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Keywords = polyethylenimine coating

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32 pages, 5531 KiB  
Review
Polyethylenimine Carriers for Drug and Gene Delivery
by Ahmed Ismail and Shih-Feng Chou
Polymers 2025, 17(15), 2150; https://doi.org/10.3390/polym17152150 - 6 Aug 2025
Abstract
Polyethylenimine (PEI) is a cationic polymer with a high density of amine groups suitable for strong electrostatic interactions with biological molecules to preserve their bioactivities during encapsulation and after delivery for biomedical applications. This review provides a comprehensive overview of PEI as a [...] Read more.
Polyethylenimine (PEI) is a cationic polymer with a high density of amine groups suitable for strong electrostatic interactions with biological molecules to preserve their bioactivities during encapsulation and after delivery for biomedical applications. This review provides a comprehensive overview of PEI as a drug and gene carrier, describing its polymerization methods in both linear and branched forms while highlighting the processing methods to manufacture PEIs into drug carriers, such as nanoparticles, coatings, nanofibers, hydrogels, and films. These various PEI carriers enable applications in non-viral gene and small molecule drug deliveries. The structure–property relationships of PEI carriers are discussed with emphasis on how molecular weights, branching degrees, and surface modifications of PEI carriers impact biocompatibility, transfection efficiency, and cellular interactions. While PEI offers remarkable potential for drug and gene delivery, its clinical translation remains limited by challenges, including cytotoxicity, non-degradability, and serum instability. Our aim is to provide an understanding of PEI and the structure–property relationships of its carrier forms to inform future research directions that may enable safe and effective clinical use of PEI carriers for drug and gene delivery. Full article
(This article belongs to the Special Issue Biocompatible and Biodegradable Polymer Materials)
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13 pages, 11463 KiB  
Article
A Facile One-Pot Preparation and Catalytic Application of Tunable Silica-Coated Aqueous Gold Nanoparticles
by Elijah Cook, Kelly Moran, Qiaxian R. Johnson, Asmaa Lakhal and Bhanu P. S. Chauhan
Molecules 2025, 30(6), 1355; https://doi.org/10.3390/molecules30061355 - 18 Mar 2025
Viewed by 489
Abstract
It is known that designer polymers can be used for the synthesis and stabilization of metallic nanoparticle systems, providing new, tailorable properties. In this work, we demonstrate the trifold utility of a designer polymer, trimethoxysilylpropyl-(polyethylenimine) (TMSP-PEI), providing reduction, stabilization, and protection in a [...] Read more.
It is known that designer polymers can be used for the synthesis and stabilization of metallic nanoparticle systems, providing new, tailorable properties. In this work, we demonstrate the trifold utility of a designer polymer, trimethoxysilylpropyl-(polyethylenimine) (TMSP-PEI), providing reduction, stabilization, and protection in a single step. Our facile and unique synthesis affords gold nanoparticles with varying sizes and morphologies in a range of solvents without the need for additional reducing agents. The use of this substituted polymer was manipulated in terms of the metal-to-ligand ratio to induce changes in the nanoparticle nucleation and growth. Upon further experimental analysis, it was discovered that adjustments to not only the metal–ligand ratio but also the solvent environment produced nanoparticles with different shape and size distributions. In addition, the synthesized gold nanoparticles were investigated for their catalytic ability to reduce Eosin Y in the presence of sodium borohydride without degradation. Full article
(This article belongs to the Special Issue 30th Anniversary of Molecules—Recent Advances in Applied Chemistry)
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20 pages, 5619 KiB  
Article
Alginate Hydrogel Beads with a Leakproof Gold Shell for Ultrasound-Triggered Release
by Marcus Flowers, Alex Paulsen, Claire R. W. Kaiser, Adam B. Tuma, Hubert H. Lim, Brenda M. Ogle and Chun Wang
Pharmaceutics 2025, 17(1), 133; https://doi.org/10.3390/pharmaceutics17010133 - 19 Jan 2025
Viewed by 1621
Abstract
Background/Objectives: Focused ultrasound has advantages as an external stimulus for drug delivery as it is non-invasive, has high precision and can penetrate deep into tissues. Here, we report a gold-plated alginate (ALG) hydrogel system that retains highly water-soluble small-molecule fluorescein for sharp off/on [...] Read more.
Background/Objectives: Focused ultrasound has advantages as an external stimulus for drug delivery as it is non-invasive, has high precision and can penetrate deep into tissues. Here, we report a gold-plated alginate (ALG) hydrogel system that retains highly water-soluble small-molecule fluorescein for sharp off/on release after ultrasound exposure. Methods: The ALG is crosslinked into beads with calcium chloride and layered with a polycation to adjust the surface charge for the adsorption of catalytic platinum nanoparticles (Pt NPs). The coated bead is subject to electroless plating, forming a gold shell. Ultrasound is applied to the gold-plated ALG beads and the release of fluorescein with or without ultrasound stimulation is quantified. Results: Polyethylenimine (PEI), not poly-L-lysine (PLL), is able to facilitate Pt NP adsorption. Gold shell thickness is proportional to the duration of electroless plating and can be controlled. Gold-plated ALG beads are impermeable to the fluorescein cargo and have nearly zero leakage. Exposure to focused ultrasound initiated the release of fluorescein with full release achieved after 72 h. Conclusions: The gold-plated ALG hydrogel is a new material platform that can retain highly water-soluble molecules with a sharp off/on release initiated by focused ultrasound. Full article
(This article belongs to the Section Drug Delivery and Controlled Release)
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23 pages, 12546 KiB  
Article
Effects of Beech Wood Surface Treatment with Polyethylenimine Solution Prior to Finishing with Water-Based Coating
by Tanja Palija, Milica Rančić, Daniela Djikanović, Ksenija Radotić, Marko Petrič, Matjaž Pavlič and Milan Jaić
Polymers 2025, 17(1), 77; https://doi.org/10.3390/polym17010077 - 30 Dec 2024
Viewed by 965
Abstract
The surfaces of beech wood samples were treated with polyethylenimine (PEI) solutions at three different concentrations—0.5%, 1% and 2%—and two molecular weights—low molecular weight (LMW) and high molecular weight (HMW). The effects of PEI surface treatment of wood were characterized by FT-IR spectroscopy, [...] Read more.
The surfaces of beech wood samples were treated with polyethylenimine (PEI) solutions at three different concentrations—0.5%, 1% and 2%—and two molecular weights—low molecular weight (LMW) and high molecular weight (HMW). The effects of PEI surface treatment of wood were characterized by FT-IR spectroscopy, the penetration depth of PEI (EPI fluorescence spectroscopy), the bonding position of PEI (by SEM), the wetting and surface energy, and the water uptake. After PEI treatment, the samples were coated with a water-based transparent acrylic coating (WTAC). The dry film thickness, the penetration depth of the coating, the adhesion strength and the surface roughness of the coated wood surface were evaluated. EPI fluorescence and SEM micrographs showed that PEI HMW chains were deposited on the surface, in contrast to PEI LMW, which penetrates deeper into layers of the wood cells. Treatment with a 1% PEI HMW solution resulted in a 72% reduction in water uptake of the wood (compared to untreated samples after 5 min of applying water droplets to the surface) and a 23.2% reduction in surface energy (compared to untreated samples) while maintaining the adhesion strength of the applied WTAC. The lower water uptake of the treated wood samples reduced the roughness of the coated surface, which is particularly important when the wood surface is finished with water-based coatings. Full article
(This article belongs to the Special Issue Advances in Polyelectrolytes and Polyelectrolyte Complexes)
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20 pages, 3445 KiB  
Article
Antibiofilm Effects of Modifying Polyvinylidene Fluoride Membranes with Polyethylenimine, Poly(acrylic acid) and Graphene Oxide
by Mario Castillo-Ruiz, Constanza Negrete, Juan Pablo Espinoza, Iván Martínez, Leslie K. Daille, Christopher González and Bárbara Rodríguez
Polymers 2024, 16(23), 3418; https://doi.org/10.3390/polym16233418 - 5 Dec 2024
Cited by 1 | Viewed by 1292
Abstract
Biofouling in membrane filtration systems poses significant operational challenges, leading to decreased permeate flux. The aim of this work was to study the anti-biofilm properties of new nanofiltration membranes produced via layer-by-layer, LBL, assembly by coating a polyvinylidene fluoride (PVDF) support with a [...] Read more.
Biofouling in membrane filtration systems poses significant operational challenges, leading to decreased permeate flux. The aim of this work was to study the anti-biofilm properties of new nanofiltration membranes produced via layer-by-layer, LBL, assembly by coating a polyvinylidene fluoride (PVDF) support with a polyethylenimine (PEI) and poly(acrylic acid)/graphene oxide (PAA-GO) mixture. The membranes were characterized according to contact angle, scanning electron microscopy (SEM), atomic force microscopy and their Z-potential. Biofilm quantification and characterization were carried out using crystal violet staining and SEM, while bacterial viability was assessed by using colony-forming units. The membrane with three bilayers ((PAA-PEI)3/PVDF) showed a roughness of 77.78 nm. The incorporation of GO ((GO/PAA-PEI)3/PVDF) produced a membrane with a smoother surface (roughness of 26.92 nm) and showed salt rejections of 16% and 68% for NaCl and Na2SO4, respectively. A significant reduction, ranging from 82.37 to 77.30%, in biofilm formation produced by S. aureus and E. coli were observed on modified membranes. Additionally, the bacterial viability on the modified membranes was markedly reduced (67.42–99.98%). Our results show that the modified membranes exhibited both antibiofilm and antimicrobial capacities, suggesting that these properties mainly depend on the properties of the modifying agents, as the initial adherence on the membrane surface was not totally suppressed, but the proliferation and formation of EPSs were prevented. Full article
(This article belongs to the Special Issue Advanced Polymer Materials for Water and Wastewater Treatment)
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13 pages, 6503 KiB  
Article
Optical pH Sensor Based on a Long-Period Fiber Grating Coated with a Polymeric Layer-by-Layer Electrostatic Self-Assembled Nanofilm
by José M. Pereira, João P. Mendes, Bernardo Dias, José M. M. M. de Almeida and Luís C. C. Coelho
Sensors 2024, 24(5), 1662; https://doi.org/10.3390/s24051662 - 4 Mar 2024
Cited by 11 | Viewed by 2237
Abstract
An optical fiber pH sensor based on a long-period fiber grating (LPFG) is reported. Two oppositely charged polymers, polyethylenimine (PEI) and polyacrylic acid (PAA), were alternately deposited on the sensing structure through a layer-by-layer (LbL) electrostatic self-assembly technique. Since the polymers are pH [...] Read more.
An optical fiber pH sensor based on a long-period fiber grating (LPFG) is reported. Two oppositely charged polymers, polyethylenimine (PEI) and polyacrylic acid (PAA), were alternately deposited on the sensing structure through a layer-by-layer (LbL) electrostatic self-assembly technique. Since the polymers are pH sensitive, their refractive index (RI) varies when the pH of the solution changes due to swelling/deswelling phenomena. The fabricated multilayer coating retained a similar property, enabling its use in pH-sensing applications. The pH of the PAA dipping solution was tuned so that a coated LPFG achieved a pH sensitivity of (6.3 ± 0.2) nm/pH in the 5.92–9.23 pH range. Only two bilayers of PEI/PAA were used as an overlay, which reduces the fabrication time and increases the reproducibility of the sensor, and its reversibility and repeatability were demonstrated by tracking the resonance band position throughout multiple cycles between different pH solutions. With simulation work and experimental results from a low-finesse Fabry–Perot (FP) cavity on a fiber tip, the coating properties were estimated. When saturated at low pH, it has a thickness of 200 nm and 1.53 ± 0.01 RI, expanding up to 310 nm with a 1.35 ± 0.01 RI at higher pH values, mostly due to the structural changes in the PAA. Full article
(This article belongs to the Special Issue Spectroscopic Chemical Sensing)
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16 pages, 6765 KiB  
Article
Ultrasensitive Detection of PSA Using Antibodies in Crowding Polyelectrolyte Multilayers on a Silicon Nanowire Field-Effect Transistor
by Galina V. Presnova, Denis E. Presnov, Mariya M. Ulyashova, Ilia I. Tsiniaikin, Artem S. Trifonov, Ekaterina V. Skorb, Vladimir A. Krupenin, Oleg V. Snigirev and Maya Yu. Rubtsova
Polymers 2024, 16(3), 332; https://doi.org/10.3390/polym16030332 - 25 Jan 2024
Cited by 3 | Viewed by 2099
Abstract
Immunosensors based on field-effect transistors with nanowire channels (NWFETs) provide fast and real-time detection of a variety of biomarkers without the need for additional labels. The key feature of the developed immunosensor is the coating of silicon NWs with multilayers of polyelectrolytes (polyethylenimine [...] Read more.
Immunosensors based on field-effect transistors with nanowire channels (NWFETs) provide fast and real-time detection of a variety of biomarkers without the need for additional labels. The key feature of the developed immunosensor is the coating of silicon NWs with multilayers of polyelectrolytes (polyethylenimine (PEI) and polystyrene sulfonate (PSS)). By causing a macromolecular crowding effect, it ensures the “soft fixation” of the antibodies into the 3-D matrix of the oppositely charged layers. We investigated the interaction of prostate-specific antigen (PSA), a biomarker of prostate cancer, and antibodies adsorbed in the PEI and PSS matrix. In order to visualize the formation of immune complexes between polyelectrolyte layers using SEM and AFM techniques, we employed a second clone of antibodies labeled with gold nanoparticles. PSA was able to penetrate the matrix and concentrate close to the surface layer, which is crucial for its detection on the nanowires. Additionally, this provides the optimal orientation of the antibodies’ active centers for interacting with the antigen and improves their mobility. NWFETs were fabricated from SOI material using high-resolution e-beam lithography, thin film vacuum deposition, and reactive-ion etching processes. The immunosensor was characterized by a high sensitivity to pH (71 mV/pH) and an ultra-low limit of detection (LOD) of 0.04 fg/mL for PSA. The response of the immunosensor takes less than a minute, and the measurement is carried out in real time. This approach seems promising for further investigation of its applicability for early screening of prostate cancer and POC systems. Full article
(This article belongs to the Special Issue Advances in Polyelectrolytes and Polyelectrolyte Complexes)
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15 pages, 4477 KiB  
Article
Single-Step Surface Hydrophilization on Ultrafiltration Membrane with Enhanced Antifouling Property for Pome Wastewater Treatment
by Norfadhilatuladha Abdullah, Norhaniza Yusof, Mohammed Abdullah Dahim, Muhammad Faris Hamid, Lau Woei Jye, Juhana Jaafar, Farhana Aziz, Wan Norhayati Wan Salleh, Ahmad Fauzi Ismail and Nurasyikin Misdan
Separations 2023, 10(3), 188; https://doi.org/10.3390/separations10030188 - 9 Mar 2023
Cited by 2 | Viewed by 2010
Abstract
High organic materials in palm oil mill effluent (POME) can result in serious water pollution. To date, biological treatment has been used to reduce the environmental risks of these effluents prior of their discharge into water streams. However, the effluents’ dark brownish colour [...] Read more.
High organic materials in palm oil mill effluent (POME) can result in serious water pollution. To date, biological treatment has been used to reduce the environmental risks of these effluents prior of their discharge into water streams. However, the effluents’ dark brownish colour remains as a significant issue that must be addressed, as it affects the overall quality of water. Although membrane technology has been frequently used to address these difficulties, membrane fouling has become a serious limitation in POME treatment. On the other hand, zwitterions with balanced charge groups have received growing interest in the fabrication of antifouling membranes due to their hydrated nature. The development of a simple and efficient covalent bonding technique to improve the stability of zwitterions on membrane surfaces remains a challenge. By grafting and co-depositing polyethylenimine (PEI)-based zwitterion (Z-PEI) with super hydrophilic polydopamine (PDA) on the surface of a commercial polysulfone (PSf) ultrafiltration membrane at ambient temperature, a new zwitterionic surface with a neutral surface charge was created (PDA/Z-PEI). This study aims to investigate the effect of different loading ratios of PDA/Z-PEI (1:1, 1:2, and 1:3) and evaluate their performance on treating brownish coloured anaerobically treated POME (AT-POME). SEM and FTIR analysis showed the successful incorporation of the PDA/Z-PEI membrane while the zwitterionic feature is indicated by zeta potential analysis. Water flux analysis demonstrated that a lower water flux was achieved for M-ZPEI membranes as compared to the PSf and PSf-MDPA membranes, attributed by the tight skin layer of PDA-ZPEI. In the development of a tight hydration layer on the membrane surface by zwitterions, zwitterionic membranes demonstrated excellent antifouling capabilities, particularly PDA/Z-PEI with a loading ratio of (1:2) with a flux recovery ratio of around 84% and colour rejection of 81.75%. Overall, this research contributes to the development of a unique coating with improved stability and antifouling properties by altering the membrane surface in a simple and reliable manner. Full article
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14 pages, 4503 KiB  
Article
Selective Detection of Escherichia coli K12 and Staphylococcus aureus in Mixed Bacterial Communities Using a Single-Walled Carbon Nanotube (SWCNT)-Functionalized Electrochemical Immunosensor with Dielectrophoretic Concentration
by Inae Lee, Heejin So, Jungyoon Kim, Joong-Hyuck Auh, Marisa M. Wall, Yong Li, Kacie Ho and Soojin Jun
Nanomaterials 2023, 13(6), 985; https://doi.org/10.3390/nano13060985 - 8 Mar 2023
Cited by 7 | Viewed by 2817
Abstract
An electrochemical immunosensor has been developed for the rapid detection and identification of potentially harmful bacteria in food and environmental samples. This study aimed to fabricate a microwire-based electrochemical immunosensor (MEI sensor) for selective detection of Escherichia coli and Staphylococcus aureus in microbial [...] Read more.
An electrochemical immunosensor has been developed for the rapid detection and identification of potentially harmful bacteria in food and environmental samples. This study aimed to fabricate a microwire-based electrochemical immunosensor (MEI sensor) for selective detection of Escherichia coli and Staphylococcus aureus in microbial cocktail samples using dielectrophoresis (DEP)-based cell concentration. A gold-coated tungsten microwire was functionalized by coating polyethylenimine, single-walled carbon nanotube (SWCNT) suspension, streptavidin, biotinylated antibodies, and then bovine serum albumin (BSA) solutions. Double-layered SWCNTs and 5% BSA solution were found to be optimized for enhanced signal enhancement and nonspecific binding barrier. The selective capture of E. coli K12 or S. aureus cells was achieved when the electric field in the bacterial sample solution was generated at a frequency of 3 MHz and 20 Vpp. A linear trend of the change in the electron transfer resistance was observed as E. coli concentrations increased from 5.32 × 102 to 1.30 × 108 CFU/mL (R2 = 0.976). The S. aureus MEI sensor fabricated with the anti-S. aureus antibodies also showed an increase in resistance with concentrations of S. aureus (8.90 × 102–3.45 × 107 CFU/mL) with a correlation of R2 = 0.983. Salmonella typhimurium and Listeria monocytogenes were used to evaluate the specificity of the MEI sensors. The functionalization process developed for the MEI sensor is expected to contribute to the sensitive and selective detection of other harmful microorganisms in food and environmental industries. Full article
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13 pages, 2975 KiB  
Article
Delivery of dCas9 Activator System Using Magnetic Nanoparticles Technology as a Vector Delivery Method for Human Skin Fibroblast
by Mahdi Mohammadi Ghanbarlou, Shahriyar Abdoli, Hamed Omid, Leila Qazizadeh, Hadi Bamehr, Mozhgan Raigani, Hosein Shahsavarani, Morteza Karimipour and Mohammad Ali Shokrgozar
Magnetochemistry 2023, 9(3), 71; https://doi.org/10.3390/magnetochemistry9030071 - 28 Feb 2023
Cited by 7 | Viewed by 2576
Abstract
The overexpression of stem cell-related genes such as octamer-binding transcription factor 4 (OCT4) and (sex determining region Y)-box 2 (SOX2) has been indicated to play several critical roles in stem cell self-renewal; moreover, the elevation of the self-renewal of cancer cells with stem [...] Read more.
The overexpression of stem cell-related genes such as octamer-binding transcription factor 4 (OCT4) and (sex determining region Y)-box 2 (SOX2) has been indicated to play several critical roles in stem cell self-renewal; moreover, the elevation of the self-renewal of cancer cells with stem cell-like properties has been suggested. The clustered and regularly interspaced short palindromic repeats-associated protein 9 (CRISPR/Cas9) protein fused to transactivation domains can be used to activate gene expression in human cells. CRISPR-mediated activation (CRISPRa) systems represent an effective genome editing tool for highly specific gene activation in which a nuclease-deficient Cas9 (dCas9) is utilized to target a transcriptional activator to the gene’s regulatory element, such as a promoter and enhancer. The main drawback of typical delivery methods for CRISPR/Cas9 components is their low transfection efficiency or toxic effects on cells; thus, we generated superparamagnetic iron oxide nanoparticles (SPIONs) coated with polyethylenimine (PEI) to improve the delivery of CRISPR/Cas9 constructs into human foreskin fibroblast cells. The delivery system with magnetic PEI-coated nanoparticles complex was applied to constitute plasmid DNA lipoplexes. CRISPRa systems were used to overexpress the endogenous OCT4 and SOX2 in fibroblast cells. The quantitative polymerase chain reaction (QPCR) assessment exhibited a three-times higher expression of OCT4 and SOX2 transfected by CRISPRa using MNPs. Moreover, no additional cytotoxicity was observed with the application of magnetic nanoparticles (MNPs) compared to lipofectamine. Our results demonstrate that MNPs enable the effective delivery of the CRISPR/Cas9 construct into human foreskin fibroblasts with low cell toxicity and a consequential overexpression of endogenous OCT4 and SOX2. Full article
(This article belongs to the Special Issue Advances in Magnetic Nanocarrier for Biomedical Applications)
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26 pages, 9617 KiB  
Article
Study on Doxorubicin Loading on Differently Functionalized Iron Oxide Nanoparticles: Implications for Controlled Drug-Delivery Application
by Vladislav R. Khabibullin, Margarita R. Chetyrkina, Sergei I. Obydennyy, Sergey V. Maksimov, Gennady V. Stepanov and Sergei N. Shtykov
Int. J. Mol. Sci. 2023, 24(5), 4480; https://doi.org/10.3390/ijms24054480 - 24 Feb 2023
Cited by 25 | Viewed by 3733
Abstract
Nanoplatforms applied for the loading of anticancer drugs is a cutting-edge approach for drug delivery to tumors and reduction of toxic effects on healthy cells. In this study, we describe the synthesis and compare the sorption properties of four types of potential doxorubicin-carriers, [...] Read more.
Nanoplatforms applied for the loading of anticancer drugs is a cutting-edge approach for drug delivery to tumors and reduction of toxic effects on healthy cells. In this study, we describe the synthesis and compare the sorption properties of four types of potential doxorubicin-carriers, in which iron oxide nanoparticles (IONs) are functionalized with cationic (polyethylenimine, PEI), anionic (polystyrenesulfonate, PSS), and nonionic (dextran) polymers, as well as with porous carbon. The IONs are thoroughly characterized by X-ray diffraction, IR spectroscopy, high resolution TEM (HRTEM), SEM, magnetic susceptibility, and the zeta-potential measurements in the pH range of 3–10. The degree of doxorubicin loading at pH 7.4, as well as the degree of desorption at pH 5.0, distinctive to cancerous tumor environment, are measured. Particles modified with PEI were shown to exhibit the highest loading capacity, while the greatest release at pH 5 (up to 30%) occurs from the surface of magnetite decorated with PSS. Such a slow release of the drug would imply a prolonged tumor-inhibiting action on the affected tissue or organ. Assessment of the toxicity (using Neuro2A cell line) for PEI- and PSS-modified IONs showed no negative effect. In conclusion, the preliminary evaluation of the effects of IONs coated with PSS and PEI on the rate of blood clotting was carried out. The results obtained can be taken into account when developing new drug delivery platforms. Full article
(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 3.0)
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17 pages, 1835 KiB  
Article
Short-Term Stability of Electrochemical Properties of Layer-by-Layer Coated Heterogeneous Ion Exchange Membranes
by Veronika Sarapulova, Ekaterina Nevakshenova, Kseniia Tsygurina, Valentina Ruleva, Anna Kirichenko and Ksenia Kirichenko
Membranes 2023, 13(1), 45; https://doi.org/10.3390/membranes13010045 - 29 Dec 2022
Cited by 1 | Viewed by 1798
Abstract
Layer-by-layer adsorption allows the creation of versatile functional coatings for ion exchange membranes, but the stability of the coating and resulting properties of modified membranes in their operation is a frequently asked question. This paper examines the changes in voltammetric curves of layer-by-layer [...] Read more.
Layer-by-layer adsorption allows the creation of versatile functional coatings for ion exchange membranes, but the stability of the coating and resulting properties of modified membranes in their operation is a frequently asked question. This paper examines the changes in voltammetric curves of layer-by-layer coated cation exchange membranes and pH-metry of desalination chamber with a studied membrane and an auxiliary anion exchange membrane after short-term tests, including over-limiting current modes. The practical operation of the membranes did not affect the voltammetric curves, but enhanced the generation of H+ and OH ions in a system with polyethylenimine modified membrane in Ca2+ containing solution. It is shown that a distinction between the voltammetric curves of the membranes modified and the different polyamines persists during the operation and that, in the case of polyethylenimine, there is an additional zone of growth of potential drop in voltammetric curves and stronger generation of H+ and OH ions as indicated by pH-metry. Full article
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16 pages, 4104 KiB  
Article
Stability of Properties of Layer-by-Layer Coated Membranes under Passage of Electric Current
by Ksenia Solonchenko, Olesya Rybalkina, Daria Chuprynina, Evgeniy Kirichenko, Ksenia Kirichenko and Victor Nikonenko
Polymers 2022, 14(23), 5172; https://doi.org/10.3390/polym14235172 - 28 Nov 2022
Cited by 5 | Viewed by 1886
Abstract
Electrodialysis with layer-by-layer coated membranes is a promising method for the separation of monovalent and polyvalent ions. Since the separation selectivity is significantly reduced in the presence of defects in the multilayer system, the stability of the modifiers becomes an important issue. This [...] Read more.
Electrodialysis with layer-by-layer coated membranes is a promising method for the separation of monovalent and polyvalent ions. Since the separation selectivity is significantly reduced in the presence of defects in the multilayer system, the stability of the modifiers becomes an important issue. This article reports the i-V curves of layer-by-layer coated membranes based on the heterogeneous MK-40 membrane before and after 50 h long electrodialysis of a solution containing sodium and calcium ions at an underlimiting current density, and the values of concentrations of cations in the desalination chamber during electrodialysis. It is shown that the transport of bivalent ions through the modified membranes is reduced throughout the electrodialysis by about 50%, but the operation results in decreased resistance of the membrane modified with polyethylenimine, which may suggest damage to the modifying layer. Even after electrodialysis, the modified membrane demonstrated experimental limiting current densities higher than that of the substrate, and in case of the membrane modified with polyallylamine, the limiting current density 10% higher than that of the substrate membrane. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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23 pages, 1227 KiB  
Article
Tuning Immobilized Enzyme Features by Combining Solid-Phase Physicochemical Modification and Mineralization
by José R. Guimarães, Diego Carballares, Javier Rocha-Martin, Paulo W. Tardioli and Roberto Fernandez-Lafuente
Int. J. Mol. Sci. 2022, 23(21), 12808; https://doi.org/10.3390/ijms232112808 - 24 Oct 2022
Cited by 7 | Viewed by 2246
Abstract
Lipase B from Candida antarctica (CALB) and lipase from Thermomyces lanuginosus (TLL) were immobilized on octyl agarose. Then, the biocatalysts were chemically modified using glutaraldehyde, trinitrobenzenesulfonic acid or ethylenediamine and carbodiimide, or physically coated with ionic polymers, such as polyethylenimine (PEI) and dextran [...] Read more.
Lipase B from Candida antarctica (CALB) and lipase from Thermomyces lanuginosus (TLL) were immobilized on octyl agarose. Then, the biocatalysts were chemically modified using glutaraldehyde, trinitrobenzenesulfonic acid or ethylenediamine and carbodiimide, or physically coated with ionic polymers, such as polyethylenimine (PEI) and dextran sulfate. These produced alterations of the enzyme activities have, in most cases, negative effects with some substrates and positive with other ones (e.g., amination of immobilized TLL increases the activity versus p-nitro phenyl butyrate (p-NPB), reduces the activity with R-methyl mandate by half and maintains the activity with S-isomer). The modification with PEI increased the biocatalyst activity 8-fold versus R-methyl mandelate. Enzyme stability was also modified, usually showing an improvement (e.g., the modification of immobilized TLL with PEI or glutaraldehyde enabled to maintain more than 70% of the initial activity, while the unmodified enzyme maintained less than 50%). The immobilized enzymes were also mineralized by using phosphate metals (Zn2+, Co2+, Cu2+, Ni2+ or Mg2+), and this affected also the enzyme activity, specificity (e.g., immobilized TLL increased its activity after zinc mineralization versus triacetin, while decreased its activity versus all the other assayed substrates) and stability (e.g., the same modification increase the residual stability from almost 0 to more than 60%). Depending on the enzyme, a metal could be positively, neutrally or negatively affected for a specific feature. Finally, we analyzed if the chemical modification could, somehow, tune the effects of the mineralization. Effectively, the same mineralization could have very different effects on the same immobilized enzyme if it was previously submitted to different physicochemical modifications. The same mineralization could present different effects on the enzyme activity, specificity or stability, depending on the previous modification performed on the enzyme, showing that these previous enzyme modifications alter the effects of the mineralization on enzyme features. For example, TLL modified with glutaraldehyde and treated with zinc salts increased its activity using R-methyl mandelate, while almost maintaining its activity versus the other unaltered substrates, whereas the aminated TLL maintained its activity with both methyl mandelate isomers, while it decreased with p-NPB and triacetin. TLL was found to be easier to tune than CALB by the strategies used in this paper. In this way, the combination of chemical or physical modifications of enzymes before their mineralization increases the range of modification of features that the immobilized enzyme can experienced, enabling to enlarge the biocatalyst library. Full article
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13 pages, 22352 KiB  
Article
Biocompatible Nanocomposite Coatings Deposited via Layer-by-Layer Assembly for the Mechanical Reinforcement of Highly Porous Interconnected Tissue-Engineered Scaffolds
by Aoife McFerran, Mary Josephine McIvor, Patrick Lemoine, Brian J. Meenan and Jonathan G. Acheson
Bioengineering 2022, 9(10), 585; https://doi.org/10.3390/bioengineering9100585 - 20 Oct 2022
Cited by 7 | Viewed by 2502
Abstract
Tissue-engineered (TE) scaffolds provide an ‘off-the-shelf’ alternative to autograft procedures and can potentially address their associated complications and limitations. The properties of TE scaffolds do not always match the surrounding bone, often sacrificing porosity for improved compressive strength. Previously, the layer-by-layer (LbL) assembly [...] Read more.
Tissue-engineered (TE) scaffolds provide an ‘off-the-shelf’ alternative to autograft procedures and can potentially address their associated complications and limitations. The properties of TE scaffolds do not always match the surrounding bone, often sacrificing porosity for improved compressive strength. Previously, the layer-by-layer (LbL) assembly technique was used to deposit nanoclay containing multilayers capable of improving the mechanical properties of open-cell structures without greatly affecting the porosity. However, the previous coatings studied contained poly(ethylenimine) (PEI), which is known to be cytotoxic due to the presence of amine groups, rendering it unsuitable for use in biomedical applications. In this work, poly(diallydimethylammonium chloride) (PDDA)- and chitosan (CHI)-based polyelectrolyte systems were investigated for the purpose of nanoclay addition as an alternative to PEI-based polyelectrolyte systems. Nanocomposite coatings comprising of PEI, poly(acrylic acid) (PAA), Na+ montmorillonite (NC), PDDA, CHI and sodium alginate (ALG) were fabricated. The coatings were deposited in the following manner: (PEI/PAA/PEI/NC), PEI-(PDDA/PAA/PDDA/NC) and (CHI/ALG/CHI/ALG). Results from scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analyses demonstrated that the nanoclay was successfully incorporated into each polymer bilayer system, creating a nanocomposite coating. Each coating was successful at tailoring the elastic modulus of the open-cell structures, with polyurethane foams exhibiting an increase from 0.15 ± 0.10 MPa when uncoated to 5.51 ± 0.40 MPa, 6.01 ± 0.36 MPa and 2.61 ± 0.41 MPa when coated with (PEI/PAA/PEI/NC), PEI-(PDDA/PAA/PDDA/NC) and (CHI/ALG/CHI/ALG), respectively. Several biological studies were conducted to determine the cytotoxicity of the coatings, including a resazurin reduction assay, scanning electron microscopy and fluorescent staining of the cell-seeded substrates. In this work, the PDDA-based system exhibited equivalent physical and mechanical properties to the PEI-based system and was significantly more biocompatible, making it a much more suitable alternative for biomaterial applications. Full article
(This article belongs to the Special Issue Multifunctional Scaffolds for Musculoskeletal Regeneration)
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