How Advancing are Mesoporous Silica Nanoparticles? A Comprehensive Review of the Literature

Figures & data

Table 1 Chemical Composition of Some Bio-Sources Ash

	Rice Husk Ash^Citation57	Whaet Husk Ash^Citation145	Corn Cob Ash^Citation76	Coffee Husk Ash^Citation146	Palm Ash^Citation147	Sugarcane bagasse Ash^Citation148
SiO2	93.2	43.22	47.78	14.65	45.50	78.34
Al2O3	0.13	–	9.40	12.07	5.40	8.55
Fe2O3	0.07	0.84	8.31	–	3.26	3.61
CaO	1.23	5.46	16.7	13.05	12.80	2.15
MgO	0.25	0.99	7.80	–	3.20	1.65
Mn2O3	–	–	2.70	–	–	–
K2O	0.78	11.30	5.42	47.45	23.30	3.46
Na2O	0.08	0.16	1.89	–	–	0.12
MnO2	–	0.02	–	–	–	–
Cr2O3	–	0.0004	–	–	–	–
MnO	0.33	–	–	–	–	0.13
P2O5	0.15	–	–	–	5.38	0.5
TiO2	0.006	–	–	–	–	0.16
BaO	–	–	–	–	–	1.07
SO3	–	–	–	–	–	–

Figure 1 Effects of pH value on the silica condensation rate, charge properties and charge density on the surface of the silica species.

Notes: Adapted from Wu S-H, Mou C-Y, Lin H-P. Synthesis of mesoporous silica nanoparticles. Chem Soc Rev. 2013;42(9):3862–3875.⁴⁰

Table 2 Composition of RHA Derived from Calcination of Rice Husk at 600 °C for 12 h

SiO2	Al2O3	Fe2O3	CaO	MgO	K2O	Na2O	MnO	TiO2	P2O5
93.2	0.13	0.07	1.23	0.25	0.78	0.08	0.33	0.006	0.15

Note: Reprinted from Int J Greenhouse Gas Cont, 3(5), Jang HT, Park Y, Ko YS, Lee JY, Margandan B. Highly siliceous MCM-48 from rice husk ash for CO2 adsorption. 545–549, Copyright 2009, with permission from Elsevier.⁵⁷

Table 3 Several Biogenic Silica Nanoparticles and Their Applications

Synthesized NP	Bio-Source	Synthesis Method	NP Size (nm)	Specific Surface Area (m^2 g^−1)	Pore Diameter (nm)	Shape	Application	Ref.
RMSN-D WMSN-D	Rice & Wheat husk	Acid-pretreatment/ Calcination then sol-gel process with CTAB surfactant	41.8, 72	950.76, 617.35	4.7, 4.1	Spherical	Drug delivery	[^Citation15]
RMSN-DAN	Rice husk	Acid-pretreatment/Calcination Acid-pretreatment/ Calcination then sol-gel process with CTAB surfactant and finally AA and NIPAAm monmers polymerization on the vinyl modifies nanoparticles surface	34	-	-	Spherical	Drug delivery	[^Citation26]
RMSN-DPAN & RMSN-DHPAN	Rice husk	Acid-pretreatment/Calcination Acid-pretreatment/ Calcination then sol-gel process with CTAB surfactant and finally AA and NIPAAm monmers polymerization on the vinyl modifies nanoparticles surface by DBD plama technique	102, 162	-	-	Spherical	Drug delivery	[^Citation27]
Biogenic-silica nanoparticle (bSN)	Rice husk	Acid-pretreatment/Calcination	10–40	289	Less than 10	Spherical	As Li-ion battery anodes	[^Citation149]
Silica nanofluids	Rice husk	Acid-pretreatment/ precipitate by Na2CO3-/dispersing the nanoparticles in water with ultrasonic vibration	Average 47	-	-	Near-spherical	Electronics cooling, industrial cooling, drug delivery, and CO2 absorption enhancement	[^Citation150]
Amine functionalized biogenic MCM-48	Rice husk	Acid-pretreatment/Calcination/ preparation sodium silicate solution/ adding templates to synthesis MCM-48 by sol-gel method/calcination to template removal/ amination by APTES	-	1024 for MCM-48/124 for amine functionalized MCM-48	4.02 for MCM-48/10.24 for amine functionalized MCM-48	Spherical with cubic Ia3d mesophase.	CO2 removal.	[^Citation57]
palladium-copper zinc loaded on biogenic MCM-41	Rice husk	Acid-pretreatment/Calcination/ preparation sodium silicate solution/ adding templates to synthesis MCM-41 by sol-gel/calcination to template removal/ Loading of metals onto MCM-41 support	30–39	851 for MCM-41/32-179 for several kinds of catalysts	3.5 for MCM-41/3.9–15.5for several kinds of catalysts	Spherical	As a catalyst to production of methanol from carbon dioxide	[^Citation151]
Composite of biogenic MCM-41 and rice husk	Rice husk	Acid-pretreatment/ adding to template solution to synthesis MCM-41/ washing with ethanol several time to remove any remaining soluble salts.	-	-	-	Aggregates of wormy and spherical particles	Phosphate removal	[^Citation152]
Biogenic MCM-41	Wheat husk	Acid-pretreatment/Calcination/ adding templates to synthesis MCM-41 by sol-gel/calcination to template removal	300–500	-	-	-	Adsorption, ion-exchange and shape-selective catalysis.	[^Citation153]
Biogenic silica nanoparticles	Corn cob	Washing with water/calcination/ adding templates to synthesis silica nanoparticles by sol-gel/calcination to template removal	44–98	-	-	Spherical	Nanoscience	[^Citation76]
Biogenic silica gel	Palm oil	Precipitation	<50 µm	-	-	Gel	Nanoscience	[^Citation154]

Table 4 Chemical Composition Analyzed by XRF, Loss on Ignition, and Total Carbon of Three RHA Types (Wt%)

Composition	RHA FB	RHA MG	RHA S
SiO2	96.71	90.02	93.61
Al2O3	0.09	0.08	0.06
Fe2O3	0.01	0.01	0.03
K2O	0.69	0.81	0.66
CaO	ND	0.00	ND
Cl	0.02	0.03	0.08
P2O5	0.23	0.34	0.30
MgO	ND	ND	ND
SO3	0.06	0.07	0.11
TiO2	ND	ND	ND
ZnO	0.01	0.01	0.01
MnO	0.01	0.00	0.01
LOI	2.96	9.88	6.73
TC	2.18	8.63	5.14

Note: Reprinted from Fuel, 165, Fernandes IJ, Calheiro D, Kieling AG, et al.Characterization of rice husk ash produced using different biomass combustion techniques for energy.  351–359, Copyright 2016, with permission from Elsevier.⁷⁹

Abbreviations: LOI, loss on ignition; TC, total carbon; ND, not detected.

Figure 2 (A) The overall procedure of mesoporous silica nanoparticles synthesis from rice husk and (B) nanoparticles surface modification synthesis by DBD plasma modification with i) Direct and ii) direct hybrid modes to pH and Temperature-responsive drug delivery system synthesis.

Note: Adapted from J Taiwan Inst Chem Eng, 123, Porrang S, Rahemi N, Davaran S, Mahdavi M, Hassanzadeh B, Gholipour AM. Direct surface modification of mesoporous silica nanoparticles by DBD plasma as a green approach to prepare dual-responsive drug delivery system. 47–58, copyright 2021, with permission from Elsevier.²⁷

Figure 3 Stimuli-responsive drug delivery systems based on MSNs. Created with BioRender.com.

Figure 4 Active targeting strategies based on MSNs. Created with BioRender.com.

Figure 5 CLSM images of MSNs-TAT with diameters of (A) 25, (B) 50, (C) 67, and (D) 105 nm after incubation with Hela cells for (i) 4, (ii) 8, and (iii) 24 h. Scale bars: 5 μm.

Figure 6 (A) Schematic illustration of MSN-BM/CD-HApt@DOX synthesis process and (B) the mechanism of targeting and cancer cells apoptosis.

Note: Reproduced from Shen Y, Li M, Liu T, et al.A dual-functional HER2 aptamer-conjugated, pH-activated mesoporous silica nanocarrier-based drug delivery system provides in vitro synergistic cytotoxicity in HER2-positive breast cancer cells. Int J Nanomedicine. 2019;14:4029-4044. Originally published by and used with permission from Dove Medical Press Ltd.¹⁴⁰

Figure 7 Schematic illustration of magnetic MSNs drug delivery systems preparation based on targeted and photothermal cancer therapy strategies.

Note: Reproduced from Tran VA, Van Giau Vo KS, Lee S-W, An SSA, An SSA. Multimodal mesoporous silica nanocarriers for dual stimuli-responsive drug release and excellent photothermal ablation of cancer cells. Int J Nanomedicine. 2020;15:7667-7685. Originally published by and used with permission from Dove Medical Press Ltd.¹⁴⁴

Abbreviations: APTMS-FITC, 3-AminoPropylTriMethoxySilane-Fluorescein IsoThioCyanate; F, Fe₃O₄ NPs; S, Silica nanoparticles (MSNs); P, Polydopamine (PDA); G, Graphene oxide; A, Au NPs; E, EGFR antibody; C, Cisplatin; GO, Graphene oxide.

Table 5 Some Examples of Drug Delivery Systems Based on MSNs

Drug Delivery Systems Based on Silica	Silica Source	Kind of SNs	Model Drug	Disease	Year of Publication	Ref.
A pH-responsive biogenic MSNs	Rice and wheat hsk	MSN	Dox	Breast cancer	2021	[^Citation15]
A dual pH and temperature-responsive drug delivery system	Rice husk	MSN	Dox	Breast cancer	2021	[^Citation155]
Polydopamine doped MSN-coated reduced graphene oxide for chemo-photothermal therapy	TEOS	MSN	Dox	Cancer	2019	[^Citation156]
Synthesis of MSN–PEI–PEG	TEOS	MCM-41	Epirubicin hydrochloride	Cancer	2015	[^Citation157]
HER2 aptamer-conjugated, pH-activated MSNs	TEOS	MSN	Dox	Breast cancer	2019	[^Citation140]
Two ligands attached to MSN through a pH-responsive hydrazone linkage	TEOS	MSN	Ruthenium	Cancer	2021	[^Citation158]
A pH-sensitive Carrier based on MSN with bilayer coating of poly (acrylic acid-co-itaconic acid)	TEOS	MCM-41	Gemcitabine	Cancer	2016	[^Citation159]
Actively targeting breast cancer cells by chitosan-coated/ aptamer conjugated mesoporous silica nanoparticle	TEOS	MSN	DOX	Breast Cancer	2022	[^Citation160]
Chitosan-modified MSNs by three different methods to amine modification of MSNs surface	TEOS	MSN	Methotroxate (MTX)	Cancer	2021	[^Citation161]
Chitosan based supramolecular polypseudorotaxane as a pH-responsive polymer and their hybridization with mesoporous silica-coated magnetic graphene oxide	TEOS	MSN	DOX	Cancer	2015	[^Citation162]
Trastuzumab-conjugated amine modified MSNs by EDC/NHS cross linker (targeted based on HER2-Antibody)	-	MSN	Dox, Trastuzumab	Dual drug delivery and imaging for breast cancer treatment	2021	[^Citation163]
Determine the feasibility of loading rifampin into MSNs	TEOS	MCM41-	Rifampin	Anti- tuberculosis drug.	2015	[^Citation164]
Bionanocomposites based on MSN and alginate for enhanced drug delivery with reduced burst effect and improved mechanical properties	TEOS	SBA-15 and SBA-16	Prednisolone	Asthma	2018	[^Citation165]
Redox- and enzyme-responsive fluorescent porous silica nanocarriers for drug delivery(pSiO2-ss-CDs/HA)	TEOS	Core-shell MSN	DOX	Cancer	2018	[^Citation166]
Self-fluorescent and stimuli-responsive multifunctional mesoporous silica nanoparticles for drug delivery by dual role curcumuin	TEOS	MCM-41	DOX and curcumin	Cancer	2018	[^Citation167]
MSN and hollow MSN for chemotherapeutic drug delivery by magnetic field	TEOS	MSN and HMSN	DOX	Cancer	2018	[^Citation168]
Amine functionalized MCM-48 for delivery of poorly soluble drugs	TEOS	MCM-48	Indomethacin	Anti-inflammatory	2018	[^Citation169]
Poly(NIPAM-co-MPS)-grafted multimodal porous silica nanoparticles as reverse thermoresponsive drug delivery system	TEOS	MSN	Ibuprofen	-	2017	[^Citation170]
Triple-stimuli (protease/redox/pH) sensitive ZnO quantum dots-gated fluorescent porous silica nanocarriers for drug delivery	TEOS	MSN	Amoxicillin	-	2017	[^Citation171]
Redox-responsive MSNs with PEG gatekeepers as carriers for controlled drug delivery	TEOS	MSN	DOX	Cancer	2015	[^Citation172]

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