2022
Autores
Queiros, C; Almodovar, VAS; Martins, F; Leite, A; Tome, AC; Silva, AMG;
Publicação
MOLECULES
Abstract
The search for accurate and sensitive methods to detect chemical substances, namely cations and anions, is urgent and widely sought due to the enormous impact that some of these chemical species have on human health and on the environment. Here, we present a new platform for the efficient sensing of Cu2+ and Li+ cations. For this purpose, two novel photoactive diketopyrrolopyrrole-rhodamine conjugates were synthesized through the condensation of a diketopyrrolopyrrole dicarbaldehyde with rhodamine B hydrazide. The resulting chemosensors 1 and 2, bearing one or two rhodamine hydrazide moieties, respectively, were characterized by H-1 and C-13 NMR and high-resolution mass spectrometry, and their photophysical and ion-responsive behaviours were investigated via absorption and fluorescence measurements. Chemosensors 1 and 2 displayed a rapid colorimetric response upon the addition of Cu2+, with a remarkable increase in the absorbance and fluorescence intensities. The addition of other metal ions caused no significant effects. Moreover, the resulting chemosensor-Cu2+ complexes revealed to be good probes for the sensing of Li+ with reversibility and low detection limits. The recognition ability of the new chemosensors was investigated by absorption and fluorescence titrations and competitive studies.
2022
Autores
Neves, JAC; Roseira, J; Queiros, P; de Sousa, HT; Pellino, G; Cunha, M;
Publicação
BRITISH JOURNAL OF SURGERY
Abstract
2021
Autores
Churro, R; Mendes, F; Araujo, P; Ribeiro, MF; Madeira, LM;
Publicação
CHEMICAL ENGINEERING & TECHNOLOGY
Abstract
Ni-based catalysts present a highly interesting performance for the reductive amination of cyclohexanol (CHOL). The stability of a commercial Ni-based catalyst was evaluated and a high stability over the tested time-on-stream (TOS) was observed. The reaction network was evaluated by analysis of selectivity profiles as a function of CHOL conversion. The formation of cyclohexylamine (CHA) was found to be consistent with the proposed borrowing hydrogen method (BHM). The formation of heavy-end (HE) by-products also follows the BHM pathway as parallel reaction. The effect of individual molar proportions of NH3 and H-2 was evaluated. It was found that when H-2 is present in a high excess, side reactions were favored, but its presence is mandatory towards keeping the catalyst active.
2021
Autores
Sousaraei, A; Queiros, C; Moscoso, FG; Silva, AMG; Lopes Costa, T; Pedrosa, JM; Cunha Silva, L; Cabanillas Gonzalez, J;
Publicação
ADVANCED MATERIALS INTERFACES
Abstract
A fast and reversible switch between the neutral and protonated porphyrin forms inside a pliable porphyrinic metal-organic framework (MOF), enabled by reversible structural deformation is unveiled. This phenomenon is applied for the development of MOF-polymer porous composites to reveal biogenic amines by color changes.
2021
Autores
Almeida, J; Zhang, GY; Wang, MD; Queiros, C; Cerqueira, AFR; Tome, AC; Barone, G; Vicente, MGH; Hey Hawkins, E; Silva, AMG; Rangel, M;
Publicação
ORGANIC & BIOMOLECULAR CHEMISTRY
Abstract
Indomethacin is a potent non-steroidal anti-inflammatory drug (NSAID) with a strong selective inhibitor activity towards cyclooxygenase-2 (COX-2), an enzyme that is highly overexpressed in various tumour cells, being involved in tumourigenesis. Concomitantly, porphyrins have gained much attention as promising photosensitizers (PSs) for the non-invasive photodynamic therapy (PDT) of cancer. Herein, we report the design, and determine the singlet oxygen generation capacity and in vitro cellular toxicity of porphyrin.- and chlorin-indomethacin conjugates (P2-Ind and C2-Ind). Both the conjugates were obtained in high yields and were characterized by H-1, F-19 and C-13 NMR as well as by high resolution mass spectrometry. The singlet oxygen generation properties were assessed by the 1,3-diphenylisobenzofuran singlet oxygen trap method, which showed that C2 and C2-Ind are the best singlet oxygen photosensitizers. in addition, it was found that the presence of indomethacin did not influence the singlet oxygen generation of porphyrin or chlorin. Cytotoxicity studies of the conjugate in human HEp2 cells revealed that the porphyrin ... and chlorin- indomethacin conjugates have similar dark cytotoxicities, while chlorin C2 was shown to be the most phototoxic. Despite having lower cellular uptake than C2-Ind after 24 hours, chlorin C2 had a broad localization in HEp2 cells while the chlorin-indomethacin conjugate C2-Ind could be detected in the form of small aggregates. DFT calculations were performed to shed light on the reaction energy involved in the formation of the indomethacin conjugates and to compare the relative stability of selected isomers in solution. Moreover, the calculated energy of their first excited triplet state structures confirmed their use as suitable photosensitizers to generate singlet oxygen for PDT.
2021
Autores
Vargas, AP; Almeida, J; Gamez, F; Roales, J; Queiros, C; Rangel, M; Lopes Costa, T; Silva, AMG; Pedrosa, JM;
Publicação
DYES AND PIGMENTS
Abstract
We describe the synthesis and characterization of a new N-methylpyrrolidine-fused meso-tetracarboxyphenyl-chlorin with highly emissive features. The synthetic approach to obtain the fluorescent chlorin involves the microwave-assisted synthesis of meso-tetrakis (4-methoxycarbonylphenyl)porphyrin, followed by a 1,3-dipolar cycloaddition reaction of this porphyrin with azomethine ylide and, finally, ester hydrolysis under basic conditions. The incorporation and anchoring of the chlorin to a nanostructured porous TiO2 matrix is achieved and optimized for its use as a fluorescent sensor. In particular, we found an efficient detection of the explosive triacetone triperoxide (TATP) in the gas phase. The optical response after analyte exposure is selective and fast, with response time t(50) values of less than 10 min under exposure to TATP saturated vapours.
The access to the final selection minute is only available to applicants.
Please check the confirmation e-mail of your application to obtain the access code.