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Luminescent copper(I)-based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self-assembly. However, for Cu(I) compounds the formation of supramolecular systems is challenging due to the coordinative diversity of copper centers. This works shows that this diversity can be exploited in the construction of responsive systems. In detail, the changes in the emissive profile of different aggregates formed in water by phosphine-thioether copper(I) derivatives were followed. Our results demonstrate that the self-assembly and disassembly of Cu(I)-based coordination polymeric nanoparticles (CPNs) is sensitive to solvent composition. The solvent-induced changes are related to modifications in the coordination sphere of copper at the molecular level, which alters not only the emission profile but also the morphology of the aggregates. Our findings are expected to inspire the construction of smart supramolecular systems based on dynamic coordinative metal centers.

Aggregation induced emission is a very interesting phenomenon that recently has attracted a lot of interest. Most of the examples deal with organic molecules or flat metal complexes. Here we demonstrate that, by design, even iridium compounds can display this process without shifting the emission energy. In order to enhance the aggregation properties we have focussed on amphiphilic complexes. We report the synthesis and photophysical characterisation of a blue-emitting bolaamphiphilic zwitterionic Ir(III) complex and an analogous cationic amphiphilic compound, used as a reference. The bolaamphiphile exhibited blue (λmax = 450 nm) emission in dilute, deaerated solution with a photoluminescence quantum yield (PLQY) of 22%, similar to the related cationic amphiphilic complex. The bolaamphiphile displayed significant emission enhancement in the solid state, with an emission quantum yield that reach 52%. Interestingly, the emission of the cationic analogue suffers from aggregation quenching in the solid state, (PLQY = 3%) as is common for these type of complexes. A correlation between the photophysical data and the arrangement in the solid state is discussed.

A family of neutral bis-cyclometalated Ir(III) complexes based on phenanthridine (phent) derivates as cyclometalating ligands and picolinate as an ancillary ligand are described. The influence of extended conjugation, rigidity, and hydrophobicity as well as the electronic nature of the substituents were investigated in relation to the photoluminescence, PL, and electrochemiluminescence, ECL, properties. A significant increase of ECL in aqueous media is observed upon extension of the aromatic system or by substituting the phenyl with a dibenzofurane moiety, in compounds

We describe, for a single platinum complex bearing a dipeptide moiety, a solvent-driven interconversion from twisted to straight micrometric assembled structures with different chirality. The photophysical and morphological properties of the aggregates have been investigated as well as the role of the media and concentration. A real-time visualization of the solvent-driven interconversion processes has been achieved by confocal microscopy. Finally, atomistic and coarse-grained simulations, providing results consistent with the experimental observations, allow to obtain a molecular-level insight into the interesting solvent-responsive behavior of this system., Visualizing the interconversion from chiral helices to ribbons like-structures of self-assembled luminescent platinum complexes.

Synthetic molecular probes, chemosensors, and nanosensors used in combination with innovative assay protocols hold great potential for the development of robust, low-cost, and fast-responding sensors that are applicable in biofluids (urine, blood, and saliva). Particularly, the development of sensors for metabolites, neurotransmitters, drugs, and inorganic ions is highly desirable due to a lack of suitable biosensors. In addition, the monitoring and analysis of metabolic and signaling networks in cells and organisms by optical probes and chemosensors is becoming increasingly important in molecular biology and medicine. Thus, new perspectives for personalized diagnostics, theranostics, and biochemical/medical research will be unlocked when standing limitations of artificial binders and receptors are overcome. In this review, we survey synthetic sensing systems that have promising (future) application potential for the detection of small molecules, cations, and anions in aqueous media and biofluids. Special attention was given to sensing systems that provide a readily measurable optical signal through dynamic covalent chemistry, supramolecular host-guest interactions, or nanoparticles featuring plasmonic effects. This review shall also enable the reader to evaluate the current performance of molecular probes, chemosensors, and nanosensors in terms of sensitivity and selectivity with respect to practical requirement, and thereby inspiring new ideas for the development of further advanced systems.

Self-assembly of biomolecules such as peptides, nucleic acids or their analogues affords supramolecular objects, exhibiting structures and physical properties dependent on the amino-acid or nucleobase composition. Conjugation of the peptide diphenylalanine (FF) to peptide nucleic acids triggers formation of self-assembled structures, mainly stabilized by interactions between FF. In this work we report formation of homogeneous chiral fibers upon self-assembly of the hybrid composed of the tetraphenylalanine peptide (4F) conjugated to the PNA dimer adenine-thymine (at). In this case nucleobases seem to play a key role in determining the morphology and chirality of the fibers. When the PNA "at" is replaced by guanine-cytosine dimer "gc", disordered structures are observed. Spectroscopic characterization of the self-assembled hybrids, along with AFM and SEM studies is reported. Finally, a structural model consistent with the experimental evidence has also been obtained, showing how the building blocks of 4Fat arrange to give helical fibers.

Stimuli-responsive particles have gained considerable interest in many fields of materials science. Among the various possible triggers, light is particularly advantageous due to its easy and effic...

Metal clusters have gained a lot of interest for their remarkable photoluminescence and catalytic properties. However, a major drawback of such materials is their poor stability in air and humidity conditions. Herein we describe a versatile method to synthesize luminescent Cu(I) clusters inside the pores of zeolites, using a sublimation technique with the help of high vacuum and high temperature. The porous materials play an essential role as a protecting media against the undesirable and easy oxidation of Cu(I). The obtained clusters show fascinating luminescence properties, and their reactivity can be triggered by insertion in the pores of organic monodentate ligands such as pyridine or triphenylphosphine. The coordinating ligands can lead to the formation of Cu(I) complexes with completely different emission properties. In the case of pyridine, the final compound was characterized and identified as a cubane-like structure. A thermochromism effect is also observed, featuring, for instance, a hypsochromic effect for a phosphine derivative at 77K. The stability of the encapsulated systems in zeolites is rather enthralling: they are stable and emissive even after several months in the air.

Biocompatible soft materials have recently found applications in interventional endoscopy to facilitate resection of mucosal tumors. When neoplastic lesions are in organs that can be easily damaged by perforation, such as stomach, intestine, and esophagus, the formation of a submucosal fluid cushion (SFC) is needed to lift the tumor from the underlying muscle during the resection of neoplasias. Such procedure is called endoscopic submucosal dissection (ESD). We describe an injectable, biodegradable, hybrid hydrogel able to form a SFC and to facilitate ESD. The hydrogel, based on polyamidoamines, contains breakable silica nanocapsules covalently bound to its network and able to release biomolecules. To promote degradation, the hydrogel is composed of cleavable disulfide moieties that are reduced by the cells through secretion of glutathione. The same stimulus triggers the breaking of the silica nanocapsules; therefore, the entire hybrid material can be completely degraded and its decomposition depends entirely on the presence of cells. Interestingly, the hydrogel precursor solution showed rapid gelation when injected in vivo and afforded a long-lasting high mucosal elevation, keeping the cushion volume constant during the dissection. This novel material can provide a solution to ESD limitations and promote healing of tissues after surgery.

Background: Image-guided liver surgery and interventions are growing as part of the current trend to translate liver procedures into minimally invasive approaches. Hands-on surgical training in such techniques is required. Consequently, a meaningful and realistic liver tumor model using multi-imaging modalities, such as ultrasound (US), computed tomography (CT), magnetic resonance (MR), cone beam-CT (CBCT), is mandatory. The first aim of this study is to develop a novel tumor-mimic model and assess it with multi-imaging modalities. The second aim is to evaluate the usefulness of the model during image-guided liver procedures. Materials and Methods: The tumor-mimic model is made of a composition of hydrogel, smashed muscle, and gadolinium contrast solution. Five ex vivo livers and three pigs were included in the study. Procedures were performed in an experimental hybrid operating room. Under general anesthesia, US guidance was required to inject the biotumor formula into the pig's liver. US, CT, CBCT, and MR acquisitions were then performed after the initial injection. In vivo models were then used to perform liver procedures, including US-guided biopsy, radiofrequency ablation, and laparoscopic resection. Results: The formula developed is easily injected generating a tissue-like material. Visualization using multi-imaging modalities was appropriate, thereby allowing to perform image-guided techniques. Conclusion: A novel design of an in vivo and ex vivo tissue-like tumor liver model is presented. Due to the multimodality imaging appraisal, it may provide a realistic and meaningful model allowing to perform image-guided liver procedures.

Abstract The discovery of aggregation-induced electrochemiluminescence (AIECL) in 2017 opened new research paths in the quest for novel, more efficient emitters and platforms for biological and environmental sensing applications. The great abundance of fluorophores presenting aggregation-induced emission in aqueous media renders AIECL a potentially powerful tool for future diagnostics. In the short time following this discovery, many scientists have found the phenomenon interesting, with research findings contributing to advances in the comprehension of the processes involved and in attempts to design new sensing platforms. Herein, we explore these advances and reflect on the future directions to take for the development of sensing devices based on AIECL. Graphic abstract

International audience; This article describes highly luminescent ionic compounds in liquid and crystalline states, where a naphthalene moiety is conjugated to an imidazolium center decorated with alkyl chains of different lengths. We have characterized, by X-ray diffraction of a single crystal and the liquid, that these compounds are organized in rod-shaped assemblies. The formation of this molecular architecture is governed by ionic interactions that dominate those of the lesser π–π and van der Waals interactions. Consequently, aromatic naphthalene rings are confined to the environment of alkyl chains (diluted in an apolar solvent), thus avoiding the extinction of luminescence by the formation of chromophore excimers, as shown in photophysical data.

The very high adsorption efficiency of Direct Blue (DB), an anionic toxic azo dye, onto amino grafted mesoporous silica nanoparticles (MCM-41), was studied in this paper, for possible industrial applications. Interesting challenges and advances are proposed in this field, presenting an adsorbent able to efficiently and rapidly remove the anionic dye from water. The important added value of this work regards the system recycle, which allows both the DB and adsorbent material recover, with a global reduction of the environmental impact, in the viewpoint of the green economy. Indeed, this paper is the first example of very fast removal and recycle of great amounts of DB with adsorbent materials characterized by impressive adsorption/desorption capacities, at least of around 300 mg/g for each adsorption cycle, potentially increasable by performing consecutive cycles of DB adsorption/desorption. In detail, the MCM-41 amino functionalization (MCM-41-NH2) was obtained after (MCM-41-POST) and during (MCM-41-PRE) the synthesis of MCM-41, obtaining materials with different behavior towards the DB adsorption. The MCM-41-NH2 surface features and porous structure, before and after the dye adsorption, were carefully characterized. Considering the adsorption process, for investigating the nature of the DB/MCM-41-NH2 interaction, several parameters were studied: the contact time, the DB solutions pH values, adsorbent material and dye amount, with the additional analysis of how the adsorption process was influenced by the presence of electrolytes. The isotherms of adsorption were also considered. Although MCM-41-PRE exhibited a higher affinity towards DB molecules, the MCM-41-POST were able to rapidly desorb it, thus recycling both DB and the adsorbent material. (C) 2018 Elsevier B.V. All rights reserved.

An electrochemical biosensor for the detection of cardiac troponin I, cTnI, an important cardiac biomarker, is described. A combination of a novel monoclonal antibody, mAb20B3, and a novel Ir(III)-based metal complex was used for detection using faradaic electrochemical impedance spectroscopy. A limit of detection of 10 ag/mL was achieved, which is significantly lower than established assays. The ability to detect these ultralow concentrations enables rapid and early stage detection of cardiac events and opens up the possibility of developing a point-of-care device.

Over the last years, advancements in the use of nanoparticles for biomedical applications have clearly showcased their potential for the preparation of improved imaging and drug-delivery systems. However, compared to the vast number of currently studied nanoparticles for such applications, only a few successfully translate into clinical practice. A common "barrier" that prevents nanoparticles from efficiently delivering their payload to the target site after administration is related to liver filtering, mainly due to nanoparticle uptake by macrophages. This work reports the physicochemical and biological investigation of disulfide-bridged organosilica nanoparticles with cage-like morphology, OSCs, assessing in detail their bioaccumulation in vivo. The fate of intravenously injected 20 nm OSCs was investigated in both healthy and tumor-bearing mice. Interestingly, OSCs exclusively colocalize with hepatic sinusoidal endothelial cells (LSECs) while avoiding Kupffer-cell uptake (less than 6%) under both physiological and pathological conditions. Our findings suggest that organosilica nanocages hold the potential to be used as nanotools for LSECs modulation, potentially impacting key biological processes such as tumor cell extravasation and hepatic immunity to invading metastatic cells or a tolerogenic state in intrahepatic immune cells in autoimmune diseases.

An important aspect in the field of supramolecular chemistry is the control of the composition and aggregation state of supramolecular polymers and the possibility of stabilizing out-of-equilibrium states. The ability to freeze metastable systems and release them on demand, under spatiotemporal control, to allow their thermodynamic evolution toward the most stable species is a very attractive concept. Such temporal blockage could be realized using stimuli-responsive "boxes" able to trap and redirect supramolecular polymers. In this work, we report the use of a redox responsive nanocontainer, an organosilica nanocage (OSCs), for controlling the dynamic self-assembly pathway of supramolecular aggregates of a luminescent platinum compound (PtAC). The aggregation of the complexes leads to different photoluminescent properties that allow visualization of the different assemblies and their evolution. We discovered that the nanocontainers can encapsulate kinetically trapped species characterized by an orange emission, preventing their evolution into the thermodynamically stable aggregation state characterized by blue-emitting fibers. Interestingly, the out-of-equilibrium trapped Pt species (PtAC@OSCs) can be released on demand by the redox-triggered degradation of OSCs, re-establishing their self-assembly toward the thermodynamically stable state. To demonstrate that control of the self-assembly pathway occurs also in complex media, we followed the evolution of the supramolecular aggregates inside living cells, where the destruction of the cages allows the intracellular release of PtAC aggregates, followed by the formation of microscopic blue emitting fibers. Our approach highlights the importance of "ondemand" confinement as a tool to temporally stabilize transient species which modulate complex self-assembly pathways in supramolecular polymerization.

Astonishingly, 3-hydroxyisonicotinealdehyde (HINA) is despite its small size a green-emitting push–pull fluorophore in water (QY of 15%) and shows ratiometric emission response to biological relevant pH differences (pKa2 ∼ 7.1). Moreover, HINA is the first small-molecule fluorophore reported that possesses three distinctly emissive protonation states. This fluorophore can be used in combination with metal complexes for fluorescent-based cysteine detection in aqueous media, and is readily taken up by cells. The theoretical description of HINA's photophysics remains challenging, even when computing Franck–Condon profiles via coupled-cluster calculations, making HINA an interesting model for future method development., Astonishingly, 3-hydroxyisonicotinealdehyde (HINA) is despite its small size a green-emitting push–pull fluorophore in water (QY of 15%) and shows ratiometric emission response to biological relevant pH differences (pKa2 ∼ 7.1).

Self‐assembly relies on the ability of smaller and discrete entities to spontaneously arrange into more organized systems by means of the structure‐encoded information. Herein, we show that the design of the media can play a role even more important than the chemical design. The media not only determines the self‐assembly pathway at a single‐component level, but in a very narrow solvent composition, a supramolecular homo‐aggregate can be non‐covalently wrapped by a second component that possesses a different crystal lattice. Such a process has been followed in real time by confocal microscopy thanks to the different emission colors of the aggregates formed by two isolated PtII complexes. This coating is reversible and controlled by the media composition. Single‐crystal X‐ray diffraction and molecular simulations based on coarse‐grained (CG) models allowed the understanding of the properties displayed by the different aggregates. Such findings could result in a new method to construct hierarchical supramolecular structures., Taking advantage of the useful emitting features of two platinum complexes, we show how the media regulates the assembly pathways from self‐sorting to an unprecedented reversible, dynamic molecular wrapping of a complex on another assembled structure.

Supplementary data to this article can be found online at https://doi. org/10.1016/j.msec.2020.111721., Zeolites have attractive features making them suitable carriers for drug delivery systems (DDS). As such, we loaded the anticancer drug 5-fluorouracil (5-FU), into two different zeolite structures, faujasite (NaY) and Linde Type L (LTL), to obtain different DDS. The prepared DDS were tested in vitro using breast cancer, colorectal carcinoma, and melanoma cell lines and in vivo using the chick embryo chorioallantoic membrane model (CAM). Both assays showed the best results for the Hs578T breast cancer cells, with a higher potentiation for 5-FU encapsulated in the zeolite LTL. To unveil the endocytic mechanisms involved in the internalization of the zeolite nanoparticles, endocytosis was inhibited pharmacologically in breast cancer and epithelial mammary human cells. The results suggest that a caveolin-mediated process was responsible for the internalized zeolite nanoparticles. Aiming to boost the DDS efficacy, the disc-shaped zeolite LTL outer surface was functionalized using amino (NH2) or carboxylic acid (COOH) groups and coated with poly-L-lysine (PLL). Positively functionalized surface LTL nanoparticles revealed to be non-toxic to human cells and, importantly, their internalization was faster and led to a higher tumor reduction in vivo. Overall, our results provide further insights into the mechanisms of interaction between zeolite-based DDS and cancer cells, and pave the way for future studies aiming to improve DDS anticancer activity., NV and ARB thank FCT (Foundation for Science and Technology) for their Ph.D. grants (SFRH/BD/97797/2013 and SFRH/BD/141058/2018, respectively). This work has been funded by ICVS Scientific Mi croscopy Platform, member of the national infrastructure PPBI - Portu guese Platform of Bioimaging (PPBI-POCI-01-0145-FEDER-022122); by National funds, through the Foundation for Science and Technology (FCT) - project UIDB/50026/2020 and UIDP/50026/2020; and by the projects NORTE-01-0145-FEDER-000013 and NORTE-01-0145-FEDER 000023, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF). This work was also supported by FCT, under the scope of the projects: PTDC/ AAGTEC/5269/2014 and Centre of Chemistry (UID/QUI/00686/2013 and UID/QUI/0686/2016)., info:eu-repo/semantics/publishedVersion

The synthesis of silicon nanoparticles in water has recently attracted a lot of attention. However, many scientists have expressed concerns on the nanomaterials obtained. We decided to explore two different routes to obtain silicon nanoparticles starting from a silane precursor. We report our findings regarding the preparation of nanomaterials under microwave irradiation and hydrothermal conditions starting from aqueous mixtures of (3-aminopropyl) triethoxysilane and sodium citrate. The microwave process, in particular, has been reported to yield silicon quantum dots bearing a surface layer of 3-aminopropyl moieties, allowing for the preparation of luminescent substrates amenable to biological-friendly amide chemistry. However, rigorous experimental design and thorough characterization of the products definitely rules out the formation of silicon nanoparticles. By highlighting the main issues linked to the proper characterization of these materials, we prove that the nanoparticles produced under both microwave and hydrothermal conditions, are a mixture of silica and carbon quantum dots.

Bio, bio, bio! This issue features the latest advances in bioinspired chemistry, biomaterials and bioelectrochemistry. Containing both original research and informative review articles, it is a must read for those committed to a multidisciplinary approach to these bio-orientated fields/topics.

The self‐assembly of platinum complexes is a well‐documented process that leads to interesting changes of the photophysical and electrochemical behavior as well as to a change in reactivity of the complexes. However, it is still not clear how many metal units must interact in order to achieve the desired properties of a large assembly. This work aimed to clarify the role of the number of interacting PtII units leading to an enhancement of the spectroscopic properties and how to address inter‐ versus intramolecular processes. Therefore, a series of neutral multinuclear PtII complexes were synthesized and characterized, and their photophysical properties at different concentration were studied. Going from the monomer to dimers, the growth of a new emission band and the enhancement of the emission properties were observed. Upon increasing the platinum units up to three, the monomeric blue emission could not be detected anymore and a concentration independent bright‐yellow/orange emission, due to the establishment of intramolecular metallophilic interactions, was observed., Three is better than two: Multinuclear PtII complexes provide valuable insight into the formation of closed shell Pt⋅⋅⋅Pt metallophilic interactions and into the corresponding MMLCT excited state. Persistent aggregation‐induced emission, which is independent from the media, is observed for the trinuclear species, demonstrating that three is better than two.

Bimodal systems for nuclear and optical imaging are currently being intensively investigated due to their comparable detection sensitivity and the complementary information they provide. In this perspective, we have implemented both modalities on biocompatible ultrasmall silicon nanoparticles (Si NPs). Such nanoparticles are particularly interesting since they are highly biocompatible, have covalent surface functionalization and demonstrate very fast body clearance. We prepared monodisperse citrate-stabilized Si NPs (2.4 ± 0.5 nm) with more than 40 accessible terminal amino groups per particle and, for the first time, simultaneously, a near-infrared dye (IR800-CW) and a radiolabel (64Cu-NOTA = 1,4,7-triazacyclononane-1,4,7-triacetic acid) have been covalently linked to the surface of such Si NPs. The obtained nanomaterials have been fully characterized using HR-TEM, XPS, UV-Vis and FT-IR spectroscopy. These dual-labelled particles do not exhibit any cytotoxicity in vitro. In vivo studies employing both positron emission tomography (PET) and optical imaging (OI) techniques revealed rapid renal clearance of dual-labelled Si NPs from mice.

Silicon nanoparticles as luminescent sensors

The formation of hybrid silica-based systems to study the effect of the confinement on the emission properties of self-assembled platinum(II) complexes is reported. The complexes behave as surfactants since they possess a hydrophobic moiety and, on the ancillary ligand, a relatively long hydrophilic chain terminated with a positively charged group. The compounds, soluble in water, self-assemble, even at very low concentration, in supramolecular structures which display an orange luminescence. The properties of the assemblies have been studied in detail and in order to stabilize these supramolecular architectures and to enhance their emission properties hybrid silica porous nanoparticles have been prepared. In particular the PtII complexes have been employed as co-surfactant for the template formation of mesoporous silica nanoparticles (MSNs) using a sol gel synthesis. Interestingly, upon encapsulation in the silica pores, the platinum aggregates exhibit an emission profile similar in energy to the complexes assembled in solution, but the photoluminescence quantum yields of the hybrid systems are significantly higher (up to 45 %), and the excited state lifetimes much longer than those recorded in solution. Such enhancement of the photophysical properties together with the possibility to process the hybrid silica nanomaterials can pave the way to new type of emitters.

Morphology control and tuning of nanomaterials are crucial to determine their properties and applications. Solutions based on different synthetic methodologies have been proposed, and in general they required variation of several parameters. Here, a new facile and cost-effective bottom-up strategy to control the morphology of mesoporous silica particles is presented. Specifically, catanionic templating systems composed of bile acids and CTAB enable the production of submicrometer MCM-41 particles of various shapes, high porosity, and remarkable features. The variation of a single component, the bile acid, leads to the preparation of particles with different morphologies. For instance, small (

The role played by the shape of mesoporous silica nanoparticles has been investigated for intra- and extracellular delivery. Specifically, we have developed the bottom-up synthesis of flat disc-shaped mesoporous silica nanoparticles, the Nanodiscs (NDs). Due to their peculiar shape and large porous system, NDs present a higher cellular uptake than commonly investigated spherical mesoporous nanoparticles. Moreover, NDs are able to efficiently perform exhaustive delivery of their therapeutic cargo when loaded with the anticancer drug Doxorubicin and administered in vitro to cancerous HeLa cells. Thanks to their aspect ratio, NDs can also be readily assembled into well-organized monolayers to be employed in HeLa cells adhesion experiments upon preliminary functionalization with a specific targeting ligand. In these conditions NDs are able to deliver a hydrophobic dye to adhered cells via the highly accessible vertically aligned pores and their flat surface that ensures optimal cell contact. This initial investigation on the performance of NDs in both intra- and extracellular delivery activities suggests the great potential of these particles.

Zeolites are crystalline porous materials with a regular framework which have non-toxic effects on a variety of human cell lines and have been explored for cell imaging and drug delivery. Understanding the interaction between zeolite nanoparticles and cells is imperative for improving their potentialities, since the process of internalization of these particles is still poorly understood. In this study, the intracellular trafficking and internalization kinetics of zeolite L into breast cancer cells and normal epithelial mammary cells were analysed using scanning electron microscopy (SEM), confocal microscopy and transmission electron microscopy (TEM). We also studied the involvement of endocytic pathways using two pharmacological inhibitors, chlorpromazine and dynasore. Zeolite nanoparticles were taken up by both cell types and the cellular uptake was fast, and started immediately after 5 min of incubation. Interestingly, the uptake was dependent on the cell type since in breast cancer cells it was faster and more efficient, with a higher number of nanoparticles being internalized by cancer cells over time, compared to that in the epithelial mammary cells. TEM results showed that the internalized nanoparticles were mainly localized in the cell vacuoles. The data obtained upon using endocytic pharmacological inhibitors suggest that the zeolite L uptake is mediated by caveolin., N. V. and F. M. S. are recipients of PhD fellowships (SFRH/BD/ 97797/2013, SFRH/BD/87139/2012) from the Foundation for Science and Technology (FCT, Portugal). R. T., E. A. P. and L. D. C. acknowledge the financial support from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement n. [2009-247365]. VM-G is a postdoctoral research fellow from the strategic funding of NORTE-01-0145-FEDER-000027 (ESTIMA-8). This work has been developed under the scope of the project NORTE-01-0145-FEDER-000013 and the project BioTecNorte (operation NORTE-01-0145-FEDER-000004), supported by the Northern Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (FEDER). This work has been funded by FEDER funds, through the Competitiveness Factors Operational Programme (COMPETE), and by National funds, through the Foundation for Science and Technology (FCT), under the scope of the projects: PTDC/AAGTEC/5269/ 2014, Centre of Chemistry (UID/QUI/00686/2013 and UID/QUI/ 0686/2016) and ICVS/3B’s POCI-01-0145-FEDER-007038., info:eu-repo/semantics/publishedVersion

Ultrasmall clearable nanoparticles possess enormous potential as cancer imaging agents. In particular, biocompatible silicon nanoparticles (Si NPs) and carbon quantum dots (CQDs) hold great potential in this regard. Their facile surface functionalization easily allows the introduction of different labels for in vivo imaging. However, to date, a thorough biodistribution study by in vivo positron emission tomography (PET) as well as a comparative study of Si vs C particles of similar size are missing. In this contribution, ultrasmall (size < 5 nm) Si NPs and CQDs were synthesized and characterized by high-resolution transmission electron microscopy (HR-TEM), Fourier-transform infrared (FTIR), absorption and steady-state emission spectroscopy. Subsequent functionalization of NPs with a near-infrared dye (Kodak-XS-670) or a radiolabel (64Cu) enabled a detailed in vitro and in vivo study of the particles. For radiolabeling experiments, the bifunctional chelating agent S-2-(4-Isothiocyanatobenzyl)-1,4,7-triaazacyclononane-1,4,7-triacetic acid (p-SCN-Bn-NOTA) was conjugated to the amino surface groups of the respective NPs. Efficient radiolabeling of NOTA-functionalized NPs with the positron emitter 64Cu was found. The biodistribution and PET studies showed a rapid renal clearance from the in vivo systems for both variants of the nanoparticles. Interestingly, the different derivatives investigated exhibited significant differences in the biodistribution and pharmacokinetic properties. This can mostly be attributed to different surface charge and hydrophilicity of the NPs, arising from the synthetic strategy used to prepare the particles.

The design and preparation of synthetic binders (SBs) applicable for small biomolecule sensing in aqueous media remains very challenging. SBs designed by the lock-and-key principle can be selective for their target analyte but usually show an insufficient binding strength in water. In contrast, SBs based on symmetric macrocycles with a hydrophobic cavity can display high binding affinities but generally suffer from indiscriminate binding of many analytes. Herein, a completely new and modular receptor design strategy based on microporous hybrid materials is presented yielding zeolite-based artificial receptors (ZARs) which reversibly bind the neurotransmitters serotonin and dopamine with unprecedented affinity and selectivity even in saline biofluids. ZARs are thought to uniquely exploit both the non-classical hydrophobic effect and direct non-covalent recognition motifs, which is supported by in-depth photophysical, and calorimetric experiments combined with full atomistic modeling. ZARs are thermally and chemically robust and can be readily prepared at gram scales. Their applicability for the label-free monitoring of important enzymatic reactions, for (two-photon) fluorescence imaging, and for high-throughput diagnostics in biofluids is demonstrated. This study showcases that artificial receptor based on microporous hybrid materials can overcome standing limitations of synthetic chemosensors, paving the way towards personalized diagnostics and metabolomics.

We report the electrochemiluminescence properties of square-planar Pt(II) complexes that result from the formation of supramolecular nanostructures. We define this new phenomenon as aggregation-induced electrochemiluminescence (AIECL). In this system, self-assembly changes the HOMO and LUMO energies, making their population accessible via ECL pathways and leading to the generation of the luminescent excited state. Significantly, the emission from the self-assembled system is the first example of electrochemiluminescence (ECL) of Pt(II) complexes in aqueous solution having higher efficiency than the standard, Ru(bpy)32+.The finding can lead to a new generation of bright emitters that can be used as ECL labels.

Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEGn, where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG16, self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters 16 complex, underwent elongation in a "living supramolecular polymerization" process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore "static" with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG16), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.

Electrochemiluminescence (ECL) based on [Ru(bpy)3 ]2+ systems is widely utilized for immunoassays. In order to extend the promising potential of ECL-based applications, IrIII complexes have recently attracted attention as probes because of their excellent luminescent properties and tunable emission wavelength. Here we describe a series of Ir complexes using a large π-conjugated ligand and different ancillary chelates. The complexes synthesized have been chemically and spectroscopically characterized and used for ECL measurements with annihilation and co-reactant methods. One of the IrIII complexes investigated exhibits the brightest, ever reported, ECL efficiency in acetonitrile employing the benzoyl peroxide (BPO) co-reactant method.

Luminescent silicon nanoparticles have recently attracted attention due to their remarkable stability, covalent functionalisation and tunable photoemission properties. Owing to their biocompatibility, low toxicity, and the small particle size that can be achieved by different synthetic approaches, these nanomaterials are candidates as cellular probes in the field of bioimaging, and potentially for in vivo applications. Tailoring the surface of the particles with active biomolecules such as sugar moieties can be an interesting strategy to increase the kinetics of internalisation or to vary the localisation of nanosystems in living cells. In this study, we synthesised and modified ultrasmall silicon nanoparticles with glucose covalently linked on their surface. Moreover, by varying the ratio between the amount of silicon nanoparticles and the saccharide groups, the amount of glucose, as a capping moiety, can be well controlled. FTIR spectroscopy, NMR spectroscopy, zeta potential measurements and anisotropy decay analysis confirmed the covalent binding of glucose to the nanoparticles. The photophysical behaviour of the surface-functionalised silicon quantum dots was not significantly different to that of the unmodified nanoparticles. In vitro studies demonstrated faster internalisation of the glucose-functionalised nanoparticles into HeLa cells. Different localisation and uptake kinetics of the glucose-modified particles compared to the unmodified particles are discussed in order to reveal the role played by the sugar molecules.

When designing a functional system, supramolecular chemists tend to only focus ‘what should be there’, i.e., the molecules and their spatial orientation towards each other, but more rarely is the m...