Acquired Superoxide‐Scavenging Ability of Ceria Nanoparticles

Ceria nanoparticles (nanoceria) are well known as a superoxide scavenger. However, inherent superoxide‐scavenging ability has only been found in the nanoceria with sizes of less than 5 nm and with very limited shape diversity. Reported herein is a strategy to significantly improve the superoxide‐scavenging activity of nanoceria sized at greater than 5 nm. The nanoceria with sizes of greater than 5 nm, with different shapes, and with a negligible Ce³⁺/Ce⁴⁺ ratio can acquire remarkable superoxide‐scavenging abilities through electron transfer. This method will make it possible to develop nanoceria‐based superoxide‐scavengers with long‐acting activity and tailorable characteristics.     

Phototunable Liquid‐Crystalline Phases Made of Nanoparticles

The properties of liquid‐crystalline (LC) hybrid systems made of inorganic nanoparticles grafted with photosensitive azo compounds are presented. For materials with a large density of azo ligands at the surface, the LC structure can be reversibly melted by UV light, and the return to the LC state does not require the absorption of visible light. For systems with a lower density of azo ligands, UV light causes shortening of the distance between metal sublayers in the lamellar phase. Interestingly, the azo derivatives attached to the nanoparticle surface show very different kinetics of cis/trans conformational change as compared to the free molecules. The cis form of free ligands in solution is stable for days, whereas the isomerization of molecules attached to the nanoparticle surface to the trans form takes only a few minutes. Apparently, owing to the crowded environment, azo ligands immobilized at a metal surface behave as they would in the condensed state.     

Oxidation‐State Analysis of Ceria by X‐ray Photoelectron Spectroscopy

Three different methods to determine the oxide‐phase concentration in mixed cerium oxide by hard X‐ray photoelectron spectroscopy are applied and quantitatively compared. Synchrotron‐based characterization of the O 1s region was used as a benchmark to introduce a method based on the weighted superposition of the Ce 3d spectra of the pure Ce³⁺ and Ce⁴⁺ phases, which was shown to lead to reliable and highly accurate determination of the mean oxidation state in mixed cerium oxides. The results obtained reveal a linear relation between the third distinct final state (u′′′) satellite peak intensity of the Ce⁴⁺ phase and the Ce⁴⁺ concentration by proper inclusion of Ce³⁺‐related plasmon satellite peaks, which contradicts previous claims of nonlinear behavior. In contrast, quantitative conventional peak‐fitting procedures were shown to be well suited for the Ce 2p region due to its relatively simple structure. Additional satellite features observed in the Ce 3d spectrum of CeO₂ were proposed to originate from plasmon contributions.     

Rationally Designed CeNP@MnMoS4 Core‐Shell Nanoparticles for Modulating Multiple Facets of Alzheimer's Disease

Alzheimer's disease (AD) is a complicated multifactorial syndrome. Lessons have been learned through failed clinical trials that targeting multiple key pathways of the AD pathogenesis is necessary to halt the disease progression. Here, we construct core‐shell nanoparticles (CeNP@MnMoS₄) targeting multiple key pathways of the AD pathogenesis, including elimination of toxic metal ions, decrease of oxidative stress, and promotion of neurite outgrowth. The SOD activity and copper removal capacity of CeNP@MnMoS₄‐n (n represents the number of layers of MnMoS₄, n=1–5) was investigated in vitro. We found that CeNP@MnMoS₄‐3 made an excellent balance between SOD activity and copper removal capacity. The effect of CeNP@MnMoS₄‐3 on Cu²⁺‐induced Aβ aggregation was studied by gel electrophoresis, transmission electron microscope (TEM), and atomic force microscopy (AFM). Compared with MnMoS₄ or CeNP alone, a synergistic effect was observed. Moreover, CeNP@MnMoS₄‐3 promoted neurite outgrowth in a dose‐dependent manner. Taken together, the results reported in this work show the potential of new multifunctional core‐shell nanoparticles as AD therapeutics.     

The Change in Antioxidant Properties of Dextran‐Coated Redox Active Nanoparticles Due to Synergetic Photoreduction–Oxidation

Nanoparticles have proven to be novel material with resourceful applications in the field of nanomedicine. Cerium oxide nanoparticles (CNPs) coated with dextran (Dex–CNPs) have been shown to exhibit anticancer properties which is attributed to the change in oxidation states mediated at the oxygen vacancies on the surface of CNPs. In this study, the extreme sensitivity of Dex–CNPs to visible light is demonstrated using room light with a clear indication of synergetic phenomenon of photoreduction of CNPs in the presence of dextran which undergoes simultaneous oxidation. The phenomenon was further confirmed through a systematic time‐based expedited study using a high intensity visible light source. The physiochemical changes of Dex–CNPs such as dispersion stability, pH, surface chemistry, antioxidant property, cytotoxicity and the surrounding microenvironment of Dex–CNPs were significantly altered on exposure to visible light, thereby affecting the biological response. Given the significance of nanoparticles which are widely researched nanomaterials, in different fields of nanotechnology and biomedicine, this study demonstrates the significant changes in physiochemical properties of Dex–CNPs with light. The photoreduction of Dex–CNPs affects its bifunctional applications in cancer therapy and thereby this study puts forward the necessity to preserve and sustain their properties through proper storage.     

Gold Nanoparticles Functionalized by a Dextran‐Based pH‐ and Temperature‐Sensitive Polymer

A dextran‐based dual‐sensitive polymer is employed to endow gold nanoparticles with stability and pH‐ and temperature‐sensitivity. The dual‐sensitive polymer is prepared by RAFT polymerization of N‐isopropylacrylamide from trithiocarbonate groups linked to dextran and succinoylation of dextran after polymerization. The functionalized nanoparticles show excellent stability under various conditions and can be stored in powder‐form. UV and DLS measurements confirm that the temperature‐induced optical changes and aggregation behaviors of the particles are strongly dependent on pH.

     

Striking Improvement in Peroxidase Activity of Cytochrome c by Modulating Hydrophobicity of Surface‐Functionalized Gold Nanoparticles within Cationic Reverse Micelles

This work demonstrates a remarkable enhancement in the peroxidase activity of mitochondrial membrane protein cytochrome c (cyt c) by perturbing its tertiary structure in the presence of surface‐functionalised gold nanoparticles (GNPs) within cetyltrimethylammonium bromide (CTAB) reverse micelles. The loss in the tertiary structure of cyt c exposes its heme moiety (which is buried inside in the native globular form), which provides greater substrate (pyrogallol and H₂O₂) accessibility to the reactive heme residue. The surfactant shell of the CTAB reverse micelle in the presence of co‐surfactant (n‐hexanol) exerted higher crowding effects on the interfacially bound cyt c than similar anionic systems. The congested interface led to protein unfolding, which resulted in a 56‐fold higher peroxidase activity of cyt c than that in water. Further perturbation in the protein’s structure was achieved by doping amphiphile‐capped GNPs with varying hydrophobicities in the water pool of the reverse micelles. The hydrophobic moiety on the surface of the GNPs was directed towards the interfacial region, which induced major steric strain at the interface. Consequently, interaction of the protein with the hydrophobic domain of the amphiphile further disrupted its tertiary structure, which led to better opening up of the heme residue and, thereby, superior activity of the cyt c. The cyt c activity in the reverse micelles proportionately enhanced with an increase in the hydrophobicity of the GNP‐capping amphiphiles. A rigid cholesterol moiety as the hydrophobic end group of the GNP strikingly improved the cyt c activity by up to 200‐fold relative to that found in aqueous buffer. Fluorescence studies with both a tryptophan residue (Trp59) of the native protein and the sodium salt of fluorescein delineated the crucial role of the hydrophobicity of the GNP‐capping amphiphiles in improving the peroxidase activity of cyt c by unfolding its tertiary structure within the reverse micelles.     

Hydrothermal Synthesis of Platinum‐Group‐Metal Nanoparticles by Using HEPES as a Reductant and Stabilizer

Platinum‐group‐metal (Ru, Os, Rh, Ir, Pd and Pt) nanoparticles are synthesized in an aqueous buffer solution of 4‐(2‐hydroxyethyl)‐1‐piperazineethanesulfonic acid (HEPES) (200 mM , pH 7.4) under hydrothermal conditions (180 °C). Monodispersed (monodispersity: 11–15 %) metal nanoparticles were obtained with an average particle size of less than 5 nm (Ru: 1.8±0.2, Os: 1.6±0.2, Rh: 4.5±0.5, Ir: 2.0±0.3, Pd: 3.8±0.4, Pt: 1.9±0.2 nm). The size, monodispersity, and stability of the as‐obtained metal nanoparticles were affected by the HEPES concentration, pH of the HEPES buffer solution, and reaction temperature. HEPES with two tertiary amines (piperazine groups) and terminal hydroxyl groups can act as a reductant and stabilizer. The HEPES molecules can bind to the surface of metal nanoparticles to prevent metal nanoparticles from aggregation. These platinum‐group‐metal nanoparticles could be deposited onto the surface of graphite, which catalyzed the aerobic oxidation of alcohols to aldehydes.     

Ultra‐Fast Synthesis of Multivalent Radical Nanoparticles by Ring‐Opening Metathesis Polymerization‐Induced Self‐Assembly

We report the straightforward, time‐efficient synthesis of radical core–shell nanoparticles (NPs) by polymerization‐induced self‐assembly. A nitroxide‐containing hydrophilic macromolecular precursor was prepared by ring‐opening metathesis copolymerization of norbornenyl derivatives of TEMPO and oligoethylene glycol and was chain‐extended in situ with norbornene in ethanolic solution, leading to simultaneous amphiphilic block copolymer formation and self‐assembly. Without any intermediate purification from the monomers to the block copolymers, radical NPs with tunable diameters ranging from 10 to 110 nm are obtained within minutes at room temperature. The high activity of the radical NPs as chemoselective and homogeneous, yet readily recyclable catalysts is demonstrated through oxidation of a variety of alcohols and recovery by simple centrifugation. Furthermore, the NPs show biocompatibility and antioxidant activity in vitro.     

Fabrication of Thymoquinone‐Loaded Albumin Nanoparticles by Microfluidic Particle Synthesis and Their Effect on Planarian Regeneration

Thymoquinone is the main bioactive component of the plant Nigella sativa, which is commonly known as black seeds and has several therapeutic effects. However, clinical applications of thymoquinone are limited due to its hydrophobic nature. In this study, thymoquinone is encapsulated in albumin nanoparticles by using a microfluidic platform to overcome this limitation. The mean particle sizes of empty and thymoquinone‐loaded nanoparticles are determined as 271.3 and 315.6 nm, respectively, with polydispersity index values both lower than 0.25. In addition to particle size distribution measurements, characterizations of the prepared nanoparticles such as zeta potential measurements, in vitro release studies, as well as scanning electron microscopy, Fourier‐transform infrared, and differential scanning calorimetry analyses are also carried out. To determine the effect of thymoquinone on neural regeneration, planarians are used as the model organism. After application of free and encapsulated thymoquinone, planarians are amputated and the fragments are observed in terms of head and tail regeneration, swimming pattern, and behavior. The results indicate that thymoquinone affects their behavior and primarily enhances head regeneration of planarians. In addition, it is shown that encapsulation of thymoquinone not only enhances the thermal stability of the molecule but also decreases its toxicity.     

Acetylcholinesterase‐capped Mesoporous Silica Nanoparticles Controlled by the Presence of Inhibitors

Two different acetylcholinesterase (AChE)‐capped mesoporous silica nanoparticles (MSNs), S1‐AChE and S2‐AChE , were prepared and characterized. MSNs were loaded with rhodamine B and the external surface was functionalized with either pyridostigmine derivative P1 (to yield solid S1 ) or neostigmine derivative P2 (to obtain S2 ). The final capped materials were obtained by coordinating grafted P1 or P2 with AChE′s active sites (to give S1‐AChE and S2‐AChE , respectively). Both materials were able to release rhodamine B in the presence of diisopropylfluorophosphate (DFP) or neostigmine in a concentration‐dependent manner via the competitive displacement of AChE through DFP and neostigmine coordination with the AChE‘s active sites. The responses of S1‐AChE and S2‐AChE were also tested with other enzyme inhibitors and substrates. These studies suggest that S1‐AChE nanoparticles can be used for the selective detection of nerve agent simulant DFP and paraoxon.     

Influence of Temperature on the Formation of Silver Nanoparticles by using a Seed‐Free Photochemical Method under Sodium‐Lamp Irradiation

Silver nanoparticles can be prepared by using a seed‐free photo‐assisted citrate reduction method under the irradiation of a sodium lamp. Under the same irradiation intensity, bath temperatures are crucial in influencing the reaction rate, morphologies of final products, and shape evolution of the silver nanostructures. For example, when the bath temperature is 80 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 38±6 %, 35±10 %, and 12±8 %, respectively. However, when the bath temperature is 30 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 6±3 %, 0 %, and 83±16 %, respectively. Time‐dependent UV/Vis spectra and TEM images show that silver nanoplates were formed at the earlier reaction stage and greatly decreased in amount at the later stage when the bath temperatures are less than or equal to 40 °C. This indicates that the silver nanoplates, which can be regarded as intermediates, are kinetically favored products. They are not thermodynamically favored products at these relatively low bath temperatures. The SERS spectra of crystal violet (CV) show that all the silver colloids synthesized at various temperatures exhibit good enhancement factors and that the colloids prepared at lower bath temperatures have a higher enhancement factor.     

Amino‐Acid‐Based Polymerizable Surfactants for the Synthesis of Chiral Nanoparticles

Amino‐acid‐based chiral surfactants with polymerizable moieties are synthesized, and a versatile approach to prepare particles thereof with a chiral surface functionality is presented. As an example of an application, the synthesized particles are tested for their ability as nucleating agents in the enantioselective crystallization of amino acid conglomerate systems, taking rac‐asparagine as a model system. Particles resulting from chiral surfactants with different tail groups are compared and the results demonstrate that only the chiral nanoparticles made of the polymerizable surfactant are able to act efficiently as nucleation agent in enantioselective crystallization.

     

Blocking Effect on Adsorption‐Controlled Electrochemiluminescence of CdSe Nanoparticles for Detection of the Neurotransmitter Serotonin

Herein, we have designed a special strategy for detection of the important neurotransmitter serotonin by coupling the electrodeposition of serotonin oxidative products with the adsorption‐controlled anodic electrochemiluminescent dynamics of the CdSe–triethylamine system. The stable electrochemiluminescent emission is found to decline in the presence of serotonin. This uncommon inhibition is attributed to the gradual accumulation of the electropolymerized serotonin products, which decrease the adsorbance of CdSe nanoparticles on the glass carbon electrode, as demonstrated by the scanning electron microscopic images (SEM) and the stripping voltammetric identification. Based on the inhibition effect, a facile strategy has been developed to sensitively detect the serotonin ranging from 0.2–10 μM , with a detection limit of 0.1 μM . The interference from the common species including ascorbic acid and uric acid has been investigated. The recovery rates in the spiked serum samples range from 94–112 %, thereby implicating its potential applications in the complex bioassays.     

Formation of Structured Polygonal Nanoparticles by Phase‐Separated Comb‐Like Polymers

A simple approach using comb‐like polymers that undergo nanophase separation between the polyester backbone and the stearoyl side chains is proposed for the preparation of structured non‐spherical nanoparticles from a nanoemulsion. Depending on the degree of esterification of the OH groups of poly(glycerol adipate) differently ordered nanostructures is obtained. A perfect lamellar arrangement is obtained for polymers with a high degree of esterification and leads to spherical nanoparticles with an internal onion‐like structure. However, when the degree of esterification is only 20 mol%, polygonal nanoparticles with an internal pseudo‐hexagonal structure are obtained. The differences in the nanoparticle shapes are related to the volume fraction of the paraffinic pool.     

Surface Roughness and Charge Influence the Uptake of Nanoparticles: Fluorescently Labeled Pickering‐Type Versus Surfactant‐Stabilized Nanoparticles

The influence of surface roughness and charge on the cellular uptake of nanoparticles in HeLa cells is investigated with fluorescent, oppositely charged, rough, and smooth nanoparticles. Flow cytometry, cLSM, and TEM reveal that rough nanoparticles are internalized by the cells more slowly and by an unidentified uptake route as no predominant endocytosis route is blocked by a variety of inhibitory drugs, while the uptake of smooth nanoparticles is strongly dependent on dynamin, F‐actin, and lipid‐raft. Negatively charged nanoparticles are taken up to a higher extent than positively charged ones, independent of the surface roughness.