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Elisa Dassie,1,2,* Diletta Arcidiacono,2,3,* Iga Wasiak,4 Nunzio Damiano,5 Luigi Dall’Olmo,6 Cinzia Giacometti,7 Sonia Facchin,3 Mauro Cassaro,7 Ennio Guido,8 Franca De Lazzari,8 Oriano Marin,9,10 Tomasz Ciach,4 Suzanne Fery-Forgues,11,12 Alfredo Alberti,1,2 Giorgio Battaglia,13 Stefano Realdon13 1Department of Molecular Medicine, University of Padua, 2Venetian Institute of Molecular Medicine, 3Department of Surgery, Oncology and Gastroenterology, University of Padua, Padua, Italy; 4Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warsaw, Poland; 5Department of Biomedical Sciences, University of Padua, Padua, 6Department of Emergency Medicine, “Santi Giovanni e Paolo” Hospital, Venice, 7Anatomic Pathology Unit, ULSS 15, Alta Padovana, Camposampiero, 8Gastroenterology Unit, Sant’Antonio Hospital, 9Interdepartmental Research Centre for Innovative Biotechnologies (CRIBI), University of Padua, 10Proteomics Facility, Azienda Ospedaliera di Padova, Padua, 11CNRS, ITAV-USR 3505, Toulouse, France; 12Université de Toulouse, ITAV-USR 3505, Toulouse, France; 13Endoscopy Unit, Veneto Institute of Oncology (IOV-IRCCS), Padua, Italy *These authors contributed equally to this work Abstract: For many years, novel strategies for cancer detection and treatment using nanoparticles (NPs) have been developed. Esophageal adenocarcinoma is the sixth leading cause of cancer-related deaths in Western countries, and despite recent advances in early detection and treatment, its prognosis is still very poor. This study investigated the use of fluorescent organic NPs as potential diagnostic tool in an experimental in vivo model of Barrett’s esophageal adenocarcinoma. NPs were made of modified polysaccharides loaded with [4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran] (DCM), a well-known fluorescent dye. The NP periphery might or might not be decorated with ASYNYDA peptide that has an affinity for esophageal cancer cells. Non-operated and operated rats in which gastroesophageal reflux was surgically induced received both types of NPs (NP-DCM and NP-DCM-ASYNYDA) by intravenous route. Localization of mucosal NPs was assessed in vivo by confocal laser endomicroscopy, a technique which enables a “real time” and in situ visualization of the tissue at a cellular level. After injection of NP-DCM and NP-DCM-ASYNYDA, fluorescence was observed in rats affected by esophageal cancer, whereas no signal was observed in control non-operated rats, or in rats with simple esophagitis or Barrett’s esophagus mucosa. Fluorescence was observable in vivo 30 minutes after the administration of NPs. Interestingly, NP-DCM-ASYNYDA induced strong fluorescence intensity 24 hours after administration. These observations suggested that NPs could reach the tumor cells, likely by enhanced permeability and retention effect, and the peptide ASYNYDA gave them high specificity for esophageal cancer cells. Thus, the combination of NP platform and confocal laser endomicroscopy could play an important role for highlighting esophageal cancer conditions. This result supports the potential of this strategy as a targeted carrier for photoactive and bioactive molecules in esophageal cancer diagnosis and treatment. Keywords: confocal laser endomicroscopy, Barrett’s esophagus, diagnostics, esophageal adenocarcinoma, fluorescent nanoparticles, heptapeptide

Grâce à sa sensibilité et à sa sélectivité, la spectroscopie de fluorescence est de plus en plus employée dans l'étude du pétrole. Dans un premier temps, les principes fondamentaux de cette technique sont rappelés, en mettant l'accent sur les difficultés inhérentes à la complexité du milieu et sur les développements récents comme la spectroscopie de fluorescence par excitation synchrone et la détection à distance. Par la suite, les principaux domaines d'application de la fluorescence à la technologie du pétrole sont successivement passés en revue, en particulier la détection de la pollution, la caractérisation rapide des bruts, l'information pour l'exploration et le forage, et enfin l'analyse fine des constituants. Les réactifs fluorogéniques ne sont utilisés qu'après minéralisation de l'échantillon et essentiellement pour détecter les traces de métaux. Due to its sensitivity and selectivity, fluorescence spectroscopy is increasingly used in petroleum technology. Firstly, the fundamentals of fluorescence are briefly presented, emphasizing the many difficulties encountered because of the medium complexity and the recent developments of methods like synchronously excited fluorescence spectroscopy and remote detection. Then, the main application fields are successively reviewed, that is identification of pollutant sources, crude oils fingerprinting, information for drilling and exploration and finally the analysis of petroleum constituents. Fluorogenic reactants are only used for trace metal detection after sample mineralization.

A spectral shift and new emission bands in the green and red regions have been observed in deep blue exciplex-based organic light-emitting diodes (OLEDs) using carbazole-based materials, namely, tris(4-carbazoyl-9-ylphenyl)amine (TCTA). To deeply understand the origin of these new bands, single-layer and bilayer TCTA-based OLEDs subjected to electrical and optical (ultraviolet (UV)) stresses were investigated by using various optical, electrical, morphological, and chemical measurements. The results showed that the stress-induced emission bands primarily originate from morphological changes rather than chemical changes. The accumulation of excitons in the TCTA layer induces molecular aggregation, leading to the formation of electrically active electronic states, namely, electroplexes and electromers, which lead to the appearance of additional emission bands in green and red regions. Impedance spectroscopy measurements on single-layer OLEDs complemented this study. The results showed that TCTA degradation affects charge injection and transport. It was concluded that the stress-induced emission bands are caused by aggregate domain formation and are closely linked to the formation of electrically active defects, which act as trap states for charge carriers in the TCTA band gap.

Dinuclear Re(I) complexes have proportionally been much less studied than mononuclear analogues. In particular, very little information is available about their solid-state emission properties. In this work, two structural isomers of dinuclear complexes (Bi-Re-metaPhe and Bi-Re-paraPhe), which differ by the relative position of the coordination spheres on a central phenyl ring, were synthesized and compared with each other and with the parent mononuclear compound (Mono-Re-Phe), from a theoretical and experimental point of view. In solution, the electronic, electrochemical and spectroscopic properties of the dinuclear complexes were almost identical, and rather close to those of the monomer. In the solid state, the photoluminescence (PL) efficiency of dimers was not higher than that of the monomer, but a clear mechanoresponsive luminescence (MRL) effect appeared only for the former ones. The positional isomerism influenced the amplitude of this effect, as well as the aggregation-induced emission (AIE) properties in a water-acetonitrile mixture. This study reveals the importance of positional isomerism to modulate the emission properties in the solid state. It also shows the advantage of dinuclear structures to access new MRL-active materials.

The tricarbonylrhenium complexes that incorporate a mesoionic carbene ligand represent an emerging and promising class of molecules, the solid-state optical properties of which have rarely been investigated. The aim of this comprehensive study is to compare three of these complexes with their 1,2,3-triazole-based analogues. The Hirshfeld surface analysis of the crystallographic data revealed that the triazolylidene derivatives are more prone to π-π interactions than their 1,2,3-triazole-based counterparts. The FT-IR and electrochemical data indicated a stronger electron donor effect from the organic ligand to the rhenium atom for triazolylidene derivatives, which was confirmed by DFT calculations. All compounds were phosphorescent in solution, where the 1,2,3-triazole-based complexes showed unusually strong dependence on dissolved oxygen. All compounds also emitted in the solid state, some of them exhibited marked solid-state luminescence enhancement (SLE) effect. The 1,2,3-triazole based complex Re-Phe even displayed astounding photoluminescence efficiency with quantum yield up to 0.69, and proved to be an excellent candidate for applications linked to aggregation-induced emission (AIE). Interestingly, one triazolylidene-based complex (Re-T-BOP) showed attractive antibacterial activity. This study highlights the potential of these new molecules for applications in the fields of photoluminescent and therapeutic materials, and provides the first bases for the design of efficient molecules in these research areas.

Since intramolecular π-π stacking interactions can modify the geometry, crystal packing mode, or even the electronic properties of transition metal complexes, they are also likely to influence the solid-state luminescence properties. Following this concept, a new tricarbonylrhenium(I) complex (Re-BPTA) was designed, based on a simple symmetrical 5,5'-dimethyl-4,4'-diphenyl-3,3'-bi-(1,2,4-triazole) organic ligand. The complex was prepared in good yield using a three-step procedure. The crystallographic study revealed that both phenyl rings are located on the same side of the molecule, and twisted by 71° and 62°, respectively, with respect to the bi-(1,2,4-triazole) unit. They overlap significantly, although they are slipped parallel to each other to minimize the intramolecular interaction energy. The π-π stacking interaction was also revealed by 1 H NMR spectroscopy, in good agreement with the results of theoretical calculations. In organic solutions, a peculiar electrochemical signature was observed compared to closely-related pyridyl-triazole (pyta)-based complexes. With regard to the optical properties, the stiffness of the Re-BPTA complex led to the stabilization of the 3 MLCT state, and thus to an enhancement of the red phosphorescence emission compared to the more flexible pyta complexes. However, an increased sensitivity to quenching by oxygen appeared. In the microcrystalline phase, the Re-BPTA complex showed strong photoluminescence (PL) emission in the green-yellow wavelength range ( λ PL = 548 nm, Φ PL = 0.52, 〈 τ PL 〉 = 713 ns), and thus a dramatic solid-state luminescence enhancement (SLE) effect. These attractive emission properties can be attributed to the fact that the molecule undergoes little distortion between the ground state and the triplet excited state, as well as to a favorable intermolecular arrangement that minimizes detrimental interactions in the crystal lattice. The aggregation-induced phosphorescence emission (AIPE) effect was clear, with a 7-fold increase in emission intensity at 546 nm, although the aggregates formed in aqueous medium were much less emissive than the native microcrystalline powder. In this work, the rigidity of the Re-BPTA complex is reinforced by the intramolecular π-π stacking interaction of the phenyl rings. This original concept provides a rhenium tricarbonyl compound with very good SLE properties, and could be used more widely to successfully develop this area of research.

Tricarbonylrhenium(I) complexes that incorporate a chloride ligand are promising photoluminescent materials, but those incorporating a bromide or iodide ligand have received very little attention regarding their solid-state properties. In this work, three rhenium(I) complexes differing only by the nature of their halide ligand (X = Cl, Br, and I) were compared. They are based on a fac-[ReX(CO) 3 (N^N)] framework where the N^N bidentate ligand is a 3-(2-pyridyl)-1,2,4-triazole unit functionalized by an appended phenyl group. DFT calculations showed that the character of the lowest energy transitions progressively changes from Re → N^N ligand (MLCT) to X → N^N ligand (XLCT) when increasing the size of the halogen atom. Regarding the electrochemical behavior, the chloride and bromide complexes 1-Cl and 1-Br were similar, while the iodide complex 1-I exhibited a strikingly different electrochemical signature in oxidation. From a spectroscopic viewpoint, all three complexes emitted weak red-orange phosphorescence in dichloromethane solution. However, in the solid state, marked differences appeared. Not only was 1-Cl a good emitter of yellow light, but it had strong solid-state luminescence enhancement (SLE) properties. In comparison, 1-Br and 1-I were less emissive and they showed better mechanoresponsive luminescence (MRL) properties, probably related to a loose molecular arrangement in the crystal packing and to the opening of vibrational non-radiative deactivation pathways. This study highlights for the first time how the nature of the halide ligand in this type of complex allows fine tuning of the solid-state optical properties, for potential applications either in bio-imaging or in the field of MRL-active materials., (© 2022. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

Strongly luminescent tricarbonylrhenium(I) complexes are promising candidates in the field of optical materials. In this study, three new complexes bearing a 3-(2-pyridyl)-1,2,4-triazole (pyta) bidentate ligand with an appended phenyl group were obtained in very good yields owing to an optimized synthetic procedure. The first member of this series, i.e. complex 1, was compared with the previously studied complex RePBO to understand the influence of the fluorescent benzoxazole unit grafted on the phenyl ring. Then, to gauge the effect of steric hindrance on the luminescence properties, the phenyl group of complex 1 was substituted in the para position by a bulky tert -butyl group or an adamantyl moiety, affording complexes 2 and 3, respectively. The results of theoretical calculations indicated that these complexes were quite similar from an electronic point of view, as evidenced by the electrochemical study. In dichloromethane solution, under excitation in the UV range, all the complexes emitted weak phosphorescence in the red region. In the solid state, they could be excited in the blue region of the visible spectrum and they emitted strong yellow light. The photoluminescence quantum yield was markedly increased with raising the size of the substituent, passing from 0.42 for 1 to 0.59 for 3. The latter complex also exhibited clear waveguiding properties, unprecedented for rhenium complexes. From this point of view, these easy-synthesized and spectroscopically attractive complexes constitute a new generation of emitters for use in imaging applications and functional materials. However, the comparison with RePBO showed that the presence of the benzoxazole group leads to unsurpassed mechanoresponsive luminescence (MRL) properties, due to the involvement of a unique photophysical mechanism that takes place only in this type of complex.

The title compound, C 9 H 7 NO 3 , crystallizes in the monoclinic ( P 2 1 ) space group. In the crystal, the almost planar mol-ecules display a flattened herringbone arrangement. Stacking mol-ecules are slipped in the lengthwise and widthwise directions and are linked by π-π inter-actions [ d ( Cg ⋯ Cg = 3.6640 (11) Å]. The structure is characterized by strong C-H⋯N and weak C-H⋯O hydrogen bonds, and further stabilized by C-O⋯π inter-actions., (© Poirot et al. 2021.)

Molecules that exhibit solid-state luminescence enhancement, i.e. the rare property to be more strongly emissive in the solid state than in solution, find an increasing number of applications in the fields of optoelectronic and nanophotonic devices, sensors, security papers, imaging, and theranostics. Benzazole (BZ) heterocycles are of particular value in this context. The simple enlargement of their π-electron system using a -C=C-Ar or -N=C-Ar moiety is enough for intrinsic solid-state luminescence enhancement (SLE) properties to appear. Their association with a variety of polyaromatic motifs leads to SLE-active molecules that frequently display attractive electroluminescent properties and are sensitive to mechanical stimuli. The excited-state intramolecular proton transfer (ESIPT) process that takes place in some hydroxy derivatives reinforces the SLE effect and enables the development of new sensors based on a protection/deprotection strategy. BZ may also be incorporated into frameworks that are prototypical aggregation-induced enhancement (AIE) luminogens, such as the popular tetraphenylethene (TPE), leading to materials with excellent optical and electroluminescent performance. This review encompasses the various ways to use BZ units in SLE systems. It underlines the significant progresses recently made in the understanding of the photophysical mechanisms involved. A brief overview of the synthesis shows that BZ units are robust building blocks, easily incorporated into a variety of structures. Generally speaking, we try to show how these small heterocycles may offer advantages for the design of increasingly efficient luminescent materials., (© 2021. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Mechanoresponsive luminescence (MRL) materials promise smart devices for sensing, optoelectronics and security. We present here the first report on the MRL activity of two Re I complexes, opening up new opportunities for applications in these fields. Both complexes exhibit marked solid-state luminescence enhancement (SLE). Furthermore, the pristine microcrystalline powders emit in the yellow-green region, and grinding led to an amorphous phase with concomitant emission redshift and shrinking of the photoluminescence (PL) quantum yields and lifetimes. Quantum chemical calculations revealed the existence of two low-lying triplet excited states with very similar energy levels, that is, 3 IL and 3 MLCT, having, respectively, almost pure intraligand (IL) and metal-to-ligand charge-transfer (MLCT) character. Transition between these states could be promoted by rotation around the pyridyltriazole-phenylbenzoxazole bond. In the microcrystals, in which rotations are hindered, the 3 IL state induces the prominent PL emission at short wavelengths. Upon grinding, rotation is facilitated and the transition to the 3 MLCT state results in a larger proportion of long-wavelength PL. FTIR and variable-temperature PL spectroscopy showed that the opening of the vibrational modes favours non-radiative deactivation of the triplet states in the amorphous phase. In solution, PL only arises from the 3 MLCT state. The same mechanism accounts for the spectroscopic differences observed when passing from crystals to amorphous powders, and then to solutions, thereby clarifying the link between SLE and MRL for these complexes., (© 2020 Wiley-VCH GmbH.)

Precise control over the production of carbon monoxide (CO) is essential to exploit the therapeutic potential of this molecule. The development of photoactive CO-releasing molecules (PhotoCORMs) is therefore a promising route for future clinical applications. Herein, a tricarbonyl-rhenium(i) complex (1-TPP), which incorporates a phosphine moiety as ancilliary ligand for boosting the photochemical reactivity, and a pyridyltriazole bidentate ligand with appended 2-phenylbenzoxazole moiety for the purpose of photoluminescence, was synthesized and characterized from a chemical and crystallographic point of view. Upon irradiation in the near-UV range, complex 1-TPP underwent fast photoreaction, which was monitored through changes of the UV-vis absorption and phosphorescence spectra. The photoproducts (i.e. the dicarbonyl solvento complex 2 and one CO molecule) were identified using FTIR, 1H NMR and HRMS. The results were interpreted on the basis of DFT/TD-DFT calculations. The effective photochemical release of CO associated with clear optical variations (the emitted light passed from green to orange-red) could make 1-TPP the prototype of new photochemically-active agents, potentially useful for integration in photoCORM materials.

Six new 2-phenylbenzoxazole (PBO) derivatives, bearing either a methoxy or hydroxy group at position 5, were prepared via an efficient one-step synthesis that allowed both analogues to be obtained in equal proportions. These PBO derivatives also differed by the presence or absence of an alkyl substituent at the para-position of the phenyl group. In organic solutions, all six compounds were strongly fluorescent in the near-UV range. In the solid state, the 5-methoxy derivatives emitted bright light, ranging from violet to deep blue according to the substitution of the phenyl group. The presence of a bulky tert-butyl group indeed resulted in the separation of molecules, but also led to a deviation from molecular planarity. Remarkably, the introduction of a methyl group had a far more beneficial effect on the optical properties. With regard to the hydroxy derivatives, none of them was photoluminescent, probably due to strong intermolecular hydrogen bonding in the crystals. The 50:50 mixtures of methoxy and hydroxy analogues showed acceptable emission properties in the solid state. The substitution pattern also influenced the crystal habit of the pure compounds and the crystallinity of the mixtures. These cheap molecules could be adapted to suit a variety of applications in the field of photoluminescent materials., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In order to improve the remarkable performance of a mononuclear tricarbonyl rhenium(i) complex (ReL1) that exhibits rare aggregation-induced phosphorescence enhancement (AIPE) behavior, two new complexes (ReL3 and ReL4) were prepared and investigated. They incorporate a 2-pyridyl-1,2,4-triazole (pyta) ligand connected to a 2-phenylbenzoxazole (PBO) moiety. Complex ReL3 differs from ReL1 by the presence of a bulky tert-butyl substituent, and ReL4 is an isomer where the PBO group is linked to the pyta ligand by its phenyl group. Theoretical calculations were in congruence with electrochemical and spectroscopic properties in solutions. Both new compounds exhibited strong AIPE and much better solid-state emission efficiency than ReL1, with photoluminescence quantum yields up to 55% for ReL4. Crystallographic data indicate that this increase in emission efficiency is due to optimum packing that prevents quenching. This work shows that minor structural changes may have major effects upon the solid-state spectroscopic properties and it provides a rational basis for accessing AIPE-active strongly emissive rhenium(i) complexes.

Two isomeric tricarbonyl rhenium(i) complexes, ReL1 and ReL2, that possess a 2-pyridyl-1,2,n-triazole (pyta) ligand (n = 4 and 3, respectively) connected to a 2-phenylbenzoxazole (PBO) moiety, were synthesized in good yields. The X-ray structures showed that in ReL1 the PBO moiety and the pyta ligand almost form a right angle hindering electron delocalization, while in ReL2 their nearly planar arrangement favors the electron delocalization in the whole organic ligand. Therefore, the nature of the ligand significantly influences the electron distribution in the two complexes, as indicated by the results of TD-DFT calculations. An electrochemical study highlighted that, by comparison with ReL2, the smaller HOMO-LUMO energy gap of ReL1 is in line with its lower first reduction potential. From a spectroscopic viewpoint, both complexes emitted phosphorescence in organic solvents, with distinct color and intensity. They also emitted in the solid state, but only ReL1 showed significant aggregation-induced phosphorescence emission (AIPE). This complete study sheds light on the crucial role of structural isomerism of the triazole group, which has been unsuspected for a long time although it can govern the geometry and electronic properties of rhenium complexes. It is shown for the first time that grafting a non-coordinated π-conjugated fragment on the N(4) atom of a 1,2,4-triazole group can be of high value for the design of efficient light-emitting materials based on rhenium complexes.

The derivatives of 2-phenylbenzoxazole (PBO) are popular fluorescent organic dyes for use in solution or after dispersion in an appropriate matrix. Their spectroscopic behavior in the solid state is, unjustly, not so well known. Many of them are strongly emissive as pure solid dyes, due to a favorable crystal packing mode. The PBO fragment lends itself well to relatively simple modifications of its chemical structure, aimed at enlarging the conjugated π-electron system. Many molecules thus designed show aggregation-induced emission (AIE). Furthermore, the derivatives of 2-(2'-hydroxyphenyl)benzoxazole (HBO) are familiar excited-state intramolecular proton transfer (ESIPT) dyes. They are particularly well suited for solid-state sensing. Mechanofluorochromism is also observed in complexes and closely-related compounds. Regarding their self-association properties, the general tendency of many PBO derivatives is to give elongated nano and microparticles. Very small chemical changes are enough to tune the shape and size of these particles. Nanofibers may be obtained by simple preparation methods and are of great value for wave-guiding. For all these reasons, as well as for its robustness and high photo- and thermal stability, the PBO fragment is an attractive building block to access new molecules that will be particularly well adapted for developments in the field of photoluminescent materials.

Six conjugates of benzoxazole and green fluorescent protein chromophore that differ by the length of their alkyl chain (from C1 to C16) are investigated. They exhibit rigidofluorochromism and clear aggregation-induced emission enhancement (AIEE) behavior with emission in the orange-red that is specific to the solid state. A preparation method based on solvent exchange is used to prepare particles. The self-association properties of these molecules depend on the length of the alkyl chain. Microfibers, platelets, and rounded microparticles are successively obtained by increasing the chain length. The same method is used to prepare nanoparticles (NPs) that are fully characterized. In particular, homogeneous populations of stable NPs measuring around 70 nm are obtained with the analogs whose chains contain four to eight carbon atoms. The behavior with respect to living cells is also influenced by the nature of the compounds. Only the dyes with intermediate hydrophobicity are efficiently uptaken by both normal and tumor cells, and fluorescence only originates from dispersed dye molecules. There is no evidence for incorporation of NPs into cells. This work shows that small variations of the chemical structure must be taken into account for making the best use of AIEE compounds in view of precise applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The arrangement of an ionic fluorophore in the crystalline state was regulated by the presence of various counter-ions and the effect on spectroscopic and self-association properties was studied. To do so, nine salts of berberine (i.e. a fluorescent natural alkaloid) were investigated. Most of them contained organic anions and were prepared using an ion-exchange process. Berberine chloride and hemisulfate were also used for the sake of comparison. The diffuse reflectance and photoluminescence spectra were recorded on powder compounds. All salts were emissive in the solid state and the emission efficiency was increased seven-fold with the nature of the anion. The optical properties were tentatively discussed on the basis of the crystal-packing mode. The possibility of implementing a bottom-up approach to generate microparticles was investigated using the reprecipitation method. Salts that contain the most hydrophobic anions gave a large number of homogeneous, elongated microparticles. This study showed that most of the berberine salts could be used as fluorescent materials, but proper choice of the anion allows using the self-association properties to best advantage.

Matrix metalloproteinases (MMP) are a family of proteolytic enzymes, the expression of which in a key step of tumor progression has recently been better defined. The overexpression of one or more MMPs is thus common among malignant tumors. It may characterize tumor progression and help predict its response to chemotherapy. Consequently, the development of a device for measuring MMP activities is an important challenge for diagnosis and prognosis. In this study, we describe an innovative supramolecular peptide/surface assembly for screening MMP activities. This sensor was used to discriminate various MMP activities and to distinguish between invasive and noninvasive cancerous cell suspensions. Our results confirm the proof-of-concept of a powerful tool for the determination of the tumor aggressiveness and a technical building block for future development of MMP lab-on-chip devices.

The fluorescence properties of four derivatives of 3-thienyl-2-(N-dicyanovinyl)iminocoumarin, bearing a diethylamino group in the 7-position or a methoxy group in the 6, 7 and 8 positions, were compared in solution and in the solid state. The 7-diethylamino derivative was strongly fluorescent in various solvents, with marked solvatochromism. Its fluorescence was quenched by aggregation. In contrast, the methoxy derivatives were only moderately or weakly fluorescent in solution, but two of them were strongly photoluminescent in the crystalline state, owing to favourable molecular packing. The 6-methoxy derivative even exhibited spectacular crystallization-enhanced emission, examples of which are particularly rare for this type of dyes. Dyes were tested for biological use. The 7-diethylamino derivative led to particularly strong fluorescence staining of the cytoplasm of HCT-116 colon cancer cells. No fading was observed over prolonged illumination by the microscope light beam, but a phototoxic effect was detected. The use of the dyes as red-emitting materials was also investigated. Using easy-to-implement preparation methods, the compounds self- assembled to give one-dimensional nano- and microsized particles, including millimeter-long microfibres that exhibited clear wave-guiding properties. This study shows the value of these low molecular-weight molecules for the preparation of new orange and red-emitting fluorescent materials based on totally pure dye., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A triethyleneglycol (TEG) chain, a linear peptide, and a cyclic peptide labeled with 7-methoxycoumarin-3-carboxylic acid (MC) and 7-diethylaminocoumarin-3-carboxylic acid (DAC) were used to thoroughly study Förster resonance energy transfer (FRET) in inclusion complexes. (1) H NMR evidence was given for the formation of a 1:1 inclusion complex between β-cyclodextrin (β-CD) and the fluorophore moieties of model compounds. The binding constant was 20 times higher for DAC than for MC derivatives. Molecular modeling provided additional information. The UV/Vis absorption and fluorescence properties were studied and the energy transfer process was quantified. Fluorescence quenching was particularly strong for the peptide derivatives. The presence of β-CDs reduced the FRET efficiency slightly. Dye-labeled peptide derivatives can thus be used to form inclusion complexes with β-CDs and retain most of their FRET properties. This paves the way for their subsequent use in analytical devices that are designed to measure the activity of matrix metalloproteinases., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Certain synthetic analogues of the green fluorescent protein (GFP) chromophore are almost nonfluorescent in dilute solutions but are strongly light-emissive in the solid state, thus exhibiting aggregation-induced emission (AIE) behavior. In the present work, two such hydrophobic derivatives of the GFP chromophore known to be fluorescent in the crystalline state (p-hexyloxy- and p-dodecyloxybenzylideneimidazolinone) were used to prepare aqueous suspensions of particles via a mild solvent-exchange reprecipitation (RP) method. This evolution was monitored at various experimental conditions by UV-vis absorption and fluorescence spectroscopy, fluorescence microscopy, as well as electron transmission and scanning microscopy. Both compounds spontaneously produced platelet-like microcrystals, the size and shape of which were influenced by the experimental conditions. The dodecyl derivative also led to the concomitant formation of nanofibers, a tendency reinforced by addition of poly(acrylic acid) to the RP medium. The photoluminescence properties of the solids produced by RP were compared to pristine microcrystalline powders obtained by crystallization in an organic solvent. Significant differences in the emission properties were found and are discussed. This study illustrates the fact that AIE fluorescence is strongly dependent on the nature of the particles and hence on the preparation methods. Being aware of these variations is important for the preparation and subsequent use of AIE-active compounds as fluorescent materials.

The recently developed fluorescent organic nanocrystals and non-doped nanoparticles (FONs) occupy a special position among other nanoparticle systems that are used for studying a variety of fundamental processes in the life sciences. Understanding their particular photophysical behavior allows proper design of FONs. The usual preparation methods are described. It is shown that FONs lead to original applications as biochemical sensors and biolabels for immunoassays. They also show high potentialities for bio-imaging of cell cultures, drug-delivery control, angiography and in vivo bio-imaging of solid tumors.

2-Phenyl-benzoxazole and five derivatives bearing an alkyl or alkoxy substituent on the phenyl ring were used to prepare aqueous suspensions of particles via a solvent-exchange method. In these conditions, the methyl and methoxy derivatives spontaneously gave nanofibers, while the other compounds led to microcrystals. This shows that minor chemical changes are enough to direct the formation of a given type of particle. From a spectroscopic viewpoint, all compounds strongly emit blue light in the solid state, with spectra much broader than those registered in n-heptane and ethanol solutions. The photoluminescence quantum yields reached 38% and were slightly affected in aqueous suspension by the polarity of the environment. The molecular arrangement, deduced from X-ray analysis for the methyl and methoxy derivatives, was used to explain the fluorescence properties in the solid state. This work shows that 2-phenyl-benzoxazole derivatives are interesting candidates for applications as fluorescent nanomaterials, including in aqueous and biological media.

Two related triphenylamine-based dipolar and octupolar fluorophores are used to prepare aqueous suspensions of fluorescent organic nanoparticles (FONs) via the reprecipitation method. The obtained spherical nanoparticles (30-40 nm in diameter) are fluorescent in aqueous solution (up to 15% fluorescence quantum yield) and exhibit extremely high one- and two-photon brightness, superior to those obtained for quantum dots. Despite the two chromophores showing similar fluorescence in solution, the fluorescence of FONs made from the octupolar derivative is significantly red-shifted compared to that generated by the dipolar FONs. In addition, the maximum two-photon absorption cross section of the FONs made from the octupolar derivative is 55% larger than that of the dipolar derivative FONs. The experimental observations provide evidence that the different molecular shape (rodlike versus three-branched) and charge distribution (dipolar versus octupolar) of the two chromophores strongly affect the packing inside the nanoparticles as well as their spectroscopic properties and colloidal stability in pure water. The use of these FONs as probes for biphotonic in-vivo imaging is investigated on Xenopus laevis tadpoles to test their utilization for angiography. When using FONs made from the octupolar dye, the formation of microagglomerates (2-5 μm scale) is observed in vivo, with subsequent lethal occlusion of the blood vessels. Conversely, the nanoparticles of the dipolar dye allow acute imaging of blood vessels thanks to their suitable size and brightness, while no toxic effect is observed. Such a goal cannot be achieved with the dissolved dye, which permeates the vessel walls., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The salt formed between the large aromatic berberine cation and the long-chain palmitate anion was synthesized and used to prepare aqueous suspensions of particles owing to a solvent-exchange method. Under these conditions, elongated particles were readily obtained. They were studied by transmission microscopy with polarized light, as well as by fluorescence and electron microscopy. They were shown to be probably crystallized nanofibers, which were stable in suspension. Unexpectedly, upon filtration and drying, these fibers evolved to give a reticulated solid. The fluorescence properties of the compound were analyzed in solution, in aqueous suspension and in the powder crystalline state. Interestingly, berberine palmitate is virtually not fluorescent in aqueous solution because of the quenching effect of water, but transition to the solid state was accompanied by a strong increase in fluorescence intensity. This phenomenon was explained by the original molecular arrangement in the solid state. Actually, in the crystal, the anions form a distinct layer, which limits parallel-stacking of the fluorescent cations. Moreover, the berberine cations are protected from the access of water molecules, and so no quenching effect can take place. This example confirms that the newly introduced concept of ion-pair aggregation-induced fluorescence enhancement can be extended to a variety of structures. It also shows the interest of ion pairs for preparing fluorescent nanofibers and reticulated solids using a solvent-exchange method that is particularly easy to implement.

We present here a new example of aggregation-induced emission enhancement (AIEE), which involves an original mechanism based on the formation of organic ion pairs. The phenol 4-hydroxy-7-nitrobenzoxadiazole (NBDOH) is dissociated in water at pH 5.0 to give the corresponding phenolate, which is poorly fluorescent in this medium. We bring evidence that fluorescence quenching is due to an interaction with water molecules. In the presence of a relatively bulky ammonium salt, specifically tetrabutylammonium bromide (TBAB), NBDOH forms a hydrophobic salt, TBA(+)NBDO(-). This has no influence on the fluorescence of the anion as long as the salt is dissolved. However, the salt readily crystallizes in the medium and transition to the solid state is accompanied by a strong increase in fluorescence intensity. This effect can be explained by two reasons. The anions are protected from water molecules, and above all, the presence of the bulky cations prevents parallel-stacking of the anions, thus leading to an original molecular arrangement that is favorable to fluorescence. As the nature of the organic cation may be easily changed, the versatility of the system is very interesting for the design of new organic micro- and nanoparticles that must be fluorescent in the solid state, possibly in an aqueous environment.