INFLUENCE OF THE POLYETHYLENE GLYCOL MOLECULAR MASS ON THERMAL TRANSITIONS OF NANOSIZED COPPER OXIDE

В данной работе получены образцы наноразмерного оксида меди, стабилизированного полиэтиленгликолем различных марок с молекулярными массами от 200 до 6000 Да. Методом рентгеновской дифрактометрии исследована кристаллическая структура полученных образцов наноразмерного оксида меди. В результате рентгенофазового анализа установлено, что структура образцов представляет собой моноклинную кристаллическую решетку, с пространственной группой C2/ c. Методом фотонно-корреляционной спектроскопии изучено влияние молекулярной массы полимера на размер наночастиц. Анализ результатов исследования показал наличие во всех образцах наноразмерного оксида меди (II), стабилизированного полиэтиленгликолем с различной молекулярной массой, одной фракции частиц, распределение которых по размеру носит мономодальный характер. Установлено, что молекулярная масса полиэтиленгликоля оказывает, влияние на размер частиц CuO в коллоидных растворах, при этом фазовый состав и размеры кристаллитов остаются неизменными. Средний гидродинамический радиус частиц CuO в полученных образцах составляет порядка 140 ± 40 нм. Наименьшие значения гидродинамического радиуса 70 ± 15 нм наблюдаются в образце наноразмерного оксида меди, стабилизированного полиэтиленгликолем с молярной массой 6000 Дa. Методом синхронного термического анализа исследовано влияние стабилизатора с различными молекулярными массами на фазовые переходы образцов при термической обработке. В результате термического анализа установлено, что оптимальной температурой прокаливания порошков наноразмерного CuO является 500°C. In this work, samples of nanosized copper oxide stabilized with polyethylene glycol of various grades with molecular weights from 200 to 6000 Da were obtained. The crystal structure of the samples was investigated by X-ray diffractometry. As a result of the XRD analysis, it was found that the samples have a monoclinic crystal lattice with space group C2 / c . The effect of the molecular weight of the polymer on the size of nanoparticles was studied by the photon correlation spectroscopy method. Analysis of the results showed the presence of one fraction of particles in all samples, the size distribution was monomodal. It was found that the molecular weight of polyethylene glycol has an effect on the CuO particle size in colloidal solutions, while the phase composition and crystallite size remain unchanged. The average hydrodynamic radius of CuO particles in the obtained samples was about 140 ± 40 nm. The smallest hydrodynamic radius of 70 ± 15 nm was observed in a sample of nanosized copper oxide stabilized with polyethylene glycol with a molecular weight of 6000 Da. The effect of stabilizers with different molecular weights on the phase transitions of samples during heat treatment was investigated by the synchronous thermal analysis. As a result of thermal analysis, it was found that the optimum temperature for calcining nanosized CuO powders was 500 °C.

Investigation of the Influence of the Molecular Weight of Polyethyleneglycols on the Optical Properties and Dispersed Characteristics of Sols of Au Nanoparticles used in Medicine

In this work, the synthesis of Au nanoparticles stabilized with polyethyleneglycols with different molecular weights from 200 to 8000 Da was carried out. The synthesis was carried out by the method of chemical reduction in an aqueous medium using sodium citrate as a reducing agent. The dependence of the optical properties on the concentration and molar mass of polyethyleneglycol was studied in the obtained samples of Au nanoparticles. The absorption spectra were recorded using an SF-56 optical spectrometer. The studies were carried out in the visible range of the spectrum from 400 to 800 nm. It was found that the type of spectrum, the position of the surface plasmon resonance band and the optical density of the samples of Au nanoparticles stabilized with PEG-8000 with a concentration of 10 and 20% did not undergo significant changes during storage, which characterizes the high aggregate stability of these sols. The dispersed characteristics of these samples of sols of Au nanoparticles were also studied. The studies were carried out using photon-correlation spectroscopy by the method of dynamic light scattering. It is established that an increase in the concentration of the stabilizer leads to an increase in the average hydrodynamic radius of the particles. This fact is associated with an increase in the thickness of the stabilizer layer and with the "stitching" of the polymer layer of Au nanoparticles with the formation of aggregates. Thus, the best result was found in PEG-8000 samples with concentrations of 10 and 20%, since the type of spectrum, the position of the surface plasmon resonance band and the optical density did not undergo significant changes. Based on the data obtained, it can be concluded that the best stabilizer for Au nanoparticles obtained by the citrate method is PEG-8000 with a concentration of at least 10 %. It is important to note that with an increase in the concentration of the stabilizer, the average hydrodynamic radius of the particles increases. This fact is associated with an increase in the thickness of the stabilizer layer and with the "stitching" of Au nanoparticles.

Sedimentation of nanoparticle titanium dioxide in the presence of ammonium

Due to its physicochemical properties, nanoparticles titanium dioxide (nTiO2) is being put into mass production and widespread applications, which inevitably results in their increasing exposure to the water body. After it entering the water body, the chemical properties of nTiO2 can be influenced by ion compositions, ion strength and pH, which affects their ecological risk. Excess of ammonium (NH4+) fertilizer has contaminated soil and water environments. In this paper, the Zeta potentials and hydrodynamic radius of nTiO2 were studied in NH4+ solution compared to those in Na+ solution. In addition, the sedimentation rate of nTiO2 was also investigated. The experiment results show that high pH inhibits the sedimentation of nTiO2. Moreover, NH4+ increases the stability of nTiO2 more than Na+ at the same IS, which was attributed the more negative Zeta potentials and the smaller hydraulic radius. Our results provide a theoretical basis for evaluating the ecological risk of nTiO2 in aqueous solution containing NH4+.

Calcium-Phosphate Nanoparticles — a System for Drug Delivery to the Anterior Eye Chamber

Purpose: to prepare and characterize calcium-phosphate nanoparticles loaded with compounds of different nature: low-molecular inhibitor of angiotensin-converting enzyme lisinopril, and high-molecular enzyme superoxide dismutase 1. To estimate the possibility of enhancing the biological efficacy of these compounds via incorporation to the nanoparticles.Material and methods. To increase the stability of calcium-phosphate nanoparticles coating with β-D-cellobiose was used. The size, surface charge (ζ-potential) of the particles and efficacy of including of the selected compounds to the particles were measured. Comparative assessment of the efficacy of lisinopril solution and lisinopril in nanoparticles was made via the estimation of their ocular hypotensive effect in normotensive rabbits. To compare the efficacy of the superoxide dismutase 1 solution and superoxide dismutase 1 in nanoparticles the rabbit model of immunogenic uveitis was used. We estimated the clinical score for several signs of uveitis, protein level, and antioxidant activity in aqueous humor.Results. Calcium-phosphate nanoparticles containing lisinopril had average hydrodynamic radius of 170–300 nm and negative ζ-potential of –17 mV. Particles containing superoxide dismutase 1 had average hydrodynamic radius of 220–450 nm and negative ζ-potential of –4 mV. Lisinopril in nanoparticles caused a significantly greater decrease of intraocular pressure than lisinopril solution. Superoxide dismutase 1 in calcium-phosphate nanoparticles more efficiently decreased the clinical manifestations of uveitis and normalized the biochemical processes in aqueous humor than the enzyme in buffer solution.Conclusion. Incorporation of both low-molecular and high-molecular drugs to the calcium-phosphate nanoparticles enhance their bioavailability and therapeutic efficiency. The data obtained give evidence of the prospectively of the using of these nanoparticles as vehicles for the ophthalmic drugs used in eyedrops.

On-chip transporting arresting and characterizing individual nano-objects in biological ionic liquids

Understanding and controlling the individual behavior of nanoscopic matter in liquids, the environment in which many such entities are functioning, is both inherently challenging and important to many natural and man-made applications. Here, we transport individual nano-objects, from an assembly in a biological ionic solution, through a nanochannel network and confine them in electrokinetic nanovalves, created by the collaborative effect of an applied ac electric field and a rationally engineered nanotopography, locally amplifying this field. The motion of so-confined fluorescent nano-objects is tracked, and its kinetics provides important information, enabling the determination of their particle diffusion coefficient, hydrodynamic radius, and electrical conductivity, which are elucidated for artificial polystyrene nanospheres and subsequently for sub–100-nm conjugated polymer nanoparticles and adenoviruses. The on-chip, individual nano-object resolution method presented here is a powerful approach to aid research and development in broad application areas such as medicine, chemistry, and biology.

Asymmetric-flow field-flow fractionation of prions reveals a strain-specific continuum of quaternary structures with protease resistance developing at a hydrodynamic radius of 15 nm

Prion diseases are transmissible neurodegenerative disorders that affect mammals, including humans. The central molecular event is the conversion of cellular prion glycoprotein, PrPC, into a plethora of assemblies, PrPSc, associated with disease. Distinct phenotypes of disease led to the concept of prion strains, which are associated with distinct PrPSc structures. However, the degree to which intra- and inter-strain PrPSc heterogeneity contributes to disease pathogenesis remains unclear. Addressing this question requires the precise isolation and characterization of all PrPSc subpopulations from the prion-infected brains. Until now, this has been challenging. We used asymmetric-flow field-flow fractionation (AF4) to isolate all PrPSc subpopulations from brains of hamsters infected with three prion strains: Hyper (HY) and 263K, which produce almost identical phenotypes, and Drowsy (DY), a strain with a distinct presentation. In-line dynamic and multi-angle light scattering (DLS/MALS) data provided accurate measurements of particle sizes and estimation of the shape and number of PrPSc particles. We found that each strain had a continuum of PrPSc assemblies, with strong correlation between PrPSc quaternary structure and phenotype. HY and 263K were enriched with large, protease-resistant PrPSc aggregates, whereas DY consisted primarily of smaller, more protease-sensitive aggregates. For all strains, a transition from protease-sensitive to protease-resistant PrPSc took place at a hydrodynamic radius (Rh) of 15 nm and was accompanied by a change in glycosylation and seeding activity. Our results show that the combination of AF4 with in-line MALS/DLS is a powerful tool for analyzing PrPSc subpopulations and demonstrate that while PrPSc quaternary structure is a major contributor to PrPSc structural heterogeneity, a fundamental change, likely in secondary/tertiary structure, prevents PrPSc particles from maintaining proteinase K resistance below an Rh of 15 nm, regardless of strain. This results in two biochemically distinctive subpopulations, the proportion, seeding activity, and stability of which correlate with prion strain phenotype.

Impact of superparamagnetic iron oxide nanoparticles on in vitro and in vivo radiosensitisation of cancer cells

Purpose The recent implementation of MR-Linacs has highlighted theranostic opportunities of contrast agents in both imaging and radiotherapy. There is a lack of data exploring the potential of superparamagnetic iron oxide nanoparticles (SPIONs) as radiosensitisers. Through preclinical 225 kVp exposures, this study aimed to characterise the uptake and radiobiological effects of SPIONs in tumour cell models in vitro and to provide proof-of-principle application in a xenograft tumour model. Methods SPIONs were also characterised to determine their hydrodynamic radius using dynamic light scattering and uptake was measured using ICP-MS in 6 cancer cell lines; H460, MiaPaCa2, DU145, MCF7, U87 and HEPG2. The impact of SPIONs on radiobiological response was determined by measuring DNA damage using 53BP1 immunofluorescence and cell survival. Sensitisation Enhancement Ratios (SERs) were compared with the predicted Dose Enhancement Ratios (DEFs) based on physical absorption estimations. In vivo efficacy was demonstrated using a subcutaneous H460 xenograft tumour model in SCID mice by following intra-tumoural injection of SPIONs. Results The hydrodynamic radius was found to be between 110 and 130 nm, with evidence of being monodisperse in nature. SPIONs significantly increased DNA damage in all cell lines with the exception of U87 cells at a dose of 1 Gy, 1 h post-irradiation. Levels of DNA damage correlated with the cell survival, in which all cell lines except U87 cells showed an increased sensitivity (P < 0.05) in the linear quadratic curve fit for 1 h exposure to 23.5 μg/ml SPIONs. There was also a 30.1% increase in the number of DNA damage foci found for HEPG2 cells at 2 Gy. No strong correlation was found between SPION uptake and DNA damage at any dose, yet the biological consequences of SPIONs on radiosensitisation were found to be much greater, with SERs up to 1.28 ± 0.03, compared with predicted physical dose enhancement levels of 1.0001. In vivo, intra-tumoural injection of SPIONs combined with radiation showed significant tumour growth delay compared to animals treated with radiation or SPIONs alone (P < 0.05). Conclusions SPIONs showed radiosensitising effects in 5 out of 6 cancer cell lines. No correlation was found between the cell-specific uptake of SPIONs into the cells and DNA damage levels. The in vivo study found a significant decrease in the tumour growth rate.

Multi-ciliated microswimmers–metachronal coordination and helical swimming

The dynamics and motion of multi-ciliated microswimmers with a spherical body and a small number N (with $$5< N < 60$$ 5 < N < 60 ) of cilia with length comparable to the body radius, is investigated by mesoscale hydrodynamics simulations. A metachronal wave is imposed for the cilia beat, for which the wave vector has both a longitudinal and a latitudinal component. The dynamics and motion is characterized by the swimming velocity, its variation over the beat cycle, the spinning velocity around the main body axis, as well as the parameters of the helical trajectory. Our simulation results show that the microswimmer motion strongly depends on the latitudinal wave number and the longitudinal phase lag. The microswimmers are found to swim smoothly and usually spin around their own axis. Chirality of the metachronal beat pattern generically generates helical trajectories. In most cases, the helices are thin and stretched, i.e., the helix radius is about an order of magnitude smaller than the pitch. The rotational diffusion of the microswimmer is significantly smaller than the passive rotational diffusion of the body alone, which indicates that the extended cilia contribute strongly to the hydrodynamic radius. The swimming velocity is found to increase with the cilia number N with a slightly sublinear power law, consistent with the behavior expected from the dependence of the transport velocity of planar cilia arrays on the cilia separation. Graphic abstract

Rheological Study of Gemini Surfactants with Amide Groups

In the present study, the micelle aggregation numbers and hydrodynamic radius distributions of the gemini surfactants (abbreviated as Cm-(EO)n-E-Cm (m = 12–16, n = 1, 2)) were investigated by fluorescence spectroscopy and dynamic light scattering (DLS). The rheological properties of these surfactants were determined using a rheometer. The Surfactants C14-(EO)-E-C14 and C16-(EO)-E-C16 formed worm-like micelles at a concentration of 200 mmol/L. It was found that longer hydrophobic chains or shorter linkage groups promoted the growth of worm-like micelles. Then, the influence of the inorganic salt NaBr and the organic salt sodium salicylate (NaSal) on the formation and properties of wormlike micelles in aqueous C16-(EO)-E-C16 solutions at a surfactant concentration of 20 mmol/L was investigated. The results showed that NaSal could penetrate deeper into the hydrophobic group of the micelle due to its good hydrophobic interaction, which promoted micelle growth and resulted in worm-like micelles. In addition, the tested systems showed a Maxwell behavior at lower frequencies, but deviated from the Maxwell mode at higher frequencies. Finally, the formation of worm-like micelles was also verified by micro polarity measurements.