Michał Wójcik

Liquid-crystalline phases made of gold nanoparticles.

Spontaneous formation of smectic and columnar structures was observed when spherical gold nanoparticles were functionalized with mesogenic thiols (see layered structure and X-ray pattern of a sample in smectic phase). The particle ordering is stimulated by softening of the interparticle potential and flexibility for deformation of the grafting layer.

Gold nanoparticles solid contact for ion-selective electrodes of highly stable potential readings

Internal solution free ion-selective electrodes were prepared applying for the first time gold nanoparticles as a solid contact layer. The presence of a layer of gold nanoparticles stabilized with aliphatic thiols at the back side of the membrane resulted in highly stable potentiometric responses of the sensors, good selectivities and close to Nernstian slopes. Electrochemical studies have confirmed that the applied material is effectively working as capacitive solid contact, yielding high stability sensors.

Multidimensional structures made by gold nanoparticles with shape-adaptive grafting layers

The ability of gold nanoparticles grafted with soft, adaptive organic layers made of two types of thiol molecules, n-alkyl and mesogenic ones, to form spontaneously long-range positionally ordered structures is shown. It was found that molecular structure of mesogenic thiols as well as the n-alkyl thiols can affect the type of the phase. A number of structures, smectic, undulated smectic and columnar phases, were obtained thanks to the self-segregation of mesogenic and simple n-alkyl ligands at the nanoparticle surface.

Metal nanoparticles with liquid-crystalline ligands: controlling nanoparticle superlattice structure and properties.

Nanoparticle ordered aggregates are promising candidates for future application in a variety of sensing, optical and electronic technologies, mainly based on collective interactions between individual nano-building blocks. Physicochemical properties of such assemblies depend on nanoparticle spacing, therefore a lot of effort throughout the last years was put on development of assembly methods allowing control over aggregates structure. In this minireview we describe efficient self-assembly process based on the utilization of liquid-crystalline ligands grafted onto nanoparticle surface. We show strategies used to synthesize liquid-crystalline nanoparticles as well as discuss parameters influencing structural and thermal characteristic of aggregates. It is also demonstrated that the liquid-crystalline approach offers access to dynamic self-assembly and metamaterials with anisotropic plasmonic properties, which makes this strategy unique among others.

Dithizone modified gold nanoparticles films for potentiometric sensing.

For the first time, application of a membrane composed of gold nanoparticles decorated with complexing ligand for potentiometric sensing is shown. Gold nanoparticles drop cast from a solution form a porous structure on a substrate electrode surface. Sample cations can penetrate the gold nanoparticles layer and interact with ligand acting as a charged ionophore, resulting in Nernstian potentiometric responses. Anchoring of complexing ligand on the gold surface abolishes the necessity of ionophore application. Moreover, it opens the possibility of preparation of potentiometric sensors using chelators of significantly different selectivity patterns further enhanced by the absence of polymeric membrane matrix. This was clearly seen, for example, for gold nanoparticles stabilizing the applied ligand-dithizone-thiol conformation leading to a high potentiometric selectivity toward copper ions, much higher than that of ionophores typically used to induce selectivity for polymeric ion-selective membranes.

Temperature-controlled liquid crystalline polymorphism of gold nanoparticles

Gold nanoparticles grafted with promesogenic ligands show temperature induced liquid crystalline polymorphism with unique phase sequence: from smectic to columnar structure. The transition is entropy driven; with increasing temperature ligands attached to nanoparticle surface require more space to fluctuate. In result smectic layer becomes deformed (‘peristaltic mode’) and voids between metal particles filled with organic molecules form a hexagonal structure.

Enhancing anti-tumor efficacy of Doxorubicin by non-covalent conjugation to gold nanoparticles - in vitro studies on feline fibrosarcoma cell lines.

Background Feline injection-site sarcomas are malignant skin tumors of mesenchymal origin, the treatment of which is a challenge for veterinary practitioners. Methods of treatment include radical surgery, radiotherapy and chemotherapy. The most commonly used cytostatic drugs are cyclophosphamide, doxorubicin and vincristine. However, the use of cytostatics as adjunctive treatment is limited due to their adverse side-effects, low biodistribution after intravenous administration and multidrug resistance. Colloid gold nanoparticles are promising drug delivery systems to overcome multidrug resistance, which is a main cause of ineffective chemotherapy treatment. The use of colloid gold nanoparticles as building blocks for drug delivery systems is preferred due to ease of surface functionalization with various molecules, chemical stability and their low toxicity. Methods Stability and structure of the glutathione-stabilized gold nanoparticles non-covalently modified with doxorubicin (Au-GSH-Dox) was confirmed using XPS, TEM, FT-IR, SAXRD and SAXS analyses. MTT assay, Annexin V and Propidium Iodide Apoptosis assay and Rhodamine 123 and Verapamil assay were performed on 4 feline fibrosarcoma cell lines (FFS1WAW, FFS1, FFS3, FFS5). Statistical analyses were performed using Graph Pad Prism 5.0 (USA). Results A novel approach, glutathione-stabilized gold nanoparticles (4.3 +/- 1.1 nm in diameter) non-covalently modified with doxorubicin (Au-GSH-Dox) was designed and synthesized. A higher cytotoxic effect (p<0.01) of Au-GSH-Dox than that of free doxorubicin has been observed in 3 (FFS1, FFS3, FFS1WAW) out of 4 feline fibrosarcoma cell lines. The effect has been correlated to the activity of glycoprotein P (main efflux pump responsible for multidrug resistance). Conclusions The results indicate that Au-GSH-Dox may be a potent new therapeutic agent to increase the efficacy of the drug by overcoming the resistance to doxorubicin in feline fibrosarcoma cell lines. Moreover, as doxorubicin is non-covalently attached to glutathione coated nanoparticles the synthesized system is potentially suitable to a wealth of different drug molecules.

Phototunable Liquid‐Crystalline Phases Made of Nanoparticles

The properties of liquid-crystalline (LC) hybrid systems made of inorganic nanoparticles grafted with photosensitive azo compounds are presented. For materials with a large density of azo ligands at the surface, the LC structure can be reversibly melted by UV light, and the return to the LC state does not require the absorption of visible light. For systems with a lower density of azo ligands, UV light causes shortening of the distance between metal sublayers in the lamellar phase. Interestingly, the azo derivatives attached to the nanoparticle surface show very different kinetics of cis/trans conformational change as compared to the free molecules. The cis form of free ligands in solution is stable for days, whereas the isomerization of molecules attached to the nanoparticle surface to the trans form takes only a few minutes. Apparently, owing to the crowded environment, azo ligands immobilized at a metal surface behave as they would in the condensed state.

Dynamic self-assembly of nanoparticles using thermotropic liquid crystals

ABSTRACT 3D nanoparticle-based materials with reconfigurable structure have gained vast attention due to the unique possibility of tailoring nanoparticle-related quantum confinement effects. These properties make active nanoparticle assemblies promising candidates for future optoelectronic and metamaterial technologies; however, integration of these materials into real-world applications is still challenging. In this context, the use of stimuli responsive liquid-crystals (LCs) offers a fascinating and industrially feasible strategy for active directing of NPs. Here, we briefly review LCs/NPs hybrid systems in which dynamic behaviour is achieved by affecting either LC matrix or LC ligands. We also experimentally evaluate a complementary strategy based on directly affecting metallic core of LC-covered NPs in an Ostwald ripening process. GRAPHICAL ABSTRACT

Doxorubicin Conjugated to Glutathione Stabilized Gold Nanoparticles (Au-GSH-Dox) as an Effective Therapeutic Agent for Feline Injection-Site Sarcomas—Chick Embryo Chorioallantoic Membrane Study

Feline injection-site sarcomas are malignant skin tumours with a high local recurrence rate, ranging from 14% to 28%. The treatment of feline injection-site sarcomas includes radical surgery, radiotherapy and/or chemotherapy. In our previous study it has been demonstrated that doxorubicin conjugated to glutathione-stabilized gold nanoparticles (Au-GSH-Dox) has higher cytotoxic effects than free doxorubicin for feline fibrosarcoma cell lines with high glycoprotein P activity (FFS1, FFS3). The aim of the present study was to assess the effectiveness of intratumoural injection of Au-GSH-Dox on the growth of tumours from the FFS1 and FFS3 cell lines on chick embryo chorioallantoic membrane. This model has been utilized both in human and veterinary medicine for preclinical oncological studies. The influence of intratumoural injections of Au-GSH-Dox, glutathione-stabilized gold nanoparticles and doxorubicin alone on the Ki-67 proliferation marker was also checked. We demonstrated that the volume ratio of tumours from the FFS1 and FFS3 cell lines was significantly (p < 0.01) decreased after a single intratumoural injection of Au-GSH-Dox, which confirms the positive results of in vitro studies and indicates that Au-GSH-Dox may be a potent new therapeutic agent for feline injection-site sarcomas.