Nanocarrier of α-Tocopheryl Succinate Based on a Copolymer Derivative of (4,7-dichloroquinolin-2-yl)methanol and Its Cytotoxicity against a Breast Cancer Cell Line.

In order to improve the water solubility and, therefore, bioavailability and therapeutic activity of anticancer hydrophobic drug α-tocopherol succinate (α-TOS), in this work, copolymers were synthesized via free radicals from QMES (1-[4,7-dichloroquinolin-2-ylmethyl]-4-methacryloyloxyethyl succinate) and VP (N-vinyl-2-pirrolidone) using different molar ratios, and were used to nanoencapsulate and deliver α-TOS into cancer cells MCF-7. QMES monomer was chosen because the QMES pendant group in the polymer tends to hydrolyze to form free 4,7-dichloro-2-quinolinemethanol (QOH), which also, like α-TOS, exhibit anti-proliferative effects on cancerous cells. From the QMES-VP 30:70 (QMES-30) and 40:60 (QMES-40) copolymers obtained, it was possible to prepare aqueous suspensions of empty nanoparticles (NPs) loaded with α-TOS by nanoprecipitation. The diameter and encapsulation efficiency (%EE) of the QMES-30 NPs loaded with α-TOS were 128.6 nm and 52%; while for the QMES-40 NPs loaded with α-TOS, they were 148.8 nm and 65%. The results of the AlamarBlue assay at 72 h of treatment show that empty QMES-30 NPs (without α-TOS) produced a marked cytotoxic effect on MCF-7 breast cancer cells, corresponding to an IC50 value of 0.043 mg mL-1, and importantly, they did not exhibit cytotoxicity against healthy HUVEC cells. Furthermore, NP-QMES-40 loaded with α-TOS were cytotoxic with an IC50 value of 0.076 mg mL-1, demonstrating a progressive release of α-TOS; however, the latter nanoparticles were also cytotoxic to healthy cells in the range of the assayed concentrations. These results contribute to the search for a new polymeric nanocarrier of QOH, α-TOS or other hydrophobic drugs for the treatment of cancer or others diseases treatable with these drugs.

MXene-Based Nanocomposites for Piezoelectric and Triboelectric Energy Harvesting Applications.

Due to its superior advantages in terms of electronegativity, metallic conductivity, mechanical flexibility, customizable surface chemistry, etc., 2D MXenes for nanogenerators have demonstrated significant progress. In order to push scientific design strategies for the practical application of nanogenerators from the viewpoints of the basic aspect and recent advancements, this systematic review covers the most recent developments of MXenes for nanogenerators in its first section. In the second section, the importance of renewable energy and an introduction to nanogenerators, major classifications, and their working principles are discussed. At the end of this section, various materials used for energy harvesting and frequent combos of MXene with other active materials are described in detail together with the essential framework of nanogenerators. In the third, fourth, and fifth sections, the materials used for nanogenerators, MXene synthesis along with its properties, and MXene nanocomposites with polymeric materials are discussed in detail with the recent progress and challenges for their use in nanogenerator applications. In the sixth section, a thorough discussion of the design strategies and internal improvement mechanisms of MXenes and the composite materials for nanogenerators with 3D printing technologies are presented. Finally, we summarize the key points discussed throughout this review and discuss some thoughts on potential approaches for nanocomposite materials based on MXenes that could be used in nanogenerators for better performance.

Gold nanoparticle-decorated earth-abundant clay nanotubes as catalyst for the degradation of phenothiazine dyes and reduction of 4-(4-nitrophenyl)morpholine.

In the present work, halloysite nanotubes modified with gold nanoparticles (AuNPs-HNT) are successfully prepared by wet chemical method for the catalytic degradation of phenothiazine dyes (azure B (AZB) and toluidine blue O (TBO)) and also cleaner reduction of 4-(4-nitrophenyl)morpholine (4NM) in the sodium borohydride (NaBH4) media. The catalyst is formulated by modifying the HNT support with a 0.964% metal loading using the HNT supports modified with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent to facilitate the anchoring sites to trap the AuNPs and to prevent their agglomeration/aggregation. The AuNPs-HNT catalyst is investigated for structural and morphological characterization to get insights about the formation of the catalyst for the effective catalytic reduction of dyes and 4NM. The microscopic studies demonstrate that AuNPs (2.75 nm) are decorated on the outer surface of HNT. The as-prepared AuNPs-HNT catalyst demonstrates AZB and TBO dye degradation efficiency up to 96% in 10 and 11 min, respectively, and catalytic reduction of 4NM to 4-morpholinoaniline (MAN) is achieved up to 97% in 11 min, in the presence of NaBH4 without the formation of any by-products. The pseudo-first-order rate constant (K1) value of the AuNPs-HNT catalyst for AZB, TBO, and 4NM were calculated to be 0.0078, 0.0055, and 0.0066 s-1, respectively. Moreover, the synthesized catalyst shows an excellent reusability with stable catalytic reduction for 7 successive cycles for both the dyes and 4NM. A plausible mechanism for the catalytic dye degradation and reduction of 4NM by AuNPs-HNT catalyst is proposed as well. The obtained results clearly indicate the potential of AuNPs-HNT as an efficient catalyst for the removal of dye contaminants from the aquatic environments and cleaner reduction of 4NM to MAN, insinuating future pharmaceutical applications.

Design and synthesis of heterocyclic azole based bioactive compounds: Molecular structures, quantum simulation, and mechanistic studies through docking as multi-target inhibitors of SARS-CoV-2 and cytotoxicity.

Two heterocyclic azole compounds, 3-(2,3-dihydrobenzo[d]thiazol-2-yl)-4H-chromen-4-one (SVS1) and 5-(1H-indol-3-yl)-4-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (SVS2) were obtained unexpectedly from 2-aminothiophenol and 4-oxo-4H-chromene-3-carbaldehyde (for SVS1), and (E)-2-((1H-indol-3-yl)methylene)-N-methylhydrazine-1-carbothioamide in the presence of anhydrous FeCl3 (for SVS2), respectively. The compounds were well characterized by analytical and spectroscopic tools. The molecular structures of both the compounds were determined by single crystal X-ray diffraction (XRD) study. The results obtained from density functional theory (DFT) study revealed the molecular geometry and electron distribution of the compounds, which were correlated well with the three-dimensional structures obtained from the single crystal XRD. DMol3 was used to calculate quantum chemical parameters [chemical potential (µ), global hardness (η), global softness (σ), absolute electronegativity (χ) and electrophilicity index (ω)] of SVS1 and SVS2. Molecular docking study was performed to elucidate the binding ability of SVS1 and SVS2 with SARS-CoV-2 main protease and human angiotensin-converting enzyme-2 (ACE-2) molecular targets. Interestingly, the binding efficiency of the compounds with the molecular targets was comparable with that of remdesivir (SARS-CoV-2), chloroquine and hydroxychloroquine. SVS1 showed better docking energy than SVS2. The molecular docking study was complemented by molecular dynamics simulation study of SARS-CoV-2 main protease-SVS1 complex, which further exemplified the binding ability of SVS1 with the target. In addition, SVS1, SVS2 and cisplatin were assessed for their cytotoxicity against a panel of three human cancer cells such as HepG-2 (hepatic carcinoma), T24 (bladder) and EA.hy926 (endothelial), as well as Vero (kidney epithelial cells extracted from an African green monkey) normal cells using MTT assay. The results showed that SVS2 has significant cytotoxicity against HepG-2 and EA.hy926 cells with the IC50 values of 33.8 µM (IC50 = 49.9 µM-cisplatin and 8.6 µM-doxorubicin) and 29.2 (IC50 = 26.6 µM-cisplatin and 3.8 µM-doxorubicin), respectively.

Fast Solution Synthesis of NiO-Gd0.1Ce0.9O1.95 Nanocomposite via Different Approach: Influence of Processing Parameters and Characterizations.

The synthesis of the nickel oxide-gadolinium doped ceria (NiO-GDC with 65:35 wt. %) nanocomposite powders with a stoichiometry of Gd0.1Ce0.9O1.95 was performed via fast solution combustion technique; using three different mixing methods: (i) CM (metal cations in an aqueous solution), (ii) HM (hand mortar), and (iii) BM (ball milling). The nanocomposite powders were calcined at 700 °C for 2 h and characterized by Transmission Electron Microscopy (TEM), X-ray fluorescence (XRF), and X-ray Diffraction XRD. The TEM and XRD analyses evidenced the well-dispersed NiO and GDC crystallites with the absence of secondary phases, respectively. Later, the calcined powders (NiO-GDC nanocomposites) were compacted and sintered at 1500 °C for 2 h. The microhardness of the sintered nanocomposites varies in accordance with the synthesis approach: a higher microhardness of 6.04 GPa was obtained for nanocomposites synthesized through CM, while 5.94 and 5.41 GPa were obtained for ball-milling and hand-mortar approach, respectively. Furthermore, it was observed that regardless of the long time-consuming ball-milling process with respect to the hand mortar, there was no significant improvement in the electrical properties.

Synthesis and Characterization of a Nearly Single Bulk Ti2AlN MAX Phase Obtained from Ti/AlN Powder Mixture through Spark Plasma Sintering.

MAX phases are an advanced class of ceramics based on ternary carbides or nitrides that combine some of the ceramic and metallic properties, which make them potential candidate materials for many engineering applications under severe conditions. The present work reports the successful synthesis of nearly single bulk Ti2AlN MAX phase (>98% purity) through solid-state reaction and from a Ti and AlN powder mixture in a molar ratio of 2:1 as starting materials. The mixture of Ti and AlN powders was subjected to reactive spark plasma sintering (SPS) under 30 MPa at 1200 °C and 1300 °C for 10 min in a vacuum atmosphere. It was found that the massive formation of Al2O3 particles at the grain boundaries during sintering inhibits the development of the Ti2AlN MAX phase in the outer zone of the samples. The effect of sintering temperature on the microstructure and mechanical properties of the Ti2AlN MAX phase was investigated and discussed.

Effect of the Processing Parameters on the Porosity and Mechanical Behavior of Titanium Samples with Bimodal Microstructure Produced via Hot Pressing.

Commercially pure (c.p.) titanium grade IV with a bimodal microstructure is a promising material for biomedical implants. The influence of the processing parameters on the physical, microstructural, and mechanical properties was investigated. The bimodal microstructure was achieved from the blends of powder particles with different sizes, while the porous structure was obtained using the space-holder technique (50 vol.% of ammonium bicarbonate). Mechanically milled powders (10 and 20 h) were mixed in 50 wt.% or 75 wt.% with c.p. titanium. Four different mixtures of powders were precompacted via uniaxial cold pressing at 400 MPa. Then, the specimens were sintered at 750 °C via hot pressing in an argon gas atmosphere. The presence of a bimodal microstructure, comprised of small-grain regions separated by coarse-grain ones, was confirmed by optical and scanning electron microscopies. The samples with a bimodal microstructure exhibited an increase in the porosity compared with the commercially available pure Ti. In addition, the hardness was increased while the Young's modulus was decreased in the specimens with 75 wt.% of the milled powders (20 h).

Colorimetric determination of cysteamine based on the aggregation of polyvinylpyrrolidone-stabilized silver nanoparticles.

A simple, colorimetric and visual method is described for the determination of cysteamine (CA) using polyvinylpyrrolidone-stabilized silver nanoparticles (PVP-AgNPs) as a colorimetric probe. The sensing method was based on the aggregation of PVP-AgNPs that led to the changes in the color and absorption profile of the probe. The aggregation of PVP-AgNPs in the presence of CA was evidenced by using transmission electron microscopy (TEM), zeta and dynamic light scattering (DLS) measurements. A distinct color transition could be observed with the naked eye from pale yellow color of PVP-AgNPs to purple. PVP-AgNPs probe showed an excellent selectivity towards CA versus other interfering biomolecules, cations and anions. Furthermore, the colorimetric probe had a linear response for CA from 0.1 to 1.0 µM concentration range with the limit of detection (LOD) of 4.9 nM. The prepared probe was successfully utilized for the determination of CA in blood serum as biological samples.

Simultaneous electrochemical determination of dopamine and epinephrine using gold nanocrystals capped with graphene quantum dots in a silica network.

Gold nanocrystals (AuNCs) were synthesized by economical and green strategy in aqueous medium by using N[3(trimethoxysilyl)propyl]ethylenediamine (TMSPED) as both a reducing and stabilizing mediator to avoid the aggregation of gold nanocrystals. Then, the AuNCs were capped with graphene quantum dots (GQDs) using an ultrasonic method. The resulting nanocomposites of GQD-TMSPED-AuNCs were characterized by X-ray photoelectron, X-ray diffraction, Raman, UV-vis and FT-IR spectroscopies. The size and shape of the nanocomposites were confirmed by using transmission electron microscopy and atomic force microscopy. The GQD-TMSPED-AuNCs placed on a glassy carbon electrode enable simultaneous determination of dopamine (DA) and epinephrine (EP) with peak potentials at 0.21 and 0.30 V (vs. Ag/AgCl). The response is linear in the 5 nM - 2.1 µM (DA) and 10 nM - 4.0 µM (EP) concentration ranges, with detection limits of 5 and 10 nM, respectively. The sensor shows good selectivity toward DP and EP in the presence of other molecules, facilitating its rapid detection in practical applications. Graphical abstract Schematic representation of gold nanocrystals capped with graphene quantum dots in the modified electrodes for simultaneous detection of dopamine and epinephrine.

Simple sonochemical synthesis of lanthanum tungstate (La2(WO4)3) nanoparticles as an enhanced electrocatalyst for the selective electrochemical determination of anti-scald-inhibitor diphenylamine.

In this work, lanthanum tungstate (La2(WO4)3) nanoparticles (NPs) were synthesized by facile sonochemical method (elmasonic P, under-sonication 37/100 kHz, ~60 W energy) and utilized as an electrode material for the selective and sensitive electrochemical determination of anti-scald inhibitor diphenylamine (DPA). The synthesized La2(WO4)3 NPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDAX), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses. The results revealed that the sonochemically synthesized La2(WO4)3 nanoparticles were with high crystallinity and uniformly distributed nanoparticles like structure. The as-prepared lanthanum tungstate NPs exhibited an excellent electrocatalytic behavior for DPA determination with the lowest detection limit of 0.0024 µM, wide linear range response of 0.01-58.06 µM and a remarkable sensitivity of 1.021 µA µM-1 cm-2. Furthermore, La2(WO4)3 NPs showed a good recovery to DPA in apple juice sample. Besides, the electrochemical mechanism of the DPA oxidation reaction was provided in detail.

A multispectroscopic and molecular docking investigation of the binding interaction between serum albumins and acid orange dye.

The interaction of Acid Orange 10 (AO10) with bovine serum albumin (BSA) was investigated comparatively with that of human serum albumin (HSA) using multispectroscopic techniques for understanding their toxic mechanism. Further, density functional theory calculations and docking studies have been carried out to gain more insights into the nature of interactions existing between AO10 and serum albumins. The fluorescence results suggest that AO10 quenched the fluorescence of BSA through the combination of static and dynamic quenching mechanism. The same trend was followed in the interaction of AO10 with HSA. In addition to the type of quenching mechanism, the fluorescence spectroscopic results suggest that the binding occurs near the tryptophan moiety of serum albumins and the binding. AO10 has more binding affinity towards BSA than HSA. An AO10-Trp model has been created to explicitly understand the CHπ interactions from Bader's quantum theory of atoms in molecules analysis which confirmed that AO10 bind more strongly with BSA than that of HSA due to the formation of three hydrogen bonds with BSA whereas it forms two hydrogen bonds in the case of HSA. These obtained results provide an in-depth understanding of the interaction of the acid azo dye AO10 with serum albumins. This interaction study provides insights into the underlying reasons for toxicity of AO10 relevant to understand its effect on bovids and humans during the blood transportation process.

Influence of imide-substituents on the H-type aggregates of perylene diimides bearing cetyloxy side-chains at bay positions.

A series of perylene-3,4:9,10-tetracarboxylic acid diimides (PDIs, namely TYR-PDI, AEP-PDI, CET-PDI, ANP-PDI and KOD-PDI), comprising long linear cetyloxy side-chains functionalized at the 1,7-bay positions and the different substituents (i.e., hydrophobic/hydrophilic segments) symmetrically linked at the two imide-positions of the perylene core were synthesized to investigate the influence of imide-substituent patterns on the aggregation behaviours of PDIs. The photophysical properties of these PDIs were studied by UV-Vis absorption, fluorescence and time-resolved photoluminescence spectroscopy. The differences in the photophysical properties of the PDIs indicate (i) blue-shifted and broadening absorption properties in both solution and thin-films, (ii) red-shifted and broadening fluorescence behavior at their emission maximum in solution, however, blue-shifted fluorescence behavior in thin-films, and (iii) obviously longer fluorescence life-times corresponding to the existence of rotationally displaced H-type aggregates. The formation of short-range ordered rod-like microstructures through face-to-face alignment of columnar rectangular H-type PDI aggregates was rationalized by scanning electron microscopy. The X-ray diffraction study revealed that the formation of well-defined columnar rectangular (Colrp) H-type PDI aggregates indicated a nearly constant intracolumnar stacking distance of ∼3.9 Å for all PDIs. All of these findings were consistent with the formation of hydrophobic/hydrophilic interactions between the imide-substituents in addition to the strong hydrophobic π-π stacking interactions between the conjugated perylene cores, which were enforced in the H-type PDI aggregates that spontaneously self-organized into Colrp structures.

Gold Triangular Nanoprisms and Nanodecahedra: Synthesis and Interaction Studies with Luminol toward Biosensor Applications.

Gold triangular nanoprisms and nanodecahedra (pentagonal bipyramids) were synthesized in the absence and presence of nanoseeds by a simple solvothermal synthesis through the reduction of Auric Chloride (HAuCl4) with poly(vinylpyrrolidone) (PVP) in N,N-dimethylformamide (DMF), respectively. These gold nanoparticles exhibit two plasmon resonance bands. The interaction of these gold nanoparticles with luminol was investigated using UV-vis and fluorescence spectroscopy since hefty number of environmental and biological sensors are based on the combination of luminol and gold nanoparticles. The gold nanoparticles quenches the fluorescence of luminol through a static quenching mechanism, i.e., ground state complex formation, which was confirmed by both absorption spectroscopy as well as time-resolved fluorescence spectroscopy. The Stern-Volmer quenching constant and the effective quenching constant determine that gold nanodecahedra has more interaction with luminol than that of triangular gold nanoprisms. The distance between the gold nanoparticles and luminol, calculated using FRET theory, is less than 8 nm, which indicates efficient energy transfer during interaction. These results are expected to be useful for the development of novel sensors.

Chemiluminescence studies between aqueous phase synthesized mercaptosuccinic acid capped cadmium telluride quantum dots and luminol-H2O2.

Mercaptosuccinic acid capped Cadmium telluride quantum dots have been successfully synthesized via aqueous phase method. The products were well characterized by a number of analytical techniques, including FT-IR, XRD, HRTEM, and a corrected particle size analysis by the statistical treatment of several AFM measurements. Chemiluminescence experiments were performed to explore the resonance energy transfer between chemiluminescence donor (luminol-H2O2 system) and acceptor CdTe QDs. The combination of such donor and acceptor dramatically reduce the fluorescence while compared to pristine CdTe QDs without any exciting light source, which is due to the occurrence of chemiluminescence resonance energy transfer (CRET) processes.

Sonophotocatalytic mineralization of Norflurazon in aqueous environment.

Norflurazon (4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)phenyl]pyridazin-3(2H)-one; C12H9ClF3N3O) is an excellent weed controlling agent being practiced in the agricultural lands. The excessive addition or the undissolved Norflurazon (maximum solubility 28 mg/L at 25 °C) enters into the aquatic environment and causes the adverse effects associated with its high concentration. To avoid the perilous effects, visible light assisted photocatalysis set-up coupled with the 42 kHz ultrasound producing bath type sonicator is used to completely mineralize the Norflurazon. TiO2, ZnO and gold loaded zinc oxide nanocatalysts were utilized to study the mineralization of Norflurazon. Au-ZnO shows the greater efficiency for the sonophotocatalytic removal of Norflurazon among the various nanocatalysts employed to study the mineralization. The order of Norflurazon mineralization was sonophotocatalysis > sonocatalysis > photocatalysis. The additive effect was achieved for the sonophotocatalytic degradation. The high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometric (LCMS) analyses were employed to identify the various intermediates produced during the mineralization. The identification of four pseudo molecular ions and various intermediates using the LCMS analysis evidently suggests the sonophotocatalytic degradation was preceded in various decay pathways. A suitable mechanism has been proposed for the sonophotocatalytic mineralization of Norflurazon.

Sonochemical synthesis of Cu2O nanocubes for enhanced chemiluminescence applications.

A facile one-step sonochemical synthesis of Cu2O nanocubes has been developed by ultrasound irradiation of copper sulfate in the presence of polyvinylpyrrolidone and ascorbic acid at pH 11. During sonication, the reaction between acoustic cavitation-generated radicals and CuSO4 produced Cu(OH)2 intermediate which then reacted with ascorbic acid to generate Cu2O nanocubes. The products were characterized by FT-IR, XRD, HRTEM, AFM and particle size analyzer. The prepared Cu2O nanocubes were found to be very effective for enhancing chemiluminescence in the presence of luminol-H2O2 system.

Low frequency ultrasound (42 kHz) assisted degradation of Acid Blue 113 in the presence of visible light driven rare earth nanoclusters loaded TiO2 nanophotocatalysts.

An attempt has been made to render the visible light driven photocatalytic activity to the TiO2 nanocatalysts by loading 1 wt% of rare earth (RE) nanoclusters (Gd(3+), Nd(3+) and Y(3+)) using a low frequency (42 kHz) producing commercial sonicator. The STEM-HAADF analysis confirms that the RE nanoclusters were residing at the surface of the TiO2. Transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses confirm that the loading of RE nanoclusters cannot make any significant changes in the crystal structure of TiO2. However, the optical properties of the resulted nanocatalysts were significantly modified and the nanocatalysts were employed to study the sonocatalytic, photocatalytic and sonophotocatalytic decolorization as well as mineralization of Acid Blue 113 (AB113). Among the experimented nanocatalysts maximum degradation of AB113 was achieved in the presence Y(3+)-TiO2 nanocatalysts. The decolorization of AB113 in the presence and absence of Y(3+) loaded TiO2 ensues the following order sonolysis

ZnO supported CoFe2O4 nanophotocatalysts for the mineralization of Direct Blue 71 in aqueous environments.

In this study, an attempt was made to render both the magnetic and photocatalytic properties in a semiconductor material to enhance the efficiency of degradation and recycling possibility of magnetic nanophotocatalysts. CoFe2O4 and CoFe2O4 loaded ZnO nanoparticles were prepared by a simple co-precipitation method and characterized using various analytical tools and in addition to check its visible light assisted photocatalytic activity. CoFe2O4/ZnO nanocatalyst coupled with acceptor, peroxomonosulphate (PMS) showed 1.69-fold enhancement in Direct Blue 71 (triazo dye; DB71) mineralization within 5h. The accomplished enrichment in decolorization was due to the production of more number of non-selective and active free radicals at the catalyst surface.