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Following an overview of the approaches and techniques used to acheive super-resolution microscopy, this review presents the advantages supplied by nanoparticle based probes for these applications. The various clases of nanoparticles that have been developed toward these goals are then critically described and these discussions are illustrated with a variety of examples from the recent literature.

Recently, the low-dimensional organic-inorganic halide perovskites (OIHP) have been exploited heavily for their favorable exciton dynamics, broad-band emission, remarkable stability, and tunable band-edge excited-state energy compared to their 3D counterparts for potential optoelectronic applications. Low-dimensional perovskites are generally good candidates for utilization as room-temperature photoluminescence (PL) materials. Further, doping divalent transition metals like Mn

The photoinduced organic transformation has stimulated the organic chemistry community to develop light-driven renewed reaction methodologies, which in many cases are complementary to standard thermal catalysis. This revitalization of photoinduced transformations is in part due to the straightforward access to powerful photosensitizers. Among those, Ru(II) and Ir(III) polypyridyl complexes have been extensively utilized as prototypical photoredox catalyst. Despite the flourish of new organic reactivity, studies of photocatalytic cycles are still scarce. The current mechanistic proposal mostly relies on luminescence quenching studies, empirical redox potentials, and bond-dissociation energy values, which provide a partial picture of the real catalytic processes occurring. Besides, quantum efficiency and overall energy efficiency of photoredox organic transformation are not usually considered merit yet. On the other hand, during the last decades, the photochemistry community has studied the energy and electron transfer mechanism of transition metal complexes from the ground and the excited-state extensively, without fully understanding the catalytic photoredox cycles probably due to its complexity. Those studies are needed to develop new photoredox organic transformations further and make them more sustainable and energy-efficient. We outline an overview of selected basic concepts of photophysics and photochemistry encountered in the photocatalytic cycles in this context. Selected examples of studies are detailed in the review to illustrate how steady-state and time-resolved optical spectroscopy can be employed to elucidate catalytic intermediates and photocatalytic mechanisms. As such, this review aims to motivate mechanistic studies on photoredox catalysis and serve as a guide to perform them to develop more sustainable and energy-efficient chemical transformations.

Postmodification of reticular materials with well‐defined catalysts is an appealing approach to produce new catalytic functional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal–organic frameworks (MOFs) to exploit the potential of crystal‐to‐crystal transformations for further characterization of the catalysts. In this regard, two new photocatalytic materials, MOF‐520‐PC1 and MOF‐520‐PC2, are straightforwardly obtained by the postfunctionalization of MOF‐520 with perylene‐3‐carboxylic acid (PC1) and perylene‐3‐butyric acid (PC2). The single crystal‐to‐crystal transformation yielded the X‐ray diffraction structure of catalytic MOF‐520‐PC2. The well‐defined disposition of the perylenes inside the MOF served as suitable model systems to gain insights into the photophysical properties and mechanism by combining steady‐state, time‐resolved, and transient absorption spectroscopy. The resulting materials are active organophotoredox catalysts in the reductive dimerization of aromatic aldehydes, benzophenones, and imines under mild reaction conditions. Moreover, MOF‐520‐PC2 can be applied for synthesizing gram‐scale quantities of products in continuous‐flow conditions under steady‐state light irradiation. This work provides an alternative approach for the construction of well‐defined, metal‐free, MOF‐based catalysts., We thank the ICIQ Foundation, the European Research Foundation for project ERC‐2014‐CoG 648304 (J.L.‐F.), MINECO (CTQ2016‐80038‐R; J.L.‐F.), and AGAUR 2017‐SGR‐1647 (J.L.‐F.) for funding. S.S.M. and N.K. are grateful to Marie‐Curie COFUND and JyC for postdoctoral scholarships, respectively.

A new family of cobalt complexes with the general formula [CoII(OTf)2(Y,XPyMetacn)] (1R,Y,XPyMetacn ¼ 1-[(4-X-3,5-Y-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, (X ¼ CN (1CN), CO2Et (1CO2Et), Cl (1Cl), H(1H), NMe2 (1NMe2)) where (Y ¼ H, and X ¼ OMe when Y ¼ Me (1DMM)) is reported. We found that the electronic tuning of the Y,XPyMetacn ligand not only has an impact on the electronic and structural properties of the metal center, but also allows for a systematic water-reduction-catalytic control. In particular, the increase of the electron-withdrawing character of the pyridine moiety promotes a 20-fold enhancement of the catalytic outcome. By UV-Vis spectroscopy, luminescence quenching studies and Transient Absorption Spectroscopy (TAS), we have studied the direct reaction of the photogenerated [IrIII(ppy)2(bpyc )] (PSIr) species to form the elusive CoI intermediates. In particular, our attention is focused on the effect of the ligand architecture in this elemental step of the catalytic mechanism. Finally, kinetic isotopic experiments together with DFT calculations provide complementary information about the rate-determining step of the catalytic cycle We would like to thank the European Commission for the ERCCG-2014-648304 (J.Ll.-F) project. The financial support from ICIQ Foundation and CELLEX Foundation through the CELLEXICIQ high throughput experimentation platform and the Starting Career Program is gratefully acknowledged. We also thank CERCA Programme (Generalitat de Catalunya); The MINECO is acknowledged for a FPU fellowship to A.C (AP2012- 6436) and ICIQ-IPMP program (F.F.) and Severo Ochoa Excellence Accreditation 2014–2018 (SEV-2013-0319). J.M.L. is grateful for financial support from the Spanish MINECO CTQ2014-52525-P and the Catalan DIUE 2014SGR931. J.P-P. gratefully acknowledge CTQ2014-60174-P (partially co-financed with FEDER funds), Maria de Maeztu (MDM-2015-0538), RyC contract to MGB) and Fundación Ramón Areces for financial support

An engineered hydrogel platform has been developed, in the absence of any toxic solvents or reagents, by the supramolecular self-assembly of three different components: a poly-β-cyclodextrin polymer, a hydrophobically modified dextran, and a photoactivatable bichromophoric molecular conjugate designed to photorelease nitric oxide (NO) with a fluorescent reporting function. The multivalent character of the interactions between the all components and the poor solubility of the conjugate in aqueous medium ensure the stability of the hydrogel and the lack of leaching of the photoactive cargo from the gel network under physiological conditions, even in the absence of protective coating agents. The photochemical properties of the molecular conjugate are retained in the supramolecular matrix, as demonstrated by the remote-controlled release of NO upon visible light excitation simultaneously to the activation of a fluorescent reporting function, which allows easy monitoring of the photoreleased NO.

Nanoparticles with photoresponsive character can be assembled from amphiphilic macromolecular components and hydrophobic chromophores. In aqueous solutions, the hydrophobic domains of these species associate to produce spontaneously nanosized hosts with multiple photoresponsive guests in their interior. The modularity of this supramolecular approach to nanostructured assemblies permits the co-encapsulation of distinct subsets of guests within the very same host. In turn, the entrapped guests can be designed to interact upon light excitation and exchange electrons, energy or protons. Such photoinduced processes permit the engineering of properties into these supramolecular constructs that would otherwise be impossible to replicate with the separate components. Alternatively, noninteracting guests with distinct functions can be entrapped in these supramolecular containers to ensure multifunctional character. In fact, biocompatible luminescent probes with unique photochemical and photophysical signatures have already emerged from these fascinating investigations. Thus, polymer nanocarriers can become invaluable supramolecular scaffolds for the realization of multifunctional and photoresponsive tools for a diversity of biomedical applications.

We report herein the design, preparation and characterisation of a new, water soluble, nanoplatform for the light-triggered release of nitric oxide (NO). This nanoconstruct has been achieved by exploiting a layer-by-layer approach to assembly a polyelectrolyte modified with a NO photochemical precursor, around citrate stabilized gold colloidal template. Combined spectroscopic and transmission electron microscopy analysis show that the layered hybrid nanoparticles remain stable under physiological conditions without any significant clustering along the different coating processes. The photochemical properties of the NO photocage are well preserved upon its covalent grafting in the polymeric skeleton, before and after the of the metal colloids. The direct and in real time monitoring of NO using an ultrasensitive electrode unambiguously shows the light-stimulated NO release from modified gold nanoparticles and demonstrates that the approach used permits the accurate regulation of the NO reservoir on the nanoparticles surface.

Hybrid gold nanoclusters exhibiting photoregulated release of nitric oxide are obtained by appropriate self-assembling of a suitable host, a photoactivable guest and Au nanoparticles. The excitation of the core, the shell or both components of the nanoclusters with visible light, together with their dark stability and water solubility, make these nanoarchitectures intriguing candidates to be tested in biomedical research studies.

Modulation in the photophysical properties and intramolecular electron transfer behavior of the flavin adenine dinucleotide (FAD) molecule has been investigated in the presence of the macrocyclic hosts, alpha-, beta- and gamma-cyclodextrins (CDs), using absorption and steady-state and time-resolved fluorescence measurements. The results demonstrate that only the beta-CD host has a suitable cavity dimension to form a weak inclusion complex with FAD by encapsulating the adenine moiety, which is the preferred binding site in the large FAD molecule. Interestingly, in spite of the weak binding interaction, a significant enhancement in the fluorescence intensity of FAD is observed on complexation with beta-CD, and this has been attributed mainly to the modulation in the conformational dynamics of FAD in the presence of beta-CD. In aqueous solutions, a good fraction of FAD molecules exist in a "closed" conformation with the adenine and isoalloxazine rings stacked on each other, thus leading to very efficient fluorescence quenching due to the ultrafast intramolecular electron transfer from adenine to the isoalloxazine moiety. Complex formation with beta-CD inhibits this intramolecular electron transfer by changing the "closed" conformation of FAD to the "open" form, wherein the adenine and isoalloxazine moieties are widely separated, thus prohibiting the fluorescence quenching process. Further evidence for the conformational changes has been obtained by the observation of a long lifetime component in the fluorescence decay of FAD in the presence of beta-CD, which corresponds to the decay of the unquenched "open" form of FAD. Fluorescence up-conversion studies also indicate the absence of any ultrafast component in the fluorescence decay arising from the complexed FAD, thus supporting the formation of the "open" form in the presence of beta-CD, with no intramolecular electron transfer.

A non-fluorescent naphthalene diimide (NDI) dimer, conjugating red and blue NDI dyes, becomes red/NIR emitting upon G-quadruplex binding. The fluorescence lifetime which is significantly different for the complexes, the G-quadruplex/dimer and the weakly emitting ds-DNA/dimer is the key feature for the development of new rationally engineered G-quadruplex sensors.

We have developed a multifunctional biocompatible nanoconstruct based on polymeric nanoparticles encapsulating a molecular conjugate, able to photorelease nitric oxide (NO) with a fluorescent reporting function. We demonstrate that two-photon excitation (TPE) using biofriendly NIR 700 nm laser light can be applied for monitoring as well as triggering the release of NO, wherein the uncaging of a strongly fluorescent co-product acts in turn as a TPE fluorescent reporter for the simultaneous NO release from the nanoassembly. This supramolecular nanodevice internalizes in skin carcinoma cells, induces significant cell death upon light excitation and preserves its TPE properties, allowing the nearly instantaneous quantification of the NO photoreleased in cancer cells by two-photon NIR fluorescence microscopy.

We have developed herein an engineered polymer-based nanoplatform showing the convergence of two-photon fluorescence imaging and bimodal phototherapeutic activity in a single nanostructure. It was achieved through the appropriate choice of three different components: a β-cyclodextrin-based polymer acting as a suitable carrier, a zinc phthalocyanine emitting red fluorescence simultaneously as being a singlet oxygen ((1)O2) photosensitizer, and a tailored nitroaniline derivative, functioning as a nitric oxide (NO) photodonor. The self-assembly of these components results in photoactivable nanoparticles, approximately 35 nm in diameter, coencapsulating a multifunctional cargo, which can be delivered to carcinoma cells. The combination of steady-state and time-resolved spectroscopic and photochemical techniques shows that the two photoresponsive guests do not interfere with each other while being enclosed in their supramolecular container and can thus be operated in parallel under control of light stimuli. Specifically, two-photon fluorescence microscopy allows mapping of the nanoassembly, here applied to epidermal cancer cells. By detecting the red emission from the phthalocyanine fluorophore it was also possible to investigate the tissue distribution after topical delivery onto human skin ex vivo. Irradiation of the nanoassembly with visible light triggers the simultaneous delivery of cytotoxic (1)O2 and NO, resulting in an amplified cell photomortality due to a combinatory effect of the two cytotoxic agents. The potential of dual therapeutic photodynamic action and two-photon fluorescence imaging capability in a single nanostructure make this system an appealing candidate for further studies in biomedical research.

A multifunctional nanoplatform with four-in-one photoresponsive functionalities has been achieved through the co-encapsulation of two chromo-fluorogenic components within biocompatible polymeric nanoparticles. This engineered nanoconstruct efficiently delivers different photosensitizers in melanoma cells, which can be detected through their dual-color fluorescence, and induces amplified cell mortality due to the simultaneous photogeneration of singlet oxygen and nitric oxide.

A viable strategy to encapsulate a fluorophore/photochrome dyad and a nitric oxide photodonor within supramolecular assemblies of a cyclodextrin-based polymer in water was developed. The two photoresponsive guests do not interact with each other within their supramolecular container and can be operated in parallel under optical control. Specifically, the dyad permits the reversible switching of fluorescence on a microsecond timescale for hundreds of cycles, and the photodonor enables the irreversible release of nitric oxide. Furthermore, these supramolecular assemblies cross the membrane of human melanoma cancer cells and transport their cargo in the cytosol. The fluorescence of one component allows the visualization of the labeled cells, and its switchable character could, in principle, be used to acquire super-resolution images, while the release of nitric oxide from the other induces significant cell mortality. Thus, our design logic for the construction of biocompatible nanoparticles with dual functionality might evolve into the realization of valuable photoresponsive probes for imaging and therapeutic applications.

Herein we report the design, preparation, and properties of a supramolecular system based on a tailored nitric oxide (NO) photodonor and a rhodamine-labeled β-cyclodextrin conjugate. The combination of spectroscopic and photochemical experiments shows the absence of significant interchromophoric interactions between the host and the guest in the excited states. As a result, the complex is able to release NO under the exclusive control of visible light, as unambiguously demonstrated by direct detection of this transient species through an amperometric technique, and exhibits the typical red fluorescence of the rhodamine appendage. The supramolecular complex effectively internalizes in HeLa cancer cells as proven by fluorescence microscopy, shows a satisfactory biocompatibility in the dark, and induces about 50% of cell mortality upon irradiation with visible light. The convergence of all these properties in one single complex makes the present host-guest ensemble an appealing candidate for further delevopment of photoactivatable nanoscaled systems addressed to photostimulated NO-based therapy.

We have developed a supramolecular nanoassembly capable of inducing remarkable levels of cancer cell mortality through a bimodal action based on the simultaneous photogeneration of nitric oxide (NO) and singlet oxygen ((1)O(2)). This was achieved through the appropriate incorporation of an anionic porphyrin (as (1)O(2) photosensitizer) and of a tailored NO photodonor in different compartments of biocompatible nanoparticles based on cationic amphiphilic cyclodextrins. The combination of steady-state and time-resolved spectroscopic techniques showed the absence of significant intra- and interchromophoric interaction between the two photoactive centers embedded in the nanoparticles, with consequent preservation of their photodynamic properties. Photodelivery of NO and (1)O(2) from the nanoassembly on visible light excitation was unambiguously demonstrated by direct and real-time monitoring of these transient species through amperometric and time-resolved infrared luminescence measurements, respectively. The typical red fluorescence of the porphyrin units was essentially unaffected in the bichromophoric nanoassembly, allowing its localization in living cells. The convergence of the dual therapeutic action and the imaging capacities in one single structure makes this supramolecular architecture an appealing, multifunctional candidate for applications in biomedical research.

The interaction of 1,4-dihydroxy-9,10-anthraquinone, (quinizarin; QZ), with alpha-, beta- and gamma-cyclodextrin (CD) hosts, has been investigated using absorption, and steady-state and time-resolved fluorescence measurements, in order to understand the effects of cavity size of CDs on the binding of QZ molecule and the changes in the photophysical properties of QZ in the microenvironment of the hosts. The results demonstrate that QZ forms inclusion complexes with all the CDs. The low binding constants as well as the thermodynamic parameters indicate that the mode of interaction between QZ and CDs is mainly hydrophobic in nature. The relative magnitudes of the binding constants and the differential enhancements in the fluorescence intensity of QZ upon complexation with the CDs can be explained by considering the relative dimensions of the host cavity and the guest molecule, as well as the orientation of the guest molecule inside the CD cavity. It is proposed that the unsubstituted benzene ring of QZ is encapsulated within alpha- and beta-CD cavities whereas the dihydroxy-substituted aromatic ring is encapsulated within the gamma-CD cavity. This is further supported by the complexation studies of the QZ.CD systems with Al(III) ions. It is observed that the complexation of QZ with the metal ion is enhanced in the QZ.alpha-CD and QZ.beta-CD systems whereas it is significantly reduced in the QZ.gamma-CD system, due to shielding of the chelating groups of the dye inside the CD cavity in the latter case.

We have developed an engineered hydrogel formed, in the absence of any toxic solvents or reagents, by spontaneous self-assembly of three key components: a poly-β-cyclodextrin polymer (1), a hydrophobically modified dextran (2) and a nitric oxide (NO) photodonor bearing an adamantyl appendage (3). The formation of this supramolecular assembly is based on a "lock-and-key" mechanism in which the alkyl side chains of 2 and the adamantane moiety of 3 form inclusion complexes with the β-CD cavities of 1. The multivalent character of the interactions between all components and the insolubility of the NO photodonor in an aqueous medium ensure the stability of the hydrogel and the total lack of leaching of the photoactive component from the gel network under physiological conditions, even in the absence of protective coating agents. The photochemical properties of the NO photodonor are well preserved in the supramolecular matrix as demonstrated by the remote-controlled release of NO through visible light excitation and its transfer to a protein such as myoglobin. The utility of this NO photoreleasing platform is demonstrated in effective and strictly light-dependent bactericidal activity against the Gram-negative Escherichia coli bacterial colony suspension.

The achievement of nanovehicles able to release therapeutic agents in a controlled fashion is a major challenge in the burgeoning field of nanomedicine. Light represents the most elegant and non-invasive trigger to deliver bio-active compounds on demand since it allows the accurate control of three key factors determining the positive therapeutic outcome such as site, timing and dosage. Monomeric and aggregate forms of both natural and modified cyclodextrins (CDs) offer useful biocompatible scaffolds to bind suitable phototherapeutic agents preserving, in most cases, their photochemical properties. In this contribution we shall illustrate some representative examples of photoresponsive CD-based nanoassemblies achieved in others and our laboratories in recent years, underlying the logical design and highlighting the potential applications in some major areas, such as photodynamic, photothermal and nitric oxide-stimulated therapy.