Table 1.

MOF-based strategies for synergistic cancer photo-immunotherapy [120,121,122,123,124,125,126,127,128,129,130,131,132,133,134,135,136,137,138,139,140,141,142,143,144].

Original MOFs/Metal Node	MOFs Composites	Further Modifications	Particle Dimensions	Irradiation In Vivo	Tumor Cell Models	Photo/Chemo/Immunotherapy		Ref
						Mechanism	Efficacy
ZIF-8/ Zn2+	HA/IR820@ZIF-8	IR820 adsorption to ZIF-8 surface + HA coating	120 nm	Laser PTT: 808 nm, 1 W/cm2, 5 min	B16F10	HA tumor targeting and ICD↑DAMPs MAN targeted DC delivery↑DC maturation and antitumoral response	↓97.7% tumor growth inhibition Systemic anti- metastatic response Immunologic memory	[120]
	MAN/(R837+1MT)@ZIF-8	Immune adjuvant R837 and immunomodulator 1-MT adsorption to ZIF-8 surface + MAN coating	221 nm
ZIF-8/ Zn2+	CuZPMn@PpIX/DOX/CpG	CuS nanoparticles + PpIX + DOX encapsulation into ZIF-8 + CpG adsorption + PDA and MnO2 nanosheets coating	120–150 nm	Laser PTT: 808 nm, 2 W/cm2, 10 min Laser PDT: 655 nm, 0.2 W/cm2, 10 min	4T1	CuS and PDA coating↑PTT MnO2 O2 generation + PpIX↑PDT PTT, PDT, DOX chemotherapy + CpG immunotherapy synergistic effect	Primary tumors eradication No recurrence or metastasis	[121]
ZIF-8/ Zn2+	HA/ZIF- 8@ICG@IMQ	ICG and IMQ encapsulation + HA coating	134 nm	Laser PTT: 808 nm, 0.1 W/cm2, 5 min	CT26	ICG↑PTT TAAs release + IMQ ↑DC maturation and antitumoral response	Elimination of primary tumors Distant tumor growth inhibition Tumor recurrence prevention	[122]
PCN-224/Zr4+	M@O-A	OXA encapsulation + aptPD-L1 adsorption	139.1 nm	LED PDT: 640 nm; 0.1 W/cm2, 30 min	MC38	aptPD-L1 specific targeting of PD-L1-positive tumor cells PDT + chemotherapy ↑ICD and antitumor immune response Synergy with ICB	Tumor growth inhibition Longer survival rates Complete distant tumor inhibition	[123]
PCN-224/Zr4+	msiPCN	sicdk4 -protamine encapsulation + CT26 cell membrane coating	≈150 nm	He−Ne laser PDT: 660 nm, 0.1 W/cm2,2 min	CT26	Tumor cells homotypic targeting Cdk4 inhibition + PDT↑ICD, antigens release and PD-L1 expression Synergy with anti-PD-L1 anti-bodies	Tumor cell cycle arrest Tumor proliferation inhibition 100% survival rate after 30 days	[124]
PCN-224/Zr4+	MnO2@CPCN	CCCP encapsulation + MnO2 shell and PAH coating	117.6 nm	Laser PDT: 660 nm, 0.2 W/cm2, 10 min	4T1	MnO2 shell↓tumor hypoxia and↑ PDT efficiency MnO2 shell GSH scavenge releases CCCP↑pro death Mitophagy PDT + CCCP synergy ↑ICD , autophagy and antitumor immune response	100% survival rate Tumor growth inhibition Tumor tissue eradication in 20% of mice Prevention of tumor metastasis and recurrence	[125]
PCN-224/Zr4+	PCN@FM	FMs (DC cells + 4T1 cells) coating.	≈175 nm	Laser PDT: 660 nm, 0.4 W/cm2, 5min	4T1	FM coating tumor homotypic targeting PDT↑ICD and antigen production FM coating + PDT synergistic effect	Primary tumors rebound proliferation inhibition Distant tumors proliferation suppression 70 days survival in 40% of the mice	[126]
PCN-224/Zr4+	PCN-ACF-CpG@HA	ACF and CpG adsorption + HA coating	105.4 -117.5 nm	Laser PDT: 670 nm, 0.25 W/cm2, 10 min	H22	HA tumor cells specific targeting PDT↑ICD and antigen release PDT+ CpG↑DCs maturation ACF HIF-1α inhibition ↓immunosuppression	Tumor growth inhibition and cell destruction Metastasis inhibition	[127]
W-TBP/W6+	W-TBP/CpG	CpG adsorption	Diameter: 114.0 ± 6.7 nm Width: 100 nm Length: 200 nm	Light PDT: 650 nm, 0.1 W/cm2, 7.5 min	TUBO	PDT↑ICD and TAAs PDT+ CpG↑DCs maturation Synergy with ICB	96.6% tumor regression Abscopal effects when synergizing with ICB	[128]
Fe-TBP/Fe3+	Fe-TBP	________	100 nm in length	LED PDT: 650 nm, 0.1 W/cm2, 7.5 min	CT26	Fe-TBP Fenton-like reaction ↑O2 and ↑ PDT PDT↑ICD Synergy with ICB	>90% regression of primary and distant tumors	[129]
Pd-TBP/Pd2+	PTP@M	4T1 cell membrane coating	165 nm	Laser PDT: 630 nm, 0.3 W/cm2, 5 min	4T1	4T1 cell membrane coating tumor cell homotypic targeting π-extended Pd-TBP in PTP ↑ PDT and ↑ ICD Synergy with ICB ↑ antitumor immune response	Tumor inhibition Anti-metastasis effect	[130]
Cu-TBP/Cu2+	Cu-TBP	________	164.1 ± 48.5 nm	LED PDT: 650 nm, 0.1 W/cm2, 30 min	B16F10 and SKOV-3	pH dependent release of Cu2+ and H4TBP Cu2+ E2 metabolism catalysation ↑ ROS E2 metabolism-ROS + PDT ↑ ICD Synergy with ICB↑ systemic antitumoral immune response	96.6% tumor growth inhibition 98.3% primary tumor regression and 94.9% in distal tumors inhibition with α-PD-L1 synergy Metastasis regression and long term antitumoral memory effects	[131]
MIL-101/Fe3+	ICG-CpG@MOF	ICG and CpG adsorption	>150 nm	Laser PDT and PTT: 808 nm, 1.5 W/cm2, 5 min	4T1	HA mediated tumor cells targeting GSH dependent delivery of CpG PDT + PTT + CpG synergy	Tumor disappearance 18 days after treatment Metastasis inhibition	[132]
MIL-101/Fe3+	MMH-NPs	MTO encapsulation + HA coating	173.9 ± 3.7 nm	Laser PTT: 671 nm, 1.0 W/cm2, 5 min	CT26	HA mediated tumor cells targeting PTT + chemotherapy ↑ICD and tumor antigen presentation αOX40 administration ↓ immunosuppressive cells	Tumor growth inhibition Abscopal effects and metastasis inhibition	[133]
MIL-100/Fe3+	OIMH NPs	ICG and OXA encapsulation + HA coating	127 nm	Laser PTT: 808 nm, 0.8 W/cm2, 10 min	CT26	PTT + chemotherapy ↑ICD and antitumor response -Synergy with ICB	Inhibition of primary and distant tumors	[134]
UCS/ Zr4+	TPZ/UCS	UCNPs core + CA coating + porphyrin MOF shell + TPZ encapsulation	38–65 nm	Laser PTT: 980 nm, 1.2 W/cm2, 20 min (5 min interval every 1 min of irradiation)	CT26	UCNP energy transference to the MOF porphyrin shell↑ ROS production pH dependent release and hypoxia activation of TPZ ↑ ROS production PDT+ TPZ ↑ICD and antitumor immunity Synergy with ICB	Complete tumor suppression Abscopal effects in synergy with α-PD-L1	[135]
TBC-Hf/Hf4+	IDOi@TBC-Hf	IDOi encapsulation	83.2 nm	LED PDT: 650 nm, 0.1 W/cm2, 15 min	CT26 and MC38	PDT ↑ICD in primary tumors IDO inhibition by IDOi ↓ immunosuppressive TME	Near elimination of the primary tumors Abscopal effect	[136]
pMOF/Zr4+	Apt/PDGs-s@pMOF	PDG adsorption + ROS-sensitive crosslinking + Periostin- targeting Apt coating.	96.96 nm	Laser PDT: 660 nm, 0.3 W/cm2, 5 min	4T1	Periotin-targeting Apt targeting of tumor cells Deeper penetration of the PDG by crosslinking destruction ↓ intratumoral MDSCs PDT↑ICD a systemic immune response	Primary tumor proliferation inhibition Abscopal effect in distant tumors	[137]
Zr-MOF/Zr4+	SNPs@Zr-MOF@RB	PAA coating of SNP core-shell + Zr ions and TCCP adsorption for in situ growth + RB incorporation	≈30 nm	Soft X-ray light for 5 min	4T1	Energy transfer from SNP to the MOF + RB ↑ROS production and ↑deep tissue PDT ↑ICD + deep tissue anti tumor immune response ↓ immunosuppressive TME	Tumor growth inhibition	[138]
Zr-MOF/Zr4+	NaLnF4@MOF	NaLnF4 NPs DHCA modification + growth of the Zr-MOF around NaLnF4	36.6 ± 2.2 nm	Light PDT: 980 nm, 0.61 W/cm2, 10 min (3 min break for each minute)	CT26	UCL from NaLnF4 to MOF ↑ PDT PDT-induced ICD synergises with ICB	Complete eradication of primary tumors 95% tumor inhibition Distant tumor suppression in synergy with α-PD-L1	[139]
PBNP/Fe3+ and Fe2+	PBNP	________	≈60–90 nm	Laser PTT: 808 nm, 1.875 W/cm2, 10 min	Neuro2a	PTT↑ICD and antigen presentation Synergize with ICB	Primary tumor shrinkage Suppression and elimination of primary tumors in synergy with aCTLA-4 Rechallenging tumors eradication	[140]
PBNP/Fe3+ and Fe2+	CpG- PBNP	CpG adsorption	100–1000 nm	Laser PTT: 808 nm, 1.5 W/cm2, 10 min	9464D	PTT↑ICD and antigen presentation PDT+ CpG↑DCs maturation	Complete tumor regression 100% survival rate after 80 days Slower distant tumor growth Rechallenged tumor regression 80% mice survival rate after 125 days	[141]
PBNP/Fe3+ and Fe2+	CpG- PBNP	CpG adsorption	100–1000 nm	Laser PTT: 808 nm, 0.75 W/cm2, 10 min	Neuro2a	PTT↑ICD and antigen presentation PDT+ CpG↑DCs maturation and ↑ synergy with ICB	Primary and distant tumor regression Fast elimination of rechallenged tumors	[142]
PBNP/Fe3+ and Fe2+	SP94-PB-SF- Cy5.5	SP94 adsorption +SF encapsulation + Cy5.5 adsorption	90–110 nm	Laser PTT: 808 nm, 1.5 W/cm2, 10 min	HepG2 and Hepa1-6	SP94 selectively targets HCC cells PTT + SF ↑ICD Synergy with ICB ↑ immune response	100% tumor inhibition 80% mice survival rate Primary, distant and rechallenged tumors suppression in synergy with ICB	[143]
PBNP/Fe3+ and Fe2+	PBNP	________	51 nm	Laser PTT: 808 nm, 2 W/cm2, 10 min	SM1	PTT- induced ICD + aCD137 ICB ↑ antitumoral response	Primary tumor elimination 60% distant tumor growth inhibition 66% rechallenged tumor rejection	[144]

1-MT, 1-methyltryptophan; ACF, acriflavine; aCTLA-4, cytotoxic T-lymphocyte-associated protein 4 antibodies; Apt, aptamer; CA, citric acid; CCCP, Carbonyl cyanide 3-chlorophenyl-hydrazone; Cdk4, Cyclin-dependent kinase 4; CpG, Cytosine-phosphate-Guanine; Cy5.5, cyanine5.5; DAMPs, Damage-associated molecular patterns; DCs, dendritic cells; DHCA, dihydroxyphenylpropionc acid; DOX, doxorubicin; FM, Fused cell cytomembrane; GEM, gemcitabine; GSH, glutathione; HA, Hyaluronic acid; HCC, Hepatocellular carcinoma; HIF-1α, Hypoxia-Inducible Factor; ICB, immune checkpoint blockade; ICD, immunogenic cell death; ICG, indocyanine green; IDOi, Indoleamine 2,3-dioxygenase inhibitor; IMQ, imiquimod; IR820, Indocyanine green; LED, light emitting diode; MAN, mannan; MIL, Material Institute Lavoisier; MOF, metal-organic frameworks; MTO, mitoxantrone; OXA, oxaliplatin; PAA, polyacrylic acid; PAH, polyallylamine hydrochloride; PBNPs, Prussian blue nanoparticles; PCN, Porous Coordination Network; PDA, polydopamine; PDG, GEM-loaded DGLs shells; PD-L1, Programmed death-ligand 1; PDT, photodynamic therapy; PpIX, protoporphyrin IX; PTT, photothermal therapy; R837, Vaccigrade Imiquimod; RB, rose bengal; ROS, reactive oxygen species; SF, sorafenib; siCdk4, small interfering Cyclin-dependent kinase 4; SNPs, scintillator nanoparticles; TAAs, tumor-associated antigens; TBP, tetrabenzoporphyrin; TPZ, tirapazamine; UCNP, lanthanide-doped upconversion nanoparticles; ZIF, Zeolitic imidazolate frameworks.