Modulation of Efficient Diiodo-BODIPY in vitro Phototoxicity to Cancer Cells by Carbon Nano-Onions

Photodynamic therapy is currently one of the most promising approaches for targeted cancer treatment. It is based on responses of vital physiological signals, namely, reactive oxygen species (ROS), which are associated with diseased condition development, such as tumors. This study presents the synthesis, incorporation, and application of a diiodo-BODIPY–based photosensitizer, based on a non-covalent functionalization of carbon nano-onions (CNOs). In vitro assays demonstrate that HeLa cells internalize the diiodo-BODIPY molecules and their CNO nanohybrids. Upon cell internalization and light exposure, the pyrene–diiodo-BODIPY molecules induce an increase of the ROS level of HeLa cells, resulting in remarkable photomediated cytotoxicity and apoptosis. Conversely, when HeLa cells internalize the diiodo-BODIPY/CNO nanohybrids, no significant cytotoxicity or ROS basal level increase can be detected. These results define a first step toward the understanding of carbon nanomaterials that function as molecular shuttles for photodynamic therapeutics, boosting the modulation of the photosensitizer

A Boron Dipyrromethene (BODIPY)-Based Cu-II-Bipyridine Complex for Highly Selective NO Detection

[EN] A BODIPY-containing Cu-II-bipyridine complex for the simple selective fluorogenic detection of NO in air and in live cells is reported. The detection mechanism is based on NO-promoted Cu-II to Cu-I reduction, followed by demetallation of the complex, which results in the clearly enhanced emission of the boron dipyrromethene (BODIPY) unit.The authors thank the DGICYT and European FEDER funds (MAT2012-38429-C04-01 and MAT2012-38429-C04-02) and the Generalitat Valenciana (PROMETEOII/2014/047) for support. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed.Juárez, LA.; Barba Bon, A.; Costero Nieto, AM.; Martínez Mañez, R.; Sancenón Galarza, F.; Parra Álvarez, M.; Gaviña Costero, P.... (2015). A Boron Dipyrromethene (BODIPY)-Based Cu-II-Bipyridine Complex for Highly Selective NO Detection. CHEMISTRY-A EUROPEAN JOURNAL. 21(44):15486-15490. https://doi.org/10.1002/chem.201502191S1548615490214

Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Accounts of Chemical Research, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ar5004384Conspectus Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and photoinduced energy/electron transfer abilities that can be modulated as a function of the electronic character of their counterparts in donor-acceptor (D-A) ensembles. In this context, carbon nanostructures such as fullerenes, carbon nanotubes (CNTs), and, more recently, graphene are among the most suitable Pc companions. Pc-C60 ensembles have been for a long time the main actors in this field, due to the commercial availability of C60 and the ell-established synthetic methods for its functionalization. As a result, many Pc-C60 architectures have been prepared, featuring different connectivities (covalent or supramolecular), intermolecular interactions (self-organized or molecularly dispersed species), and Pc HOMO/LUMO levels. All these elements provide a versatile toolbox for tuning the photophysical properties in terms of the type of process (photoinduced energy/electron transfer), the nature of the interactions beteen the electroactive units (through bond or space), and the kinetics of the formation/decay of the photogenerated species. Some recent trends in this field include the preparation of stimuli-responsive multicomponent systems ith tunable photophysical properties and highly ordered nanoarchitectures and surface-supported systems shoing high charge mobilities. A breakthrough in the Pc-nanocarbon field as the appearance of CNTs and graphene, hich opened a ne avenue for the preparation of intriguing photoresponsive hybrid ensembles shoing light-stimulated charge separation. The scarce solubility of these 1-D and 2-D nanocarbons, together ith their loer reactivity ith respect to C60 stemming from their less strained sp2 carbon netorks, has not meant an unsurmountable limitation for the preparation of variety of Pc-based hybrids. These systems, hich sho improved solubility and dispersibility features, bring together the unique electronic transport properties of CNTs and graphene ith the excellent light-harvesting and tunable redox properties of Pcs. A singular and distinctive feature of these Pc-CNT/graphene (single- or fe-layers) hybrid materials is the control of the direction of the photoinduced charge transfer as a result of the band-like electronic structure of these carbon nanoforms and the adjustable electronic levels of Pcs. Moreover, these conjugates present intensified light-harvesting capabilities resulting from the grafting of several chromophores on the same nanocarbon platform.In this Account, recent progress in the construction of covalent and supramolecular Pc-nanocarbon ensembles is summarized, ith a particular emphasis on their photoinduced behavior. e believe that the high degree of control achieved in the preparation of Pc-carbon nanostructures, together ith the increasing knoledge of the factors governing their photophysics, ill allo for the design of next-generation light-fueled electroactive systems. Possible implementation of these Pc-nanocarbons in high performance devices is envisioned, finally turning into reality much of the expectations generated by these materialsFinancial support from the Spanish MICINN (CTQ2011-24187/BQU), the Comunidad de Madrid (S2013/MIT-2841 FOTOCARBON) and the EU (“SO2S” FP7-PEOPLE-2012-ITN, no.: 316975) is acknowledge

Hybrid materials of pyrene substituted phthalocyanines with single-walled carbon nanotubes: structure and sensing properties

Hybrid materials of single walled carbon nanotubes (SWCNT) were obtained by their non-covalent functionalization with asymmetrically polyoxyethylene substituted phthalocyanines (MPc-py (M = Cu, Co, 2H)) bearing one pyrene group as a substituent. The attachment of MPc-py molecules onto the SWCNT surface have been confirmed using Raman spectroscopy, SEM, TEM and thermogravimetric analysis. The pyrene substituents were introduced to the phthalocyanine macrocycle in order to improve π–π interaction between the MPc-py and SWCNT. The effect of the central metal on the formation and sensor properties of the MPc-py within the hybrids has been verified. It has been shown that the electrical response of the hybrid films to ammonia vapor in the concentration range of 10–50 ppm changes in the following order CuPc-py > CoPc-py > H2Pc-py, which was found to be in good correlation with the amount of phthalocyanine molecules adsorbed onto the SWCNT walls, as estimated by thermogravimetric analysis (TGA)

Functionalization of Carbon Nanomaterial Surface by Doxorubicin and Antibodies to Tumor Markers

The actual task of oncology is effective treatment of cancer while causing a minimum harm to the patient. The appearance of polymer nanomaterials and technologies launched new applications and approaches of delivery and release of anticancer drugs. The goal of work was to test ultra dispersed diamonds (UDDs) and onion-like carbon (OLCs) as new vehicles for delivery of antitumor drug (doxorubicin (DOX)) and specific antibodies to tumor receptors. Stable compounds of UDDs and OLCs with DOX were obtained. As results of work, an effectiveness of functionalization was 2.94 % w/w for OLC-DOX and 2.98 % w/w for UDD-DOX. Also, there was demonstrated that UDD-DOX and OLC-DOX constructs had dose-dependent cytotoxic effect on tumor cells in the presence of trypsin. The survival of adenocarcinoma cells reduced from 52 to 28 % in case of incubation with the UDD-DOX in concentrations from 8.4–2.5 to 670–20 μg/ml and from 72 to 30 % after incubation with OLC-DOX. Simultaneously, antibodies to epidermal growth factor maintained 75 % of the functional activity and specificity after matrix-assisted pulsed laser evaporation deposition. Thus, the conclusion has been made about the prospects of selected new methods and approaches for creating an antitumor agent with capabilities targeted delivery of drugs

Compression efficiency of different picture coding structures in High Efficiency Video Coding (HEVC)

Video content is expected to account for 80 percent of all Internet traffic in 2019. There is therefore an increasing need for better video compression methods, to decrease the use of internet bandwidth. One way of achieving high video compression is to predict pixel values for a video frame based on prior and succeeding pictures in the video. The H.265 video compression standard supports this method, and in particular makes it possible to specify in which order pictures are coded, and which pictures are predicted from which. The coding order is specified for Groups Of Pictures (GOP), where a number of pictures are grouped together and predicted from each other in a specified order. This thesis evaluates how the GOPs should be structured, for instance in terms of sizing, to maximize the compression efficiency relative to the video quality. It also investigates the effect of multiple reference pictures, a functionality that enables the picture that renders the best prediction to be selected. The results show that the largest tested GOP size of 32 pictures is preferable for all tested video characteristics, and that support for multiple reference pictures renders a similar increase in compression efficiency for all GOP sizes

Compression efficiency of different picture coding structures in High Efficiency Video Coding (HEVC)

Video content is expected to account for 80 percent of all Internet traffic in 2019. There is therefore an increasing need for better video compression methods, to decrease the use of internet bandwidth. One way of achieving high video compression is to predict pixel values for a video frame based on prior and succeeding pictures in the video. The H.265 video compression standard supports this method, and in particular makes it possible to specify in which order pictures are coded, and which pictures are predicted from which. The coding order is specified for Groups Of Pictures (GOP), where a number of pictures are grouped together and predicted from each other in a specified order. This thesis evaluates how the GOPs should be structured, for instance in terms of sizing, to maximize the compression efficiency relative to the video quality. It also investigates the effect of multiple reference pictures, a functionality that enables the picture that renders the best prediction to be selected. The results show that the largest tested GOP size of 32 pictures is preferable for all tested video characteristics, and that support for multiple reference pictures renders a similar increase in compression efficiency for all GOP sizes