Ferritin Protein Regulates the Degradation of Iron Oxide Nanoparticles

Proteins implicated in iron homeostasis are assumed to be also involved in the cellular processing of iron oxide nanoparticles. In this work, the role of an endogenous iron storage protein—namely the ferritin—is examined in the remediation and biodegradation of magnetic iron oxide nanoparticles. Previous in vivo studies suggest the intracellular transfer of the iron ions released during the degradation of nanoparticles to endogenous protein cages within lysosomal compartments. Here, the capacity of ferritin cages to accommodate and store the degradation products of nanoparticles is investigated in vitro in the physiological acidic environment of the lysosomes. Moreover, it is questioned whether ferritin proteins can play an active role in the degradation of the nanoparticles. The magnetic, colloidal, and structural follow‐up of iron oxide nanoparticles and proteins in lysosome‐like medium confirms the efficient remediation of potentially harmful iron ions generated by nanoparticles within ferritins. The presence of ferritins, however, delays the degradation of particles due to a complex colloidal behavior of the mixture in acidic medium. This study exemplifies the important implications of intracellular proteins in processes of degradation and metabolization of iron oxide nanoparticles.     

Nanopatterning of ferritin molecules and the controlled size reduction of their magnetic cores

A nanopatterning method to deposit ferritin proteins with nanoscale accuracy over large areas is reported. Selective deposition is driven by the electrostatic interactions existing between the proteins and nanoscale features. Upon deposition, the protein shell can be removed by heating the patterns in an oxygen atmosphere. This leaves exposed the iron oxide core, which can be further reduced in size by plasma-etching methods. In this way, the initial ferritin molecules, which have a nominal size of 12 nm, are reduced to 2 nm nanoparticles. Magnetic force measurements confirm the magnetic activity of the as-deposited and etched nanoparticles.     

Synthesis of ordered iron oxide nanoparticle arrays in planar DNA complexes

The formation of iron oxide nanoparticles in planar DNA complexes immobilized on substrates has been studied in reactions involving only biogenic reagents (ferritin and ascorbic acid) in aqueous solutions under normal conditions. Using transmission electron microscopy, we revealed ordered quasi-linear arrays of iron oxide nanoparticles 2–4 nm in diameter, which probably resulted from nanoparticle binding to linear DNA molecules. The electron diffraction patterns of the synthesized nanoparticles are characteristic of polycrystalline magnetic iron oxide (magnetite of maghemite) nanoparticles and point to good crystallinity of the nanoparticles. Our results demonstrate the feasibility of the synthesis of ordered arrays of iron oxide nanoparticles using DNA complexes and may have direct implications for the understanding of biomineralization processes and iron metabolism in living systems.     

Damage-free top-down processes for fabricating two-dimensional arrays of 7 nm GaAs nanodiscs using bio-templates and neutral beam etching

The first damage-free top-down fabrication processes for a two-dimensional array of 7 nm GaAs nanodiscs was developed by using ferritin (a protein which includes a 7 nm diameter iron core) bio-templates and neutral beam etching. The photoluminescence of GaAs etched with a neutral beam clearly revealed that the processes could accomplish defect-free etching for GaAs. In the bio-template process, to remove the ferritin protein shell without thermal damage to the GaAs, we firstly developed an oxygen-radical treatment method with a low temperature of 280?°C. Then, the neutral beam etched the defect-free nanodisc structure of the GaAs using the iron core as an etching mask. As a result, a two-dimensional array of GaAs quantum dots with a diameter of ～ 7 nm, a height of ～ 10 nm, a high taper angle of 88° and a quantum dot density of more than 7 × 10(11) cm(-2) was successfully fabricated without causing any damage to the GaAs.     

Biological synthesis of gold and silver nanoparticles mediated by the bacteria Bacillus subtilis

Biological synthesis of gold and silver nanoparticles was carried out using the bacteria Bacillus subtilis. The reduction processes of chloroaurate and silver ions by B. subtilis were found to be different. Gold nanoparticles were synthesized both intra- and extracellularly, while silver nanoparticles were exclusively formed extracellularly. The gold nanoparticles were formed after 1 day of addition of chloroaurate ions, while the silver nanoparticles were formed after 7 days. The nanoparticles were characterized by X-ray diffraction, UV-vis spectra and transmission electron spectroscopy. X-ray diffraction revealed the formation of face-centered cubic (fcc) crystalline gold nanoparticles in the supernatant, broth solution and bacterial pellet. Silver nanoparticles also exhibited diffraction peaks corresponding to fcc metallic silver. UV-vis spectra showed surface plasmon vibrations for gold and silver nanoparticles centered at 530 and 456 nm, respectively. TEM micrographs depicted the formation of gold nanoparticles intra- and extracellularly, which had an average size of 7.6 +/- 1.8 and 7.3 +/- 2.3 nm, respectively, while silver nanoparticles were exclusively formed extracellularly, with an average size of 6.1 +/- 1.6 nm. The bacterial proteins were analyzed by sodium dodecyl sulfonate-polyacrylamide electrophoresis (SDS-PAGE) before and after the addition of metal ion solutions. We believe that proteins of a molecular weight between 25 and 66 kDa could be responsible for chloroaurate ions reduction, while the formation of silver nanoparticles can be attributed to proteins of a molecular weight between 66 and 116 kDa. We also believe that the nanoparticles were stabilized by the surface-active molecules i.e., surfactin or other biomolecules released into the solution by B. subtilis.     

Application of supramolecular nanostamping to the replication of DNA nanoarrays

The rapid development of molecular biology is creating a pressing need for arrays of biomolecules that are able to detect smaller and smaller volumes of analytes. This goal can be achieved by shrinking the average size and spacing of the arrays' constituent features. While bioarrays with dot size and spacing on the nanometer scale have been successfully fabricated via scanning probe microscopy-based techniques, such fabrication methods are serial in nature and consequently slow and expensive. Additionally, the development of truly small arrays able to analyze scarce volumes of liquids is hindered by the present use of optical detection, which sets the minimum dot spacing on the order of roughly half the excitation wavelength. Here, we show that supramolecular nanostamping, a recently introduced truly parallel method for the stamping of DNA features, can efficiently reproduce DNA arrays with features as small as 14 +/- 2 nm spaced 77 +/- 10 nm. Moreover, we demonstrate that hybridization of these nanoarrays can be detected using atomic force microscopy in a simple and scaleable way that additionally does not require labeling of the DNA strands.     

Nanostructured biointerfaces

Colloidal lithography is used to create nanostructured interfaces suitable for studying and interacting with cellular biosystems. Large areas of patterned surface can be produced. We investigate the use of plasma etching for transfer of the pattern of individual colloidal particles into the substrates to create short-range ordered arrays of topographic and/or chemical nanostructures. Colloidal masks perform differently to traditional photoresist masks and local redeposition of material around the particle has significant impact on the resultant structures. The colloidal particles can be reshaped to allow the fabrication of flat-topped structures. Topographic and chemical nanostructures can be used to template the self assembly of macromolecules. The phase separation of thin films of PS-PMMA symmetric block copolymers above nanostructure sites is aligned at the surface nanostructure by topographic features. PLL-PEG assembly at alkanethiol-modified nanoscale chemical patterns of gold/silicon allows the production of nanoscale protein patterns. Patterns of ferritin 100 nm in diameter are demonstrated.     

Formation of water-soluble iron oxide nanoparticles derived from iron storage protein

This paper reports novel findings of an investigation of the formation of water-soluble iron oxide nanoparticles from iron-storage protein ferritin. The strategy couples thermal removal of the protein shell on a planar substrate and subsequent sonication in aqueous solution under controlled temperature. Advantages of using ferritin as a precursor include well-defined core size, core composition, water-solubility and processibility. The formation of the nanoparticles was characterized using TEM, UV-Vis and FTIR techniques. Iron oxide nanoparticles in the size range of 5-20 nm diameters were produced. In addition to thermal treatment conditions, the sonication temperature of the nanoparticles in water was found to play an important role in determining the resulting particle size. This simple and effective route has important implications to the design of composite nanoparticles for potential magnetic, catalytic, biomedical sensing and other nanotechnological applications.     

Formation of nanoparticle arrays on S-layer protein lattices

Crystalline bacterial cell surface layers (S-layers) composed of identical protein units have been used as binding templates for well-organized arrangements of nanoparticles. Isolated S-layer proteins were recrystallized into monomolecular arrays on solid substrates (such as silicon wafers and SiO2-coated grids) and in suspension forming so-called self-assembly products. These S-layer assemblies were studied by atomic force microscopy and transmission electron microscopy (TEM). The orientation of the S-layer lattice, exhibiting anisotropic surface properties, on the solid surface and on the self-assembly products, was compared with the orientation on the bacterial cell. On both bacterial cells and SiO2 surfaces the outer face of the S-layer protein was exposed. On the self-assembly products occasionally the inner face was also visible. Metal- and semiconductor nanoparticles 2 to 10 nm in mean diameter were covalently or electrostatically bound to the solid-supported S-layers and self-assembly products. TEM studies reveal that upon activation of carboxyl groups in the S-layer lattice with 1-ethyl-3,3'(dimethylaminopropyl)carbodiimide (EDC), a close-packed monolayer of 4-nm amino-functionalized CdSe nanoparticles could be covalently established on the S-layer lattice. Because of electrostatic interactions, anionic citrate-stabilized Au nanoparticles (5 nm in diameter) formed a superlattice at those sites where the inner face of the S-layer lattice was exposed. In contrast, cationic semiconductor nanoparticles (such as amino-functionalized CdSe particles) formed arrays on the outer face of the solid-supported S-layer lattices.     

Optical investigations on indium oxide nano-particles prepared through precipitation method

Visible light emitting indium oxide nanoparticles were synthesized by precipitation method. Sodium hydroxide dissolved in ethanol was used as a precipitating agent to obtain indium hydroxide precipitates. Precipitates, thus formed were calcined at 600 °C for 1 h to obtain indium oxide nanoparticles. The structure of the particles as determined from the X-Ray diffraction pattern was found to be body centered cubic. The phase transformation of the prepared nanoparticles was analyzed using thermogravimetry. Surface morphology of the prepared nanoparticles was analyzed using high resolution-scanning electron microscopy and transmission electron microscopy. The results of the analysis show cube-like aggregates of size around 50 nm. It was found that the nanoparticles have a strong emission at 427 nm and a weak emission at 530 nm. These emissions were due to the presence of singly ionized oxygen vacancies and the nature of the defect was confirmed through Electron paramagnetic resonance analysis.     

Template-assisted self-assembly of individual and clusters of magnetic nanoparticles

The deliberate control over the spatial arrangement of nanostructures is the desired goal for many applications such as, for example, in data storage, plasmonics or sensor arrays. Here we present a novel method to assist the self-assembly process of magnetic nanoparticles. The method makes use of nanostructured aluminum templates obtained after anodization of aluminum discs and the subsequent growth and removal of the newly formed alumina layer, resulting in a regular honeycomb-type array of hexagonally shaped valleys. The iron oxide nanoparticles, 20 nm in diameter, are spin-coated onto the surface of honeycomb nanostructured Al templates. Depending on the size, each hexagon site can host up to 30 nanoparticles. These nanoparticles form clusters of different arrangements within the valleys, such as collars, chains and hexagonally closed islands. Ultimately, it is possible to isolate individual nanoparticles. The strengths of the magnetic interaction between particles in a cluster are probed using the memory effect known from the coupled state in superspin glass systems.     

Growth of two-dimensional arrays of uncapped gold nanoparticles on silicon substrates

A method of preparing large area patterned 2D arrays of uncapped gold (Au) nanoparticles has been developed. The pattern has been formed using self-assembly of uncapped Au nanoparticles. The Au nanoparticles were synthesized via toluene/water two phase systems using a reducing agent and colloidal solution of Au nanoparticles was produced. These nanoparticles have been prepared without using any kind of capping agent. Analysis by TEM showed discrete Au nanoparticles of 4 nm average diameter. AFM analysis also showed similar result. The TEM studies showed that these nanoparticles formed self-assembled coherent patterns with dimensions exceeding 500 nm. Spin coating on silicon substrate by suitably adjusting the speed can self-assemble these nanoparticles to lengths exceeding 1 μm.     

Design of superparamagnetic iron oxide nanoparticle for purification of recombinant proteins

This article reports the synthesis, characterization and also the use of surface modified iron oxide nanoparticles in affinity separation of his-tagged protein. Magnetite particles were prepared by simple coprecipitation of Fe3+/Fe2+ in aqueous medium and then subsequently coated with silica following a sol-gel route. Iminodiacetate was immobilized on them through a silane-coupling agent and charged with Ni2+. These Ni2+ charged magnetic silica nanoparticles have been shown as an efficient carrier, binder and anchor to obtain his-tagged protein directly from total cell lysate. The structural characteristics of the powders were studied by XRD. Magnetic silica particles with 12 nm and aggregate size 90 nm containing inverse spinel magnetite core were observed by transmission electron micrograph and dynamic light scattering. The presence of surface-iminodiacetate groups was shown by FTIR and X-ray photoelectron spectra. The immobilization of Ni2+ through the surface chelating iminodiacetate groups was also studied by XPS. VSM measurement shows these iminodiacetate functionalized magnetic carriers have saturation magnetization 56 e.m.u./g at room temperature. Due to its high efficiency, cost-effectiveness, biocompatibility, and versatility, this magnetic nano-adsorbent may be used as a novel purification system for 6xHis-Tagged recombinant proteins.     

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.     

Magnetic properties of iron nanoparticles prepared by exploding wire technique

Nanoparticles of iron were prepared in distilled water using very thin iron wires and sheets, by the electro-exploding wire technique. Transmission electron microscopy reveals the size of the nanoparticles to be in the range 10 to 50 nm. However, particles of different sizes can be segregated by using ultrahigh centrifuge. X-ray diffraction studies confirm the presence of the cubic phase of iron. These iron nanoparticles were found to exhibit fluorescence in the visible region in contrast to the normal bulk material. The room temperature hysteresis measurements upto a field of 1.0 tesla were performed on a suspension of iron particles in the solution as well as in the powders obtained by filtration. The hysteresis loops indicate that the particles are superparamagnetic in nature. The saturation magnetizations was approximately 60 emu/gm. As these iron particles are very sensitive to oxygen a coating of non-magnetic iron oxide tends to form around the particles giving it a core-shell structure. The core particle size is estimated theoretically from the magnetization measurements. Suspensions of iron nanoparticles in water have been proposed to be used as an effective decontaminant for ground water.     

A novel route for the synthesis of indium nanoparticles in ionic liquid

In this paper, we report a novel preparation of indium nanoparticles by the reduction of indium chloride in ionic liquid by methanolic solution of NaBH₄. The particles are characterized by means of transmission electron microscopy (TEM), X-ray diffraction and UV-visible studies indicated that the powder consist of the cubic phase of indium. The particle size of indium nanoparticles is in the range of 20 nm mean diameter by Transmission electron microscopy (TEM). The samples display a strong surface plasma absorption band at 231 nm, which indicates that the sample is metal indium and the particle size is less than 20 nm. The thermal analysis of the sample indicate indium not indium oxide. Electrochemical studies show that indium nanoparticles have very good electrical properties.     

Formation of nanoparticles in flames; measurement by particle mass spectrometry and numerical simulation

The size distributions of nanoparticles in flames are measured using a novel particle mass spectrometer (PMS), which is developed for the size range between 0.3 and 50?nm and for number concentrations between 10(9) and 10(13). Using this instrument the particles are sampled without prior dilution from the flame into a molecular beam. The charged nanoparticles are then deflected by an electric field, to determine the mass according to the time-of-flight principle. The PMS is installed in a low pressure combustion chamber operated at 30?mbar. Measurements are made on primary soot particles and iron oxide particles in a laminar, premixed acetylene/oxygen flame. The soot particles increase in size as a function of the height above the burner and the C/O ratio from 2 up to 10?nm. Iron oxide particles of 3-5?nm are detected as a function of burner height. The soot particles form more rapidly than the iron oxide particles. A model calculation for the formation of silica and iron oxide in hydrogen/oxygen flames is developed, based on previously published reaction mechanisms. On adding a mono-disperse particle coagulation scheme, the time history of the particle number concentration and the particle size is calculated. In agreement with experimental data, the calculations show that iron oxide particles are formed more slowly than silica particles.     

Dumbbell-like bifunctional Au-Fe3O4 nanoparticles

Dumbbell-like Au-Fe(3)O(4) nanoparticles are synthesized using decomposition of Fe(CO)(5) on the surface of the Au nanoparticles followed by oxidation in 1-octadecene solvent. The size of the particles is tuned from 2 to 8 nm for Au and 4 nm to 20 nm for Fe(3)O(4). The particles show the characteristic surface plasmon absorption of Au and the magnetic properties of Fe(3)O(4) that are affected by the interactions between Au and Fe(3)O(4). The dumbbell is formed through epitaxial growth of iron oxide on the Au seeds, and the growth can be affected by the polarity of the solvent, as the use of diphenyl ether results in flower-like Au-Fe(3)O(4) nanoparticles.     

Tuning of catalytic CO oxidation by changing composition of Rh-Pt bimetallic nanoparticles

Recent breakthroughs in synthesis in nanoscience have achieved control of size and composition of nanoparticles that are relevant for catalyst design. Here, we show that the catalytic activity of CO oxidation by Rh/Pt bimetallic nanoparticles can be changed by varying the composition at a constant size (9+/-1 nm). Two-dimensional Rh/Pt bimetallic nanoparticle arrays were formed on a silicon surface via the Langmuir-Blodgett technique. Composition analysis with X-ray photoelectron spectroscopy agrees with the reaction stoichiometry of Rh/(Pt+Rh). CO oxidation rates that exhibit a 20-fold increase from pure Pt to pure Rh show a nonlinear increase with surface composition of the bimetallic nanoparticles that is consistent with the surface segregation of Pt. The results demonstrate the possibility of controlling catalytic activity in metal nanoparticle-oxide systems via tuning the composition of nanoparticles with potential applications for nanoscale design of industrial catalysts.