Advanced Technologies in Polymer-Protected and Gel-Immobilized Nanocomposites

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (30 November 2020) | Viewed by 25998

Special Issue Editors


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Guest Editor
1. Institute of Polymer Materials and Technology, Satbayev University, Almaty 050019, Kazakhstan
2. Laboratory of Engineering Profile, Satbayev University, Almaty 050013, Kazakhstan
Interests: functional polymers; polyampholytes; interpolymer complexes; polymeric composites; nanomaterails; catalysis; oil recovery

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Guest Editor
Engineering Department, Moscow Aviation Institute (National Research University), 125993 Moscow, Russia
Interests: Metal-containing polymers; Macromolecular metal carboxylates; Coordination polymers; Metallopolymer nanocomposites; Nanomaterials

Special Issue Information

Dear Colleagues,

Polymer-protected metal nanoparticles,  nanoclay minerals, including silica and titanium dioxides,  proteins, enzymes, polyelectrolytes, semiconductors, dyes, surfactants, and drugs immobilized within the hydrogel and cryogel matrix, provide superior functionality to nanocomposite materials with potential applications in various fields, including catalysis, photocatalysis, biotechnology, biomedicine, nanomedicine, drug delivery, EOR, and environmental remediation. The nature of interaction between the components can have a covalent, ionic and donor–acceptor character and be stabilized by hydrogen bonds, hydrophobic interactions, entanglement of macromolecular chains producing interpenetrating and semi-interpenetrating polymer networks. Due to their composite structure and unique properties, such as improved mechanical, thermal, electrical, and optical characteristics, they have found a wide application in medicine, membrane technology, optical engineering, and catalysis. Hybrid nanostructures composed of organic, inorganic, and polymer materials considerably expand our fundamental representations on nanocomposites that are “smart”, fast-developing and emerging fields of advanced materials and technology. The aim of this Special Issue is to demonstrate the multidisciplinary aspect of the selected subject and to bring together a number of original papers and reviews covering (but not restricted to) the following topics:  

  1. Advanced strategy on designing of nanocomposites with participation of functional polymers and nanoparticles;
  2. Polymer-supported and gel-immobilized metal- and bimetallic nanoparticles in catalysis;
  3. Immobilization of nano- and microsized clay minerals within gel matrix and development of polymer-inorganic nanocomposite materials;
  4. Development of controlled delivery systems based on polymer-protected and gel-immobilized nanoparticles;
  5. Photocatalytic water-splitting nanocomposites fabricated from nanoparticles and semiconductors;
  6. Gel-immobilized anticancer drugs and metal nanoparticles in nanomedicine;
  7. Design of smart nano-objects for target applications in EOR (enhanced oil recovery), pharmacy, agriculture, and water purification.

Prof. Sarkyt Kudaibergenov
Prof. Gulzhian Dzhardimalieva
Guest Editors

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Keywords

  • linear and crosslinked amphiphilic polymers
  • polymer-–inorganic hybrid nanocomposites
  • immobilization
  • metal nanoparticles
  • nanoclays
  • nanocomposite materials
  • catalysis

Published Papers (6 papers)

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Research

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15 pages, 6274 KiB  
Article
Synthesis and Stabilization of Gold Nanoparticles Using Water-Soluble Synthetic and Natural Polymers
by Zhanara A. Nurakhmetova, Aiganym N. Azhkeyeva, Ivan A. Klassen and Gulnur S. Tatykhanova
Polymers 2020, 12(11), 2625; https://doi.org/10.3390/polym12112625 - 8 Nov 2020
Cited by 20 | Viewed by 3421
Abstract
Gold nanoparticles (AuNPs) were synthesized and stabilized using the one-pot method and growth seeding, through utilization of synthetic polymers, including poly(N-vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), and poly(vinylcaprolactame) (PVCL), as well as natural polysaccharides, including gellan, welan, pectin, and κ-carrageenan. The absorption [...] Read more.
Gold nanoparticles (AuNPs) were synthesized and stabilized using the one-pot method and growth seeding, through utilization of synthetic polymers, including poly(N-vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), and poly(vinylcaprolactame) (PVCL), as well as natural polysaccharides, including gellan, welan, pectin, and κ-carrageenan. The absorption spectra, average hydrodynamic size, ζ-potential, and morphology of the gold nanoparticles were evaluated based on various factors, such as polymer concentration, molecular mass of polymers, temperature, and storage time. The optimal polymer concentration for stabilization of AuNPs was found to be 4.0 wt % for PVP, 0.5 wt % for gellan, and 0.2 wt % for pectin, welan, and κ-carrageenan. The values of the ζ-potential of polymer-stabilized AuNPs show that their surfaces are negatively charged. Most of the AuNPs are polydisperse particles, though very monodisperse AuNPs were detected in the presence of a 0.5 wt % gellan solution. At a constant polymer concentration of PVP (4 wt %), the average size of the PVP–AuNPs decreased with the decrease of molecular weight, and in the following order: PVP 350 kDa (~25 nm) > PVP 40 kDa (~8 nm) > PVP 10 kDa (~4 nm). The combination of Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy revealed that the functional groups of polymers that are responsible for stabilization of AuNPs are lactam ring in PVP, carboxylic groups in gellan and welan, esterified carboxylic groups in pectin, and SO2 groups in κ-carrageenan. Viscometric and proton nuclear magnetic resonance (1H NMR) spectroscopic measurements showed that the temperature-dependent change in the size of AuNPs, and the gradual increase of the intensity of AuNPs at 550 nm in the presence of gellan, is due to the rigid and disordered conformation of gellan that affects the stabilization of AuNPs. The AuNPs synthesized in the presence of water-soluble polymers were stable over a period of 36 days. Preliminary results on the synthesis and characterization of gold nanorods stabilized by polymers are also presented. Full article
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14 pages, 1971 KiB  
Article
Influence of Buffers, Ionic Strength, and pH on the Volume Phase Transition Behavior of Acrylamide-Based Nanogels
by Harriet Louise Judah, Pengfei Liu, Ali Zarbakhsh and Marina Resmini
Polymers 2020, 12(11), 2590; https://doi.org/10.3390/polym12112590 - 4 Nov 2020
Cited by 13 | Viewed by 4575
Abstract
The use of covalently crosslinked nanogels for applications in biology and medicine is dependent on their properties and characteristics, which often change because of the biological media involved. Understanding the role of salts, ionic strength and pH in altering specific properties is key [...] Read more.
The use of covalently crosslinked nanogels for applications in biology and medicine is dependent on their properties and characteristics, which often change because of the biological media involved. Understanding the role of salts, ionic strength and pH in altering specific properties is key to progress in this area. We studied the effect of both chemical structure and media environment on the thermoresponsive behavior of nanogels. A small library of methylenebisacrylamide (MBA) crosslinked nanogels were prepared using N-isopropylacrylamide (NIPAM) or N-n-propylacrylamide (NPAM), in combination with functional monomers N-hydroxyethylacrylamide (HEAM) and N-acryloyl-l-proline (APrOH). The thermoresponsive properties of nanogels were evaluated in phosphate buffer, tris-acetate buffer and Ringer HEPES, with varying concentrations and ionic strengths. The presence of ions facilitates the phase separation of nanogels, and this “salting-out” effect strongly depends on the electrolyte concentration as well as the specificity of individual anions, e.g., their positions in the Hofmeister series. A subtle change in the chemical structure of the side chain of the monomer from NIPAM to NPAM leads to a reduction of the volume phase transition temperature (VPTT) value by ~10 °C. The addition of hydrophilic comonomers such as HEAM, on the other hand, causes a ~20 °C shift in VPTT to higher values. The data highlight the significant role played by the chemical structure of the monomers used, with hydrophobicity and rigidity closely interlinked in determining thermoresponsive behavior. Furthermore, the volume phase transition temperature (VPTT) of nanogels copolymerized with ionizable APrOH comonomer can be tailored by changes in the pH of buffer solutions. This temperature-controlled phase transition is driven by intricate interplay involving the entropy of mixing, electrostatic interactions, conformational transitions, and structural rigidity. These results highlight the importance of understanding the physiochemical properties and behavior of covalently crosslinked nanogels in a biological environment prior to their applications in life-science, such as temperature/pH-triggered drug delivery systems. Full article
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22 pages, 7082 KiB  
Article
Synthesis of Copper(II) Trimesinate Coordination Polymer and Its Use as a Sorbent for Organic Dyes and a Precursor for Nanostructured Material
by Gulzhian I. Dzhardimalieva, Rose K. Baimuratova, Evgeniya I. Knerelman, Galina I. Davydova, Sarkyt E. Kudaibergenov, Oxana V. Kharissova, Vladimir A. Zhinzhilo and Igor E. Uflyand
Polymers 2020, 12(5), 1024; https://doi.org/10.3390/polym12051024 - 1 May 2020
Cited by 45 | Viewed by 4110
Abstract
Several important synthesis pathways for metal-organic frameworks (MOFs) were applied to determine how the synthesis methods and conditions affect the structure and adsorption capacity of the resulting samples. In the present work, three different synthesis routes were used to obtain copper trimesinate coordination [...] Read more.
Several important synthesis pathways for metal-organic frameworks (MOFs) were applied to determine how the synthesis methods and conditions affect the structure and adsorption capacity of the resulting samples. In the present work, three different synthesis routes were used to obtain copper trimesinate coordination polymer: Slow evaporation (A), solvothermal synthesis using a polyethylene glycol (PEG-1500) modulator (B), and green synthesis in water (C). This MOF was characterized by elemental analysis, infrared spectrometry, X-ray diffraction, scanning electron microscopy, thermogravimetry and volumetric nitrogen adsorption/desorption. The samples have permanent porosity and a microporous structure with a large surface area corresponding to the adsorption type I. The obtained MOF was tested as a sorbent to remove organic dyes methylene blue (МВ), Congo red (CR) and methyl violet (MV) as examples. Dye adsorption followed pseudo-first-order kinetics. The equilibrium data were fitted to the Langmuir and Freundlich isotherm models, and the isotherm constants were determined. Thermodynamic parameters, such as changes in the free energy of adsorption (∆G0), enthalpy (∆H0), and entropy (∆S0), were calculated. Thermolysis of copper trimesinate leads to the formation of carbon materials Cu@C with a high purity. Full article
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10 pages, 5283 KiB  
Article
Electrorheological Behavior of Suspensions of Polyimide-Based on the Sodium Salt of 2,5-Diaminobenzenesulfonic Acid
by Nikolay Semenov, Alexander Danilin, Yulia Karnet and Elena Kelbysheva
Polymers 2020, 12(5), 1015; https://doi.org/10.3390/polym12051015 - 29 Apr 2020
Cited by 5 | Viewed by 2795
Abstract
Electrorheological suspensions (ERS) of polyimide particles with organoelement fragments from the sodium salt of 2,5-diaminobenzene sulfonic acid were obtained for the first time. Their rheological and electrorheological characteristics, their dependence on the parameters of deformation, and the intensity of the external electric field [...] Read more.
Electrorheological suspensions (ERS) of polyimide particles with organoelement fragments from the sodium salt of 2,5-diaminobenzene sulfonic acid were obtained for the first time. Their rheological and electrorheological characteristics, their dependence on the parameters of deformation, and the intensity of the external electric field were studied. It was found that the ERS of PI-Na polyimide particles have a significant electrorheological response. Solid-polyimide materials were previously studied using a scanning electron microscope. The effect of the polyimide concentration on the properties of the solution was studied by spectrophotometry. It was shown that polyimide suspension is a result of increasing intensity as the electric field changes the flow type from Newtonian to pseudoplastic due to polarization of the particles and formation of the chain structures along the power lines of the electric field. The influence of temperature on the change of rheological and electrorheological properties of a polyimide ERS in constant electric fields was investigated. Full article
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Review

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52 pages, 85506 KiB  
Review
Basic Approaches to the Design of Intrinsic Self-Healing Polymers for Triboelectric Nanogenerators
by Gulzhian I. Dzhardimalieva, Bal C. Yadav, Sarkyt E. Kudaibergenov and Igor E. Uflyand
Polymers 2020, 12(11), 2594; https://doi.org/10.3390/polym12112594 - 4 Nov 2020
Cited by 18 | Viewed by 6085
Abstract
Triboelectric nanogenerators (TENGs) as a revolutionary system for harvesting mechanical energy have demonstrated high vitality and great advantage, which open up great prospects for their application in various areas of the society of the future. The past few years have seen exponential growth [...] Read more.
Triboelectric nanogenerators (TENGs) as a revolutionary system for harvesting mechanical energy have demonstrated high vitality and great advantage, which open up great prospects for their application in various areas of the society of the future. The past few years have seen exponential growth in many new classes of self-healing polymers (SHPs) for TENGs. This review presents and evaluates the SHP range for TENGs, and also attempts to assess the impact of modern polymer chemistry on the development of advanced materials for TENGs. Among the most widely used SHPs for TENGs, the analysis of non-covalent (hydrogen bond, metal–ligand bond), covalent (imine bond, disulfide bond, borate bond) and multiple bond-based SHPs in TENGs has been performed. Particular attention is paid to the use of SHPs with shape memory as components of TENGs. Finally, the problems and prospects for the development of SHPs for TENGs are outlined. Full article
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19 pages, 11143 KiB  
Review
Flow-Through Catalytic Reactors Based on Metal Nanoparticles Immobilized within Porous Polymeric Gels and Surfaces/Hollows of Polymeric Membranes
by Sarkyt E. Kudaibergenov and Gulzhian I. Dzhardimalieva
Polymers 2020, 12(3), 572; https://doi.org/10.3390/polym12030572 - 4 Mar 2020
Cited by 17 | Viewed by 4108
Abstract
State-of-the-art of flow-through catalytic reactors based on metal nanoparticles immobilized within the pores of nano-, micro- and macrosized polymeric gels and in the surface or hollow of polymeric membranes is discussed in this mini-review. The unique advantages of continuous flow-through nanocatalysis over the [...] Read more.
State-of-the-art of flow-through catalytic reactors based on metal nanoparticles immobilized within the pores of nano-, micro- and macrosized polymeric gels and in the surface or hollow of polymeric membranes is discussed in this mini-review. The unique advantages of continuous flow-through nanocatalysis over the traditional batch-type analog are high activity, selectivity, productivity, recyclability, continuous operation, and purity of reaction products etc. The methods of fabrication of polymeric carriers and immobilization technique for metal nanoparticles on the surface of porous or hollow structures are considered. Several catalytic model reactions comprising of hydrolysis, decomposition, hydrogenation, oxidation, Suzuki coupling and enzymatic reactions in the flow system are exemplified. Realization of “on-off” switching mechanism for regulation of the rate of catalytic process through controlling the mass transfers of reactants in liquid media with the help of stimuli-responsive polymers is demonstrated. Comparative analysis of the efficiency of different flow-through catalytic reactors for various reactions is also surveyed. Full article
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