Nanoparticles alloying in liquids: Laser-ablation-generated Ag or Pd nanoparticles and laser irradiation-induced AgPd nanoparticle alloying

International audienceLaser irradiation of a mixture of single element micro/nanomaterials may lead to their alloying and fabrication of multielement structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere which forms the basis of the field of additive manufacturing technology another interesting problem is the laser induced alloying of a mixture of single element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed nanoparticles colloidal solutions. In this work Ag and Pd bare, surface ligand-free nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials separately in water, the two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser induced nanoparticles alloying in liquid. Nanoparticles alloying and formation of AgPd alloyed nanoparticles takes place with the decrease of the intensity of the surface plasmon resonance peak of the Ag nanoparticles (at ~405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for times even as long as 30 mins. The alloyed nanoparticles have lattice constants with values between those of the pure metals which indicates that they consist of Ag and Pd in approximately 1:1 ratio similar to the atomic composition of the starting mixed nanoparticles solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles which remain as single elements even after the end of the irradiation, joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time also a typical characteristic of AgPd alloyed nanoparticles

Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage

The technique of laser ablation in liquids (LAL) has already demonstrated its flexibility and capability for the synthesis of a large variety of surfactant-free nanomaterials with a high purity. However, high purity can cause trouble for nanomaterial synthesis, because active high-purity particles can spontaneously grow into different nanocrystals, which makes it difficult to accurately tailor the size and shape of the synthesized nanomaterials. Therefore, a series of questions arise with regards to whether particle growth occurs during colloid storage, how large the particle size increases to, and into which shape the particles evolve. To obtain answers to these questions, here, Ag particles that are synthesized by femtosecond (fs) laser ablation of Ag in acetone are used as precursors to witness the spontaneous growth behavior of the LAL-generated surfactant-free Ag dots (2–10 nm) into different polygonal particles (5–50 nm), and the spontaneous size separation phenomenon by the carbon-encapsulation induced precipitation of large particles, after six months of colloid storage. The colloids obtained by LAL at a higher power (600 mW) possess a greater ability and higher efficiency to yield colloids with sizes of <40 nm than the colloids obtained at lower power (300 mW), because of the generation of a larger amount of carbon ‘captors’ by the decomposition of acetone and the stronger particle fragmentation. Both the size increase and the shape alteration lead to a redshift of the surface plasmon resonance (SPR) band of the Ag colloid from 404 nm to 414 nm, after storage. The Fourier transform infrared spectroscopy (FTIR) analysis shows that the Ag particles are conjugated with COO– and OH– groups, both of which may lead to the growth of polygonal particles. The CO and CO2 molecules are adsorbed on the particle surfaces to form Ag(CO)x and Ag(CO2)x complexes. Complementary nanosecond LAL experiments confirmed that the particle growth was inherent to LAL in acetone, and independent of pulse duration, although some differences in the final particle sizes were observed. The nanosecond-LAL yields monomodal colloids, whereas the size-separated, initially bimodal colloids from the fs-LAL provide a higher fraction of very small particles that are <5 nm. The spontaneous growth of the LAL-generated metallic particles presented in this work should arouse the special attention of academia, especially regarding the detailed discussion on how long the colloids can be preserved for particle characterization and applications, without causing a mismatch between the colloid properties and their performance. The spontaneous size separation phenomenon may help researchers to realize a more reproducible synthesis for small metallic colloids, without concern for the generation of large particles

Anti-biofilm properties of laser-synthesized, ultrapure silver–gold-alloy nanoparticles against Staphylococcus aureus

Abstract Staphylococcus aureus biofilm-associated infections are a common complication in modern medicine. Due to inherent resilience of biofilms to antibiotics and the rising number of antibiotic-resistant bacterial strains, new treatment options are required. For this purpose, ultrapure, spherical silver–gold-alloy nanoparticles with homogenous elemental distribution were synthesized by laser ablation in liquids and analyzed for their antibacterial activity on different stages of S. aureus biofilm formation as well as for different viability parameters. First, the effect of nanoparticles against planktonic bacteria was tested with metabolic activity measurements. Next, nanoparticles were incubated with differently matured S. aureus biofilms, which were then analyzed by metabolic activity measurements and three dimensional live/dead fluorescent staining to determine biofilm volume and membrane integrity. It could be shown that AgAu NPs exhibit antibacterial properties against planktonic bacteria but also against early-stage and even mature biofilms, with a complete diffusion through the biofilm matrix. Furthermore, AgAu NPs primarily targeted metabolic activity, to a smaller extend membrane integrity, but not the biofilm volume. Additional molecular analyses using qRT-PCR confirmed the influence on different metabolic pathways, like glycolysis, stress response and biofilm formation. As this shows clear similarities to the mechanism of pure silver ions, the results strengthen silver ions to be the major antibacterial agent of the synthesized nanoparticles. In summary, the results of this study provide initial evidence of promising anti-biofilm characteristics of silver–gold-alloy nanoparticles and support the importance of further translation-oriented analyses in the future

Current state of laser synthesis of metal and alloy nanoparticles as ligand-free reference materials for nano-toxicological assays

Due to the abundance of nanomaterials in medical devices and everyday products, toxicological effects related to nanoparticles released from these materials, e.g., by mechanical wear, are a growing matter of concern. Unfortunately, appropriate nanoparticles required for systematic toxicological evaluation of these materials are still lacking. Here, the ubiquitous presence of surface ligands, remaining from chemical synthesis are a major drawback as these organic residues may cause cross-contaminations in toxicological studies. Nanoparticles synthesized by pulsed laser ablation in liquid are a promising alternative as this synthesis route provides totally ligand-free nanoparticles. The first part of this article reviews recent methods that allow the size control of laser-fabricated nanoparticles, focusing on laser post irradiation, delayed bioconjugation and in situ size quenching by low salinity electrolytes. Subsequent or parallel applications of these methods enable precise tuning of the particle diameters in a regime from 4–400 nm without utilization of any artificial surface ligands. The second paragraph of this article highlights the recent progress concerning the synthesis of composition controlled alloy nanoparticles by laser ablation in liquids. Here, binary and ternary alloy nanoparticles with totally homogeneous elemental distribution could be fabricated and the composition of these particles closely resembled bulk implant material. Finally, the model AuAg was used to systematically evaluate composition related toxicological effects of alloy nanoparticles. Here Ag+ ion release is identified as the most probable mechanism of toxicity when recent toxicological studies with gametes, mammalian cells and bacteria are considered

Laser-based ion doping is a suitable alternative to dope biologically active ions into colloidal bioglass nanoparticles

Bioactive glass nanoparticles (nBGs) have demonstrated promising properties for bone regeneration due to their bone-binding ability. Incorporating multiple ions into nBGs can improve their bioactivity and provide them with additional functionalities aiding bone repair. However, incorporating multiple ions into nBGs combining different functionalities is still challenging as the additional ions often interfere with the nanoparticle properties. To overcome these challenges, here we report the use of pulsed laser doping and co-doping techniques as an alternative method for ion incorporation into colloidal nBGs. We demonstrate the simultaneous laser-induced incorporation of iron (Fe), strontium (Sr), and/or copper (Cu) ions into nBGs from simple salt solutions without altering the particles' morphology. Furthermore, laser-doped nBGs were biocompatible and could significantly increase alkaline phosphatase (ALP) production in human mesenchymal stromal cells (hMSC). Moreover, laser-co-doped nBGs containing Fe and Sr ions significantly increased vessel formation by human umbilical vein endothelial cells (HUVEC). Therefore, pulsed laser doping in liquids was shown to be a versatile technique to incorporate multiple ions into nBGs and allow systematic studies on cooperative effects of dopants in active biomaterials

Effects of Silver Nitrate and Silver Nanoparticles on a Planktonic Community: General Trends after Short-Term Exposure

<div><p>Among metal pollutants silver ions are one of the most toxic forms, and have thus been assigned to the highest toxicity class. Its toxicity to a wide range of microorganisms combined with its low toxicity to humans lead to the development of a wealth of silver-based products in many bactericidal applications accounting to more than 1000 nano-technology-based consumer products. Accordingly, silver is a widely distributed metal in the environment originating from its different forms of application as metal, salt and nanoparticle. A realistic assessment of silver nanoparticle toxicity in natural waters is, however, problematic and needs to be linked to experimental approaches. Here we apply metatranscriptome sequencing allowing for elucidating reactions of whole communities present in a water sample to stressors. We compared the toxicity of ionic silver and ligand-free silver nanoparticles by short term exposure on a natural community of aquatic microorganisms. We analyzed the effects of the treatments on metabolic pathways and species composition on the eukaryote metatranscriptome level in order to describe immediate molecular responses of organisms using a community approach. We found significant differences between the samples treated with 5 µg/L AgNO₃ compared to the controls, but no significant differences in the samples treated with AgNP compared to the control samples. Statistical analysis yielded 126 genes (KO-IDs) with significant differential expression with a false discovery rate (FDR) <0.05 between the control (KO) and AgNO₃ (NO3) groups. A KEGG pathway enrichment analysis showed significant results with a FDR below 0.05 for pathways related to photosynthesis. Our study therefore supports the view that ionic silver rather than silver nanoparticles are responsible for silver toxicity. Nevertheless, our results highlight the strength of metatranscriptome approaches for assessing metal toxicity on aquatic communities.</p></div

a) Absorption spectrum and b) size distribution data from analytical disc centrifugation of laser-generated silver nanoparticles with an exemplary TEM micrograph (insert).

<p>a) Absorption spectrum and b) size distribution data from analytical disc centrifugation of laser-generated silver nanoparticles with an exemplary TEM micrograph (insert).</p

Correspondence analysis of normalized count matrix.

<p>Location of samples (RAW, KO, NP, NO3), each in three replicates (−1, −2, −3) is shown after correspondence analysis on the first two principal axes (A: axes CA1, CA2) and on the second and third principal axis (B: axes CA2, CA3). Roughly, the first two axes cluster according to replicate group, while the second and third axes cluster according to treatment.</p