Curved Nanographenes as Stoppers in a [2]Rotaxane with Two-Photon Excited Emission.

Heptagon-containing distorted nanographenes are used as stoppers for the capping of a [2]rotaxane through a Michael-type addition reaction to vinyl sulfone groups. These curved aromatics are bulky enough to prevent the disassembly of the rotaxane but also give emissive and nonlinear (two-photon absorption and emission) optical properties to the structure.

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons.

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.

A Triskelion-Shaped Saddle-Helix Hybrid Nanographene.

A unique rippled nanographene consisting of 52 fused rings is presented in which six out-of-plane motifs are fully fused into a triangular aromatic surface with a size of approximately 2.5 nm. Three units of an unprecedented fully lateral π-extended octabenzo[5]helicene together with three units of saddle-shaped heptagonal rings are combined in a single structure, leading to a well-soluble warped nanographene. The two diastereomeric pairs of possible enantiomers were isolated, and their linear, non-linear, and chiroptical properties were evaluated, revealing outstanding quantum yield and brightness values at low energy, together with good chiroptical responses in both absorption and emission.

Porphyrin-Oligopyridine Triads: Synthesis and Optical Properties.

The synthesis of two triads with two porphyrinyl units linked by oligopyridine derivatives and a new ß-functionalized porphyrin-dihydroazepine is described. One of the porphyrin-oligopyridine triads has a quinquepyridine unit connecting the porphyrins ß-pyrrolic positions, while the other one has an asymmetric quaterpyridine with one of the pyridines fused to the porphyrin. All compounds have fluorescence emission quantum yields in the range of meso-tetraphenylporphyrin (16-22%).

Undecabenzo[7]superhelicene: A Helical Nanographene Ribbon as a Circularly Polarized Luminescence Emitter.

The synthesis and characterization of an enantiopure superhelicene nanographene is reported in which two saddle-shaped and one planar hexabenzocoronene (HBC) units are arranged in a helicoidal shape to form an undecabenzo[7]carbohelicene. The described compound is the first fully π-extended [7]helicene. Racemic resolution of the helical nanographene permitted analysis of the chiroptical properties and revealed dissymmetry factors in the range of 2×10-3 both in the absorption and in the emission measurements. Remarkably, non-linear photophysical analysis demonstrated a two-photon absorption cross-section of 870 GM at 800 nm and a perfect overlap between linear, non-linear, and chiral emissions.

Cryptolepine and quindoline: understanding their photophysics.

Quindoline (QUIND, indolo[3,2-b]quinoline) and cryptolepine (CRYPT, 5-methyl-10H-indolo[3,2-b]quinoline) together with their corresponding derivatives have been studied for decades due to their important biological activity against diseases like malaria. The biological activity of drugs is routinely investigated using fluorescence based methods. However, recent reports show that the photophysics of CRYPT and its analogues is not yet understood. Herein, the photophysics of CRYPT and QUIND is studied in aqueous solutions at different pH values and in both protic and aprotic solvents of different polarities. CRYPT and QUIND are shown to exist in different prototropic forms depending on pH and solvent polarity. CRYPT is found to be more sensitive to the solvent nature. Both compounds are shown to have two-photon stimulated emission. Their two-photon absorption (TPA) cross-sections were measured in the 710-960 nm range. The TPA cross-section is relatively low but allows for the observation of both compounds in HEK 293 T cells, where CRYPT is found mostly in the nucleus and QUIND accumulates in the cytoplasm.

Effect of Molecular Stacking on Exciton Diffusion in Crystalline Organic Semiconductors.

Exciton diffusion is at the heart of most organic optoelectronic devices' operation, and it is currently the most limiting factor to their achieving high efficiency. It is deeply related to molecular organization, as it depends on intermolecular distances and orbital overlap. However, there is no clear guideline for how to improve exciton diffusion with regard to molecular design and structure. Here, we use single-crystal charge-transfer interfaces to probe favorable exciton diffusion. Photoresponse measurements on interfaces between perylenediimides and rubrene show a higher photocurrent yield (+50%) and extended spectral coverage (+100 nm) when there is increased dimensionality of the percolation network and stronger orbital overlap. This is achieved by very short interstack distances in different directional axes, which favors exciton diffusion by a Dexter mechanism. Even if the core of the molecule shows strong deviation from planarity, the similar electrical resistance of the different systems, planar and nonplanar, shows that electronic transport is not compromised. These results highlight the impact of molecular organization in device performance and the necessity of optimizing it to take full advantage of the materials' properties.

Role of vibrational dynamics in electronic relaxation of Cr(acac)3.

Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with a time constant of ∼7 ps and on the ground electronic state with a time constant of ∼12 ps. A kinetic model that explains the observed dynamics is presented. The key point of the model is that the ground-state recovery occurs via thermally activated back-intersystem-crossing (b-ISC) to the quartet manifold presumably via multiple curve crossings that are sampled while the system is vibrationally hot. This underlines the importance of vibrational cooling as a determining factor for the electronic relaxation chain. Vibrational excitation of the νC═C and νCO vibrations also revealed a subpicosecond (300-700 fs) intramolecular vibrational redistribution (IVR) process from the localized vibrational states to the bath of vibrational excitations.

Nonlinear emission of quinolizinium-based dyes with application in fluorescence lifetime imaging.

Charged molecules based on the quinolizinum cation have potential applications as labels in fluorescence imaging in biological media under nonlinear excitation. A systematic study of the linear and nonlinear photophysics of derivatives of the quinolizinum cation substituted by either dimethylaniline or methoxyphenyl electron donors is performed. The effects of donor strength, conjugation length, and symmetry in the two-photon emission efficiency are analyzed in detail. The best performing nonlinear fluorophore, with two-photon absorption cross sections of 1140 GM and an emission quantum yield of 0.22, is characterized by a symmetric D-π-A(+)-π-D architecture based on the methoxyphenyl substituent. Application of this molecule as a fluorescent marker in optical microscopy of living cells revealed that, under favorable conditions, the fluorophore can be localized in the cytoplasmatic compartment of the cell, staining vesicular shape organelles. At higher dye concentrations and longer staining times, the fluorophore can also penetrate into the nucleus. The nonlinearly excited fluorescence lifetime imaging shows that the fluorophore lifetime is sensitive to its location in the different cell compartments. Using fluorescence lifetime microscopy, a multicolor map of the cell is drafted with a single dye.

"Click and go": simple and fast folic acid conjugation.

Folic acid targeting by functionalization of the terminal γ-carboxylic acid is one of the most important strategies to selectively deliver chemotherapeutics and dyes to cancer cells which overexpress folate receptors. However, conjugation of folic acid is limited by its unique solubility and by selectivity issues imposing the need for expensive preparative reverse-phase chromatographic purification to isolate γ-folate conjugates. Herein is provided a novel synthetic tool for the synthesis of new folic acid conjugates with excellent γ-purity based on strain-promoted alkyne-azide cycloadditions with a γ-folate-cyclooctyne conjugate 3. To demonstrate the potential of this methodology several new folate conjugates were synthesized with high γ-purity and without using any type of chromatographic purification by reacting conjugate 3 with several fluorescent probes, polymers and siliceous materials bearing azide. In addition, the cycloaddition reaction between conjugate 3 and an azido-derived fluorescent dye was successfully performed in cellular media leading to an increase of fluorescence in the cells which overexpress folate receptors (NCI-H460).

Atomically Precise Distorted Nanographenes: The Effect of Different Edge Functionalization on the Photophysical Properties down to the Femtosecond Scale.

Nanographenes (NGs) have been attracting widespread interest since they combine peculiar properties of graphene with molecular features, such as bright visible photoluminescence. However, our understanding of the fundamental properties of NGs is still hampered by the high degree of heterogeneity usually characterizing most of these materials. In this context, NGs obtained by atomically precise synthesis routes represent optimal benchmarks to unambiguously relate their properties to well-defined structures. Here we investigate in deep detail the optical response of three curved hexa-peri-hexabenzocoronene (HBC) derivatives obtained by atomically precise synthesis routes. They are constituted by the same graphenic core, characterized by the presence of a heptagon ring determining a saddle distortion of their sp2 network, and differ from each other for slightly different edge functionalization. The quite similar structure allows for performing a direct comparison of their spectroscopic features, from steady-state down to the femtosecond scale, and precisely disentangling the role played by the different edge chemistry.

Safety assessment of new nanodiamonds@corrole hybrids addressed by the response of RAW-264.7 macrophages.

Safety assessment of carbon nanomaterials is of paramount importance since they are on the frontline for applications in sensing, bioimaging and drug delivery. The biocompatibility and safety of functionalized nanodiamonds (NDs) are here addressed through the study of the pro-inflammatory response of RAW-264.7 macrophages exposed to new nanodiamonds@corrole hybrids. The corrole unit selected is as a prototype for a hydrophobic organic molecule that can function as a NIR fluorophore reporter, an optical sensor, a photodynamic therapy agent or a photocatalyst. The new functional nanohybrids containing detonated nanodiamonds (NDs) were obtained through esterification using carboxylated NDs and glycol corroles. The success of the covalent functionalization via carbodiimide activation was confirmed through X-ray photoelectron spectroscopy (XPS), Raman and Fourier transform infrared (FTIR) spectroscopy. The UV-vis absorption and emission spectra of the hybrids are additive with respect to the corrole features. The cellular uptake, localization, cell viability and effects on immune cell activation of the new hybrids and of the precursors were carefully investigated using RAW-264.7 macrophages. Overall results showed that the ND@corrole hybrids had no pro-inflammatory effects on the RAW-264.7 macrophage cell line, making them an ideal candidate for a wide range of biomedical applications.

A Fluorescent Nanosensor for Silver (Ag+) and Mercury (Hg2+) Ions Using Eu (III)-Doped Carbon Dots.

Carbon dots doped with Eu3+ ions (Eu-Cdots) were prepared by a hydrothermal treatment, using citric acid and urea as precursors and Eu (NO3)3 as a europium source. The Eu3+ ions are strongly coordinated with the carboxylate groups at the surface of the Cdots and incorporated within the nanographene network in the carbon core. Vibrational spectroscopy provides evidence of such interaction with identification of bands assigned to the stretching of the Eu-O bond. Eu3+ doped Cdots have larger diameters then undoped Cdots, but they are divided into smaller domains of sp2 carbon. The UV-vis excitation spectrum provides evidence of energy transfer from the Cdots to the Eu3+. The luminescence spectrum shows the characteristic sharp peaks of Eu3+ in the red part of the visible spectrum and a broad emission of Cdots centered at 450 nm. The luminescence of the Cdots is strongly quenched by Hg2+ and Ag+, but not by other cations. The quenching mechanism differs significantly depending on the nature of the ion. Both the blue emission of Cdots and the red emission of Eu3+ are quenched in the presence of Hg2+ while only the emission of the Cdots is affected by the presence of Ag+. A ratiometric sensor can be built using the ratio of luminescence intensities of the Cdots to the Eu3+ peaks.

Graphene Quantum Dots and Phthalocyanines Turn-OFF-ON Photoluminescence Nanosensor for ds-DNA.

Supramolecular hybrids of graphene quantum dots (GQDs) and phthalocyanine (Pc) dyes were studied as turn-OFF-ON photoluminescence nanosensors for detection of ds-DNA. Pcs with four (Pc4) and eight (Pc8) positive charges were selected to interact with negatively charged GQDs. The photoluminescence of the GQDs was quenched upon interaction with the Pcs, due to the formation of non-emissive complexes. In the presence of ds-DNA, the Pcs interacted preferentially with the negatively charged ds-DNA, lifting the quenching effect over the photoluminescence of the GQDs and restoring their emission intensity. The best performance as a sensor of ds-DNA was registered for the GQD-Pc8, with a limit of detection (LOD) in the picomolar range. The LOD for GQD-Pc8 was more than one order of magnitude lower and its sensitivity was about a factor of three higher than that of the analogue GQD-Pc4 nanosensor. The sensitivity and selectivity of this simple GQD-Pc8 nanosensor is comparable to those of the more sophisticated carbon-based nanosensors for DNA reported previously.

Combining metal nanoclusters and carbon nanomaterials: Opportunities and challenges in advanced nanohybrids.

The development of functional materials with uniquely advanced properties lies at the core of nanoscience and nanotechnology. From the myriad possible combinations of organic and/or inorganic blocks, hybrids combining metal nanoclusters and carbon nanomaterials have emerged as highly attractive colloidal materials for imaging, sensing (optical and electrochemical) and catalysis, among other applications. While the metal nanoclusters provide extraordinary luminescent and electronic properties, the carbon nanomaterials (of zero, one or two dimensions) convey versatility, as well as unique interfacial, electronic, thermal, optical, and mechanical properties, which altogether can be put to use for the desired application. Herein, we present an overview of the field, for experts and non-experts, encompassing the basic properties of the building blocks, a systematic view of the chemical preparation routes and physicochemical properties of the hybrids, and a critical analysis of their ongoing and emerging applications. Challenges and opportunities, including directions towards green chemistry approaches, are also discussed.

Highly contorted superhelicene hits near-infrared circularly polarized luminescence.

Herein we describe a novel superhelicene structure consisting of three hexa-peri-hexabenzocoronene (HBC) units arranged in a helical geometry and creating two carbo[5]helicenes and a carbo[7]helicene. The central HBC bears a tropone moiety, which induces a saddle-helix hybrid geometry into the 3D structure of the prepared nanographene. The introduction of multiple helicenes and the position of the tropone unit trigger near-infrared circularly polarized luminescence (NIR-CPL, up to 850 nm, |g lum| = 3.0 × 10-3) combined with good photoluminescence quantum yields (ϕ F = 0.43) and upconverted emission based on two-photon absorption (TPA). Compared to previously reported superhelicenes of similar size, higher quantum yields, CPL brightness, and red-shifted absorption and emission spectra are achieved. Besides, chiroptical properties of enantiopure thin films were evaluated. These findings place this novel superhelicene as the first NIR-CPL superhelicene ever reported and make it a promising candidate for use as a chiral luminescent material in optoelectronic devices.

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core.

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.

Reflectance Confocal Microscopy: A Powerful Tool for Large Scale Characterization of Ordered/Disordered Morphology in Colloidal Photonic Structures.

The development of appropriate methods to correlate the structure and optical properties of colloidal photonic structures is still a challenge. Structural information is mostly obtained by electron, X-ray, or optical microscopy methods and X-ray diffraction, while bulk spectroscopic methods and low resolution bright-field microscopy are used for optical characterization. Here, we describe the use of reflectance confocal microscopy as a simple and intuitive technique to provide a direct correlation between the ordered/disordered structural morphology of colloidal crystals and glasses, and their corresponding optical properties.

Investigation of the mechanical properties and biocompatibility of planar and electrospun alkene-styrene copolymers against P(VDF-TrFE) and porcine skin: Potential use as second skin substrates.

Elastomers have been used in a variety of biomedical fields, including tissue engineering, soft robotics, prostheses, and cosmetics. Elastomers used for skin grafting scaffolds tend to be biodegradable, but other applications require perdurable elastomers. Advances in perdurable elastomers would allow for the development of a range of substrates useful in the creation of joint prostheses, chronic neural electrodes, implantables, and wearables. Still, for these, tailored mechanical properties and biocompatibility are required. In this work, several perdurable alkene-styrene elastomers and novel polymer blends are investigated for their stress-strain curves; with quantification of Young's moduli, fatigue behavior and standard biocompatibility. In particular, this study attempts to study polymers with mechanical properties similar to the complex characteristics of skin, through comparison with porcine skin samples. Poly (vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), a flexible polymer previously used as a wearable sensor and second skin component, was here used for comparison studies. Interestingly, this study points out that elastomer mechanical properties can be modulated to better replicate the elastic modulus of skin, in particular for KratonTM D1152, a Styrene-Butadiene-Styrene block copolymer. Namely, this is the case when such an elastomer is prepared as an electrospun matrix or as a flat dense film under low temperatures. Moreover, a specific method was optimized to obtain electrospun fibers of this alkene-styrene copolymer.

Two-photon activated precision molecular photosensitizer targeting mitochondria.

Mitochondria metabolism is an emergent target for the development of novel anticancer agents. It is amply recognized that strategies that allow for modulation of mitochondrial function in specific cell populations need to be developed for the therapeutic potential of mitochondria-targeting agents to become a reality in the clinic. In this work, we report dipolar and quadrupolar quinolizinium and benzimidazolium cations that show mitochondria targeting ability and localized light-induced mitochondria damage in live animal cells. Some of the dyes induce a very efficient disruption of mitochondrial potential and subsequent cell death under two-photon excitation in the Near-infrared (NIR) opening up possible applications of azonia/azolium aromatic heterocycles as precision photosensitizers. The dipolar compounds could be excited in the NIR due to a high two-photon brightness while exhibiting emission in the red part of the visible spectra (600-700 nm). Interaction with the mitochondria leads to an unexpected blue-shift of the emission of the far-red emitting compounds, which we assign to emission from the locally excited state. Interaction and possibly aggregation at the mitochondria prevents access to the intramolecular charge transfer state responsible for far-red emission.