Utilization of Functionalized Metal-Organic Framework Nanoparticle as Targeted Drug Delivery System for Cancer Therapy.

Cancer is a multifaceted disease that results from the complex interaction between genetic and environmental factors. Cancer is a mortal disease with the biggest clinical, societal, and economic burden. Research on better methods of the detection, diagnosis, and treatment of cancer is crucial. Recent advancements in material science have led to the development of metal-organic frameworks, also known as MOFs. MOFs have recently been established as promising and adaptable delivery platforms and target vehicles for cancer therapy. These MOFs have been constructed in a fashion that offers them the capability of drug release that is stimuli-responsive. This feature has the potential to be exploited for cancer therapy that is externally led. This review presents an in-depth summary of the research that has been conducted to date in the field of MOF-based nanoplatforms for cancer therapeutics.

Correction: Highly efficient degradation of reactive black KN-B dye by ultraviolet light responsive ZIF-8 photocatalysts with different morphologies.

[This corrects the article DOI: 10.1039/D2RA08312D.].

Application Prospects of MXenes Materials Modifications for Sensors.

The first two-dimensional (2D) substance sparked a boom in research since this type of material showed potential promise for applications in field sensors. A class of 2D transition metal nitrides, carbides, and carbonitrides are referred to as MXenes. Following the 2011 synthesis of Ti3C2 from Ti3AlC2, much research has been published. Since these materials have several advantages over conventional 2D materials, they have been extensively researched, synthesized, and studied by many research organizations. To give readers a general understanding of these well-liked materials, this review examines the structures of MXenes, discusses various synthesis procedures, and analyzes physicochemistry properties, particularly optical, electronic, structural, and mechanical properties. The focus of this review is the analysis of modern advancements in the development of MXene-based sensors, including electrochemical sensors, gas sensors, biosensors, optical sensors, and wearable sensors. Finally, the opportunities and challenges for further study on the creation of MXenes-based sensors are discussed.

Highly efficient degradation of reactive black KN-B dye by ultraviolet light responsive ZIF-8 photocatalysts with different morphologies.

Zeolitic imidazolate framework ZIF-8, a type of metal-organic framework, has diverse applications in multiple catalytic fields due to its outstanding properties. Herein, ZIF-8 photocatalysts with three different morphologies (dodecahedral, pitaya-like, and leaf-like) are successfully synthesized under ambient conditions from zinc salts by altering the volume ratio of methanol and water used as a solvent. The as-synthesized ZIFs have high crystallinity with distinct BET surface areas. The experiments indicate that the ZIFs have high photocatalytic efficiency, in which the leaf-like structure (ZIF-8-F3) is the most efficient in the degradation of reactive black KN-B dye (RB5) under 365 nm UV irradiation. This is due to the efficient inhibition of electron-hole recombination or the higher migration of charge carriers in ZIF-8-F3, thus producing more reactive oxygen species, resulting in greater photocatalytic efficiency. At pH = 11, more than 95% of RB5 is degraded within 2 hours when using 1.0 g L-1 of ZIF-8-F3. Besides, the photocatalytic and kinetic performances of ZIF-8-F3 are also investigated by optimizing the pH, initial RB5 concentration, and dosage of the used catalyst. These ZIF-8-F3 plates have been shown to be a promising material with high photostability and effective reusability, beneficial to various potential applications in environmental remediation issues.

High-efficient reduction of methylene blue and 4-nitrophenol by silver nanoparticles embedded in magnetic graphene oxide.

In this study, a ternary magnetically separable nanocomposite of silver nanoparticles (AgNPs) embedded in magnetic graphene oxide (Ag/Fe3O4@GO) was designed and synthesized. Beta-cyclodextrin was used as a green reducing and capping agent for decorating of AgNPs on Fe3O4@GO. The fabricated material was characterized using X-ray diffractometry, Fourier transform infrared spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and energy-dispersive X-ray spectroscopy. The catalytic properties of the prepared Ag/Fe3O4@GO for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB) dye with sodium borohydride were investigated in detail. The morphological and structural studies revealed that Fe3O4 and AgNPs with a mean size of 12 nm were uniformly distributed on the GO sheet at high densities. The catalytic tests showed that Ag/Fe3O4@GO exhibited an ultrafast catalytic reduction of 4-NP and MB with a reduction rate constant of 0.304 min-1 and 0.448 min-1, respectively. Moreover, the catalyst demonstrated excellent stability and reusability, as evidenced by the more than 97% removal efficiency maintained after five reuse cycles. The Ag/Fe3O4@GO catalyst could be easily recovered by the magnetic separation due to the superparamagnetic nature of Fe3O4 with high saturated magnetization (45.7 emu/g). Besides, the formation of networking between the formed AgNPs and ß-CD through hydrogen bonding prevented the agglomeration of AgNPs, ensuring their high catalytic ability. The leaching study showed that the dissolution of Fe and Ag from Ag/Fe3O4@GO was negligible, indicating the environmental friendliness of the synthesized catalyst. Finally, the high catalytic performance, excellent stability, and recoverability of Ag/Fe3O4@GO make it a potential candidate for the reduction of organic pollutants in wastewater.

Evaluation of methyl orange adsorption potential of green synthesized chitosan-silver nanocomposite (CS-AgNC) and its notable biocompatibility on freshwater Tilapia (Oreochromis nitoticus).

Nanomaterials mainly nanocomposites possess unique physical and chemical properties which makes them superior and indispensable. Though much research has been focused on the properties and application of nanocomposites, the eco-toxicity assessment is one among top priority, which aims to protect the population of concerned biological component and their ecosystem. With this objective, the present study has undertaken an initiation to evaluate the efficacy of chitosan-silver nanocomposite for methyl orange adsorption property (CS-AgNC) and also assessed the toxicity impact on growth parameters of freshwater Tilapia. Batch in vitro studies showed that all the tested dosages of the nanocomposite were effectively adsorbing maximum concentration of methyl orange. The synthesized nanocomposite was administrated to the tested fishes followed by the determination of various growth, nutritional parameters, gene expression of enzymatic antioxidants and liver, and intestinal tissues histology. Obtained results indicated that nanocomposite treatment was not projected as a toxic impact on all the tested growth, and nutritional parameters. Histology study showed that the exposure of Tilapia to nanocomposite has not shown any detrimental effect on antioxidants gene expression and liver, intestinal tissue architecture. Hence, all these findings indicated that chitosan-silver nanocomposite prepared in our present system was found to be biocompatible which suggested the possible utilization and release of the nanocomposite into the divergent ecosystem without affecting non-target organisms (NTO).

Novel biogenic gold nanoparticles stabilized on poly(styrene-co-maleic anhydride) as an effective material for reduction of nitrophenols and colorimetric detection of Pb(II).

Biogenic gold nanoparticles (AuNPs) have been extensively studied for the catalytic conversion of nitrophenols (NP) into aminophenols and the colorimetric quantification of heavy metal ions in aqueous solutions. However, the high self-agglomeration ability of colloidal nanoparticles is one of the major obstacles hindering their application. In the present study, we offered novel biogenic AuNPs synthesized by a green approach using Cistanche deserticola (CD) extract as a bioreducing agent and stabilized on poly(styrene-co-maleic anhydride) (PSMA). The prepared Au@PSMA nanoparticles were characterized by various techniques (HR-TEM, SEAD, FE-SEM, DLS, TGA, XRD, and FTIR) and studied for two applications: the catalytic reduction of 3-NP by NaBH4 and the sensing detection of Pb2+ ions. The optimal conditions for the synthesis of AuNPs were investigated and established at 60 °C, 20 min, pH of 9, and 0.5 mM Au3+. Morphological studies showed that AuNPs synthesized by CD extract were mostly spherical with a mean diameter of 25 nm, while the size of polymer-integrated AuNPs was more than two-fold larger. Since PSMA acted as a matrix keeping the nanoparticles from coagulation and maintaining the optimal surface area, AuNPs integrated with PSMA showed higher catalytic efficiency with a faster reaction rate and lower activation energy than conventional nanoparticles. Au@PSMA could completely reduce 3-NP within 10 min with a rate constant of 0.127 min-1 and activation energy of 9.96 kJ/mol. The presence of PSMA also improved the stability and recyclability of AuNPs. Used as a sensor, Au@PSMA exhibited excellent sensitivity and selectivity for Pb2+ ions with a limit of detection of 0.03 µM in the linear range of 0-100 µM. The study results suggested that Au@PSMA could be used as a promising catalyst for the reduction of NP and the colorimetric sensor for detection of Pb2+ ions in aqueous environmental samples.

Dual Stimuli-Responsive Multifunctional Silicon Nanocarriers for Specifically Targeting Mitochondria in Human Cancer Cells.

Specific targeting, selective stimuli-responsiveness, and controlled release of anticancer agents are requested for high therapeutic efficiency with a minimal adverse effect. Herein, we report the sophisticated synthesis and functionalization of fluorescent mesoporous silicon (FMPSi) nanoparticles decorated with graphene oxide (GO) nanosheets. GO-wrapped FMPSi (FMPSi@GO) was loaded with a cisplatin (Cis) anticancer agent, and Cis-loaded FMPSi@GO (FMPSi-Cis@GO) exhibited the dual stimuli (pH and NIR)-responsiveness of controlled drug release, i.e., the drug release rate was distinctly enhanced at acidic pH 5.5 than at neutral pH 7.0 and further enhanced under NIR irradiation at acidic pH condition. Notably, dequalinium-conjugated FMPSi-Cis@GO (FMPSi-Cis@GO@DQA) demonstrated an excellent specificity for mitochondrial targeting in cancer cells without noticeable toxicity to normal human cells. Our novel silicon nanocarriers demonstrated not only stimuli (pH and NIR)-responsive controlled drug release, but also selective accumulation in the mitochondria of cancer cells and destroying them.

Flexible and high-sensitivity sensor based on Ti3C2-MoS2 MXene composite for the detection of toxic gases.

It is vital to have high sensitivity in gas sensors to allow the exact detection of dangerous gases in the air and at room temperature. In this study, we used 2D MXenes and MoS2 materials to create a Ti3C2-MoS2 composite with high metallic conductivity and a wholly functionalized surface for a significant signal. At room temperature, the Ti3C2-MoS2 composite demonstrated clear signals, cyclic response curves to NO2 gas, and gas concentration-dependent. The sensitivities of the standard Ti3C2-MoS2 (TM_2) composite (20 wt% MoS2) rose dramatically to 35.8%, 63.4%, and 72.5% when increasing NO2 concentrations to 10 ppm, 50 ppm, and 100 ppm, respectively. In addition, the composite showed reaction signals to additional hazardous gases, such as ammonia and methane. Our findings suggest that highly functionalized metallic sensing channels could be used to construct multigas-detecting sensors that are very sensitive in air and at room temperature.

TiO2/Ti3C2/g-C3N4 ternary heterojunction for photocatalytic hydrogen evolution.

Photocatalytic hydrogen (H2) generation derived by water has been considered as a renewable energy to solve environmental problems and global energy crises. Thus, it is necessary to explore the most effective photocatalysts by using multi-cocatalysts, due to an intimate interaction between different components. Therefore, we already synthesized the TiO2/Ti3C2/g-C3N4 (TTC) photocatalyst from g-C3N4 and Ti3C2 MXene via a calcination technique, and applied this composite for H2 evolution. By making use of titanium atom from Ti3C2 MXene, titanium dioxide (TiO2) was in-body developed, which leads to form a close heterostructure between metallic material and semiconductors. Besides, g-C3N4 amorphous with highly surface area also contributes to harvest light irradiation during photocatalytic activity. The optimized TTC-450 heterostructure showed a super H2 generation efficiency than those of pure g-C3N4 and other samples. Besides, TTC-450 sample also exhibited great recyclability after 4 runs. The proposed mechanism illustrates the efficient movement of generated electrons in TTC system, which leads to high H2 evolution efficiency. Moreover, the obtained results consistently emphasize the TiO2/Ti3C2/g-C3N4 composite would be a unique material for H2 production and broaden applications of MXene materials.

Photocatalytic degradation of methyl orange dye by Ti3C2-TiO2 heterojunction under solar light.

Photocatalytic activity is a feasible solution to tackle environmental pollution caused by industrial pollutants. In this research, Ti3C2-TiO2 composite with a unique structure was fabricated successfully via a hydrothermal method. Especially, the in-situ transformation of TiO2 from Ti3C2 MXene creates an intimate heterostructure, which leads to prolonging separation and migration of charged carriers. Thus, this Ti3C2-TiO2 composite enhances effectively methyl orange (MO) degradation efficiency (around 99%) after 40 light-exposed minutes. Besides, the optimal concentration of MO solution was estimated at 40 mg/L and Ti3C2-TiO2 photocatalyst also exhibited good stability after five runs. Moreover, the radical trapping test and the MO photodegradation mechanism over Ti3C2-TiO2 system were also demonstrated. This research illustrates the potential of MXenes as effective co-catalysts for photocatalysis and extends the applications of two-dimensional materials.

Fabrication of Fe3O4/CuO@C composite from MOF-based materials as an efficient and magnetically separable photocatalyst for degradation of ciprofloxacin antibiotic.

In this work, a novel ternary Fe3O4/CuO@C composite was fabricated using iron-doped copper 1,4-benzenedicarboxylate metal-organic frameworks as a self-sacrificing template. The morphological, structural, and optical properties of the prepared composite were determined by various techniques, and its photocatalytic behavior was investigated for degradation of ciprofloxacin under visible light irradiation. The Fe3O4/CuO@C material presented a porous structure with a rough surface of about 4-20 µm, and was composed of the Fe3O4/CuO nanocomposite uniformly distributed on a carbon support. The band gap energy of the obtained composite was found to be 2.0 eV, which was nearly two times lower than that of Fe3O4@C and CuO@C. As a result, Fe3O4/CuO@C exhibited high photocatalytic activity, achieving a degradation efficiency of 98.5% after 120 min irradiation at the optimum conditions (a catalyst dosage of 0.5 g L-1, pH of 7, CIP concentration of 15 mg L-1). The mechanism of ciprofloxacin degradation by Fe3O4/CuO@C was elucidated with the main contribution of O2-and OH reactive radicals. The new composite catalyst could easily be recovered from the treated solution using an external magnetic field due to its superparamagnetic nature. Fe3O4/CuO@C also showed good reusability and stability. The overall results indicated that the synthesized composite has significant application potential for controlling the risk of antibiotics in wastewater.

Natural core-shell structure activated carbon beads derived from Litsea glutinosa seeds for removal of methylene blue: Facile preparation, characterization, and adsorption properties.

In this study, natural core-shell structure activated carbon beads (ACBs) from Litsea glutinosa seeds were successfully produced, characterized, and applied for adsorption of methylene blue (MB). The ACBs were prepared using single-step carbonization-activation with NaHCO3 at the optimized activation temperature, time, and activating agent concentration of 450 °C, 60 min, and 5%, respectively. Batch experiments were performed to determine the optimum adsorption conditions, suitable kinetic and isotherm models, and thermodynamic parameters for the adsorption of MB onto ACBs. The results showed that the ACBs were displayed as highly porous natural core-shell spheres with a diameter of about 5 mm. The adsorption of MB dye on ACBs was a spontaneous endothermic process, followed the Langmuir isotherm and the pseudo-second-order kinetic models with the rate-controlling step of both external diffusion and intra-particle diffusion. At the optimum conditions (pH of 9, the contact time of 10 h, the temperature of 40 °C, and an adsorbent dosage of 6 g/L), the maximum adsorption capacity reached 29.03 mg/g. The thermal method turned out to be more suitable for regenerating ACBs compared to the chemical method. The ACBs exhibited high reusability and stability, its adsorption efficiency could maintain more than 90% after five consecutive cycles of use. The electrostatic attraction, π-π interaction, hydrogen bonding, and pore-filling were identified as primary contributions to the adsorption mechanism. The overall results revealed that the ACBs could be used as a potential adsorbent for removing MB from water media.

pH-triggered degradation and release of doxorubicin from zeolitic imidazolate framework-8 (ZIF8) decorated with polyacrylic acid.

Zeolite imidazolate framework-8 (ZIF8) represents a class of highly porous materials with a very high surface area, large pore volume, thermal stability, and biocompatibility. In this study, ZIF8-based nanostructures demonstrated a high loading capacity for doxorubicin (62 mg Dox per g ZIF8) through the combination of π-π stacking, hydrogen bonding, and electrostatic interactions. Dox-loaded ZIF8 was subsequently decorated with polyacrylic acid (PAA) (ZIF8-Dox@PAA) that showed good dispersity, fluorescent imaging capability, and pH-responsive drug release. The stable localization and association of Dox in ZIF8@PAA were investigated by C13 nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. The NMR chemical shifts suggest the formation of hydrogen bonding interactions and π-π stacking interactions between the imidazole ring of ZIF8 and the benzene ring of Dox that can significantly improve the storage of Dox in the ZIF8 nanostructure. Additionally, the release mechanism of ZIF8-Dox@PAA was discussed based on the detachment of the PAA layer, enhanced solubility of Dox, and destruction of ZIF8 at different pH conditions. In vitro release test of ZIF8-Dox@PAA at pH 7.4 showed the low release rate of 24.7% even after 100 h. However, ZIF8-Dox@PAA at pH 4.0 exhibited four stages of release profiles, significantly enhanced release rate of 84.7% at the final release stage after 30 h. The release kinetics of ZIF8-Dox@PAA was analyzed by the sigmoidal Hill, exponential Weibull, and two-stage BiDoseResp models. The ZIF8-Dox@PAA nanocarrier demonstrated a promising theranostic nanoplatform equipped with fluorescent bioimaging, pH-responsive controlled drug release, and high drug loading capacity.

Multimodal Mesoporous Silica Nanocarriers for Dual Stimuli-Responsive Drug Release and Excellent Photothermal Ablation of Cancer Cells.

BACKGROUND: Core-shell types of mesoporous silica nanoparticles (MSNs) with multimodal functionalities were developed for bio-imaging, controlled drug release associated with external pH, and near-infrared radiation (NIR) stimuli, and targeted and effective chemo-photothermal therapeutics. MATERIALS AND METHODS: We synthesized and developed a core-shell type of mesoporous silica nanocarriers for fluorescent imaging, stimuli-responsive drug release, magnetic separation, antibody targeting, and chemo-photothermal therapeutics. Also, the biocompatibility, cellular uptake, cytotoxicity, and photothermal therapy on these FS3-based nanocarriers were systematically investigated. RESULTS: Magnetic mesoporous silica nanoparticles was prepared by coating a Fe3O4 core with a mesoporous silica shell, followed by grafting with fluorescent conjugates, so-called FS3. The resulting FM3 was preloaded with therapeutic cisplatin and coated with polydopamine layer, so-called FS3P/C. Eventually, graphene oxide-wrapped FS3P/C (FS3P-G/C) exhibited high sensitivity in the dual stimuli (pH, NIR)-responsive controlled release behavior. On the other hand, Au NPs-coated FS3P/C (FS3P-A/C) exhibited more stable release behavior, irrespective of pH changes, and exhibited much more enhanced release rate under the same NIR irradiation. Notably, FS3P-A/C showed strong NIR absorption, enabling photothermal destruction of HeLa cells by its chemo-photothermal therapeutic effects under NIR irradiation (808 nm, 1.5 W/cm2). The selective uptake of FS3-based nanocarriers was confirmed in cancer cell lines including HeLa (American Type Culture Collection - ATCC) and SHSY5Y (ATCC 2266) by the images obtained from confocal laser scanning microscopy, flow cytometry, and transmission electron microscopy instruments. Cisplatin-free FS3-based nanocarriers revealed good cellular uptake and low cytotoxicity against cancerous HeLa and SH-SY5Y cells, but showed no obvious toxicity to normal HEK293 (ATCC 1573) cell. CONCLUSION: Along with the facile synthesis of FS3-based nanocarriers, the integration of all these strategies into one single unit will be a prospective candidate for biomedical applications, especially in chemo-photothermal therapeutics, targeted delivery, and stimuli-responsive controlled drug release against multiple cancer cell types.

A prominent anchoring effect on the kinetic control of drug release from mesoporous silica nanoparticles (MSNs).

This work demonstrated kinetically controlled release of model drugs (ibuprofen, FITC) from well-tailored mesoporous silica nanoparticles (MSNs) depending on the surface charges and molecular sizes of the drugs. The molecular interactions between entrapped drugs and the pore walls of MSNs controlled the release of the drugs through the pore channels of MSNs. Also, polydopamine (PDA) layer-coated MSNs (MSNs@PDA) was quite effective to retard the release of large FITC, in contrast to a slight retardation effect on relatively small Ibuprofen. Of all things, FITC (Fluorescein isothiocyanate)-labeled APTMS (3-aminopropyltrimethoxysilane) (APTMS-FITC conjugates) grafted onto the MSNs generate a pinch-effect on the pore channel (so-called a prominent anchoring effect), which was highly effective in trapping (or blocking) drug molecules at the pore mouth of the MSNs. The anchored APTMS-FITC conjugates provided not only tortuous pathways to the diffusing molecules, but also sustained release of the ibuprofen over a long period of time (∼7days). The fast release kinetics was predicted by an exponential equation based on Fick's law, while the slow release kinetics was predicted by Higuchi model.