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Host−guest complexes of cyclopentadienyl iron dicarbonyl (CpFe(CO)2) CO-releasi...

Monteiro, Rodrigo P.; Calhau, Isabel B.; Gomes, Ana C.; Mendes, Ricardo F.; Paz, Filipe A. Almeida; D. Lopes, André; Silva, José Paulo da

Iron(II) cyclopentadienyl carbonyl complexes are promising as CO-releasing molecules (CORMs) for therapeutic applications. In common with other metallodrugs, the practical application of Fe-CORMs may require their conjugation with biocompatible carriers to improve their bioavailability and protect them from premature degradation. Here, we show that the CO-releasing properties of the complexes [CpFe(CO)2Cl] (1) ...


Host-guest complexes of cucurbit[8]uril and [(η5-C5H4R)Mo(CO)3CH3] (R = H, CO2C...

Gomes, Ana C.; Monteiro, Rodrigo P.; Calhau, Isabel B.; Lopes, André D.; Gonçalves, Isabel S.; Pillinger, Martyn

The monosubstituted cyclopentadienyl half-sandwich molybdenum(II) tricarbonyl complex [(η5 -C5H4CO2CH3) Mo(CO)3CH3] (1) and its 1:1 inclusion compound with cucurbit[8]uril (1@CB8) have been prepared and characterised by elemental and thermogravimetric analyses, powder X-ray diffraction, diffuse reflectance UV–vis, solid-state 13C{1 H} MAS NMR, FT-IR, and Raman spectroscopies. The CO-releasing behaviours of 1, 1...


An organic-organometallic CO-releasing material comprising 4,4'-bipyridine and ...

Calhau, Isabel B.; Gomes, Ana C.; Mendes, Ricardo F.; Almeida Paz, Filipe A.; Gonçalves, Isabel S.; Pillinger, Martyn

Over the past two decades, following the discovery of the important biological roles of carbon monoxide (CO), metal carbonyl complexes have been intensively studied as CO-releasing molecules (CORMs) for therapeutic applications. To improve the properties of "bare" low molecular weight CORMs, attention has been drawn to conjugating CORMs with macromolecular and inorganic scaffolds to produce CO-releasing materia...


Host-guest complexes of cucurbit[8]uril and [(η5-C5H4R)Mo(CO)3CH3] (R = H, CO2C...

Gomes, Ana C.; Monteiro, Rodrigo P.; Calhau, Isabel B.; D. Lopes, André; Gonçalves, Isabel S.; Pillinger, Martyn

The monosubstituted cyclopentadienyl half-sandwich molybdenum(II) tricarbonyl complex [(eta 5-C5H4CO2CH3) Mo(CO)3CH3] (1) and its 1:1 inclusion compound with cucurbit[8]uril (1@CB8) have been prepared and characterised by elemental and thermogravimetric analyses, powder X-ray diffraction, diffuse reflectance UV-vis, solid-state 13C{1H} MAS NMR, FT-IR, and Raman spectroscopies. The CO-releasing behaviours of 1, ...


β-Cyclodextrin and cucurbit[7]uril as protective encapsulation agents of the CO...

Monteiro, Rodrigo P.; Calhau, Isabel B.; Gomes, Ana C.; D. Lopes, André; Silva, José Paulo da; Gonçalves, Isabel P.; Pillinger, Martyn

The CO releasing ability of the complex [CpMo(CO)3Me] (1) (Cp = eta 5-C5H5) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted...


Effect of β-cyclodextrin on the CO release kinetics and antimicrobial activity ...

Monteiro, Rodrigo P.; Calhau, Isabel B.; Gomes, Ana C.; Pereira, Carla; Vieira, Cátia; Faustino, M. Amparo F.; Almeida, Adelaide; Pillinger, Martyn

In the present work the possibility of improving the solubility, bioavailability and bactericidal activity of the carbon monoxide releasing molecule (CORM) [Mo(CO)5Br]− (as its tetraethylammonium salt) (1) by solvent-free co-grinding with β-cyclodextrin (βCD) in a planetary ball mill was investigated. Data obtained by FT-IR spectroscopy, Raman spectroscopy, powder X-ray diffraction and thermogravimetric analysi...


Tricarbonyl-pyrazine-molybdenum(0) metal-organic frameworks for the storage and...

Silva, Andreia F.; Calhau, Isabel B.; Gomes, Ana C.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn

Metal-organic frameworks (MOFs) have high potential as nanoplatforms for the storage and delivery of therapeutic gasotransmitters or gas-releasing molecules. The aim of the present study was to open an investigation into the viability of tricarbonyl-pyrazine-molybdenum(0) MOFs as carbon monoxide-releasing materials (CORMAs). A previous investigation found that the reaction of Mo(CO)6 with excess pyrazine (pyz) ...


A hafnium-based metal-organic framework for the entrapment of molybdenum hexaca...

Silva, Andreia F.; Calhau, Isabel B.; Gomes, Ana C.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn

A carbon monoxide-releasing material (CORMA) has been prepared by inclusion of molybdenum hexacarbonyl in a hafnium-based metal-organic framework (MOF) with the UiO-66 architecture. Mo(CO)6 was adsorbed from solution to give supported materials containing 6.0-6.6 wt% Mo. As confirmed by powder X-ray diffraction (PXRD) and SEM coupled with energy dispersive X-ray spectroscopy, neither the crystallinity nor the m...


One-pot intercalation strategy for the encapsulation of a CO-releasing organome...

Calhau, Isabel B.; Gomes, Ana C.; Bruno, Sofia M.; Coelho, Ana C.; Magalhães, Clara I. R.; Romão, Carlos C.; Valente, Anabela A.; Gonçalves, Isabel S.

The photoactivatable CO‐releasing molecule (photoCORM) [Mo(CO)3(CNCH2COOH)3] (ALF795) has been incorporated into a Zn,Al layered double hydroxide (LDH) host by a coprecipitation synthesis strategy. Powder X‐ray diffraction (PXRD) of the resultant material Zn,Al‐ALF795 showed that the ALF795 guest molecules assembled into a monolayer to give a basal spacing of 16.0 Å. FTIR and 13C{1H} CP MAS NMR spectroscopy con...


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