The employment of molecular tools with nucleic acid binding ability to specifically control crucial cellular functions represents an important scientific area at the border between biochemistry and pharmaceutical chemistry. In this review we describe several molecular systems of natural or artificial origin, which are able to bind polyriboadenylic acid (poly(rA)) both in its single-stranded or structured forms. Due to the fundamental role played by the poly(rA) tail in the maturation and stability of mRNA, as well as in the initiation of the translation process, compounds able to bind this RNA tract, influencing the mRNA fate, are of special interest for developing innovative biomedical strategies mainly in the field of anticancer therapy.
nucleopeptides; poly(rA) binders; RNA; self-structures
We present here the behavior of the resonance frequency of porous anodic alumina cantilever arrays during water vapor adsorption and emphasize their possible use in the micromechanical sensing of humidity levels at least in the range of 10–22%. The sensitivity of porous anodic aluminium oxide cantilevers (Δf/Δm) and the humidity sensitivity equal about 56 Hz/pg and about 100 Hz/%, respectively. The approach presented here for the design of anodic alumina cantilever arrays by the combination of anodic oxidation and photolithography enables easy control over porosity, surface area, geometric and mechanical characteristics of the cantilever arrays for micromechanical sensing.
anodic aluminium oxide; atomic force microscopy (AFM); cantilever arrays; humidity; mechanical sensor; porous alumina
Iron nanostructures grown by focused electron beam induced deposition (FEBID) are promising for applications in magnetic sensing, storage and logic. Such applications require a precise design and determination of the coercive field (H
C), which depends on the shape of the nanostructure. In the present work, we have used the Fe2(CO)9 precursor to grow iron nanowires by FEBID in the thickness range from 10 to 45 nm and width range from 50 to 500 nm. These nanowires exhibit an Fe content between 80 and 85%, thus giving a high ferromagnetic signal. Magneto-optical Kerr characterization indicates that H
C decreases for increasing thickness and width, providing a route to control the magnetization reversal field through the modification of the nanowire dimensions. Transmission electron microscopy experiments indicate that these wires have a bell-type shape with a surface oxide layer of about 5 nm. Such features are decisive in the actual value of H
C as micromagnetic simulations demonstrate. These results will help to make appropriate designs of magnetic nanowires grown by FEBID.
coercive field; focused electron beam induced deposition; iron nanowires; magnetization reversal; magneto-optical Kerr effect; transmission electron microscopy
Poly(lactic-co-glycolic acid) (PLGA) nanoparticles were studied as drug delivery vehicles for calcitriol, the active form of vitamin D3. In vitro effects of calcitriol encapsulated in PLGA nanoparticles were evaluated with respect to free calcitriol on human pancreatic cell lines, S2-013 and hTERT-HPNE, and the lung cancer cell line A549. Encapsulated calcitriol retained its biological activity, reducing the cell growth. Cytotoxicity assays demonstrated that encapsulation of calcitriol enhanced its inhibitory effect on cell growth at a concentration of 2.4 μM for the S2-013 cells (91%) and for A549 cells (70%) comparared to the free calcitriol results. At this concentration the inhibitory effect on nontumor cells (hTERT-HPNE) decreased to 65%. This study highlights the ability of PLGA nanoparticles to deliver vitamin D3 into cancer cells, with major effects regarding cancer cell cycle arrest and major changes in the cell morphological features.
1α,25-dihydroxyvitamin D3; calcitriol; cancer therapy; drug delivery; poly(lactic-co-glycolic acid)
Suspended nanowires (SNWs) have been deposited from Co–carbonyl precursor (Co2(CO)8) by focused electron beam induced deposition (FEBID). The SNWs dimensions are about 30–50 nm in diameter and 600–850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC) and hexagonal close-packed (HCP) Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM) analysis and by energy-dispersive X-ray (EDX) spectroscopy, respectively. Current (I)–voltage (V) measurements with current densities up to 107 A/cm2 determine different structural transitions in the SNWs, depending on the I–V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 107 A/cm2. The role played by resistive heating and electromigration in these transitions is discussed.
cobalt; electromigration; focused electron beam induced deposition (FEBID); metallic nanowires
Heterometal clusters containing Ru and Au, Co and/or Pt are anchored onto carbon nanotubes and nanofibers functionalized with chelating phosphine groups. The cluster anchoring yield is related to the amount of phosphine groups available on the nanocarbon surface. The ligands of the anchored molecular species are then removed by gentle thermal treatment in order to form nanoparticles. In the case of Au-containing clusters, removal of gold atoms from the clusters and agglomeration leads to a bimodal distribution of nanoparticles at the nanocarbon surface. In the case of Ru–Pt species, anchoring occurs without reorganization through a ligand exchange mechanism. After thermal treatment, ultrasmall (1–3 nm) bimetal Ru–Pt nanoparticles are formed on the surface of the nanocarbons. Characterization by high resolution transmission electron microscopy (HRTEM) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) confirms their bimetal nature on the nanoscale. The obtained bimetal nanoparticles supported on nanocarbon were tested as catalysts in ammonia synthesis and are shown to be active at low temperature and atmospheric pressure with very low Ru loading.
ammonia synthesis; cluster; nanofibers; nanoparticles; nanotubes
In this letter, we report a novel V-doped SrTiO3 photocatalyst synthesized via electrospinning followed by a thermal diffusion process at low temperature. The morphological and crystalline structural investigations reveal not only that the V-doped SrTiO3 photocatalyst possesses a uniform, porous, fibrous structure, but also that some V5+ ions are introduced into the SrTiO3 lattice. The photocatalytic capability of V-doped SrTiO3 porous nanofibers was evaluated through photodegrading methyl orange (MO) in aqueous solution under artificial UV–vis light. The results indicated that V-doped SrTiO3 porous nanofibers have excellent catalytic efficiency. Furthermore, the excellent catalytic activity was maintained even after five cycle tests, indicating that they have outstanding photocatalytic endurance. It is suggested that the excellent photocatalytic performance of doped SrTiO3 nanofibers is possibly attributed to the V5+ ion doping increasing the light utilization as well as to the outstanding porous features, the excellent component and structure stability.
electrospinning; photocatalysis; porous nanofibers; SrTiO3; thermal diffusion; vanadium-ion doping
Background: Multicomponent heterostructure nanowires and nanogaps are of great interest for applications in sensorics. Pulsed electrodeposition in ion-track etched polymer templates is a suitable method to synthesise segmented nanowires with segments consisting of two different types of materials. For a well-controlled synthesis process, detailed analysis of the deposition parameters and the size-distribution of the segmented wires is crucial.
Results: The fabrication of electrodeposited AuAg alloy nanowires and segmented Au-rich/Ag-rich/Au-rich nanowires with controlled composition and segment length in ion-track etched polymer templates was developed. Detailed analysis by cyclic voltammetry in ion-track membranes, energy-dispersive X-ray spectroscopy and scanning electron microscopy was performed to determine the dependency between the chosen potential and the segment composition. Additionally, we have dissolved the middle Ag-rich segments in order to create small nanogaps with controlled gap sizes. Annealing of the created structures allows us to influence their morphology.
Conclusion: AuAg alloy nanowires, segmented wires and nanogaps with controlled composition and size can be synthesised by electrodeposition in membranes, and are ideal model systems for investigation of surface plasmons.
AuAg alloy; cyclic voltammetry; electrodeposition; ion-track technology; nanogaps; segmented nanowires
Ni/Cu composite nanowires were synthesized in an aqueous solution for the first time. The synthetic process consisted of two steps. Firstly, pure nickel nanowires were prepared through chemical reduction in solution under a magnetic field. Secondly, copper was reduced on the surface of the nickel nanowires, during which Ni/Cu composite nanowires with an average length of 80 µm and diameter of about 200 nm were synthesized. The products were characterized by XRD, SEM and TEM. The method has notable advantages: It is template-free, inexpensive, easy-to-operate, and it only needs a short reaction time, which makes it suitable for large-scale preparation.
copper nanoparticles; nickel nanowires; Ni/Cu composite nanowires
The aim of the present overview article is to raise awareness of an essential aspect that is usually not accounted for in the modelling of electron transport for focused-electron-beam-induced deposition (FEBID) of nanostructures: Surface excitations are on the one hand responsible for a sizeable fraction of the intensity in reflection-electron-energy-loss spectra for primary electron energies of up to a few kiloelectronvolts and, on the other hand, they play a key role in the emission of secondary electrons from solids, regardless of the primary energy. In this overview work we present a general perspective of recent works on the subject of surface excitations and on low-energy electron transport, highlighting the most relevant aspects for the modelling of electron transport in FEBID simulations.
focused-electron-beam-induced deposition (FEBID); Monte Carlo simulation of electron transport; surface excitations; secondary-electron emission
Using benzenediamine and benzenedithiol molecular junctions as benchmarks, we investigate the widespread analysis of the quantum transport conductance in terms of the projected density of states (PDOS) onto molecular orbitals (MOs). We first consider two different methods for identifying the relevant MOs: (1) diagonalization of the Hamiltonian of the isolated molecule and (2) diagonalization of a submatrix of the junction Hamiltonian constructed by considering only basis elements localized on the molecule. We find that these two methods can lead to substantially different MOs and hence PDOS. Furthermore, within Method 1, the PDOS can differ depending on the isolated molecule chosen to represent the molecular junction (e.g., with or without dangling bonds); within Method 2, the PDOS depends on the chosen basis set. We show that these differences can be critical when the PDOS is used to provide a physical interpretation of the conductance (especially when its value is small, as it happens typically at zero bias). In this work, we propose a new approach in an attempt to reconcile the two traditional methods. Although some improvements were achieved, the main problems remain unsolved. Our results raise more general questions and doubts on a PDOS-based analysis of the conductance.
benzene-diamine; benzene-dithiol; DFT-Landauer; molecular electronics; nanoelectronics; quantum transport
Zinc-doped InP(Zn) colloidal quantum dots (QDs) with narrow size distribution and low defect concentration were grown for the first time via a novel phosphine synthetic route and over a wide range of Zn doping. We report the influence of Zn on the optical properties of the obtained quantum dots. We propose a mechanism for the introduction of Zn in the QDs and show that the incorporation of Zn atoms into the InP lattice leads to the formation of Zn acceptor levels and a luminescence tail in the red region of the spectra. Using photochemical etching with HF, we confirmed that the Zn dopant atoms are situated inside the InP nanoparticles. Moreover, doping with Zn is accompanied with the coverage of the QDs by a zinc shell. During the synthesis Zn myristate covers the QD nucleus and inhibits the particle growth. At the same time the zinc shell leads to an increase of the luminescence quantum yield through the reduction of phosphorous dangling bonds. A scenario for the growth of the colloidal InP(Zn) QDs was proposed and discussed.
core–shell nanoparticles; doped semiconductor nanocrystals; InP(Zn) quantum dots; luminescence; zinc
Background: Highly ordered three-dimensional colloidal crystals (supracrystals) comprised of 7.4 nm diameter Au nanocrystals (with a 5% size dispersion) have been imaged and analysed using a combination of scanning tunnelling microscopy and dynamic force microscopy.
Results: By exploring the evolution of both the force and tunnel current with respect to tip–sample separation, we arrive at the surprising finding that single nanocrystal resolution is readily obtained in tunnelling microscopy images acquired more than 1 nm into the repulsive (i.e., positive force) regime of the probe–nanocrystal interaction potential. Constant height force microscopy has been used to map tip–sample interactions in this regime, revealing inhomogeneities which arise from the convolution of the tip structure with the ligand distribution at the nanocrystal surface.
Conclusion: Our combined STM–AFM measurements show that the contrast mechanism underpinning high resolution imaging of nanoparticle supracrystals involves a form of nanoscale contact imaging, rather than the through-vacuum tunnelling which underpins traditional tunnelling microscopy and spectroscopy.
dynamic force microscopy; nanoparticle; non-contact atomic force microscopy; point contact imaging; scanning probe microscopy; supracrystal
We simulated and analyzed in detail the behavior of ultrashort optical pulses, which are typically used in telecommunications, propagating through graphene-based nanoribbon waveguides. In this work, we showed the changes that occur in the Gaussian and hyperbolic secant input pulses due to the attenuation, high-order dispersive effects and nonlinear effects. We concluded that it is possible to control the shape of the output pulses with the value of the input signal power and the chemical potential of the graphene nanoribbon. We believe that the obtained results will be highly relevant since they can be applied to other nanophotonic devices, for example, filters, modulators, antennas, switches and other devices.
graphene; nanophotonics; waveguide
Alloyed silver–gold nanoparticles were prepared in nine different metal compositions with silver/gold molar ratios of ranging from 90:10 to 10:90. The one-pot synthesis in aqueous medium can easily be modified to gain control over the final particle diameter and the stabilizing agents. The purification of the particles to remove synthesis by-products (which is an important factor for subsequent in vitro experiments) was carried out by multiple ultracentrifugation steps. Characterization by transmission electron microscopy (TEM), differential centrifugal sedimentation (DCS), dynamic light scattering (DLS), UV–vis spectroscopy and atomic absorption spectroscopy (AAS) showed spherical, monodisperse, colloidally stable silver–gold nanoparticles of ≈7 nm diameter with measured molar metal compositions very close to the theoretical values. The examination of the nanoparticle cytotoxicity towards HeLa cells and human mesenchymal stem cells (hMSCs) showed that the toxicity is not proportional to the silver content. Nanoparticles with a silver/gold molar composition of 80:20 showed the highest toxicity.
cytotoxicity; gold; nanoalloys; nanoparticles; silver
Polymer blend lithography (PBL) is a spin-coating-based technique that makes use of the purely lateral phase separation between two immiscible polymers to fabricate large area nanoscale patterns. In our earlier work (Huang et al. 2012), PBL was demonstrated for the fabrication of patterned self-assembled monolayers. Here, we report a new method based on the technique of polymer blend lithography that allows for the fabrication of metal island arrays or perforated metal films on the nanometer scale, the metal PBL. As the polymer blend system in this work, a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA), dissolved in methyl ethyl ketone (MEK) is used. This system forms a purely lateral structure on the substrate at controlled humidity, which means that PS droplets are formed in a PMMA matrix, whereby both phases have direct contact both to the substrate and to the air interface. Therefore, a subsequent selective dissolution of either the PS or PMMA component leaves behind a nanostructured film which can be used as a lithographic mask. We use this lithographic mask for the fabrication of metal patterns by thermal evaporation of the metal, followed by a lift-off process. As a consequence, the resulting metal nanostructure is an exact replica of the pattern of the selectively removed polymer (either a perforated metal film or metal islands). The minimum diameter of these holes or metal islands demonstrated here is about 50 nm. Au, Pd, Cu, Cr and Al templates were fabricated in this work by metal PBL. The wavelength-selective optical transmission spectra due to the localized surface plasmonic effect of the holes in perforated Al films were investigated and compared to the respective hole diameter histograms.
localized surface plasmonic resonance; metal islands; metal nanostructures; metal polymer blend lithography (metal PBL); nano-patterned template; nanoscale discs; optical transmission; perforated metal film; polymer phase separation; poly(methyl methacrylate) (PMMA); polystyrene (PS); self-assembly; spin-coating; surface plasmons
For practical application, optical limiting materials must exhibit a fast response and a low threshold in order to be used for the protection of the human eye and electro-optical sensors against intense light. Many nanomaterials have been found to exhibit optical limiting properties. Laser ablation offers the possibility of fabricating nanoparticles from a wide range of target materials. For practical use of these materials, their optical limiting performance, including optical limiting threshold and the ability to efficiently attenuate high intensity light, needs to be improved. In this paper, we fabricate nanoparticles of different metals by laser ablation in liquid. We study the optical nonlinear properties of the laser-generated nanoparticle dispersion. Silica microspheres are used to enhance the optical limiting performance of the nanoparticle dispersion. The change in the optical nonlinear properties of the laser-generated nanoparticle dispersion caused by silica microspheres is studied. It is found that the incident laser beam is locally focused by the microspheres, leading to an increased optical nonlinearity of the nanoparticle dispersion.
laser ablation; local field enhancement; microspheres; nanoparticles; optical limiting
A novel approach for the in situ synthesis of zerovalent aryl-coated iron nanoparticles (NPs) based on diazonium salt chemistry is proposed. Surface-modified zerovalent iron NPs (ZVI NPs) were prepared by simple chemical reduction of iron(III) chloride aqueous solution followed by in situ modification using water soluble arenediazonium tosylate. The resulting NPs, with average iron core diameter of 21 nm, were coated with a 10 nm thick organic layer to provide long-term protection in air for the highly reactive zerovalent iron core up to 180 °C. The surface-modified iron NPs possess a high grafting density of the aryl group on the NPs surface of 1.23 mmol/g. FTIR spectroscopy, XRD, HRTEM, TGA/DTA, and elemental analysis were performed in order to characterize the resulting material.
arenediazonium salts; chemical reduction; covalent modification; surface-modified nanoparticles; zerovalent iron nanoparticles
Tattooing has long been practised in various societies all around the world and is becoming increasingly common and widespread in the West. Tattoo ink suspensions unquestionably contain pigments composed of nanoparticles, i.e., particles of sub-100 nm dimensions. It is widely acknowledged that nanoparticles have higher levels of chemical activity than their larger particle equivalents. However, assessment of the toxicity of tattoo inks has been the subject of little research and ink manufacturers are not obliged to disclose the exact composition of their products. This study examines tattoo ink particles in two fundamental skin components at the nanometre level. We use atomic force microscopy and light microscopy to examine cryosections of tattooed skin, exploring the collagen fibril networks in the dermis that contain ink nanoparticles. Further, we culture fibroblasts in diluted tattoo ink to explore both the immediate impact of ink pigment on cell viability and also to observe the interaction between particles and the cells.
atomic force microscopy (AFM); dermis; nanoparticles; skin; tattoo ink
We demonstrate that thermoelectric properties of graphene nanoribbons can be dramatically improved by introducing nanopores. In monolayer graphene, this increases the electronic thermoelectric figure of merit ZT
e from 0.01 to 0.5. The largest values of ZT
e are found when a nanopore is introduced into bilayer graphene, such that the current flows from one layer to the other via the inner surface of the pore, for which values as high as ZT
e = 2.45 are obtained. All thermoelectric properties can be further enhanced by tuning the Fermi energy of the leads.
graphene nanoribbons; quantum transport; thermal conductance; thermoelectric figure of merit; thermopower
The first experiment showing the effects of specific interaction forces using lateral force microscopy (LFM) was demonstrated for lectin–carbohydrate interactions some years ago. Such measurements are possible under the assumption that specific forces strongly dominate over the non-specific ones. However, obtaining quantitative results requires the complex and tedious calibration of a torsional force. Here, a new and relatively simple method for the calibration of the torsional force is presented. The proposed calibration method is validated through the measurement of the interaction forces between human fibronectin and its monoclonal antibody. The results obtained using LFM and AFM-based classical force spectroscopies showed similar unbinding forces recorded at similar loading rates. Our studies verify that the proposed lateral force calibration method can be applied to study single molecule interactions.
fibronectin; lateral force microscopy; molecular recognition; torsional forces calibration
A custom-designed apparatus was used for the fine-tuned co-deposition of preformed Fe clusters into antiferromagnetic Cr matrices. Three series of samples with precisely defined cluster sizes, with accuracy to a few atoms, and controlled concentrations were fabricated, followed by a complete characterization of structure and magnetic performance. Relevant magnetic characteristics, reflecting the ferromagnetic/antiferromagnetic coupling between Fe clusters and the Cr matrix, i.e., blocking temperature, coercivity field, and exchange bias were measured and their dependence on cluster size and cluster concentration in the matrix was analyzed. It is evident that the blocking temperatures are clearly affected by both the cluster size and their concentration in the Cr matrix. In contrast the coercivity shows hardly any dependence on size or inter-cluster distance. The exchange bias was found to be strongly sensitive to the cluster size but not to the inter-cluster distances. Therefore, it was concluded to be an effect that is purely localized at the interfaces.
cluster; cluster deposition; exchange bias; matrix
Monolayer Langmuir–Blodgett (LB) films of 1,4-bis(pyridin-4-ylethynyl)benzene (1) together with the “STM touch-to-contact” method have been used to study the nature of metal–monolayer–metal junctions in which the pyridyl group provides the contact at both molecule–surface interfaces. Surface pressure vs area per molecule isotherms and Brewster angle microscopy images indicate that 1 forms true monolayers at the air–water interface. LB films of 1 were fabricated by deposition of the Langmuir films onto solid supports resulting in monolayers with surface coverage of 0.98 × 10−9 mol·cm−2. The morphology of the LB films that incorporate compound 1 was studied using atomic force microscopy (AFM). AFM images indicate the formation of homogeneous, monomolecular films at a surface pressure of transference of 16 mN·m−1. The UV–vis spectra of the Langmuir and LB films reveal that 1 forms two dimensional J-aggregates. Scanning tunneling microscopy (STM), in particular the “STM touch-to-contact” method, was used to determine the electrical properties of LB films of 1. From these STM studies symmetrical I–V curves were obtained. A junction conductance of 5.17 × 10−5
0 results from the analysis of the pseudolinear (ohmic) region of the I–V curves. This value is higher than that of the conductance values of LB films of phenylene-ethynylene derivatives contacted by amines, thiols, carboxylate, trimethylsilylethynyl or acetylide groups. In addition, the single molecule I–V curve of 1 determined using the I(s) method is in good agreement with the I–V curve obtained for the LB film, and both curves fit well with the Simmons model. Together, these results not only indicate that the mechanism of transport through these metal–molecule–metal junctions is non-resonant tunneling, but that lateral interactions between molecules within the LB film do not strongly influence the molecule conductance. The results presented here complement earlier studies of single molecule conductance of 1 using STM-BJ methods, and support the growing evidence that the pyridyl group is an efficient and effective anchoring group in sandwiched metal–monolayer–metal junctions prepared under a number of different conditions.
Langmuir–Blodgett films; molecular electronics; STM touch-to-contact method
The mechanisms that control the photophysics of composite films made of a semiconducting conjugated polymer (poly(paraphenylene vinylene), PPV) mixed with single-walled carbon nanotubes (SWNT) up to a concentration of 64 wt % are determined by using photoexcitation techniques and density functional theory. Charge separation is confirmed experimentally by rapid quenching of PPV photoluminescence and changes in photocurrent starting at relatively low concentrations of SWNT. Calculations predict strong electronic interaction between the polymer and the SWNT network when nanotubes are semiconducting.
composite; conjugated polymer; DFT calculations; energy transfer; photoconductivity; single wall carbon nanotubes; time-resolved photoluminescence
Reflection ion microscopy (RIM) is a technique that uses a low angle of incidence and scattered ions to form an image of the specimen surface. This paper reports on the development of the instrumentation and the analysis of the capabilities and limitations of the scanning RIM in a helium ion microscope (HIM). The reflected ions were detected by their “conversion” to secondary electrons on a platinum surface. An angle of incidence in the range 5–10° was used in the experimental setup. It was shown that the RIM image contrast was determined mostly by surface morphology but not by the atomic composition. A simple geometrical analysis of the reflection process was performed together with a Monte Carlo simulation of the angular dependence of the reflected ion yield. An interpretation of the RIM image formation and a quantification of the height of the surface steps were performed. The minimum detectable step height was found to be approximately 5 nm. RIM imaging of an insulator surface without the need for charge compensation was successfully demonstrated.
helium ion microscope; low-angle ion scattering; reflection microscopy; surface imaging; surface morphology