The control and prediction of soft systems exhibiting self-organization behavior can be realized by different means but still remains a highlighted task. Novel advanced nanocomposite system has been designed by filling of a stretched porous polyethylene (PE) film with pore dimensions of hundreds of nanometers by chiral ferroelectric liquid crystalline (LC) compound possessing polar self-assembling behavior. Lactic acid derivative exhibiting the paraelectric orthogonal smectic A* and the ferroelectric tilted smectic C* phases over a broad temperature range is used as a self-assembling compound. The morphology of nanocomposite film has been checked by Atomic Force Microscopy (AFM). The designed nanocomposite has been studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small and wide-angle X-ray scattering and broadband dielectric spectroscopy. The effect of a porous PE confinement on self-assembling, structural, and dielectric behavior of the chiral LC compound has been established and discussed. While the mesomorphic and structural properties of the nanocomposite are found not to be much influenced in comparison to that of a pure LC compound, the polar properties have been toughly suppressed by the specific confinement. Nevertheless, the electro-optic switching was clearly observed under applied electric field of low frequency (210 V, 19 Hz). The dielectric spectroscopy and X-ray results reveal that the helical structure of the ferroelectric liquid crystal inside the PE matrix is completely unwound, and the molecules are aligned along stretching direction. Obtained results demonstrate possibilities of using stretched porous polyolefins as promising matrices for the design of new nanocomposites.

• Klíčová slova
• ferroelectric liquid crystal, nanocomposite, nanomaterials, polar order, porous polyethylene film, self-assembling behavior, smectic phase,
• Publikační typ
• časopisecké články MeSH

Smart self-organising systems attract considerable attention in the scientific community. In order to control and stabilise the liquid crystalline behaviour, and hence the self-organisation, the polymerisation process can be effectively used. Mesogenic units incorporated into the backbones as functional side chains of weakly cross-linked macromolecules can become orientationally ordered. Several new calamitic reactive mesogens possessing the vinyl terminal group with varying flexible chain lengths and with/without lateral substitution by the methyl (methoxy) groups have been designed and studied. Depending on the molecular structure, namely, the type and position of the lateral substituents, the resulting materials form the nematic, the orthogonal SmA and the tilted SmC phases in a reasonably broad temperature range, and the structure of the mesophases was confirmed by X-ray diffraction experiments. The main objective of this work is to contribute to better understanding of the molecular structure-mesomorphic property relationship for new functional reactive mesogens, aiming at further design of smart self-assembling macromolecular materials for novel sensor systems.

• Klíčová slova
• liquid crystal, reactive mesogen, self-assembling behaviour, smectic phases, vinyl group,
• Publikační typ
• časopisecké články MeSH

In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH₂ that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5-200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization.

• Klíčová slova
• NEXAFS, XPS, bioactive materials, nanostructures, self-assembling peptides, synchrotron radiation induced spectroscopies, titanium alloy,
• Publikační typ
• časopisecké články MeSH

Self-assembling peptides (SAPs) are fully defined nanobiomaterials offering unprecedented opportunities to control nanostructure and chemical attributes to investigate and manipulate cellular signals. To investigate the influence of chemical and morphological characteristics on inflammatory signaling in native immunity, we designed five β-sheet SAPs: EFEFKFEFK (EF8), YEFEFKFEFK (YEF8), EFEFKFEFKY (EF8Y), YEFEFKFEFKY (YEF8Y), and EYEFKFEFK (EYF8) (F: phenylalanine; E: glutamic acid; K: lysine, Y: tyrosine). The position of tyrosine in the peptide sequence dictated the self-assembly into nanostructures, with all SAPs self-assembling into thin constituent nanofibers with d ≈ 3.8 ± 0.4 nm, and sequences YEF8 and EF8 showing a propensity for associative bundling. These distinct SAPs induced contrasting inflammatory responses of monocytic model THP-1 cells-derived macrophages (MΦs). Presence of soluble EF8 nanofibers (at 2 mM) induced an anti-inflammatory response and polarization toward an M2 state, whereas YEF8 (at 2 mM) displayed a tendency for inducing a pro-inflammatory response and polarization toward an M1 state. EF8Y, YEF8Y, and EYF8 SAPs did not induce an inflammatory response in our models. These results were validated using peripheral blood mononuclear cells (PBMCs)-derived MΦs from human donors, confirming the critical role of EF8 and YEF8 SAPs as possible orchestrators of the repair of tissues or inducers of pro-inflammatory state, respectively. The same MΦs polarization responses from THP-1-derived MΦs cultured on 20 mM hydrogels were obtained. These findings will facilitate the utilization of this family of SAPs as immunomodulatory nanobiomaterials potentially changing the course of inflammation during the progression of various diseases.

• Klíčová slova
• immunomodulation, inflammation, macrophage polarization, nanostructured peptides, tyrosine-modified self-assembling peptides,
• MeSH
• konformace proteinů, beta-řetězec MeSH
• lidé MeSH
• makrofágy * účinky léků   metabolismus   cytologie   imunologie   MeSH
• nanovlákna chemie   MeSH
• peptidy * chemie   farmakologie   MeSH
• THP-1 buňky MeSH
• tyrosin * chemie   MeSH
• zánět * MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• peptidy * MeSH
• tyrosin * MeSH

In this work, amphiphilic hyaluronan was synthesized by grafting succinylated N-oleoyl-phytosphingosine via esters bonds. Succinylated N-oleoyl-phytosphingosine (sCER) was first prepared by esterification of hydroxyl moieties of the ceramide with succinic anhydride. The esterification of hyaluronan was governed by crowding effect. The oligomeric HA-sCER derivatives exhibited a strong self-aggregation as evidenced by a very low critical aggregation concentration (1.9 μg mL-1), higher pyrene binding constant (KB), and the smallest particle size (30 nm) in solution. The self-aggregation properties demonstrated to be a function of the substitution degree and molecular weight of HA. The prepared derivatives were non-cytotoxic towards cell lines NIH-3T3. Nanoparticles prepared using oligomeric HA-sCER derivatives improved the penetration of Nile red dye through the stratum corneum due to their smaller size (≤50 nm). The fluorescence intensity localized at the stratum corneum was higher for oligomeric HA-sCER. A significant inhibition of the pro-inflammatory cytokine interleukin-6 production was observed in vitro in macrophages differentiated from THP-1 cells. These findings showed that HA-sCER constituted a promising active ingredient for cosmetics use.

• Klíčová slova
• Amphiphilic polysaccharides, Ceramides, Hyaluronan, IL-6, Self-assembling, Skin penetration,
• MeSH
• ceramidy MeSH
• esterifikace MeSH
• kyselina hyaluronová * MeSH
• lékové transportní systémy * MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• ceramidy MeSH
• kyselina hyaluronová * MeSH
• phytosphingosine MeSH Prohlížeč

Single crystal sapphire and diamond surfaces are used as planar, atomically flat insulating surfaces, for the deposition of the diacetylene compound 10,12-nonacosadiynoic acid. The surface assembly is compared with results on hexagonal boron nitride (h-BN), highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces. A perfectly flat-lying monolayer of 10,12-nonacosadiynoic acid self-assembles on h-BN like on HOPG and MoS2. On sapphire and oxidized diamond surfaces, we observed assemblies of standing-up molecular layers. Surface assembly is driven by surface electrostatic dipoles. Surface polarity is partially controlled using a hydrogenated diamond surface or totally screened by the deposition of a graphene layer on the sapphire surface. This results in a perfectly flat and organized SAM on graphene, which is ready for on-surface polymerization of long and isolated molecular wires under ambient conditions.

• Publikační typ
• časopisecké články MeSH

We report the successful assembly of a tripeptide in the presence of nanodiamonds (NDs) into nanocomposite hydrogels. While the presence of NDs does not hinder peptide self-assembly and gelation kinetics are not affected, NDs improve the viscoelastic properties and significantly increase the elastic moduli of the peptide hydrogels. Increased resistance of the gels against applied stress can also be attained depending on the amount of NDs loaded in the nanocomposite. Raman micro-spectroscopy and TEM confirmed the presence of NDs on the surface, and not in the interior, of peptide nanofibers. Peptide-ND non-covalent interactions are also probed by Raman and Fourier-transformed infrared spectroscopies. Overall, this work enables the embedding of NDs into nanocomposite hydrogels formed through the self-assembly of a simple tripeptide at physiological pH, and it provides key insights to open the way for their future applications in biomaterials, for instance exploiting their luminescence and near-infrared responsiveness.

• Klíčová slova
• Gels, Nanocomposites, Nanodiamonds, Peptides, Self-Assembly,
• Publikační typ
• časopisecké články MeSH

Zoledronic Acid (ZA) rapidly concentrates into the bone and reduces skeletal-related events and pain in bone metastatic prostate cancer (PCa), but exerts only a limited or absent impact as anti-cancer activity. Recently, we developed self-assembling nanoparticles (NPS) encapsulating zoledronic acid (NZ) that allowed a higher intratumor delivery of the drug compared with free zoledronic acid (ZA) in in vivo cancer models of PCa. Increasing evidence suggests that Bone Marrow (BM) Mesenchymal stromal cells (BM-MSCs) are recruited into the stroma of developing tumors where they contribute to progression by enhancing tumor growth and metastasis.We demonstrated that treatment with NZ decreased migration and differentiation into adipocytes and osteoblasts of MSCs and inhibited osteoclastogenesis. Treatment with NZ reduced the capability of MSCs to promote the migration and the clonogenic growth of the prostate cancer cell lines PC3 and DU145. The levels of Interleukin-6 and of the pro-angiogenic factors VEGF and FGF-2 were significantly reduced in MSC-CM derived from MSCs treated with NZ, and CCL5 secretion was almost totally abolished. Moreover, treatment of MSCs with supernatants from PC3 cells, leading to tumor-educated MSCs (TE-MSCs), increased the secretion of IL-6, CCL5, VEGF and FGF-2 by MSCs and increased their capability to increase PC3 cells clonogenic growth. Treatment with NZ decreased cytokine secretion and the pro-tumorigenic effects also of TE-MSCS. In conclusion, demonstrating that NZ is capable to inhibit the cross talk between MSCs and PCa, this study provides a novel insight to explain the powerful anticancer activity of NZ on PCa.

• Klíčová slova
• mesenchymal stromal cells, prostate cancer, self-assembling nanoparticles, tumor microenvironment, zoledronic acid,
• MeSH
• bisfosfonáty aplikace a dávkování   MeSH
• buněčná diferenciace účinky léků   MeSH
• cytokiny metabolismus   MeSH
• imidazoly aplikace a dávkování   MeSH
• kyselina zoledronová MeSH
• látky indukující angiogenezi metabolismus   MeSH
• lidé MeSH
• mezenchymální kmenové buňky cytologie   účinky léků   metabolismus   MeSH
• mezibuněčná komunikace účinky léků   MeSH
• nádorové buněčné linie MeSH
• nádorové mikroprostředí účinky léků   MeSH
• nádory prostaty metabolismus   patologie   MeSH
• nanočástice MeSH
• osteoblasty cytologie   účinky léků   metabolismus   MeSH
• osteoklasty cytologie   účinky léků   metabolismus   MeSH
• pohyb buněk účinky léků   MeSH
• tukové buňky cytologie   účinky léků   metabolismus   MeSH
• viabilita buněk účinky léků   MeSH
• Check Tag
• lidé MeSH
• mužské pohlaví MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• bisfosfonáty MeSH
• cytokiny MeSH
• imidazoly MeSH
• kyselina zoledronová MeSH
• látky indukující angiogenezi MeSH

Solid meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS(4))-chitosan supramolecular complexes were prepared by addition of porphyrin to an aqueous solution of chitosan at pH values. The precipitates obtained were assigned as 1 (pH 6.8) and 2 (pH 2.5) and characterized by spectroscopic, thermal, and microscopic methods. Spectroscopic investigation confirmed the presence of TPPS(4) and chitosan in both products and that the porphyrin is highly self-associated. H-type (stacked) of TPPS(4) aggregation was proposed for 1 and J-type (tilted) for 2. Thermal analysis revealed different pyrolysis routes of the complexes depending on their structural diversity. Light microscopic analysis indicated fibrous and lamellar microstructures, respectively, for 1 and 2. SEM and AFM analysis showed that both complexes consist of compact nanostructures; their size and interconnection is different for 1 and 2. Based on structural inferences, self-assembling hierarchy models were proposed for both of the TPPS(4)-chitosan supramolecular complexes.

• MeSH
• blízká infračervená spektroskopie MeSH
• chitosan chemie   MeSH
• koncentrace vodíkových iontů MeSH
• magnetická rezonanční spektroskopie MeSH
• mikroskopie atomárních sil MeSH
• molekulární struktura MeSH
• nanostruktury chemie   MeSH
• porfyriny chemie   MeSH
• povrchové vlastnosti MeSH
• teplota MeSH
• velikost částic MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chitosan MeSH
• meso-tetrakis(4-sulfonatophenyl)porphyrin MeSH Prohlížeč
• porfyriny MeSH

Several new lactic acid derivatives containing the keto linkage group far from the chiral part and short alkyl chains have been synthesized and characterised by polarising optical microscopy, differential scanning calorimetry, as well as electro-optic and dielectric spectroscopy. The materials possess a self-assembling behaviour on the nanoscale level as they form polar smectic liquid crystalline mesophases, namely the orthogonal paraelectric SmA* and the tilted ferroelectric SmC* phases, in a broad temperature range down to room temperature. A short helical pitch (≈120-320 nm), relatively high spontaneous polarisation (≈150 nC/cm2) and reasonable tilt angle values have been determined within the temperature range of the tilted ferroelectric SmC* phase. The obtained results make the new materials useful for the advanced mixture design and for further utilisation in electro-optic devices based on the deformed helix ferroelectric effect.

• Klíčová slova
• ferroelectric liquid crystal, keto group, self-assembly on the nanoscale, soft ferroelectrics, submicrometre helical pitch length,
• Publikační typ
• časopisecké články MeSH