Polyfunctional Materials Research Articles

Pyrene Derivatives Containing Triphenylacrylonitrile as Aggregation Induced Emissive Mechanochromic Materials

AbstractOrganic materials possessing multiple functional properties such as aggregation induced emission, mechanochromism and acidochromism are rare. In this paper we demonstrate the design of polyfunctional materials using the aggregation quenching chromophore, pyrene. The pyrene derivatives possessing 2,3,3‐triphenylacrylonitrile as aggregation induced emission chromophore and phenanthroimidazole or N‐phenylcarbazole as auxiliary electron‐rich chromophore are designed, synthesized by Suzuki coupling reactions and characterized as aggregation induced emissive mechanochromic materials. Though all the dyes exhibit aggregation induced emission, the dyes containing para‐linked 2,3,3‐triphenylacrylonitrile and auxiliary chromophore such as phenanthroimidazole or N‐phenylcarbazole display mechanochromism. Additionally, the phenanthroimidazole containing dyes show acidochromism attributable to the protonation of phenanthroimidazole moiety.

Optical properties of the O3+-ion implanted and femtosecond-laser ablated ridge waveguide in the Er3+-doped germanate glass

Er3+-doped germanate glass is a kind of polyfunctional material for optical and photonic applications. The work reports on the preparation and properties of O3+-ion implanted and femtosecond-laser ablated Er3+-doped germanate glass optical ridge waveguide. The energy is 6.0 MeV and the fluence is 5 × 1014 ions cm−2 for the O3+-ion implantation. The pulse energy and the scanning speed of the femtosecond-laser ablation are 3 μJ and 50 μm s−1, respectively. The SRIM 2013 is used to calculate the vacancy profile induced by the implantation in the Er3+-doped germanate glass for the physical mechanisms of the waveguide formation. The optical microscopy images of the cross-section of the waveguide are captured by the Nikon microscope. The light-guiding properties of the ion-implanted and laser-ablated waveguides are studied by the end-face coupling system. The ridge waveguide has been produced by combining the FS ablation with ion implantation technologies for the first time in the Er3+-doped germanate glass. The propagation of light field indicates that it has the potential for photonics applications based on the planar and ridge Er3+-doped germanate glass waveguides.

Cadmium (II) metal–organic architecture based on versatile multi‐N‐donor “3,5‐diaminotriazole” and dicarboxylate spacer: Synthesis, crystal structure, and its photocatalytic degradation of organic dye

Herein, we have designed polyfunctional materials of d10‐configuration Cd (II) “Cd‐CP.” The coordination polymer Cd‐CP was synthesized using benzene‐1,4‐dicarboxylic acid and 3,5‐diaminotriazole via solvothermal reaction. The Cd‐CP has been fully characterized by using single X‐ray crystallography, thermogravimetric analysis (TGA), Fourier transform–infrared (FT‐IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), powder X‐ray diffraction (PXRD), and Brunauer–Emmett–Teller (BET) analysis. Single crystal X‐ray crystallography revealed that the CP‐Cd crystallized in triclinic space group P – 1 with the chemical composition [(BDC)(DAT)2Cd2Cl] (CH3)2 NH2+ · H2O. The present study investigated the impact of different reaction parameters, including the concentration of MG, the dosage of catalyst, and the duration of irradiation, on the outcome demonstrating a high level of photocatalytic efficacy at 99.19% under visible light irradiation. The obtained kinetic data exhibited conformity with a pseudo‐first‐order model, indicating that the rate‐determining step is likely to be photo‐absorption. The value of the apparent rate constant was found to be 0.019 min−1 for 50 mg L−1, 0.016 min−1 for 100 mg L−1, and 0.015 min−1 for 150 mg L−1 MG concentration. The corresponding half‐life time was found to be 36.44, 43.31, and 46.20 min with values of correlation coefficient (R2) as 0.99, 0.93, and 0.98, respectively. Moreover, a trapping experiment was conducted to demonstrate that hydroxy radicals (•OH) are the principal reactive oxygen species (ROS) responsible for the degradation of MG. The results of the total organic carbon (TOC) study indicated a mineralization value of around 89%, suggesting that the dye has been completely degraded into non‐toxic by‐products such as carbon dioxide (CO2) and water (H2O).

Study of the Possibility of Using Sol-Gel Technology to Obtain Magnetic Nanoparticles Based on Transition Metal Ferrites.

The article presents results for the magnetic nanoparticles sol-gel method synthesis of cobalt (II) ferrite and organic-inorganic composite materials based on it. The obtained materials were characterized using X-ray phase analysis, scanning and transmission electron microscopy, Scherrer, Brunauer-Emmett-Teller (BET) methods. A composite materials formation mechanism is proposed, which includes a gelation stage where transition element cation chelate complexes react with citric acid and subsequently decompose under heating. The fundamental possibility of obtaining an organo-inorganic composite material based on cobalt (II) ferrite and an organic carrier using the presented method has been proved. Composite materials formation is established to lead to a significant (5-9 times) increase in the sample surface area. Materials with a developed surface are formed: the surface area measured by the BET method is 83-143 m2/g. The resulting composite materials have sufficient magnetic properties to be mobile in a magnetic field. Consequently, wide possibilities for polyfunctional materials synthesis open up for various applications in medicine.

EXTRACTION OF Al3+, Pb2+, Cd2+ AND Sr2+ IONS WITH A PHOSPHORUS-CONTAINING PRODUCT FROM RICE FLOUR

Materials of natural origin can serve as raw materials for the production of environmentally friendly inexpensive polyfunctional materials with a wide range of applications. Agricultural waste from rice production (rice husks, straw and flour) can serve as a source of such substances. In this work, the process and conditions for the extraction of aluminum, lead, strontium and cadmium ions from aqueous solutions by an organophosphorus product (derivative of inositol hexaphosphoric, phytic acid) obtained from rice flour production waste are studied. Phytic acid and its derivatives are highly effective ligands capable of chelating metal cations, which allows them to be considered as a natural material suitable for removing heavy metal ions from aqueous solutions. The degree of extraction of aluminum ions reaches 97%, lead and strontium – 89%, and cadmium – 93%. It is shown that the absorption decreases in the series Cr3+ > Al3+ > Bi3+ (from 13.0 mg/g to 4.9 mg/g) and Cd2+ > Pb2+ > Sr2+ (from 8.9 mg/g to 7.5 mg/g). These studies allow us to offer a fundamental possibility of using a natural phosphorus-containing compound as an environmentally friendly sorbent.

Polyfunctional materials based on ferrites for the treatment of colored wastewater

Problem. Large volumes of metalcontaining wastewater necessitate their processing to obtain new materials. Goal. The goal is obtaining mixed zinc and copper ferrites from spent technological sulfate copper-zinc solutions and to substantiate their technically useful properties. Methodology. Composite materials containing copper-zinc ferrites (FC) were obtained by coprecipitation from spent technological sulfate copper-zinc solutions. The ratio of copper, zinc and iron in ferrites has been determined. Research methods used X-ray phase analysis, electron probe microanalysis, IR spectroscopy, macroelectrophoresis, determination of ferrite magnetization using a ballistic magnetometer, spectrophotometry. Results. Zinc is more fully included in ternary ferrites than copper. It is proved that the surface groups of ferrites are O–H in adsorbed associates and end groups of water, deformation vibrations of the Zn–O–H, Fe–O–H and O–H groups have been recorded. Originality. The specific saturation magnetization of ferrite particles varies in the range of 6– 46 emu/g decreasing with an increase in the proportion of nonmagnetic Zn and Cu. There is no residual magnetization in ferrites. The synthesized ferrites belong to superparamagnets with a particle size of 7‒14 nm. Practical value. FCs are active in the processes of purification of the aqueous phase from the dye methyl violet (MV). For most FCs, cleaning is effective when the mass of ferrite exceeds the mass of MV by 1000 times, when at the same time a high purification efficiency and the degree of conversion of MV per unit of FC mass is achieved. Within 5 hours the solutions can be purified from MV by 99 %. Simultaneous photocatalysis and adsorption is possible. The photocatalytic activity of FCs manifests itself at the beginning of the process, with a further decrease when the FC surface is screened by the MV layer.

Pull‐Pull Alkenes in the Aza‐Michael Reaction

AbstractAza‐Michael addition is known to be one of the most exploited reactions in organic chemistry. Taking into account the fact that each seventh reaction in pharmaceutical industry involves the formation of at least one C−N bond, it is not surprising that this reaction is especially valuable for the synthesis of bioactive compounds and drugs. Traditionally, only push‐pull alkenes are regarded as starting material for this reaction. The participation of pull‐pull alkenes as Michael acceptors is much less studied. The presence of two vicinal electron‐withdrawing groups makes them highly reactive in nucleophilic reactions especially with nitrogen‐centered nucleophiles. This feature allows them to be excellent building blocks in the synthesis of bioactive molecules and polyfunctional materials. The review considers the most important and sometimes unexpected results obtained over the last two decades on the conjugate addition of nitrogen nucleophiles to pull‐pull alkenes bearing various acceptor moieties (alkoxycarbonyl‐, carbonyl‐, formyl‐, cyano‐, trifluoromethyl‐ or nitro group) in various combinations.magnified image

Luminescence behavior of PMMA films doped with Tb(III) and Eu(III) complexes

Novel hybrid systems based on the poly(methyl methacrylate) (PMMA) matrix and Eu(III) and Tb(III) tris(β-diketonates) complexes with 1,10-phenanthroline were synthesized and analyzed as light-conversion materials. Solutions of the Tb(III) and Eu(III) complexes doped into PMMA were spin-coated to fabricate films with various concentrations of luminophores. Long hydrocarbon substituents in the structure of complexes inhibit their crystallization. In turn, it allows to vary the luminophore content in a polymer matrix in a broader range and achieve the maximum of emission with higher concentrations of dopants. The addition of the Tb(III) complex to the system results in a 26% increase in the relative luminescence quantum yield of the Eu(III) ions due to an additional energy transfer from the Tb(III) compound. The results of this work illustrate that although the Eu(III) and Tb(III) complexes exhibit lower rate and efficiency of energy transfer than their well-known Tb(acac)3 and Eu(tta)3 analogues, the structural features of lanthanide complexes allow to efficiently dope a PMMA matrix with considerably larger amounts of luminophores. It offers broader application opportunities for the coordination Ln(III) compounds as polyfunctional materials for optics and optoelectronics.

The Experimental Study of Innovative Methods Regarding the Removal of Sm(III)

The modern development of the construction materials sector determines the use of rare earth metals (REM) for various purposes. In particular, REM are added as basic alloying elements into magnesium alloys to increase alloy durability and strength. The complex systematic study of structural components and REM interaction are the basis for the phase state monitoring of multicomponent oxide polyfunctional materials. In addition, on the preparatory stage, layers with specified construction material coatings are formed. The paper presents experimental and theoretical results of studies of adsorptive bubble methods in the systems containing Samarium cations and surfactants, namely sodium dodecyl sulphate (NaDS). To identify the process mechanisms and prediction of optimal conditions of metal cations’ removal and separation by extraction, flotation, and ion flotation methods, one should know the pH of metal hydroxo-complexes and pH of the hydrate formation. The possibility of lanthanide ions’ removal (by the example of Samarium ions) by the solvent sublation method with NaDS as a collector and isooctyl alcohol as an extractant was studied. From the obtained experimental data, it was clear that the Sm3+ removal in acidic mediums is practically non-existent. The results obtained in this paper are topical in the production of electrode coating components, welding fluxes, sorbents for nuclear wastewater burial, wastewater treatment, highly porous heat-insulating and fire-resistant materials, cement, and concrete with improved frost resistance.

Environmentally Friendly, High-Performance Fire Retardant Made from Cellulose and Graphite.

Many materials and additives perform well as fire retardants and suppressants, but there is an ever-growing list of unfulfilled demands requiring new developments. This work explores the outstanding dispersant and adhesive performances of cellulose to create a new effective fire-retardant: exfoliated and reassembled graphite (ERG). This is a new 2D polyfunctional material formed by drying aqueous dispersions of graphite and cellulose on wood, canvas, and other lignocellulosic materials, thus producing adherent layers that reduce the damage caused by a flame to the substrates. Visual observation, thermal images and surface temperature measurements reveal fast heat transfer away from the flamed spots, suppressing flare formation. Pinewood coated with ERG underwent standard flame resistance tests in an accredited laboratory, reaching the highest possible class for combustible substrates. The fire-retardant performance of ERG derives from its thermal stability in air and from its ability to transfer heat to the environment, by conduction and radiation. This new material may thus lead a new class of flame-retardant coatings based on a hitherto unexplored mechanism for fire retardation and showing several technical advantages: the precursor dispersions are water-based, the raw materials used are commodities, and the production process can be performed on commonly used equipment with minimal waste.

Study on Adsorption Performance of MgO/Calcium Alginate Composite for Congo Red in Wastewater

This research prepared a poly-functional material which has outstanding adsorption performance and easily recyclable for Congo red dye removal. The multifunctional gel yarn composed of calcium alginate and nano-magnesium oxide was prepared by wet spinning. For the morphology and structure of MgO/CA composite, the compound product was characterized by Field Emission Scanning Electron Microscope (FE-SEM), Fourier Transform infrared spectroscopy (FTIR) and Thermogravimetric analysis (TGA). Then, the adsorption performance of MgO/CA aerogel for Congo red was studied, including the influence of four factors (adsorbent dosage, pH, initial concentration, contact time), adsorption isotherm, adsorption kinetics and adsorption thermodynamics. The results show that the adsorption properties of MgO/CA aerogel on Congo red largely depend on these factors. The best contact time for MgO/CA aerogel to remove Congo red is 24 h. Besides, the maximum adsorption capacity of the adsorbents is usually very high (312.5, 322.6 and 344.8 mg/g at 303, 313 and 323 K, respectively). The adsorption kinetics can be best described by a pseudo second-order reaction, and the adsorption data agree well with the Langmuir model. Thermodynamic parameters including the changes in entropy (ΔS0), free energy (ΔG0) and enthalpy (ΔH0), and stated that adsorption by the MgO/CA aerogel was endothermic and spontaneous.

MICROBIAL POLYSACCHARIDES – THE BASIS FOR NEW GENERATION POLYFUNCTIONAL MATERIALS

New generation polyfunctional materials based on such microbial polysaccharides as bacterial cellulose, alginate, xanthan, chitosan have been obtained. The possibility of their application as materials with antibacterial, regenerative and haemostatic properties, ultra-low thermal conductivity, density, high noise-absorbing and sorption properties has been shown.

New water-soluble derivatives of chitin and their based nanoparticles: Antibacterial and catalytic activity

A facile route towards new chitin derivatives with both catalytical and biological activities is proposed in the course of methodology development aimed at the design of polyfunctional materials on the basis of renewable and accessible natural polysaccharides. Ultrasound-promoted and Cu(I)-catalyzed azido-alkyne click cycloaddition of the propargylic ester of nicotinic acid and its N-methylated analogue to the azido chitin derivative allowed us to obtain previously unknown non-toxic water-soluble derivatives of chitin. The obtained polymers and their based nanoparticles demonstrated a high antibacterial activity in vitro, which is comparable or even superior to that of commercial antibiotics ampicillin and gentamicin. New derivatives of chitin were also shown to be highly efficient and reusable (at least for 10 times) green catalysts for the aldol reaction in water. The catalysts can be easily separated from the reaction mixture by their precipitation with ethanol. The results obtained highlight prospects of further studies on chitin's application in the rational design of novel functional materials with valuable properties.

A Practical Method for Continuous Production of sp3-Rich Compounds from (Hetero)Aryl Halides and Redox-Active Esters.

A practically useful coupling reaction between aromatic halides and redox-active esters was realized by nickel catalysis through the use of a packed zinc bed column in continuous flow. Multiple reuse of the column showed a negligible decrease in efficiency, affording high space/time yields. A wide range of substrates, including a number of heteroaryl halides and polyfunctional materials were coupled in generally good yields. Longer-time and larger-scale experiments further demonstrates the robustness of the system.

Formation of multifunctional nano-layered oxide REE-containing materials using nitrate precursors

Complex system research of the interaction of structural components in nitrate systems of rare-earth and IA, IIA elements ofthe periodic system – precursors of modern multicomponent oxide polyfunctional materials on their basis – established theformation of a class of lanthanides alkaline coordination nitrates. The obtained data are the basis for identifying, controllingthe formed phases in the preparatory stages of processing in innovative technologies using nitrate predecessors of differentelectronic structures elements and various combinational methods of their activation, establishing technological andfunctional dependencies, controlling the modification of the synthesis products properties.

Polyfunctional Materials—Effective Sorbents for Purification of Liquid Radioactive Wastes

The comparison assessment of the efficiency of sorption purification of low-level active liquid radioactive wastes by polyfunctional materials based of layered double hydroxides and hexacyanoferrates of metals is carried out. The values of the distribution coefficients of radionuclides on these sorbents reach 103–105 cm3/g and are comparable with obtained world analogues. It was established that heat treatment of waste materials (600–800°C) provides reliable isolation of ecotoxicants.

Polyfunctional Materials Based on Collagen Hydrolysate Obtained from Swim Bladders of Northern Fish Species

In recent years biopolymer fillers are widely used to development of composite materials for various purposes. In this respect collagen hydrolysate (HC) is one of the most promising biopolymer for modification of synthetic polymers to produce different types of item. In this work, a new source of collagen has been tested - collagen hydrolysate obtained from a swim bladder of northern fishes. The cure characteristics, mechanical and relaxation properties, abrasion resistance of the Butadiene–acrylonitrile rubber composites containing the collagen hydrolysate have been discussed. The chemical compositions, properties, morphology of collagen hydrolysates have been studied. It was shown by means of IR spectroscopy that the bands of Amide I, Amide II, Amide III, Amide A, which is related to the vibrations of the polypeptide bond of the protein, are recorded in the infrared spectra of the samples. The morphological structure of collagen was investigated by scanning electron microscope JSM-7800F ("JEOL", Japan). The size and the zeta potential of collagen hydrolysate were investigated by Dynamic Light Scattering (DLS) on the Zetasizer nanoZS instruments (Malvern Instruments Ltd., UK).

Features of transformations in REE-containing systems of nitrate precursors in preparatory processes of formation of multifunctional oxide materials

The complex study provides a reliable idea of ​​the trends in the joint behavior of structural components in the water-salt systems of nitrate precursors of REE, alkaline, alkaline earth metals in the preparatory stages of the processes of forming multicomponent oxide polyfunctional materials on their basis with thermal activation. Stages of such transformations are revealed; The regularities of complex and phase formation in systems and factors influencing them are determined; A number of physicochemical properties of the intermediate phases formed - coordination lanthanides nitrates: their composition, types of compounds, atomic-crystalline structure, regularities of transformations during heat treatment were studied.

Acetocatechol functionalized viologen as polyfunctional material that responds to anion, cation and reductant in aqueous and organic solvents

Both viologen and catechol have been studied extensively. However, the stability of catechol-Fe(III) without additional oxidant is still not well understood. In this paper, we introduced acetocatechol into viologen to investigate its interactions with anion, cation, and reductant, as well as the stability of its Fe(III) complexes. This acetocatechol functionalized viologen, 1,1′-bis(2-(3,4-dihydroxyphenyl)-2-oxoethyl)- [4,4′-bipyridine]-1,1′-diium chloride (H6V·Cl2) exists in central symmetric ketone cation form in solid state. Viologen cation increased the acidity of the aceto group and deprotonated the enolic proton to form monodeprotonated enolic H5V+ in the presence of anion/base, which had the deepest color in organic solvents. The absorbance maximum of H5V+ increased with the decrease of solvent polarity. It also interacted with B4O72− and MoO42− by forming catechol ester in DMSO solution. The catechol moiety can coordinate to metal ion, especially Fe(III), in both aqueous and DMSO solution. In particular, it coordinated to Fe(III) much more readily in aqueous solution than in DMSO. Green monocatecholato Fe(III) and red-brown bis-catecholato Fe(III) complex also formed in aqueous solution. The monocatecholato Fe(III) complex first-order dimerized in aqueous solution at room temperature but underwent second-order decomposition to Fe(II) complex at 60 °C. The biscatecholato Fe(III) complex also transferred to other Fe(III) complexes at first- and second-order at room-temperature and 60 °C respectively. The t1/2 varied from several hours at room-temperature and several minutes at 60 °C at 10−4 M concentration. The interactions of Fe(III) in DMSO is much more complex than that of acetocatecholate without viologen. Fe(III) can also be reduced to free viologen radicals in the presence of sodium Na2S2O4, but not N2H4. In conclusion, this polyfunctional compound responds to anion via aceto and catechol, metal ion via catechol hydroxyl, while reductant via viologen.

Microcapsules from diverse polyfunctional materials: synergistic interactions for a sharp response to pH changes

Responsive microcapsules with strong synergistic interactions were prepared using a copolymer, silver nanoparticles and carbon nanotubes.