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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 high-performance 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.

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.

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 IC50 values of 54 and 81 μM for HL-60 and Jurkat E6.1 cells, respectively.

A series of sixteen hitherto unknown Cytarabine analogues bearing a bicyclic 3 H -pyrrolo[2,3- d ]pyrimidin-2(7 H )-one base modified with aryl, pyridyl, benzyl and alkyl substituents was prepared in a straightforward approach. This is the one of the few examples of the synthesis of pyrrolo[2,3- d ]pyrimidin-2(7 H )-one nucleosides and the first example of pyrrolo[2,3- d ]pyrimidin-2(7 H )-one nucleosides possessing arabinose moiety. For the first time, the conversion of the furopyrimidine arabinoside products to a series of novel pyrrolopyrimidines by ammonolysis reaction was thoroughly investigated using aqueous and methanolic reaction conditions under classical and micro-wave heating. This approach resulted in a small library of compounds, which were evaluated for their antiproliferative properties against HL-60 and Jurkat E6.1 cell lines. All synthesized compounds exhibited a weaker cytotoxic effect in comparison to the mother compound. Of all the tested compounds, the derivative bearing a 4- n -pentylphenyl substituent exhibited the highest antiproliferative activity.

A series of analogues of anhydrouridine have been synthesized and their crystal structures established using X-ray diffraction. For all cases, the ribose ring has O(4′)-exo, C(4′)-endo pucker and the pyrimidine base is in the anti conformation. Investigated compounds crystallize in different crystal systems (monoclinic, orthorhombic), have different space group symmetry ( P 2 1 , P 2 1 2 1 2 1 ) and exhibit different intermolecular interactions (halogen and hydrogen bonds) among molecules in their crystal lattices. Moreover, in the case of the 5-benzyl-6,5′- O -anhydrouridine a significant positional disorder is present with the phenyl rings existing in two orientations.

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 a...