Mariette M Pereira

University of Coimbra | UC · Department of Chemistry

Carbon monoxide (CO) has become one of the most relevant and versatile renewable C1 building blocks for chemical synthesis, especially in the fine chemicals industry, due to the development of efficient and selective catalysts for its activation. In this review, we present a comprehensive critical analysis of the last 10 years literature on the use...

The COVID-19 pandemic exposes our vulnerability to viruses that acquire the ability to infect our cells. Classical disinfection methods are limited by toxicity. Existing medicines performed poorly against SARS-CoV-2 because of their specificity to targets in different organisms. We address the challenge of mitigating known and prospective viral inf...

A new fluorinated manganese porphyrin, (Mn-TPP-p-CF3 ) is reported capable of providing, based on the Mn(III)/Mn(II) equilibrium, dual 1 H relaxivity and 19 F NMR response to redox changes. The physical-chemical characterization of both redox states in DMSO-d6 /H2 O evidenced that the 1 H relaxometric and 19 F NMR properties are appropriate for dif...

Carbon monoxide (CO) has become one of the most relevant and versatile renewable C1 building blocks for chemical synthesis, especially in the fine chemicals industry, due to the development of efficient and selective catalysts for its activation. In this review, we present a comprehensive critical analysis of the last 10 years literature on the use...

We offer a personal account of the discovery and development of a photosensitizer for photodynamic therapy (PDT) of cancer, from bench to bedside. We emphasize the more chemical aspects of drug discovery and drug development, namely the chemical landscape at the time of the discovery, the breakthrough in the field offered by stable bacteriochlorins...

Herein we describe the design of natural curcumin ester and ether derivatives and their application as potential bioplasticizers, to prepare photosensitive phthalate-free PVC-based materials. The preparation of PVC-based films incorporating several loadings of newly synthesized curcumin derivatives along with their standard solid-state characteriza...

ABAB porphyrins are promising platforms for potential use in several applications, particularly in medical imaging. Herein, the synthetic optimization studies for preparing such porphyrins via the statistical condensation of 4-trifluoromethylphenyl and 1-methylimidazol-2-yl aldehydes with pyrrole, are described, with emphasis on the use of microwav...

The combination of photodynamic therapy with antibiotics or antimicrobial peptides for inactivation of bacteria is an area of growing interest due to the synergistic effect already observed by many authors. It has been shown that the efficiency of this dual antimicrobial therapy is highly dependent on the structure of the photosensitizer, being tet...

Background Manganese porphyrins have several therapeutic/imaging applications, including their use as radioprotectants (in clinical trials) and as paramagnetic MRI contrast agents. The affinity of porphyrins for lipid bilayers also makes them candidates for cell/liposome labelling. We hypothesised that metalation with the positron emission tomograp...

The aqueous photocatalyzed degradation of trimethoprim (TMP) and sulfamethoxazole (SMX), highly prescribed antibiotics, often found in hospital wastewaters and/or surface/ground waters in high concentrations, is described, using a 400 W medium pressure mercury lamp as irradiation source, air as oxidant and a porphyrin based photocatalyst. The new p...

The intrinsic challenge of large molecules to cross the cell membrane and reach intracellular targets is a major obstacle for the development of new medicines. We report how rotation along a single C–C bond, between separable atropisomers, of a drug in clinical trials improves cell uptake and therapeutic efficacy. The atropisomers of redaporfin (a...

The emergence of new microorganisms with resistance to current antimicrobials is one of the key issues of modern healthcare that must be urgently addressed with the development of new molecules and therapies. Photodynamic inactivation (PDI) in combination with antibiotics has been recently regarded as a promising wide-spectrum therapy for the treat...

The development of stable vectorized probes for application in medical imaging, particularly in PET, has been of great interest over the last few years. In this work, we report an efficient and straightforward (5 minute) radiolabeling methodology using [[Formula: see text]Ni](p,n)[[Formula: see text]Cu], produced in ICNAS medical cyclotron, using w...

Manganese porphyrins have several therapeutic/imaging applications, including their use as radioprotectants (in clinical trials) and as paramagnetic MRI contrast agents. The affinity of porphyrins for lipid bilayers also makes them candidates for cell/liposome labelling. We hypothesised that metalation with the positron emission tomography (PET) ra...

Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (−)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phos...

A pneumonia associada à intubação endotraqueal e a ventilação mecânica (PAV) ocorre em cerca de 10 a 25% dos pacientes que necessitam de suporte ventilatório mecânico invasivo.¹ O uso do tubo endotraqueal (TE) apresenta-se como um ambiente favorável para adesão microbiana e consequente formação de biofilme na superfície do dispositivo médico, resul...

Manganese porphyrins have several therapeutic/imaging applications; including their use as radioprotectants (in clinical trials), and as paramagnetic MRI contrast agents. The affinity of porphyrins for lipid bilayers also makes them candidates for cell/liposome labelling. We hypothesised that metalation with the positron emission tomography (PET) r...

Nowadays, society’s widespread consumption of pharmaceutical drugs and the consequent accumulation of such compounds or their metabolites in effluents requires the development of efficient strategies and systems that lead to their effective degradation. This can be done through oxidative processes, in which tetrapyrrolic macrocycles (porphyrins, ph...

Photodynamic therapy is witnessing a revival of its origins as a response to the rise of multi-drug resistant infections and the shortage of new classes of antibiotics. Photodynamic disinfection (PDDI) of microorganisms is making progresses in preclinical models and in clinical cases, and the perception of its role in the clinical armamentarium for...

The development of efficient and reliable membranes for redox flow batteries (RFBs) with high ionic conductivity and selectivity is challenging. Aiming the development of better membranes, we have synthesized porphyrin-containing sulfonated poly(etheretherketone) (SPEEK). In particular, the effect of water soluble 5,10,15,20-tetrakis(N-methyl-4-pyr...

The design and synthesis of new near infrared (NIR) biocompatible dyes have been of great interest over the last years. Herein, the synthesis of two new water soluble NIR dyes is reported: a PEGylated (PEG = polyethyleneglycol) fluorinated bacteriochlorin [5,10,15,20-tetrakis(4-PEG500-2,3,5,6-fluorophenyl)bacteriochlorin], prepared in a straightfor...

A sustainable synthetic methodology to prepare bifunctional cationic imidazolyl and neutral tert-butylphenoxy Al(III)-phthalocyanine complexes is described, using ultrasound irradiation to synthesize the phthalonitrile precursors, followed by microwave-assisted cyclotetramerization. The metallophthalocyanine catalysts were applied in the coupling r...

The Front Cover establishes an analogy between a metal music concert and the catalytic hydroformylation reaction. It shows a drummer, who represents the reusable metal catalyst performing a concert (the hydroformylation reaction) under the flag of Green Chemistry. The drum components symbolize the reagents (olefin, carbon monoxide, and hydrogen) th...

Over the last centuries, the Influenza virus has been one of the deadliest and most concerning respiratory tract infections. Besides being annually responsible for thousands of deaths worldwide, it's capable of originating pandemics that can affect millions of people, like COVID-19. Photodynamic inactivation (PDI) is an emerging alternative solutio...

An amendment to this paper has been published and can be accessed via the original article.

Two heterogeneous catalysts, MNP@SiO2-N-Xantphos/Rh(I) and MNP@SiO2-NH-C-scorpionate/Fe(II), were prepared by reaction of chloro-functionalized MNP@SiO2 with N-Xantphos and amino-functionalized MNP@SiO2 with iron(II)/C-allyl-scorpionate through nucleophilic substitution and hydroaminomethylation reactions, respectively. All catalysts were character...

Lignin has recently attracted the attention of the scientific community, as a suitable raw material for biomedical applications. In this work, acetylated lignin was used to encapsulate five different porphyrins, aiming to preserve their photophysical properties, and for further use as antibacterial treatment. The obtained nanoparticles were physica...

The catalytic hydroformylation is an important reaction, widely studied by academics and applied in chemical industry, and is a paradigmatic example of a chemical reaction that is aligned with most of the Green Chemistry principles. In the last years, the global requirement for more sustainable chemical processes has boosted the development of more...

A pharmacophore model for inhibitors of Escherichia coli’s DNA Gyrase B was developed, using computer-aided drug design. Subsequently, docking studies showed that 2,5(6)-substituted benzimidazole derivatives are promising molecules, as they possess key hydrogen bond donor/acceptor groups for an efficient interaction with this bacterial target. Furt...

The preparation of covalently linked manganese(III) meso-tetrakis(2,6-dichlorophenyl)porphyrin acetate to aminopropyl functionalized silica gel and its full characterization by standard spectroscopic methods including Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and scanning electronic microscopy (SEM) is described. The sup...

Photoacoustic imaging of small animals plays an increasingly important role in preclinical studies and is poised to become a valuable diagnostic imaging tool for a large diversity of human diseases. Exogenous contrast agents absorbing in the near-infrared (NIR) window where tissues are most transparent (650–950 nm) may help to increase the resoluti...

This chapter covers the most relevant literature published during the year 2019, related to tervalent phosphorus acid derivatives. Some of the most relevant concepts are reported, regarding synthetic methodologies to halogenophosphorus compounds, phosphorus esters (phosphites, phosphonites and phosphinites), phosphorus amides (aminophosphines phosp...

The Front Cover shows the structure of a novel iron intermediate species with an N‐heterocyclic carbene ligand containing a deprotonated amidate moiety. The presence of the amidate functionality is responsible for the excellent catalytic activity displayed by the iron complex in transfer hydrogenation of ketones to alcohols. The background image sh...

The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scannin...

The need for alternative strategies to fight bacteria is evident from the emergence of antimicrobial resistance. To that respect, photodynamic antimicrobial chemotherapy steadily rises in bacterial eradication by using light, a photosensitizer and oxygen, which generates reactive oxygen species that may kill bacteria. Herein, we report the encapsul...

The development of efficient chemical processes capable of transforming carbon dioxide (CO2) into value-added products constitutes one of the greatest challenges for the scientific community. In this context, the use of carbon dioxide as a C1 source is a relevant topic and, over the last decade, there has been remarkable scientific and technologica...

Carbon nanotubes (CNT) functionalized with siloxane groups were dissolved in polystyrene/tetrahydrofuran to produce thin films that generate broadband and intense ultrasound pulses when excited by pulsed lasers. These films absorb >99% of light in the visible and near-infrared and show no signs of fatigue after thousands of laser pulses. Picosecond...

Two piano‐stool iron(II) complexes bearing N‐heterocyclic carbene ligands outfitted with acetamide‐ and amine‐pendant arms [Cp*Fe(NHCR)(CO)I] {Cp* = η5‐tetramethylcyclopentadienyl; R = CH2CONEt2 (3), (CH2)2NEt2 (4)}, have been prepared and fully characterized. Their catalytic activity in transfer hydrogenation (TH) of ketones using iPrOH as a hydro...

Hospital-acquired infections are a global health problem that threatens patients’ treatment in intensive care units, causing thousands of deaths and a considerable increase in hospitalization costs. The endotracheal tube (ETT) is a medical device placed in the patient’s trachea to assist breathing and delivering oxygen into the lungs. However, bact...

The sustainable synthesis of highly functionalised formylcarboxamide compounds with biological relevance is reported through a sequential aminocarbonylation/hydroformylation approach. The optimisation of palladium-catalysed aminocarbonylation of iodoaromatic substrates, using allylamine as nucleophile was first performed, with molybdenum hexacarbon...

The synthesis and structural modulation of five pro-ligand salts was achieved using alternative sustainable synthetic strategies, the use of microwaves being the method of choice, with an 81% yield and an E factor of 43 for 3d. After complexation with Fe3(CO)12 by direct reaction with the appropriate pro-ligands at 130 °C, a set of iron(II) N-heter...

Mechanochemistry is an alternative for sustainable solvent-free processes that has taken the big step to become, in the near future, a useful synthetic method for academia and the fine chemical industry. The apparatus available, based on ball milling systems possessing several optimizable variables, requires too many control and optimization experi...

A class of amphiphilic photosensitizers for photodynamic therapy (PDT) was developed. Sulfonate esters of modified porphyrins bearing-F substituents in the ortho positions of the phenyl rings have adequate properties for PDT, including absorption in the red, increased cellular uptake, favorable intracellular localization, low cytotoxicity, and high...

This chapter covers the most relevant literature published during the year 2018, related to tervalent phosphorus acid derivatives. Some of the most relevant concepts are reported, regarding synthetic methodologies to halogenophosphorus compounds, phosphorus amides (aminophosphines, phosphoramidites and diamidophosphites), phosphorus esters (phosphi...

Antimicrobial resistance is threatening to overshadow last century’s medical advances. Previously eradicated infectious diseases are now resurgent as multi-drug resistant strains, leading to expensive, toxic and, in some cases, ineffective antimicrobial treatments. Given this outlook, researchers are willing to investigate novel antimicrobial treat...

Tetra-substituted zinc(II) and copper(II) phthalocyanines bearing peripheral alkoxy-monoterpene groups were prepared by conventional vs. non-conventional synthetic approaches (ultrasound and microwave irradiation). The synthesis of (1[Formula: see text]-(–)-myrtenol (a) and (1[Formula: see text],2[Formula: see text],5[Formula: see text]-([Formula:...

Gram-negative bacteria and bacteria in biofilms are very difficult to eradicate and are at the origin of the most antibiotic-resistant bacteria. Therapeutic alternatives less susceptible to mechanisms of resistance are urgently needed to respond to an alarming increase of resistant nosocomial infections. Antibacterial photodynamic inactivation (PDI...

The increasingly limited therapeutic options for the treatment of infections caused by multi-resistant Gram-negative bacteria due to the alarming increase in bacteria resistance, renewed interest in photodynamic inactivation (PDI) of bacteria. We address PDI of multi-resistant bacteria with a new family of cationic tetra-imidazolyl phthalocyanines...

Atropisomerism is a frequently overlooked source of structural diversity in drug development. Photosensitizer development for photodynamic therapy (PDT) is not an exception. The present work aimed at investigating the efficacy of redaporfin (and precursor porphyrin) atropisomers for use in PDT. Redaporfin is a synthetic sulphonamide fluorinated bac...

Unsymmetrical porphyrins were rationally-designed and synthesized to investigate the relation between their structure, properties and adsorption geometries, and their relative performance as dyes in dye-sensitized solar cells. Photophysics, electrochemical and TiO2 anchoring properties of the new unsymmetrical N-glycolic acid amino phenyl porphyrin...

This paper describes a new efficient synthetic methodology to prepare Rh/phosphine functionalized carbon nanotubes and iron oxide magnetic nanoparticles via hydroaminomethylation reaction. These hybrid nanomaterials were fully characterized and evaluated in rhodium catalyzed styrene hydroformylation. The iron oxide magnetic nanoparticle based catal...

This review article briefly describes the available synthetic approaches for meso-arylporphyrins giving particular emphasis for one-pot nitrobenzene and nitrobenzene/NaY methods regarding the synthesis of meso-halogenated arylporphyrins. The review also describes the relevant applications of these halogenated porphyrins and their metalloporphyrin c...

This chapter covers the most relevant literature published during the year 2017, related to tervalent phosphorus acid derivatives. Some of the most relevant concepts are reported, regarding synthetic methodologies to halogenophosphorus compounds, phosphorus amides (aminophosphines, phosphoramidites and diamidophosphites), phosphorus esters (phosphi...

For the development of redox responsive MRI probes based on the MnIII/MnII couple, stable complexation of both reduced and oxidized forms of the metal ion and appropriate tuning of the redox potential in the biologically relevant range are key elements. The water soluble fluorinated Mn-porphyrin derivative Mn-3 satisfies both requirements. In aqueo...

In the present study, we developed a green epoxidation approach for the synthesis of the diastereomers of (−)-isopulegol benzyl ether epoxide using molecular oxygen as the oxidant and a hybrid manganese(III)-porphyrin magnetic reusable nanocomposite as the catalyst. High activity, selectivity, and stability were obtained, with up to four recycling...

The amide peptide bond type linkage is one of the most natural conjugations available, present in many biological synthons and pharmaceutical drugs. Hence, aiming the direct conjugation of potentially biologically active compounds to phthalocyanines, herein we disclose a new strategy for direct modulation of phthalonitriles, inspired by an attracti...

The utilization of metalloporphyrins as bioinspired oxidation catalysts is an evolutionary topic of research. From the understanding of the cytochrome P-450 mechanism of action, chemists have successfully mimicked several types of oxidation reactions using metalloporphyrins as catalysts. At first, homogeneous systems presented the most amenable str...

An unprecedented palladium-catalysed sequential aminocarbonylation/cyclization synthetic strategy, using carbon monoxide and structurally different aliphatic diamines as N-nucleophiles, gives access, in one pot, to a new family of indole-based N-heterocyclic derivatives (hydropyrazinones, benzodiazepinones and hydroquinoxalines). Optimization of th...

The utilization of metalloporphyrin analogues as biomimetic oxidation catalysts is an evolutionary topic of research. Current environmental concerns have directed research in this field for the design, synthesis and application of heterogeneous catalysts, as well as avoiding the use of highly pollutant co‐oxidants and/or co‐catalysts. Herein, we re...

We report a synthetic strategy to combine different moieties in a single structure using cyanuric chloride (2,4,6-trichlorotriazine) as a starting platform for preparing potential bioimaging agents. This reacted with macrocycles of the porphyrin family and DOTA type metal chelators through mono-, di- and tri- substitution of its chlorine atoms by a...

The synthesis and full characterization of manganese and chromium metalloporphyrins and hybrid magnetic nanocomposites prepared thereof is described. Their application in homogeneous and heterogeneous sequential epoxidation/CO2 cycloaddition reactions using O2 or H2O2 as oxidant showed high activity and selectivity for the preparation of a variety...

Objective To compare hydrophilic and lipophilic bacteriochlorin photosensitizers in the photodynamic therapy of cancer, and relate their properties and in vitro phototoxicities to the efficacy of in vivo PDT treatments. Materials and Methods Photochemical characterization of a hydrophilic bacteriochlorin (F2BOH) photosensitizer, and its use in PDT...

Microwave-assisted extraction of volatile oils (MAE) potentially offers a more efficient and bio-sustainable method than conventional extraction by Clevenger apparatus (CE). This study aimed to optimise the MAE of the volatile oil fromPterodon emarginatusfruits and characterise the volatile compounds. A 2³ full-factorial central composite design an...

The synthesis and characterization of a hybrid Mn(III)-porphyrin magnetic nanocomposite is described. Moreover, a sustainable methodology for epoxidation of olefins is reported, using O(Formula presented.) as a green oxidant and the magnetic nanoparticle as a recyclable catalyst. High activity in alkene oxidation was observed, with full selectivity...

This book focuses on different techniques of asymmetric synthesis of important compounds, such as drugs and natural products. It gives insightful information on recent asymmetric synthesis by Inorganic, Organic and Enzymatic combinations.

In the Funding section, the grant number from the funder National Science Center (NCN), Poland within the Sonata Bis is listed incorrectly. The correct grant number is: 2016/22/E/ NZ7/00420. There is an error in the ninth sentence of the third paragraph in the “Photophysical and photochemical properties of halogenated porphyrins” section of the Res...

The development of sustainable processes for synthesis of new active pharmaceutical ingredients (APIs) continues to be one of the great challenges for medicinal chemistry at universities and in the pharmaceutical industry. This chapter provides a synopsis of this book, highlighting the topics discussed and pointing out the main conclusions from eac...

In this work, we have used thin films of the multiporphyrin, 1,3-di[5-(3-hydroxyphenyl)-10,15,20-(triphenyl)porphyrin]-2-(5-(3-hydroxy-phenyl)-10,15,20-(triphenyl)porphyrin)-2-methylpropane (Triad), its monomer 5-(3-hydroxyphenyl)-10,15,20-triphenylporphyrin (TPPOH) and the simple porphyrin 5,10,15,20-tetraphenyl-porphyrin (TPP), to detect explosiv...

The impact of substituents on the photochemical and biological properties of tetraphenylporphyrin-based photosensitizers for photodynamic therapy of cancer (PDT) as well as photodynamic inactivation of microorganisms (PDI) was examined. Spectroscopic and physicochemical properties were related with therapeutic efficacy in PDT of cancer and PDI of m...