Transport Gap of Nanoparticle‐Passivated Silicon Substrates

The transport gap of nanoparticle‐passivated Si substrates is measured by scanning tunneling microscopy. Passivation is achieved using a monolayer of CdSe nanoparticles. It is shown that the transport gap and conduction‐band edge of the system change upon passivation. The size of the nanoparticles that passivate the Si substrate is varied to study its effect on the transport gap of the system. Plots of the tunneling current versus voltage show that the transport gap of the system can be tuned by the binding of just a monolayer of suitable nanoparticles. From the normalized density of states, it is shown that the conduction‐band edge of the system responds to the size of the nanoparticles. Here, a monolayer of the nanoparticles, which were capped with suitable functional groups, has been formed via electrostatic adsorption with the substrate.     

One Step Synthesis of Gold‐Loaded Radial Mesoporous Silica Nanospheres and Supported Lipid Bilayer Functionalization: Towards Bio‐Multifunctional Sensors

A simple synthetic route is developed to achieve gold functionalized radial mesoporous silica nanoparticles (Au‐MsNP) synthesized by a one step procedure fully compatible with basic conditions required for the preparation of monodispersed nanospheres. In a second step, Au‐MsNP particles have been coated with phospholipid bilayers in order to design an advanced biofunctional platform with the gold metallic nanoparticles previously grown into the pore channels and responsible for a plasmonic activity relevant for biosensing. The size of Au‐MsNP is checked by dynamic light scattering while zeta potential measurements reflect their surface charge. The particle morphology is characterized by transmission and scanning electron microscopy and the Si/Au ratios are obtained from energy dispersive X‐ray analysis. The textural properties of Au‐MsNP, specific surface area and pore size, are determined from N₂ adsorption. The supported bilayers are achieved from vesicles of different phospholipids incubated with Au‐MsNP particles. The coating efficiency is investigated by zeta potential and cryo‐ transmission electron microscopy. The plasmonic activities of bare Au‐MsNP particles and coated lipid bilayer Au‐MsNP platform are evidenced for two model systems: direct adsorption of bovine serum albumin and molecular recognition events between avidin molecules and biotin receptors integrated in the supported lipid bilayer.     

Graphene‐Bonded and ‐Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high‐capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one‐step aerosol spraying of surface‐modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50–100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene‐encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open‐ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g^?1 (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g^?1 at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene‐encapsulated Si anodes combined with the scalable and one‐step aerosol synthesis technique makes this material very promising for lithium ion batteries.     

AFM‐Based Spin‐Exchange Microscopy Using Chiral Molecules

Local magnetic imaging at nanoscale resolution is desirable for basic studies of magnetic materials and for magnetic logic and memories. However, such local imaging is hard to achieve by means of standard magnetic force microscopy. Other techniques require low temperatures, high vacuum, or strict limitations on the sample conditions. A simple and robust method is presented for locally resolved magnetic imaging based on short‐range spin‐exchange interactions that can be scaled down to atomic resolution. The presented method requires a conventional AFM tip functionalized with a chiral molecule. In proximity to the measured magnetic sample, charge redistribution in the chiral molecule leads to a transient spin state, caused by the chiral‐induced spin‐selectivity effect, followed by the exchange interaction with the imaged sample. While magnetic force microscopy imaging strongly depends on a large working distance, an accurate image is achieved using the molecular tip in proximity to the sample. The chiral molecules' spin‐exchange interaction is found to be 150 meV. Using the tip with the adsorbed chiral molecules, two oppositely magnetized samples are characterized, and a magnetic imaging is performed. This method is simple to perform at room temperature and does not require high‐vacuum conditions.     

Nematic‐like Organization of Magnetic Mesogen‐Hybridized Nanoparticles

A fluid nematic‐like phase is induced in monodisperse iron oxide nanoparticles with a diameter of 3.3 nm. This supramolecular arrangement is governed by the covalent functionalization of the nanoparticle surface with cyanobiphenyl‐based ligands as mesogenic promoters. The design and synthesis of these hybrid materials and the study of their mesogenic properties are reported. In addition, the modifications of the magnetic properties of the hybridized nanoparticles are investigated as a function of the different grafted ligands. Owing to the rather large interparticular distances (about 7 nm), the dipolar interaction between nanoparticles is shown to play only a minor role. Conversely, the surface magnetic anisotropy of the particles is significantly affected by the surface derivatization.     

Grafting Single Molecule Magnets on Gold Nanoparticles

The chemical synthesis and characterization of the first hybrid material composed by gold nanoparticles and single molecule magnets (SMMs) are described. Gold nanoparticles are functionalized via ligand exchange using a tetrairon(III) SMM containing two 1,2‐dithiolane end groups. The grafting is evidenced by the shift of the plasmon resonance peak recorded with a UV–vis spectrometer, by the suppression of nuclear magnetic resonance signals, by X‐ray photoemission spectroscopy peaks, and by transmission electron microscopy images. The latter evidence the formation of aggregates of nanoparticles as a consequence of the cross‐linking ability of Fe₄ through the two 1,2‐dithiolane rings located on opposite sides of the metal core. The presence of intact Fe₄ molecules is directly proven by synchrotron‐based X‐ray absorption spectroscopy and X‐ray magnetic circular dichroism spectroscopy, while a detailed magnetic characterization, obtained using electron paramagnetic resonance and alternating‐current susceptibility, confirms the persistence of SMM behavior in this new hybrid nanostructure.     

Lithiumpyridinyl‐Driven Synthesis of High‐Purity Zero‐Valent Iron Nanoparticles and Their Use in Follow‐Up Reactions

The synthesis of zero‐valent iron (Fe(0)) nanoparticles in pyridine using lithium bipyridinyl ([LiBipy]) or lithium pyridinyl ([LiPy]) is presented. FeCl₃ is used as the most simple starting material and reduced either in a [LiBipy]‐driven two‐step approach or in a [LiPy]‐driven one‐pot synthesis. High‐quality nanoparticles are obtained with uniform, spherical shape, and mean diameters of 2.9 ± 0.5 nm ([LiBipy]) or 4.1 ± 0.7 nm ([LiPy]). The as‐prepared, high purity Fe(0) nanoparticles are monocrystalline. In addition to particle characterization (high‐resolution transmission electron microscopy, scanning transmission electron microscopy, dynamic light scattering), composition and purity are examined in detail based on electron diffraction, X‐ray powder diffraction, elemental analysis, infrared spectroscopy, ⁵⁷Fe Mössbauer spectroscopy, and magnetic measurements. Due to their small size and high purity, the Fe(0) nanoparticles are highly reactive. They can be used in follow‐up reactions to obtain a variety of iron compounds, which is exemplarily shown for the transformation to iron carbide (Fe₃C) nanoparticles, the reaction with sulfur to obtain FeS nanoparticles, or the direct reaction with pentamethylcyclopentadiene to FeCp*₂ (Cp*: pentamethylcyclopentadienyl).     

Temperature‐Enhanced Solvent Vapor Annealing of a C3 Symmetric Hexa‐peri‐Hexabenzocoronene: Controlling the Self‐Assembly from Nano‐ to Macroscale

Temperature‐enhanced solvent vapor annealing (TESVA) is used to self‐assemble functionalized polycyclic aromatic hydrocarbon molecules into ordered macroscopic layers and crystals on solid surfaces. A novel C₃ symmetric hexa‐peri‐hexabenzocoronene functionalized with alternating hydrophilic and hydrophobic side chains is used as a model system since its multivalent character can be expected to offer unique self‐assembly properties and behavior in different solvents. TESVA promotes the molecule's long‐range mobility, as proven by their diffusion on a Si/SiO_x surface on a scale of hundreds of micrometers. This leads to self‐assembly into large, ordered crystals featuring an edge‐on columnar type of arrangement, which differs from the morphologies obtained using conventional solution‐processing methods such as spin‐coating or drop‐casting. The temperature modulation in the TESVA makes it possible to achieve an additional control over the role of hydrodynamic forces in the self‐assembly at surfaces, leading to a macroscopic self‐healing within the adsorbed film notably improved as compared to conventional solvent vapor annealing. This surface re‐organization can be monitored in real time by optical and atomic force microscopy.     

Nanoparticles of Mesoporous SO3H‐Functionalized Si‐MCM‐41 with Superior Proton Conductivity

Nanometer‐sized mesoporous silica particles of around 100‐nm diameter functionalized with a large amount of sulfonic acid groups are prepared using a simple and fast in situ co‐condensation procedure. A highly ordered hexagonal pore structure is established by applying a pre‐hydrolysis step in a high‐dilution synthesis approach, followed by adding the functionalization agent to the reaction mixture. The high‐dilution approach is advantageous for the in situ functionalization since no secondary reagents for an effective particle and framework formation are needed. Structural data are determined via electron microscopy, nitrogen adsorption, and X‐ray diffraction, proton conductivity values of the functionalized samples are measured via impedance spectroscopy. The obtained mesoporous SO₃H‐MCM‐41 nanoparticles demonstrate superior proton conductivity than their equally loaded micrometer‐sized counterparts, up to 5 × 10^?2 S cm^?1. The mesoporosity of the particles turns out to be very important for effective proton transport since non‐porous silica nanoparticles exhibit worse efficient proton transport, and the obtained particle size dependence might open up a new route in rational design of highly proton conductive materials.     

Functionalized Cluster‐Assembled Magnetic Nanostructures for Applications to high Integration‐Density Devices

This paper presents recent results on the preparation and characterization of original magnetic nanostructures from nanoclusters preformed in the gas phase. Magnetic binary‐clusters (i.e. Co‐Sm, Co‐Pt, Co‐Ag) with rather well controlled sizes, structures and compositions, are prepared in the gas phase using a combined laser vaporization‐rare gas condensation source and subsequently deposited at low energy (LECBD : Low Energy Cluster Beam Deposition) on various functionalized substrates to grow cluster‐assembled magnetic nanostructures exhibiting specific magnetic properties. Especially a high magnetic anisotropy and consequently a high magnetic blocking temperature compatible with future applications to high density memory devices and spin electronics are expected. In this context of applications, 2D‐organized arrays of functionalized binary‐cluster assembled dots are prepared by LECBD on FIB‐functionalized substrates (FIB: Focussed Ion Beam) with the ultimate objective to reach areal densities in the range of the Tbits/in².     

Grafting polymers to titania nanoparticles by radical polymerization initiated by diazonium salt

The grafting of biocompatible poly(hydroxyethyl) methacrylate (PHEMA) by a very simple method onto titanium dioxide nanoparticles is reported. The selected grafting process is based on the chemical reduction of diazonium salts by reducing agents in presence of the vinylic monomer. As previously demonstrated on flat surfaces, it leads to strongly grafted and stable polymer films and has many advantages residing in a short one-step reaction occurring at atmospheric pressure, ambient air and room temperature in water. TiO₂ nanoparticles were synthesized by laser pyrolysis, giving nanoparticles with controlled size and composition. The coating, the composition, the chemical structure, and the grafted PHEMA quantities of the resulting products were investigated by Transmission electron microscopy, Infrared-attenuated total reflection, X-ray photoelectron spectroscopy, and Thermogravimetric analysis. It was demonstrated that the PHEMA shell was successfully chemically grafted onto the surface of the TiO₂ core without any significant influence on the morphology of the nanoparticles.     

Preparation,characterization, and properties of disulfide-containing polyethyleneimine grafted carbon nanotubes

Novel functionalized carbon nanotubes (CNTs) were prepared by grafting disulfide-containing polyethyleneimine (SSPEI) to CNTs. The SSPEI were synthesized by Michael addition between cystamine bisacrylamide and low molecular weight branched 1.8 kDa PEI. Three SSPEI grafted carbon nanotubes (CNTs-SSPEI) were successfully prepared through grafting SSPEI to CNTs. The grafted ratios were 32.26%, 43.11%, and 51.50%, respectively. Moreover, the grafted ratio could be tuned by adjusting the CNTs/SSPEI ratio during the process of preparation. The CNTs-SSPEI was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The CNTs-SSPEI showed better dispersability and stability in water than CNTs. In addition, the SSPEI on the surface of CNTs-SSPEI could be degraded in the presence of dithiothreitol.     

Fluorescence‐Encoded Gold Nanoparticles: Library Design and Modulation of Cellular Uptake into Dendritic Cells

In order to harness the unique properties of nanoparticles for novel clinical applications and to modulate their uptake into specific immune cells we designed a new library of homo‐ and hetero‐functional fluorescence‐encoded gold nanoparticles (Au‐NPs) using different poly(vinyl alcohol) and poly(ethylene glycol)‐based polymers for particle coating and stabilization. The encoded particles were fully characterized by UV‐Vis and fluorescence spectroscopy, zeta potential and dynamic light scattering. The uptake by human monocyte derived dendritic cells in vitro was studied by confocal laser scanning microscopy and quantified by fluorescence‐activated cell sorting and inductively coupled plasma atomic emission spectroscopy. We show how the chemical modification of particle surfaces, for instance by attaching fluorescent dyes, can conceal fundamental particle properties and modulate cellular uptake. In order to mask the influence of fluorescent dyes on cellular uptake while still exploiting its fluorescence for detection, we have created hetero‐functionalized Au‐NPs, which again show typical particle dependent cellular interactions. Our study clearly prove that the thorough characterization of nanoparticles at each modification step in the engineering process is absolutely essential and that it can be necessary to make substantial adjustments of the particles in order to obtain reliable cellular uptake data, which truly reflects particle properties.     

利用开环聚合和原子转移自由基聚合在纳米二氧化硅表面接枝聚合物

利用硅烷偶联剂KH-550处理纳米二氧化硅(SiO_2)表面,得到氨基化的SiO_2,再通过溴异丁酸缩水甘油酯与氨基的开环反应,在SiO_2表面同时键接了开环聚合(ROP)的引发剂-OH和原子转移自由基聚合(ATRP)的引发剂-Br(SNPs-fOH/Br)。以SNPs-f-OH/Br为引发剂,分别进行ROP和ATRP,在纳米SiO_2表面接枝了聚己内酯(PCL)和聚苯乙烯(PS)混合聚合物刷(Mixed brush)。采用红外光谱、透射电镜、热失重、凝胶渗透色谱等方法对所得到的复合粒子进行了表征和测试。研究结果表明,混合聚合物刷成功接枝到了纳米SiO_2表面,通过控制聚合时间可以控制2种接枝聚合物的相对分子质量。本方法为纳米粒子表面接枝混合聚合物刷提供了一种简便的方法。     

Epirubicin‐Loaded Superparamagnetic Iron‐Oxide Nanoparticles for Transdermal Delivery: Cancer Therapy by Circumventing the Skin Barrier

The transdermal administration of chemotherapeutic agents is a persistent challenge for tumor treatments. A model anticancer agent, epirubicin (EPI), is attached to functionalized superparamagnetic iron‐oxide nanoparticles (SPION). The covalent modification of the SPION results in EPI–SPION, a potential drug delivery vector that uses magnetism for the targeted transdermal chemotherapy of skin tumors. The spherical EPI–SPION composite exhibits excellent magnetic responsiveness with a saturation magnetization intensity of 77.8 emu g^?1. They feature specific pH‐sensitive drug release, targeting the acidic microenvironment typical in common tumor tissues or endosomes/lysosomes. Cellular uptake studies using human keratinocyte HaCaT cells and melanoma WM266 cells demonstrate that SPION have good biocompatibility. After conjugation with EPI, the nanoparticles can inhibit WM266 cell proliferation; its inhibitory effect on tumor proliferation is determined to be dose‐dependent. In vitro transdermal studies demonstrate that the EPI–SPION composites can penetrate deep inside the skin driven by an external magnetic field. The magnetic‐field‐assisted SPION transdermal vector can circumvent the stratum corneum via follicular pathways. The study indicates the potential of a SPION‐based vector for feasible transdermal therapy of skin cancer.     

Gold Nanoparticles Thin Films with Thermo‐ and Photoresponsive Plasmonic Properties Realized with Liquid‐Crystalline Ligands

Robust synthesis of large‐scale self‐assembled nanostructures with long‐range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV‐light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long‐range ordered structures which exhibit a novel dual‐responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV‐light irradiation. These results present an efficient way to obtain bulk quantities of self‐assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix‐assisted or DNA‐mediated organization.     

Enhanced Magnetism in Highly Ordered Magnetite Nanoparticle‐Filled Nanohole Arrays

A new approach to develop highly ordered magnetite (Fe₃O₄) nanoparticle‐patterned nanohole arrays with desirable magnetic properties for a variety of technological applications is presented. In this work, the sub‐100 nm nanohole arrays are successfully fabricated from a pre‐ceramic polymer mold using spin‐on nanoprinting (SNAP). These nanoholes a then filled with monodispersed, spherical Fe₃O₄ nanoparticles of about 10 nm diameter using a novel magnetic drag and drop procedure. The nanohole arrays filled with magnetic nanoparticles a imaged using magnetic force microscopy (MFM). Magnetometry and MFM measurements reveal room temperature ferromagnetism in the Fe₃O₄‐filled nanohole arrays, while the as‐synthesized Fe₃O₄ nanoparticles exhibit superparamagnetic behavior. As revealed by MFM measurements, the enhanced magnetism in the Fe₃O₄‐filled nanohole arrays originates mainly from the enhanced magnetic dipole interactions of Fe₃O₄ nanoparticles within the nanoholes and between adjacent nanoholes. Nanoparticle filled nanohole arrays can be highly beneficial in magnetic data storage and other applications such as microwave devices and biosensor arrays that require tunable and anisotropic magnetic properties.     

Super‐Resolution Microscopy Unveils Dynamic Heterogeneities in Nanoparticle Protein Corona

The adsorption of serum proteins, leading to the formation of a biomolecular corona, is a key determinant of the biological identity of nanoparticles in vivo. Therefore, gaining knowledge on the formation, composition, and temporal evolution of the corona is of utmost importance for the development of nanoparticle‐based therapies. Here, it is shown that the use of super‐resolution optical microscopy enables the imaging of the protein corona on mesoporous silica nanoparticles with single protein sensitivity. Particle‐by‐particle quantification reveals a significant heterogeneity in protein absorption under native conditions. Moreover, the diversity of the corona evolves over time depending on the surface chemistry and degradability of the particles. This paper investigates the consequences of protein adsorption for specific cell targeting by antibody‐functionalized nanoparticles providing a detailed understanding of corona‐activity relations. The methodology is widely applicable to a variety of nanostructures and complements the existing ensemble approaches for protein corona study.     

Patterning corrosion‐susceptible metallic alloys for digital image correlation in a scanning electron microscope

We investigate the self‐assembly of gold nanoparticles on the surface of magnesium functionalized with 3‐(aminopropyl)trimethoxysilane or 3‐(mercaptopropyl)trimethoxysilane. These nanoparticles served as a speckle pattern for high magnification deformation tracking via digital image correlation combined with scanning electron microscopy. Controlling the pH of the gold nanoparticle suspension to a specific basicity passivated corrosion in magnesium and in three of its alloys to enable proper nanoparticle bonding and self‐assembly. Magnesium was used as a model material as it is particularly difficult to modify for self‐assembly because of its propensity to quickly form a thick oxide, hydroxide, and carbonate layer in the presence of oxygen, water, and carbon dioxide, respectively. Moreover, it corrodes in acidic and slightly basic solutions, further complicating the self‐assembly process. Due to these difficulties, the successful self‐assembly of nanoparticles on magnesium has not previously been reported, to the best of the authors' knowledge. This technique is potentially amendable to other corrosion‐susceptible materials. Gold nanoparticles were self‐assembled in a uniformly dispersed random distribution on pure cast magnesium, cast AM60 (Mg‐6Al‐0.5Mn), rolled WE43 (Mg‐4Y‐3Nd/Gd), and extruded ZE20 (Mg‐2Zn‐0.2Ce).     

Magneto‐Ionic Switching of Superparamagnetism

Electrochemical reactions represent a promising approach to control magnetization via electric fields. Favorable reaction kinetics have made nanoporous materials particularly interesting for magnetic tuning experiments. A fully reversible ON and OFF switching of magnetism in nanoporous Pd(Co) at room temperature is demonstrated, triggered by electrochemical hydrogen sorption. Comprehensive magnetic characterization in combination with high‐resolution scanning transmission electron microscopy reveals the presence of Co‐rich, nanometer‐sized clusters in the nanoporous Pd matrix with distinct superparamagnetic behavior. The strong magneto‐ionic effect arises from coupling of the magnetic clusters via a Ruderman–Kittel–Kasuya–Yoshida‐type interaction in the Pd matrix which is strengthened upon hydrogen sorption. This approach offers a new pathway for the voltage control of magnetism, for application in spintronic or microelectromagnetic devices.