Valery N. Bliznyuk

Clemson University | CU · Department of Environmental Engineering and Earth Science

A scoping study of a commercially available resin selective for aqueous plutonium (Pu), AnaLig® Pu-02, modified with scintillator was investigated as a scheme to simultaneously concentrate and detect Pu in aquatic matrices. The extractive scintillating resin was comprised of a silica base, functionalized for plutonium extraction, grafted with plast...

Development of miniature sensors for radionuclides is a challenging goal. In this paper we have applied specially developed vinyl-functionalized organic fluorophores for fabrication of nanoscale polymer brush scintillator coatings on artificially created 3D mesoporous structures. The applied 3D printing based on 2-photon polymerization is a modern...

We explored two approaches to recover uranium and plutonium from aqueous solutions at pH 4 and pH 7 using water-soluble star-like polyacrylamide polymers with a dextran core. In the first approach, a solution comprising a neutral or ionomer polymer was mixed with a radionuclide solution to form polymer–metal complexes that were then retained by ult...

Aiming to develop new magnetic materials for neutron shielding applications, B- and Gd-containing magnetic nanoparticles were synthesized. Following bottom-up synthetic approach, core-shell Fe 3 O 4 / Gd 2 O 3 nanocomposite particles were synthesized at the first stage. In the next stage, magnetic core-shell particles were modified with amino group...

We consider physico-chemical specificity (open circuit potential and pH changes) of the chemical oxidative aniline polymerization in the presence of halloysite nanotubes (HNTs) and morphology, structure and properties of the new nanocomposites of HNTs with polyaniline (PANI) doped by p-toluenesulfonic acid. We find that specificity of the PANI prop...

The study proves relevance of specialized software use to solve problems of emergencies prevention of radioactive liquids spills to teach students and graduate students. Main assessment criteria of accidents at radiation-hazardous objects associated with radioactive liquids spillage is identified. A model of radioactive substances transport in emer...

Surface plasmon resonance (SPR) is a proven technique in sensorics. Wide application of the method is still limited by a necessity of a complex optical equipment using special dispersion elements like a prism or diffraction grating (DG). We have implemented a novel and inexpensive way for fabrication of the DG on a silicon substrate using femtoseco...

Plastic scintillators (PS) allow design of portative lightweight devices for quantification of low‐activity radiation sources. We have recently suggested a new type of organic fluorophores based on triphenyl pyrazoline (PZ) derivatives with high fluorescence quantum yield showing high radioluminescence when combined with a polyvinyltoluene (PVT) ma...

A hybrid extractive scintillating resin (HESR) was developed for the concentration and detection of radiocesium. The HESR comprised a cesium-selective potassium ferrierite ion-exchange powder embedded in porous polymeric scintillating beads. It was prepared by carrying out suspension polymerization of 4-methylstyrene with divinylbenzene, 2-(1-napht...

Spills of liquid radioactive material are reviewed as potential event that can be associated with release into the atmosphere. Existing approaches to radiological impact assessment for onsite as well as offsite of facility are presented. The example of using the actual Java version of the European RODOS system as prototype of the decision support s...

Back Cover: In article number 2100085 by Valery Shevchenko, Mariana Gumenna, and co‐workers, coordination polymers based on Co²⁺, Ni²⁺ ions and amphiphilic oligomeric silsesquioxanes, containing various ratios of n‐octadecylurethane and carboxyl groups (OSS‐C18H37‐x‐COOH‐y), form a hierarchical stimuli‐responsive supramolecular structure stabilized...

Synthesis, structural organization, thermal, and magnetic properties of coordination polymers (OSS‐polymer‐Me) based on amphiphilic oligomeric silsesquioxanes (OSS) and transition metal ions (Co2+, Ni2+) are reported. The initial amphiphilic OSS containing various ratios of n‐octadecylurethane and carboxyl groups (OSS‐C18H37‐x‐COOH‐y) are character...

We report on the structure and properties of dextran-graft-polyacrylamide star-lake polymers, which are efficient flocculant aids. Demonstrated in this paper is that these polymers form complexes with three common radionuclide contaminants: uranium, strontium, and cesium. Application of these polymers as flocculant aids together with inexpensive ka...

In this mini-review, we address the importance of specific interactions in core-shell structures composed with intrinsically conducting polymers (ICPs) as a shell and various nanoparticles used as a core. These interactions that can appear during the polymerization process of corresponding monomers or in the course of subsequent treatments of alrea...

Sorption properties of polydopamine (PDA) for uranium and plutonium from an aqueous environment are reported at three different pH values (2, 4 and 6.5–7). In addition to deionized (DI) water, artificial groundwater (GW) and seawater (SW) were used with U uptake close to 100% in each case. PDA polymer has been identified as a material with extremel...

Sorption properties of polydopamine (PDA) for uranium and plutonium from an aqueous environment are reported at three different pH values (2, 4 and 6.5–7). In addition to deionized (DI) water, artificial groundwater (GW) and seawater (SW) were used with U uptake close to 100% in each case. PDA polymer has been identified as a material with extremel...

A method was developed for the synthesis of ion-coordinated polysilsesquioxanes (OSS-M) by reaction of amphiphilic carboxyl-containing oligosilsesquioxanes (OSS-COOH) with Co and Ni acetates. The OSS-M contain two types of crystalline phases, one of which is formed as a result of interaction of the alkyl chains while the other results from the form...

Diglycolamide ligands are widely applied in the analysis of radionuclides, especially lanthanides and actinides. They are used in liquid-liquid extraction procedures or in solid-phase extraction sorbents where they are adsorbed on the surface of hydrophobic polymers. The main objective of this study was to synthesize the N,N,N'N′-tetrahexyl diglyco...

Polybenzoxazines belong to next-generation highly crosslinked thermostable resins with physical properties that go far beyond traditional high temperature polymer networks. Due to a unique set of properties, they have significant advantages over other existing thermosets. Commercial availability and wide structural diversity of the starting feedsto...

Inside Front Cover: In article 1700651, Valery Bliznyuk and co‐workers demonstrate real‐time detection of low‐level concentration of 90Sr in water, with a hybrid extractive scintillating resin (HESR). This HESR is comprised of a commercial Superlig 620 resin coated with halloysite nanotubes, which were previously modified with a polyvinyltoluene br...

In this work, we describe the design and synthesis of novel isomeric (para- and meta-) core-fluorinated polybenzoxazines from bis(benzoxazine)-containing monomers with 1,4-tetrafluorobenzene or 4,4′-octafluorobiphenylene dioxyphenylene central units. The new core-fluorinated polybenzoxazines were prepared as dimensionally stable free-standing films...

Water can become contaminated as a result of a leak from a nuclear facility, such as a waste facility, or from clandestine nuclear activity. Low-level on-line radiation monitoring is needed to detect these events in real time. A Bayesian control chart method, Shiryaev-Roberts (SR) procedure, was compared with classical methods, 3-σ and cumulative s...

We report on significant improvements in the structure and electronic properties of a poly(3-alkylthiophene) representative namely poly(3-methylthiophene) (P3MT) when it is synthesized in the presence of submicron electroactive poly(vinylidene fluoride) (PVDF) particles. The applied template oxidative synthesis leads to formation of the PVDF/P3MT c...

Coordination of uranyl (U(VI)) with carboxylate groups on functionalized graphene oxide (GO) surfaces has been shown to alter the reduction potential of the sorbed uranium ion. A quantitative measure of the reduction potential and qualitative estimation of sorption/desorption processes was determined using cyclic voltammetry and a proposed coordina...

Combining extraction and scintillation properties within the same material is a relatively new approach in development of sensors for detection of radioactive elements. Structural organization of such materials at a nanoscale typically offers higher efficiency of detection and shorter response time. In this contribution, several new protocols are d...

The research presented here is the development of sensor materials that are applicable for real-time in situ quantification of radiostrontium in aqueous solutions. Two different approaches were applied to prepare highly selective structures for simultaneous extraction and detection of radiostrontium using online detection methods. Online data were...

This paper presents the results of our studies on the deposition and characterization of multi wall carbon nanotube films in combination with polyurethane (PU) and N-methyl- 2-pyrrolidone (NMP). These studies mainly focused on the effect of ultra violet Ozone plasma treatment on the on the contact angle and wettability characteristics of the substr...

This contribution characterizes the stability of scintillating resins for ionizing radiation detection that were synthesized with 2-(1-naphthyl)-5-phenyloxazole (α-NPO) or 2-(1-naphthyl)-4-vinyl-5-phenyloxazole (v-NPO) fluor in polystyrene (PS) or poly(4-methyl styrene) (PVT) matrices. Leaching studies of the PS and PVT resins with methyl acetate s...

We report on the synthesis, spectroscopic and scintillation properties of three new pyrazoline core based fluorophores. Fluorescence properties of the fluorophores have been studied both in a solution state and in a solid polyvinyltoluene (PVT) resin matrix of different porosity. The synthesized fluorophores were found to be promising candidates fo...

Herein, we present a novel acid-less synthetic approach for in-situ polymerization of aniline synchronized with reduction of graphene oxide to graphene. This method provides uniform deposition of ordered polyaniline nanotubes over the surface of graphene nanosheets. The synthesized graphene-polyaniline nanocomposite has the ability of complete remo...

Structure–property relationships of nanocomposites of multiwall carbon nanotubes (MWCNTs) and polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA) are studied and discussed in terms of contribution of the PANI phase properties. Two phases of PANI-DBSA with different properties, such as a shell-wrapping carbon nanotube and separate neat...

Polymerization procedure: We prepared the reaction mixture constituted with 30 mL of distilled water, 0.2683 g (0.83 mmol) of DBSA (Acros Organics) and 0.0513 g (0.55 mmol) of aniline monomer (An) was prepared. The mixture was stirred for 60 min followed by addition of the required quantity of MWCNT and cooling down to 10°C under stirring for 60 mi...

In this work, we describe the design and synthesis of novel core-fluorinated Schiff base monomers and conjugated polymers based on them. The new fully aromatic highly fluorinated poly(azomethine ether)s (PAMEs) were prepared by polycondensation of core-fluorinated azomethine-containing compounds. The structure of the monomers and polymers were conf...

The synthesis, chemical characterization and optical properties of 2-(1-naphthyl)-4-vinyl-5-phenyloxazole (vNPO) and 2-(1-naphthyl)-4-allyl-5-phenyloxazole (allylNPO) monomers are reported. Starting with the organic fluor 2-(1-naphthyl)-5-phenyloxazole (αNPO), the vNPO and allylNPO monomers were synthesized using Stille coupling followed by purific...

We demonstrate that fluorescence properties of organic fluors embedded in a porous polystyrene matrix are highly sensitive to the average pore size and pore-size distribution of the matrix. The effect can be understood as two different types of confinement imposed to the fluor molecules by the matrix. First, there is geometrical confinement that re...

Dibromomethylene-containing monomers with a tetrafluorobenzene central unit were synthesized using 2,3,5,6-tetrafluoro-1,4-bis(4-methylphenoxy)benzene as the starting material. This enabled preparation of several fluorinated poly(arylene ether)s containing isomeric fragments, with or without allyl or acetyl side groups, which were prepared by inter...

Traditional methods of quantifying alpha- and beta-emitting radionuclides in environmental water samples involve time-intensive, batch style analytical techniques that utilize bulky instruments. A recent development in environmental sensing is a portable, flow cell detector that utilizes extractive scintillating resin. The extractive scintillating...

Due to their high sorption capacity, nanoporous polymer resins can be used as an active material for ionizing radiation sensor applications. This contribution reports on the molecular design and synthesis of scintillating styrene-based resins with controlled bead size, porosity and surface functionality. In a working sensor device, the adsorption o...

Protic oligomeric cationic ionic liquids of the oligo(ether urethane) type are synthesized via the reaction of an isocyanate prepolymer based on oligo(oxy ethylene)glycol with M = 1000 with hexamethylene-diisocyanate followed by blocking of the terminal isocyanate groups with the use of amine derivatives of imidazole, pyridine, and 3-methylpyridine...

We report on synthesis of linear and hyperbranched protic and aprotic anionic oligomeric ionic liquids (OlLs). alpha,omega-Dicarboxy- and alpha,omega-disulfooligo(ethylene oxide)s, alpha-carboxy- and alpha-sulfooligo(ethylene oxide monomethyl ether)s, and di[alpha-carboxyoligo(ethylene oxide monomethyl ether)] were synthesized using reaction of oli...

Helium ion microscopy (HIM) is a relatively new high-resolution nanotechnology imaging and nanofabrication tool. HIM offers a near-molecular resolution (approaching that of TEM) combined with a simplicity of sample preparation and high depth of field similar to SEM. Simultaneously, the technique is not limited by the surface roughness as scanning p...

A method of obtaining new organic–inorganic nanostructured proton�exchange membranes operating via the anhydrous proton�conduction mechanism is proposed. An oligo(ethylene oxide) compo� nent serves as a proton�conducting phase in these membranes, and the sulfo derivatives of octahedral oli� gosilsesquioxanes of the acidic and acid–base types are us...

As electronic devices are scaled down to submicron sizes, it has become critical to obtain uniform and robust insulating nanoscale polymer films. For that reason, we address the electrical properties of grafted polymer layers made of poly(glycidyl methacrylate), polyacrylic acid, poly(2-vinylpyridine), and polystyrene with thicknesses of 10-20 nm....

We report on the synthesis of core-fluorinated phenylene- and biphenyldianilines, which was accomplished by diazotization reaction of diamines followed by coupling of the obtained diazonium salts with 2-[ethyl(phenyl)amino]-ethanol. Two types of core-fluorinated aromatic units were used in a molecular design of azo-chromophore monomers with enhance...

The specific features of nonlinear-optical properties of polymers and the principles of the molecular design of macromolecules containing chromophore groups are considered. Approaches to the design of hydroxyl-containing azo monomers and polyurethanes with nonlinear-optical properties formed on their basis are generalized. The classification of azo...

We studied peculiarities of the structural reconstruction within holographically recorded gratings on the surface of several different amorphous azobenzene-containing polymers. Under illumination with a light interference pattern, two processes take place in this type of polymer. The first process is the light-induced orientation of azobenzene unit...

The near-surface crystallization behaviour of poly(ethylene terephthalate) films of various thickness, spin-cast from solution onto silicon substrates, has been studied. In the as-cast state, the films are amorphous, with featureless morphology. A relationship is mapped between the film thickness (in the range 3 nm–700 nm), the isothermal annealing...

We present a detailed analysis of the Raman spectra of polyurethane (PU)/single wall carbon nanotube (SWCNT) composites obtained at room temperature using 488 and 514.5 nm laser excitation. The spectra reveal a significant influence of the polymeric matrix on the carbon nanotube bundles. The nanocomposite Raman bands become broader and are shifted...

A new type of inelastic light scattering in a disordered condensed matter is considered, in which, contrary to the conventional Raman scattering with fixed frequencies of vibrations, a shift of vibrational band positions is observed under variation of the excitation radiation frequency. This phonon-like scattering is inherent to intermediate states...

We have analyzed the influence of the annealing temperature, structural disorder, and the frequency of a continuous excitation laser radiation νL on the first- and the second-order Raman spectra of several nanostructured carbon materials including single-wall carbon nanotubes (SWNT), SWNT-polymer composites, and nanostructured single-crystalline gr...

Micro-Raman spectroscopy (μRS) involves acquiring spatially resolved Raman spectra by combining the conventional Raman spectrometer with a microscopic tool, typically an optical microscope. This chapter introduces the basic methodology of micro-Raman spectroscopy and presents an overview of its application to organic and inorganic nanostructures us...

The thin (1- 40 μm) films of nanostructured polyaniline (PANI) based composites have been adopted for ppb range ammonia sensing. Three types of composites were studied. The two core-shell systems with a poly(butyl acrylate) (PBuA) or poly(vinylidene fluoride) (PVDF) core and a PANI shell doped either with hydrochloric acid or with dodecylbenzenesul...

Nanostructured magnetic materials have a variety of promising applications spreading from nano-scale electronic devices, sensors and high-density data storage media to controlled drug delivery and cancer diagnostics/treatment systems. Magnetic nanoparticles offer the most natural and elegant way for fabrication of such (multi-) functional materials...

The thin (1- 40 μm) films of nanostructured polyaniline (PANI) based composites have been adopted for ppb range ammonia sensing. Three types of composites were studied. The two core-shell systems with a poly(butyl acrylate) (PBuA) or poly(vinylidene fluoride) (PVDF) core and a PANI shell doped either with hydrochloric acid or with dodecylbenzenesul...

Peculiarities of the structural organization and electrical properties of two core-shell polymer systems under different fabrication protocols have been studied with a combination of helium ion microscopy �HIM� and current-voltage characterization. The systems under study included a submicrometer core of a ferroelectric polymer polyvinylidene fluor...

Submicron poly(vinylidene fluoride) (PVDF)/polyaniline (PANI) core–shell latex particles are synthesized and examined as an active component in a simple conductometric chemical sensor. The structure and physical properties of these particles and nanostructured composite PVDF–PANI polymer films built of them are characterized with transmission elect...

In this paper, we report on the magnetic properties of isolated nanoparticles and interacting nanochains formed by the self-assembly of Ni nanoparticles. The magnetic properties were studied using superconducting quantum interference device (SQUID) magnetometry and magnetic force microscopy (MFM). We demonstrate that single-domain Ni nanoparticles...

BACKGROUND: There has been a recent surge of interest in the synthesis and applications of electroactive polymers with incorporated metal nanoparticles. These hybrid systems are expected to display synergistic properties between the conjugated polymers and the metal nanoparticles, making them potential candidates for applications in sensors and ele...

Polyhedral oligomeric silsesquioxanes (POSS) with an empirical formula [RSiO1.5]n (where n = 6, 8,…14, and R is a reactive organic group) represent a new type of nanomodifiers for polyurethanes (PUs) to produce organic–inorganic hybrids (OIHs), which are promising candidates for modern applications spreading from biomedical to airspace technologies...

Atomic force microscopy (AFM) and ultrasonic force microscopy (UFM) have been used to study the properties of adsorption layers formed by two incompatible polymers, polystyrene and poly(butyl methacrylate), in the course of simultaneous adsorption on the surface of silica (naturally oxidized surface of a silicon wafer). The adsorption was performed...

Present work reports on electrical properties of polyurethane elastomer/polyaniline (PU/PANI–HCl) composite films under tensile deformation. Two types of surface-modified and one type of volume-modified composite of PU and PANI–HCl were prepared. Surface modification of PU film was performed by swelling the parent film in aniline followed by its co...

The primary goal of printing electronics is to create structures and devices that are functionally similar to conventional electronics, but at greater speed, lower cost and less production complexity. The applications that will be affected by lower cost of electronics include RFID tags, solar cells, displays, chemical sensors, etc. In this work, ef...

Since the discovery of conductive polymers in the mid-1970, they have been very popular and widely researched among scientists worldwide. Nowadays, polymeric materials exhibiting electrical conductivity are very promising for applications in low-cost and disposable electronics. In addition, some polymeric materials can be solution processable, whic...

We report a spontaneous ignition of carbon nanotubes/polyurethane composite under He–Ne laser. The ignition of the composite is caused by rapid increase of the temperature to at least 660 K due to absorption of light by carbon nanotubes. This temperature was estimated from G band downshift of the carbon nanotube caused due to the bond loosening due...