7Uniqueness of properties and robustness of structure makes porphyrins nature's favorite catalysts. 8 They have grabbed human attention since decades due to its intense colours and in modern times the 9 interest in these molecules has sharply increased, owing to their use for handling some tough 10 problems, including medical and environmental issues. Nowadays much attention is being focused 11 on the development of materials for the capture and conversion of CO 2 into value added products and 12 porphyrins are not lagging behind in extending their favor. The idea that porphyrins are poor 13 absorption materials since are generally plnar compounds has been belied by the development of new 14 efficient porphyrin-based materials, and the development of reliable synthetic routes for porphyrin 15 based nanoreactors such as covalent-organic frameworks (COF) and metal-organic frameworks 16 (MOF) as porous materials has facilitated to overcome the underlying CO 2 reactivity challenges.17Porphyrin-based materials behaving as nanoreactors are very promising for CO 2 capture and 18 conversion due to the presence of basic pyrrole containing macrocyclic cavity and large aromatic 19 rings which facilitates strong interactions with CO 2 . This review is intended to provide an overview 20 of up-to-date progress made in the area of the CO 2 capture and conversion involving porphyrin-based 21 molecular materials and nanoreactors, bearing important structural features in terms of surface area, 22 porosity, CO 2 uptake and the possibility of its catalytic conversion to chemically valuable products.

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Photodynamic therapy (PDT) is a selective and minimally invasive therapeutic approach, involving the combination of a light-sensitive compound, called a photosensitizer (PS), visible light and molecular oxygen. The interaction of these per se harmless agents results in the production of reactive species. This triggers a series of cellular events that culminate in the selective destruction of cancer cells, inside which the photosensitizer preferentially accumulates. The search for ideal PDT photosensitizers has been a very active field of research, with a special focus on porphyrins and porphyrin-related macrocycle molecules. The present study describes the photophysical characterization and in vitro phototoxicity evaluation of 5,10,15,20-tetra(quinolin-2-yl)porphyrin (2-TQP) as a potential PDT photosensitizer. Molar absorption coefficients were determined from the corresponding absorption spectrum, the fluorescence quantum yield was calculated using 5,10,15,20-tetraphenylporphyrin (TPP) as a standard and the quantum yield of singlet oxygen generation was determined by direct phosphorescence measurements. Toxicity evaluations (in the presence and absence of irradiation) were performed against HT29 colorectal adenocarcinoma cancer cells. The results from this preliminary study show that the hydrophobic 2-TQP fulfills several critical requirements for a good PDT photosensitizer, namely a high quantum yield of singlet oxygen generation (Φ∆ 0.62), absence of dark toxicity and significant in vitro phototoxicity for concentrations in the micromolar range.

Experimental and Theoretical Studies of the Second-and Third-Order NLO Properties of a semi-organic compound: 6-Aminoquinolinium Iodide Monohydrate, Chemical Physics (2013), doi: http:// dx.doi.org/10. 1016/j.chemphys.2013.11.001 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractA new semi-organic compound, 6-aminoquinolinium iodide monohydrate (I), has been synthesized and characterized by single crystal X-ray diffraction, UV-Vis absorption and fluorescence spectroscopy and nonlinear optical (NLO) measurements. The second-and third-order NLO responses were investigated with the second-and third-harmonic Maker fringes techniques, carried out on thin films at a fundamental wavelength of 1064 nm. From the molecular structure, the molecular hyperpolarizability tensors were determined with density functional theory and second-order Møller-Plesset perturbation method. The second-and third-order susceptibility tensors of the reported crystal were evaluated using the oriented gas model with the Lorenz-Lorentz and the Wortmann-Bishop local-field corrections. The calculations using the Wortmann-Bishop local-field were able to reproduce the correct order of magnitude of the experimental third-order susceptibilities. The value of χobtained by summing the effective third-order polarizability calculated for the asymmetric unit surrounded by ESP-derived charges have also the same order of magnitude of the experimental.

A new 5,10,15,20-tetra-(phenoxy-3-carbonyl-1-amino-naphthyl)-porphyrin was prepared by an isocyanate condensation reaction and its photophysical properties fully evaluated, both in terms of photostability and singlet oxygen production. It shows considerably enhanced photostability when compared with the parent 5,10,15,20-tetra-(3-hydroxy-phenyl)-porphyrin, with the photodegradation quantum yields for T(NAF)PP and T(OH)PP being 4.65×10(-4) and 5.19×10(-3) , respectively. Its photodynamic effect in human carcinoma HT-29 cells was evaluated. The new porphyrin showed good properties as a sensitizer in photodynamic therapy with an in vitro cytotoxicity IC(50) value of 6.80μg mL(-1) for a 24h incubation. In addition to the potential of this compound, the synthetic route used provides possibilities of extension to a wide range of new sensitizers.