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Water-dispersible up-converting nanoparticles (UCNPs) are known to be very effective in biomedical applications. Research groups have paid special attention to the synthesis of hydrophilic UCNPs with good physicochemical properties. Being aware of this, we decided to improve the ligand-free modification method of OA-capped NaYF4:Yb3+,Er3+/NaYF4 UCNPs prepared by precipitation in high-boiling-point solvents as the thus-far reported methods do not provide satisfactory results. Different molarities of hydrochloric acid and various mixing times were selected to remove the organic ligand from the NPs’ surface and to discover the most promising modification approach. Highly water-stable colloids were obtained with a very high reaction yield of up to 96%. Moreover, the acid treatment did not affect the morphology and the size of the product. All of the crystals exhibited a bright up-conversion emission under 975-nm excitation, which confirmed the two-photon excitation and effective energy transfer between the used dopant ions. Thus, we could establish the most successful ligand-free modification procedure.

Colloidal quantum dots (QDs) are nanoparticles that are able to photoreduce redox proteins by electron transfer (ET). QDs are also able to transfer energy by resonance energy transfer (RET). Here, we address the question of the competition between these two routes of QDs' excitation quenching, using cadmium telluride QDs and cytochrome c (CytC) or its metal-substituted derivatives. We used both oxidized and reduced versions of native CytC, as well as fluorescent, nonreducible Zn(II)CytC, Sn(II)CytC, and metal-free porphyrin CytC. We found that all of the CytC versions quench QD fluorescence, although the interaction may be described differently in terms of static and dynamic quenching. QDs may be quenchers of fluorescent CytC derivatives, with significant differences in effectiveness depending on QD size. SnCytC and porphyrin CytC increased the rate of Fe(III)CytC photoreduction, and Fe(II)CytC slightly decreased the rate and ZnCytC presence significantly decreased the rate and final level of reduced FeCytC. These might be partially explained by the tendency to form a stable complex between protein and QDs, which promoted RET and collisional quenching. Our findings show that there is a net preference for photoinduced ET over other ways of energy transfer, at least partially, due to a lack of donors, regenerating a hole at QDs and leading to irreversibility of ET events. There may also be a common part of pathways leading to photoinduced ET and RET. The nature of synergistic action observed in some cases allows the hypothesis that RET may be an additional way to power up the ET.

Control of morphology and spectroscopic properties during the synthesis of up-converting nanoparticles (NPs) is a great challenge. One of the most popular ways of NPs synthesis is the hydrothermal method, which is relatively simple, effective, environmentally friendly and permits easy control of synthesis parameters. For these reasons, the hydrothermal method was applied for the synthesis of CaF2:Yb3+,Er3+ NPs and optimized. The effects of synthesis conditions on the properties of the product were carefully analysed. The tests were performed to check the impact of two surfactants: sodium citrate (NaCit) and ammonium citrate (NH4Cit), different excess of ammonium fluoride used as a precipitation agent and different volumes of solution with reactants. The type of co-reagent was found to influence the size of the obtained NPs and charge compensation, required after Yb3+ and Er3+ doping into Ca2+ sites. Depending on the synthesis conditions, the formation of Yb3+ clusters and alterations in the Yb3+ site symmetry were detected. The excitation and emission spectra revealed the importance of the presence of the Na+ ions on the energy transfer mechanism and the resulting emission intensity. The presented results show that applying stirring during the synthesis or changing the type of anti-agglomeration agent has a great influence on the luminescence intensity and colour as well as maximum of excitation when Yb3+ ions are used. Analysis of the excitation spectra and Yb3+ emission decays showed the complex structure of CaF2:Yb3+,Er3+ NPs, with Yb3+ ions in two different environments within the volume of NPs with different site symmetries. The samples prepared in the presence of Na+ ions were characterized by long Yb3+ emission rise times, revealing energy migration between Yb3+ at different symmetries and, at the same time, improved the overall luminescence intensity of NPs.

In this research, we describe the properties of three-component composite foam scaffolds based on poly(ε-caprolactone) (PCL) as a matrix and hydroxyapatite whiskers (HAP) and L-Lysine as fillers (PCL/HAP/Lys with wt% ratio 50/48/2). The scaffolds were prepared using a thermally induced phase separation technique supported by salt leaching (TIPS-SL). All materials were precisely characterized: porosity, density, water uptake, wettability, DSC, and TGA measurements and compression tests were carried out. The microstructure of the obtained scaffolds was analyzed via SEM. It was found that the PCL/HAP/Lys scaffold has a 45% higher Young’s modulus and better wettability compared to the PCL/HAP system. At the same time, the porosity of the system was ~90%. The osteoblast hFOB 1.19 cell response was also investigated in osteogenic conditions (39 °C) and the cytokine release profile of interleukin (IL)-1β, IL-6, and tumor necrosis factor (TNF)-α was determined. Modification of PCL scaffolds with HAP and L-Lysine significantly improved the proliferation of pre-osteoblasts cultured on such materials.

Plastoglobules (PGs) might be characterised as microdomains of the thylakoid membrane that serve as a platform to recruit proteins and metabolites in their spatial proximity in order to facilitate metabolic channelling or signal transduction. This study provides new insight into changes in PGs isolated from two plant species with different responses to chilling stress, namely chilling-tolerant pea (Pisum sativum) and chilling-sensitive bean (Phaseolus coccineus). Using multiple analytical methods, such as high-performance liquid chromatography and visualisation techniques including transmission electron microscopy and atomic force microscopy, we determined changes in PGs’ biochemical and biophysical characteristics as a function of chilling stress. Some of the observed alterations occurred in both studied plant species, such as increased particle size and plastoquinone-9 content, while others were more typical of a particular type of response to chilling stress. Additionally, PGs of first green leaves were examined to highlight differences at this stage of development. Observed changes appear to be a dynamic response to the demands of photosynthetic membranes under stress conditions.

The use of functional nanomaterials and their combination with organic polymers leads to the formation of advanced composites and hybrid inorganic–organic systems having unique properties. The use of such materials as anti-counterfeiting agents (invisible under ambient conditions) is crucial for modern security systems and for further identification of labelled items and documents in various industrial applications. Here, the fabrication of functional paper by in situ incorporation of luminescent cellulose fibres into its structure, during the formation of paper pulp, is shown. In order to produce luminescent fibres, an in situ modification is made during the spinning process, using lanthanide-doped upconverting nanoparticles (SrF2:Yb3+,Er3+). At first glance (in daylight), the functionalized paper cannot be distinguished from its unmodified form. However, when exposed to invisible near-infrared laser light (975 nm), bright green illumination appears. The modified paper preserves good mechanical durability, which is important for its potential for further processing in documents and other commercially available forms. Protecting documents and various materials with this kind of paper may open new horizons in materials engineering, forensics, and other industrial applications.

The utilization of solar light to induce a photocatalytic reaction in the presence of wide band gap semiconductors requires the modification of their surface and optical properties. The Vis-to-UV up-conversion process (UCP) that occurs in lanthanide ions could be employed to induce TiO2. Thus, having in mind solar-forced photocatalysis, nanostructured TiO2 co-modified with Tm and Li was prepared via a hydrothermal method. In addition to the exhaustive surface characterization of the as-prepared samples, the partial density of states (PDOS) was computed to better understand the electronic structure and physicochemical properties of the prepared photocatalysts. It was demonstrated that Tm ions were beneficial for phenol degradation in the aqueous phase under visible irradiation, whereas the co-presence of Tm and Li ions was profitable for enhanced luminescence. Although action spectra revealed that excitation of Tm-TiO2 in the range from 400 to 490 nm led to the photodegradation of phenol and 2-propanol, the UCP was not responsible for the photocatalytic activity under Vis irradiation. Therefore, it is proposed that the formation of sub-band gap states from the lanthanide 4f level played a key role in the phenol degradation process.

While quantum dots (QDs) are useful as fluorescent labels, their application in biosciences is limited due to the stability and hydrophobicity of their surface. In this study, we tested two types of proteins for use as a cover for spherical QDs, composed of cadmium selenide. Pumilio homology domain (Puf), which is mostly α-helical, and leucine-rich repeat (LRR) domain, which is rich in β-sheets, were selected to determine if there is a preference for one of these secondary structure types for nanoparticle covers. The protein sequences were optimized to improve their interaction with the surface of QDs. The solubilization of the apoproteins and their assembly with nanoparticles required the application of a detergent, which was removed in subsequent steps. Finally, only the Puf-based cover was successful enough as a QD hydrophilic cover. We showed that a single polypeptide dimer of Puf, PufPuf, can form a cover. We characterized the size and fluorescent properties of the obtained QD:protein assemblies. We showed that the secondary structure of the Puf proteins was not destroyed upon contact with the QDs. We demonstrated that these assemblies do not promote the formation of reactive oxygen species during illumination of the nanoparticles. The data represent advances in the effort to obtain a stable biocompatible cover for QDs.

Due to their photon up-converting capability, lanthanide ions are ideal candidates dopants for semiconductors for developing visible light-driven photocatalytic activity. Of particular relevance, the low luminescence efficiency of Ln-based nanoparticles is one of the main factors that limits their further applications. Carbon, which is present on the surface of all TiO2 photocatalysts, can be responsible for luminescence quenching processes and, thus, decreasing the photocatalytic activity of TiO2. This article presents a systematic experimental and theoretical study of the effects of carbon on the photocatalytic performance of Ho3+-modified TiO2. Ho3+-TiO2 photocatalysts modified with various carbon contents (from 0.5 to 20 mol.%) were successfully prepared using a simple hydrothermal method. As-obtained samples were characterized by UV–Vis diffuse reflectance spectroscopy (DRS/UV–Vis), X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), N2 adsorption measurements, photoluminescent spectroscopy (PL), field-emission scanning electron microscopy (FE-SEM) and scanning transmission microscopy (STEM). The photodegradation efficiency of phenol was estimated for visible light (λ > 420 nm and λ > 455 nm). The XPS and XRD analyses and theoretical calculations revealed that the substitutional doping of holmium and carbon in the TiO2 anatase structure resulted in the appearance of a new sub-band-gap. Changes in the material texture, BET surface area and pore volume can be easily controlled via carbon content in samples. Doping of the Ho3+-TiO2 photocatalysts with carbon resulted in quenching of the emission of Ho3+ and, thus, the photodegradation of phenol, was observed in samples containing smaller amounts of carbon. Sixty minutes of irradiation resulted in 89% of phenol degradation under visible light (λ > 420 nm).

Herring (Clupea harengus) shows the unique behavior of reproductive biology in which spermatozoa remains in the surrounding media for extended periods. It is an excellent model for studying the malic enzyme (ME) and creatine kinase (CK) biochemical properties because of their high activity and variability of molecular isoforms. The specific activity of NAD-preferring ME in herring spermatozoa is the highest among other fish spermatozoa and is localized in its large mitochondrion. Two different CK isoforms, dimer and octamer, were detected in herring spermatozoa. It has already been shown that CK isoforms play an important role in energy homeostasis by catalyzing a reversible transfer of the phosphate of ATP to creatine to yield ADP and creatine phosphate (CP) (creatine/CP circuit). Two lactate dehydrogenase (LDH) isoenzymes were also shown in herring spermatozoa, LDH-B4 and LDH-A2B2. In this mini-review, the role of ME and energy transport system with easily diffusible creatine and CP in herring spermatozoa is discussed.

The article describes the properties of LuF3 and NaLuF4 fluorides doped with Yb3+ and Er3+ or Tm3+ ions, their comparison and application in latent fingermarks imaging. The single-phase materials were successfully synthesized by the hydrothermal method. They exhibited up-conversion (UC) phenomenon under excitation by the near-infrared (NIR) radiation at 975 nm. Under excitation, the energy transfer between Yb3+ and Er3+ or Tm3+ ions occurred and emissions in the visible range were recorded (green or blue for Er3+ or Tm3+ dopants respectively). The luminescence decays of as-prepared samples were measured allowing the calculation of luminescence lifetimes. The dependencies of integrated UC intensity on laser power density were measured for the obtained samples, revealing up to three-photon process for Yb3+ and Tm3+ co-doped and two-photon process for Yb3+ and Er3+ co-doped materials. Furthermore, up-converting lutetium fluorides synthesized in this report were successfully used to visualize latent fingermarks on various non-porous surfaces.

The application of natural polymer matrices as medical device components or food packaging materials has gained a considerable popularity in recent years, this has occurred in response to the increasing plastic pollution hazard. Currently, constant progress is being made in designing two-component or three-component systems that combine natural materials which help to achieve a quality comparable to the purely synthetic counterparts. This study describes a green synthesis preparation of new bionanocomposites consisting of starch/chitosan/graphene oxide (GO), that possess improved biological activities, namely, good tolerability by human cells with concomitant antimicrobial activity. The structural and morphological properties of bionanocomposites were analyzed using the following techniques: dynamic light scattering,&nbsp, scanning and transmission electron microscopy,&nbsp, wettability and free surface energy determination, and Fourier transform infrared spectroscopy. The study confirmed the homogenous distribution of GO layers within the starch/chitosan matrix and their large particle size. The interactions among the components were stronger in thin films. Additionally, differential scanning calorimetry analysis, UV–vis spectroscopy, surface colour measurements, transparency, water content, solubility, and swelling degree of composites were also performed. The mechanical parameters, such as tensile strength and elongation at break (EAB) were measured in order to characterise the functional properties of obtained nanocomposites. The GO additive altered the thermal features of the composites and decreased their brightness. The EAB of composite was improved by the introduction of GO. Importantly, cell-based analyses revealed no toxic effect of the composites on HaCat keratinocytes and HepG2 hepatoma cells, although a pronounced bacteriostatic effect against various strains of pathogenic bacteria was observed. In conclusion, the starch/chitosan/GO nanocomposites reveal numerous useful physicochemical and biological features, which make them a promising alternative for purely synthetic materials.

Nitrogen (N) is widely distributed in the lithosphere, hydrosphere, atmosphere and biosphere. It is a basic component of every plant cell as well as microorganisms, as a component of proteins, nucleic acids and chlorophyll. It enters soil with organic and mineral fertilizers, plant and animal residues and biological nitrogen fixation. There are various forms of nitrogen in soil, and this element is usually transformed by microorganisms. The transformation of nitrogen compounds (ammonification, nitrification and immobilization) is significantly influenced by climatic conditions and the physicochemical properties of soil. Microbial mineralization of nitrogen organic matter results in the enrichment of soil with this element, which is necessary to generate a yield. The amount of nitrogen entering soil through the mineralization of crop residues ranges from 15 to 45 kg N/ha in cereal residues and from 80 to 144 kg N/ha in winter rape residues. Biological nitrogen fixation can increase the nitrogen content in soil by 30–50 kg/ha/year. In recent decades, the mismanagement of mineral fertilizers has drastically changed the natural balance of the nitrogen cycle. Every year huge amounts of nitrogen compounds enter the aquatic ecosystems and cause their eutrophication. That is why it is important to have adequate knowledge of sustainable fertilization so as to practice integrated crop management.

The right choice of synthesis route for upconverting nanoparticles (UCNPs) is crucial for obtaining a well-defined product with a specific application capability. Thus we decided to compare the physicochemical, cytotoxic, and temperature-sensing properties of UCNPs obtained from different rare earth (RE) ions, which has been made for the first time in a single study. The core/shell NaYF4:Yb3+,Er3+/NaYF4 UCNPs were obtained by reaction in a mixture of oleic acid and octadecene, and their highly stable water colloids were prepared using the ligand-free modification method. Both oleate-capped and ligand-free UCNPs exhibited a bright upconversion emission upon 975 nm excitation. Moreover, slope values, emission quantum yields, and luminescence lifetimes confirmed an effective energy transfer between the Yb3+ and Er3+ ions. Additionally, the water colloids of the UCNPs showed temperature-sensing properties with a good thermal sensitivity level, higher than 1 % K−1 at 358 K. Evaluation of the cytotoxicity profiles of the obtained products indicated that cell viability was decreased in a dose-dependent manner in the analyzed concentration range.

The study provides deep insight into the origin of photocatalytic deactivation of Nb2O5 after modification with ceria. Of particular interest was to fully understand the role of ceria species in diminishing the photocatalytic performance of CeO2/Nb2O5 heterostructures. For this purpose, ceria was loaded on niobia surfaces by wet impregnation. The as-prepared materials were characterized by powder X-ray diffraction, nitrogen physisorption, UV-visible spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. Photocatalytic activity of parent metal oxides (i.e., Nb2O5 and CeO2) and as-prepared CeO2/Nb2O5 heterostructures with different ceria loadings were tested in methanol photooxidation, a model gas-phase reaction. Deep insight into the photocatalytic process provided by operando-IR techniques combined with results of photoluminescence studies revealed that deactivation of CeO2/Nb2O5 heterostructures resulted from increased recombination of photo-excited electrons and holes. The main factor contributing to more efficient recombination of the charge carriers in the heterostructures was the ultrafine size of the ceria species. The presence of such highly dispersed ceria species on the niobia surface provided a strong interface between these two semiconductors, enabling efficient charge transfer from Nb2O5 to CeO2. However, the ceria species supported on niobia exhibited a high defect site concentration, which acted as highly active recombination centers for the photo-induced charge carriers.

Somatic embryogenesis is the formation of a plant embryo from a cell other than the product of gametic fusion. The need to recognize the determinants of somatic cell fate has prompted investigations on how endogenous factors of donor tissues can determine the pattern of somatic embryo origin. The undertaking of this study was enabled by the newly developed experimental system of somatic embryogenesis of the tree fern Cyathea delgadii Sternb., in which the embryos are produced in hormone-free medium. The contents of 89 endogenous compounds (such as sugars, auxins, cytokinins, gibberellins, stress-related hormones, phenolic acids, polyamines, and amino acids) and cytomorphological features were compared between two types of explants giving rise to somatic embryos of unicellular or multicellular origin. We found that a large content of maltose, 1-kestose, abscisic acid, biologically active gibberellins, and phenolic acids was characteristic for single-cell somatic embryo formation pattern. In contrast, high levels of starch, callose, kinetin riboside, arginine, and ethylene promoted their multicellular origin. Networks for visualization of the relations between studied compounds were constructed based on the data obtained from analyses of a Pearson correlation coefficient heatmap. Our findings present for the first time detailed features of donor tissue that can play an important role in the somatic-to-embryogenic transition and the somatic embryo origin.

Understanding of the metabolic pathways connected with a removal of micropollutant bisphenol A (BPA) may help to better design effective wastewater treatment processes. The aim of this study was to determine changes in gene expression in an aerobic granular sludge (AGS) community exposed to BPA. In the study, AGS adapted to BPA degradation was used. In this sludge, BPA was dosed; as a control sample, granules without BPA addition were used. mRNA was isolated from both samples and sequenced using the Illumina platform. Metatranscriptome analysis of AGS exposed to BPA indicated direct biodegradation as the main mechanism of BPA removal from wastewater. High expression of genes coding pilus and flagellin proteins in the BPA-exposed biomass indicated that exposition to BPA stimulated aggregation of microbial cells and formation of biofilm. In the BPA-exposed biomass, nitrogen was mainly used as an energy source, as indicated by the presence of genes coding nitrification enzymes and urease. Moreover, exposition to BPA stimulated expression of genes coding proteins responsible for xenobiotic degradation, including enzymes responsible for benzoate degradation. These results increase knowledge about BPA metabolism in complex microbial communities in wastewater treatment systems and indicate that AGS is suitable for efficiently removing BPA from wastewater.

Polymer nanocomposites containing nanometals became a subject of interest due to their bactericidal properties. Different polysaccharides have been used as matrices for nanosilver and nanogold synthesis. In this study, we present a novel, environmentally friendly method for the preparation of sodium alginate/nanosilver/graphene oxide (GOX) and sodium alginate/nanogold/graphene oxide GOX nanocomposites and their characteristics. The formation of approximately 10–20 nm ball-shaped Ag and Au nanoparticles was confirmed by UV–vis spectroscopy, scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectra. The incorporation of GOX sheets within the ALG matrix improved the thermal stability of the nanocomposites film, which was measured using the differential scanning calorimetry (DSC). We also estimated the molecular weights of polysaccharide chains of the matrix with the size exclusion chromatography coupled with multiangle laser light scattering and refractometric detectors (HPSEC-MALLS-RI). The composites were more prone to enzymatic hydrolysis. The strongest bacteriostatic activity was observed for the sample containing nanosilver.

Nanoparticles (NPs) based on host compound NaYF4 with core@shell structures were synthesised by the precipitation reaction in high-boiling point octadecene/oleic acid solvent. Four laser wavelengths were used (808, 975, 1208, or 1532 nm) for excitation of the obtained NPs. The resulting emission and mechanisms responsible for spectroscopic properties were studied in detail. Depending on NP compositions, i.e. type of doping ion (Er3+, Tm3+, or Yb3+) or presence of dopants in the same or different phases, adjustable up-conversion (UC) could be obtained with emission peaks covering the visible to near-infrared range (475 to 1625 nm). The presented results demonstrated multifunctionality of the prepared NPs. NaYF4:2%Tm3+@NaYF4 NPs exhibited emission at 700 and 1450 nm under 808 nm laser excitation or 800 and 1625 nm emission under 1208 nm laser radiation, as a result of ground- and excited-state absorption processes (GSA and ESA, respectively). However, NaYF4:5%Er3+,2%Tm3+@NaYF4 NPs showed the most interesting properties, as they can convert all studied laser wavelengths due to the absorption of Tm3+ (808, 1208 nm) or Er3+ ions (808, 975, 1532 nm), revealing a photon avalanche process under 1208 nm laser excitation, as well as GSA and ESA at other excitation wavelengths. The NaYF4:2%Tm3+@NaYF4:5%Er3+ NPs revealed the resultant emission properties, as the dopant ions were separated within core and shell phases. The NaYF4:18%Yb3+,2%Tm3+@NaYF4 and NaYF4:18%Yb3+,2%Tm3+@NaYF4:5%Er3+ samples showed the brightest emission, around 800 nm, under 975 nm excitation, though other laser wavelengths allowed for observation of luminescence, as well, especially in NPs with Er3+ in the outer shell, capable of UC under 1532 nm. The presented results highlight the unique and universal properties of lanthanide ions for designing luminescent NPs for a variety of potential applications, such as confocal microscopy.

Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO•) play an important role, being the most aggressive towards biomolecules. The reactions of HO• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO•, and by CB triplets allowed for assigning transient species to the pathways of products formation.

For a number of years nanomaterials have been continuously devised and comprehensively investigated because of the growing demand for them and their multifarious applications, especially in medicine. This paper reports on the properties of SrF2 nanoparticles (NPs) for applications in biomedicine, showing effective ways of their synthesis and luminescence under near infrared radiation - upconversion. NPs doped with lanthanide, Ln3+ ions (where Ln = Yb, Ho, Er, Tm) were prepared by the hydrothermal method and subjected to comprehensive studies, from determination of their structure and morphology, revealing small, 15 nm structures, through spectroscopic properties, to cytotoxicity in vitro. The effects of such factors as the reaction time, type and amount of precipitating compounds and complexing agents on the properties of products were characterized. The cytotoxicity of the synthesized and functionalized NPs was investigated, using human fibroblast cell line (MSU-1.1). The synthesized structures may decrease cells’ proliferation in a dose-dependent manner in the measured concentration range (up to 100 µg/mL). However, the cells remain alive according to the fluorescent assay. Moreover, the treated cells were imaged using confocal laser scanning microscopy. Cellular uptake was confirmed by the presence of upconversion luminescence in the cells.

This paper reports on the influence of internal device parasitics of a high-speed SiGe HBT, its bias operation range, and circuit-antenna co-design aspects on frequency-dependent rectification efficiency of the room-temperature operated antenna-coupled THz direct detectors in 130-nm technology leading to their low-NEP operation in a near-THz fractional bandwidth. In particular, an optical NEP below 36 pW/√Hz was measured across 220–1000 GHz for the single and dual linearly-polarized detectors with minimum NEP values of 1.9 pW/√Hz at 292 GHz and 2.7 pW/√Hz at 449 GHz for the former and the latter, respectively.

Contaminated surface sediments were removed from a coastal marsh and replaced with clean engineered sediments before marsh vegetation was replanted and the site was reopened to the tide. Differences in trace metal concentrations (Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn) were monitored for 11 years at different sediment depths, under two types of engineered sediments (with and without compost), and at three marsh surface elevations. Except for Hg and Cd, all others followed the patterns of Fe and Mn of decreasing concentration during drought years and increasing concentration during wet years. Metals in deep sediments (> 25 cm) are always higher than on the surface. Surfaces higher in the terrain had fewer metal concentrations compared to lower elevations. The compost treatment had no insignificant effect on metal concentration. The main pathways involved in remobilization from the buried legacy sediments are organic metal complexation, reductive dissolution, and oxidation of metal sulfides. Hg showed an enrichment pattern throughout the study period suggesting atmospheric deposition as the main pathway. Similarly, sources of Cd are most likely from atmospheric wet deposition since most of the Cd variation is explained by changes in the amounts of rain. Metal concentration in the sediments decreased up to 50% from pre-restoration conditions; the only exceptions were Hg and Cd which continue to accumulate. Increasing dry periods and storm frequencies from changing global weather patterns have the potential to create conditions for greater bioavailability of metals from this and similar world estuaries.

Hepatitis C virus (HCV) infection with associated chronic liver diseases is a major health problem worldwide. Here, we designed hepatitis B virus (HBV) small surface antigen (sHBsAg) virus-like particles (VLPs) presenting different epitopes derived from the HCV E2 glycoprotein (residues 412&ndash, 425, 434&ndash, 446, 502&ndash, 520, and 523&ndash, 535 of isolate H77C). Epitopes were selected based on their amino acid sequence conservation and were previously reported as targets of HCV neutralizing antibodies. Chimeric VLPs obtained in the Leishmania tarentolae expression system, in combination with the adjuvant Addavax, were used to immunize mice. Although all VLPs induced strong humoral responses, only antibodies directed against HCV 412&ndash, 425 and 523&ndash, 535 epitopes were able to react with the native E1E2 glycoprotein complexes of different HCV genotypes in ELISA. Neutralization assays against genotype 1&ndash, 6 cell culture infectious HCV (HCVcc), revealed that only VLPs carrying the 412&ndash, 425 epitope induced efficient HCV cross-neutralizing antibodies, but with isolate specific variations in efficacy that could not necessarily be explained by differences in epitope sequences. In contrast, antibodies targeting 434&ndash, 535 epitopes were not neutralizing HCVcc, highlighting the importance of conformational antibodies for efficient virus neutralization. Thus, 412&ndash, 425 remains the most promising linear E2 epitope for further bivalent, rationally designed vaccine research.

The present work shows the results of the synthesis of multiphasic calcium phosphate whiskers from a mixture of biphasic calcium phosphate (?-tricalcium phosphate (?-TCP) and calcium pyrophosphate (CPP)) in the hydrogen peroxide solution-mediated process carried out in different time ranges. The process was performed at considerably lower temperature than typical hydrothermal methods used for obtaining of whiskers. Test results show that using the above-mentioned procedure triphasic calcium phosphate consisting of hydroxyapatite (HA),(?-TCP) and CPP can be obtained, where the whiskers are formed mainly from hydroxyapatite. It was found that morphology, phase composition and specific surface area of the reaction product can be controlled by changing the reaction time. The obtained triphasic HA/?-TCP/CPP short whiskers may be considered as a promising biocompatible and resorbable reinforcement in composites for bone tissue engineering with a faster resorption rate than that of HA.

Ultrasmall (9–30 nm) Yb3+/Er3+-doped, upconverting alkaline rare-earth fluorides that are promising for future applications were synthesized by the microwave-assisted hydrothermal method. The formation mechanism was proposed, indicating the influence of the stability of metal ions complexes with ethylenediaminetetraacetic acid on the composition of the product and tendency to form M2REF7 (M0.67RE0.33F2.33) cubic compounds in the M–RE–F systems. Their physicochemical properties (structure, morphology, and spectroscopic properties) are compared and discussed. The obtained nanoparticles exhibited emission of light in the visible spectra under excitation by 976 nm laser radiation. Excitation and emission spectra, luminescence decays, laser energy dependencies, and upconversion quantum yields were measured to determine the spectroscopic properties of prepared materials. The Yb3+/Er3+ pair of ions used as dopants was responsible for an intense yellowish-green emission. The upconversion quantum yields determined...

Graphene-based electrochemical sensors are promising devices for direct and easy dopamine determination. In this work, N-doped reduced graphene oxides (N-rGOs) were prepared via hydrothermal treatment of graphene oxide (GO) and amitrole (3-amino-1,2,4-triazole) under different experimental conditions (varying reaction temperature and time), which resulted in each material having different oxygen content. Furthermore, the dopant nitrogen content was comparable in the three N-rGOs and it was primarily pyridinic in nature. The three synthesized N-rGOs were characterized by X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy, scanning electron microscopy, and nitrogen sorption at 77 K. Glassy carbon electrodes modified with N-rGOs were prepared and used as active electrode materials in electrochemical sensors of dopamine (DA). The optimal operational pH was determined to be 7.4, which is also the physiological value. During the electrochemical detection of DA, it was found that there is a direct relationship between the oxygen content in N-rGO and electrochemical performance of these sensors. Thus, the detection of DA in the presence of ascorbic and uric acids was more sensitive and selective when the least reduced N-rGO sample was used. The attraction between the electronegative oxygen in the graphene structure and cationic DA facilitates the adsorption process which could explain these results. However, the limit of detection (LOD) was also higher in this case due to decreased conductivity.

Direct interaction of ferredoxin:NADP+ oxidoreductase (FNR) with thylakoid membranes was postulated as a part of the cyclic electron flow mechanism. In vitro binding of FNR to digalactosyldiacylglycerol and monogalactosyldiacylglycerol membranes was also shown. In this paper we deal with the latter interaction in more detail describing the effect for two FNR forms of Synechocystis PCC 6803. The so-called short FNR (sFNR) is homologous to FNR from higher plant chloroplasts. The long FNR (lFNR) form contains an additional domain, responsible for the interaction with phycobilisomes. We compare the binding of both sFNR and lFNR forms to native and non-native lipids. We also include factors which could modulate this process: pH change, temperature change, presence of ferredoxin, NADP+ and NADPH and heavy metals. For the lFNR, we also include phycobilisomes as a modulating factor. The membrane binding is generally faster at lower pH. The sFNR was binding faster than lFNR. Ferredoxin isoforms with higher midpoint potential, as well as NADPH and NADP+, weakened the binding. Charged lipids and high phosphate promoted the binding. Heavy metal ions decreased the rate of membrane binding only when FNR was preincubated with them before injection beneath the monolayer. FNR binding was limited to surface lipid groups and did not influence hydrophobic chain packing. Taken together, FNR interaction with lipids appears to be non-specific, with an electrostatic component. This suggests that the direct FNR interaction with lipids is most likely not a factor in directing electron transfer, but should be taken into account during in vitro studies.

In this study, qualitative tests were carried out to compare the behaviour of selected slabs exposed to short- and long-term loading. Full-scale models of the half-slab and hollow-core slab with dimensions of 6.30 m × 6.30 m, built of four different precast panels, were tested. The first two were semi-precast lattice girder slabs, the third semi-precast prestressed ribbed panels, and the last was composed of hollow-core panels. A common feature was the lack of joint reinforcement and the same modular width of 600 mm. The short-term load was applied sequentially in the first stage, and displacement was measured using an electronic method. In the second stage of long-term testing, the load was mainly applied to one part of the slab. Testing under short-term and long-term load allows determining the change in the performance of panel slabs over time. The panels maintained the ability of load redistribution based on their interaction despite the work of the longitudinal joints being only through the concrete cross-section. The behaviour of slabs with concrete topping shows more significant lateral interactions than elements connected only by shear key. Comparative calculations were made based on four computational models. Comparative analysis showed that the current design procedures lead to a safe but conservative estimation of the slab behaviour.

A series of CaF2-doped phosphors was synthesized in situ in hydrothermal conditions (in a DAB- 2 reactor), in the presence of sodium citrate as a complexing agent preventing premature precipitation. The materials were doped with Yb3+/Er3+ pair of ions, which resulted in up-conversion emission. Additionally, Mn2+ ions were incorporated into the structure of the CaF2 to analyse their influence on the chromaticity of the luminescence colour, in view of their application in bioimaging. Detailed structural analysis showed that the structure of the nanoparticles obtained resembled the core@shell like structure. Finally, the emission colour was tuned from green to orange – red. It was confirmed that the quantity of Mn2+ ions incorporated in the CaF2 matrix definitely differs from the expected one. The real concentration of Mn2+ ions in the structure is frequently ignored, which leads to incorrect conclusions. For this reason, a detailed structural and spectroscopic analysis was conducted and the effect of Mn2+ ions on the structure and the average size of the CaF2-doped phosphors was studied. Moreover, the in vitro cytotoxicity of the nanoparticles was evaluated. Obtained results showed that CaF2:15%Yb3+, 2%Er3+, 2.6%Mn2+ reduces cell viability of fibroblast at lower concentrations (50, 100 and 200 μg/ml) than CaF2:15%Yb3+, 2%Er3+ (200 μg/ml). Moreover, CaF2:15%Yb3+, 2%Er3+ caused increase of the fibroblast proliferation rate at the lowest tested concentration (10 μg/ml).

The aim of this study was to provide deep insight into photocatalytic degradation of ciprofloxacin (CIP) over CeO2/ZnO nanocomposites. Catalysts used in this work were synthesized by a simple co-precipitation method and fully characterized by means of XRD, nitrogen physisorption, TEM, UV-vis, PL and XPS. Degradation of CIP was tracked by UV-vis and LC-MS techniques and the mineralization efficiency was determined by TOC analyses. It was documented that CeO2/ZnO nanocomposites were ca. twice more active than undoped ZnO and ca. 10 times more active than pristine CeO2. The improved activity of the nanocomposites resulted from the formation of a Z-scheme heterojunction in which photo-excited electrons from the conduction band of ZnO migrate to the valence band of CeO2. Photocatalytic degradation of CIP over the nanocomposites was found to be a surface reaction in which CIP molecules adsorbed onto ZnO are directly oxidized by photogenerated holes (h+). Degradation of the antibiotic proceeded through two parallel pathways: i) pathway I (dominant) in which piperazine moiety of CIP molecules was selectively oxidized by h+, and ii) pathway II in which both fluoroquinolone and piperazine moieties of the antibiotic were degraded. The latter pathway required participation of both h+ and hydroxyl radicals (HO•).

Ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is one of the best studied enzymes. It is crucial for photosynthesis, and thus for all of biosphere’s productivity. There are four isoforms of this enzyme, differing by amino acid sequence composition and quaternary structure. However, there is still a group of organisms, dinoflagellates, single-cell eukaryotes, that are confirmed to possess Rubisco, but no successful purification of the enzyme of such origin, and hence a generation of a crystal structure was reported to date. Here, we are using in silico tools to generate the possible structure of Rubisco from a dinoflagellate representative, Symbiodinium sp. We selected two templates: Rubisco from Rhodospirillum rubrum and Rhodopseudomonas palustris. Both enzymes are the so-called form II Rubiscos, but the first is exclusively a homodimer, while the second one forms homo-hexamers. Obtained models show no differences in amino acids crucial for Rubisco activity. The variation was found at two closely located inserts in the C-terminal domain, of which one extends a helix and the other forms a loop. These inserts most probably do not play a direct role in the enzyme’s activity, but may be responsible for interaction with an unknown protein partner, possibly a regulator or a chaperone. Analysis of the possible oligomerization interface indicated that Symbiodinium sp. Rubisco most likely forms a trimer of homodimers, not just a homodimer. This hypothesis was empowered by calculation of binding energies. Additionally, we found that the protein of study is significantly richer in cysteine residues, which may be the cause for its activity loss shortly after cell lysis. Furthermore, we evaluated the influence of the loop insert, identified exclusively in the Symbiodinium sp. protein, on the functionality of the recombinantly expressed R. rubrum Rubisco. All these findings shed new light onto dinoflagellate Rubisco and may help in future obtainment of a native, active enzyme.

A series of lanthanide doped yttrium vanadates were prepared by Pechini's method (sol-gel process). The as-prepared precursors, in the presence of citric acid, were calcined in the temperature range of 600–900 °C. The obtained products were composed of small nanoparticles, in the size range of 20–50 nm, depending on the annealing temperature, exhibiting a bright green up-conversion emission, under NIR laser irradiation, and emission lifetimes in the range of 4.7–18.3 μs. Their structural, morphological and spectroscopic properties were investigated in detail by XRD, HR-TEM including FFT analysis, EDX and spectroscopic techniques (emission, power dependence and emission kinetics). The luminescence quenching phenomenon, manifested in a decrease of up-conversion intensity and shortening of emission lifetime, was observed with increasing of the Yb 3+ ion concentration and decreasing the particle size. The optimal concentration of the Yb 3+ ions was found to be 15 mol% (YVO 4 : Yb 3+ 15 mol%, Er 3+ 2 mol%).

Background The underlying mechanism of liver regeneration after Associating Liver Partition and Portal vein ligation (PVL) for Staged hepatectomy (ALPPS) is still unclear. The aim of this study was to evaluate the relationship between future liver remnant (FLR) volume, liver regeneration characteristics and restoration of function in an experimental model of ALPPS. Methods An ALPPS model in rats was developed with selective PVL, parenchymal transection and partial hepatectomy (step 1), followed by resection of the liver (step 2). Three different ALPPS groups with FLR sizes of 30, 20 and 10 per cent of total liver volume were compared with sham-operated controls and animals undergoing resection of left lateral lobe and 90 per cent PVL with respect to morbidity, mortality, liver regeneration and function. Results Three of 15 animals that had ALPPS with 10 per cent FLR (ALPPS10) died after step 1. Ascites developed in two of five rats that had ALPPS with 20 per cent FLR and in three of four animals in the ALPPS10 group after step 2. Although the relative increments in FLR size and growth rates were highest in the ALPPS groups, small FLR size was associated with a sustained increase in levels of serum aminotransferases and bilirubin, a lower albumin concentration, severe sinusoidal injury, increased expression of proliferation markers and increased activation of hepatic progenitor cells after step 2. Conclusion There is discordance between FLR volume increase and functional restoration after the ALPPS procedure.

Titanium dioxide (TiO2) nanoparticles (NPs) modified with neodymium (Nd) in the range between 0.1 and 1.0 mol% were prepared via the hydrothermal method. The samples obtained were characterized by diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), X-ray fluorescence (EDX), Brunauer–Emmett–Teller (BET) method, X-ray powder diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL). The photocatalytic activity of the obtained samples was evaluated by photodegradation of phenol in aqueous solution under ultraviolet–visible (UV–Vis, λ > 350 nm) and visible (Vis, λ > 420 nm) irradiation. Experimental results showed that the photocatalysts exhibited high photocatalytic activity under Vis light. The sample showing the highest photoactivity under Vis irradiation was in the form of anatase; its surface area equalled 124 m2/g (1.16 times larger than that of pristine TiO2). The average crystal size was 10.9 nm, and it was modified with 0.1 mol% of Nd3+ (28% of phenol was degraded after 60 min of irradiation). The photocatalytic tests of phenol degradation in the presence of scavengers confirm that e− and were responsible for the visible light degradation of organic compounds in the aqueous phase. Action spectra analysis revealed that although Nd-modified TiO2 could be excited under visible light in the range of 400–480 nm, the up-conversion process is not responsible for the degradation of phenol under Vis irradiation.

The study presents the results of the study on porous composite biomaterials obtained using lyophilization method based on polymer solutions: chitosan solution, sodium alginate solution, or polylactide solution, and ZnO-doped bioglass from CaO-SiO2-P2O5 system. The properties of zinc ions were used, which have bactericidal, immune-stimulating, and tissue-regenerating functions in the organism. The effects of the polymer type, granulation, and bioglass amount, as well as the amount of solvent on composite microstructure, were studied. SEM-EDS technique was used to visualize and describe the surface results occurring after incubation of composite in the Simulated Body Fluid (SBF). The selected method of preparation, used substrates, and the process conditions resulted in porous composites of the open, connected pore structure. It was proved that composite microstructure may be controlled by the appropriately selected amount of bioglass in relation to the polymer and its appropriate grain sizes. The morphology of the obtained composites is also affected by the amount of the solvent in lyophilizated dispersions. It was proved that bioactivity in composite material is induced by bioglass because after SBF incubation the surface layer is enriched with Ca and P, what may lead to a gradual formation of apatite layer. The obtained results enabled selection of the composites for further in vitro studies concerning cytotoxicity and antibacterial activity.

Using cyto-morphological analysis of somatic embryogenesis (SE) in the tree fern Cyathea delgadii as a guide, we performed a comparative proteomic analysis in stipe explants undergoing direct SE. Plant material was cultured on hormone-free medium supplemented with 2% sucrose. Phenol extracted proteins were separated using two-dimensional gel electrophoresis (2-DE) and mass spectrometry was performed for protein identification. A total number of 114 differentially regulated proteins was identified during early SE, i.e. when the first cell divisions started and several-cell pro-embryos were formed. Proteins were assigned to seven functional categories: carbohydrate metabolism, protein metabolism, cell organization, defense and stress responses, amino acid metabolism, purine metabolism, and fatty acid metabolism. Carbohydrate and protein metabolism were found to be the most sensitive SE functions with the greatest number of alterations in the intensity of spots in gel. Differences, especially in non-enzymatic and structural protein abundance, are indicative for cell organization, including cytoskeleton rearrangement and changes in cell wall components. The highest induced changes concern those enzymes related to fatty acid metabolism. Global analysis of the proteome reveals several proteins that can represent markers for the first 16 days of SE induction and expression in fern. The findings of this research improve the understanding of molecular processes involved in direct SE in C. delgadii .

Nitrogen-doped reduced graphene oxides (N-rGOs) have been synthesized at various temperatures by a facile hydrothermal route involving the doping of an aqueous graphene oxide dispersion with amitrole. The N-rGOs had a nitrogen content ranging from 10.9 to 13.4 at%, which is among the highest reported for this type of material. The predominant nitrogen species were pyridinic followed by amide/amine, pyrrolic, and quaternary nitrogen. Cyclic voltammetry and impedance spectroscopy measurements performed on the N-doped and nitrogen-free samples revealed that nitrogen fixation provided the material with pseudocapacitive behaviour and improved ion diffusion and charge propagation. A high specific capacitance of 244 F g −1 was obtained at a high scan rate of 100 mV s −1 for the N-rGO with the highest nitrogen content. An outstanding rate capability for the N-rGO, with increasing scan rates, of 98% was obtained, while only 70% was obtained for the non-doped rGO. 92% of the initial capacitance was maintained over 5000 charge/discharge cycles due to the high stability of the electrochemically active nitrogen moieties. Hydrothermal synthesis using amitrole as a nitrogen dopant represents a simple route for the synthesis of graphene with very high nitrogen content and exceptional behaviour for use as electrode material in high-power supercapacitors.