Crumpling and Unfolding of Montmorillonite Hybrid Nanocoatings as Stretchable Flame‐Retardant Skin

Flame‐retardant coatings are widely used in a variety of personnel or product protection, and many applications would benefit from film stretchability if suitable materials are available. It is challenging to develop flame‐retardant coatings that are stretchable, eco‐friendly, and capable of being integrated on mechanically dynamic devices. Here, a concept is reported that uses pretextured montmorillonite (MMT) hybrid nanocoatings that can undergo programed unfolding to mimic the stretchability of elastomeric materials. These textured MMT coatings can be transferred onto an elastomeric substrate to achieve an MMT/elastomer bilayer device with high stretchability (225% areal strain) and effective flame retardancy. The bilayer composite is utilized as flame‐retardant skin for a soft robotic gripper, and it is demonstrated that the actuated response can manipulate and rescue irregularly shaped objects from a fire scene. Furthermore, by depositing the conformal MMT nanocoatings on nitrile gloves, the firefree gloves can endure direct flame contact without ignition.     

Microlandscaping of Au Nanoparticles on Few‐Layer MoS2 Films for Chemical Sensing

Surface modification or decoration of ultrathin MoS₂ films with chemical moieties is appealing since nanointerfacing can functionalize MoS₂ films with bonus potentials. In this work, a facile and effective method for microlandscaping of Au nanoparticles (NPs) on few‐layer MoS₂ films is developed. This approach first employs a focused laser beam to premodify the MoS₂ films to achieve active surface domains with unbound sulfur. When the activated surface is subsequently immersed in AuCl₃ solution, Au NPs are found to preferentially decorate onto the modified regions. As a result, Au NPs can be selectively and locally anchored onto designated regions on the MoS₂ surface. With a scanning laser beam, microlandscapes comprising of Au NPs decorated on laser‐defined micropatterns are constructed. By varying the laser power, reaction time and thickness of the MoS₂ films, the size and density of the NPs can be controlled. The resulting hybrid materials are demonstrated as efficient Raman active surfaces for the detection of aromatic molecules with high sensitivity.     

Bioinspired Superhydrophobic Fe3O4@Polydopamine@Ag Hybrid Nanoparticles for Liquid Marble and Oil Spill

Fe₃O₄ nanoparticles (NPs) with Ag NPs evenly distributed on the surface are fabricated by using polydopamine (PDA) as the intermediate layer. Silanization and thiol chemistry are used to firmly combine the Fe₃O₄@ PDA core and outer surface Ag NPs. The spherical and hybrid nanoparticles are termed Fe₃O₄@PDA@Ag NPs, which possess a core–shell and hierarchical structure. After surface modification with 1H,1H,2H,2H‐perfluorodecanethiol, the hybrid Fe₃O₄@PDA@Ag NPs become highly hydrophobic. Slight rolling of a water droplet on the as‐prepared NPs causes the formation of a “liquid marble”, which is capable of performing remote actuation on various solid surfaces, such as glass sheet, paper, plastic, textile, and ceramic, and at the liquid–air interface using a permanent magnet. Liquid marbles with self‐assembled NPs on the liquid surface have potential to act as a miniaturized reactor for manipulation of inner liquid droplet with high positioning precision. In addition, the Fe₃O₄@PDA@Ag NPs are multifunctional and can be applied for oil/water separation and antibacterial purpose.     

Generalized Scheme for High Performing Photodetectors with a p‐Type 2D Channel Layer and n‐Type Nanoparticles

A generalized scheme for the fabrication of high performance photodetectors consisting of a p‐type channel material and n‐type nanoparticles is proposed. The high performance of the proposed hybrid photodetector is achieved through enhanced photoabsorption and the photocurrent gain arising from its effective charge transfer mechanism. In this paper, the realization of this design is presented in a hybrid photodetector consisting of 2D p‐type black phosphorus (BP) and n‐type molybdenum disulfide nanoparticles (MoS₂ NPs), and it is demonstrated that it exhibits enhanced photoresponsivity and detectivity compared to pristine BP photodetectors. It is found that the performance of hybrid photodetector depends on the density of NPs on BP layer and that the response time can be reduced with increasing density of MoS₂ NPs. The rising and falling times of this photodetector are smaller than those of BP photodetectors without NPs. This proposed scheme is expected to work equally well for a photodetector with an n‐type channel material and p‐type nanoparticles.     

Biosynthesis and Characterization of Copper Nanoparticles Using Shewanella oneidensis: Application for Click Chemistry

Copper nanoparticles (Cu‐NPs) have a wide range of applications as heterogeneous catalysts. In this study, a novel green biosynthesis route for producing Cu‐NPs using the metal‐reducing bacterium, Shewanella oneidensis is demonstrated. Thin section transmission electron microscopy shows that the Cu‐NPs are predominantly intracellular and present in a typical size range of 20–40 nm. Serial block‐face scanning electron microscopy demonstrates the Cu‐NPs are well‐dispersed across the 3D structure of the cells. X‐ray absorption near‐edge spectroscopy and extended X‐ray absorption fine‐structure spectroscopy analysis show the nanoparticles are Cu(0), however, atomic resolution images and electron energy loss spectroscopy suggest partial oxidation of the surface layer to Cu₂O upon exposure to air. The catalytic activity of the Cu‐NPs is demonstrated in an archetypal “click chemistry” reaction, generating good yields during azide‐alkyne cycloadditions, most likely catalyzed by the Cu(I) surface layer of the nanoparticles. Furthermore, cytochrome deletion mutants suggest a novel metal reduction system is involved in enzymatic Cu(II) reduction and Cu‐NP synthesis, which is not dependent on the Mtr pathway commonly used to reduce other high oxidation state metals in this bacterium. This work demonstrates a novel, simple, green biosynthesis method for producing efficient copper nanoparticle catalysts.     

Hydrophobe Grenzflächenmodifikationen

Hydrophobic surface modification Through the application of easy‐to‐clean nanocoatings, it is possible to modifiy surfaces, without influencing the substrate's original functional properties. However, nanocoatings composed by different building blocks and produced by wet chemical methods present an irregular structure that also contains polar and hydrophilic groups. These disadvantages can be overcome by using Chemical Vapor Deposition methods. By applying CVD methods under vacuum conditions, it is possible to control the coating parameters and to obtain a homogeneous self‐organizing hydrophobic nanostructure. A protective coating can be produced in this way without influencing the substrate's original optical properties.     

A Novel Hierarchical Nanostructure for Enhanced Optical Nonlinearity Based on Scattering Mechanism

Surface modification of nonlinear optical materials (NOMs) is widely applied to fabricate diverse photonic devices, such as frequency combs, modulators, and all‐optical switches. In this work, a double‐layer nanostructure with heterogeneous nanoparticles (NPs) is proposed to achieve enhanced third‐order optical nonlinearity of NOMs. The mechanism of modified optical nonlinearity is elucidated to be the scattering‐induced energy transfer between adjacent NPs layers. Based on the LiNbO₃ platform, as a typical example, double layers of embedded Cu and Ag NPs are synthesized by sequential ion implantation, demonstrating twofold magnitude of near‐infrared enhancement factor and modulation depth in comparison with a single layer of Cu NPs. With the elastic collision model and thermolysis theory being considered, the shift of the localized surface plasmon resonance (LSPR) peak reveals the formation mechanism of the double‐layer nanostructure. Utilizing the enhanced optical nonlinearity of LiNbO₃ as modulators, a Q‐switched mode‐locked waveguide laser at 1 µm is achieved with shorter pulse duration. It suggests potential applications to improve the performance of nonlinear photonic devices by using double‐layer metallic nanostructures.     

Control of colloidal behavior of polystyrene latex nanoparticles and their cytotoxicity toward yeast cells using water-soluble polymers

Positively charged polystyrene latex (PSL) nanoparticles (NPs) dispersed in physiological saline (154?mM NaCl solution) are taken up by yeast cells. However, in low ionic strength solutions, the yeast cells are covered with the NPs, leading to cell death. The environmental conditions under which NPs are taken up are therefore limited. In this study, we attempted to control the uptake of positively charged PSL NPs by Saccharomyces cerevisiae in 5?mM NaCl solution using a water-soluble polymer. Addition of a small amount of anionic sodium carboxymethylcellulose (CMC), which has a carboxyl group, to 5?mM NaCl solution allowed the uptake of PSL NPs by living yeast cells. In contrast, non-ionic methylcellulose did not affect the NP behavior. This is because the negatively charged CMC adhered to the positively charged PSL NP surfaces and the surface charge changed from positive to negative. Atomic force microscopy using a single-NP probe consisting of one NP immobilized on the flattened end of the silicon nitride tip showed that CMC significantly reduced the interaction force between a negatively charged living yeast cell and a positively charged PSL NP.     

Formation of a Monolayer Protein Corona around Polystyrene Nanoparticles and Implications for Nanoparticle Agglomeration

Nanoparticle (NP) interactions with cells and organisms are mediated by a biomolecular adsorption layer, the so‐called “protein corona.” An in‐depth understanding of the corona is a prerequisite to successful and safe application of NPs in biology and medicine. In this work, earlier in situ investigations on small NPs are extended to large polystyrene (PS) NPs of up to 100 nm diameter, using human transferrin (Tf) and human serum albumin (HSA) as model proteins. Direct NP sizing experiments reveal a reversibly bound monolayer protein shell (under saturating conditions) on hydrophilic, carboxyl‐functionalized (PS‐COOH) NPs, as was earlier observed for much smaller NPs. In contrast, protein binding on hydrophobic, sulfated (PS‐OSO₃H) NPs in solvent of low ionic strength is completely irreversible; nevertheless, the thickness of the observed protein corona again corresponds to a protein monolayer. Under conditions of reduced charge repulsion (higher ionic strength), the NPs are colloidally unstable and form large clusters below a certain protein–NP stoichiometric ratio, indicating that the adsorbed proteins induce NP agglomeration. This comprehensive characterization of the persistent protein corona on PS‐OSO₃H NPs by nanoparticle sizing and quantitative fluorescence microscopy/nanoscopy reveals mechanistic aspects of molecular interactions occurring during exposure of NPs to biofluids.     

Comparative Evaluation of Intestinal Nitric Oxide in Embryonic Zebrafish Exposed to Metal Oxide Nanoparticles

Nanoparticle (NP) exposure may induce oxidative stress through generation of reactive oxygen and nitrogen species, which can lead to cellular and tissue damage. The digestive system is one of the initial organs affected by NP exposure. Here, it is demonstrated that exposure to metal oxide NPs induces differential changes in zebrafish intestinal NO concentrations. Intestinal NO concentrations are quantified electrochemically with a carbon fiber microelectrode inserted in the intestine of live embryos. Specificity of the electrochemical signals is demonstrated by NO‐specific pharmacological manipulations and the results are correlated with the 4,5‐diaminofluorescein‐diacetate (DAF‐FM‐DA). NPs are demonstrated to either induce or reduce physiological NO levels depending on their redox reactivity, type and dose. NO level is altered following exposure of zebrafish embryos to CuO and CeO₂ NPs at various stages and concentrations. CuO NPs increase NO concentration, suggesting an intestinal oxidative damage. In contrast, low CeO₂ NP concentration exposure significantly reduces NO levels, suggesting NO scavenging activity. However, high concentration exposure results in increased NO. Alterations in NO concentration suggest changes in intestinal physiology and oxidative stress, which will ultimately correspond to NPs toxicity. This work also demonstrates the use of electrochemistry to monitor in vivo changes of NO within zebrafish organs.     

Resistive Switching of Individual,Chemically Synthesized TiO2 Nanoparticles

Resistively switching devices are considered promising for next‐generation nonvolatile random‐access memories. Today, such memories are fabricated by means of “top–down approaches” applying thin films sandwiched between nanoscaled electrodes. In contrast, this work presents a “bottom–up approach” disclosing for the first time the resistive switching (RS) of individual TiO₂ nanoparticles (NPs). The NPs, which have sizes of 80 and 350 nm, respectively, are obtained by wet chemical synthesis and thermally treated under oxidizing or vacuum conditions for crystallization, respectively. These NPs are deposited on a Pt/Ir bottom electrode and individual NPs are electrically characterized by means of a nanomanipulator system in situ, in a scanning electron microscope. While amorphous NPs and calcined NPs reveal no switching hysteresis, a very interesting behavior is found for the vacuum‐annealed, crystalline TiO_2–x NPs. These NPs reveal forming‐free RS behavior, dominantly complementary switching (CS) and, to a small degree, bipolar switching (BS) characteristics. In contrast, similarly vacuum‐annealed TiO₂ thin films grown by atomic layer deposition show standard BS behavior under the same conditions. The interesting CS behavior of the TiO_2–x NPs is attributed to the formation of a core–shell‐like structure by re‐oxidation of the reduced NPs as a unique feature.     

A general synthetic approach for obtaining cationic and anionic inorganic nanoparticles via encapsulation in amphiphilic copolymers

A series of amphiphilic copolymers with variable charge densities on their backbone is synthesized. Positively charged N,N,N-trimethylammonium-2-ethyl methacrylate iodide or negatively charged 2-(methacryloyloxy)ethylphosphonic acid and lauryl methacrylate are used as building blocks. When wrapped around hydrophobically capped inorganic nanoparticles (NPs), the latter are able to disperse in aqueous solutions. Using this method, positively as well as negatively charged colloidal NPs can be synthesized in a reliable way. The method presented herein allows the charge on the NPs to be adjusted to different negative and positive values by using polymers with a variable ratio of charged monomers and lauryl methacrylate. Virtually all kinds of hydrophobic inorganic NPs could be coated with these amphiphilic polymers. The coating procedure is demonstrated for Au particles as well as for CdSe/ZnS quantum dots. To date, wrapping amphiphilic polymers around NPs has led only to anionic NPs. The polymers synthesized in this work allow for positively charged NPs with a high colloidal stability.     

TiO2 Nanoparticles and Commensal Bacteria Alter Mucus Layer Thickness and Composition in a Gastrointestinal Tract Model

Nanoparticles (NPs) are used in food packaging and processing and have become an integral part of many commonly ingested products. There are few studies that have focused on the interaction between ingested NPs, gut function, the mucus layer, and the gut microbiota. In this work, an in vitro model of gastrointestinal (GI) tract is used to determine whether, and how, the mucus layer is affected by the presence of Gram‐positive, commensal Lactobacillus rhamnosus; Gram‐negative, opportunistic Escherichia coli; and/or exposure to physiologically relevant doses of pristine or digested TiO₂ NPs. Caco‐2/HT29‐MTX‐E12 cell monolayers are exposed to physiological concentrations of bacteria (expressing fluorescent proteins) and/or TiO₂ nanoparticles for a period of 4 h. To determine mucus thickness and composition, cell monolayers are stained with alcian blue, periodic acid schiff, or an Alexa Fluor 488 conjugate of wheat germ agglutinin. It is found that the presence of both bacteria and nanoparticles alter the thickness and composition of the mucus layer. Changes in the distribution or pattern of mucins can be indicative of pathological conditions, and this model provides a platform for understanding how bacteria and/or NPs may interact with and alter the mucus layer.     

Controlled Vectorial Electron Transfer and Photoelectrochemical Applications of Layered Relay/Photosensitizer‐Imprinted Au Nanoparticle Architectures on Electrodes

Two configurations of molecularly imprinted bis‐aniline‐bridged Au nanoparticles (NPs) for the specific binding of the electron acceptor N,N′‐dimethyl‐4,4′‐bipyridinium (MV²⁺) and for the photosensitizer Zn(II)‐protoporphyrin IX (Zn(II)‐PP‐IX) are assembled on electrodes, and the photoelectrochemical features of the two configurations are discussed. Configuration I includes the MV²⁺‐imprinted Au NPs matrix as a base layer, on which the Zn(II)‐PP‐IX‐imprinted Au NPs layer is deposited, while configuration II consists of a bilayer corresponding to the reversed imprinting order. Irradiation of the two electrodes in the presence of a benzoquinone/benzohydroquinone redox probe yields photocurrents of unique features: (i) Whereas configuration I yields an anodic photocurrent, the photocurrent generated by configuration II is cathodic. (ii) The photocurrents obtained upon irradiation of the imprinted electrodes are substantially higher as compared to the nonimprinted surfaces. The high photocurrents generated by the imprinted Au NPs‐modified electrodes are attributed to the effective loading of the imprinted matrices with the MV²⁺ and Zn(II)‐PP‐IX units and to the effective charge separation proceeding in the systems. The directional anodic/cathodic photocurrents are rationalized in terms of vectorial electron transfer processes dictated by the imprinting order and by the redox potentials of the photosensitizer/electron acceptor units associated with the imprinted sites in the two configurations.     

High‐Density Sb2Te3 Nanopillars Arrays by Templated,Bottom‐Up MOCVD Growth

Sb₂Te₃ exhibits several technologically relevant properties, such as high thermoelectric efficiency, topological insulator character, and phase change memory behavior. Improved performances are observed and novel effects are predicted for this and other chalcogenide alloys when synthetized in the form of high‐aspect‐ratio nanostructures. The ability to grow chalcogenide nanowires and nanopillars (NPs) with high crystal quality in a controlled fashion, in terms of their size and position, can boost the realization of novel thermoelectric, spintronic, and memory devices. Here, it is shown that highly dense arrays of ultrascaled Sb₂Te₃ NPs can be grown by metal organic chemical vapor deposition (MOCVD) on patterned substrates. In particular, crystalline Sb₂Te₃ NPs with a diameter of 20 nm and a height of 200 nm are obtained in Au‐functionalized, anodized aluminum oxide (AAO) templates with a pore density of ≈5 × 10¹⁰ cm^?2. Also, MOCVD growth of Sb₂Te₃ can be followed either by mechanical polishing and chemical etching to produce Sb₂Te₃ NPs arrays with planar surfaces or by chemical dissolution of the AAO templates to obtain freestanding Sb₂Te₃ NPs forests. The illustrated growth method can be further scaled to smaller pore sizes and employed for other MOCVD‐grown chalcogenide alloys and patterned substrates.     

Ultra‐Smooth,Chemically Functional Silica Surfaces for Surface Interaction Measurements and Optical/Interferometry‐Based Techniques

The study of interfacial phenomena is central to a range of chemical, physical, optical, and electromagnetic systems such as surface imaging, polymer interactions, friction/wear, and ion‐transport in batteries. Studying intermolecular forces and processes of interfaces at the sub‐nano scale has proven difficult due to limitations in surface preparation methods. Here, we describe a method for fabricating reflective, deformable composite layers that expose an ultra‐smooth silica (SiO₂) surface (RMS roughness < 0.4 nm) with interferometric applications. The robust design allows for cleaning and reusing the same surfaces for over a week of continuous experimentation without degradation. The electric double‐layer forces measured using the composite surfaces are within 10% of the theoretically predicted values. We also demonstrate that standard chemisorption and physisorption procedures on silica can be applied to chemically modify the surfaces; as a demonstration of this, the composite surfaces are successfully modified with octadecyltrichlorosilane (OTS) to study their hydrophobic interactions in water using a surface force apparatus (SFA). These composite surfaces provide a basis for the preparation of a variety of new surfaces, and should be particularly beneficial for the SFA and colloidal probe methods that employ optical/interferometric and electrochemical techniques, enabling characterization of previously unattainable surface and interfacial phenomena.

     

Design of Bistable Gold@Spin‐Crossover Core–Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching

A simple chemical protocol to prepare core–shell gold@spin‐crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin‐crossover [Fe(Htrz)₂(trz)](BF₄) coordination polymer is reported. The synthesis relies on a two‐step approach consisting of a partial surface ligand substitution of the citrate‐stabilized Au NPs followed by the controlled growth of a very thin layer of the SCO polymer. As a result, colloidally stable core@shell spherical NPs with a Au core of ca. 12 nm and a thin SCO shell 4 nm thick, are obtained, exhibiting a narrow distribution in sizes. Differential scanning calorimetry proves that a cooperative spin transition in the range 340–360 K is maintained in these Au@SCO NPs, in full agreement with the values reported for pristine 4 nm SCO NPs. Temperature‐dependent charge‐transport measurements of an electrical device based on assemblies of these Au@SCO NPs also support this spin transition. Thus, a large change in conductance upon spin state switching, as compared with other memory devices based on the pristine SCO NPs, is detected. This results in a large improvement in the sensitivity of the device to the spin transition, with values for the ON/OFF ratio which are an order of magnitude better than the best ones obtained in previous SCO devices.     

Photonic Reactions Leading to Fluorescence in a Polymeric System Induced by the Photothermal Effect of Magnetite Nanoparticles Using a 780 nm Multiphoton Laser

Recently, polymer‐coated magnetite (Fe₃O₄) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe₃O₄ NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe₃O₄ NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe₃O₄ NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe₃O₄ NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe₃O₄ NPs, and a stronger intensity is observed in large‐sized NPs.     

Molecular Nanowire Bonding to Epitaxial Single‐Layer MoS2 by an On‐Surface Ullmann Coupling Reaction

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self‐assembled organic nanowire‐TMDC system, a method to link and interconnect epitaxial single‐layer MoS₂ flakes with organic molecules is demonstrated. Whereas pristine epitaxial single‐layer MoS₂ has no affinity for molecular attachment, it is found that single‐layer MoS₂ will selectively bind the organic molecule 2,8‐dibromodibenzothiophene (DBDBT) in a surface‐assisted Ullmann coupling reaction when the MoS₂ has been activated by pre‐exposing it to hydrogen. Atom‐resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig‐zag edges available in a hexagonal single layer MoS₂ sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic‐TMDC hybrid materials.