rotaxanes and psuedorotaxanes to yield mechanized silica nanoparticles (MSNPs). These MIMs can be designed in such a way that they either change shape or shed off some of their parts in response to a specific stimulus, allowing a theranostic payload to be released from the nanopores to a precise location at the most ideal time. In this Account, we chronicle the evolution of various MSNPs which came about as a result of our decade-long collaboration, and discuss advances that have been made in synthesizing novel hybrid mesoporous silica nanoparticles, and the various MIMs which have been attached to their surfaces. Recognizing the theranostics of the future, we aim to start moving out of the chemical domain and into the biological one, with some MSNPs already being subjected to biological testing.

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Time and time again humanity is faced with a unifying global crisis that crosses the many great divides in different societies and serves to bring once segregated communities back together as a collective whole. This global community instinctively turns to science to develop the means of addressing its most pressing problems. More often than not, these forces dictate the direction that scientific research takes. This influence is no more apparent than in the field of supramolecular chemistry where, for decades now, its responsibility to tackle such issues has been put on the back burner as a consequence of a lack of platforms with which to deliver this contemporary brand of chemistry to meaningful applications. However, the tide is slowly turning as new materials emerge from the field of nanotechnology that are poised to host the many attractive attributes that are inherent in the chemistry of these supermolecules and also in the mechanostereochemistry of mechanically interlocked molecules (MIMs), which can be reused as a sequel to supramolecular chemistry. Mesoporous silica nanoparticles (SNPs) have proven to be supremely effective solid supports as their surfaces are easily functionalised with either supermolecules or MIMs. In turn, the blending of supramolecular chemistry and mechanostereochemistry with mesoporous SNPs has led to a new class of materials - namely, mechanised SNPs that are effectively biological nanoscale 'bombs' that have the potential to infiltrate cells and then, upon the pulling of a chemical trigger, explode! The development of these materials has been driven by the need to devise new therapies for the treatment of cancer. Recent progress in research promises not only to control the acuteness of this widespread and insidious disease, but also to make the harsh treatment less debilitating to patients. This global scourge is the unifying force that has brought together supramolecular chemistry, mechanostereochemistry and nanotechnology, uniting these three communities for the common good. At the nanoscale level, the mechanism for the release of cargos from the confines of the nanopores in the SNPs is accomplished by way of mechanical modifications made on the surface of these functionalised supports. These mechanical motions rely on both supramolecular, i.e., host-guest complexes, and mechanostereochemical phenomena (e.g., bistable rotaxanes), which are often stimulated by changes in pH, light and redox potentials, in addition to enzymatic catalysis. The future of this field lies in the development of 'smart bombs' wherein the loaded mechanised SNPs are endocytosed selectively by cancer cells, whereupon an intracellular trigger causes release of a cytotoxin, effectively leading to apoptosis. This review serves to highlight (1) the evolution of surface-functionalisation of SNPs with supermolecules and also with MIMs, (2) the mechanisms through which controlled-release of cargo from mechanised SNPs occurs, and (3) results from the in vitro application of these mechanised SNPs.