Bioinspired Magnetite Crystallization Directed by Random Copolypeptides

Control over magnetite (Fe₃O₄) formation is difficult to achieve in synthetic systems without using non‐aqueous media and high temperatures. In contrast, Nature employs often intrinsically disordered proteins to tightly tailor the size, shape, purity, and organization of the nanocrystals to optimize their magnetic properties. Inspired by such “flexible polyelectrolytes,” here random copolypeptides having different amino acid compositions are used as control agents in the bioinspired coprecipitation of magnetite through a ferrihydrite precursor, following a recently developed mineralization protocol. Importantly, the copolypeptide library is designed such that the amino acid composition can be optimized to simultaneously direct the size of the nanoparticles as well as their dispersibility in aqueous media in a one‐pot manner. Acidic amino acids are demonstrated to regulate the crystal size by delaying nucleation and reducing growth. Their relative content thus can be balanced to tune between the superparamagnetic and ferrimagnetic regimes, and high contents of negatively charged amino acids result in colloidal stabilization of superparamagnetic nanoparticles at high pH. Conversely, with positively charged lysine‐rich copolypeptides ferrimagnetic crystals are obtained which are stabilized at neutral pH and self‐organize in chains, as visualized by cryo‐transmission electron microscopy. Altogether, the presented findings give important insights for the future development of additive‐mediated nanomaterial syntheses.     

Biocatalytic Nanoscale Coatings Through Biomimetic Layer‐by‐Layer Mineralization

Recent insight into the molecular mechanisms of biological mineral formation (biomineralization) has enabled biomimetic approaches for the synthesis of functional organic‐inorganic hybrid materials under mild reaction conditions. Here we describe a novel method for enzyme immobilization in thin (nanoscale) conformal mineral coatings using biomimetic layer‐by‐layer (LbL) mineralization. The method utilizes a multifunctional molecule comprised of a naturally‐occurring peptide, protamine (PA), covalently bound to the redox enzyme Glucose oxidase (GOx). PA mimics the mineralizing properties of biomolecules involved in silica biomineralization in diatoms, and its covalent attachment to GOx does not interfere with the catalytic activity. Highly efficient and stable incorporation of this modified enzyme (GOx‐PA) into nanoscale layers (～5–7 nm thickness) of Ti‐O and Si‐O is accomplished during protamine‐enabled LbL mineralization on silica spheres. Depending on the layer location of the enzyme and the type of mineral (silica or titania) within which the enzyme is incorporated, the resulting multilayer biocatalytic hybrid materials exhibit between 20–100% of the activity of the free enzyme in solution. Analyses of kinetic properties (V_max, K_M) of the immobilized enzyme, coupled with characterization of physical properties of the mineral‐bearing layers (thickness, porosity, pore size distribution), indicates that the catalytic activities of the synthesized hybrid nanoscale coatings are largely determined by substrate diffusion rather than enzyme functionality. The GOx‐PA immobilized in these nanoscale layers is substantially stabilized against heat‐induced denaturation and largely protected from proteolytic attack. The method for enzyme immobilization described here enables, for the first time, the high yield immobilization and stabilization of enzymes within continuous, conformal, and nanoscale coatings through biomimetic LbL mineralization. This approach will likely be applicable to a wide variety of surfaces and functional biomolecules. The ability to synthesize thin (nanoscale) conformal enzyme‐loaded layers is of interest for numerous applications, including enzyme‐based biofuel cells and biosensors.     

Quantitative Recovery of Magnetic Nanoparticles from Flowing Blood: Trace Analysis and the Role of Magnetization

Magnetic nanomaterials find increasing application as separation agents to rapidly isolate target compounds from complex biological media (i.e., blood purification). The responsiveness of the used materials to external magnetic fields (i.e., their saturation magnetization) is one of the most critical parameters for a fast and thorough separation. In the present study, magnetite (Fe₃O₄) and non‐oxidic cementite (Fe₃C) based carbon‐coated nanomagnets are characterized in detail and compared regarding their separation behavior from human whole blood. A quantification approach for iron‐based nanomaterials in biological samples with strong matrix effects (here, salts in blood) based on platinum spiking is shown. Both materials are functionalized with polyethyleneglycol (PEG) to improve cytocompatibility (confirmed by cell toxicity tests) and dispersability. The separation performance is tested in two setups, namely under stationary and different flow‐conditions using fresh human blood. The results reveal a superior separation behavior of the cementite based nanomagnets and strongly suggest the use of nanomaterials with high saturation magnetizations for magnetic retention under common blood flow conditions such as in veins.     

Highly Flexible and Twistable Freestanding Single Crystalline Magnetite Film with Robust Magnetism

Magnetic materials and devices that can be folded and twisted without sacrificing their functional properties are highly desirable for flexible electronic applications in wearable products and implantable systems. In this work, a high‐quality single crystalline freestanding Fe₃O₄ thin film with strong magnetism has been synthesized by pulsed laser deposition using a water‐dissolvable Sr₃Al₂O₆ sacrificial layer, and the resulting freestanding film, with magnetism confirmed at multiple length scales, is highly flexible with a bending radius as small as 7.18 µm and twist angle as large as 122°, in sharp contrast with bulk magnetite that is quite brittle. When transferred to a polydimethylsiloxane support layer, the Fe₃O₄ film can be bent with large deformation without affecting its magnetization, demonstrating its robust magnetism. The work thus offers a viable solution for flexible magnetic materials that can be utilized in a range of applications.     

Phase Transformations and Structural Developments in the Radular Teeth of Cryptochiton Stelleri

During mineralization, the hard outer magnetite‐containing shell of the radular teeth of Cryptochiton stelleri undergoes four distinct stages of structural and phase transformations: (i) the formation of a crystalline α‐chitin organic matrix that forms the structural framework of the non‐mineralized teeth, (ii) the templated synthesis of ferrihydrite crystal aggregates along these organic fibers, (iii) subsequent solid state phase transformation from ferrihydrite to magnetite, and (iv) progressive magnetite crystal growth to form continuous parallel rods within the mature teeth. The underlying α‐chitin organic matrix appears to influence magnetite crystal aggregate density and the diameter and curvature of the resulting rods, both of which likely play critical roles in determining the local mechanical properties of the mature radular teeth.     

Template‐Assisted Synthesis of Mesoporous Magnetic Nanocomposite Particles

A new concept is proposed to synthesize mesoporous magnetic nanocomposite particles of great scientific and technological importance. Mesoporous silica coatings were created on micrometer‐sized magnetite (Fe₃O₄) particles using cetyltrimethylammonium chloride micelles as molecular templates. The characterization by transmission electron microscopy (TEM), nitrogen adsorption–desorption, diffuse‐reflectance Fourier‐transform infrared spectroscopy, and zeta‐potential measurements confirmed the deposition of mesoporous silica thin layers on the magnetite particles. The synthesized particles showed a drastic increase in specific surface area with an average pore size of 2.5 nm. The coating material showed a negligible effect on the saturation magnetization of the original particles that were fully protected by silica coatings. The synthesized mesoporous magnetic nanocomposite particles have a wide range of applications in toxin removal, waste remediation, catalysis, reactive sorbents, and biological cell separations.     

Preparation of Uniform,Water‐Soluble,and Multifunctional Nanocomposites with Tunable Sizes

Novel, thiol‐functionalized, and superparamagnetic, silica composite nanospheres (SH‐SSCNs) with diameters smaller than 100 nm are successfully fabricated through the self‐assembly of Fe₃O₄ nanoparticles and polystyrene₁₀₀‐block‐poly(acrylic acid)₁₆ and a subsequent sol‐gel process. The size and magnetic properties of the SH‐SSCNs can be easily tuned by simply varying the initial concentrations of the magnetite nanoparticles in the oil phase. By incorporating fluorescent dye molecules into the silica network, the composite nanospheres can be further fluorescent‐functionalized. The toxicity of the SH‐SSCNs is evaluated by choosing three typical cell lines (HUVEC, RAW264.7, and A549) as model cells, and no toxic effects are observed. It is also demonstrated that SH‐SSCNs can be used as a new class of magnetic resonance imaging (MRI) probes, having a remarkably high spin–spin (T₂) relaxivity (r₂* = 176.1 mM ^?1 S^?1). The combination of the sub‐100‐nm particle size, monodispersity in aqueous solution, superparamagnetism, and fluorescent properties of the SH‐SSCNs, as well as the non‐cytotoxicity in vitro, provides a novel and potential candidate for an earlier MRI diagnostic method of cancer.     

Syntheses,Properties and Electrochemical Activity of Carbon Microtubes Modified with Amino Groups

Amine‐modified carbon micro/sub‐microtubes that encapsulate magnetite cores have been synthesized by decomposing a ferrocene/hexabromobenzene mixture in the presence of ammonia under solvothermal conditions at 250 °C for 24 h in a one‐step process. The as‐prepared carbon microstructures (NH₂‐ME‐CMTs) were 90–2000 nm in diameter and from tens to hundreds of micrometers in length that could be tuned in various solvents. The surface of the carbon microtubes can be modified with amino groups by the synthetic process, as confirmed by infra‐red (IR) spectroscopy and X‐ray photoelectron spectroscopy (XPS). Ammonia in the reaction system plays a key role in the formation of the microtube morphology and was the source of the surface functionalization groups. Fluorescent fluorescein isothiocyanate (FITC) was selected as a model compound and successively attached to the amino groups of the carbon microtubes. This result confirms the reactivity of the amino groups on the surface of the carbon microtubes. The inner magnetite cores were removed after immersion in 1 M HCl solution at room temperature over two months, and hollow carbon microtubes (NH₂‐H‐CMTs) were obtained. The magnetite‐encapsulated carbon microtubes and the hollow carbon microtubes were coated on gold electrodes to prepare carbon microtube‐modified gold electrodes. The two electrodes have been used to investigate the oxidative properties of dopamine (DA) and ascorbic acid (AA). Different from the magnetite‐encapsulated microtube‐modified electrode, the hollow microtube‐modified electrode can be utilized in the selective detection of DA in the presence of a large excess of AA. The electrochemical behaviour of DA and AA on the hollow carbon microtubes modified with amino groups is similar to that on carbon nanotubes. This result suggests that the one‐step synthesis method will not change the electrochemical properties or break the backbone structure of the carbon microtubes.     

High-frequency reactive diode sputtering of magnetite films on the sapphire surface

The conditions (oxygen partial pressure and growth rate) for the deposition of magnetite (iron oxide) Fe₃O₄ on the r plane of the single-crystalline sapphire using the high-frequency reactive diode sputtering of the Fe target are determined. The resulting ferromagnetic layers exhibit polycrystalline structure with a typical block size of 100–200 nm. The X-ray analysis is used to demonstrate that the textured phase of magnetite that is normally oriented with respect to the substrate dominates in the blocks and Fe and Fe₂O₃ impurities are almost absent.     

Engineering Iron Oxide Hollow Nanospheres to Enhance Antimicrobial Property: Understanding the Cytotoxic Origin in Organic Rich Environment

Engineered magnetic iron oxide nanoparticles with surprisingly high antimicrobial activity and excellent safety profiles to mammalian cell lines have been developed. Hematite hollow nanospheres (HNSs) are prepared by a facile hard templating method; reduction of hematite HNSs by H₂ leads to magnetite HNSs. The antimicrobial activity of magnetite HNSs towards Gram negative (Escherichia coli) and Gram positive (Staphylococcus epidermidis) bacteria is evaluated against hematite HNSs and conventional magnetite (C‐magnetite; diameter <50 nm). Superior antibacterial performance is observed for magnetite HNSs towards both E. coli and S. epidermidis over hematite HNSs and C‐magnetite. The origin of the antimicrobial activity of magnetite HNSs is the high leaching of iron ions in the presence of microorganisms, which leads to high generation of reactive oxygen species. Magnetite HNSs allow multiple‐fold increase in the generation of soluble iron ions over hematite HNSs and C‐magnetite, showing that control over both the composition and nanostructure is crucial to tune the antimicrobial activity of iron oxides. Based on the current findings, magnetic HNSs show promising potential antimicrobial applications.     

Sequential Hydroboration–Alcoholysis and Epoxidation–Ring Opening Reactions of Vinyl Groups in Mesoporous Vinylsilica

We report the sequential transformation of vinyl groups into hydroborate and alcohol as well as vinyl into epoxide and diol functional groups in hexagonal mesoporous vinylsilica materials, denoted meso‐vinyl‐SiO₂. The first transformation proceeds quantitatively through the hydroborylated derivative. After appropriate quenching, the hydroborylated materials are stable at ambient conditions and can undergo transformation into alcohols and various other functional groups. The pore volume and pore size uniformity were found not to be greatly affected by quenching of the hydroboranes with methanol, but they were reduced by quenching with water due to the deposition of boron‐containing species in the channels. Complete conversion of hydroborylated materials to alcohol‐functionalized materials required basic conditions and treatment time of several hours. Although this led to a significant structural shrinkage, decrease in pore volume, and decrease in ordering, there was no evidence of a partial collapse or removal of substantial parts of the pore walls under optimized synthesis conditions. This is the first successful conversion of organic groups of a functionalized ordered mesoporous silica host in alkaline solution, conditions known to be detrimental for silica frameworks. Epoxidation of the vinyl groups and subsequent conversion of the resulting epoxides into diols are also briefly described. The chemical transformation through epoxidation affords ordered mesoporous silica materials functionalized with potentially chiral organic groups, which could find applications in asymmetric catalysis and chiral separations. It was found that the epoxidation was slower than hydroboration and resulted in a lower degree of conversion. These two examples of hydroboration–alcoholysis and epoxidation–ring opening reactions of terminally bonded vinyl groups in meso‐vinyl‐SiO₂ demonstrate the novel concept of sequential organic chemical transformations harbored inside the ordered channels of mesoporous organosilica materials.     

A Universal Approach to Fabricate Various Nanoring Arrays Based on a Colloidal‐Crystal‐Assisted‐Lithography Strategy

In this paper a convenient and universal strategy for preparing nanoring arrays of different compositions based on a colloidal‐crystal‐template strategy is reported. Large‐area arrays of polystyrene, magnetite, Au, Si, magnetite nanoparticle/polystyrene and Au/polystyrene double‐layer composite nanorings are prepared. Many kinds of nanoring structures, including Fe₃O₄ nanoparticle/polystyrene and Au/polystyrene double‐layer nanorings, can be released from the substrates, resulting in free‐standing composite nanorings, which might be used as self‐assembly building blocks and ultrasensitive bio‐ and chemical sensors.     

A New Approach to Tuning Carbon Ultramicropore Size at Sub‐Angstrom Level for Maximizing Specific Capacitance and CO2 Uptake

Ultramicroporous carbon materials with uniform pore size accurately adjusted to the dimension of electrolyte ions or CO₂ molecule are highly desirable for maximizing specific capacitance and CO₂ uptake. However, efficient ways to fine‐tuning ultramicropore size at angstrom level are scarce. A completely new approach to precisely tuning carbon ultramicropore size at sub‐angstrom level is proposed herein. Due to the varying activating strength and size of the alkali ions, the ultramicropore size can be finely tuned in the range of 0.60–0.76 nm as the activation ion varies from Li⁺ to Cs⁺. The carbons prepared by direct pyrolysis of alkali salts of carboxylic phenolic resins yield ultrahigh capacitances of up to 223 F g^‐1 (205 F cm^‐3) in ionic liquid electrolyte, and superior CO₂ uptake of 5.20 mmol g^‐1 at 1.0 bar and 25 °C. Such outstanding performance of the finely tuned carbons lies in its adjustable pore size perfectly adapted to the electrolyte ions and CO₂ molecule. This work paves the way for a new route to finely tuning ultramicropore size at the sub‐angstrom level in carbon materials.     

Colloidal Bi2S3 Nanocrystals: Quantum Size Effects and Midgap States

Among solution‐processed nanocrystals containing environmentally benign elements, bismuth sulfide (Bi₂S₃) is a very promising n‐type semiconductor for solar energy conversion. Despite the prompt success in the fabrication of optoelectronic devices deploying Bi₂S₃ nanocrystals, the limited understanding of electronic properties represents a hurdle for further materials developments. Here, two key materials science issues for light‐energy conversion are addressed: bandgap tunability via the quantum size effect, and photocarrier trapping. Nanocrystals are synthesized with controlled sizes varying from 3 to 30 nm. In this size range, bandgap tunability is found to be very small, a few tens of meV. First principles calculations show that a useful blueshift, in the range of hundreds of meV, is achieved in ultra‐small nanocrystals, below 1.5 nm in size. Similar conclusions are envisaged for the class of pnictide chalcogenides with a ribbon‐like structure [Pn₄Ch₆]_n (Pn = Bi, Sb; Ch = S, Se). Time‐resolved differential transmission spectroscopy demonstrates that only photoexcited holes are quickly captured by intragap states. Photoexcitation dynamics are consistent with the scenario emerging in other metal–chalcogenide nanocrystals: traps are created in metal‐rich nanocrystal surfaces by incomplete passivation by long fatty acid ligands. In large nanocrystals, a lower bound to surface trap density of one trap every sixteen Bi₂S₃ units is found.     

In Situ Study of Nanostructure and Electrical Resistance of Nanocluster Films Irradiated with Ion Beams

An in situ study is reported on the structural evolution in nanocluster films under He⁺ ion irradiation using an advanced helium ion microscope. The films consist of loosely interconnected nanoclusters of magnetite or iron‐magnetite (Fe‐Fe₃O₄) core‐shells. The nanostructure is observed to undergo dramatic changes under ion‐beam irradiation, featuring grain growth, phase transition, particle aggregation, and formation of nanowire‐like network and nanopores. Studies based on ion irradiation, thermal annealing and electron irradiation have indicated that the major structural evolution is activated by elastic nuclear collisions, while both electronic and thermal processes can play a significant role once the evolution starts. The electrical resistance of the Fe‐Fe₃O₄ films measured in situ exhibits a super‐exponential decay with dose. The behavior suggests that the nanocluster films possess an intrinsic merit for development of an advanced online monitor for fast neutron radiation with both high detection sensitivity and long‐term applicability, which can enhance safety measures in many nuclear operations.     

Epoxy Ring Opening Phase Transfer as a General Route to Water Dispersible Superparamagnetic Fe3O4 Nanoparticles and Their Application as Positive MRI Contrast Agents

A novel and efficient method to produce water dispersible superparamagnetic Fe₃O₄ nanoparticles is described. Nanoparticles prepared by non‐hydrolytic organic phase methods are subsequently functionalized with (3‐glycidyloxypropyl)trimethoxysilane, a linker that prevents aggregation and is available for subsequent coupling reactions with a wide range of polymers and biomolecules. Ring opening coupling reactions were used to coat the epoxy‐functionalized magnetite nanoparticles with aminated polymers (polyetheramines) or small molecules (arginine). The resulting nanoparticles, with hydrodynamic size of 13 nm, are found to be very stable over extended periods in water or PBS due to the presence of a dense stabilizer layer covalently anchored to the surface. Exceptionally high spin‐lattice relaxivity, r₁, values of 17 s^?1 mM^?1, and low r₂/r₁ ratios of 3.3–3.8 were exhibited in the clinical MRI frequency range, irrespective of the molecule selected for nanoparticle stabilization. As a result the dispersions are excellent candidates for incorporation into multi‐functional assemblies or for use as positive contrast agent for MRI.     

Synthesis and Characterization of Gelatin‐Based Magnetic Hydrogels

A simple preparation of thermoreversible gelatin‐based ferrogels in water provides a constant structure defined by the crosslinking degree for gelatin contents between 6 and 18 wt%. The possibility of varying magnetite nanoparticle concentration between 20 and 70 wt% is also reported. Simulation studies hint at the suitability of collagen to bind iron and hydroxide ions, suggesting that collagen acts as a nucleation seed to iron hydroxide aggregation, and thus the intergrowth of collagen and magnetite nanoparticles already at the precursor stage. The detailed structure of the individual ferrogel components is characterized by small‐angle neutron scattering (SANS) using contrast matching. The magnetite structure characterization is supplemented by small‐angle X‐ray scattering and microscopy only visualizing magnetite. SANS shows an unchanged gelatin structure of average mesh size larger than the nanoparticles with respect to gel concentration while the magnetite nanoparticles size of around 10 nm seems to be limited by the gel mesh size. Swelling measurements underline that magnetite acts as additional crosslinker and therefore varying the magnetic and mechanical properties of the ferrogels. Overall, the simple and variable synthesis protocol, the cheap and easy accessibility of the components as well as the biocompatibility of the gelatin‐based materials suggest them for a number of applications including actuators.     

Spheres of Microporous Titanosilicate Umbite with Hierarchical Pore Systems

Micrometric polycrystalline spheres of up to 1 mm diameter of microporous titanosilicate K₂TiSi₃O₉·H₂O with umbite structure have been prepared without the use of organic structuring agents. These spheres are organized as micro/macroporous hierarchical materials with macropores in the 0.2–1.4 µm range of average size, showing that intraparticular resistance to water transport is not limiting. Also, similar ion exchange performance can be observed in the Ti‐umbite spheres and in the single crystals obtained under the same synthesis conditions.     

Tristate Memory Using Ferroelectric–Insulator–Semiconductor Heterojunctions for 50% Increased Data Storage

Ferroelectric random‐access memory (FeRAM) is considered to be one of the best candidates for universal memory. However, difficult scaling of the memory cell size has hindered the realization of high density FeRAM. Given that size scaling is inherently limited by the complicated crystal structure and processing of ferroelectric materials, the highly stable and step‐wise three memory state of one cell can be another pathway to high‐density FeRAM. A feasible structure and actual operation of a tristate memory function for high‐density FeRAM is presented that uses stacked ferroelectric Pb(Zr,Ti)O₃/insulating Al₂O₃/semiconducting ZnO layers with Pt top and bottom electrodes. The complicated electrical responses of the stacked structure to external stimuli are well understood based on the separated trapping of the compensating charges at the Pb(Zr,Ti)O₃/Al₂O₃ and Al₂O₃/ZnO interfaces and the discrete dissipation of the trapped charges during polarization switching in one direction. This unique function of the structure induces three discrete charge states that can be used to increase the memory density by 50% compared to conventional FeRAM at a given cell size.     

Layered Double Hydroxide Nano‐ and Microstructures Grown Directly on Metal Substrates and Their Calcined Products for Application as Li‐Ion Battery Electrodes

Layered double hydroxide (LDH) nano‐ and microstructures with controllable size and morphology have been fabricated on “bivalent metal” substrates such as zinc and copper by a one‐step, room‐temperature process, in which metal substrates act as both reactants and supports. By manipulating the concentration of NH₃ · H₂O, the thickness and lateral size of the LDH materials can be tuned from several tens of nanometers to several hundreds of nanometers and from several hundreds of nanometers to several micrometers, respectively. This method is general and may be readily extended to any other alkali‐resisted substrate coated with Zn and Cu. As an example, Zn‐covered stainless steel foil has been shown to be effective for the growth of a Zn? Al LDH film. After calcinating the as‐grown LDH at high temperature (650 °C) in argon gas, a ZnO/ZnAl₂O₄ porous nanosheet film is obtained, which is then directly used for the first time as the anode material for Li‐ion batteries with the operating voltage window of 0.05–2.5 V (vs. Li). The result demonstrates that ZnO/ZnAl₂O₄ has higher discharge and charge capacities and considerably better cycling stability compared to pure ZnO (Li insertion/extraction rate: 200 or 500 mA g^?1). The improved electrochemical performance can be ascribed to the buffering effect of the inactive matrix ZnAl₂O₄ by relieving the stress caused by the volume change during charge–discharge cycling. This work represents a successful example for the development of promising ZnO‐based anode materials for Li‐ion batteries.