PMID- 36996427
OWN - NLM
STAT- MEDLINE
DCOM- 20230411
LR  - 20230415
IS  - 2373-9878 (Electronic)
IS  - 2373-9878 (Linking)
VI  - 9
IP  - 4
DP  - 2023 Apr 10
TI  - Tricarbonyl-Pyrazine-Molybdenum(0) Metal-Organic Frameworks for the Storage and 
      Delivery of Biologically Active Carbon Monoxide.
PG  - 1909-1918
LID - 10.1021/acsbiomaterials.3c00140 [doi]
AB  - 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) in a sealed ampoule gave a mixture comprising a major 
      triclinic phase with pyz-occupied hexagonal channels, formulated as 
      fac-Mo(CO)(3)(pyz)(3/2).1/2pyz (Mo-hex), and a minor dense cubic phase, 
      formulated as fac-Mo(CO)(3)(pyz)(3/2) (Mo-cub). In the present work, an open 
      reflux method in toluene has been optimized for the large-scale synthesis of the 
      pure Mo-cub phase. The crystalline solids Mo-hex and Mo-cub were characterized by 
      powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), 
      thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and 
      (13)C(1)H cross-polarization (CP) magic-angle spinning (MAS) NMR spectroscopy. 
      The release of CO from the MOFs was studied by the deoxy-myoglobin 
      (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. Mo-hex and Mo-cub release 
      CO upon contact with a physiological buffer in the dark, delivering 0.35 and 0.22 
      equiv (based on Mo), respectively, after 24 h, with half-lives of 3-4 h. Both 
      materials display high photostability such that the CO-releasing kinetics is not 
      affected by irradiation of the materials with UV light. These materials are 
      attractive as potential CORMAs due to the slow release of a high CO payload. In 
      the solid-state and under open air, Mo-cub underwent almost complete 
      decarbonylation over a period of 4 days, corresponding to a theoretical CO 
      release of 10 mmol per gram of material.
FAU - Silva, Andreia F
AU  - Silva AF
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
FAU - Calhau, Isabel B
AU  - Calhau IB
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
FAU - Gomes, Ana C
AU  - Gomes AC
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
FAU - Valente, Anabela A
AU  - Valente AA
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
FAU - Goncalves, Isabel S
AU  - Goncalves IS
AUID- ORCID: 0000-0002-2836-7715
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
FAU - Pillinger, Martyn
AU  - Pillinger M
AUID- ORCID: 0000-0002-6243-7692
AD  - CICECO - Aveiro Institute of Materials, Department of Chemistry, University of 
      Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20230330
PL  - United States
TA  - ACS Biomater Sci Eng
JT  - ACS biomaterials science & engineering
JID - 101654670
RN  - 0 (Metal-Organic Frameworks)
RN  - 7U1EE4V452 (Carbon Monoxide)
RN  - 81AH48963U (Molybdenum)
RN  - 0 (Myoglobin)
RN  - 0 (Pyrazines)
SB  - IM
MH  - *Metal-Organic Frameworks/chemistry
MH  - Carbon Monoxide/chemistry
MH  - Molybdenum/chemistry
MH  - Myoglobin/chemistry
MH  - Spectroscopy, Fourier Transform Infrared
MH  - Pyrazines
PMC - PMC10091354
OTO - NOTNLM
OT  - CO-releasing materials
OT  - carbon monoxide
OT  - metal-organic frameworks
OT  - molybdenum
OT  - pyrazine
COIS- The authors declare no competing financial interest.
EDAT- 2023/03/31 06:00
MHDA- 2023/04/11 06:41
PMCR- 2023/04/12
CRDT- 2023/03/30 16:33
PHST- 2023/04/11 06:41 [medline]
PHST- 2023/03/31 06:00 [pubmed]
PHST- 2023/03/30 16:33 [entrez]
PHST- 2023/04/12 00:00 [pmc-release]
AID - 10.1021/acsbiomaterials.3c00140 [doi]
PST - ppublish
SO  - ACS Biomater Sci Eng. 2023 Apr 10;9(4):1909-1918. doi: 
      10.1021/acsbiomaterials.3c00140. Epub 2023 Mar 30.