journal article·2022-09Open access

Enhancement of photoactivity and cellular uptake of (Bu4N)2[Mo6I8(CH3COO)6] complex by loading on porous MCM-41 support. Photodynamic studies as an anticancer agent

Cristina de la Torre, Raquel Gavara, Alba García-Fernández, Maxim Mikhaylov, Maxim N. Sokolov, Juan F. Miravet, Félix Sancenón, Ramón Martínez-Máñez, Francisco Galindo

Abstract

The incorporation by ionic assembly of the hexanuclear molybdenum cluster (Bu 4 N) 2 [Mo 6 I 8 (CH 3 CO 2 ) 6 ] (1) in amino-decorated mesoporous silica nanoparticles MCM-41, has yielded the new molybdenum-based hybrid photosensitizer 1@MCM-41. The new photoactive material presents a high porosity, due to the intrinsic high specific surface area of MCM-41 nanoparticles (989 m 2 g -1 ) which is responsible for the good dispersion of the hexamolybdenum clusters on the nanoparticles surface, as observed by STEM analysis. The hybrid photosensitizer can generate efficiently singlet oxygen, which was demonstrated by using the benchmark photooxygenation reaction of 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABDA) in water. The photodynamic therapy activity has been tested using LED light as an irradiation source ( irr ~ 400-700 nm; 15.6 mW/cm 2 ). The results show a good activity of the hybrid photosensitizer against human cervical cancer (HeLa) cells, reducing up to 70 % their viability after 20 min of irradiation, whereas low cytotoxicity is detected in the darkness. The main finding of this research is that the incorporation of molybdenum complexes at porous MCM-41 supports enhances their photoactivity and improves cellular uptake, compared to free clusters.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Inorganic Chemistry and Materials · Nanocluster Synthesis and Applications · MXene and MAX Phase Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (86)

Show source-provided references
1. Porous organic polymers: a promising platform for efficient photocatalysis10.1039/C9QM00633H ↗
2. Materials for selective photo-oxygenation vs. photocatalysis: preparation, properties and applications in environmental and health fields10.1039/C5CY01929J ↗
3. Transparent organosilica photocatalysts activated by visible light: photophysical and oxidative properties at the gas-solid interface10.1021/am404175y ↗
4. Organic photocatalysts for the oxidation of pollutants and model compounds10.1021/cr2000543 ↗
5. Hybrid silver nanocubes for improved plasmon-enhanced singlet oxygen production and inactivation of bacteria10.1021/jacs.8b12206 ↗
6. Antimicrobial photodynamic therapy–what we know and what we don’t10.1080/1040841X.2018.1467876 ↗
7. Attaching the NorA efflux pump inhibitor INF55 to methylene blue enhances antimicrobial photodynamic inactivation of methicillin-resistant Staphylococcus aureus in vitro and in vivo10.1021/acsinfecdis.7b00095 ↗
8. Superior performance of macroporous over gel type polystyrene as a support for the development of photo-bactericidal materials10.1039/C7TB01478C ↗
9. A photobleaching resistant polymer supported hexanuclear molybdenum iodide cluster for photocatalytic oxygenations and photodynamic inactivation of: Staphylococcus aureus10.1039/C6TB01966H ↗
10. Photosensitizers for photodynamic therapy10.1002/adhm.201900132 ↗
11. Synthesis, spectroscopic studies and biological evaluation of acridine derivatives: the role of aggregation on the photodynamic efficiency10.1016/j.bmcl.2018.02.005 ↗
12. Imaging intracellular viscosity of a single cell during photoinduced cell death10.1038/nchem.120 ↗
13. Proteasome inhibition potentiates antitumor effects of photodynamic therapy in mice through induction of endoplasmic reticulum stress and unfolded protein response10.1158/0008-5472.CAN-08-3439 ↗
14. Singlet oxygen generation using a porous monolithic polymer supported photosensitizer: potential application to the photodynamic destruction of melanoma cells10.1039/b810921d ↗
15. Modeling the effect of solvents on nonradiative singlet oxygen deactivation: going beyond weak coupling in intermolecular electronic-to-vibrational energy transfer
16. Singlet oxygen photophysics in liquid solvents: converging on a unified picture10.1021/acs.accounts.7b00169 ↗
17. Singlet oxygen: there is indeed something new under the sun10.1039/b926014p ↗
18. Physical mechanisms of generation and deactivation of singlet oxygen10.1021/cr010371d ↗
19. Spectroscopic, electrochemical, and photochemical properties of molybdenum(II) and tungsten(II) halide clusters10.1021/ja00345a034 ↗
20. Oxygen quenching of electronically excited hexanuclear mdybdenum and tungsten halide clusters10.1021/j100374a029 ↗
21. The octahedral M6Y8 and M6Y12 clusters of group 4 and 5 transition metals10.1016/S0898-8838(08)60148-8 ↗
22. A comparative study of the redox and excited state properties of (nBu 4 N) 2 [Mo 6 X 14 ] and (nBu 4 N) 2 [Mo 6 X 8 (CF 3 COO) 6 ] (X = Cl, Br, or I)10.1039/c3dt32863e ↗
23. Molybdenum iodides – from obscurity to bright luminescence10.1002/ejic.201900630 ↗
24. Preparation and characterization of hollow silica nanocomposite functionalized with UV absorbable molybdenum cluster10.1016/j.apt.2019.12.009 ↗
25. Tuned red NIR phosphorescence of polyurethane hybrid composites embedding metallic nanoclusters for oxygen sensing10.1039/C5CC01867F ↗
26. Fiber-optic oxygen sensor using molybdenum chloride cluster luminescence10.1063/1.125180 ↗
27. When a red–NIR-emissive Cs2[Mo6Br14] interacts with an active diureasil–PEO matrix: design of tunable and white-light-emitting hybrid material10.1002/chem.201903892 ↗
28. Direct integration of red-NIR emissive ceramic-like AnM6Xi8Xa6 metal cluster salts in organic copolymers using supramolecular interactions10.1002/chem.201800860 ↗
29. Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex10.1039/C5TC03204K ↗
30. Luminescent hydrogel particles prepared by self-assembly of β-cyclodextrin polymer and octahedral molybdenum cluster complexes10.1021/ic502144z ↗
31. Extended investigations on luminescent Cs2[Mo6Br 14]@SiO2 nanoparticles: physico-structural characterizations and toxicity studies10.1021/jp405836q ↗
32. Visible tunable lighting system based on polymer composites embedding ZnO and metallic clusters: from colloids to thin films10.1080/14686996.2016.1202724 ↗
33. Design and integration in electro-optic devices of highly efficient and robust red-NIR phosphorescent nematic hybrid liquid crystals containing [Mo6I8(OCOCnF2n+1)6]2- (n = 1, 2, 3) nanoclusters10.1002/adfm.201501876 ↗
34. Time-gated luminescence bioimaging with new luminescent nanocolloids based on [Mo 6 I 8 (C 2 F 5 COO) 6 ] 2− metal atom clusters10.1039/C6CP05290H ↗
35. Luminescent silica mesoparticles for protein transduction10.1016/j.msec.2018.11.056 ↗
36. Hexamolybdenum clusters supported on exfoliated h-BN nanosheets for photocatalytic water purification10.1021/acs.inorgchem.0c00528 ↗
37. Hexasubstituted iodide tungsten cluster complexes with azide and isothiocyanate ligands10.1002/ejic.202000204 ↗
38. Supramolecular anchoring of octahedral molybdenum clusters onto graphene and their synergies in photocatalytic water reduction10.1021/acs.inorgchem.9b02529 ↗
39. Synergetic effect of Mo6 clusters and gold nanoparticles on the photophysical properties of both components10.1002/chem.202004618 ↗
40. The role of gold nanoparticles’ aspect ratio in plasmon-enhanced luminescence and the singlet oxygen generation rate of Mo6clusters10.1039/D1CC03347F ↗
41. Cationic octahedral molybdenum cluster complexes functionalized with mitochondria-targeting ligands: photodynamic anticancer and antibacterial activities10.1039/C8BM01564C ↗
42. Octahedral molybdenum cluster as a photoactive antimicrobial additive to a fluoroplastic10.1016/j.msec.2019.110150 ↗
43. Interfacial uploading of luminescent hexamolybdenum cluster units onto amino-decorated silica nanoparticles as new design of nanomaterial for cellular imaging and photodynamic therapy10.1016/j.jcis.2018.12.013 ↗
44. Molybdenum cluster loaded PLGA nanoparticles: an innovative theranostic approach for the treatment of ovarian cancer10.1016/j.ejpb.2018.01.007 ↗
45. Octahedral molybdenum clusters as radiosensitizers for X-ray induced photodynamic therapy10.1039/C8TB00893K ↗
46. Nanosized mesoporous metal–organic framework MIL-101 as a nanocarrier for photoactive hexamolybdenum cluster compounds10.1016/j.jinorgbio.2016.11.014 ↗
47. Water-soluble hybrid materials based on {Mo 6 X 8 } 4+ (X = Cl, Br, I) cluster complexes and sodium polystyrene sulfonate10.1039/C6NJ03469A ↗
48. Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo 6 I 8 } 4+ metal clusters10.1039/C6TB00723F ↗
49. ROS-generation and cellular uptake behavior of amino-silica nanoparticles arisen from their uploading by both iron-oxides and hexamolybdenum clusters10.1016/j.msec.2020.111305 ↗
50. Cluster aqua/hydroxocomplexes supporting extended hydrogen bonding networks. Preparation and structure of a unique series of cluster hydrates [Mo6I8(OH)4(H2O)2]·nH2O (n = 2, 12, 14)10.1016/j.poly.2016.11.011 ↗
51. Hexaazide octahedral molybdenum cluster complexes: synthesis, properties and the evidence of hydrolysis10.1016/j.molstruc.2016.12.052 ↗
52. Water-soluble octahedral molybdenum cluster compounds Na2[Mo6I8(N3)6] and Na2[Mo6I8(NCS)6]: syntheses, luminescence, and in vitro studies10.1016/j.ica.2015.10.043 ↗
53. Root uptake and phytotoxicity of nanosized molybdenum octahedral clusters10.1016/j.jhazmat.2012.03.058 ↗
54. Molybdenum cluster loaded PLGA nanoparticles as efficient tools against epithelial ovarian cancer10.1016/j.ijpharm.2020.120079 ↗
55. Functionalized mesoporous silica nanoparticles and biomedical applications10.1016/j.msec.2019.01.129 ↗
56. Mesoporous silica nanoparticles in recent photodynamic therapy applications10.1039/c8pp00143j ↗
57. Gated mesoporous silica nanoparticles for the controlled delivery of drugs in cancer cells10.1021/acs.langmuir.5b00139 ↗
58. Cathepsin-B induced controlled release from peptide-capped mesoporous silica nanoparticles10.1002/chem.201404382 ↗
59. Glucose-triggered release using enzyme-gated mesoporous silica nanoparticles10.1039/c3cc42210k ↗
60. Surface functionalization of silica nanoparticles supports colloidal stability in physiological media and facilitates internalization in cells10.1021/la204913t ↗
61. New advances in in vivo applications of gated mesoporous silica as drug delivery nanocarriers10.1002/smll.201902242 ↗
62. Effect of surface functionalization of MCM-41-type mesoporous silica nanoparticles on the endocytosis by human cancer cells10.1021/ja0645943 ↗
63. Toxic potential of materials at the nanolevel10.1126/science.1114397 ↗
64. Mesoporous silica nanoparticles functionalized with an oxygen-sensing probe for cell photodynamic therapy: potential cancer theranostics10.1039/b816636f ↗
65. In vitro studies of functionalized mesoporous silica nanoparticles for photodynamic therapy10.1002/adma.200800548 ↗
66. Mannose-targeted mesoporous silica nanoparticles for photodynamic therapy10.1039/b900427k ↗
67. Verteporfin-loaded mesoporous silica nanoparticles inhibit mouse melanoma proliferation in vitro and in vivo10.1016/j.jphotobiol.2019.111533 ↗
68. Mesoporous silica nanoparticles loaded with cisplatin and phthalocyanine for combination chemotherapy and photodynamic therapy in vitro10.3390/nano5042302 ↗
69. Nanocarriers as phototherapeutic drug delivery system: appraisal of three different nanosystems in an in vivo and in vitro exploratory study10.1016/j.pdpdt.2017.11.003 ↗
70. Magnetic and pH dual-responsive mesoporous silica nanocomposites for effective and low-toxic photodynamic therapy10.2147/IJN.S127528 ↗
71. Mesoporous silica nanoparticles incorporating squaraine-based photosensitizers: a combined experimental and computational approach10.1039/C7DT03735J ↗
72. Synthetic tuning of redox, spectroscopic, and photophysical properties of {Mo6I8}4+ core cluster complexes by terminal carboxylate ligands10.1021/acs.inorgchem.6b01042 ↗
73. Photoactive hexanuclear molybdenum nanoclusters embedded in molecular organogels10.1021/acs.inorgchem.9b00916 ↗
74. Versatility of the ionic assembling method to design highly luminescent PMMA nanocomposites containing [M6Qi8La6]n- octahedral nano-building blocks10.1039/C5DT03734D ↗
75. Deep red luminescent hybrid copolymer materials with high transition metal cluster content10.1039/C3TC31309C ↗
76. Inverse correlation between efficiency of singlet oxygen production and rate constant for oxygen quenching in the S1 state of anthracene derivatives10.1039/b312398g ↗
77. Encapsulation of folic acid in different silica porous supports: a comparative study10.1016/j.foodchem.2015.09.017 ↗
78. Mesoporous silica materials for controlled delivery based on enzymes10.1039/C7TB00348J ↗
79. Real-time in vivo detection of cellular senescence through the controlled release of the NIR fluorescent dye Nile blue10.1002/anie.202004142 ↗
80. When “metal atom clusters” meet ZnO nanocrystals: a ((n-C 4H9)4N)2Mo6Br 14@ZnO hybrid10.1002/adma.200701845 ↗
81. Water-in-oil microemulsion preparation and characterization of Cs 2[Mo6X14]@SiO2 phosphor nanoparticles based on transition metal clusters (X = Cl, Br, and I)10.1002/adma.200701686 ↗
82. A highly luminescent hexanuclear molybdenum cluster - a promising candidate toward photoactive materials10.1002/ejic.201200402 ↗
83. On the synthesis and characterisation of luminescent hybrid particles: Mo6 metal cluster complex/SiO210.1039/C6RA04321F ↗
84. A self-reporting AIE probe with a built-in singlet oxygen sensor for targeted photodynamic ablation of cancer cells10.1039/C5SC03583J ↗
85. Molybdenum cluster loaded PLGA nanoparticles as efficient tools against epithelial ovarian cancer
86. Octahedral molybdenum cluster complexes with optimized properties for photodynamic applications10.1021/acs.inorgchem.0c01173 ↗