Magnetic, thermal and martensitic phase transitions in Ni-Co nanoparticles.

The nickel-cobalt system is an important alloy in nanotechnology because of its ferromagnetic properties, high thermal stability and shape memory effect. At the nanoscale, its physico-chemical properties become size-, shape- and composition- dependent. However, those properties are still mostly unknown at the nanoscale. Therefore, this manuscript fills this gap in knowledge. Indeed, when the size of the alloy is reduced, the entire phase diagram undergoes a vertical shift downward to lower temperatures, and a tilt caused by a larger size effect affecting cobalt than nickel. Among the most commonly observed shapes, the thermal stability of nickel-cobalt nanoparticles was determined as a function of their size and composition. Furthermore, the ferromagnetic-paramagnetic phase transition and martensitic transformation for those shapes were calculated as a function of the nickel-cobalt alloy composition. As expected, the ferromagnetic and martensitic regions shrunk at the nanoscale; but the martensitic transformation was less affected by size effects compared to magnetic and thermal (melting) transitions.

Bimetallic Pt-Pd nano-catalyst: size, shape and composition matter.

The goal of this work is to understand how the phase diagram (PHAD) of the platinum-palladium (Pt-Pd) alloy changes with size and shape and how it correlates with catalytic properties. By using nano-thermodynamics, the size and shape effects on the PHAD of Pt-Pd nanoparticles were determined theoretically. The PHAD of some nanoparticles (sphere, tetrahedron, octahedron, decahedron, cube, cuboctahedron and rhombic dodecahedron) exhibits a congruent melting point that becomes more and more pronounced when the size decreases. At the right of the congruent melting point i.e. close to the Pt-rich side, the coexistence region exhibits a contraction while an expansion is noticed at larger palladium concentrations. From the Gibbs free energy analysis, the stability of all the considered shapes has been determined versus temperature and composition. Furthermore, the surface segregation was also calculated and it is shown that the surface segregation is reversed at very small sizes. Indeed, below a critical size, Pd does not segregate anymore at the surface like it normally does for larger nanoparticles; but Pt does. The critical size range has been determined for each considered shape; and within this range Pt and Pd co-exist at the surface. Finally, the most catalytically active shapes are predicted to be the tetrahedron and the cube in agreement with the available experimental data and other theoretical results.

The Decmon: a new nanoparticle shape along the truncation path from the icosahedron to the decahedron.

The idea that shape and structure determines functionality is one of the leiv-motifs that drives research and applications on fields such as catalysis and plasmonics. The growth and stability of metallic clusters is extensively discussed through faceting and energy minimization mechanisms, respectively. Facet truncations on the regular Mackay-icosahedron (m-Ih) give rise to two sub-families exhibiting five-fold symmetry and external decahedral shape. Such successive truncations made to the regular m-Ih, led to a decahedral motif called 'Decmon' (Montejano's decahedron). This structure expose facets (111) and (100), that after a total energy minimization through molecular dynamics simulations using the embedded atom model, proved to be thermally stable. This result has been confirmed by using nano-thermodynamics. The surface energy competition between the (111) and (100) facets explains its stability at some given cluster sizes, and this truncation path permits to glimpse the potential energy surface in the growth path of nanoparticles from the decahedral (s-Dh) to icosahedral (m-Ih) structures.

Synthesis and Properties of the Self-Assembly of Gold-Copper Nanoparticles into Nanoribbons.

We report the efficient wet-chemical production of self-assembled gold-copper bimetallic nanoparticles (diameter of ∼2 nm) into two-dimensional flexible ribbonlike nanostructures. The direct observation of a layered arrangement of particles into nanoribbons was provided through high-resolution transmission electron microscopy and electron tomography. These nanoribbons showed photoluminesce and efficient photocatalytic activity for the conversion of 4-nitrophenol. The thermal stability of the nanoribbons was also measured by in situ heat treatment in the electron microscope, confirming that the self-assembled gold-copper nanoribbons efficiently supported up to 350 °C. The final morphology of the nanoparticles and their ability to self-assemble into flexible nanoribbons were dependent on concentration and the ratio of precursors. Therefore, these experimental factors were discussed. Remarkably, the presence of copper was found to be critical to triggering the self-assembly of nanoparticles into ordered layered structures. These results for the synthesis and stability of self-assemblies of metallic nanoparticles present a potential extension of the method to producing materials with catalytic applications.

Thermal stability and optical properties of Si-Ge nanoparticles.

Silicon-germanium is an important alloy mainly used in thermoelectricity and electronics. However, its thermal and optical properties still need further investigation at the nanoscale. That is why in this study, the size and shape effect on the silicon-germanium phase diagram is investigated through the nano-thermodynamics methodology. As expected, the phase diagram undergoes a shift down in temperature when the size decreases. However, it is demonstrated and explained why the size effect on the solidus-liquidus curves is much stronger than the one on the miscibility gap. Moreover, the shape effect is investigated for various faceted polyhedral nanoparticles as well as for the sphere. Phase maps are then provided as a function of the number of facets, at 4 and 10 nm, in order to determine the structure of the alloy. Furthermore, the size and shape effects on the energy bandgap are also studied. The energy bandgap increases when the size is reduced. The cube and tetrahedral shapes exhibit the largest size effect on the thermal and optical properties of the silicon-germanium alloy. Finally, this paper provides a useful roadmap for experimentalists willing to tune the properties of this alloy.

Inhibition of Candida albicans biofilm by pure selenium nanoparticles synthesized by pulsed laser ablation in liquids.

Selenoproteins play an important role in the human body by accomplishing essential biological functions like oxido-reductions, antioxidant defense, thyroid hormone metabolism and immune response; therefore, the possibility to synthesize selenium nanoparticles free of any contaminants is exciting for future nano-medical applications. This paper reports the first synthesis of selenium nanoparticles by femtosecond pulsed laser ablation in de-ionized water. Those pure nanoparticles have been successfully used to inhibit the formation of Candida albicans biofilms. Advanced electron microscopy images showed that selenium nanoparticles easily adhere on the biofilm, then penetrate into the pathogen, and consequently damage the cell structure by substituting with sulfur. 50% inhibition of Candida albicans biofilm was obtained at only 25 ppm. Finally, the two physical parameters proved to affect strongly the viability of Candida albicans are the crystallinity and particle size.

Helical Growth of Ultrathin Gold-Copper Nanowires.

In this work, we report the synthesis and detailed structural characterization of novel helical gold-copper nanowires. The nanowires possess the Boerdijk-Coxeter-Bernal structure, based on the pile up of octahedral, icosahedral, and/or decahedral seeds. They are self-assembled into a coiled manner as individual wires or into a parallel-ordering way as groups of wires. The helical nanowires are ultrathin with a diameter of less than 10 nm and variable length of several micrometers, presenting a high density of twin boundaries and stacking faults. To the best of our knowledge, such gold-copper nanowires have never been reported previously.

Gold-copper nano-alloy, "Tumbaga", in the era of nano: phase diagram and segregation.

Gold-copper (Au-Cu) phases were employed already by pre-Columbian civilizations, essentially in decorative arts, whereas nowadays, they emerge in nanotechnology as an important catalyst. The knowledge of the phase diagram is critical to understanding the performance of a material. However, experimental determination of nanophase diagrams is rare because calorimetry remains quite challenging at the nanoscale; theoretical investigations, therefore, are welcomed. Using nanothermodynamics, this paper presents the phase diagrams of various polyhedral nanoparticles (tetrahedron, cube, octahedron, decahedron, dodecahedron, rhombic dodecahedron, truncated octahedron, cuboctahedron, and icosahedron) at sizes 4 and 10 nm. One finds, for all the shapes investigated, that the congruent melting point of these nanoparticles is shifted with respect to both size and composition (copper enrichment). Segregation reveals a gold enrichment at the surface, leading to a kind of core-shell structure, reminiscent of the historical artifacts. Finally, the most stable structures were determined to be the dodecahedron, truncated octahedron, and icosahedron with a Cu-rich core/Au-rich surface. The results of the thermodynamic approach are compared and supported by molecular-dynamics simulations and by electron-microscopy (EDX) observations.

Synthesis of Ultrawide Band Gap TeO2 Nanoparticles by Pulsed Laser Ablation in Liquids: Top Ablation versus Bottom Ablation.

Ultrawide band gap (UWBG) semiconductors are the future components of electronic devices due to their large energy band gap (>3.2 eV). In this article, spherical TeO2 nanoparticles, with sizes around ∼39 ± 12 and ∼29 ± 6 nm, were successfully synthesized by irradiating a pure tellurium target, totally submerged in ethanol, using a "Top-ablation" or "Bottom-ablation" synthesis protocol, respectively. Mostly, α-TeO2 nanoparticles were created (>95%) with only a small amount of γ-TeO2 nanoparticles being produced (<5%). Both colloids exhibited a ζ-potential larger than |30 mV|, indicating a stable colloidal solution. The energy band gaps of the TeO2 nanoparticles synthesized by the Top-ablation and Bottom-ablation synthesis protocols were determined to be around 5.3 and 5.8 eV, respectively. Finally, TeO2 UWBG nanoparticles were successfully synthesized using either a Top-ablation or Bottom-ablation synthesis protocol. The main advantage of the Bottom-ablation synthesis protocol is its ability to obtain smaller nanoparticles compared to that of the Top-ablation synthesis protocol.

Synthesis of Antibacterial Copper Oxide Nanoparticles by Pulsed Laser Ablation in Liquids: Potential Application against Foodborne Pathogens.

Spherical copper oxide nanoparticles (CuO/Cu2O NPs) were synthesized by pulsed laser ablation in liquids (PLAL). The copper target was totally submerged in deionized (DI) water and irradiated by an infrared laser beam at 1064 nm for 30 min. The NPs were then characterized by dynamic light scattering (DLS) and atomic emission spectroscopy (AES) to determine their size distribution and concentration, respectively. The phases of copper oxide were identified by Raman spectroscopy. Then, the antibacterial activity of CuO/Cu2O NPs against foodborne pathogens, such as Salmonella enterica subsp. enterica serotype Typhimurium DT7, Escherichia coli O157:H7, Shigella sonnei ATCC 9290, Yersinia enterocolitica ATCC 27729, Vibrio parahaemolyticus ATCC 49398, Bacillus cereus ATCC 11778, and Listeria monocytogenes EGD, was tested. At a 3 ppm concentration, the CuO/Cu2O NPs exhibited an outstanding antimicrobial effect by killing most bacteria after 5 h incubation at 25 °C. Field emission scanning electron microscope (FESEM) confirmed that the CuO/Cu2O NPs destructed the bacterial cell wall.

Anticancer and antibacterial properties of carbon nanotubes are governed by their functional groups.

Due to their high strength, low weight, and biologically-inspired dimensions, carbon nanotubes have found wide interest across all of medicine. In this study, four types of highly dispersible multi-walled carbon nanotubes (CNTs) of similar dimensions, but slightly different chemical compositions, were compared with an unmodified material to verify the impact their surface chemistry has on cytocompatibility, anticancer, inflammation, and antibacterial properties. Minute changes in the chemical composition were found to greatly affect the biological performance of the CNTs. Specifically, the CNTs with a large number of carbon atoms with a +2 coordination number induced cytotoxicity in macrophages and melanoma cells, and had a moderate antibacterial effect against Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria strains, all while being cytocompatible towards human dermal fibroblasts. Moreover, substituting some of the OH groups with ammonia diminished their cytotoxicity towards macrophages while still maintaining the aforementioned positive qualities. At the same time, CNTs with a large number of carbon atoms with a +3 coordination number had a high innate cytocompatibility towards normal healthy cells but were toxic towards cancer cells and bacteria. The latter was further boosted by reacting the CNTs' carboxyl groups with ammonia. Although requiring further analyses, the results of this study, thus, introduce new CNTs that without drugs can treat cancer, inflammation, and/or infection while still remaining cytocompatible with mammalian cells.

Synthesis of "Naked" TeO2 Nanoparticles for Biomedical Applications.

Chalcogenide nanoparticles have become a very active field of research for their optoelectronic and biological properties. This article shows the production of tellurium dioxide nanoparticles (TeO2 NPs) by pulsed laser ablation in liquids. The produced nanoparticles were spherical with a diameter of around 70 nm. The energy band gap of those nanoparticles was determined to be around 5.2 eV. Moreover, TeO2 NPs displayed a dose-dependent antibacterial effect against antibiotic-resistant bacteria such as multidrug-resistant Escherichia coli (MDR E. coli) and methicillin-resistant Staphylococcus aureus (MR S. aureus). The "naked" nature of the nanoparticle surface helped to eradicate the antibiotic-resistant bacteria at a very low concentration, with IC50 values of ∼4.3 ± 0.9 and 3.7 ± 0.2 ppm for MDR E. coli and MR S. aureus, respectively, after just 8 h of culture. Further, the IC50 values of the naked TeO2 NPs against melanoma (skin cancer) and healthy fibroblasts were 1.6 ± 0.7 and 5.5 ± 0.2 ppm, respectively, for up to 72 h. Finally, to understand these optimal antibacterial and anticancer properties of the TeO2 NPs, the reactive oxygen species generated by the nanoparticles were measured. In summary, the present in vitro results demonstrate much promise for the presently prepared TeO2 NPs and they should be studied for a wide range of safe antibacterial and anticancer applications.

Physico-chemical properties of selenium-tellurium alloys across the scales.

Selenium and tellurium are both energy critical elements as defined by the American Physical Society and the Materials Research Society. When mixed together, both elements form an alloy. The size- and shape-dependent thermal and optical properties of this alloy are investigated in this manuscript by using nano-thermodynamics and machine learning techniques. This alloy is found to have particularly interesting properties for solar cell applications.

Tunable Cytotoxicity and Selectivity of Phosphonium Ionic Liquid with Aniline Blue Dye.

Ionic liquids are an interesting class of materials that have recently been utilized as chemotherapeutic agents in cancer therapy. Aniline blue, a commonly used biological staining agent, was used as a counter ion to trihexyltetradecylphosphonium, a known cytotoxic cation. A facile, single step ion exchange reaction was performed to synthesize a fluorescent ionic liquid, trihexyltetradecylphosphonium aniline blue. Aqueous nanoparticles of this hydrophobic ionic liquid were prepared using reprecipitationmethod. The newly synthesized ionic liquid and subsequent nanoparticles were characterized using various spectroscopic techniques. Transmission electron microscopy and zeta potential measurements were performed to characterize the nanoparticles' morphology and surface charge. The photophysical properties of the nanoparticles and the parent aniline blue compound were studied using absorption and fluorescence spectroscopy. Cell viability studies were conducted to investigate the cytotoxicity of the newly developed trihexyltetradecylphosphonium aniline blue nanoparticles in human breast epithelial cancer cell line (MCF-7) and its corresponding normal epithelial cell line (MCF-10A) in vitro. The results revealed that the synthesized ionic nanomedicines were more cytotoxic (lower IC50) than the parent chemotherapeutic compound in MCF-7 cells. Nanoparticles of the synthesized ionic liquid were also shown to be more stable in both aqueous and cellular media and more selective than parent compounds towards cancer cells.

Synthesis of naked vanadium pentoxide nanoparticles.

Vanadium pentoxide is the most important vanadium compound by being the precursor to most vanadium alloys. It also plays an essential role in the production of sulfuric acid as well as in metal-ion batteries and supercapacitors. In this paper, pulsed laser ablation in liquids is used to synthesize "naked" vanadium pentoxide nanostructures. The resulting particles take up "nearly-spherical" and "flower-like" morphologies, composed of α-V2O5 and ß-V2O5 crystalline phases. Even "naked", the nanostructures are stable in time with a zeta potential of -51 ± 7 mV. In order to maximize the production of vanadium pentoxide nanostructure, the optimal repetition rate was determined to be @ ∼6600 Hz when irradiating a pure vanadium target in DI-water. This corresponds to a cavitation bubble lifetime of around ∼0.15 ms. At that repetition rate, the production reached ∼10 ppm per minute of irradiation. Finally, from the characterization of the α-V2O5 and ß-V2O5 nanostructures, the surface energy of each phase has been carefully determined at 0.308 and 1.483 J cm-2, respectively. Consequently, the ß-phase was found to display a surface energy very close to platinum. The exciton Bohr radius has been determined at 3.5 ± 0.7 nm and 2.0 ± 0.6 nm for α-V2O5 and ß-V2O5 phases, respectively.

Substitutional-interstitial structural transition in Cu-Pt nano-alloys.

Copper-platinum alloys are important binary alloys in catalysis. In this communication, we demonstrate that it is possible to preserve the thermal properties of platinum with a copper-platinum alloy by converting the substitutional alloy into an interstitial one. This conversion occurs when the size of the copper-platinum system is reduced down to the nanoscale. The size-dependent phase diagram of Cu-Pt for a spherical nanoparticle is calculated at various sizes (50, 10 and 5 nm) demonstrating that Cu-Pt alloyed nanoparticles can be formed all over the composition range. Experimentally, the electron microscopy characterization of copper-platinum alloyed nanoparticles synthesized by wet chemistry supports the predicted structural transition.

Green nanomedicine: the path to the next generation of nanomaterials for diagnosing brain tumors and therapeutics?

Introduction: Current brain cancer treatments, based on radiotherapy and chemotherapy, are sometimes successful, but they are not free of drawbacks.Areas covered: Traditional methods for the treatment of brain tumors are discussed here with new solutions presented, among which the application of nanotechnology has demonstrated promising results over the past decade. The traditional synthesis of nanostructures, which relies on the use of physicochemical methodologies are discussed, and their associated concerns in terms of environmental and health impact due to the production of toxic by-products, need for toxic catalysts, and their lack of biocompatibility are presented. An overview of the current situation for treating brain tumors using nanotechnological-based approaches is introduced, and some of the latest advances in the application of green nanomaterials (NMs) for the effective targeting of brain tumors are presented.Expert opinion: Green nanotechnology is introduced as a potential solution to toxic NMs through the application of environmentally friendly and cost-effective protocols using living organisms and biomolecules. The current status of this field, such as those involving clinical trials, is included, and the possible limitations of green-NMs and potential ways to avoid those limitations are discussed so that the field can potentially evolve.

Tuning the Surface Plasmon Resonance of Gold Dumbbell Nanorods.

Gold has always fascinated humans, occupying an important functional and symbolic role in civilization. In earlier times, gold was predominantly used in jewelry; today, this noble metal's surface properties are taken advantage of in catalysis and plasmonics. In this article, the plasmon resonance of gold dumbbell nanorods is investigated. This unusual morphology was obtained by a seed-mediated growth method. The concentration of chemical precursors such as cetyltrimethylammonium bromide and silver nitrate plays a significant role in controlling the shape of the nanorods. Indeed, the aspect ratio of dumbbell nanostructures was varied from 2.6 to 4. UV-visible absorption spectra revealed a shift of the longitudinal surface plasmon resonance peak from 669 to 789 nm. Having the plasmon resonance in the near infrared region helps to use those nanostructures as photothermal agents.

Electric-Field-Induced Phase Change in Copper Oxide Nanostructures.

Transition-metal oxides such as cupric and cuprous oxides are strongly correlated materials made of earth-abundant chemical elements displaying energy band gaps of around 1.2 and 2.1 eV. The ability to design nanostructures of cupric and cuprous oxide semiconductors with in situ phase change and morphological transition will benefit several applications including photovoltaic energy conversion and photoelectrochemical water splitting. Here, we have developed a physicochemical route to synthesize copper oxide nanostructures, enabling the phase change of cupric oxide into cuprous oxide using an electric field of 105 V/m in deionized water via a new synthetic design protocol called electric-field-assisted pulsed laser ablation in liquids (EFA-PLAL). The morphology of the nanostructures can also be tuned from a sphere of ∼20 nm to an elongated leaf of ∼3 µm by controlling the intensity of the applied electric field. Futuristically, the materials chemistry occurring during the EFA-PLAL synthesis protocol developed here can be leveraged to design various strongly correlated nanomaterials and heterostructures of other 3d transition-metal oxides.

Improved Photophysical Properties of Ionic Material-Based Combination Chemo/PDT Nanomedicine.

Herein, a cost-effective and prompt approach to develop ionic material-based combination nanodrugs for cancer therapy is presented. A chemotherapeutic (phosphonium) cation and photodynamic therapeutic (porphyrin) anion are combined using a single step ion exchange reaction. Afterward, a nanomedicine is prepared from this ionic materials-based combination drug using a simplistic strategy of reprecipitation. Improved photophysical characteristics such as a slower nonradiative rate constant, an enhanced phosphorescence emission, a longer lifetime, and a bathochromic shift in absorbance spectra of porphyrin are observed in the presence of a chemotherapeutic countercation. The photodynamic therapeutic activity of nanomedicines is investigated by measuring the singlet oxygen quantum yield using two probes. As compared to the parent porphyrin compound, the synthesized combination material showed a 2-fold increase in the reactive oxygen species quantum yield, due to inhibition of face-to-face aggregation of porphyrin units in the presence of bulky chemotherapeutic ions. The dark cytotoxicity of combination therapy nanomedicines in the MCF-7 (cancerous breast) cell line is also increased as compared to their corresponding parent compounds in vitro. This is due to the high cellular uptake of the combination nanomedicines as compared to that of the free drug. Further, selective toxicity toward cancer cells was acquired by functionalizing nanomedicine with folic acid followed by incubation with MCF-7 and MCF-10A (noncancerous breast). Light toxicity experiments indicate that the synthesized ionic nanomedicine shows a greater cell death than either parent drug due to the improved photophysical properties and effective combination effect. This facile and economical strategy can easily be utilized in the future to develop many other combination ionic nanomedicines with improved photodynamics.