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Noble metal nanoparticles are efficient converters of light into heat but typically cover a limited spectral range or have intense light scattering, resulting in unsuited for broadband thermoplasmonic applications and sunlight-driven heat generation. Here, Au-Ag alloy nanoparticles were deliberately molded with an irregular nanocoral (NC) shape to obtain broadband plasmon absorption from the visible to the near-infrared yet at a lower cost compared to pure Au nanostructures. The Au-Ag NCs are produced through a green and scalable methodology that relies on pulsed laser fragmentation in a liquid, without chemicals or capping molecules, leaving the particles surface free for conjugation with thiolated molecules and enabling full processability and easy inclusion in various matrixes. Numerical calculations showed that panchromism, i.e., the occurrence of a broadband absorption from the visible to the near-infrared region, is due to the special morphology of Au-Ag alloy NCs and consists of a purely absorptive behavior superior to monometallic Au or Ag NCs. The thermoplasmonic properties were assessed by multiwavelength light-to-heat conversion experiments and exploited for the realization of a cellulose-based solar-steam generation device with low-cost, simple design but competitive performances. Overall, here it is shown how laser light can be used to harvest solar light. Besides, the optimized broadband plasmon absorption, the green synthetic procedure, and the other set of positive features for thermoplasmonic applications of Au-Ag NCs will contribute to the development of environmentally friendly devices of practical utility in a sustainable world.

In the large field of bioactive peptides, peptaibols represent a unique class of compounds. They are membrane-active peptides, produced by fungi of the genus Trichoderma and known to elicit plant defenses. Among the short-length peptaibols, trichogin GA IV is nonhemolytic, proteolysis-resistant, antibacterial, and cytotoxic. Several trichogin analogs are endowed with potent activity against phytopathogens, thus representing a sustainable alternative to copper for plant protection. In this work, we tested the activity of trichogin analogs against a breast cancer cell line and a normal cell line of the same derivation. Lys-containing trichogins showed an IC50 below 12 µM, a peptide concentration not significantly affecting the viability of normal cells. Two analogs were found to be membrane-active but noncytotoxic. They were anchored to gold nanoparticles (GNPs) and further investigated for their ability to act as targeting agents. GNP uptake by cancer cells increased with peptide decoration, while it decreased in the corresponding normal epithelial cells. This work highlights the promising biological properties of peptaibol analogs in the field of cancer therapy either as cytotoxic molecules or as active targeting agents in drug delivery.

Metastable alloy nanoparticles are investigated for their variety of appealing properties exploitable for photonics, magnetism, catalysis and nanobiotechnology. Notably, nanophases out of thermodynamic equilibrium feature a complex "ultrastructure" leading to a dynamic evolution of composition and atomic arrangement in response to physical-chemical stimuli. In this manuscript, metastable Au-Fe alloy nanoparticles were produced by laser ablation in liquid, an emerging versatile synthetic approach for freezing multielement nanosystems in non-equilibrium conditions. The Au-Fe nanoalloys were characterized through electron microscopy, elemental analysis, X-ray diffraction and Mössbauer spectroscopy. The dynamics of the structure of the Au-Fe system was tracked at high temperature under vacuum and atmospheric conditions, evidencing the intrinsic transformative nature of the metastable nanoalloy produced by laser ablation in liquid. This dynamic structure is relevant to possible application in several fields, from photocatalysis to nanomedicine, as demonstrated through an experiment of magnetic resonance imaging in biological fluids.

Bimetallic nanoparticles allow new and synergistic properties compared to the monometallic equivalents, often leading to unexpected results. Here we present on silver-iron nanoparticles coated with polyethylene glycol, which exhibit a high transverse relaxivity (316 ± 13 mM-1s−1, > 3 times that of the most common clinical benchmark based on iron oxide), excellent colloidal stability and biocompatibility in vivo. Ag-Fe nanoparticles are obtained through a one-step, low-cost laser-assisted synthesis, which makes surface functionalization with the desired biomolecules very easy. Besides, Ag-Fe nanoparticles show biodegradation over a few months, as indicated by incubation in the physiological environment. This is crucial for nanomaterials removal from the living organism and, in fact, in vivo biodistribution studies evidenced that Ag-Fe nanoparticles tend to be cleared from liver over a period in which the benchmark iron oxide contrast agent persisted. Therefore, the Ag-Fe NPs offer positive prospects for solving the problems of biopersistence, contrast efficiency, difficulties of synthesis and surface functionalization usually encountered in nanoparticulate contrast agents.

Despite the traditional plasmonic materials are counted on one hand, there are a lot of possible combinations leading to alloys with other elements of the periodic table, in particular those renowned for magnetic or catalytic properties. It is not a surprise, therefore, that nanoalloys are considered for their ability to open new perspectives in the panorama of plasmonics, representing a leading research sector nowadays. This is demonstrated by a long list of studies describing multiple applications of nanoalloys in photonics, photocatalysis, sensing and magneto-optics, where plasmons are combined with other physical and chemical phenomena. In some remarkable cases, the amplification of the conventional properties and even new effects emerged. However, this field is still in its infancy and several challenges must be overcome, starting with the synthesis (control of composition, crystalline order, size, processability, achievement of metastable phases and disordered compounds) as well as the modelling of the structure and properties (accuracy of results, reliability of structural predictions, description of disordered phases, evolution over time) of nanoalloys. To foster the research on plasmonic nanoalloys, here we provide an overview of the most recent results and developments in the field, organized according to synthetic strategies, modelling approaches, dominant properties and reported applications. Considering the several plasmonic nanoalloys under development as well as the large number of those still awaiting synthesis, modelling, properties assessment and technological exploitation, we expect a great impact on the forthcoming solutions for sustainability, ultrasensitive and accurate detection, information processing and many other fields.

The binding of glucosamine to gold in water solutions of glucosamine hydrochloride mixed with clean colloidal gold nanoparticles obtained by laser ablation in liquid was studied using surface-enhanced Raman scattering (SERS), dynamic light scattering (DLS) and UV–VIS spectroscopy. The purpose of this study was to establish whether the binding of charged aminogroup to gold nanoparticles (AuNPs) is taking place, and if it does, how can it be identified by means of SERS. The average size of dried gold nanoparticles was (20 ± 4) nm determined by averaging the sizes observed in transmission electron microscopy micrographs, which is smaller than the average size of gold nanoparticles in water solution as determined by DLS: (52 ± 2) nm. Upon adding the glucosamine solutions to gold colloid, average hydrodynamic diameter of ions was slightly larger for 0.1 mM glucosamine solution (55 ± 2 nm), while it increased to (105 ± 22) nm in the case of 1 mM solution, and was (398 ± 54) nm when 10 mM glucosamine solution was added. Most prominent Raman bands observed both for 0.1 mM and 1 mM glucosamine solutions were located at 1165 cm−1, 1532 and 1586 cm−1 and assigned to C-N coupled with C-C stretching, and C-NH3+ deformation angles bending. In SERS spectrum of 1 mM GlcN+ solution, two strong bands at 999 and 1075 cm−1 were found and attributed to C-Oring stretching coupled with C-NH3+ bending (999 cm−1) and to dominantly C-O stretching vibration. The differences in SERS spectra are attributed to different number of glucosamine molecules that attach to gold nanoparticles and their orientation with respect to the metal particle surface, partly due to presence of beta anomers protonated at anomeric oxygen position. The assignment of glucosamine bands was further corroborated by comparison with vibrational spectra of alpha and beta glucose and of polycrystalline powder of glucosamine hydrochloride. For all three substances comprehensive calculation of vibrational density of states was conducted using density functional theory. Benchmark bands for polycrystalline glucose anomers distinction are 846 and 915 cm−1 for alpha glucose, and 902 cm−1 for beta glucose. However, the bands observed in SERS spectra of 0.1 mM glucosamine solution at 831, 899, and 946 cm−1 or in 1 mM solution at 934 cm−1 cannot be easily identified as belonging either to alpha or beta glucosamine anomer, due to complexity of atomic motions involved. The identification of vibrational bands associated with –CNH3+ group will aid SERS studies on amino acids, especially in cases when several atomic groups could possibly bind to AuNPs.

Decades of antibiotic use and misuse have generated selective pressure toward the rise of antibiotic-resistant bacteria, which now contaminate our environment and pose a major threat to humanity. According to the evolutionary "Red queen theory", developing new antimicrobial technologies is both urgent and mandatory. While new antibiotics and antibacterial technologies have been developed, most fail to penetrate the biofilm that protects bacteria against external antimicrobial attacks. Hence, new antimicrobial formulations should combine toxicity for bacteria, biofilm permeation ability, biofilm deterioration capability, and tolerability by the organism without renouncing compatibility with a sustainable, low-cost, and scalable production route as well as an acceptable ecological impact after the ineluctable release of the antibacterial compound in the environment. Here, we report on the use of silver nanoparticles (NPs) doped with magnetic elements (Co and Fe) that allow standard silver antibacterial agents to perforate bacterial biofilms through magnetophoretic migration upon the application of an external magnetic field. The method has been proved to be effective in opening micrometric channels and reducing the thicknesses of models of biofilms containing bacteria such as

Vincenzo Amendola is Professor of Physical Chemistry at Padova University, where he established and directs the Laser-Assisted Synthesis and Plasmonics (LASP) lab. He obtained a PhD in Materials Science and Engineering in 2008 and the Italian qualification as Full Professor in 2017, after research experience at Massachusetts Institute of Technology and Cambridge University. He is part of the Program Committee of the ANGEL conference series and he is a current member of the ChemPhysChem Editorial Advisory Board.

Nonequilibrium nanoalloys are metastable solids obtained at the nanoscale under nonequilibrium conditions that allow the study of kinetically frozen atoms and the discovery of new physical and chemical properties. However, the stabilization of metastable phases in the nanometric size regime is challenging and the synthetic route should be easy and sustainable, for the nonequilibrium nanoalloys to be practically available. Here we report on the one-step laser ablation synthesis in solution (LASiS) of nonequilibrium Au-Co alloy nanoparticles (NPs) and their characterization on ensembles and at the single nanoparticle level. The NPs are obtained as a polycrystalline solid solution stable in air and water, although surface cobalt atoms undergo oxidation to Co(II). Since gold is a renowned plasmonic material and metallic cobalt is ferromagnetic at room temperature, these properties are both found in the NPs. Besides, surface conjugation with thiolated molecules is possible and it was exploited to obtain colloidally stable solutions in water. Taking advantage of these features, an array of magnetic-plasmonic dots was obtained and used for surface-enhanced Raman scattering experiments. Overall, this study confirms that LASiS is an effective method for the formation of kinetically stable nonequilibrium nanoalloys and shows that Au-Co alloy NPs are appealing magnetically responsive plasmonic building blocks for several nanotechnological applications.

Appealing physical and chemical properties are foreseen in nanoparticles containing immiscible elements, despite their synthesis is challenging due to the unfavorable thermodynamics. Here we show that silver nanoparticles doped with Co can be achieved by a facile one-step route relying on laser ablation in liquid. Structural analysis suggests that the bimetallic nanoparticles consist of a matrix of face-centred cubic Ag rich of cobalt as point defects or dislocations, in a structure that is stable over time even in aqueous solution. This happens despite the complete immiscibility of the two metals at any temperature in the solid and liquid phase, as confirmed also by density functional theory calculations. The nonequilibrium Co-Ag nanoparticles benefit of silver features such as the plasmonic response and the easy surface chemistry with thiolated ligands, combined with the magnetic properties of cobalt. Importantly, plasmonics and magnetism are not quenched after mixing, contrary to what was observed in other bimetallic systems like the Au-Fe one. This opens the way to several technologically relevant applications and, as a proof of concept, we demonstrate magnetophoretic assembly of Co-Ag nanoparticles into arrays of plasmonic dots exploitable for surface-enhanced Raman spectroscopy.

The combination of multiple functions in a single nanoparticle (NP) represents a key advantage of nanomedicine compared to traditional medical approaches. This is well represented by radiotherapy in which the dose of ionizing radiation should be calibrated on sensitizers biodistribution. Ideally, this is possible when the drug acts both as radiation enhancer and imaging contrast agent. Here, an easy, one-step, laser-assisted synthetic procedure is used to generate iron-boron (Fe-B) NPs featuring the set of functions required to assist neutron capture therapy (NCT) with magnetic resonance imaging. The Fe-B NPs exceed by three orders of magnitude the payload of boron isotopes contained in clinical sensitizers. The Fe-B NPs have magnetic properties of interest also for magnetophoretic accumulation in tissues and magnetic hyperthermia to assist drug permeation in tissues. Besides, Fe-B NPs are biocompatible and undergo slow degradation in the lysosomal environment that facilitates in vivo clearance through the liver-spleen-kidneys pathway. Overall, the Fe-B NPs represent a new promising tool for future exploitation in magnetic resonance imaging-guided boron NCT at higher levels of efficacy and tolerability.

Several examples of nanosized therapeutic and imaging agents have been proposed to date, yet for most of them there is a low chance of clinical translation due to long-term in vivo retention and toxicity risks. The realization of nanoagents that can be removed from the body after use remains thus a great challenge. Here, we demonstrate that nonequilibrium gold–iron alloys behave as shape-morphing nanocrystals with the properties of self-degradable multifunctional nanomedicines. DFT calculations combined with mixing enthalpy-weighted alloying simulations predict that Au–Fe solid solutions can exhibit self-degradation in an aqueous environment if the Fe content exceeds a threshold that depends upon element topology in the nanocrystals. Exploiting a laser-assisted synthesis route, we experimentally confirm that nonequilibrium Au–Fe nanoalloys have a 4D behavior, that is, the ability to change shape, size, and structure over time, becoming ultrasmall Au-rich nanocrystals. In vivo tests show the potential of these transformable Au–Fe nanoalloys as efficient multimodal contrast agents for magnetic resonance imaging and computed X-ray absorption tomography and further demonstrate their self-degradation over time, with a significant reduction of long-term accumulation in the body, when compared to benchmark gold or iron oxide contrast agents. Hence, Au–Fe alloy nanoparticles exhibiting 4D behavior can respond to the need for safe and degradable inorganic multifunctional nanomedicines required in clinical translation., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Instituto de Física La Plata

Although oxide nanoparticles are ubiquitous in science and technology, a multitude of compositions, phases, structures, and doping levels exist, each one requiring a variety of conditions for their synthesis and modification. Besides, experimental procedures are frequently dominated by high temperatures or pressures and by chemical contaminants or waste. In recent years, laser synthesis of colloids emerged as a versatile approach to access a library of clean oxide nanoparticles relying on only four main strategies running at room temperature and ambient pressure: laser ablation in liquid, laser fragmentation in liquid, laser melting in liquid and laser defect‐engineering in liquid. Here, established laser‐based methodologies are reviewed through the presentation of a panorama of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non‐equilibrium compounds, metal‐oxide core–shells and other anisotropic morphologies. So far, these materials showed several useful properties that are discussed with special emphasis on catalytic, biomedical and optical application. Yet, given the endless number of mixed compounds accessible by the laser‐assisted methodologies, there is still a lot of room to expand the library of nano‐crystals and to refine the control over products as well as to improve the understanding of the whole process of nanoparticle formation. To that end, this review aims to identify the perspectives and unique opportunities of laser‐based synthesis and processing of colloids for future studies of oxide nanomaterial‐oriented sciences., Laser‐assisted synthesis of colloids emerged as a versatile approach to access a library of oxide nanoparticles and related nanostructures at room temperature and ambient pressure. This review provides a critical presentation of laser‐based methodologies, of the various oxide nanoparticles achieved so far, and of their applications in catalysis, optics, biotechnology and further emerging fields.

Homogeneous sandwich immunofluorimetric assays are valued for the rapid, low-cost and accurate detection of analytes in liquid phase. However, their exploitation with analytes covering a wide range of concentrations is limited by low sensitivity and the hook effect. Here, we describe a homogeneous immunofluorimetric system based on the quenching of fluorescence in a Forster resonance energy transfer (FRET) donor/acceptor couple of antibody functionalized with two different dyes, respectively fluorescein (donor) and eosin (acceptor), which form a sandwich multi-component assembly with antibody-functionalized gold nanoparticles (GNPs) in the presence of the analyte. The resulting cooperative fluorescence quenching is assisted by the GNPs scaffold through the nanomaterial-surface energy transfer (NSET) effect, which gives an extended linear response versus the antigen concentration that is not possible with the bi-component assays. This immunofluorimetric method allows accurate, reproducible and immediate detection of C-reactive protein (CRP) in the wide concentration range of clinical interest (over two orders of magnitude from 3.5 to 455 nM, 0.4-52 mg/L), without the hook effect. Moreover, the method does not require sample treatment or washing steps. The concept of this multi-component FRET/NSET fluorescence quenching system can be extended to any analyte amenable to the detection with homogeneous sandwich assays.

According to Norskov d-band theory, the PtxY alloy was predicted to be among the most active catalysts for the oxygen reduction reaction (ORR). To achieve the high surface area needed in proton exchange membrane fuel cells, this alloy must be synthesized as a nanophase in a scalable fashion. However, the synthesis of PtxY nanoparticles cannot be accomplished with the common chemical methods due to the high oxophilicity of yttrium. Here we present the successful preparation of PtxY nanoparticles in one step by laser ablation in liquid of a Pt3Y target. The formation of PtxY nanoparticles was confirmed by TEM, XRD and XPS analyses. The ORR activity was evaluated in 0.1 M HClO4 revealing superior mass activity (483 A g−1) and specific activity (0.562 mA cm−2) to a Pt/C TKK standard.

Traditionally, the synthesis of nanomaterials in the ultra-small size regime (1–3 nm diameter) has been linked with the employment of excessive amounts of hazardous chemicals, inevitably leading to significant environmentally detrimental effects. In the current work, we demonstrate the potential of laser fragmentation in liquids (LFL) to produce highly pure and stable iron ultra-small nanoparticles. This is carried out by reducing the size of carbonyl iron microparticles dispersed in various polar solvents (water, ethanol, ethylene glycol, polyethylene glycol 400) and liquid nitrogen. The explored method enables the fabrication of ligand-free iron oxide ultra-small nanoparticles with diameter in the 1–3 nm range, a tight size distribution, and excellent hydrodynamic stability (zeta potential > 50 mV). The generated particles can be found in different forms, including separated ultra-small NPs, ultra-small NPs forming agglomerates, and ultra-small NPs together with zero-valent iron, iron carbide, or iron oxide NPs embedded in matrices, depending on the employed solvent and their dipolar moment. The LFL technique, aside from avoiding chemical waste generation, does not require any additional chemical agent, other than the precursor microparticles immersed in the corresponding solvent. In contrast to their widely exploited chemically synthesized counterparts, the lack of additives and chemical residuals may be of fundamental interest in sectors requiring colloidal stability and the largest possible number of chemically active sites, making the presented pathway a promising alternative for the clean design of new-generation nanomaterials. © 2020 by the authors. Licensee MDPI, Basel, Switzerland., Internal Grant at the Institute for Nanomaterials, Advanced Technologies and Innovation of the Technical University of Liberec [8106]; Ministry of Education, Youth and Sports in the Czech Republic under the Research Infrastructures NanoEnviCz [LM2018124]; European Structural and Investment Funds [CZ.02.1.01/0.0/0.0/16_019/0000843]; project DKRVO by the Ministry of Education, Youth and Sports of the Czech Republic [RP/CPS/2020/006]; Visegrad International Scholarship Grant [52011086], Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT: CZ.02.1.01/0.0/0.0/16_019/0000843, LM2018124, RP/CPS/2020/006; Technická Univerzita v Liberci: 8106

Oxygen evolution reaction (OER) is the most critical step in water splitting, still limiting the development of efficient alkaline water electrolyzers. Here we investigate the OER activity of Au–Fe nanoalloys obtained by laser-ablation synthesis in solution. This method allows a high amount of iron (up to 11 at %) to be incorporated into the gold lattice, which is not possible in Au–Fe alloys synthesized by other routes, due to thermodynamic constraints. The Au0.89Fe0.11 nanoalloys exhibit strongly enhanced OER in comparison to the individual pure metal nanoparticles, lowering the onset of OER and increasing up to 20 times the current density in alkaline aqueous solutions. Such a remarkable electrocatalytic activity is associated to nanoalloying, as demonstrated by comparative examples with physical mixtures of gold and iron nanoparticles. These results open attractive scenarios to the use of kinetically stable nanoalloys for catalysis and energy conversion.

Laser ablation in liquids (LAL) emerged as a powerful technique for the synthesis of multielement nanoparticles (NPs) such as metal alloys with thermodynamically forbidden composition. Consequently, there is a great interest in expanding the current knowledge about NPs formation during LAL, in order to improve the control on product structure and to extend the range of compositions accessible by this technique. Here we performed a systematic investigation on alloy NPs formation by nanosecond LAL of Au/Fe/glass multilayers with different thickness and order of deposition. The experiments were carried out in ethanol and water, which have, respectively, favourable and unfavourable effects on alloy formation. Results were analyzed with optical absorption spectroscopy, transmission electron microscopy and Mie theory for simple and core-shell spheres. Since alloy NPs were obtained in all cases, our findings provide the evidence that the two metals are mixed during particles formation. Besides, our results suggest that the probability of interaction between ablated matter and solution species is higher for the topmost layer of the target, i.e. the one closer to the solid/liquid interface. This provides useful insight for the synthesis of nanoalloys with new compositions, that are of interest in several fields, from catalysis to photonics and nanomedicine.

The relationship between composition and plasmonic properties in noble metal nanoalloys is still largely unexplored. Yet, nanoalloys of noble metals, such as gold, with transition elements, such as iron, have unique properties and a number of potential applications, ranging from nanomedicine to magneto-plasmonics and plasmon-enhanced catalysis. Here, we investigate the localized surface plasmon resonance at the level of the single Au-Fe nanoparticle by applying a strategy that combines experimental measurements using near field electron energy loss spectroscopy with theoretical studies via a full wave numerical analysis and density functional theory calculations of electronic structure. We show that, as the iron fraction increases, the plasmon resonance is blue-shifted and significantly damped, as a consequence of the changes in the electronic band structure of the alloy. This allows the identification of three relevant phenomena to be considered in the design and realization of any plasmonic nanoalloy, specifically: the appearance of new states around the Fermi level; the change in the free electron density of the metal; and the blue shift of interband transitions. Overall, this study provides new opportunities for the control of the optical response in Au-Fe and other plasmonic nanoalloys, which are useful for the realization of magneto-plasmonic devices for molecular sensing, thermo-plasmonics, bioimaging, photocatalysis, and the amplification of spectroscopic signals by local field enhancement.

Nanoparticles find applications in multiple technological and scientific fields, and laser ablation in liquid (LAL) emerged as a versatile method for providing colloidal solutions of nanomaterials with various composition, by a low cost, simple, self-standing, and “green” procedure. However, the use of high energy and high power laser beams is harmful, especially when coupled with flammable or toxic liquids, and in situ operation is required for starting, monitoring the LAL synthesis, and stopping it at the desired point. Here we describe the hardware and software design and the test results of a system for the production of nanoparticles by laser ablation synthesis in liquid solution (LASiS), which is remotely controllable with a personal computer or a smartphone. In this system, laser energy and solution flux are selectable, and the synthesis status can be monitored and managed at any time off site. Only commercially available components and software are employed, making the whole apparatus easily reproducible in any LAL laboratory. The system has proven its reliability in various conditions, including intercontinental remote control experiments. Overall, this apparatus represents a step forward to improve the safety and to more efficiently exploit the time of people working with LASiS, thus contributing to the increasing demand for off-site real time monitoring of experimental equipment in many scientific and industrial laboratories, due to safety and efficiency requirements. Fil: Crivellaro, Simone. Università di Padova; Italia Fil: Guadagnini, Andrea. Università di Padova; Italia Fil: Muñetón Arboleda, David. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; Argentina Fil: Schinca, Daniel Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; Argentina Fil: Amendola, Vincenzo. Università di Padova; Italia

Plasmonic nanostructures are intensively studied for their ability to create electromagnetic hot spots, where a great variety of optical and spectroscopic processes can be amplified. Understanding how to control the formation of hot spots in a dynamic and reversible way is crucial to further expand the panorama of plasmon enhanced phenomena. In this work, we investigate the ability to modulate the hot spots in magnetic–plasmonic iron-doped silver nanoparticles dispersed in aqueous solution, by applying an external magnetic field. Evidence of magnetic field induction of hot spots was achieved by measuring the amplification of surface enhanced Raman scattering (SERS) from analytes dispersed in the solution containing Ag–Fe NPs. A polymeric shell was introduced around Ag–Fe NPs to confer colloidal stability, and it was found that the length and density of the polymer chains have a significant influence on SERS performance, and therefore on the formation of electromagnetic hot spots, under the action of the external magnetic field. These findings are expected to provide an important contribution to understanding the growing field of tuneable electromagnetic enhancement by external stimuli, such as magnetic fields applied to magnetic–plasmonic nanoparticles.

Multielement nanocrystals made of noble metals and transition metals are at the focus of theoretical and experimental studies for their promising performances in several key electrochemical processes of the renewable energies landscape. However, the preparation of bimetallic nanocrystals often requires expensive and tedious procedures, sometimes resulting in nanocrystals contaminated at their surface by synthesis byproducts. In this paper we describe the synthesis of Pd3Y alloy nanoparticles (NPs) by a robust laser assisted method in pure organic solvents and their performances as electrocatalysts for oxygen reduction reaction (ORR). The electrochemical properties of Pd3Y NPs for ORR, investigated in acid and alkaline electrolytes, exhibited higher activity than standard Pd/C or Pt/C systems, in terms of half wave potential, mass activity and specific activity, in agreement with the predictions of the Norskov d-band center model for Pd alloys. The effect of ClO4− and Cl− anions was also investigated revealing a surprising poisoning effect of both anions for the Pd3Y alloys. Overall, laser generated Pd3Y alloy NPs emerged as highly active nanosystems for ORR, opening the way to the realization of other nanoalloys of potential interest in the perspective of Pt replacement by the same synthetic route.

Directing the assembly of atoms into core–shell particles generally requires elegant but sophisticated procedures. Here we show how the thermodynamic driving force to minimization of surface and interface energy can be exploited to produce colloidal Fe–Au core–shell nanoparticles in one step and with a yield approaching 99.7% in mass. This is obtained by laser ablation with nanosecond pulses of thin bimetallic films immersed in acetone. The Fe–Au core–shell nanoparticles show magnetic and plasmonic properties, and a surface available to bioconjugation and analytical assays. This laser assisted synthetic method represents a step forward in the facile preparation of core–shell nanospheres with multiple appealing functionalities.

Precisely positioning functionalized gold nanoparticles assemblies at planar donor-acceptor interfaces results in 14-fold enhancement of power conversion efficiency in P3HT/PCBM organic solar cells on plastic (ITO/PET) substrates. This result has been achieved by employing naphthalenethiol-capped gold nanoparticles (NT-Au-NPs) produced by laser ablation in liquid and size varied in the 10-30 nm range. Upon surface functionalization with the aromatic thiol, these particles self-assemble in submicrometer aggregates, which give increased light scattering. When these aggregates are deposited in the planar heterojunction between the donor and the acceptor systems, the localized scattering leads to a larger exciton formation just in the region of interest for charge transfer. (Graph Presented).

Laser ablation of solid targets in liquid environment allows the generation of nanoparticles (NPs) with several useful properties such as high purity, easily functionalizable surface, metastable composition, or complex structure, including doped nanocrystals, core–shells, hollow microspheres, nanotruffles, or nanocrescents. However, the mechanisms of NPs formation is still not well understood, and challenges remain in size control and productivity. Here, we investigate how the asymmetry intrinsic of laser-matter interaction can influence the structure and yield of gold NPs produced with nanosecond pulses. In particular, we confined the geometry of the laser ablation configuration in three ways: by reducing the thickness of the solid target from bulk size to a few tens of nanometers, by reducing the size of the laser spot on the solid target, and finally, by reducing the lateral size of the bulk target. The interpretation of results was supported with numerical simulations of heat distribution inside the m...

Laser ablation in liquid (LAL) emerged as a versatile technique for the synthesis of nanoparticles with various structures and compositions, although the control over products remains challenging in most cases. For instance, it is still difficult to drive the size of metal oxide crystalline domains down to the level of few atom clusters with LAL. Here we demonstrate that laser ablation of a bulk iron target in aqueous solution of phosphonates gives phosphonate-grafted iron oxo-clusters polymerized into nanoaggregates with Fe: ligand ratio of 2:1, instead of the usual nanocrystalline iron oxides. We attribute this result to the strong ability of phosphonate groups to bind iron oxide clusters and prevent their further growth into crystalline iron oxide. These laser generated poly-oxo-clusters are biocompatible and trackable by magnetic resonance imaging, providing interesting features for use in biological environments, such as nano-vehicles for iron administration. Besides, this method is promising for the generation of atom-scale metal-oxide clusters, which are ubiquitary in chemistry and of interest in biochemistry, catalysis, molecular magnetism and materials science. (C) 2018 Elsevier Inc. All rights reserved.

Alloy nanoparticles are characterized by the combination of multiple interesting properties, which are attractive for technological and scientific purposes. A frontier topic of this field is nanoalloys with compositions not thermodynamically allowed at ordinary temperature and pressure (i.e. metastable), because they require out-of-equilibrium synthetic approaches. Recently, laser ablation synthesis in solution (LASiS) was successfully applied for the realization of metastable nanoalloys because of the fast kinetics of nanoparticle formation. However, the role played by the chemical environment on the final composition and structure of laser generated nanoalloys still has to be fully elucidated. Here, we investigated the influence of different synthetic conditions on the LASiS of metastable nanoalloys composed of Au and Fe, such as the use of water instead of ethanol, the bubbling of inert gases and the addition of a few vol% of H2O2 and H2O. The two elements showed different reactivity when LASiS was performed in water instead of ethanol, while minor effects were observed from bubbling pure gases such as N2, Ar and CO2 in the liquid solution. Moreover, the plasmonic response and the structure of the nanoalloys were sensibly modified by adding H2O2 to water. We also found that nanoparticle production is dramatically influenced just by adding 0.2% of H2O in ethanol. These results suggest that the formation of a cavitation bubble with long lifetime and large size during LASiS is useful for the preservation of the metastable alloy composition, whereas an oxidative environment hampers the formation of metastable alloy nanoparticles. Overall, by acting on the type of solvent and solutes, we were able to switch from a traditional synthetic approach for the composition of Au-Fe nanoalloys to one using a reactive environment, which gives unconventional structures such as metal@iron-oxide nanoshells and nanocrescents of oxide supported on metal nanospheres. These results expand the knowledge about the mechanism of the formation of nanoalloys using LASiS and show how to obtain multielement nanoparticles of enormous interest for nanomedicine, plasmonics, magneto-plasmonics and catalysis.

The widespread application of surface-enhanced Raman scattering (SERS) would benefit from simple and scalable self-assembly procedures for the realization of plasmonic arrays with a high density of electromagnetic hot-spots. To this aim, the exploitation of iron-doped silver nanoparticles (NPs) synthesized by laser ablation of a bulk bimetallic iron–silver target immersed in ethanol is described. The use of laser ablation in liquid is key to achieving bimetallic NPs in one step with a clean surface available for functionalization with the desired thiolated molecules. These iron–silver NPs show SERS performances, a ready response to external magnetic fields and complete flexibility in surface coating. All these characteristics were used for the magnetic assembly of plasmonic arrays which served as SERS substrates for the identification of molecules of analytical interest. The magnetic assembly of NPs allowed a 28-fold increase in the SERS signal of analytes compared to not-assembled NPs. The versatility of substrate preparation and the SERS performances were investigated as a function of NPs surface coating among different thiolated ligands. These results show a simple procedure to obtain magnetically assembled regenerable plasmonic arrays for repeated SERS investigation of different samples, and it can be of inspiration for the realization of other self-assembled and reconfigurable magnetic–plasmonic devices. Fil: Scaramuzza, Stefano. Università di Padova; Italia Fil: Badocco, Denis. Università di Padova; Italia Fil: Pastore, Paolo. Università di Padova; Italia Fil: Coral, Diego Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Fernández van Raap, Marcela Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Amendola, Vincenzo. Università di Padova; Italia

Nanoparticles of hybrid organic-inorganic perovskites have attracted a great deal of attention due to their variety of optoelectronic properties, their low cost, and their easier integration into devices with complex geometry, compared with microcrystalline, thin-film, or bulk metal halides. Here we present a novel one-step synthesis of organolead bromide perovskite nanocrystals based on pulsed-laser irradiation in a liquid environment (PLIL). Starting from a bulk CH3 NH3 PbBr3 crystal, our PLIL procedure does not involve the use of high-boiling-point polar solvents or templating agents, and runs at room temperature. The resulting nanoparticles are characterized by high crystallinity and are completely free of any microscopic product or organic coating layer. We also demonstrate the straightforward inclusion of laser-generated perovskite nanocrystals in a polymeric matrix to form a nanocomposite with single- and two-photon luminescence properties.

Nanoclusters with plasmonic and magnetic properties are obtained with naked gold (AuNP) and iron oxide nanoparticles (FeOxNP) separately synthesized by laser ablation in water and simply assembled by using their opposite surface charges. Controlling the amount of AuNP and FeOxNP, we obtained nanoclusters with both good surface-enhanced resonance Raman scattering (SERRS) signals and superparamagnetic properties. Nanoclusters are incubated with murine macrophage cells which, after mixing with other macrophages, can be magnetically guided in solution by sorting them in less than 10 min. SERRS signals, observed at the single cell level, were recorded for the sorted macrophages, showing that the nanoclusters are active also in a biological environment and allow the identification of the incubated macrophage cells.

Laser ablation synthesis in liquid solution (LASiS) is a "green" technique that gives access to the preparation of a library of nanomaterials. Bare noble metal spherical particles, multiphase core-shell oxides, metal-semiconductor heterostructures, layered organometallic compounds and other complex nanostructures can be obtained with the same experimental set up, just by varying a few synthetic parameters. How to govern such versatility is one of the current challenges of LASiS and requires a thorough understanding of the physical and chemical processes involved in the synthesis. In this perspective, the fundamental mechanisms of laser ablation in liquids are summarized, organized according to their temporal sequence and correlated with relevant examples taken from the library of nanomaterials disclosed by LASiS, in order to show how synthesis parameters influence the composition and the structure of products. The resulting framework suggests that, to date, much attention has been devoted to the physical aspects of laser-matter interaction and to the characterization of the final products of the synthesis. Conversely, the clarification of chemical processes active during LASiS deserves more research efforts and requires the synergy among multiple investigation techniques.

Many advanced industrial and biomedical applications that use silver nanoparticles (AgNPs), require that particles are not only nano-sized, but also well dispersed, not aggregated and not agglomerated. This study presents two methods able to give rapidly sizes of monodispersed AgNPs suspensions in the dimensional range of 20-100nm. The first method, based on the application of Mie's theory, determines the particle sizes from the values of the surface plasmon resonance wavelength (SPRMAX), read from the optical absorption spectra, recorded between 190nm and 800nm. The computed sizes were compared with those determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) and resulted in agreement with the nominal values in a range between 13% (for 20nm NPs) and 1% (for 100nm NPs), The second method is based on the masterly combination of the Sedimentation Field Flow Fractionation (SdFFF - now sold as Centrifugal FFF-CFFF) and the Optical Absorption Spectroscopy (OAS) techniques to accomplish sizes and quantitative particle size distributions for monodispersed, non-aggregated AgNPs suspensions. The SdFFF separation abilities, well exploited to size NPs, greatly benefits from the application of Mie's theory to the UV-vis signal elaboration, producing quantitative mass-based particle size distributions, from which trusted number-sized particle size distributions can be derived. The silver mass distributions were verified and supported by detecting off-line the Ag concentration with the graphite furnace atomic absorption spectrometry (GF-AAS).

The integration of silver and gold nanoparticles with graphene is frequently sought for the realization of hybrid materials with superior optical, photoelectric and photocatalytic performances. A crucial aspect for these applications is how the surface plasmon resonance of metal nanoparticles is modified after assembly with graphene. Here, we used the discrete dipole approximation method to study the surface plasmon resonance of silver and gold nanoparticles in the proximity of a graphene flake or embedded in graphene structures. Surface plasmon resonance modifications were investigated for various shapes of metal nanoparticles and for different morphologies of the nanoparticle–graphene nanohybrids, in a step-by-step approach. Calculations show that the surface plasmon resonance of Ag nanoparticles is quenched in nanohybrids, whereas either surface plasmon quenching or enhancement can be obtained with Au nanoparticles, depending on the configuration adopted. However, graphene effects on the surface plasmon resonance are rapidly lost already at a distance of the order of 5 nm. These results provide useful indications for characterization and monitoring the synthesis of hybrid nanostructures, as well as for the development of hybrid metal nanoparticle/graphene nanomaterials with desired optical properties.