Controlling stability, complexity and optical response of reversibly reconfigurable plasmonic nanocrystal superlattices is of critical importance for emergent optoelectronic technologies and can be achieved by engineering the chemical nature of the ligand shell. In this work, we experimentally explore how the design of surface ligands with semifluorinated alkyl chains impacts dynamic self-assembly of nanoparticles. A series of three promesogenic thiols was synthesized and grafted onto plasmonic nanocrystals via ligand exchange reaction. In all cases, after solvent evaporation, we obtained reversibly reconfigurable, thermally responsive assemblies. We examined these nanomaterials using a variety of techniques such as transmission electron microscopy, UV−vis, and small-angle X-ray scattering. We show that the number of aromatic rings and the length of the fluorinated chain strongly affects symmetry and reconfiguration temperatures of the assemblies. For an optimized material we show that it is possible to achieve relatively quick switching between 3 distinct longrange ordered phases, including nonclose packed structures. Using numerical simulations, we confirm that observed plasmonic response of the material comes from the reconfiguration process. Uniquely, we confirm durability of the material in a 400 cycle switching experiment. Overall, these results guide our understanding of influence chemistry of the ligands on reversible reconfiguration of nanocrystal superlattices.

PurposeWe studied the effects of silver nanoparticles (AgNPs) on human blood platelet function. We hypothesized that AgNPs, a known antimicrobial agent, can be used as blood-compatible, “ideal material’’ in medical devices or as a drug delivery system. Therefore, the aim of the current study was to investigate if functionalized AgNPs affect platelet function and platelets as well as endothelial cell viability in vitro.Methods AgNPs, functionalized with reduced glutathione (GSH), polyethylene glycol (PEG) and lipoic acid (LA) were synthesized. Quartz crystal microbalance with dissipation was used to measure the effect of AgNPs on platelet aggregation. Platelet aggregation was measured by changes in frequency and dissipation, and the presence of platelets on the sensor surface was confirmed and imaged by phase contrast microscopy. Flow cytometry was used to detect surface abundance of platelet receptors. Lactate dehydrogenase test was used to assess the potential cytotoxicity of AgNPs on human blood platelets, endothelial cells, and fibroblasts. Commercially available ELISA tests were used to measure the levels of thromboxane B2 and metalloproteinases (MMP-1, MMP-2) released by platelets as markers of platelet activation.Results2 nm AgNPs-GSH, 3.7 nm AgNPs-PEG both at 50 and 100 µg/mL, and 2.5 nm AgNPs-LA at 100 µg/mL reduced platelet aggregation, inhibited collagen-mediated increase in total P-selectin and GPIIb/IIIa, TXB2 formation, MMP-1, and MMP-2 release. The tested AgNPs concentrations were not cytotoxic as they did not affect, platelet, endothelial cell, or fibroblast viability.ConclusionAll tested functionalized AgNPs inhibited platelet aggregation at nontoxic concentrations. Therefore, functionalized AgNPs can be used as an antiplatelet agent or in design and manufacturing of blood-facing medical devices, such as vascular grafts, stents, heart valves, and catheters.

Robust synthesis of large‐scale self‐assembled nanostructures with long‐range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV‐light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long‐range ordered structures which exhibit a novel dual‐responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV‐light irradiation. These results present an efficient way to obtain bulk quantities of self‐assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix‐assisted or DNA‐mediated organization.

The crystallization of nanomaterials is a primary source of solid-state, photonic structures. Thus, a detailed understanding of this process is of paramount importance for the successful application of photonic nanomaterials in emerging optoelectronic technologies. While colloidal crystallization has been thoroughly studied, for example, with advanced in situ electron microscopy methods, the noncolloidal crystallization (freezing) of nanoparticles (NPs) remains so far unexplored. To fill this gap, in this work, we present proof-of-principle experiments decoding a crystallization of reconfigurable assemblies of NPs at a solid state. The chosen material corresponds to an excellent testing bed, as it enables both in situ and ex situ investigation using X-ray diffraction (XRD), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), atomic force microscopy (AFM), and optical spectroscopy in visible and ultraviolet range (UV–vis) techniques. In particular, ensemble measurements with small-angle XRD highlighted the dependence of the correlation length in the NPs assemblies on the number of heating/cooling cycles and the rate of cooling. Ex situ TEM imaging further supported these results by revealing a dependence of domain size and structure on the sample preparation route and by showing we can control the domain size over 2 orders of magnitude. The application of HAADF-STEM tomography, combined with in situ thermal control, provided three-dimensional single-particle level information on the positional order evolution within assemblies. This combination of real and reciprocal space provides insightful information on the anisotropic, reversibly reconfigurable assemblies of NPs. TEM measurements also highlighted the importance of interfaces in the polydomain structure of nanoparticle solids, allowing us to understand experimentally observed differences in UV–vis extinction spectra of the differently prepared crystallites. Overall, the obtained results show that the combination of in situ heating HAADF-STEM tomography with XRD and ex situ TEM techniques is a powerful approach to study nanoparticle freezing processes and to reveal the crucial impact of disorder in the solid-state aggregates of NPs on their plasmonic properties.

Due to the high toxicity of currently used chemotherapeutics, novel methods of cancer treatment are needed. Gold nanoparticles (AuNPs) seem to be an interesting alternative due to penetration through biological membranes and systemic barriers. AuNPs as carriers of chemotherapeutics allow for reduced concentrations whilst maintaining the expected effect, and thus reducing the costs of therapy and adverse effects. We synthesized AuNPs stabilized with reduced glutathione (GSH) and conjugated with doxorubicin (DOX), gemcitabine (GEM) or cytarabine (CTA). This is the first study in which cytarabine-AuNPs were synthesized and characterized. Transmission electron microscopy (TEM), thermogravimetric analysis (TGA), nuclear magnetic resonance spectroscopy (NMR) and highperformance liquid chromatography (HPLC) were used to chemically characterize obtained nanoparticles. Antitumor activity and safety of application were assessed by MTT assay in in vitro model (human osteosarcoma cells -143B, human osteoblast-hFOB1.19, breast cancer cells -MCF7, breast epithelial cells -MCF10A, pancreatic cancer cells -PANC-1, and pancreatic cells -hTERT-HPNE cells). We have shown that cellular response varies according to the type and concentration of AuNPs. At some concentrations, we were able to show selective cytotoxicity of our AuNPs conjugates only to cancer cell lines. Synthesized nanoparticles were more cytotoxic to tumor cell lines than chemotherapeutics alone.

Purpose: To study and compare the antibacterial properties and the potential cytotoxic effects of commercially available uncoated silver nanoparticles (AgNPs) with lipoic acid coated silver nanoparticles (AgNPsLA) developed by our group. The antibacterial, cytotoxic, and hemolytic properties of those NPs were assessed with the main objective of investigating if AgNPsLA could maintain their antibacterial properties while improving their biosafety profile over uncoated AgNPs within the blood vessel’s microenvironment.Methods: Comercially available uncoated 2.6 nm AgNPs and 2.5 nm AgNPsLA synthesized and characterized as previously described by our group, were used in this study. Antimicrobial activity was assessed on a wide range of pathogens and expressed by minimal inhibitory concentrations (MIC). Assessment of cytotoxicity was carried out on human umbilical vein endothelial cells (HUVEC) using an MTT test. Detection of reactive oxygen species, cell apoptosis/necrosis in HUVEC, and measurement of mitochondrial destabilization in HUVEC and platelets were performed by flow cytometry. The potential harmful effect of nanoparticles on red blood cells (RBCs) was investigated measuring hemoglobin and LDH released after exposure to NPs. Transmission electron microscopy was also used to determine if AgNPs and AgNPsLA could induce any ultrastructural changes on HUVEC cells and Staphylococcus aureus bacteria.Results: AgNPs and AgNPsLA had antimicrobial properties against pathogens associated with catheter-related bloodstream infections. AgNPs, in contrast to AgNPsLA, induced ROS production and apoptosis in HUVEC, ultrastructural changes in HUVEC and S. aureus, depolarization of mitochondrial membrane in HUVEC and platelets, and also hemolysis.Conclusion: AgNPsLA synthesized by our group have antimicrobial activity and a better biosafety profile than uncoated AgNPs of similar size. Those observations are of critical importance for the future in vivo investigations and the potential application of AgNPsLA in medical devices for human use.

A series of nine hitherto unknown bicyclic pyrimidine nucleoside analogues (BCNAs) bearing bicyclic furo[2,3-d]pyrimidin-2(3H)one, 3H-pyrrolo[2,3-d]pyrimidin-2(7H)-one and 5,6-dihydropyrimido[4,5-c]pyridazin-7(8H)-one bases were prepared in a straightforward approach. Each of the synthesized compounds possesses a β-D-ribofuranose, β-D-2-deoxyribofuranose or β-D-arabinofuranose moiety attached to the heterocyclic ring system. This is one of few examples of the synthesis of pyrrolo[2,3-d]pyrimidin-2(7H)-one and dihydropyrimido[4,5-c]pyridazin-7(8H)-one nucleosides, and the first example of such nucleosides possessing an arabinose moiety. A key synthetic step involved a Sonogashira coupling reaction. For the coupling with 4-phenyl-1-butyne, deprotected 5-iodouridine, 5-iodo-2′-deoxyuridine and 5-iodoarabinouridine were used, and this reaction was followed by cycloisomerization and subsequent conversion of the furan ring into a pyrrole or a pyridazine ring. This approach resulted in the creation of a small library of compounds, which were evaluated for their antiproliferative properties against HL-60 and Jurkat E6.1 cell lines. Of all tested compounds, only 6-(2-phenylethyl)-3-(β-D-ribofuranosyl)furo[2,3-d]pyrimidin-2(3H)-one exhibited weak antiproliferative activity, with IC 50 values of 54 and 81 μM for HL-60 and Jurkat E6.1 cells, respectively.

No abstract