Enhancing radioprotection: A chitosan-based chelating polymer is a versatile radioprotective agent for prophylactic and therapeutic interventions against radionuclide contamination.

To mitigate the risk of radioactive isotope dissemination, the development of preventative and curative measures is of particular interest. For mass treatment, the developed solution must be easily administered, preferably orally, with effective, nontoxic decorporating properties against a wide range of radioactive isotopes. Currently, most orally administered chelation therapy products are quickly absorbed into the blood circulation, where chelation of the radioactive isotope is a race against time due to the short circulation half-life of the therapeutic. This report presents an alternative therapeutic approach by using a functionalized chitosan (chitosan@DOTAGA) with chelating properties that remains within the gastrointestinal tract and is eliminated in feces, that can protect against ingested radioactive isotopes. The polymer shows important in vitro chelation properties towards different metallic cations of importance, including (Cs(I), Ir(III), Th(IV), Tl(I), Sr(II), U(VI) and Co(II)), at different pH (from 1 to 7) representing the different environments in the gastrointestinal tract. An in vivo proof of concept is presented on a rodent model of uranium contamination following an oral administration of Chitosan@DOTAGA. The polymer partially prevents the accumulation of uranium within the kidneys (providing a protective effect) and completely prevents its uptake by the spleen.

In vitro and in vivo toxicity of carbon dots with different chemical compositions.

Carbon dots (CDs) are easy-obtained nanoparticles with wide range of biological activity; however, their toxicity after prolonged exposure is poorly investigated. So, in vitro and in vivo toxicity of CDs with the surfaces enriched with hydroxylated hydrocarbon chains and methylene groups (CD_GE), carboxyl and phenol groups accompanied with nitrogen (CD_3011), trifluoromethyl (CDF19) or toluidine and aniline groups (CDN19) were aimed to be discovered. CDs' in vitro toxicity was assessed on A549 cells (real-time cell analysis of impedance, fluorescence microscopy) after 24 h of incubation, and we observed no changes in cell viability and morphology. CDs' in vivo toxicity was assessed on C57Bl6 mice after multiple dosages (5 mg/kg subcutaneously) for 14 days. Lethality (up to 50%) was observed in CDN19 and CD_3011 groups on different days of dosing, accompanied by toxicity signs in case of CD_3011. There were no changes in serum biochemical parameters except Urea (increased in CDF19 and CD_3011 groups), nor substantial kidney, liver, and spleen injuries. The most impactful for all organs were also CD_3011 and CDF19, causing renal tubule injury and liver blood supply violation. Thus, CDs with a surface enriched with oxygen- and nitrogen-containing functional groups might be toxic after multiple everyday dosing, without, however, significant damages of internal organs in survived animals.

A comparative multi-level toxicity assessment of carbon-based Gd-free dots and Gd-doped nanohybrids from coffee waste: hematology, biochemistry, histopathology and neurobiology study.

Here, a comparative toxicity assessment of precursor carbon dots from coffee waste (cofCDs) obtained using green chemistry principles and Gd-doped nanohybrids (cofNHs) was performed using hematological, biochemical, histopathological assays in vivo (CD1 mice, intraperitoneal administration, 14 days), and neurochemical approach in vitro (rat cortex nerve terminals, synaptosomes). Serum biochemistry data revealed similar changes in cofCDs and cofNHs-treated groups, i.e. no changes in liver enzymes' activities and creatinine, but decreased urea and total protein values. Hematology data demonstrated increased lymphocytes and concomitantly decreased granulocytes in both groups, which could evidence inflammatory processes in the organism and was confirmed by liver histopathology; decreased red blood cell-associated parameters and platelet count, and increased mean platelet volume, which might indicate concerns with platelet maturation and was confirmed by spleen histopathology. So, relative safety of both cofCDs and cofNHs for kidney, liver and spleen was shown, whereas there were concerns about platelet maturation and erythropoiesis. In acute neurotoxicity study, cofCDs and cofNHs (0.01 mg/ml) did not affect the extracellular level of L-[14C]glutamate and [3H]GABA in nerve terminal preparations. Therefore, cofNHs demonstrated minimal changes in serum biochemistry and hematology assays, had no acute neurotoxicity signs, and can be considered as perspective biocompatible non-toxic theragnostic agent.

Combating lead and cadmium exposure with an orally administered chitosan-based chelating polymer.

Heavy metals present a threat to human health, even at minimal concentrations within the body. One source of exposure is due to the consumption of low-level contaminated foodstuff and water. Lead and cadmium have been shown to be absorbed by and accumulate within organs like the kidneys and liver, and they have also been associated to many diseases including cardiovascular disease and kidney dysfunction as well as developmental disorders and neurodegenerative diseases. Since this contamination of lead and cadmium is found worldwide, limiting the exposure is complicated and novel strategies are required to prevent the absorption and accumulation of these metals by forcing their elimination. In this study, a DOTAGA-functionalized chitosan polymer is evaluated for this preventative strategy. It shows promising results when orally administered in mice to force the elimination and negate the toxic effects of lead and cadmium found within foodstuff.

Genotoxic and morpho-physiological responses of ZnO macro- and nano-forms in plants.

In the current study, two plants, viz., Pisum sativum L. and Hordeum vulgare L., were exposed to nano- and macro-dispersed ZnO at 1, 10, and 30 times of maximal permissible concentration (MPC). The main objective of the study is to depict and compare the genotoxicity in terms of chromosomal anomalies, cytotoxicity (i.e., mitotic index), and phytotoxicity (viz., germination, morphometry, maximal quantum yield, and chlorophyll fluorescence imaging) of macro- and nano-forms of ZnO along with their accumulation and translocation. In the case of genotoxic and cytotoxic responses, the maximal effect was observed at 30 MPC, regardless of the macro- or nano-forms of ZnO. The phytotoxic observations revealed that the treatment with macro- and nano-forms of ZnO significantly affected the germination rate, germination energy, and length of roots and shoots of H. vulgare in a dose-dependent manner. The factor toxicity index of treated soil demonstrated that toxicity soared as concentrations increased and that at 30 MPC, toxicity was average and high in macro- and nano-dispersed ZnO, respectively. Furthermore, the photosynthetic parameters were observed to be negatively affected in both treatments, but the maximal effect was observed in the case of nano-dispersed form. It was noted that the mobility of nano-dispersed ZnO in the soil was higher than macro-dispersed. The increased mobility of nano-dispersed ZnO might have boosted their accumulation and translocation that subsequently led to the oxidative stress due to the accelerated production of reactive oxygen species, thus strengthen toxicity implications in plants.

Chlorophyll fluorometry in evaluating photosynthetic performance: key limitations, possibilities, perspectives and alternatives.

Non-destructive methods for the assessment of photosynthetic parameters of plants are widely applied to evaluate rapidly the photosynthetic performance, plant health, and shifts in plant productivity induced by environmental and cultivation conditions. Most of these methods are based on measurements of chlorophyll fluorescence kinetics, particularly on pulse modulation (PAM) fluorometry. In this paper, fluorescence methods are critically discussed in regard to some their possibilities and limitations inherent to vascular plants and microalgae. Attention is paid to the potential errors related to the underestimation of thylakoidal cyclic electron transport and anoxygenic photosynthesis. PAM-methods are also observed considering the color-addressed measurements. Photoacoustic methods are discussed as an alternative and supplement to fluorometry. Novel Fourier modifications of PAM-fluorometry and photoacoustics are noted as tools allowing simultaneous application of a dual or multi frequency measuring light for one sample.

Bio-distribution of Carbon Nanoparticles Studied by Photoacoustic Measurements.

Carbon-based nanomaterials are promising for a wide range of biomedical applications, i.e. drug delivery, therapy, and imaging including photoacoustic tomography, where they can serve as contrast agents, biocompatibility and biodistribution of which should be assessed before clinical setting. In this paper, localization of carbon flurooxide nanoparticles, carbon nanodots from ß-alanine, carbon nanodots from urea and citric acid and glucose-ethylenediamine nanoparticles (NPs) in organs of Wistar rats were studied by photoacoustic measurements after 24 h of their intravenous injection. 16 ns light pulse from a Q-switched Nd:YAG laser with 1064 nm wavelength was used as an excitation source. The laser-induced photoacoustic signals were recorded with a ring piezoelectric detector. Light absorption by carbon NPs resulted in noticeable enhancement of the photoacoustic amplitude in the tissues where the NPs were accumulated. The NPs were preferably accumulated in liver, kidneys and spleen, and to a lesser extent in heart and gastrocnemius muscles. Together with remarkable fluorescent properties of the studied carbon nanomaterials, their photoacoustic responses allow their application for bi-modal fluorescence-photoacoustic bio-imaging.

Photo- and Radiofrequency-Induced Heating of Photoluminescent Colloidal Carbon Dots.

Nitrogen- and oxygen-containing carbon nanoparticles (O, N-CDs) were prepared by a facile one-step solvothermal method using urea and citric acid precursors. This method is cost-effective and easily scalable, and the resulting O, N-CDs can be used without additional functionalization and sample pretreatment. The structure of O, N-CDs was characterized by TEM, AFM, Raman, UV-vis, and FTIR spectroscopies. The obtained O, N-CDs with a mean diameter of 4.4 nm can be easily dispersed in aqueous solutions. The colloidal aqueous solutions of O, N-CDs show significant photothermal responses under red-IR and radiofrequency (RF) irradiations. The as-prepared O, N-CDs have a bright temperature-dependent photoluminescence (PL). PL/PLE spectral maps were shown to be used for temperature evaluation purposes in the range of 30-50 °C. In such a way, the O, N-CDs could be used for biomedicine-related applications such as hyperthermia with simultaneous temperature estimation with PL imaging.

High levels of anoxygenic photosynthesis revealed by dual-frequency Fourier photoacoustics in Ailanthus altissima leaves.

In contrast to oxygenic photosynthesis, true anoxygenic photosynthesis is not associated with O2 evolution originated from water photolysis but still converts light energy to that of the phosphoanhydride bonds of ATP. In a narrow sense, anoxygenic photosynthesis is mainly known as to be related to the purple and green sulfur bacteria, but in a broad sense, it also occurs in the vascular plants. The portion of photosynthetic water photolysis that is compensated by the processes of O2 uptake (respiration, photorespiration, Mehler cycle, etc.) may be referred to as 'quasi' anoxygenic photosynthesis. Photoacoustic method allows for the separate detection of photolytic O2 at frequencies of measuring light about 20-40Hz, whereas at 250-400Hz, it detects the photochemical energy storage. We have developed a fast-Fourier transform photoacoustic method enabling measurements of both these signals simultaneously in one sample. This method allows to calculate oxygenic coefficients, which reflect the part of photochemically stored light energy that is used for the water photolysis. We show that the true anoxygenic photosynthesis in Ailanthus altissima Mill. leaves reached very high levels under low light, under moderate light at the beginning of the 1-h period, and at the end of the 40-min period under saturating light.

Application of the Photoacoustic Approach in the Characterization of Nanostructured Materials.

A new generation of sensors can be engineered based on the sensing of several markers to satisfy the conditions of the multimodal detection principle. From this point of view, photoacoustic-based sensing approaches are essential. The photoacoustic effect relies on the generation of light-induced deformation (pressure) perturbations in media, which is essential for sensing applications since the photoacoustic response is formed due to a contrast in the optical, thermal, and acoustical properties. It is also particularly important to mention that photoacoustic light-based approaches are flexible enough for the measurement of thermal/elastic parameters. Moreover, the photoacoustic approach can be used for imaging and visualization in material research and biomedical applications. The advantages of photoacoustic devices are their compact sizes and the possibility of on-site measurements, enabling the online monitoring of material parameters. The latter has significance for the development of various sensing applications, including biomedical ones, such as monitoring of the biodistribution of biomolecules. To extend sensing abilities and to find reliable measurement conditions, one needs to clearly understand all the phenomena taking place during energy transformation during photoacoustic signal formation. Therefore, the current paper is devoted to an overview of the main measurement principles used in the photoacoustic setup configurations, with a special focus on the key physical parameters.

A scientometric analysis of agricultural pollution by using bibliometric software VoSViewer and Histcite™.

While modern agriculture brings more food to people, it causes environmental pollution as well. Agricultural pollution has attracted extensive public attention. A lot of reviews on agricultural research were conducted from different research aspects, but there is a lack of work on analyzing the research trend from large volumes of publications in the field of agricultural pollution. In the present work, a scientometric analysis of agricultural pollution was conducted to fill the gap by using the software of VoSviewer and HistCite™. The datasets are collected from the core database of Web of Science from 1991 to 2019, totally 1338 records on the topic of agricultural pollutions. In most years (1996, 1999, 2002, 2006, 2009, 2011, and 2013), the total local citation score (TLCS) and total global citation score (TGCS) have coincident peaks. Zhang, Ju, and Zhu have the highest TLCS and TGCS. In terms of institutes, Chinese Acad Sci and China Agr Univ are the leading institutes in this field. The Univ Calif Davis, INRA, and USDA ARS have very high global impacts. From the research hot topics, the representative words include "soil," "agriculture," "contamination," "environment," "lead," and "balance." Representative words like "heavy-metals," "groundwater," "land-use," and "water" are emerging in the latter time period. Five leading research co-cited reference clusters are identified, including environment management, underground water, monitoring and alarming for the agriculture-environment standards, intrinsic mechanism to the circulatory system, and ecology system and land use. The recent trend is revealed from the bibliographical-coupling network, focusing on classical and old-fashion research, like pollution chemicals including N management, pesticides, and heavy metal. This work provides a holistic picture on the research in the field of agriculture pollution.

Impact of Carbon Fluoroxide Nanoparticles on Cell Proliferation.

Cytotoxicity of fluorescent carbon fluoroxide (CFO) nanoparticles (NPs) was studied in a label-free manner on several cancer and non-cancer cell lines. A direct cytotoxic effect of the CFO NPs was clearly observed by a suppression of cell proliferation. The real-time measurement of cell activities allowed to quantify the impact of the uptaken NPs on cell proliferation and after washout of the NPs from the cell culture medium. The results show more toxic effects of the CFO NPs on cancer than on non-cancer cell lines. The notion of NPs biocompatibility must be related to a maximum concentration value of the NPs acceptable for a given cell type. Furthermore, the cytotoxicity effects of NPs should be studied not only during their direct exposure to cells but also after their washout from the culture medium.

Photothermal Effects and Heat Conduction in Nanogranular Silicon Films.

We present results on the photothermal (PT) and heat conductive properties of nanogranular silicon (Si) films synthesized by evaporation of colloidal droplets (drop-casting) of 100 ± 50 nm-sized crystalline Si nanoparticles (NP) deposited on glass substrates. Simulations of the absorbed light intensity and photo-induced temperature distribution across the Si NP films were carried out by using the Finite difference time domain (FDTD) and finite element mesh (FEM) modeling and the obtained data were compared with the local temperatures measured by micro-Raman spectroscopy and then was used for determining the heat conductivities k in the films of various thicknesses. The cubic-to-hexagonal phase transition in Si NP films caused by laser-induced heating was found to be heavily influenced by the film thickness and heat-conductive properties of glass substrate, on which the films were deposited. The k values in drop-casted Si nanogranular films were found to be in the range of lowest k of other types of nanostructurely voided Si films due to enhanced phonon scattering across inherently voided topology, weak NP-NP and NP-substrate interface bonding within nanogranular Si films.

Photoluminescent Recognition of Strong Alcoholic Beverages with Carbon Nanoparticles.

A simple sensitive method for nonspecific recognition of armagnac, cognac, whiskey, and ethanol/water mixture was developed by using photoluminescence (PL) of carbon nanoparticles (NPs). The carbon NPs were synthesized from the mixture of urea and anhydrous citric acid, followed by few annealing processes to achieve the full effect by solvothermal carbonization. PL features of carbon NPs depend on the alcohol environments in which the NPs are dispersed. PL/PL excitation maps of the alcoholic beverages were mathematically treated, and a final principal component analysis diagram allows visualization of different clusters corresponding to each beverage. The optimal measurement conditions (concentration of NPs in colloidal solution and excitation wavelength) were defined to ensure a reliable recognition level.

Intracellular Detection and Localization of Nanoparticles by Refractive Index Measurement.

The measuring of nanoparticle toxicity faces an important limitation since it is based on metrics exposure, the concentration at which cells are exposed instead the true concentration inside the cells. In vitro studies of nanomaterials would benefit from the direct measuring of the true intracellular dose of nanoparticles. The objective of the present study was to state whether the intracellular detection of nanodiamonds is possible by measuring the refractive index. Based on optical diffraction tomography of treated live cells, the results show that unlabeled nanoparticles can be detected and localized inside cells. The results were confirmed by fluorescence measurements. Optical diffraction tomography paves the way to measuring the true intracellular concentrations and the localization of nanoparticles which will improve the dose-response paradigm of pharmacology and toxicology in the field of nanomaterials.

Effects of Zinc Oxide Nanoparticles on Physiological and Anatomical Indices in Spring Barley Tissues.

The aim of the present work was to investigate the toxic effects of zinc oxide nanoparticles (ZnO NPs, particle size < 50 nm) on the physiological and anatomical indices of spring barley (Hordeum sativum L.). The results show that ZnO NPs inhibited H. sativum growth by affecting the chlorophyll fluorescence emissions and causing deformations of the stomatal and trichome morphology, alterations to the cellular organizations, including irregularities of the chloroplasts, and disruptions to the grana and thylakoid organizations. There was a lower number of chloroplasts per cell observed in the H. sativum leaf cells treated with ZnO NPs as compared to the non-treated plants. Cytomorphometric quantification revealed that ZnO NPs decreased the size of the chloroplast by 1.5 and 4 times in 300 and 2000 mg/L ZnO NP-treated plants, respectively. The elemental analysis showed higher Zn accumulation in the treated leaf tissues (3.8 and 10.18-fold with 300 and 2000 mg/L ZnO NPs, respectively) than the untreated. High contents of Zn were observed in several spots in ZnO NP-treated leaf tissues using X-ray fluorescence. Deviations in the anatomical indices were significantly correlated with physiological observations. The accumulation of Zn content in plant tissues that originated from ZnO NPs was shown to cause damage to the structural organization of the photosynthetic apparatus and reduced the photosynthetic activities.

Chlorophyll fluorescence kinetics and oxygen evolution in Chlorella vulgaris cells: Blue vs. red light.

Oxygen evolution and chlorophyll fluorescence kinetics in cells of the Chlorella vulgaris strain (Europolytest, Russia) were studied under low, moderate and high photosynthetic photon flux densities (PPFD 40, 130 and 350 µmol photons m-2 s-1) of the red and blue actinic light. A novel method of a pulse amplitude modulated (PAM) Fourier chlorophyll fluorometry was applied to obtain photoinduction curves simultaneously for the red and blue measuring light for one sample. It was found that the red light did not induce oxygen evolution at low and moderate PPFD, whereas at high PPFD it caused a declining oxygen release. There was only a trace fluorescence kinetics at the low PPFD, but noticeable fluorescence kinetics under the red light was observed at the low and moderate PPFD. Particularly, the moderate red illumination of Chlorella cells excited a high chlorophyll fluorescence kinetics along with the absence of oxygen evolution that suggests anoxygenic photosynthesis. In contrast, the blue light induced a significant oxygen evolution as well as fluorescence kinetics already at low PPFD which were both further increased with the PPFD increasing. In addition, a high value of the chromatic divergence of quantum yield of photosystem II was revealed between the red and blue measuring light under high PPFD of the red actinic light.

Unique features of brain metastases-targeted AGuIX nanoparticles vs their constituents: A focus on glutamate-/GABA-ergic neurotransmission in cortex nerve terminals.

Gadolinium-based radiosensitizing AGuIX nanoparticles (AGuIX) currently tested two phase 2 clinical trials in association with radiotherapy for the treatment of brain metastases. Here, excitatory/inhibitory neurotransmission was assessed in rat cortex nerve terminals in the presence of AGuIX and their constituents (DOTAGA and DOTAGA/Gd3+) at concentrations used for medical treatment, and those 5-24 times higher. The ambient level, transporter-mediated, tonic and exocytotic release of L-[14C]glutamate and [3H]GABA, the membrane potential of nerve terminals were not changed in the presence of AGuIX at concentrations used for medical treatment ([Gd3+] = 0.25 mM, corresponding to 0.25 g.L-1), and DOTAGA (0.25 mM) and DOTAGA/Gd3+ (0.25 mM/0.01 mM). Difference between AGuIX and the precursors was uncovered, when their concentrations were increased. AGuIX (1.25-6 mM) did not change any transport characteristics of L-[14C]glutamate and [3H]GABA, whereas, DOTAGA (1.25-6 mM) affected the membrane potential, ambient level, and exocytotic release of L-[14C]glutamate and [3H]GABA. Gd3+ did not mask, but even enhanced above effects of DOTAGA. Therefore, AGuIX did not influence glutamate- and GABA-ergic neurotransmission at the presynaptic site. In contrast, DOTAGA and mixture DOTAGA/Gd3+ significantly affected synaptic neurotransmission at high concentrations. AGuIX own structure that overcomes neurotoxic features of their constituents.

The influence of application of biochar and metal-tolerant bacteria in polluted soil on morpho-physiological and anatomical parameters of spring barley.

The paper presents the results of the model experiment on spring barley (Hordeum vulgare L.) grown in polluted soil. The influence of separate and combined application of wood biochar and heavy metal-tolerant bacteria on morpho-physiological, anatomical and ultrastructural parameters of H. vulgare L. has been studied. The joint application of biochar and bacteria increased the shoot length by 2.1-fold, root length by 1.7-fold, leaf length by 2.3-fold and dry weight by threefold compared to polluted variant, bringing the plant parameters to the control level. The maximal quantum yield of photosystem II decreased by 8.3% in H. vulgare L. grown in contaminated soil, whereas this decrease was less in biochar (7%), bacteria (6%) and in combined application of bacteria and biochar (5%). As for the transpiration rate, the H. vulgare L. grown in polluted soil has shown a decrease in transpiration rate by 26%. At the same time, the simultaneous application of biochar and bacteria has led to a significant improvement in the transpiration rate (14%). The H. vulgare L. also showed anatomical (integrity of epidermal, vascular bundles, parenchymal and chlorenchymal cells) and ultrastructural (chloroplasts, thylakoid system, plastoglobules, starch grains, mitochondria, peroxisomes, ribosomes, endoplasmic reticulum, vacuoles) changes, revealed by light-optical and transmission electron microscopy of leaf sections. The effects were most prominent in H. vulgare L., grown in polluted soil but gradually improved with application of biochar, bacteria and their combination. The use of biochar in combination with metal-tolerant bacteria is an efficient tool for remediation of soils, contaminated with heavy metals. The positive changes caused by the treatment can be consistently traced at all levels of plant organization.

Kinetics of Hydrogen Generation from Oxidation of Hydrogenated Silicon Nanocrystals in Aqueous Solutions.

Hydrogen generation rate is one of the most important parameters which must be considered for the development of engineering solutions in the field of hydrogen energy applications. In this paper, the kinetics of hydrogen generation from oxidation of hydrogenated porous silicon nanopowders in water are analyzed in detail. The splitting of the Si-H bonds of the nanopowders and water molecules during the oxidation reaction results in powerful hydrogen generation. The described technology is shown to be perfectly tunable and allows us to manage the kinetics by: (i) varying size distribution and porosity of silicon nanoparticles; (ii) chemical composition of oxidizing solutions; (iii) ambient temperature. In particular, hydrogen release below 0 °C is one of the significant advantages of such a technological way of performing hydrogen generation.