Strategies for Corrole Functionalization Barata, Joana F. B; Neves, M. Graça P. M. S; Faustino, M. Amparo F ...
Chemical reviews,
02/2017, Letnik:
117, Številka:
4
Journal Article
Recenzirano
This review covers the functionalization reactions of meso-arylcorroles, both at the inner core, as well as the peripheral positions of the macrocycle. Experimental details for the synthesis of all ...known metallocorrole types and for the N-alkylation reactions are presented. Key peripheral functionalization reactions such as halogenation, formylation, carboxylation, nitration, sulfonation, and others are discussed in detail, particularly the nucleophilic aromatic substitution and the participation of corroles in cycloaddition reactions as 2π or 4π components (covering Diels–Alder and 1,3-dipolar cycloadditions). Other functionalizations of corroles include a large diversity of reactions, namely Wittig reactions, reactions with methylene active compounds, formation of amines, amides, and imines, and metal catalyzed reactions. At the final section, the reactions involving oxidation and ring expansion of the corrole macrocycle are described comprehensively.
The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and ...basic properties, without changing its textural parameters significantly. Different techniques (N
2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H
2 flow at 700 °C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH
pzc of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.
The adsorption of reactive dyes on activated carbon involves electrostatic and dispersive interactions. High adsorbent basicity and pH values not higher than pH
pzc favor the dye uptake.
A ocupação da Amazônia Brasileira passa a ser intensiva na década de 1970, a partir da implantação dos projetos de colonização dirigida, convergindo para um intenso desmatamento e ocupações ...irregulares, conhecida como a “Década da Destruição”. O Estado de Rondônia recebeu diversos destes projetos, sofrendo grande ocupação, estimulada por programas oficiais de colonização. A busca por áreas de produção agrícola e agropecuária e de exploração madeireira propiciou a rápida ocupação de todos os espaços disponíveis para tais fins, em Rondônia, restando apenas as áreas destinadas a preservação. Entretanto estas áreas não ficaram isentas de ocupação ilegal. Muitos fatores favoreceram e contribuíram para este tipo de ação criminosa. A ocupação efetiva de áreas protegidas serviu de argumento para o Governo do Estado de Rondônia propor a revogação das várias Unidades de Conservação (UC), entregando as terras definitivamente aos prevaricadores ambientais. Este trabalho analisa a situação da Floresta Estadual de Rendimento Sustentável do Rio Mequéns (FERS), UC criada no ano de 1990 e revogada por solicitação do Governo do Estado de Rondônia, no ano de 2010. Neste trabalho são apresentados os resultados dos estudos realizados sobre a FERS do Rio Mequéns, especialmente nos primeiros anos de existência. A partir da análise de tais dados, elaborou-se um perfil fundiário da referida Unidade de Conservação, com indicadores dos imóveis, dimensão, uso, tempo de ocupação entre outros elementos, bem como um perfil dos proprietários destes imóveis e da po pulação que habita o espaço da UC em tel a. Elencam-se, também, os principais fatores que contribuíram para a ocupação da FERS do Rio Mequéns.https://doi.org/10.14195/0871-1623_35_7
Transparent corrole grafted-chitosan films were prepared by chemical modification of chitosan with a corrole macrocycle, namely, 5,10,15-tris(pentafluorophenyl)corrole (TPFC), followed by solvent ...casting. The obtained films were characterized in terms of absorption spectra (UV–vis), FLIM (fluorescence lifetime imaging microscopy), structure (FTIR, XPS), thermal stability (TGA), thermomechanical properties (DMA), and antibacterial activity. The results showed that the chemical grafting of chitosan with corrole units did not affect its film-forming ability and that the grafting yield increased with the reaction time. The obtained transparent films presented fluorescence which increases with the amount of grafted corrole units. Additionally, all films showed bacteriostatic effect against S. aureus, as well as good thermomechanical properties and thermal stability. Considering these features, promising applications may be envisaged for these corrole-chitosan films, such as biosensors, bioimaging agents, and bioactive optical devices.
Because of a soaring number of opioid-related deaths during the past decade, opioid use disorder has become a prominent issue in both the scientific literature and lay press. Although most of the ...focus within the emergency medicine community has been on opioid prescribing—specifically, on reducing the incidence of opioid prescribing and examining alternative pain treatment—interest is heightening in identifying and managing patients with opioid use disorder in an effective and evidence-based manner. In this clinical review article, we examine current strategies for identifying patients with opioid use disorder, the treatment of patients with acute opioid withdrawal syndrome, approaches to medication-assisted therapy, and the transition of patients with opioid use disorder from the emergency department to outpatient services.
A simple methodology giving access to the metal-free corroles of trans-A2B type, 5,15-bis(pentafluorophenyl)-10-{3-2-(pyridin-4-yl)vinylphenyl}corrole and ...5,15-bis(pentafluorophenyl)-10-{4-2-(pyridin-4-yl)vinylphenyl}corrole, and to the corresponding bipyridyl platinum(II) complexes is described. These new positional isomers were fully characterized and spectroscopic studies demonstrated the ability of Pt(II)–corrole complexes to establish non-covalent interactions with calf-thymus DNA (ct-DNA) and human serum albumin (HSA). Additionally, gel electrophoresis experiments demonstrated that Pt(II)–corrole complexes are able to bind plasmid pMT123 DNA, inducing alterations on its secondary structure.
New mono-pyridylcorroles coordinated with a bipyridylplatinum(II) unit show interesting interactions with biomolecules, such as HSA and calf thymus and plasmid DNA. Display omitted
•Synthesis of trans-A2B corroles with pyridyl units and of bipyridyl platinum(II) complexes.•Ability of the Pt(II)-corrole complexes to establish non-covalent interactions with ct-DNA and HSA.•The binding of the Pt(II) complexes to ct-DNA is stronger for the corrole with the para-pyridyl moiety.
Details on the unexpected formation of two new (dimethylamino)methyl corrole isomers from the reaction of 5,10,15-tris(pentafluorophenyl)corrolatogallium(III) with sarcosine and paraformaldehyde are ...presented. Semi-empirical calculations on possible mechanism pathways seem to indicate that the new compounds are probably formed through a Mannich-type reaction. The extension of the protocol to the free-base 5,10,15-tris(pentafluorophenyl)corrole afforded an unexpected new seven-membered ring corrole derivative, confirming the peculiar behavior of corroles towards known reactions when compared to the well-behaved porphyrin counterparts.
Introduction
Patient and public involvement (PPI) initiatives involving patients with chronic respiratory disease (CRD) are rare. Therefore, this study aimed to explore the perspectives of patients ...with CRD, carers and interested citizens regarding the relevance and need for a PPI network and suggestions for its implementation.
Methods
A qualitative study based on focus groups was conducted. Recruitment occurred through invitations on social media platforms and to patients who have participated in previous asthma studies of the team. Three focus groups were conducted, via video conference, using a semi‐structured guide. Thematic analysis was performed by two independent researchers and discussed with the extended team.
Results
Fifteen patients with CRD, one carer and one interested citizen (13 females, median 36 (range: 18–72) years) participated. All participants acknowledged the importance of implementing a collaborative network and demonstrated interest in being integrated. Participants acknowledged the importance of their involvement in several phases of the research cycle. The main aim identified for this network was to facilitate communication between patients and researchers. Participants regarded the integration of patients, carers, researchers and healthcare professionals from different scientific areas as relevant. The use of digital platforms to attract members and support the work, together with group dynamics and regular meetings, were some of the most relevant practical considerations for implementing the network. The identified facilitators for their engagement were sharing experiences, researchers' and healthcare professionals' support and feedback and schedule flexibility. The identified barriers included the amount of time dedicated, low health/digital literacy and the potential detachment of nondiagnosed patients or those with low symptom impact in daily life.
Conclusion
Patients, carers and citizens acknowledged the relevance of implementing a collaborative network and demonstrated interest in active participation in every stage of the health research cycle. A deeper knowledge of the barriers and facilitators identified in this study could support implementing these initiatives in Portugal.
Patient or Public Contribution
This study was designed by a research team that included one patient with asthma and one carer. They were specifically involved in building the study protocol and the interview guide. They also gave feedback regarding the electronic consent form and the short sociodemographic questionnaire created, namely by removing noncontributing words or phrases and rewording expressions. The lay summary was written by another patient with asthma. All participants of this study were invited to implement and integrate the ConectAR network—a collaborative network of research in respiratory health.
Public Summary
In Portugal, chronic respiratory patients do not have an active role as ‘coinvestigators’. This study aimed to acknowledge if patients and citizens considered a patient and public involvement network useful, whose main purpose would be to facilitate communication between patients and researchers. A study based on online group interviews was carried out with patients with chronic respiratory diseases and interested citizens, both recruited on social media platforms. Participants considered that bringing together patients, carers, researchers and healthcare professionals is valuable because sharing different experiences and perspectives may help patients to improve their daily lives and increase research quality. In conclusion, patients agree that implementing a collaborative network with researchers and healthcare professionals and participating in the health research cycle is quite preponderant. Acknowledging what can help and deter this network may be beneficial to implementing this type of initiative in Portugal.
The aim of this work was to synthesize new corrole β-cyclodextrin conjugates βCD1 (with one β-cyclodextrin moiety) and βCD2 (with two β-cyclodextrin moieties) from ...5,10,15-tris(pentafluorophenyl)corrole (TPFC) and to test in vitro the efficacy of these compounds towards tumoral HeLa cells. No dark cytotoxicity was observed for TPFC and βCD1 at the concentration used for PDT cell treatment, even during long incubation periods (24 h). Fluorescence microscopy showed that TPFC and βCD1 accumulate in HeLa cells at lysosomes and in the Golgi apparatus, respectively.
The cell survival after the PDT treatment with visible light was dependent on light exposure level and compound concentration. βCD1 was able to penetrate efficiently in the cytoplasm of the HeLa cells. In particular, we have analyzed the photodynamic effect of the corrole derivatives on the microtubules of HeLa cells and the morphological alterations on the mitotic spindle. TPFC and βCD1 caused photocytotoxicity in tumoral HeLa cells and induced a rapid metaphase blockage of cells that also showed clearly altered configurations of the mitotic spindle. The results showed that TPFC has the highest photosensitizing efficiency on tumoral cells.
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•Corrole conjugates with β-cyclodextrin moieties as potential photosensitizers in PDT.•Photodynamic effect of β-cyclodextrin-corrole conjugates on cytoskeleton of HeLa cell.•Pentafluorophenylcorrole has the highest photosensitizing efficiency on tumoral cells.
Corrole macrocycles are very appealing dyes for incorporation into light harvesting devices. This work shows the sensorial ability of 5,10,15-tris(pentafluorophenyl)corrole 1 and its monoanionic ...species toward Na+, Ca2+, Cu2+, Cd2+, Pb2+, Hg2+, Ag+, and Al3+ metal ions in toluene and acetonitrile. The photophysical studies toward metal ions were carried out by absorption and emission spectroscopy. From all metal ions studied, corrole 1 shows to be colorimetric for Hg2+ allowing a naked-eye detection of Hg2+ through a change of color from purple to blue in acetonitrile and from green to yellow in toluene. In addition a new β-imine corrole 4 was successful synthesized and further functionalized with 3-isocyanatopropyl-trimethoxysilane resulting in an alkoxysilane derivative 5. The grafting of alkoxysilane derivative 5 with optically transparent silica nanoparticles (SiNPs) was achieved succesfully. The new-coated silica nanoparticles with corrole 5 were studied in the presence of Cu2+, Hg2+, and Ag+ as metal ion probes. Interestingly, upon addition of Ag+, groups of satellite AgNPs were formed around the SiNPs and were checked by transmission electron microscopy (TEM). At same time, a change of color from green to yellow was observed.
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