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In this work the flower-like hierarchical structures (HS) based on 3D pristine ZnO, ZnO:Eu3+ and ZnO:Eu3+@Au were successfully obtained by a template-free solvothermal and deposition-precipitation method. The decolorization/photodegradation of these structures towards model organic dye (rhodamine 6G) was studied. The synthesized ZnO-based HS were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis and photoluminescence (PL) spectroscopies. The proposed synthesis approaches allow to obtain highly crystalline 3D ZnO, ZnO:Eu3+ and ZnO:Eu3+@Au composites. Results of scanning microscopy show that ZnO flower-like HS are assemblies from smaller components, forming larger ones, the whole ZnO structure was approximately 3 μm. Au nanoparticles (size ∼ 10 nm) are successfully deposited on ZnO HS surface. Luminescent studies show that ZnO is an ideal matrix for incorporation of Eu3+ ions in broad concentration range (Eu3+ = 1.0 at%–5.0 at%) with an efficient red luminescence. The strong UV emission in ZnO, as well as ZnO:Eu3+ HS is observed under 325 nm excitation. Doping of ZnO HS matrix by Eu3+ ions leads to the red shift of deep level emission peak (DLE). The PL intensity reaches the maximum up to 5 at% Eu3+. The photocatalytic properties of ZnO and ZnO:Eu3+@Au HS were investigated under UV–Vis light irradiation towards rhodamine 6G. The obtained results demonstrate the synergetic effect of the deposited gold nanoparticles and Eu3+ doping on photocatalytic activity of ZnO:Eu3+@Au HS in comparison to pristine ZnO and ZnO:Eu3+ HS.

ZnO (nano)structures remain of great interest in biomedical applications due to their unique properties and possible morphologies. Biocompatibility of typically fabricated ZnO structures remains questionable and they still lack desired biological functions, whence their functionalization is of high interest. In this work, we fabricated micro-sized ZnO hierarchical flower-like structures using facile template-free hydrothermal method to act as carriers for the delivery of gold nanoparticles (Au) and/or Biotin (Vitamin B) to cells. Au nanoparticles (~24 nm), as well as Biotin molecules were successfully deposited on the ZnO surface due to non-covalent physical interactions. We have then cultured two cells lines: SH-SY5Y (human malignant neural) and HEK-293 (human non-malignant) and observed that ZnO hierarchical particles exhibited cell line-dependent cytotoxicity. It appeared that further functionalization of ZnO with Au nanoparticles and subsequently with Biotin led to lower discrepancy between the two cell lines response indicating that cytotoxic pathways of pure ZnO were masked by the available surface adsorbed particles (Au/Biotin). Two-photon immunocytochemistry microscopy further confirmed that Biotin decorated particles affected neuroblastoma cells cytoskeleton. These findings contribute to the understanding of cytotoxic pathways of surface-decorated nano-micro-structures made from ZnO with two molecules typically used in anticancer and regenerative medicine therapies.

The year 1961 went down in history with exceptional scientific achievements. On May 13, the journal Nature published two articles on the first isolation of messenger ribonucleic acid (mRNA), which is an intermediate product between a gene and a protein. Just two weeks later, on May 27, the first letter of the genetic code, phenylalanine, was discovered. These discoveries made it possible to understand how genetic information is encoded and processed, thus causing the dynamic development of molecular biology. The breakthroughs of 1961 concerned not only nucleic acids. On April 12, the first human, Yuri Gagarin, entered space. Eight years later, in 1969, Neil Armstrong made his first walk on the moon, uttering the famous phrase: It is a small step for man, but a great leap for humanity. The era of conquering and learning about the cosmos has begun, mainly motivated by the natural curiosity of man and the desire to learn about the surrounding reality. The environmental factors in space are very different from terrestrial conditions, which raises questions about their effects on living organisms. In search of answers, a variety of scientific research has been carried out at the International Space Station (ISS) for over twenty years. As space travel is set to become more common in the near future, detailed studies of the effects of long-term space missions on the human body are required. These studies are currently carried out, among others using molecular biology techniques that enable detailed analysis of nucleic acids and proteins, but not only. The breakthrough achievements of 1961 initiated the development both in the field of molecular biology and the science of space, thanks to which today, 60 years after those events, we can combine knowledge and technological achievements from both fields to analyze and understand changes at the molecular level that occur as a result of being in organisms in outer space.Lata 60. XX wieku odznaczyły się przełomowymi dokonaniami naukowymi. Po raz pierwszy wyizolowano informacyjny RNA oraz rozszyfrowano kod genetyczny, co zainicjowało rozwój biologii molekularnej. Pierwszy spacer człowieka na Księżycu rozpoczął nową erę w nauce o kosmosie. Po 60 latach od tamtych wydarzeń, możemy połączyć wiedzę z obu dziedzin w celu pełniejszego zrozumienia zmian zachodzących w organizmie w przestrzeni kosmicznej. Z tej okazji wspominamy narodziny epigenetyki - nauki o zmianach funkcji genów, które nie wynikają ze zmian w sekwencji DNA, lecz są związane ze środowiskiem. Podsumowujemy wyniki badania NASA z udziałem bliźniąt jednojajowych, ukazującego wpływ długoterminowej misji kosmicznej na organizm człowieka. Przedstawiamy rolę stresu oksydacyjnego, którego wzrost zaobserwowano w przestrzeni kosmicznej, a który leży u postaw licznych chorób i procesu starzenia się. Badania zmian epigenetycznych na Ziemi i w kosmosie mogą pomóc nam lepiej zrozumieć rolę czynników środowiska w procesach chorobotwórczych.

Studies revolving around mechanisms responsible for the development of amyloid-based diseases lay the foundations for the recognition of molecular targets of future to-be-developed treatments. However, the vast number of peptides and proteins known to be responsible for fibril formation, combined with their complexity and complexity of their interactions with various cellular components, renders this task extremely difficult and time-consuming. One of these proteins, human cystatin C (hCC), is a well-known and studied cysteine-protease inhibitor. While being a monomer in physiological conditions, under the necessary stimulus&mdash, usually a mutation, it tends to form fibrils, which later participate in the disease development. This process can potentially be regulated (in several ways) by many cellular components and it is being hypothesized that the cell membrane might play a key role in the oligomerization pathway. Studies involving cell membranes pose several difficulties, therefore, an alternative in the form of membrane mimetics is a very attractive solution. Here, we would like to present the first study on hCC oligomerization under the influence of phospholipid liposomes, acting as a membrane mimetic. The protein&ndash, mimetic interactions are studied utilizing circular dichroism, nuclear magnetic resonance, and size exclusion chromatography.

We used the topological insulator (TI) Bi2Te3 and a high-temperature superconductor (HTSC) hybrid device for investigations of proximity-induced superconductivity (PS) in the TI. Application of the superconductor YBa2Cu3O7-δ (YBCO) enabled us to access higher temperature and energy scales for this phenomenon. The HTSC in the hybrid device exhibits emergence of a pseudogap state for T > Tc that converts into a superconducting state with a reduced gap for T c. The conversion process has been reflected in Raman spectra collected from the TI. Complementary charge transport experiments revealed emergence of the proximity-induced superconducting gap in the TI and the reduced superconducting gap in the HTSC, but no signature of the pseudogap. This allowed us to conclude that Raman spectroscopy reveals formation of the pseudogap state but cannot distinguish the proximity-induced superconducting state in the TI from the superconducting state in the HTSC characterised by the reduced gap. Results of our experiments have shown that Raman spectroscopy is a complementary technique to classic charge transport experiments and is a powerful tool for investigation of the proximity-induced superconductivity in the Bi2Te3.

“Western diet” containing high concentrations of sugar and fat consumed during pregnancy contributes to development of obesity and diabetes type 2 in offspring. To mimic effects of this diet in animals, a cafeteria (CAF) diet is used. We hypothesized that CAF diet given to rats before, and during pregnancy and lactation differently influences fat content, metabolic and inflammation profiles in offspring. Females were exposed to CAF or control diets before pregnancy, during pregnancy and lactation. At postnatal day 25 (PND 25), body composition, fat contents were measured, and blood was collected for assessment of metabolic and inflammation profiles. We have found that CAF diet lead to sex-specific alterations in offspring. At PND25, CAF offspring had: (1) higher percentage of fat content, and were lighter; (2) sex-specific differences in levels of glucose; (3) higher levels of interleukin 6 (IL-6), interleukin-10 (IL-10) and tumor necrosis factor (TNF-α); (4) sex-specific differences in concentration of IL-6 and TNF-α, with an increase in CAF females; (5) higher level of IL-10 in both sexes, with a more pronounced increase in females. We concluded that maternal CAF diet affects fat content, metabolic profiles, and inflammation parameters in offspring. Above effects are sex-specific, with female offspring being more susceptible to the diet.

Amyotrophic lateral sclerosis (ALS) is an incurable neurodegenerative disease, causing motor neuron and skeletal muscle loss and death. One of the promising therapeutic approaches is stem cell graft application into the brain, however, an immune reaction against it creates serious limitations. This study aimed to research the efficiency of glial restricted progenitors (GRPs) grafted into murine CNS (central nervous system) in healthy models and the SOD1G93A ALS disease model. The cellular grafts were administered in semiallogenic and allogeneic settings. To investigate the models of immune reaction against grafted GRPs, we applied three immunosuppressive/immunomodulatory regimens: preimplantation factor (PiF), Tacrolimus, and CTLA-4, MR1 co-stimulatory blockade. We tracked the cells with bioluminescence imaging (BLI) in vivo to study their survival. The immune response character was evaluated with brain tissue assays and multiplex ELISA in serum and cerebrospinal fluid (CSF). The application of immunosuppressive drugs is disputable when considering cellular transplants into the immune-privileged site/brain. However, our data revealed that semiallogenic GRP graft might survive inside murine CNS without the necessity to apply any immunomodulation or immunosuppression, whereas, in the situation of allogeneic mouse setting, the combination of CTLA-4, MR1 blockade can be considered as the best immunosuppressive option.

The structural characterization of glass slides surface-modified with 3-azidopropyltrimethoxysilane and used for anchoring nucleic acids, resulting in the so-called DNA microarrays, is presented. Depending on the silanization conditions, the slides were found to show different oligonucleotide binding efficiency, thus, an attempt was made to correlate this efficiency with the structural characteristics of the silane layers. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry (XRR) measurements provided information on the surface topography, chemical composition and thickness of the silane films, respectively. The surface for which the best oligonucleotides binding efficiency is observed, has been found to consist of a densely-packed silane layer, decorated with a high-number of additional clusters that are believed to host exposed azide groups.

The year 2021 marks not only 60 years since the discovery of messenger RNA and the genetic code. Already 100 yaers passed since RNA was discovered. On the occasion of this special anniversary, we would like to recall the most important events in the history of nucleic acids that led to the above discoveries. We remind the beginning of a new era in science caused by the isolation of nuclein and then nucleic acid, whose components and properties were gradually learned, often by little-known researchers. The distinction of RNA and DNA and the analysis of their occurrence in cells made it possible to formulate the first conclusions about the functions of these compounds. Conclusions on the ratio of nitrogenous bases in DNA led to the knowledge of the structure of the double helix, triggering an avalanche of questions about the essence of transmission of genetic information. Answers began to emerge with the discovery of mRNA, and knowledge of the first three nucleotides encoding an amino acid caused a race to decipher the genetic code. The above discoveries are the foundation of molecular biology. The diamond jubilee coincided with the development of an mRNA-based vaccine against the SARS-CoV-2.W 2021 roku mija 100 lat od poznania kwasu rybonukleinowego oraz 60 lat od odkrycia informacyjnego (messenger) RNA i kodu genetycznego. Z okazji tego wyjątkowego jubileuszu pragniemy przypomnieć najważniejsze wydarzenia w historii kwasów nukleinowych, które doprowadziły do powyższych odkryć. Wspomniany początek nowej ery w nauce spowodowany izolacją nukleiny, a następnie kwasu rybonukleinowego, którego składniki i właściwości były stopniowo poznawane, często przez mało znanych badaczy. Wyróżnienie RNA i DNA oraz analiza ich występowania w komórkach pozwoliły sformułować pierwsze wnioski dotyczące funkcji tych molekuł. Konkluzje dotyczące proporcji zasad azotowych w DNA doprowadziły do poznania struktury podwójnej helisy, wywołując lawinę pytań o istotę przekazywania informacji genetycznej. Odpowiedzi zaczęły nasuwać się wraz z odkryciem mRNA, a poznanie pierwszej trójki nukleotydów kodującej fenyloalaninę rozpoczęło wyścig o rozszyfrowanie kodu genetycznego. Powyższe odkrycia stanowią fundament biologii molekularnej. Diamentowy jubileusz zbiegł się z opracowaniem szczepionki przeciwko SARS-CoV-2 opartej o mRNA.

The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, catalysts, media in separation science, or electrolytes to that as task-specific, tunable molecular machines with appropriate properties. A thorough understanding of these properties and structure–property relationships is needed to fully exploit their potential, open new directions in IL-based research and, finally, properly implement the appropriate applications. In this work, we investigated the structure–properties relationships of a series of alkyltriethylammonium bis(trifluoromethanesulfonyl)imide [TEA-R][TFSI] ionic liquids in relation to their thermal behavior, structure organization, and self-diffusion coefficients in the bulk state using DSC, FT-IR, SAXS, and NMR diffusometry techniques. The phase transition temperatures were determined, indicating alkyl chain dependency. Fourier-transformed infrared spectroscopy studies revealed the structuration of the ionic liquids along with alkyl chain elongation. SAXS experiments clearly demonstrated the existence of polar/non-polar domains. The alkyl chain length influenced the expansion of the non-polar domains, leading to the expansion between cation heads in polar regions of the structured IL. 1H NMR self-diffusion coefficients indicated that alkyl chain elongation generally caused the lowering of the self-diffusion coefficients. Moreover, we show that the diffusion of anions and cations of ILs is similar, even though they vary in their size.

The aim of the study was to establish the influence of a co-precipitation agent (i.e., NaOH–immediate precipitation, hexamethylenetetramine/urea–gradual precipitation and growth of nanostructures) on the properties and catalytic activity of as-synthesized Au-CeO2 nanocomposites. All catalysts were fully characterized with the use of XRD, nitrogen physisorption, ICP-OES, SEM, HR-TEM, UV-vis, XPS, and tested in low-temperature oxidation of benzyl alcohol as a model oxidation reaction. The results obtained in this study indicated that the type of co-precipitation agent has a significant impact on the growth of gold species. Immediate co-precipitation of Au-CeO2 nanostructures with the use of NaOH allowed obtainment of considerably smaller and more homogeneous in size gold nanoparticles than those formed by gradual co-precipitation and growth of Au-CeO2 nanostructures in the presence of hexamethylenetetramine or urea. In the catalytic tests, it was established that the key factor promoting high activity in low-temperature oxidation of benzyl alcohol was size of gold nanoparticles. The highest conversion of the alcohol was observed for the catalyst containing the smallest Au particle size (i.e., Au-CeO2 nanocomposite prepared with the use of NaOH as a co-precipitation agent).

It is already known that cells respond strongly to topography and chemistry of 2D surfaces. In this work we study cell-material interactions; in particular, we investigated the attachment and alignment of SH-SY5Y cells of neuronal origin on grooved-patterns made from Silicon (Si) and Gold (Au). The Au-Si groove-pattern stimulated 93% of SH-SY5Y cells to differentiate into neuroblast-like type (N-type) in 2 days and outgrown neurites exhibited strong anisotropy along the grooves with 90% of cells having one or two neurites. In comparison, random distribution of morphology type, neurite number, and alignment were observed on control flat surfaces (Si and Au). We further show that designed Au-Si groove-patterns can be used to form reversed groove patterns on polycarolactone surface via soft lithography approach. Sixty-nine percentage of SH-SY5Y cells aligned along the obtained reversed groove patterns of the same dimensional characteristics to Si-Au grooves. In particular, this work demonstrated that the Au-Si grooves pattern stimulates neurite polarity, elongation, and morphological differentiation of neuroblastoma cells without any exogenous supply of growth factors or stimulants in just 2 days, which can lead to selective procedure of obtaining homologous population of neuron-like cells for future nerve regeneration therapies.

In this review, significant applications of lanthanides and their compounds in bone tissue engineering are described, with an emphasis on coordination compounds based on wide variety of ligands, crystalline structure and their properties, stability as well as cytotoxicity. The current challenges and several scientific discoveries related to the use of lanthanides in bone disease treatment are summarized. The influence of lanthanide compounds with different ligands on the bone remodeling cycle and their potential application in the treatment and prevention of bone diseases is presented. According to the knowledge gained so far numerous applications of lanthanides cause that these elements and their compounds especially the lanthanide-based nanomaterials were tested in bone disorders therapy: radiation therapies, drug delivery systems, biosensing, bioimaging, as well as in implants, and tissue engineering. Revealing was also the structural studies which indicated why Ln-doped Hydroxyapatite was an excellent treatment for orthopedic injuries.

Evolution of bacteria to selective chemical pressure (e.g. antibiotics) is well studied in contrast to the influence of physical stressors. Here we show that instantaneous physical stress in a homogeneous environment (without concentration gradient) induces fast adaptation of Escherichia coli. We exposed E. coli to a large number of collisions of around 105 per bacterium per second with sharp ZnO nanorods. The pressure exerted on the bacterial cell wall was up to 10 GPa and induced phenotype changes. The bacteria’s shape became more spherical, the density of their periplasm increased by around 15% and the average thickness of the cell wall by 30%. Such E. coli cells appeared almost as Gram-positive bacteria in the standard Gram staining. Additionally, we observed a combination of changes occurring at the genomic level (mutations identified in form of single nucleotide polymorphisms) and down-regulation of expression of 61 genes encoding proteins involved in β-oxidation of fatty acids, glycolysis, the citric acid cycle, as well as uptake of amino acids and enzyme cofactors. Thus, we show that bacteria undergo phenotypic changes upon instantaneous, acute physical stress without any obviously available time for gradual adaptation.

Novel magnesium(II) porphyrazine with peripheral methyl(3,5-dibromophenylmethyl)amine groups was synthesized in a multi-step procedure starting from commercially available diaminomaleonitrile. All intermediates and the final macrocycle were characterized using UV–Vis, FT-IR, MS and various NMR techniques. The absorption and emission properties of the macrocycle were evaluated in N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane. The potential photosensitizing activity was evaluated by assessing the ability of the macrocycle to generate singlet oxygen in dimethyl sulfoxide and N,N-dimethylformamide.

Currently, an increase in the awareness of a healthy lifestyle has been observed in society. People are seeking added health benefits from their dietary intake. Thus, functional foods with supplemented components that promote wellness are becoming popular. Lycopene is a carotenoid that gives vegetables and fruits their red color. Due to its chemical structure, lycopene acts as an antioxidant, which is the basis for its health-promoting properties. Oxidative stress is recognized as an important agent of many chronic diseases; thus, lycopene appears to be a universal medicine. Lycopene has the greatest antioxidant potential among carotenoids. Nutraceutical effects of lycopene have been reported for patients with cancer, infertility, metabolic syndrome and liver damage. Therefore, its supplementation can function as a proper causative treatment of disease. In this review, we highlight primary research and clinical trials involving lycopene and its impact on human health.

Modern medicine widely uses exogenous collagen as a good material for tissue regeneration, also as a natural substrate for cell attachment and proliferation, used to create dressings and to support the treatment of burn and diabetic wounds, or finally as a source of amino acids in the form of a dietary supplement. Collagen is a safe material that has high biocompatibility and biodegradability as well as good cell adhesion. Due to the possibility of transferring Creutzfeld-Jacob’s disease (Bovine Spongiform Encephalopathy) from animals to the human body, interest in collagen from fish is currently increasing. The collagen we examined was derived from the skin of the silver carp fish (Hypophtalmichthys molitrix) and was obtained by the method of hydration in an aqueous lactic acid solution. The topography of the test sample was performed with the AFM method, showing its fibrillar structure with dimensions equivalent to those given in iterature. Raman spectroscopy was used to study fish collagen using a Renishaw Ramanscope with a helium-neon laser at a wavelength of 633 nm. Analysis of Raman spectra allowed to determine the content of amino acids in collagen, as well as glycine, proline and hydroxyproline. It also showed the native nature of the material at 20 °C. The partial renaturation of the secondary structure of this material heated to about 85 °C and cooled was also proved. Raman spectroscopy has been presented as an effective method for testing biopolymers.

A novel approach using a zwitterionic sulfobetaine-based surfactant for the synthesis of spherical copper oxide nanoparticles (Cu

In this study, GNF@ZnO composites (gelatin nanofibers (GNF) with zinc oxide (ZnO) nanoparticles (NPs)) as a novel antibacterial agent were obtained using a wet chemistry approach. The physicochemical characterization of ZnO nanoparticles (NPs) and GNF@ZnO composites, as well as the evaluation of their antibacterial activity toward Gram-positive (Staphyloccocus aureus and Bacillus pumilus) and Gram-negative (Escherichia coli and Pseudomonas fluorescens) bacteria were performed. ZnO NPs were synthesized using a facile sol-gel approach. Gelatin nanofibers (GNF) were obtained by an electrospinning technique. GNF@ZnO composites were obtained by adding previously produced GNF into a Zn2+ methanol solution during ZnO NPs synthesis. Crystal structure, phase, and elemental compositions, morphology, as well as photoluminescent properties of pristine ZnO NPs, pristine GNF, and GNF@ZnO composites were characterized using powder X-ray diffraction (XRD), FTIR analysis, transmission and scanning electron microscopies (TEM/SEM), and photoluminescence spectroscopy. SEM, EDX, as well as FTIR analyses, confirmed the adsorption of ZnO NPs on the GNF surface. The pristine ZnO NPs were highly crystalline and monodispersed with a size of approximately 7 nm and had a high surface area (83 m2/g). The thickness of the pristine gelatin nanofiber was around 1 &micro, m. The antibacterial properties of GNF@ZnO composites were investigated by a disk diffusion assay on agar plates. Results show that both pristine ZnO NPs and their GNF-based composites have the strongest antibacterial properties against Pseudomonas fluorescence and Staphylococcus aureus, with the zone of inhibition above 10 mm. Right behind them is Escherichia coli with slightly less inhibition of bacterial growth. These properties of GNF@ZnO composites suggest their suitability for a range of antimicrobial uses, such as in the food industry or in biomedical applications.

A new mechanism of RNA circularization driven by specific binding of miRNAs is described. We identified the 71 CUUCC pentanucleotide motifs distributed regularly throughout the entire molecule of CDR1as RNA that bind to 71 miRNAs through their seed sequence GGAAG. The sequential binding of miR-7 RNAs (71 molecules) brings both ends of CDR1as RNA (1 molecule) together and stimulate phosphodiester bond formation between nucleotides C

Tissue engineering (TE) is a rapidly growing interdisciplinary field, which aims to restore or improve lost tissue function. Despite that TE was introduced more than 20 years ago, innovative and more sophisticated trends and technologies point to new challenges and development. Current challenges involve the demand for multifunctional bioscaffolds which can stimulate tissue regrowth by biochemical curves, biomimetic patterns, active agents and proper cell types. For those purposes especially promising are carefully chosen primary cells or stem cells due to its high proliferative and differentiation potential. This review summarized a variety of recently reported advanced bioscaffolds which present new functions by combining polymers, nanomaterials, bioactive agents and cells depending on its desired application. In particular necessity of study biomaterial-cell interactions with in vitro cell culture models, and studies using animals with in vivo systems were discuss to permit the analysis of full material biocompatibility. Although these bioscaffolds have shown a significant therapeutic effect in nervous, cardiovascular and muscle, tissue engineering, there are still many remaining unsolved challenges for scaffolds improvement., Graphical abstract Image 1, Highlights • Challenges, limitations and future prospects in tissue engineering are presented. • Strategies for enhanced neural, cardiovascular and muscle regeneration are discussed. • Topographical, mechanical and chemical guiding enhance nerves regeneration. • Multifunctional scaffolds provide cardiac tissue-like environment. • Hybrid biomaterials mimic and improve regeneration of muscle tissue.

Although less attention was paid to understanding physical localization changes in cell nuclei recently, depicting chromatin interaction maps is a topic of high interest. Here, we focused on defining extensive physical changes in chromatin organization in the process of skeletal myoblast differentiation. Based on RNA profiling data and 3D imaging of myogenic (NCAM1, DES, MYOG, ACTN3, MYF5, MYF6, ACTN2, and MYH2) and other selected genes (HPRT1, CDH15, DPP4 and VCAM1), we observed correlations between the following: (1) expression change and localization, (2) a gene and its genomic neighbourhood expression and (3) intra-chromosome and microscopical locus-centromere distances. In particular, we demonstrated the negative regulation of DPP4 mRNA (p DPP4 locus towards the nuclear lamina (p VCAM1 and MYH2). Overall, we describe for the first time existing mechanisms of spatial gene expression regulation in myoblasts that might explain the issue of heterogenic responses observed during muscle regenerative therapies.

Introduction AT101, the R-(-)-enantiomer of the cottonseed-derived polyphenol gossypol, is a promising drug in glioblastoma multiforme (GBM) therapy due to its ability to trigger autophagic cell death but also to facilitate apoptosis in tumor cells. It does have some limitations such as poor solubility in water-based media and consequent low bioavailability, which affect its response rate during treatment. To overcome this drawback and to improve the anti-cancer potential of AT101, the use of cubosome-based formulation for AT101 drug delivery has been proposed. This is the first report on the use of cubosomes as AT101 drug carriers in GBM cells. Materials and Methods Cubosomes loaded with AT101 were prepared from glyceryl monooleate (GMO) and the surfactant Pluronic F-127 using the top–down approach. The drug was introduced into the lipid prior to dispersion. Prepared formulations were then subjected to complex physicochemical and biological characterization. Results Formulations of AT101-loaded cubosomes were highly stable colloids with a high drug entrapment efficiency (97.7%) and a continuous, sustained drug release approaching 35% over 72 h. Using selective and sensitive NMR diffusometry, the drug was shown to be efficiently bound to the lipid-based cubosomes. In vitro imaging studies showed the high efficiency of cubosomal nanoparticles uptake into GBM cells, as well as their marked ability to penetrate into tumor spheroids. Treatment of GBM cells with the AT101-loaded cubosomes, but not with the free drug, induced cytoskeletal rearrangement and shortening of actin fibers. The prepared nanoparticles revealed stronger in vitro cytotoxic effects against GBM cells (A172 and LN229 cell lines), than against normal brain cells (SVGA and HMC3 cell lines). Conclusion The results indicate that GMO-AT101 cubosome formulations are a promising basic tool for alternative approaches to GBM treatment.

In this work, we show synthesis that leads to thermoreponsive poly-N-isopropyl acrylamide (pNIPAM) nanogels with sizes below 100 nm, irrespectively of the surfactant to crosslinker ratio. We also show that in many environments the temperature induced pNIPAM collapse at Lower Critical Solution Temperature (LCST) of 32.5 °C is accompanied by gel nanoparticles' aggregation. Thus, the proper information on the nanoparticle (NP) structure and deswelling can be obtained only if the routinely measured hydrodynamic radius is supplemented by information on the molecular weight, which can be obtained from the intensity of scattered light. We measured the dynamics and reversibility of the deswelling and subsequent aggregation processes. Furthermore, we show that the highly concentrated pNIPAM gel NPs reversibly form bulk hydrogel networks of varied interconnected porous structure. We show, that in case of drying pNIPAM gel NPs above the LCST, it is possible to obtain films with 20-fold increase in storage modulus (G′) compared to hydrogel networks measured at room temperature. They exhibit temperature hysteresis behavior around LCST of 32.5 °C similar to pNIPAM films. Finally, we show that these hydrogel films, lead to extended proliferation of cells across three different types: fibroblast, endothelial and cancer cells. Additionally, none of the films exhibited any cytotoxic effects. Our study brings new insights into physicochemical characterization of pNIPAM gel NPs and networks behavior in realistic conditions of in vitro measurements, especially by means of dynamic light scattering as well as final unique properties of both gel NPs and formed porous films for possible tissue engineering applications.

A novel, (1-adamantylsulfanyl)-octasubstituted tetrapyrazinoporphyrazine has been synthesized and analyzed for its key physicochemical properties. Also, two 1-adamantylsulfanyl-substituted pyrazine derivatives were compared, and their crystallographic structures as well as chemical reactivity were assessed and discussed. Porphyrazine macrocycle showed good fluorescence and singlet oxygen generation properties as well as photostability. In addition, studied adamantylsulfanyl porphyrazine, despite its hydrophobic nature, revealed good solubility in polar solvents. Electrochemical studies revealed that the macrocycle underwent oxidation by one one-electron process and reduction with two one-electron processes.

Multilayered design showed itself to advantage for improvement of functional nitride coatings, which are widely required in various industry applications. This article reports on deposition and detailed characterization series of combined nano-multilayered coatings based on (TiAlSiY)N with changes in components of alternating binary layers. Vacuum-arc deposited (TiAlSiY)N/MoN, (TiAlSiY)N/CrN and (TiAlSiY)N/ZrN coatings were analyzed by means of various experimental techniques such as SEM with EDS, XRD and GIXRD, SIMS, XPS and Raman spectroscopy. Microstructure of (TiAlSiY)N/MoN coating was characterized by creation of fine-grained fcc-AlTiN phase of (200) plane with congruent growth of γ-Mo2N (200) due to high isostruturality of lattices of alternating layers. The formation of fcc-AlYTiN phase of (111) plane and fcc-TiCrN phase of (200) plane were observed in multilayered (TiAlSiY)N/CrN coating and referred to the loss of clear interfaces and the formation of transition layers due to the diffusion of Ti atoms. Nano-multilayered (TiAlSiY)N/ZrN system showed the formation of stoichiometric fcc compounds of TiN with (200) plane and ZrN with (111) plane, respectively. The evaluation of mechanical properties as nanohardness, reduced elastic modulus, elastic strain prior to failure, and resistance to plastic deformation measurements was performed. The presented results showed important information about the physical and mechanical properties of new nano-multilayered systems for their subsequent application, as well as improvement of existing achievements.

The (TiZrNbHfTa)N/WN multicomponent coatings were deposited by vacuum arc evaporation under different substrate bias (−90 and −280 V). X-ray photoelectron spectroscopy was used for analyzing of complex composition of investigated coatings by reflecting of atomic scale chemical interactions. The structural investigations showed the formation of a simple disordered solid solution in (TiZrNbHfTa)N layer, β-W2N phase in WN layer with fcc crystal structure and highly disordered bcc (1 1 0) and (2 2 0)-oriented high-entropy alloy phases, regardless of the applied bias potential. It was shown that with increasing of substrate bias from −90 to −280 V, there is a slight decrease of hardness from 34 to 31 GPa and increase of Young’s modulus from 325 to 337 GPa, which can be explained by annihilation of point defects and precipitation of relatively softer metallic phase.

This paper reports on the deposition and characterization of (TiAlSiY)N nanocomposite and (TiAlSiY)N/MoN nano-scale multilayer coatings obtained by means of arc-PVD method. The investigation of structural-phase composition and mechanical properties is carried out by means of scanning electron microscopy (SEM), equipped with energy dispersive spectrum (EDS), High resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and nanoindentation. The microstructure of the (TiAlSiY)N nanocomposite coating shows preferential (111) growth of fcc-(Ti, Al)N grains. Multilayers coating of (TiAlSiY)N/MoN with a bilayer period of 10 nm was synthesized, showing that the fcc-MoN layer grows coherently with the fcc-(Ti,Al)N, due to the template effect of the latter, which results in a local cube on cube fcc(Ti,Al)N||fcc(MoN) epitaxial growth with (200) preferential orientation. The hardness, reduced elastic modulus, elastic strain prior to plastic deformation and resistance to plastic deformation of the nanocomposite (TiAlSiY)N coating are determined as 24.6 GPa, 243 GPa, ~0.09 and 0.29 GPa, respectively. The enhancement of the mechanical properties of the multilayer coating up to 38.37, 392.5 GPa, ~0.09 and 0.38 GPa is also observed.

Main regularities of the formation of microstructure and properties of multilayer nanostructured CrN/MoN films with periodically changing architecture of layers were considered. Coatings were fabricated by vacuum-arc evaporation of the cathodes (Arc-PVD) in nitrogen atmosphere (pN was 0.4, 0.09 and 0.03 Pa). CrN and γ-Mo2N nitride phases with fcc lattices and a small volume of metastable MoNx cubic phase were formed in the films at pN = 0.4 Pa. The decrease of pN to 0.09 Pa causes the formation of β-Cr2N hexagonal phase. Preferential crystallographic orientation changes from [311] to [111] and [200] when bias voltage Ub is −20, −150 and −300 V respectively. The nanocrystallites size in coatings with bilayer thickness λ = 44 nm decreases to 5.8 nm. The microdeformation grows from 0.4 to 2.3% when Ub changes to −20 V. Coatings show high hardness of 38–42 GPa and H/E = 0.107. In a couple with results of tribological tests, coatings demonstrate strong wear resistance, which makes them appropriate and promising for industrial applications as protective ones. The effect of deposition conditions (pN, Ub, λ) on composition, structure, hardness, toughness and wear resistance was studied to achieve superior mechanical and physical properties of coatings with long lifetime in harsh environment. Keywords: Multilayers, Microstructure, Phase composition, Hardness, H/E ratio, Wear

International audience; Structural, electronic and mechanical properties of ZnO/Graphene (ZnO/G) nanolaminates fabricated by low temperature atomic layer deposition (ALD) and chemical vapor deposition (CVD) were investigated. We performed scanning and transmission electron microscopy (SEM/TEM), X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-Ray photoelectron spectroscopy (XPS) and nanoindentation to characterize the ZnO/G nanolaminates. The main structural and mechanical parameters of ZnO/G nanolaminates were calculated. The obtained results were analyzed and interpreted taking into account mechanical interaction and charge effects occurring at the G-ZnO interface. The influence of graphene sublayers number on the mechanical behavior of the ZnO/G nanolaminates was studied. By reducing the bilayer thickness, the mechanical parameters of the films can be tuned (Young's modulus 100-200 GPa, hardness 3-9 GPa). The softer response of the multilayers as compared to the single layers of ZnO and graphene was attributed to the structural changes in the ZnO layer and the interfaces. This study shows the mechanical behavior of ZnO/G nanolaminates and their influence on the development of novel electro-optical devices based on these structures. (C) 2018 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.

A novel (TiZrNbTaHf)N/MoN nanocomposite coatings, which consist of the nitride of the high-entropy alloy and the binary nitride, were synthesized by vacuum-arc deposition at various substrate biases. The elemental composition, chemical bonding state, phase structure, microstructure and mechanical properties of the coatings were studied by high-resolution experimental methods: SIMS, GDMS, XPS, XRD, HR-TEM and nano-indentation. It was found that the chemical state of the (TiZrNbTaHf)N/MoN coatings has a complex nature, which consist of a mixture of nitrides of constituting elements. It was also shown that the coatings are based on B1 NaCl-structured γ-Mo2N-phase with a mixture of crystallographic orientations (111), (200), (220) and (311) together with the B1 NaCl-structured (TiZrNbTaHf)N solid-solution phase. First-principles calculations demonstrated that the metal sub-lattice of the (TiZrNbTaHf)N solid solution can be based on Ti1-xHfyTa1-x-y, Zr1-xHfyTa1-x-y, Zr0.25Ti0.25Ta0.5 ternary alloys, which have the lowest mixing energy. The HR-TEM results showed that the nanocomposite nitride coatings have nano-scale multilayer structure with modulation periods ranged from 20 nm to 25 nm. The maximum hardness of approximately 29 GPa demonstrated the coating deposited at a higher energy condition (−200 V) with the thinnest modulation period of bilayer of 20 nm (15 nm of (TiZrNbTaHf)N and 5 nm of Mo2N).

Nanoscale multilayered TiN/SiC films are of great importance in many electronic and industrial fields. The careful control over the structure of the laminates, nanocrystalline or amorphous, is crucial for their further applicability and study. However, several limitations in their fabrication have revealed important gaps in the understanding of this system. Here, we study influence of temperature on the physico-chemical and functional properties of TiN/SiC multilayers. We will show the clear increment on hardness of the samples, while the nanocomposite structure of the layers is maintained with no increment in crystal size. We will investigate the interstitial effects and rearrangements, between the TiN/SiC phases and their role in the enhanced mechanical response. Our experiments will clearly show a change in the modulation period of the samples, pointing to interfacial reactions, diffusion of ions or crystallization of new phases. Full Investigations of the film properties were carried out using several methods of analysis: XRD, XPS, FTIR, HR-TEM and SIMS Additionally, results were combined with First Principles MD computations of TiN/SiC heterostructures.

5,7-Diaryl-substituted symmetrical diazepinoporphyrazine and tribenzodiazepinoporphyrazine were synthesized and characterized using UV–Vis, MS MALDI, and various NMR techniques. The expected photosensitizing potentials of these porphyrazines were evaluated by measuring their abilities to generate singlet oxygen in organic solvents and by comparing them with that of the recently obtained dendrimeric G1-type diazepinoporhyrazine. Absorbance and fluorescence measurements were performed to study the aggregation properties of the novel macrocycles. The photocytotoxicity of tribenzodiazepinoporphyrazine towards LNCaP cells in its free form and after its incorporation into liposomes was examined using MTT assay under normoxic and hypoxic conditions. It is interesting that all tested liposome formulations maintained their phototoxic activity in hypoxia. Also, tribenzodiazepinoporphyrazine incorporated into liposomes revealed better photocytotoxic effect (IC50 values of 0.600 ± 0.357 μM and 0.378 ± 0.002 μM) than its free form (IC50 values of 3.135 ± 0.156 μM). Following the in vitro experiments, the most promising liposomal formulation containing l -α-phosphatidyl-DL-glycerol for tribenzodiazepinoporphyrazine was found. Moreover, tribenzodiazepinoporphyrazine incorporated into liposomes containing 1,2-dioleoyl-3-trimethylammonium-propane (chloride salt) revealed moderate phototoxicity at 5 × 10−5 μM for antibacterial photodynamic therapy. It was established that an irradiation of planktonic bacterial strains significantly reduced CFUs of Staphylococcus aureus ATCC 25923 in comparison to tribenzodiazepinoporphyrazine containing l -α-phosphatidyl-DL-glycerol liposomes.

The present study is focused on the development of liposomes bearing gadolinium chelate (GdLip) providing two functionalities for magnetic resonance imaging (MRI) and photodynamic therapy of cancer. A lipid derivative of gadolinium(III) diethylenetriamine pentaacetic acid salt (GdDTPA1) was inserted in the liposomal membrane and served as MRI contrast agent whereas a zinc phthalocyanine (ZnPc) was used as a model photosensitizer. In addition to conventional liposomes, pegylated lipids were used for the preparation of "stealth" liposomes. The characterization of different GdLip formulations involved evaluation of the liposomes size by nanoparticle tracking analysis, thermal phase behavior by differential scanning calorimetry and ZnPc-mediated singlet oxygen production. Furthermore, relaxivity measurements were performed as well as cytotoxicity and photodynamic activity against cancerous and normal cell lines was studied. Size and thermal behavior were only slightly influenced by GdLip composition, however it distinctly affected singlet oxygen production of ZnPc-loaded GdLip. The quantum yields of singlet oxygen generation by zinc phthalocyanine incorporated in GdLip containing cationic or/and pegylated lipids were smaller than those obtained for non-pegylated carriers with l-α-phosphatidylglycerol. In general, all formulations of GdLip, irrespectively of composition, were characterized by relaxivities higher than those of commercially used contrast agents (e.g. Magnevist®). NMR study has shown that the incorporation of ZnPc into the formulations of GdLip increases the relaxation parameters r1 and r2, compared to the values for the non-loaded vesicles. GdDTPA1 did not influence the photodynamic activity of ZnPc against HeLa cells.

Reduced graphene oxide–magnetite hybrid aerogels attract great interest thanks to their potential applications, e.g., as magnetic actuators. However, the tendency of magnetite particles to migrate within the matrix and, ultimately, escape from the aerogel structure, remains a technological challenge. In this article we show that coating magnetite particles with polydopamine anchors them on graphene oxide defects, immobilizing the particles in the matrix and, at the same time, improving the aerogel structure. Polydopamine coating does not affect the magnetic properties of magnetite particles, making the fabricated materials promising for industrial applications.

Low environmental stability of ZnO nanostructures in hydrophilic systems is a crucial factor limiting their practical applications. ZnO nanomaterials need surface passivation with different water-insoluble compounds. This study describes a one-step passivation process of polycrystalline ZnO films with ZnS as a facile method of ZnO surface coating. A simple sulfidation reaction was carried out in gas-phase H2S and it resulted in formation of a ZnS thin layer on the ZnO surface. The ZnS layer not only inhibited the ZnO dissolving process in water but additionally improved its mechanical and electrical properties. After the passivation process, ZnO/ZnS films remained stable in water for over seven days. The electrical conductivity of the ZnO films increased about 500-fold as a result of surface defect passivation and the removal of oxygen molecules which can trap free carriers. The nanohardness and Young's modulus of the samples increased about 64% and 14%, respectively after the ZnS coating formation. Nanowear tests performed using nanoindentation methods revealed reduced values of surface displacements for the ZnO/ZnS system. Moreover, both ZnO and ZnO/ZnS films showed antimicrobial properties against Escherichia coli.

Block copolymers represent an interesting class of materials, combining properties of individual components and capable of developing nanoscopic domain morphologies. Copolymers which comprise polystyrene and poly(dimethylsiloxane) attract special attention due to their effective segregation and the highly contrasting thermal properties of individual blocks. This work covers structural studies of copolymeric domain architecture and investigates the molecular dynamics observed in bulk PDMS, diblock PS-PDMS and triblock PS-PDMS-PS. Utilization of atomic force microscopy and NMR spin diffusion provide a thorough picture of phase separated systems. Dielectric spectroscopy reveals the dynamic heterogeneity of PDMS amorphous phase. Two distinct structural relaxations, namely α and αc, were observed and attributed correspondingly to PDMS mobile amorphous fraction and PDMS rigid amorphous fraction. Unexpectedly, the segmental reorientations observed in the case of copolymers were faster that that observed for bulk PDMS.

Nanostructured Si/TiO 2 core-shell nanopillar (NP) photoanodes were synthesized to overcome photodegradation stability of Si and to enhance the efficiency for photoelectrochemical water splitting. The core-shell structures were fabricated by atomic layer deposition of TiO 2 onto Si nanopillars synthesized by metal-assisted chemical etching and nanosphere lithography. Scanning electron microscopy, transmission electron microscopy, Raman and reflectance spectroscopies were utilized to characterize fabricated photoanodes. The obtained Si/TiO 2 core-shell NP arrays exhibit less than 6% of optical reflectance in UV and visible region, providing good optical absorption. Photoelectrochemical (PEC) water oxidation of fabricated photoanodes was studied. We showed that n-Si/n-TiO 2 NP exhibited a larger photocurrent than p-Si/n-TiO 2 due to a barrier at the heterojunction. Optimal morphological parameter of Si/TiO 2 NP for enhanced PEC water splitting were found. We demonstrated its enhanced PEC performance with a photocurrent density of 1.5 mA/cm 2 under simulated solar radiation with intensity of 100 mW/cm 2 . The relationship between the PEC performance and the electrolyte pH was also discussed. The design of the geometry of Si/TiO 2 core-shell NP arrays offers a new approach for preparing stable and highly efficient photoanodes for PEC water splitting.

The TiO2 modified by monometallic (Au-TiO2, Pt-TiO2) and bimetallic (Pt/Au-TiO2) NPs have been synthesized by a simple sol-gel method. The optimal dosage of individual components in Pt/Au composition on photocatalytic activity has been systematically investigated. The obtained photocatalysts were thoroughly characterized by BET surface area measurements, UV–vis diffuse-reflectance spectroscopy (DRS), X-ray diffraction analysis (XRD), scanning transmission microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity under visible light (λ > 420 nm and λ > 455 nm) has been estimated in phenol degradation reaction in an aqueous phase. The best photocatalytic activity has been observed for −mono (0.5)Pt_TiO2 and bimetallic (0.5)Pt/(0.5)Au_TiO2 samples with an optimum platinum content. The Pt/Au_TiO2 radical formation mechanism was systematically investigated with the selected scavenger for the degradation process under vis light irradiation. The formation of O 2− with (0.5)Pt/(0.5)Au_TiO2 was established from the high inhibition of phenol degradation. Based on the XPS analysis it was observed that the greater photoactivity of bimetallic sample (0.5)Pt/(0.5)Au_TiO2 could result from a relatively higher content of platinum compared to gold on the surface layer. It must be noted that only platinum takes a significant part in Pt/Au composites on the photoactivity. Furthermore, in this work we present a linear relationship between the crystal size of TiO2 and the reaction rate of Au-TiO2, Pt-TiO2 and Pt/Au-TiO2.

Nanoscale multilayered TiN/ZrN films were deposited using sequential vacuum-arc deposition of Ti and Zr targets in a nitrogen atmosphere. Studies of film's properties were carried out using various modern methods of analysis, such as XRD, STEM, HRTEM, SIMS combined with results of nanoindentation and tribological tests. To interpret the mechanical properties of the deposited multilayer films first-principles calculations of TiN(111), ZrN(111) structures and TiN(111)/ZrN(111) multilayer were carried out. To study the influence of thermal annealing, several samples were annealed in air at the temperature 700 °C. All deposited samples were highly polycrystalline with quite large 20–25 nm crystals. The crystalline planes were very ordinated and demonstrated an excellent coordinated growth. The nanohardness and elastic modulus of non-annealed coatings reached 42 GPa and 348 GPa, respectively. Annealing in air at the temperature 700 °C led to partial oxidation of the multilayered coatings, however hardness of the non-oxidized part of the coatings remained as high, as for initial coatings. All deposited coatings demonstrate good wear resistance.