Search

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe and effective application of nanoparticles, for instance, in the oil industry. As conventional oil reserves are depleted, it is necessary to advance chemical enhanced oil recovery (cEOR) techniques to develop unconventional oil reservoirs. Nanoparticles modified by surfactants can be a promising reagent in cEOR. These nanomaterials can reduce interfacial tension and change the wettability of reservoir rock, which leads to an increase in oil recovery. However, the application of nanoparticles is limited by their substantial aggregation in aqueous solutions. The purpose of this work is to select nanoparticles for obtaining stable sols in water in the presence of an anionic surfactant and to optimize the conditions (pH) for further modifying the nanoparticles with the anionic surfactant. Sodium dodecyl sulfate (SDS) is used as an anionic surfactant. The aggregation of oxide and carbon nanoparticles in water and anionic surfactant solutions was studied by laser diffraction, dynamic and electrophoretic light scattering methods. Most of the studied nanoparticles in water form aggregates with bi-, three- and polymodal particle size distributions. TiO2 nanoparticles obtained by plasma dynamic synthesis form the most stable sols in anionic surfactant solutions. The range of 5–7 pH is defined as optimal for their modification with surfactants. The stability of carbon nanoparticles in aqueous solutions increases significantly in the presence of a surfactant. The obtained results form the basis for further research on the modification of marked nanoparticles in surfactant solutions.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose long-term conformational dynamics are similar to the dynamics of bistable mechanical systems such as Euler arches and Duffing oscillators. Collective synchrony in bistable dynamics of molecular-sized systems has attracted immense attention as a potential pathway to amplify the output signals of molecular nanodevices. Recently, pyridine-furan oligomers of helical shape that are a few nanometers in size and exhibit bistable dynamics similar to a Duffing oscillator have been identified through molecular dynamics simulations. In this article, we present the case of dynamical synchronization of these bistable systems. We show that two pyridine-furan springs connected by a rigid oligomeric bridge spontaneously synchronize vibrations and stochastic resonance enhances the synchronization effect.

There is growing interest in molecular structures that exhibit dynamics similar to bistable mechanical systems. These structures have the potential to be used as two-state operating units for various functional purposes. Particularly intriguing are the bistable systems that display spontaneous vibrations and stochastic resonance. Previously, via molecular dynamics simulations, it was discovered that short pyridine–furan springs in water, when subjected to stretching with power loads, exhibit the bistable dynamics of a Duffing oscillator. In this study, we extend these simulations to include short pyridine–pyrrole and pyridine–furan springs in a hydrophobic solvent. Our findings demonstrate that these systems also display the bistable dynamics, accompanied by spontaneous vibrations and stochastic resonance activated by thermal noise.

In this study, we investigated the conformational abilities of n,n’-(Alkanediyl)-bis(2-phenyl-3,5-dihydro-4H-imidazol-4-one)s (1) to gain insight into their biological potential as a platform for the generation of various QACs. Among the conformers of 1, due to the flexibility of the polymethylene fragment, the phenyl rings can take on different mutual arrangements, while there is a clear tendency for the formation of π–π interactions. From the point of view of the reactivity to alkylating agents, a preliminary conclusion can be drawn about the favorable mutual arrangement of imidazolone rings located at a sufficient distance to carry out both mono- and bisalkylation to obtain bis-QAC.

The conversion of semicarbazones to 1,2,4-triazolidin-3-ones and vice versa (ring-chain isomerism) was studied using the DFT B3LYP/6-311++G(d,p) method. The thermodynamic and kinetic characteristics of this reaction were calculated and discussed.

Metal-Organic CVD method (MOCVD) allows for deposition of ultrathin 2D transition metal dichalcogenides (TMD) films of electronic quality onto wafer-scale substrates. In this work, the effect of temperature on structure, chemical states, and electronic qualities of the MOCVD MoS2 films were investigated. The results demonstrate that the temperature increase in the range of 650 °C to 950 °C results in non-monotonic average crystallite size variation. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and Raman spectroscopy investigation has established the film crystal structure improvement with temperature increase in this range. At the same time, X-Ray photoelectron spectroscopy (XPS) method allowed to reveal non-stoichiometric phase fraction increase, corresponding to increased sulfur vacancies (VS) concentration from approximately 0.9 at.% to 3.6 at.%. Established dependency between the crystallite domains size and VS concentration suggests that these vacancies are form predominantly at the grain boundaries. The results suggest that an increased Vs concentration and enhanced charge carriers scattering at the grains’ boundaries should be the primary reasons of films’ resistivity increase from 4 kΩ·cm to 39 kΩ·cm.

The acquisition of reliable knowledge about the mechanism of short laser pulse interactions with semiconductor materials is an important step for high-tech technologies towards the development of new electronic devices, the functionalization of material surfaces with predesigned optical properties, and the manufacturing of nanorobots (such as nanoparticles) for bio-medical applications. The laser-induced nanostructuring of semiconductors, however, is a complex phenomenon with several interplaying processes occurring on a wide spatial and temporal scale. In this work, we apply the atomistic–continuum approach for modeling the interaction of an fs-laser pulse with a semiconductor target, using monolithic crystalline silicon (c-Si) and porous silicon (Si). This model addresses the kinetics of non-equilibrium laser-induced phase transitions with atomic resolution via molecular dynamics, whereas the effect of the laser-generated free carriers (electron–hole pairs) is accounted for via the dynamics of their density and temperature. The combined model was applied to study the microscopic mechanism of phase transitions during the laser-induced melting and ablation of monolithic crystalline (c-Si) and porous Si targets in a vacuum. The melting thresholds for the monolithic and porous targets were found to be 0.32 J/cm2 and 0.29 J/cm2, respectively. The limited heat conduction mechanism and the absence of internal stress accumulation were found to be involved in the processes responsible for the lowering of the melting threshold in the porous target. The results of this modeling were validated by comparing the melting thresholds obtained in the simulations to the experimental values. A difference in the mechanisms of ablation of the c-Si and porous Si targets was considered. Based on the simulation results, a prediction regarding the mechanism of the laser-assisted production of Si nanoparticles with the desired properties is drawn.

Three-layer structures based on various multi-component films of III–V semiconductors heavily doped with Fe were grown using the pulsed laser sputtering of InSb, GaSb, InAs, GaAs and Fe solid targets. The structures comprising these InAsSb:Fe, InGaSb:Fe and InSb:Fe layers with Fe concentrations up to 24 at. % and separated by GaAs spacers were deposited on (001) i-GaAs substrates at 200 °C. Transmission electron microscopy showed that the structures have a rather high crystalline quality and do not contain secondary-phase inclusions. X-ray photoelectron spectroscopy investigations revealed a significant diffusion of Ga atoms from the GaAs regions into the InAsSb:Fe layers, which has led to the formation of an InGaAsSb:Fe compound with a Ga content up to 20 at. %. It has been found that the ferromagnetic properties of the InAsSb:Fe magnetic semiconductor improve with an increasing Sb:As ratio. It has been concluded that the indirect ferromagnetic exchange interaction between Fe atoms occurs predominantly via Sb atoms.

Orbital Battleship, published in 2016 in this "Journal," is a hands-on competitive exercise which has been shown to be an efficient tool to reinforce the knowledge of the atomic structure. We decided to give it a more futuristic look and are presenting VR Orbital Battleship, a completely immersive collaborative experience which, in contrast to the pen-and-paper version, guarantees that students are unable to fill in an erroneous electron configuration thanks to the special control elements of the game. Hence, they are motivated to do their best in order to apply Madelung's rule and Hund's rule right to be able to start the game. The game design makes full use of what the immersive virtual reality has to offer: the headset completely immerses the player in the process of the game, resulting in less distraction compared to the classic version. Furthermore, the game's design is user-friendly and intuitive, and thus, it adds to the overall immersive experience. The game is recommended for use as an interactive addition to school and university classes that are dedicated to the atomic structure. VR Orbital Battleship is available for free worldwide in both a portable mobile platform (Oculus Go) and a PC version by downloading the game (see the Supporting Information of this paper).

Glycerol has found its applications as a heat-transfer fluid in heat exchangers, and as a component of functional liquids in biosensor analysis. Flowing non-aqueous fluids are known to be able to induce electromagnetic fields due to the triboelectric effect. These triboelectrically generated electromagnetic fields can affect biological macromolecules. Horseradish peroxidase (HRP) is widely employed as a convenient model object for studying how external electric, magnetic, and electromagnetic fields affect enzymes. Herein, we have studied whether the flow of glycerol in a ground-shielded cylindrical coil affects the HRP enzyme incubated at a 2 cm distance near the coil’s side. Atomic force microscopy (AFM) has been employed in order to study the effect of glycerol flow on HRP at the nanoscale. An increased aggregation of HRP on mica has been observed after the incubation of the enzyme near the coil. Moreover, the enzymatic activity of HRP has also been affected. The results reported that their application can be found in biotechnology, food technology and life sciences applications, considering the development of triboelectric generators, enzyme-based biosensors and bioreactors with surface-immobilized enzymes. Our work can also be of interest for scientists studying triboelectric phenomena, representing one more step toward understanding the mechanism of the indirect action of the flow of a dielectric liquid on biological macromolecules.

Treatment of 4a-acetyl-8a-hydroxydecahydroquinazoline-2-thione with NaH in acetonitrile leads to its isomerization into 1-hydroxy-1-methyl-3-thioxo-2,4-diazaspiro[5.5]undecan-7-one followed by the C1-C6 bond cleavage to give N-acetyl-N’-[(2-oxocyclohexyl)methyl]thiourea. The starting compound as a single diastereomer was prepared by the reaction between the K-enolate of 2-acetylcyclohexanone and N-(tosylmethyl)thiourea or N-(azidomethyl)thiourea.

The effect of a dielectric conical structure on the adsorption properties of an enzyme on mica was studied by atomic force microscopy (AFM) with the example of horseradish peroxidase (HRP). The cone used was a cellulose cone with a 60° apex angle. Namely, AFM allowed us to reveal an increase in the enzyme’s aggregation during its adsorption onto mica from the solution incubated near the cone apex for 40 min—as compared with the control enzyme samples incubated far away from the cone. In contrast, no change in the HRP adsorption properties was observed after shorter (10 min) incubation of the sample near the cone. The enzymatic activity of HRP was found to be the same for all the enzyme samples studied. Our findings should be considered upon designing biosensors (in particular, those intended for highly sensitive diagnostic applications) and bioreactors containing conical structural elements. Furthermore, since HRP is widely employed as a model enzyme in studies of external impacts on enzymes determining food quality, our data can be of use in the development of food-processing methods based on the use of electromagnetic radiation (microwave treatment, radiofrequency heating, etc.).

Bacterial contamination of meat products during its preparation at the enterprise is an important problem for the global food industry. Cutting boards are one of the main sources of infection. In order to solve this problem, the creation of mechanically stable coatings with antibacterial activity is one of the most promising strategies. For such a coating, we developed a composite material based on “liquid” Teflon and zinc oxide nanoparticles (ZnO-NPs). The nanoparticles obtained with laser ablation had a rod-like morphology, an average size of ~60 nm, and a ζ-potential of +30 mV. The polymer composite material was obtained by adding the ZnO-NPs to the polymer matrix at a concentration of 0.001–0.1% using the low-temperature technology developed by the research team. When applying a composite material to a surface with damage, the elimination of defects on a micrometer scale was observed. The effect of the composite material on the generation of reactive oxygen species (H2O2, •OH), 8-oxoguanine in DNA in vitro, and long-lived reactive protein species (LRPS) was evaluated. The composite coating increased the generation of all of the studied compounds by 50–200%. The effect depended on the concentration of added ZnO-NPs. The antibacterial and antibiofilm effects of the Teflon/ZnO NP coating against L. monocytogenes, S. aureus, P. aeruginosa, and S. typhimurium, as well as cytotoxicity against the primary culture of mouse fibroblasts, were studied. The conducted microbiological study showed that the fluoroplast/ZnO-NPs coating has a strong bacteriostatic effect against both Gram-positive and Gram-negative bacteria. In addition, the fluoroplast/ZnO-NPs composite material only showed potential cytotoxicity against primary mammalian cell culture at a concentration of 0.1%. Thus, a composite material has been obtained, the use of which may be promising for the creation of antibacterial coatings in the meat processing industry.

А new way of the free radical ROS- and HOCl-induced destruction of serine, threonine, and their peptide derivatives due to the nitrogen-centered radicals formation and their subsequent decomposition with the side chain elimination has been established. It has been shown that substances with reducing properties are inhibitors of this process, while oxygen does not affect the probability of its occurrence. The data obtained are relevant for the development of novel approaches to the search for effective free radical processes regulators.

Here, we report a new di(hydroxyphenyl)imidazolate ligand with an N2O2 donor set synthesized by a modified Debus–Radziszewski procedure. Its binuclear nickel(II) complexes feature a weak antiferromagnetic interaction with J12 = −3.16 cm−1 between the two nickel(II) ions identified by magnetometry measurements. As follows from cyclic voltammetry experiments and DFT calculations, they undergo ligand-centered oxidation via the formation of cation radicals with short lifetimes that can be potentially stabilized by bulkier t-butyl groups in the ortho-positions of the ligand. The reported ligand widens the range of the building blocks available to molecular magnetism community and thus provides new ways to the design of magnetic materials with switchable properties.

The Teacher Academy in the Natural Sciences (TANS) provided middle school (U.S. Grades 6-8) teachers (N = 81) with intensive professional development (PD) in chemistry, geosciences, and physics, with teachers enrolled in one scientific discipline per year. Because some teachers were retained and rotated into different disciplines, the TANS program investigated retention of science content 1-2 years beyond an instructional year. All teacher participants exhibited significant gains (p < 0.001), in chemistry, geosciences, or physics content, between their incoming knowledge and the 10-day summer academy's conclusion. Chemistry and geosciences content were retained until the end of the PD year. Physics participants reported a significant loss (p < 0.001), although gains from teachers' incoming knowledge were still significant. When retention was measured beyond the instructional year, only the geosciences content was retained. Chemistry and physics gains were not retained, with no significant differences between incoming teachers' knowledge and content 1-2 years post instruction. Our research indicates that science content support is needed after PD programs, and importantly, that the support differs between scientific disciplines.

The results of studies on the wettability properties and preparation of porous anodic alumina (PAA) membranes with a 3.3 ± 0.2 μm thickness and a variety of pore sizes are presented in this article. The wettability feature results, as well as the fabrication processing characteristics and morphology, are presented. The microstructure effect of these surfaces on wettability properties is analyzed in comparison to outer PAA surfaces. The interfacial contact angle was measured for amorphous PAA membranes as-fabricated and after a modification technique (pore widening), with pore sizes ranging from 20 to 130 nm. Different surface morphologies of such alumina can be obtained by adjusting synthesis conditions, which allows the surface properties to change from hydrophilic (contact angle is approximately 13°) to hydrophobic (contact angle is 100°). This research could propose a new method for designing functional surfaces with tunable wettability. The potential applications of ordinary alumina as multifunctional films are demonstrated.

Bacterial antibiotic resistance is one of the most serious modern biomedical problems that prioritizes the search for new agents to combat bacterial pathogens. It is known that nanoparticles of many metals and metal oxides can have an antibacterial effect. However, the antibacterial efficacy of aluminum oxide nanoparticles has been studied little compared to the well-known antimicrobial properties of nanoparticles of oxides of metals such as zinc, silver, iron, and copper. In this review, we have focused on the experimental studies accumulated to date demonstrating the antibacterial effect of aluminum oxide nanoparticles. The review discusses the main ways of synthesis and modification of these nanoparticles, provides the proposed mechanisms of their antibacterial action against gram-positive and gram-negative bacteria, and also compares the antibacterial efficacy depending on morphological characteristics. We have also partially considered the activity of aluminum oxide nanoparticles against water microalgae and fungi. In general, a more detailed study of the antibacterial properties of aluminum oxide nanoparticles is of great interest due to their low toxicity to eukaryotic cells.

The W–Cu composites with nanosized grain boundaries and high effective density were fabricated using a new fast isostatic hot pressing method. A significantly faster method was proposed for the formation of W–Cu composites in comparison to the traditional ones. The influence of both the high temperature and pressure conditions on the microstructure, structure, chemical composition, and density values were observed. It has been shown that W–Cu samples have a polycrystalline well-packed microstructure. The copper performs the function of a matrix that surrounds the tungsten grains. The W–Cu composites have mixed bcc-W (sp. gr. Im 3¯ m) and fcc-Cu (sp. gr. Fm 3¯ m) phases. The W crystallite sizes vary from 107 to 175 nm depending on the sintering conditions. The optimal sintering regimes of the W–Cu composites with the highest density value of 16.37 g/cm3 were determined. Tungsten–copper composites with thicknesses of 0.06–0.27 cm have been fabricated for the radiation protection efficiency investigation against gamma rays. It has been shown that W–Cu samples have a high shielding efficiency from gamma radiation in the 0.276–1.25 MeV range of energies, which makes them excellent candidates as materials for radiation protection.

In this work, the conditions for the synthesis of open vase-like microcapsules with a size of 1–5 μm and 20–40 nm walls of NiFe0.3(OH)x layered double hydroxide were studied. These microcapsules were obtained by the rapid hydrolysis of microdroplets of a solution of a mixture of NiSO4 and FeSO4 salts at the surface of an alkali solution. A hypothetical model of successive chemical processes occurring at the interface during synthesis is presented. The features of the “rim” formation around each microcapsule hole from the wall material with a peculiar nozzle-like shape are noted. These microcapsules can be transferred to the surface of a nickel foil using the Langmuir–Schaefer (LS) method. During the transfer process, they are fixed to the surface in an oriented position with a “rim” that contacts the nickel surface. It was established that electrodes made of such a foil with a layer of microcapsules exhibit active electrocatalytic properties in the oxygen evolution reaction during the electrolysis of water in an alkaline medium.

In recent years, research related to the search and study of the mode of action of new and used in medicine nootropic agents has been carried out at a high rate. The research related to the search for new combined drugs of nootropic action based on the substances of d-gamma-Pantothenate of calcium and succinic acid, which have neurometabolic, atigipoxic, and adaptogenic properties, is of interest. The purpose of this study was to develop and justify the optimal composition and manufacturing technologies of tablets with nootropic effect and standardise the proposed dosage forms containing Pantogam and succinic acid. The method for preparing the tablet mixture is as follows: all components were weighed in the required amount, Pantogam was placed in the mortar, then succinic acid was added and ground to a consistent white powder. The tablets were pressed on a manual press at a pressure of 120 mn/m2. The coating was applied on a laboratory fluidised bed unit with a single nozzle in a perforated drum with a volume of 1000 ml. The obtained tablets were evaluated according to the requirements for State Pharmacopoeia XIII and State Pharmacopoeia XIV. The comparison of the Pantogam tablets with succinic acid obtained by direct pressing and by wet granulation showed that the method of direct pressing allows obtaining tablets with good physical and mechanical properties and bioavailability. The methods based on acid-base titration and spectrophotometric determination were developed for the quantitative determination of Pantogam in tablets. The method of quantitative determination of succinic acid in dosage forms was validated. Based on the study of physicochemical and technological properties of substances and excipients, the compositions and technology for obtaining tablets containing Pantogam and succinic acid were justified and developed. It was found that solid-phase interactions occur with the combined presence of Pantogam and succinic acid in the tablets. The methods of qualitative and quantitative analysis of dosage forms containing Pantogam and succinic acid based on complexometric titration and high-performance liquid chromatography were developed. The procedure of validation of the method for determining succinic acid by HPLC in the developed dosage forms confirmed the validity of the proposed method.

The paper discusses the formation of Ta2O5 pillars with Ni tips during thin porous anodic alumina through-mask anodization on Si/SiO2 substrates. The tantalum nanopillars were formed through porous masks in electrolytes of phosphoric and oxalic acid. The Ni tips on the Ta2O5 pillars were formed via vacuum evaporation through the porous mask. The morphology, structure, and magnetic properties at 4.2 and 300 K of the Ta2O5 nanopillars with Ni tips have been studied using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. The main mechanism of the formation of the Ta2O5 pillars during through-mask anodization was revealed. The superparamagnetic behavior of the magnetic hysteresis loop of the Ta2O5 nanopillars with Ni tips was observed. Such nanostructures can be used to develop novel functional nanomaterials for magnetic, electronic, biomedical, and optical nano-scale devices.

The incubation of a solution of horseradish peroxidase (HRP) enzyme either below the apex or near the base of an inversely oriented square pyramid (inverted square pyramid; ISP) has been found to influence the enzyme’s aggregation and adsorption properties. The HRP enzyme is used herein as a model object due to its importance in analytical chemistry applications. Atomic force microscopy (AFM) is employed to investigate the HRP’s adsorption on mica substrates at the single-molecule level. Conventional spectrophotometry is used in parallel as a reference method for the determination of the HRP’s enzymatic activity. Using AFM, we reveal a significant change in the adsorption properties of HRP on mica substrates after the incubation of the HRP solutions either above the base or below the apex of the ISP in comparison with the control HRP solution. The same situation is observed after the incubation of the enzyme solution above the center of the ISP’s base. Here, the enzymatic activity of HRP remained unaffected in both cases. Since pyramidal structures of positive and inverted orientation are employed in biosensor devices, it is important to take into account the results obtained herein in the development of highly sensitive biosensor systems, in which pyramidal structures are employed as sensor (such as AFM probes) or construction elements.

Mixtures of aqueous solutions of chitosan hydrochloride (CS·HCl, 1–4 wt.%) and Pluronic F-127 (Pl F-127, 25 wt.%) were studied using vibrational and rotational viscometry; the optimal aminopolysaccharide concentration (3 wt.%) and the CS·HCl:Pl F-127 ratio (30:70) to obtain a thermosensitive hydrogel were found. It was shown that at 4 °C, such mixed compositions were viscous liquids, while at 37 °C for 1–2 min, they undergo a thermally reversible transition to a shape-stable hydrogel with a developed level of structure formation, satisfactory viscosity and high mucoadhesive parameters (maximum pull-off force Fmax = 1.5 kN/m2; work of adhesion W = 66.6 × 10−3 J). Adding D-ascorbic acid to the hydrogel led to orientational ordering of the supramolecular structure of the mixed system and significantly improved mucoadhesion (Fmax = 4.1 kN/m2, W = 145.1 × 10−3 J). A microbiological study revealed the high antibacterial activity of the hydrogel against Gram-negative and Gram-positive bacterial strains. The treatment of mixed bacterial infection in cows demonstrated the possibility of the in situ formation of a viscoelastic gel and revealed its high therapeutic effect. It has been suggested that our thermosensitive mucoadhesive CS·HCl:Pl F-127 hydrogels could be considered as independent veterinary drugs and pharmaceuticals.

The introduction of modern methods for the mathematical processing of geological data is one of the promising areas of study and development in the field of geosciences. For example, today mathematical geology makes it possible to reliably identify astronomical cycles by measuring the scalar magnetic parameters of rocks (magnetic susceptibility). The main aim of this study is to develop a mathematical tool for identifying stable oscillation cycles (periods) in the dataset of the magnetic susceptibility of rocks in a geological section. The author’s method (algorithm) is based on the concept of discrete mathematical analysis—an innovative mathematical approach to the analysis of discrete geological and geophysical data. Its reliability is also demonstrated, by comparison with the results obtained by classical methods: Fourier analysis, Lomb periodogram, and REDFIT. The proposed algorithm was applied by the authors to analyze the material of field geological studies of the Zhelezny Rog section (Taman Peninsula). As a result, stable cycles were determined for the Pontian and Lower Maeotian sedimentary strata of the Black Sea Basin (Paratethys).

Our present study concerns the influence of the picosecond rise-time-pulsed electromagnetic field, and the impact of nanosecond pulsed pressure on the aggregation state of horseradish peroxidase (HRP) as a model enzyme. The influence of a 640 kV/m pulsed electromagnetic field with a pulse rise-time of ~200 ps on the activity and aggregation state of an enzyme is studied by the single-molecule atomic force microscopy (AFM) method. The influence of such a field is shown to lead to aggregation of the protein and to a decrease in its enzymatic activity. Moreover, the effect of a shock wave with a pressure front rise-time of 80 ns on the increase in the HRP aggregation is demonstrated. The results obtained herein can be of use in modeling the impact of electromagnetic and pressure pulses on enzymes and on whole living organisms. Our results are also important for taking into account the effect of pulsed fields on the body in the development of drugs, therapeutic procedures, and novel highly sensitive medical diagnosticums.

The reaction of NaCN with N-(tosylmethyl)ureas, prepared by condensation of urea with aldehydes and p-toluenesulfinic acid, was studied. Generally, this reaction afforded the corresponding α-ureido nitriles. Some mechanistic aspects of cyanide-anion amidoalkylation with N-(tosylmethyl)ureas were discussed based on DFT calculations.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose dynamics are similar to those of bistable mechanical systems, such as Euler arches and Duffing oscillators. Of particular interest are the molecular structures capable of spontaneous vibrations and stochastic resonance. Recently, oligomeric molecules that were a few nanometers in size and exhibited the bistable dynamics of an Euler arch were identified through molecular dynamics simulations of short fragments of thermo-responsive polymers subject to force loading. In this article, we present molecular dynamics simulations of short pyridine-furan springs a few nanometers in size and demonstrate the bistable dynamics of a Duffing oscillator with thermally-activated spontaneous vibrations and stochastic resonance.

The theoretical and experimental evaluation of the cyclostationary random data transferring process corrupted by the individually and jointly cyclostationary crosstalk interference is presented. The interference and the message signals were measured by the real time digital oscilloscope. Autocorrelation functions were evaluated by synchronous cyclic averaging procedure. The analyzed periodic two-dimensional impulse response of the time-varying filter allows to obtain the output random process with the same cyclic frequency at the output of the filter by separation of orthogonal stationary waveforms constituting the input cyclostationary random process (CSRP). The filtering of the measured random process was implemented by the cyclic Wiener filter. The evaluation of the two-dimensional autocorrelation function and eye diagrams at the output of the cyclic Wiener filter showed significant reduction of the independent interference components in the estimated message signal.

The Teacher Academy in the Natural Sciences (TANS) provided middle school (U.S. Grades 6-8) teachers (N = 81) with intensive professional development in chemistry, geosciences, and physics through 13 days of face-to-face instruction that was extended with 2 online science modules per discipline. Because we administered online module assessments before the summer academy (pretest), after the summer academy (Post 1), and after the online module was assigned (Post 2), we were able to analyze via dependent "t" tests the learning components contributed by the online module. Only 1 geosciences module resulted in significant gains after it was assigned. Other modules (2 physics, 1 geosciences) resulted in gains before module assignments, at the end of the 10-day summer academy. Although the 2 chemistry modules exhibited positive score increases, no significant gains were made. Calculated Pearson correlation coefficients revealed no association between participants' online access times and science content gains. This research documents benefits of hybrid teacher professional development programs and offers recommendations for their optimized effectiveness, including more consistent instructor/participant online access.

In this work, we have proposed a novel universal stimulus-sensitive nanosized polymer system based on decasubstituted macrocyclic structures—pillar[5]arenes and tetrazole-containing polymers. Decasubstituted pillar[5]arenes containing a large, good leaving tosylate, and phthalimide groups were first synthesized and characterized. Pillar[5]arenes containing primary and tertiary amino groups, capable of interacting with tetrazole-containing polymers, were obtained with high yield by removing the tosylate and phthalimide protection. According to the fluorescence spectroscopy data, a dramatic fluorescence enhancement in the pillar[5]arene/fluorescein/polymer system was observed with decreasing pH from neutral (pH = 7) to acidic (pH = 5). This indicates the destruction of associates and the release of the dye at a pH close to 5. The presented results open a broad range of opportunities for the development of new universal stimulus-sensitive drug delivery systems containing macrocycles and nontoxic tetrazole-based polymers.

Atomic force microscopy is employed to study the influence of the motion of a glycerol solution through a coiled (spiral-wound) polymeric communication pipe on the aggregation state of a protein, with the example of a horseradish peroxidase (HRP) enzyme. The measuring cell with the buffered solution of the protein was placed within the experimental setup over the pipe coil, through which glycerol was pumped. It is demonstrated that, in such a system, the flow of a non-aqueous liquid (glycerol) leads to a change in the physicochemical properties of a protein, whose solution was incubated in the measuring cell placed over the coil. Namely, changes in both the adsorbability onto mica and the aggregation state of the model HRP protein were observed. As glycerol-containing liquids are commonly used in biosensor operations, the results reported herein can be useful to the development of biosensor systems, in which polymeric communications are employed in sample delivery and thermal stabilization systems. The data obtained herein can also be of use for the development of specified hydrodynamic models.

The influence of liquid motion in flow-based systems on the aggregation state of an enzyme and on its enzymatic activity was studied, with horseradish peroxidase (HRP) as an example. Our experiments were carried out in a setup modeling the flow section of the biosensor communication with a measuring cell containing a protein solution. Studies were conducted for a biosensor measuring cell located along the axis of a spiral-moving liquid flow. The aggregation state of the protein was determined with an atomic force microscopy-based sensor (AFM sensor). It has been demonstrated that upon flowing of water through silicone biosensor communications, an increased aggregation of HRP protein was observed, but, at the same time, its enzymatic activity did not change. Our results obtained herein are useful in the development of models describing the influence of liquid flow in biosensor communications on the properties of enzymes and other proteins. This is particularly important for the development of serologic protein biosensors, which are beginning to be used for the early diagnosis of oncological diseases (such as brain cancer, prostate cancer, breast cancer etc.). The results obtained herein should also be taken into account when considering possible changes in hemodynamics due to increased protein aggregation.

Highly sensitive biosensor systems are particularly sensitive to the charge state of an analyte. This charge state can have either a positive (for instance, in case of increasing the efficiency of fishing of low-abundant proteins) or negative effect (for instance, in case of the appearance of charge jumps upon the injection of analyte solution into a measuring cell, what can cause undesirable parasitic signals). Previously, it was demonstrated that upon the pumping of analyte solution through polymeric communications of biosensors with a peristaltic pump at a low (~1 mL/min) flow rate, an accumulation of charge, transferred by the liquid drops from the feeding system into the measuring cell, is observed. At this point, the time dependence of charge accumulation has a linear-stepwise form. In the present study, the influence of the flow rate of water on the parameters of the time dependence of the accumulation of charge in such a system—including the influence on the stepwise charge accumulation—has been investigated. The measurements have been performed with a highly sensitive electrometer sensor at 38 °C, which corresponds to a pathological state of a human body. It has been found that a linear-stepwise time dependence of charge accumulation is observed in a wide range of water flow rates (V= 0.9 to 7.2 mL/min). At that point, upon increasing the flow rate with the transition from the drop-by-drop mode of water supply (0.9 mL/min) to the jet flow (7.2 mL/min), an increase in the absolute value of accumulated charge is observed, but the magnitude of the charge jumps does not change significantly. Thus, the amount of charge accumulated in the cell ambiguously depends on the water flow rate—i.e., this dependence can be non-linear. Accounting for the discovered phenomenon is important in the development of new, more accurate models describing physicochemical properties of aqueous solutions and hemodynamics. This effect should also be taken into account in the development of highly sensitive diagnostic systems intended for the detection of single biomarkers of pathologies in humans and crops, as well as in other living systems. In low-concentration systems, the occurrence of a charge can become a significant factor affecting the efficiency of detection of biomolecules and the reliability of the data obtained. The detection of biomolecules present in the solution at low concentrations is in high demand in medical diagnostics for the revelation of biomarkers at the early asymptomatic stage of various diseases, including aggressive forms of cancer.

The electrochemical reduction of CO2 has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO2 in water, the maximum CO2 reduction current which could be drawn falls in the range of 0.01–0.02 A cm–2. This is at least an order of magnitude lower current density than the requirement to make CO2-electrolysis a technically and economically feasible option for transformation of CO2 into chemical feedstock or fuel thereby closing the CO2 cycle. This work attempts to give a short overview on the status of electrochemical CO2 reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

Novel side chain [omega]-fluorinated ecdysteroid analogues were obtained starting from [omega]-functionalized ecdysteroids. Thus, the reaction of diacetonides of 25RS-hydroxy- and 24-hydroxy 27-nor- and 25,26,27-tris-nor-20-hydroxyecdysone derivatives with diethylaminosulfur trifluoride (DAST) involves replacement of the terminal hydroxyl group and dehydration at the 14-position to give 25RS-fluoro- and 24-fluoro-14-anhydro analogues of ecdysteroids. Key words: 20-hydroxyecdysone, fluorinated ecdysteroids, DAST fluorination, hydride reduction. Nous avons synthétisé de nouveaux analogues d'ecdystéroïdes à chaîne latérale [omega]-fluorée à partir d'analogues ecdystéroïdes fonctionnalisés à la position terminale. Ainsi, la réaction entre les diacétonides les dérivés 25RS-hydroxy- et 24-hydroxy- de la 27-nor- et de la 25,26,27-tris-nor-20-hydroxyecdysone, respectivement, et le trifluorure de diéthylaminosulfure (diethylaminosulfur trifluoride, DASÖ) procède par remplacement du groupe hydroxyle terminal et déshydratation à la position 14 pour produire les analogues 25RS-fluoro-14-anhydro et 24-fluoro-14-anhydro des ecdystéroïdes. [Traduit par la Rédaction] Mots-clés : 20-hydroxyecdysone, ecdystéroïdes fluorés, fluoration par DAST, réduction par hydrure., Introduction Ecdysteroids are known as insect hormones that control molting, metamorphosis, and reproduction. (1) Some ecdysteroids act as hormone antagonists, disturbing the insect molting process; (2) however, these compounds cannot [...]

Abstract: This article reports the comparison of different chemical methods to produce graphite-based particles with varying degrees of oxidation, as well as graphene oxide (GO) and pristine graphite (PG). Detailed [...]