Ahmed Mohamed El-Toni

Anisotropic Growth-Induced Synthesis of Dual-Compartment Janus Mesoporous Silica Nanoparticles for Bimodal Triggered Drugs Delivery

Multifunctional dual-compartment Janus mesoporous silica nanocomposites of UCNP@SiO2@mSiO2&PMO (UCNP = upconversion nanoparticle, PMO = periodic mesoporous organosilica) containing core@shell@shell structured UCNP@SiO2@mSiO2 nanospheres and PMO single-crystal nanocubes have been successfully synthesized via a novel anisotropic island nucleation and growth approach with the ordered mesostructure. The asymmetric Janus nanocomposites show a very uniform size of ~300 nm and high surface area of ~1290 m(2)/g. Most importantly, the Janus nanocomposites possess the unique dual independent mesopores with different pore sizes (2.1 nm and 3.5-5.5 nm) and hydrophobicity/hydrophilicity for loading of multiple guests. The distinct chemical properties of the silica sources and the different mesostructures of the dual-compartments are the necessary prerequisites for the formation of the Janus nanostructure. With the assistance of the near-infrared (NIR) to ultraviolet/visible (UV-vis) optical properties of UCNPs and heat-sensitive phase change materials, the dual-compartment Janus mesoporous silica nanocomposites can be further applied into nanobiomedicine for heat and NIR light bimodal-triggered dual-drugs controllable release. It realizes significantly higher efficiency for cancer cell killing (more than 50%) compared to that of the single-triggered drugs delivery system (~25%).

Anisotropic Encapsulation-Induced Synthesis of Asymmetric Single-Hole Mesoporous Nanocages

Asymmetric single-hole mesoporous silica nanocages, which are eccentric hollow structured spheres and consist of mesoporous shell with an open hole on their surface, with uniform particle size (100-240 nm), have successfully been synthesized via a novel anisotropic encapsulation of the mesoporous silica. In this unique nanocarrier, the eccentric hollow cavity and big hole (∼25 nm) can serve as a storage space and passage for large guest molecules. Meanwhile, the uniform mesopores (2-10 nm) with a high surface area (∼500 m(2)/g) in the silica shells of the nanocages can provide storage space for small guest molecules. The obtained single-hole mesoporous nanocages can be endowed upconversion luminescence. The obtained upconversion nanoparticles functionalized eccentric single-hole nanorattles were used to codeliver bovine serum albumin and doxorubicin dual-sized guests. The release of the dual-sized guests can be well controlled independently by heat and near-infrared (NIR) light with the assistance of NIR to ultraviolet/visible (UV/vis) optical properties of upconversion nanoparticles and heat-sensitive phase change materials.

Mesoporous Silica-Coated Plasmonic Nanostructures for Surface-Enhanced Raman Scattering Detection and Photothermal Therapy

The design and fabrication of core-shell and yolk-shell nanostructures with surface plasmon resonance (SPR)-active center protected by permeable mesoporous channels can raise the new vitality into the catalysis and biological applications. Hybrid plasmonic-mesoporous silica nanocarriers consisting of Ag and Au-Ag alloy nanoparticles are fabricated through spatially confined galvanic replacement approach. The plasmonic absorption peaks can be finely controlled to the near-infrared (NIR) region (500-790 nm) that is beneficial for tissue transmittance. The mesoporous silica shell facilitates also protection of Au-Ag cores and affords the channels between the exterior and interior capsule environments, thereby endowing the multiple applications. In the present work, it is successfully demonstrated that mesoporous silica-coated Au-Ag alloy core-shell and yolk-shell nanocarriers can serve as good substrates for surface-enhanced Raman scattering (SERS) detection. The SERS signal intensities of nanocarriers are highly dependent on the SPR peaks and the contents of gold. Simultaneously, the synthesized Au-Ag@mSiO2 nanocarriers with SPR peak at ≈790 nm can be applied in NIR-sensitive SERS detection and photothermal therapy.

Synthesis and application of Fe3O4@SiO2@TiO2 for photocatalytic decomposition of organic matrix simultaneously with magnetic solid phase extraction of heavy metals prior to ICP-MS analysis

Interference of organic compounds in the matrix of heavy metal solution could suppress their pre-concentration and detection processes. Therefore, this work aimed to develop simple and facile methods for separation of heavy metals before ICP-MS analysis. Fe3O4@SiO2@TiO2 core-double shell magnetic adsorbent was prepared and characterized by TEM, SEM, FTIR, XRD and surface area, and tested for Magnetic Solid Phase Extraction (MSPE) of Cu(II), Zn(II), Cd(II) and Pb(II). TEM micrograph of Fe3O4@SiO2@TiO2 reveals the uniform coating of TiO2 layer of about 20nm onto the Fe3O4@SiO2 nanoparticles and indicates that all nanoparticles are monodispersed and uniform. The saturation magnetization from the room-temperature hysteresis loops of Fe3O4 and Fe3O4@SiO2@TiO2 was found to be 72 and 40emug(-1), respectively, suggesting good separability of the nanoparticles. The Fe3O4@SiO2@TiO2 showed maximum adsorption capacity of 125, 137, 148 and 160mgg(-1) for Cu(II), Zn(II), Cd(II) and Pb(II) respectively, and the process was found to fit with the second order kinetic model and Langmuir isotherm. Fe3O4@SiO2@TiO2 showed efficient photocatalytic decomposition for tartrazine and sunset yellow (consider as Interfering organic compounds) in aqueous solution under the irradiation of UV light. The maximum recovery% was achieved at pH 5, by elution with 10mL of 2M nitric acid solution. The LODs were found to be 0.066, 0.049, 0.041 and 0.082µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively while the LOQs were found to be 0.20, 0.15, 0.12 and 0.25µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively.

Walterinnesia aegyptia venom combined with silica nanoparticles enhances the functioning of normal lymphocytes through PI3K/AKT, NFκB and ERK signaling

BackgroundThe toxicity of snake venom varies over time in some species. The venom of newborn and small juvenile snakes appears to be more potent than adults of the same species, and a bite from a snake that has not fed recently, such as one that has just emerged from hibernation, is more dangerous than one that has recently fed due to the larger volume of venom injected. Therefore, the potency of a snakes venom is typically determined using the LD50 or IC50 tests. In the present study, we evaluated the anti-tumor potential of snake venom from Walterinnesia aegyptia (WEV) on the human breast carcinoma cell line MDA-MB-231, as well as its effect on the normal mice peripheral blood mononuclear cells (PBMCs).ResultsThis venom was used alone (WEV) or in combination with silica nanoparticles (WEV+NP). The IC50 values of WEV alone and WEV+NP in the MDA-MB-231 cells were determined to be 50 ng/ml and 20 ng/ml, respectively. Interestingly, at these concentrations, the venom did not affect the viability of normal human PBMCs. To investigate the in vivo effects of this venom further, three groups of mice were used (15 mice in each group): Group I was the control, Group II was subcutaneously injected with WEV, and Group III was injected with WEV+NP. Using flow cytometry and western blot analysis, we found that the blood lymphocytes of WEV-injected mice exhibited a significant increase in actin polymerization and cytoskeletal rearrangement in response to CXCL12 through the activation of AKT, NF-κB and ERK. These lymphocytes also showed a significant increase in their proliferative capacity in response to mitogen stimulation compared with those isolated from the control mice (P < 0.05). More importantly, in the WEV+NP-treated mice, the biological functions of normal lymphocytes were significantly (P < 0.05) enhanced in comparison with those of WEV-treated mice.ConclusionOur data reveal the unique biological effects of WEV, and we demonstrated that its combination with nanoparticles strongly enhanced these biological effects.

Periodic Mesoporous Organosilica Nanocubes with Ultrahigh Surface Areas for Efficient CO₂ Adsorption.

Ultrahigh surface area single-crystals of periodic mesoporous organosilica (PMOs) with uniform cubic or truncated-cubic morphology and organic/inorganic components homogeneously distributed over the whole frameworks have successfully been prepared by a sol-gel surfactant-templating method. By tuning the porous feature and polymerization degree, the surface areas of the obtained PMO nanocubes can reach as high as 2370 m2/g, which is the highest for silica-based mesoporous materials. The ultrahigh surface area of the obtained PMO single crystals is mainly resulted from abundant micropores in the mesoporous frameworks. Furthermore, the diameter of the nanocubes can also be well controlled from 150 to 600 nm. The materials show ultrahigh CO2 adsorption capacity (up to 1.42 mmol/g at 273 K) which is much higher than other porous silica materials and comparable to some carbonaceous materials. The adsorption of CO2 into the PMO nanocubes is mainly in physical interaction, therefore the adsorption-desorption process is highly reversible and the adsorption capacity is much dependent on the surface area of the materials. Moreover, the selectivity is also very high (~11 times to N2) towards CO2 adsorption.

Carbon‐Dot‐Sensitized, Nitrogen‐Doped TiO2 in Mesoporous Silica for Water Decontamination through Nonhydrophobic Enrichment–Degradation Mode

Mesoporous silica synthesized from the cocondensation of tetraethoxysilane and silylated carbon dots containing an amide group has been adopted as the carrier for the in situ growth of TiO2 through an impregnation-hydrothermal crystallization process. Benefitting from initial complexation between the titania precursor and carbon dot, highly dispersed anatase TiO2 nanoparticles can be formed inside the mesoporous channel. The hybrid material possesses an ordered hexagonal mesostructure with p6mm symmetry, a high specific surface area (446.27 m(2)  g(-1) ), large pore volume (0.57 cm(3)  g(-1) ), uniform pore size (5.11 nm), and a wide absorption band between λ=300 and 550 nm. TiO2 nanocrystals are anchored to the carbon dot through TiON and TiOC bonds, as revealed by X-ray photoelectron spectroscopy. Moreover, the nitrogen doping of TiO2 is also verified by the formation of the TiN bond. This composite shows excellent adsorption capabilities for 2,4-dichlorophenol and acid orange 7, with an electron-deficient aromatic ring, through electron donor-acceptor interactions between the carbon dot and organic compounds instead of the hydrophobic effect, as analyzed by the contact angle analysis. The composite can be photocatalytically recycled through visible-light irradiation after adsorption. The narrowed band gap, as a result of nitrogen doping, and the photosensitization effect of carbon dots are revealed to be coresponsible for the visible-light activity of TiO2 . The adsorption capacity does not suffer any clear losses after being recycled three times.

Coating and photochemical properties of calcia-doped ceria with amorphous silica by a seeded polymerization technique

Calcia doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products because of its excellent UV light absorption properties and its low catalytic ability for the oxidation of organic materials is superior to undoped ceria. In order to reduce the oxidation catalytic activity further, calcia doped ceria was coated with amorphous silica by means of a seeded polymerization technique. The silica shell was confirmed using scanning electron microscopy, TEM, XPS and FT-IR. Silica coating by seeded polymerization was much more efficient in the reduction of the oxidation catalytic activity without loss of the UV-shielding ability, than coating by acid hydrolysis of a sodium silicate solution.

Orthogonal near-infrared upconversion co-regulated site-specific O2 delivery and photodynamic therapy for hypoxia tumor by using red blood cell microcarriers

Pre-existing hypoxia in tumors can result in an inadequate oxygen supply during photodynamic therapy (PDT), which in turn hampers photodynamic efficacy. To overcome this problem, we developed an orthogonal near-infrared upconversion controlled red blood cell (RBC) microcarriers to selectively deliver O2 in hypoxia area. Moreover, this RBC microcarriers are able to overcome a series of complex biological barriers which include transporting across the inflamed endothelium, evading mononuclear phagocyte system, reducing reticuloendothelial system uptake. Based on these abilities, RBC microcarriers have efficient tumors accumulation and are capable of delivery a large amount of O2 for PDT under near-infrared (NIR) irradiation to realize effective solid tumor eradication.

Synthesis of double mesoporous core–shell silica spheres with tunable core porosity and their drug release and cancer cell apoptosis properties

In this work, we demonstrate a simple two-pot approach to double mesoporous core-shell silica spheres (DMCSSs) with uniform size of 245-790 nm, shell thickness of 41-80 nm and surface area and total pore volume of 141-618 m(2) g(-1) and 0.14-0.585 cc g(-1), respectively. First, solid silica spherical particles were synthesized by the Stöber method and used as a core. Second, a mesoporous shell could be formed around the silica cores by using an anionic surfactant and a co-structure directing agent. It was found that mesopores can be anchored within dense silica cores during mesoporous silica shell formation, synchronously the base group with surfactant assistant can etch the dense silica cores to re-organize new mesostructure, so that double mesoporous core-shell silica sphere (DMCSS) structure can be obtained by a single surfactant-templating step. The spherical size and porosity of the silica cores of DMCSS together with shell thickness can be tuned by controlling Stöber parameters, including the concentrations of ammonia, solvent and tetraethoxysilane and the reaction time. DMCSS were loaded with ketoprofen and thymoquinone, which are an anti-inflammatory and a potential novel anti-cancer drug, respectively. Both drugs showed controlled release behavior from the pores of DMCSS. Drug uptakes within DMCSS were ~27 and 81 wt.% for ketoprofen and thymoquinone, respectively. Furthermore, DMCSS loaded with thymoquinone was more effective in inducing cancer cell apoptosis than uncontained thymoquinone, because of the slow release of the drug from the mesoporous structure.