In Vitro Safety Assessment of In-House Synthesized Titanium Dioxide Nanoparticles: Impact of Washing and Temperature Conditions.

Titanium dioxide nanoparticles (TiO2 NPs) have been widely used in food, cosmetics, and biomedical research. However, human safety following exposure to TiO2 NPs remains to be fully understood. The aim of this study was to evaluate the in vitro safety and toxicity of TiO2 NPs synthesized via the Stöber method under different washing and temperature conditions. TiO2 NPs were characterized by their size, shape, surface charge, surface area, crystalline pattern, and band gap. Biological studies were conducted on phagocytic (RAW 264.7) and non-phagocytic (HEK-239) cells. Results showed that washing amorphous as-prepared TiO2 NPs (T1) with ethanol while applying heat at 550 °C (T2) resulted in a reduction in the surface area and charge compared to washing with water (T3) or a higher temperature (800 °C) (T4) and influenced the formation of crystalline structures with the anatase phase in T2 and T3 and rutile/anatase mixture in T4. Biological and toxicological responses varied among TiO2 NPs. T1 was associated with significant cellular internalization and toxicity in both cell types compared to other TiO2 NPs. Furthermore, the formation of the crystalline structure induced toxicity independent of other physicochemical properties. Compared with anatase, the rutile phase (T4) reduced cellular internalization and toxicity. However, comparable levels of reactive oxygen species were generated following exposure to the different types of TiO2, indicating that toxicity is partially driven via non-oxidative pathways. TiO2 NPs were able to trigger an inflammatory response, with varying trends among the two tested cell types. Together, the findings emphasize the importance of standardizing engineered nanomaterial synthesis conditions and evaluating the associated biological and toxicological consequences arising from changes in synthesis conditions.

Gold nanoparticles plated porous silicon nanopowder for nonenzymatic voltammetric detection of hydrogen peroxide.

A voltammetric approach was developed for the selective and sensitive determination of hydrogen peroxide using Au plated porous silicon (PSi) nanopowder modified glassy carbon electrode (GCE). The AuNPs-PSi hybrid structure was synthesized via stain etching procedure followed by an immersion plating method to deposit AuNPs onto PSi via a simple galvanic displacement reaction with no external reducing agent to convert Au3+ to Au0. The as-fabricated AuNPs-PSi catalyst was successfully characterized by XRD, Raman, FTIR, XPS, SEM, TEM and EDS techniques. Well crystalline nature of the as-fabricated hybrid structure with AuNPs size ranging from 5 to 40 nm was observed. The specific surface area and total pore volume for both PSi and AuNPs plated PSi were evaluated using N2 adsorption isotherm technique. Cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied to investigate the catalytic efficiency of AuNPs-PSi modified electrode compared to pure PSi/GCE and unmodified GCE. The sensing performance of the active material modified GCE was thoroughly examined with linear sweep voltammetry (LSV) and square wave voltammetry (SWV) techniques. The AuNPs-PSi/GCE exhibited a remarkable linear dynamic range between 2.0 and 13.81 mM (for LSV) and 0.5-6.91 mM for (SWV) with high sensitivity and low detection limit of 10.65 µAmM-1cm-2 and 14.84 µM for LSV, whereas 10.41 µAmM-1cm-2 and 15.16 µM using SWV techniques, respectively. The fabricated sensor electrode showed excellent anti-interfering ability in the presence of several common biomolecules as well as demonstrated good operational stability and reproducibility with low relative standard deviation. Moreover, the modified electrode showed acceptable recovery of H2O2 in a real sample analysis. Thus, the developed AuNPs-PSi hybrid nanomaterial represents an excellent electrocatalyst for the efficient detection and quantification of H2O2 by the electrochemical approach.

High-Fidelity NIR-II Multiplexed Lifetime Bioimaging with Bright Double Interfaced Lanthanide Nanoparticles.

Fluorescence lifetime imaging provides more possibility of in vivo multiplexing in second near infrared (NIR-II) window. However, it still faces the obstacle that fluorescent probes with differentiable lifetime often exhibit quite different fluorescence intensity, especially the short lifetime usually accompanies with a weak fluorescence intensity, resulting in the difficulty for simultaneously decoding multiplexed lifetime information due to the interference of background noise. To facilitate high-fidelity lifetime multiplexed imaging, we developed a series of Er3+ doped double interface fluorescent nanoprobes (Er-DINPs): α-NaYF4 @NaErF4 : Ce@NaYbF4 @NaErF4 : Ce@NaYF4 with strong fluorescence intensity and easily distinguishable fluorescence lifetime. Both in vitro and in vivo experimental results confirmed the advantage of these probes with comparable fluorescence intensity for high-fidelity multiplexed lifetime bioimaging.

In Vivo High-resolution Ratiometric Fluorescence Imaging of Inflammation Using NIR-II Nanoprobes with 1550 nm Emission.

Quantitatively imaging the spatiotemporal distribution of biological events in living organisms is essential to understand fundamental biological processes. Self-calibrating ratiometric fluorescent probes enable accurate and reliable imaging and sensing, but conventional probes using wavelength of 400-900 nm suffer from extremely low resolution for in vivo application due to the disastrous photon scattering and tissue autofluorescence background. Here, we develop a NIR-IIb (1500-1700 nm) emissive nanoprobe for high-resolution ratiometric fluorescence imaging in vivo. The obtained nanoprobe shows fast ratiometric response to hypochlorous acid (HOCl) with a detection limit down to 500 nM, through an absorption competition-induced emission (ACIE) bioimaging system between lanthanide-based downconversion nanoparticles and Cy7.5 fluorophores. Additionally, we demonstrate the superior spatial resolution of 1550 nm to a penetration depth of 3.5 mm in a scattering tissue phantom, which is 7.1-fold and 2.1-fold higher than that of 1064 and 1344 nm, respectively. With this nanoprobe, clear anatomical structures of lymphatic inflammation in ratiometric channel are observed with a precise resolution of ∼477 µm. This study will motivate the further research on the development of NIR-II probes for high-resolution biosensing in vivo.

Peroxynitrite Activatable NIR-II Fluorescent Molecular Probe for Drug-Induced Hepatotoxicity Monitoring.

Drug-induced hepatotoxicity represents an important challenge for safety in drug development. The production of peroxynitrite (ONOO-) is proposed as an early sign in the progression of drug-induced hepatotoxicity. Currently, reported ONOO- probes mainly emit in the visible range or the first NIR window, which have limited in vivo biosensing application due to the autofluorescence and photon scattering. Herein, we developed a peroxynitrite activatable second near-infrared window (NIR-II) molecular probe for drug-induced hepatotoxicity monitoring, based on the fusion of an NIR-II fluorescence turn-on benzothiopyrylium cyanines skeleton and the phenyl borate. In the presence of ONOO-, the probe IRBTP-B can turn on its NIR-II fluorescence by yielding its fluorophore IRBTP-O and display good linear response to ONOO-. Tissue phantom study confirmed reliable activated signals could be acquired at a penetration depth up to 5 mm. Using this probe, we disclose the upregulation of ONOO- in a preclinical drug-induced liver injury model and the remediation with N-acetyl cysteine (NAC) in vivo. We expect that this strategy will serve as a general method for the development of an activatable NIR-II probe based on the hydroxyl functionalized reactive sites by analyte-specific triggering.

Small-Molecule Lanthanide Complexes Probe for Second Near-Infrared Window Bioimaging.

Over the past few years, significant efforts have been made to create new fluorescent probes operating at longer wavelengths, particularly in the second near-infrared (NIR-II) window from 1000 to 1700 nm, offering enhanced tissue penetration compared to light in the visible and first near-infrared window (700-900 nm). However, most of the reported NIR-II fluorophores meet such dilemmas; they are excreted slowly and largely retained within the reticuloendothelial system. Here, we report a rapidly excreted NIR-II lanthanide complex Nd-DOTA (over 50% excreted through the kidneys within 3 h postinjection) with a molecular mass only 0.54 kDa. The NIR-II imaging quality of Nd-DOTA was far superior to that of clinically approved ICG with good photostability and deep tissue penetration (7 mm). Superior tumor-to-normal tissue ratio was successfully achieved to facilitate the abdominal ovarian metastases surgical delineation. Metastases with ≤1 mm can be completely excised under NIR-II bioimaging guidance. Significantly, since the Nd-DOTA structure is same to the clinically approved magnetic resonance imaging (MRI) contrast Gd-DOTA, it will speed up the clinical translation for this novel kind of NIR-II probes in the future.

Near-Infrared-Activated Upconversion Nanoprobes for Sensitive Endogenous Zn2+ Detection and Selective On-Demand Photodynamic Therapy.

As a light-activated noninvasive cancer treatment paradigm, photodynamic therapy (PDT) has attracted extensive attention because of its high treatment efficacy and low side effects. Especially, spatiotemporal control of singlet oxygen (1O2) release is highly desirable for realizing on-demand PDT, which, however, still remains a huge challenge. To address this issue, a novel switchable near-infrared (NIR)-responsive upconversion nanoprobe has been designed and successfully applied for controlled PDT that can be optically activated by tumor-associated disruption of labile Zn2+ (denoted as Zn2+ hereafter) homeostasis stimuli. Upon NIR irradiation, this theranostic probe can not only quantitatively detect the intracellular endogenous Zn2+ in situ but also selectively generate a great deal of cytotoxic reactive oxygen species (ROS) for efficiently killing breast cancer cells under the activation of excessive endogenous Zn2+, so as to maximally avoid adverse damage to normal cells. This study aims to propose a new tumor-specific PDT paradigm and, more importantly, provide a new avenue of thought for efficient cancer theranostics based on our designed highly sensitive upconversion nanoprobes.

Intracellular and in Vivo Cyanide Mapping via Surface Plasmon Spectroscopy of Single Au-Ag Nanoboxes.

Cyanide is extremely toxic to organisms but difficult to detect in living biological specimens. Here, we report a new CN- sensing platform based on unmodified Au-Ag alloy nanoboxes that etch in the presence of this analyte, yielding a shift in plasmon frequency that correlates with the analyte concentration. Significantly, when combined with dark field microscopy, these particle probes can be used to measure CN- concentrations in HeLa cells and in vivo in Zebra fish embryos. The limit of detection (LOD) of the novel method is 1 nM (below the acceptable limit defined by the World Health Organization), and finite-difference time-domain (FDTD) calculations are used to understand the CN- induced spectral shifts.

One-Step Carbon Coating and Polyacrylamide Functionalization of Fe3O4 Nanoparticles for Enhancing Magnetic Adsorptive-Remediation of Heavy Metals.

Magnetic nanoparticles are used in adsorptive removal of heavy metals from polluted wastewater. However, their poor stability in an acidic medium necessitates their protection with a coating layer. Coating magnetic nanoparticles with carbon showed proper protection but the heavy metal removal efficiency was slightly weak. However, to boost the removal efficiencies of surface functionalization, polyacrylamide was applied to carbon-coated Fe3O4 nanoparticles. In this paper, to facilitate the synthesis process, one-step carbon coating and polyacrylamide functionalization were conducted using the hydrothermal technique with the aim of enhancing the adsorptive removal capacity of Fe3O4 nanoparticles towards some heavy metals such as Cu(II), Ni(II), Co(II), and Cd(II). The results showed that the one-step process succeeded in developing a carbon coating layer and polyacrylamide functionality on Fe3O4 nanoparticles. The stability of the magnetic Fe3O4 nanoparticles as an adsorbent in an acidic medium was improved due to its resistance to the dissolution that was gained during carbon coating and surface functionalization with polyacrylamide. The adsorptive removal process was investigated in relation to various parameters such as pH, time of contact, metal ion concentrations, adsorbent dose, and temperature. The polyacrylamide functionalized Fe3O4 showed an improvement in the adsorption capacity as compared with the unfunctionalized one. The conditions for superior adsorption were obtained at pH 6; time of contact, 90 min; metal solution concentration, 200 mg/L; adsorbent dose, 0.3 g/L. The modeling of the adsorption data was found to be consistent with the pseudo-second-order kinetic model, which suggests a fast adsorption process. However, the equilibrium data modeling was consistent with both the Langmuir and Freundlich isotherms. Furthermore, the thermodynamic parameters of the adsorptive removal process, including ΔG°, ΔH°, and ΔS°, indicated a spontaneous and endothermic sorption process. The developed adsorbent can be utilized further for industrial-based applications.

Facile Peptides Functionalization of Lanthanide-Based Nanocrystals through Phosphorylation Tethering for Efficient in Vivo NIR-to-NIR Bioimaging.

Peptide modification of nanoparticles is a challenging task for bioapplications. Here, we show that noncovalent surface engineering based on ligand exchange of peptides for lanthanide based upconversion and downconversion near-infrared (NIR) luminescent nanoparticles can be efficiently realized by modifying the hydroxyl functional group of a side grafted serine of peptides into a phosphate group (phosphorylation). By using the phosphorylated peptide with the arginine-glycine-aspartic acid (RGD) targeting motifs as typical examples, the modification allows improving the selectivity, sensitivity, and signal-to-noise ratio for the cancer targeting and bioimaging and reducing the toxicity derived from nonspecific interactions of nanoparticles with cells. The in vivo NIR bioimaging signal could even be detected at low injection amounts down to 20 µg per animal.

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.

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.

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%).

Optimization of synthesis parameters for mesoporous shell formation on magnetic nanocores and their application as nanocarriers for docetaxel cancer drug.

In this work, Fe3O4@SiO2 nanoparticles were coated with mesoporous silica shell by S-N+I- pathway by using anionic surfactant (S-) and co-structure directing agent (N+). The role of co-structure directing agent (CSDA) is to assist the electrostatic interaction between negatively charged silica layers and the negatively charged surfactant molecules. Prior to the mesoporous shell formation step, magnetic cores were coated with a dense silica layer to prevent iron oxide cores from leaching into the mother system under any acidic circumstances. However, it was found that both dense and mesoporous coating parameters affect the textural properties of the produced mesoporous silica shell (i.e., surface area, pore volume and shell thickness). The synthesized Fe3O4@SiO2@m-SiO2 (MCMSS) nanoparticles have been characterized by low-angle X-ray diffraction, transmission electron microscopy (TEM), and N2 adsorption-desorption analysis, and magnetic properties. The synthesized particles had dense and mesoporous silica shells of 8-37 nm and 26-50 nm, respectively. Furthermore, MCMSS possessed surface area of ca. 259-621 m2·g-1, and pore volume of ca. 0.216-0.443 cc·g-1. MCMSS showed docetaxcel cancer drug storage capacity of 25-33 w/w% and possessed control release from their mesochannels which suggest them as proper nanocarriers for docetaxcel molecules.

Facile Strategy for Fabricating an Organosilica-Modified Fe3O4 (OS/Fe3O4) Hetero-nanocore and OS/Fe3O4@SiO2 Core-Shell Structure for Wastewater Treatment with Promising Recyclable Efficiency.

The development of a sustainable process for heavy metal ion remediation has become a point of interest in various fields of research, including wastewater treatment, industrial development, and health and environmental safety. In the present study, a promising sustainable adsorbent was fabricated through continuous controlled adsorption/desorption processes for heavy metal uptake. The fabrication strategy is based on a simple modification of Fe3O4 magnetic nanoparticles with organosilica in a one-pot solvothermal process, carried out in order to insert the organosilica moieties into the Fe3O4 nanocore during their formation. The developed organosilica-modified Fe3O4 hetero-nanocores had hydrophilic citrate moieties, together with hydrophobic organosilica ones, on their surfaces, which facilitated the further surface coating procedures. To prevent the formed nanoparticles from leaching into the acidic medium, a dense silica layer was coated on the fabricated organosilica/Fe3O4 (OS/Fe3O4). In addition, the prepared OS/Fe3O4@SiO2 was utilized for the adsorption of cobalt(II), lead(II), and manganese(II) from the solutions. The data for the adsorption processes of cobalt(II), lead(II), and manganese(II) on OS/(Fe3O4)@SiO2 were found to follow the pseudo-second-order kinetic model, indicating the fast uptake of heavy metals. The Freundlich isotherm was found to be more suitable for describing the uptake of heavy metals by OS/Fe3O4@SiO2 nanoparticles. The negative values of the ΔG° showed a spontaneous adsorption process of a physical nature. The super-regeneration and recycling capacities of the OS/Fe3O4@SiO2 were achieved, comparing the results to those of previous adsorbents, with a recyclable efficiency of 91% up to the seventh cycle, which is promising for environmental sustainability.

Optimization of Pulsed Laser Ablation and Radio-Frequency Sputtering Tandem System for Synthesis of 2D/3D Al2O3-ZnO Nanostructures: A Hybrid Approach to Synthesis of Nanostructures for Gas Sensing Applications.

In this paper, a unique hybrid approach to design and synthesize 2D/3D Al2O3-ZnO nanostructures by simultaneous deposition is presented. Pulsed laser deposition (PLD) and RF magnetron sputtering (RFMS) methods are redeveloped into a single tandem system to create a mixed-species plasma to grow ZnO nanostructures for gas sensing applications. In this set-up, the parameters of PLD have been optimized and explored with RFMS parameters to design 2D/3D Al2O3-ZnO nanostructures, including nanoneedles/nanospikes, nanowalls, and nanorods, among others. The RF power of magnetron system with Al2O3 target is explored from 10 to 50 W, while the ZnO-loaded PLD's laser fluence and background gases are optimized to simultaneously grow ZnO and Al2O3-ZnO nanostructures. The nanostructures are either grown via 2-step template approach, or by direct growth on Si (111) and MgO<0001> substrates. In this approach, a thin ZnO template/film was initially grown on the substrate by PLD at ~300 °C under ~10 milliTorr (1.3 Pa) O2 background pressure, followed by growth of either ZnO or Al2O3-ZnO, using PLD and RFMS simultaneously under 0.1-0.5 Torr (13-67 Pa), and Ar or Ar/O2 background in the substrate temperate range of 550-700 °C. Growth mechanisms are then proposed to explain the formation of Al2O3-ZnO nanostructures. The optimized parameters from PLD-RFMS are then used to grow nanostructures on Au-patterned Al2O3-based gas sensor to test its response to CO gas from 200 to 400 °C, and a good response is observed at ~350 °C. The grown ZnO and Al2O3-ZnO nanostructures are quite exceptional and remarkable and have potential applications in optoelectronics, such in bio/gas sensors.

Thermal Fabrication of Magnetic Fe3O4 (Nanoparticle)@Carbon Sheets from Waste Resources for the Adsorption of Dyes: Kinetic, Equilibrium, and UV-Visible Spectroscopy Investigations.

Thermal treatment is applied for the direct conversion of palm stalk waste to Fe3O4 (np)@carbon sheets (Fe3O4 (np)@CSs). The effect of conversion temperature was investigated. The TEM examination of the prepared magnetic Fe3O4 (np)@CSs showed the formation of Fe3O4 (np) in a matrix of carbon sheets as a coated layer with surface functional groups including carbonyl and hydroxyl groups. Removal of dyes such as methyl orange, methylene blue, and neutral red was achieved using fabricated Fe3O4 (np)@CSs which were prepared at 250 °C, 400 °C, and 700 °C in a weak acidic medium. By studying the contact time effect for the adsorption of methylene blue, neutral red, and methyl orange, using the fabricated Fe3O4 (np)@CSs which were prepared at 250 °C and 400 °C, equilibrium occurred between 120 min and 180 min. In addition, the first-order and second-order kinetic models were applied to the adsorption data. The results revealed that the adsorption data fit better with the second-order kinetic model. Furthermore, the Freundlich model was found to be more suitable for describing the process of the separation of the dyes onto Fe3O4 (np)@CSs which were prepared at 250 °C and 400 °C, suggesting heterogenous surfaces and multi-layer adsorption.

Fabrication of Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 Double Shell Nanoparticles for Methylene Blue Adsorption: Kinetic, Isotherms and Thermodynamic Characterization.

Herein, Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 double shell nanoparticles were prepared by first (R1) and second (R2) routes and applied for the removal of methylene blue. The reported adsorption capacities for R1-0.2, R1-0.4 and R2 samples were 128, 118 and 133 mg.g-1, respectively, which were obtained after 80 min as equilibrium contact time, and pH of 6 using a methylene blue concentration of 200 ppm. The adsorption of methylene blue using the prepared Fe3O4 core-meso SiO2/TiO2 double shell was analyzed by kinetic and isotherms models. In addition, thermodynamic investigations were applied to assess the spontaneous nature of the process. The obtained results confirmed that the pseudo-second order model is well fitted with the adsorption data and the Freundlich-isotherm assumption suggested a multilayer adsorption mechanism. In addition, results of the thermodynamic investigation indicated that ΔG° was in the range of -2.3 to -6.8 kJ/mol for R1-0.2, -2.8 to -6.3 kJ/mol for R1-0.4 and -2.0 to -5.2 kJ/mol for R2. In addition, the ΔH° and ΔS° values were found in the range of 26.4 to 36.19 kJ.mol-1 and 94.9 to 126.3 Jmol-1 K-1, respectively. These results confirm that the surfaces of Fe3O4 core-mesoSiO2/TiO2 and Fe3O4 core-TiO2/mesoSiO2 double shell exhibit a spontaneous tendency to adsorb methylene blue from the aqueous solutions. The achieved performance of Fe3O4 core-meso SiO2/TiO2 and Fe3O4 core-TiO2/meso SiO2 double shell as adsorbent for methylene blue removal will encourage future research investigations on the removal of a broad range of contaminants from wastewater.

Fabrication of mesoporous silica shells on solid silica spheres using anionic surfactants and their potential application in controlling drug release.

In this work, mesoporous shells were constructed on solid silica cores by employing anionic surfactante. A co-structure directing agent (CSDA) has assisted the electrostatic interaction between negatively charged silica particles and the negatively charged surfactant molecules. Synthetic parameters such as reaction time and temperature had a significant impact on the formation of mesoporous silica shelld and their textural properties such as surface area and pore volume. Core-mesoporous shell silica spheres were characterized by small angle X-ray scattering, transmission electron microscopy, and N(2) adsorption–desorption analysis. The synthesized particles have a uniformly mesoporous shell of 34–65 nm and possess a surface area of ca. 7–324 m2/g, and pore volume of ca. 0.008–0.261 cc/g. The core-mesoporous shell silica spheres were loaded with ketoprofen drug molecules. The in vitro drug release study suggested that core-mesoporous shell silica spheres are a suitable nanocarrier for drug molecules offering the possibility of having control over their release rate.