Cascading of Molecular Logic Gates for Advanced Functions: A Self-Reporting, Activatable Photosensitizer

Cataloged from PDF version of article.Logical progress: Independent molecular logic gates have been designed and characterized. Then, the individual molecular logic gates were coerced to work together within a micelle. Information relay between the two logic gates was achieved through the intermediacy of singlet oxygen. Working together, these concatenated logic gates result in a self-reporting and activatable photosensitizer. GSH=glutathione

Selective photosensitization through an and logic response: Optimization of the pH and glutathione response of activatable photosensitizers

A series of pH and GSH responsive photosensitizers were designed and synthesized. pKa values were optimized by adjusting the inductive contribution of substituents to reach a pH range (6.0-7.4) relevant to the tumour microenvironment. pH-Activatable behaviour and redox mediated release of the quencher from the PS by GSH allow the construction of an AND logic operator for selective photodynamic action in aqueous solutions. © The Royal Society of Chemistry 2015

Proof of principle for a molecular 1:2 demultiplexer to function as an autonomously switching theranostic device

Cataloged from PDF version of article.Guided by the digital design concepts, we synthesized a two-module molecular demultiplexer (DEMUX) where the output is switched between emission at near IR, and cytotoxic singlet oxygen, with light at 625 nm as the input (I), and acid as the control (c). In the neutral form, the compound fluoresces brightly under excitation at 625 nm, however, acid addition moves the absorption bands of the two modules in opposite directions, resulting in an effective reversal of excitation energy transfer direction, with a concomitant upsurge of singlet oxygen generation and decrease in emission intensity

Toward singlet oxygen delivery at a measured rate: A self-reporting photosensitizer

A Bodipy-based energy transfer cassette with a singlet oxygen reactive linker between the donor and acceptor modules has an interesting emergent property, if the acceptor module is also a photosensitizer. Singlet oxygen produced by the photosensitizer reacts rapidly with the molecule itself to liberate the energy donor, resulting in an enhanced fluorescence emission. The result is a self-reporting photosensitizer providing an assessment of the singlet oxygen production rate under the operational conditions. © 2014 American Chemical Society

Proof of principle for a molecular 1 : 2 demultiplexer to function as an autonomously switching theranostic device

Guided by the digital design concepts, we synthesized a two-module molecular demultiplexer (DEMUX) where the output is switched between emission at near IR, and cytotoxic singlet oxygen, with light at 625 nm as the input (I), and acid as the control (c). In the neutral form, the compound fluoresces brightly under excitation at 625 nm, however, acid addition moves the absorption bands of the two modules in opposite directions, resulting in an effective reversal of excitation energy transfer direction, with a concomitant upsurge of singlet oxygen generation and decrease in emission intensity. © The Royal Society of Chemistry 2013

Towards unimolecular luminescent solar concentrators: bodipy-based dendritic energy-transfer cascade with panchromatic absorption and monochromatized emission

Cataloged from PDF version of article.Ein in ein Polymer eingebetteter, panchromatischer Bodipy-Absorber mit eingebautem Energiegradienten konzentriert einfallende Sonnenstrahlung an einem endständigen Chromophor und erzeugt so eine monochromatische Emission an den Seiten des Polymer-Wellenleiters (siehe Bild). Dieses besondere Design minimiert Selbstabsorptionsverluste der peripheren Antennen-Einheiten mit einem beeindruckenden S-Faktor von 10 000

Near-IR-Triggered, Remote-Controlled Release of Metal Ions: A Novel Strategy for Caged Ions

Cataloged from PDF version of article.A ligand incorporating a dithioethenyl moiety is cleaved into fragments which have a lower metal-ion affinity upon irradiation with low-energy red/near-IR light. The cleavage is a result of singlet oxygen generation which occurs on excitation of the photosensitizer modules. The method has many tunable factors that could make it a satisfactory caging strategy for metal ions

Towards unimolecular luminescent solar concentrators: Bodipy-based dendritic energy-transfer cascade with panchromatic absorption and monochromatized emission

A polymer-embedded dendritic, bodipy-based panchromatic absorber with a built-in energy gradient concentrates incident solar radiation at a terminal chromophore, resulting in a monochromatized emission directed to the sides of the polymer waveguide (see picture). This particular design minimizes self-absorption losses from the peripheral antenna units with an impressive S factor of 10 000. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Energy consumption in chemical fuel-driven self-assembly

Nature extensively exploits high-energy transient self-assembly structures that are able to perform work through a dissipative process. Often, self-assembly relies on the use of molecules as fuel that is consumed to drive thermodynamically unfavourable reactions away from equilibrium. Implementing this kind of non-equilibrium self-assembly process in synthetic systems is bound to profoundly impact the fields of chemistry, materials science and synthetic biology, leading to innovative dissipative structures able to convert and store chemical energy. Yet, despite increasing efforts, the basic principles underlying chemical fuel-driven dissipative self-assembly are often overlooked, generating confusion around the meaning and definition of scientific terms, which does not favour progress in the field. The scope of this Perspective is to bring closer together current experimental approaches and conceptual frameworks. From our analysis it also emerges that chemically fuelled dissipative processes may have played a crucial role in evolutionary processes

An autonomous chemically fuelled small-molecule motor

Molecular machines are among the most complex of all functional molecules and lie at the heart of nearly every biological process. A number of synthetic small-molecule machines have been developed, including molecular muscles, synthesizers, pumps, walkers, transporters and light-driven and electrically driven rotary motors. However, although biological molecular motors are powered by chemical gradients or the hydrolysis of adenosine triphosphate (ATP), so far there are no synthetic small-molecule motors that can operate autonomously using chemical energy (that is, the components move with net directionality as long as a chemical fuel is present). Here we describe a system in which a small molecular ring (macrocycle) is continuously transported directionally around a cyclic molecular track when powered by irreversible reactions of a chemical fuel, 9-fluorenylmethoxycarbonyl chloride. Key to the design is that the rate of reaction of this fuel with reactive sites on the cyclic track is faster when the macrocycle is far from the reactive site than when it is near to it. We find that a bulky pyridine-based catalyst promotes carbonate-forming reactions that ratchet the displacement of the macrocycle away from the reactive sites on the track. Under reaction conditions where both attachment and cleavage of the 9-fluorenylmethoxycarbonyl groups occur through different processes, and the cleavage reaction occurs at a rate independent of macrocycle location, net directional rotation of the molecular motor continues for as long as unreacted fuel remains. We anticipate that autonomous chemically fuelled molecular motors will find application as engines in molecular nanotechnology.</p