Polymeric Amine Research Articles

A facile fabrication of functionalized rGO crosslinked chemically stable polysulfone-based anion exchange membranes with enhanced performance

Introducing more ionic conductive groups in polymer-based anion exchange membranes (AEMs) can improve the ion exchange capacity and further overcome the disadvantage of low ion conductivity for AEMs. However, the excessive swelling of AEMs caused by exorbitant IEC value may reduce the dimensional stability of membranes. So it is extremely important to modify the structures of AEMs. Herein, we proposed a facile strategy to construct reduced graphene oxide (rGO) stable crosslinked polysulfone-based AEMs with improved properties. rGO was non-covalently modified with pyrene-containing tertiary amine small molecule and polymer via π-π interactions. The as-prepared functionalized rGO (TrGO and PrGO) as both cross-linkers and fillers to fabricate quaternized polysulfone (QPSU)-based AEMs (CQPSU-X-TrGO and CQPSU-X-PrGO) for the first time. The cross-linked membranes can tighten the internal packing structure, and enhance the alkaline resistance, ion conductivity and oxidative stability of AEMs. Furthermore, the hydrophilicity and flexibility of the CQPSU-X-PrGO membranes were significantly improved as compared with that of CQPSU-X-TrGO membranes. PrGO-crosslinked membranes (CQPSU-2%-PrGO, σOH− = 117.7 mS/cm) displayed higher ionic conductivities at 80 °C than TrGO-crosslinked membranes (CQPSU-1%-TrGO, σOH− = 87.2 mS/cm). The remarkable nanophase separation can be observed in the CQPSU-X-PrGO membranes by TEM. This feasible strategy can be efficiently used to prepare new type of crosslinked organic-inorganic nanohybrid AEMs with excellent chemical stability and high ionic conductivity.

Tagging synthetic polymers with coumarin group for study nucleic acid interaction with gene delivery agents

Polymeric amines and complex amine containing system are actively studied and applied as gene delivery agents in gene therapy and genetic engineering. Optimizing polymer – nucleic acid ratio is the key stage in elaboration of procedures in this area. Application of fluorescent tagged oligonucleotides is widespread approach which allows to visualize nucleic acid in gel electrophoresis experiments and to find conditions of the full binding of the nucleic acid. We suggest to use succinimidyl ester of 7-(diethylamino)coumarin-3-carboxylic acid as an agent for fluorescent labeling of polymeric amines and to use the tagged polymers in optimizing polymer – nucleic acid ratio. This approach allows to see unbound polymer and to study various nucleic acids in interaction with the same polymer.•Labeling of gene delivery agents with fluorescence groups increases efficiency of optimization of gene delivery compositions.•Polymeric amines tagged with succinimidyl ester of 7-(diethylamino)coumarin-3-carboxylic acid are suitable for study polymer – nucleic acid interaction with gel electrophoresis.

Properties and Characteristic of Amine-Polymer Blend Membrane

Polymer blend technology has earned a significant position in the field of polymer science. Current membrane technology can easily and simply remove and separates carbon dioxide as pressure, temperature, costs, and energy requirements are low. There is also no corrosion problem from the straightforward process of removing CO2 from natural gas, especially in remote or offshore locations that are easily scaled up. However, glassy polymeric membranes suffer from a lack of permeability causing performance degradation and higher selectivity. Nevertheless, amine solutions are capable of purifying naturally acidic gas. Within this framework, the blending of the polysulfone (PSU) glassy polymer with amines such as diethanolamine (DEA), methyl diethanolamine (MDEA), and monoethanolamine (MEA) in a dimethylacetamide solvent, resulted in the development of flat sheet membranes with the desired properties. The findings showed good miscibility between PSU and amines blends, all the original functional groups were shown by FTIR. The synthesized amine polymer blend membrane were found to have homogenous surfaces and a packed bed sphere structure (PBSS) as shown by FESEM images. Furthermore the addition of different amine solution, have increased the size of PBSS due to incorporation of amine molecule into the sphere.

A combined experimental and theoretical study on gas adsorption performance of amine and amide porous polymers

In this manuscript, we report synthesis, characterization and application of amine and amide type covalent organic frameworks as CO2 adsorbent materials at various isotherms and wide pressure conditions. Furthermore, we also report a detailed density functional theory investigation of the studied adsorbents in order to explain their adsorption behaviors and provide comparisons with experimental results. The objective of this work was to investigate custom design porous polymers by building amine and amide functionalities in the final structures, whether they have efficient CO2 capturing performances at wide process conditions that covers both low and high pressure end applications to cover either pre- or post-combustion processes. On the other hand, energy storage performances of these materials were tested by performing H2 sorption experiments as well. Two porous polymers, namely COP-9 and COP-10, were characterized with BET, TGA and FTIR to evaluate the physical properties of studied porous polymers and then were tested for CO2, N2 and H2 adsorption both at low and high pressures. Studied materials were found to have compelling adsorption capacity mostly at high pressures and have very good selectivity for CO2/N2 and CO2/H2 respectively.

Shale inhibition by low-molecular-weight cationic polymer in water-based mud

The presence of oligomers possessing amine or ammonium functionality in drilling fluid plays an important role in stabilizing the shale formations during drilling with water-based mud. In this study, we have compared the activity of neutral to charged amine polymers towards shale stabilization. Low-molecular-weight polymer possessing charged moieties provided superior inhibitive capacity compared to that of the neutral amine functionality-based polymer. The polymer with cationic functionality (polyAETMAC) exhibited higher shale recovery, lesser shale swelling and lower capillary suction time compared to that of the neutral amine-based system (polyDMAPMA) supporting the above. Shale recovery in shale disintegration test improved from 92.3 to 98.7% for polyAETMAC concentration of 0.625 w/v% in water-based mud. The prodigious shale recovery is attributed to the strong interaction between the cationic sites of the polymer with the minerals present in the shale. The overall rheological properties of drilling fluids also improved in the presence of charged amine polymer before and after hot rolling. Apparent viscosity of mud increased by ~ 29% for polyAETMAC as compared to ~ 25% for polyDMAPMA at a concentration of 0.625 w/v%. Plastic viscosity and yield point of base mud were also improved by ~ 43% and ~ 15% at 0.0625 w/v% concentration of polyAETMAC and to a similar extent by polyDMAPMA for the same concentration. The decrease in API fluid loss after hot rolling of drilling fluid at 100 °C for 16 h was ~ 20% for polyDMAPMA and ~ 13% for polyAETMAC compared to base mud for the same concentration of the polymers. These polymers can be used as a potential shale stabilizer for water-based drilling fluids.Graphical abstract

Design of Oligonucleotide Carriers: Importance of Polyamine Chain Length.

Amine containing polymers are extensively studied as special carriers for short-chain RNA (13–25 nucleotides), which are applied as gene silencing agents in gene therapy of various diseases including cancer. Elaboration of the oligonucleotide carriers requires knowledge about peculiarities of the oligonucleotide–polymeric amine interaction. The critical length of the interacting chains is an important parameter which allows us to design sophisticated constructions containing oligonucleotide binding segments, solubilizing, protective and aiming parts. We studied interactions of (TCAG)n, n = 1–6 DNA oligonucleotides with polyethylenimine and poly(N-(3-((3-(dimethylamino)propyl)(methyl)amino)propyl)-N-methylacrylamide). The critical length for oligonucleotides in interaction with polymeric amines is 8–12 units and complexation at these length can be accompanied by “all-or-nothing” effects. New dimethylacrylamide based polymers with grafted polyamine chains were obtained and studied in complexation with DNA and RNA oligonucleotides. The most effective interaction and transfection activity into A549 cancer cells and silencing efficiency against vascular endothelial growth factor (VEGF) was found for a sample with average number of nitrogens in polyamine chain equal to 27, i.e., for a sample in which all grafted chains are longer than the critical length for polymeric amine–oligonucleotide complexation.

Aminophosphonic groups grafted onto the structure of macroporous styrene–divinylbenzene copolymer: preparation and studies on the antimicrobial effect

This paper has investigated the preparation, characterization and antimicrobial effect of two new compounds. α-Aminophosphonic acid groups were grafted onto the structure of a styrene-6.7% divinylbenzene (S-6.7% DVB) copolymer. The compounds bearing the N–C–P skeleton in α-aminophosphonic acids groups were synthesized following a “one-pot” modified Kabachnik–Fields reaction performed with three components (polymeric amine, aldehyde and phosphorous acid) in tetrahydrofuran at 55 °C. The presence of 2 novel products: aminobenzylphosphonic acid (BzAmPhonic) and aminopropylphosphonic acid (PrAmPhonic) grafted on (S-6.7% DVB) copolymer was indicated by characterization using FT-IR spectroscopy, EDX, TGA, measurement of the phosphorus content and the degree of functionalization with pendant α-aminophosphonic acid group. It was proved that novel products have an antimicrobial effect in vitro after 1 h of contact against Staphylococcus aureus (S. aureus), Escherichia coli (E. coli), Bacillus cereus (B. cereus), Pseudomonas aeruginosa (P. aeruginosa) and a species of yeast Candida albicans (C. albicans). The best antibacterial activity was obtained by the PrAmPhonic sample. We were interested in obtaining new polymeric functionalized compounds endowed with very good antimicrobial properties. The main advantage of the novel antibacterial agents synthesized in this work is that they can be easily recovered in order not to contaminate the environment.

Carbon nanotube silica composite hollow fibers impregnated with polyethylenimine for CO2 capture

The capture of carbon dioxide from flue gases or air using sorption technologies is an adequate means to stop the increase in CO2 emissions that are the main contributor to climate change. Hollow fibers for sorption processes are a promising approach with several improved characteristics such as a decreased pressure drop, lower energy consumption as well as higher CO2 recovery and purity compared to conventional packed-beds. To overcome thermal and chemical limitations of a polymeric matrix we propose carbon nanotube (CNT) based hollow fiber sorbents. Silica particles are dispersed in the CNT network and polyethylenimine is immobilized within the hollow fibers to enhance the sorption performance. Polymeric amines exhibit high CO2 adsorption capacities even at very low partial pressures. The incorporation of silica particles improves the specific surface area of the so-called microtubes from 203.6 m2 g−1 to 283.2 m2 g−1 and yields a CO2 uptake of 1.92 mmol g−1 at 0.15 bar CO2 partial pressure. A gas tight polymer layer coated on the shell side allows the use of a thermal moderator for isothermal operation. Adsorption isotherms and kinetics are presented, discussed and fitted applying appropriate models. The results presented here prove the adaptiveness of the carbon nanotube based hollow fibers and emphasize the possibilities they open up as a platform for different sorption tasks that extend beyond carbon capture.

Quantification of Lipid Corona Formation on Colloidal Nanoparticles from Lipid Vesicles.

Formation of a protein corona around nanoparticles when immersed into biological fluids is well-known; less studied is the formation of lipid coronas around nanoparticles. In many cases, the identity of a nanoparticle-acquired corona determines nanoparticle fate within a biological system and its interactions with cells and organisms. This work systematically explores the impact of nanoparticle surface chemistry and lipid character on the formation of lipid coronas for 3 different nanoparticle surface chemistries (2 cationic, 1 anionic) on 14 nm gold nanoparticles exposed to a series of lipid vesicles of 4 different compositions. Qualitative (plasmon band shifting, ζ-potential analysis, dynamic light scattering on the part of the nanoparticles) and quantitative (lipid liquid chromatography/mass spectrometry) methods are developed with a "pull-down" scheme to assess the degree of lipid corona formation in these systems. In general, cationic nanoparticles extract 60-95% of the lipids available in vesicles under the described experimental conditions, while anionic nanoparticles extract almost none. While electrostatics apparently dominate the lipid-nanoparticle interactions, primary amine polymer surfaces extract more lipids than quaternary ammonium surfaces. Free cationic species can act as lipid-binding competitors in solution.

Camelina protein adhesives enhanced by polyelectrolyte interaction for plywood applications

Camelina protein is a major by-product created after oil extraction from camelina seeds; it has drawn research attention as an economical material for bio-industrial implications. The present study investigates the influence of polyelectrolyte interaction on camelina protein structure and effects on wood bonding performance when used as a bio-adhesive. Infrared spectroscopy (IR) and transmission electron microscopy (TEM) images revealed that after interacting with polymeric amine epichlorohydrin (PAE), a cationic polyelectrolyte, camelina protein is partly unfolded with more flexible chain structures. PAE works as a bridge among different protein molecules primarily through electrostatic and hydrophobic interactions. Separation by size exclusion chromatography showed that soluble PAE modified proteins are smaller in molecular size. Polymeric amine epichlorohydrin modified proteins had reduced solubility, possibly indicating increased hydrophobicity. The PAE treatment of camelina protein greatly improved both dry and wet adhesion strength when used as an adhesive. Dry bond strength increased from 2.39 ± 0.52 MPa to 5.39 ± 0.50 MPa with 100% wood failure and wet bond strength was dramatically increased from 0.37 ± 0.22 to 2.35 ± 0.17 MPa on two layer cherry wood tests. Two aliphatic structures with hydrophobic chains were introduced into the PAE modified protein system to further improve water resistance and get wet bond strength increase from 0 to 1.30 ± 0.23 MPa on three layer yellow pine wood tests. This study demonstrates the possibility of camelina as a green resource for the adhesive industry.

Rational Design of the Polymeric Amines in Solid Adsorbents for Postcombustion Carbon Dioxide Capture.

Substantial efforts have been made to increase the CO2 working capacity of amine adsorbents for an efficient CO2 capture. However, the more important metric for assessing adsorbents is the regeneration heat required for capturing a fixed amount of CO2. In this work, we synthesized polyethyleneimine (PEI)/SiO2 adsorbents functionalized with various epoxides. This provided adsorbents with six different amine structures showing various CO2/H2O adsorption properties. Our studies revealed that the CO2 working capacity was not a decisive factor in determining the regeneration heat required for CO2 capture. This is because the benefit of large CO2 working capacity was canceled out by the difficulty of CO2 desorption. Instead, the suppression of H2O co-adsorption was critical for reducing the regeneration heat because substantial latent heat is required for H2O desorption. Consequently, the PEI/SiO2 functionalized with 1,2-epoxybutane required a much lower regeneration heat (2.66 GJ tCO2-1) than the conventional PEI/SiO2 (4.03 GJ tCO2-1) because of suppressed H2O co-adsorption as well as moderately high CO2 working capacity.

In-vitro Equilibrium Phosphate Binding Study of Sevelamer Carbonate by UV-Vis Spectrophotometry.

Sevelamer carbonate is a cross-linked polymeric amine; it is the active ingredient in Renvela® tablets. US FDA provides recommendation for demonstrating bioequivalence for the development of a generic product of sevelamer carbonte using in-vitro equilibrium binding study. A simple UV-vis spectrophotometry method was developed and validated for quantification of free phosphate to determine the binding parameter constant of sevelamer. The method validation demonstrated the specificity, limit of quantification, accuracy and precision of measurements. The validated method has been successfully used to analyze samples in in-vitro equilibrium binding study for demonstrating bioequivalence.

Polymer electrets with quadratic nonlinear-optical activity

The nonlinear-optical (NLO) activities of composite materials with a binary set of chromophores are measured with the Second Harmonic Generation technique (λ=1064 nm). In these materials the host matrix is an epoxy amine polymer with an azochromophore, covalently attached in such a way that its donor-group is included in the main chain. Apart from this chromophore functionalized epoxy amine oligomer, CFAO, a guest azochromophore dispersed orange, DO3, is added. The addition of DO3 in two concentrations (10 and 20 wt%) enhances the NLO coefficient compared to that for CFAO by ca. 40%. Molecular modeling in an amorphous cell is used for estimating the local mobility of different groups and fragments of the polymeric chain, in particular, that of the azochromophores. The information obtained from the modeling can be used for the development of an effective time-temperature poling protocol. It is shown that for a high chromophores orientation the poling temperature should be some 20–30 K higher than the glass transition Tg.

Poly(vinyl amine) as a matrix for a new class of polymers

Abstract Poly(vinyl amine) was utilized as a matrix for the synthesis of polymers bearing short polyamine chains (1–3 amine groups) grafted to the main macromolecular chain with long (eight atoms) spacers. The new polymers were characterized with nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, size exclusion chromatography and potentiometry. Poly(vinyl amine) was applied in the form of narrow molecular mass fractions and the modification proceeded without destruction of the main chain. Condensation of silicic acid in the presence of the polymeric amines gives rise to composite nanoparticles which are stable in aqueous medium. New polymers and composite nanoparticles effectively complex with DNA and RNA oligonucleotides and were found to display good internalization in cancer cells which indicates their promise towards gene delivery applications.

Naphthyl Substitution-Induced Fine Tuning of Porosity and Gas Uptake Capacity in Microporous Hyper-Cross-Linked Amine Polymers

Exploring the effect of functional group substitution on the porous structure and gas adsorption performance of polymer materials is becoming much fascinating. Here, three novel polymers, based on various amine building blocks, were efficiently prepared by the solvent knitting method. It is intriguingly found that with the gradual functional group substitution of phenyl by naphthyl in building blocks both porosity and gas uptake capacity of these hyper-cross-linked polymers can be finely tuned, with SBET increased from 874 to 1717 m2 g–1, and CO2 adsorption capacity tuned from 12.76 to 18.85 wt % (273.15 K/1.00 bar). Besides, these polymers could reveal CO2/N2 selectivity up to 24.9 and CO2/CH4 selectivity of 6.3 at 298.15 K. This work has proved that increasing the number of naphthyl in precursors will be in favor of knitting microporous with improved porosity and enhanced gas uptake ability, and naphthyl outweighs phenyl in their contributions to bettering the porosity parameters and gas uptake capacity...

Salicylaldimine‐functionalized poly(m‐phenyleneethynylene) as turn‐on chemosensor for ferric ion

ABSTRACTA new turn on fluorescent probe for ferric ion based on poly(m‐phenyleneethynylene salicylaldimine) (PPE‐IM) has been developed. The preparation of PPE‐IM involves post‐polymerization functionalization of the corresponding polymeric amine, PPE‐AM, via the condensation with salicylaldehyde. The degree of polymerization of both PPE‐IM and PPE‐IM is 17 with polydispersity index of 1.5. In aqueous solution, the polymeric PPE‐IM is highly stable unlike its small molecule analog which is gradually hydrolyzed. The weak fluorescence of initial PPE‐IM (λem = 470) is greatly enhanced by 300 folds upon the addition of Fe3+. The 1H NMR reveals that the fluorescence enhancement is caused by Fe3+‐induced hydrolysis of the imine group. The sensing system shows a detection limit of 0.14 μM of Fe3+. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1155–1161

Photolabile protecting groups: a strategy for making primary amine polymers by RAFT

Photolabile amine protecting groups are combined with RAFT polymerization to create well-defined amine containing polymers, which is typically a challenge for RAFT polymerization.

Polymeric Amines and Ampholytes Derived from Poly(acryloyl chloride): Synthesis, Influence on Silicic Acid Condensation and Interaction with Nucleic Acid.

Polymeric amines are intensively studied due to various valuable properties. This study describes the synthesis of new polymeric amines and ampholytes by the reaction of poly(acryloyl chloride) with trimethylene-based polyamines containing one secondary and several (1–3) tertiary amine groups. The polymers contain polyamine side chains and carboxylic groups when the polyamine was in deficiency. These polymers differ in structure of side groups, but they are identical in polymerization degree and polydispersity, which facilitates the study of composition-properties relationships. The structure of the obtained polymers was confirmed with 13C nuclear magnetic resonance infrared spectroscopy, and acid-base properties were studied with potentiometry titration. Placement of the amine groups in the side chains influences their acid-base properties: protonation of the amine group exerts a larger impact on the amine in the same side chain than on the amines in the neighboring side chains. The obtained polymers are prone to aggregation in aqueous solutions tending to insolubility at definite pH values in the case of polyampholytes. Silicic acid condensation in the presence of new polymers results in soluble composite nanoparticles and composite materials which consist of ordered submicrometer particles according to dynamic light scattering and electron microscopy. Polymeric amines, ampholytes, and composite nanoparticles are capable of interacting with oligonucleotides, giving rise to complexes that hold promise for gene delivery applications.

Poly(tris(4-carbazoyl-9-ylphenyl)amine)/Three Poly(3,4-ethylenedioxythiophene) Derivatives in Complementary High-Contrast Electrochromic Devices.

A carbazole-based polymer (poly(tris(4-carbazoyl-9-ylphenyl)amine) (PtCz)) is electrosynthesized on an indium tin oxide (ITO) electrode. PtCz film displays light yellow at 0.0 V, earthy yellow at 1.3 V, grey at 1.5 V, and dark grey at 1.8 V in 0.2 M LiClO4/ACN/DCM (ACN/DCM = 1:3, by volume) solution. The ΔT and coloration efficiency (η) of PtCz film are 30.5% and 54.8 cm2∙C−1, respectively, in a solution state. Three dual-type electrochromic devices (ECDs) are fabricated using the PtCz as the anodic layer, poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,3-dimethyl-3,4-dihydro-thieno[3,4-b][1,4]dioxepine) (PProDOT-Me2), and poly(3,4-(2,2-diethylpropylenedioxy)thiophene) (PProDOT-Et2) as the cathodic layers. PtCz/PProDOT-Me2 ECD shows high ΔTmax (36%), high ηmax (343.4 cm2·C−1), and fast switching speed (0.2 s) at 572 nm. In addition, PtCz/PEDOT, PtCz/PProDOT-Me2, and PtCz/PProDOT-Et2 ECDs show satisfactory open circuit memory and long-term stability.

Persistent inhibition performance of amine polymers to inhibit clay swelling

Abstract Clay hydration and swelling can cause shale instability in the drilling of oil and gas wells. The persistent inhibition performance of polyether amine (PEA) and poly(vinyl alcohol-g-dimethyl aminopropyl methacrylamide) (PVA-g-DMAPMA) as amine clay inhibitors has been investigated through hot rolling dispersion test, bulk hardness test, and bentonite inhibition test. The micro-mechanism has also been explained by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), and X-ray diffraction (XRD) analyses. Through the interaction of PEA and PVA-g-DMAPMA, the PEA can enter into clay platelets to exclude water molecules from entering and hydrating the clay, and the PVA-g-DMAPMA can affect the surface of clay minerals to prevent further intrusion of water molecules. Due to the effect of multiple cationic sites, both PEA and PVA-g-DMAPMA can maintain persistent clay inhibition and are less susceptible to reversing the adsorption.