Concept: Mesoporous material
Drug molecules with lack of specificity and solubility lead patients to take high doses of the drug to achieve sufficient therapeutic effects. This is a leading cause of adverse drug reactions, particularly for drugs with narrow therapeutic window or cytotoxic chemotherapeutics. To address these problems, there are various functional biocompatible drug carriers available in the market, which can deliver therapeutic agents to the target site in a controlled manner. Among the carriers developed thus far, mesoporous materials emerged as a promising candidate that can deliver a variety of drug molecules in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles are widely used as a delivery reagent because silica possesses favourable chemical properties, thermal stability and biocompatibility. Currently, sol-gel-derived mesoporous silica nanoparticles in soft conditions are of main interest due to simplicity in production and modification and the capacity to maintain function of bioactive agents. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release. The properties of mesopores, including pore size and porosity as well as the surface properties, can be altered depending on additives used to fabricate mesoporous silica nanoparticles. Active surface enables functionalisation to modify surface properties and link therapeutic molecules. The tuneable mesopore structure and modifiable surface of mesoporous silica nanoparticle allow incorporation of various classes of drug molecules and controlled delivery to the target sites. This review aims to present the state of knowledge of currently available drug delivery system and identify properties of an ideal drug carrier for specific application, focusing on mesoporous silica nanoparticles.
Hierarchical zeolites are a class of microporous catalysts and adsorbents that also contain mesopores, which allow for fast transport of bulky molecules and thereby enable improved performance in petrochemical and biomass processing. We used repetitive branching during one-step hydrothermal crystal growth to synthesize a new hierarchical zeolite made of orthogonally connected microporous nanosheets. The nanosheets are 2 nanometers thick and contain a network of 0.5-nanometer micropores. The house-of-cards arrangement of the nanosheets creates a permanent network of 2- to 7-nanometer mesopores, which, along with the high external surface area and reduced micropore diffusion length, account for higher reaction rates for bulky molecules relative to those of other mesoporous and conventional MFI zeolites.
A facile vacuum-assisted vapor deposition process has been developed to control the pore size of ordered mesoporous silica materials in a stepwise manner with angstrom precision, providing an unprecedented paradigm to screen a designer hydrophobic drug nano-carrier with optimized pore diameter to maximize drug solubility.
A new technique that allows direct three-dimensional (3D) investigations of mesopores in carbon materials and quantitative characterization of their physical properties is reported. Focused ion beam nanotomography (FIB-nt) is performed by a serial sectioning procedure with a dual beam FIB-scanning electron microscopy instrument. Mesoporous carbons (MPCs) with tailored mesopore size are produced by carbonization of resorcinol-formaldehyde gels in the presence of a cationic surfactant as a pore stabilizer. A visual 3D morphology representation of disordered porous carbon is shown. Pore size distribution of MPCs is determined by the FIB-nt technique and nitrogen sorption isotherm methods to compare both results. The obtained MPCs exhibit pore sizes of 4.7, 7.2, and 18.3 nm, and a specific surface area of ca. 560 m2/g.
The ability to tune polymer monolith porosity on multiple length scales is desirable for applications in liquid separations, catalysis, and bioengineering. To this end, we have developed a facile synthetic route to nanoporous polymer monoliths based on controlled polymerization of styrene and divinylbenzene from a poly(lactide) macro-chain transfer agent in the presence of nonreactive poly(ethylene oxide) (PEO). Simple variations in the volume fraction and/or molar mass of PEO lead to either polymerization-induced microphase separation or simultaneous macro- and microphase separation. These processes dictate the resultant morphology and allow for control of the macro- and microstructure of the monoliths. Subsequent selective etching produces monoliths with morphologies that can be tailored from mesoporous, with control over mesopore size, to hierarchically meso- and macroporous, with percolating macropores. This convenient synthetic route to porous polymer monoliths has the potential to be useful in applications where both rapid mass transport and a high surface area are required.
Mesoporous cobalt phosphide (meso-CoP) was prepared by the phosphorization of ordered mesoporous cobalt oxide (meso-Co3 O4 ). The electrical conductivity of meso-CoP is 37 times higher than that of nonporous CoP, and it displays semimetallic behavior with a negligibly small activation energy of 26 meV at temperatures below 296 K. Above this temperature, only materials with mesopores underwent a change in conductivity from semimetallic to semiconducting behavior. These properties were attributed to the coexistence of nanocrystalline Co2 P phases. The poor crystallinity of mesoporous materials has often been considered to be a problem but this example clearly shows its positive aspects. The concept introduced here should thus lead to new routes for the synthesis of materials with high electronic conductivity.
Mesoporous silica nanoparticles loaded with fluorescein and capped by a pseudorotaxane, formed between a naphthalene derivative and cyclobis(paraquat-p-phenylene) (CBPQT(4+)), were used for the selective and sensitive fluorogenic detection of 3,4-methylenedioxymethamphetamine (MDMA).
We have optimized mesoporous silica nanoparticles (MSNs) functionalized with pH-sensitive nanovalves for the delivery of the broad spectrum fluoroquinolone, moxifloxacin (MXF), and demonstrated its efficacy in treating Francisella tularensis infections both in vitro and in vivo. We compared two different nanovalve systems, positive and negative charge modifications of the mesopores, and different loading conditions - varying pH, cargo concentration, and duration of loading - and identified conditions that maximize both the uptake and release capacity of MXF by MSNs. We have demonstrated in macrophage cell culture that the MSN-MXF delivery platform is highly effective in killing F. tularensis in infected macrophages, and in a mouse model of lethal pneumonic tularemia, we have shown that the drug-loaded MSNs are much more effective in killing F. tularensis than an equivalent amount of free MXF.
A stepwise ligand exchange strategy is utilized to prepare a series of isoreticular bio-MOF-100 analogues. Specifically, in situ ligand exchange with progressively longer dicarboxylate linkers is performed on single crystalline starting materials to synthesize products with progressively larger mesoporous cavities. The new members of this series of materials, bio-MOFs 101-103, each exhibit permanent mesoporosity and pore sizes ranging from ~2.1-2.9 nm and surface areas ranging from 2704 m2/g to 4410 m2/g. The pore volume for bio-MOF 101 is 2.83 cc/g. Bio-MOF-102 and 103 have pore volumes of 4.36 cc/g and 4.13 cc/g, respectively. Collectively, these data establish this unique family of MOFs as one of the most porous reported to date.
Morphology-controlled nanomaterials such as silica play a crucial role in the development of technologies for addressing challenges in the fields of energy, environment and health. After the discovery of Stöber silica, followed by the discovery of mesoporous silica materials, such as MCM-41 and SBA-15, a significant surge in the design and synthesis of nanosilica with various sizes, shapes, morphologies and textural properties (surface area, pore size and pore volume) has been observed in recent years. One notable invention is dendritic fibrous nanosilica (DFNS), also known as KCC-1. This material possesses a unique fibrous morphology, unlike the tubular porous structure of various conventional silica materials. It has a high surface area with improved accessibility to the internal surface, tunable pore size and pore volume, controllable particle size, and importantly, improved stability. After its discovery, a large number of reports appeared in the literature citing its successful use in a range of applications, such as catalysis, solar energy harvesting (photocatalysis, solar cells, etc.), energy storage, self-cleaning antireflective coatings, surface plasmon resonance (SPR)-based ultra-sensitive sensors, CO2 capture and biomedical applications (drug delivery, protein and gene delivery, bioimaging, photothermal ablation, and Ayurvedic and radiotherapeutics drug delivery, among others). These reports indicate that dendritic fibrous nanosilica has excellent potential as an alternative to popular silica materials such as MCM-41, SBA-15, Stöber silica, and mesoporous silica nanoparticles (MSNs), among others. This review provides a critical survey of the dendritic fibrous nanosilica family of materials, and the discussion includes i) the synthesis and formation mechanism, ii) applications in catalysis and photocatalysis, iii) applications in energy harvesting and storage, iv) applications in magnetic and composite materials, v) applications in CO2 mitigation, v) biomedical applications, and vi) analytical applications (sensing, extraction, and chromatography). Wherever possible, the comparison of dendritic fibrous nanosilica -based materials with conventional mesoporous materials, such as MCM-41, SBA-15, Stöber silica, and MSNs, is presented.