Polyethylenimine (PEI) or polyaziridine is a polymer with repeating units composed of the
amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituen ...
group and two carbon aliphatic ''CHCH'' spacers. Linear polyethyleneimines contain all secondary amines, in contrast to branched PEIs which contain primary, secondary and tertiary amino groups. Totally branched,
dendrimer
Dendrimers are highly ordered, branched polymeric molecules. Synonymous terms for dendrimer include arborols and cascade molecules. Typically, dendrimers are symmetric about the core, and often adopt a spherical three-dimensional morphology. The ...
ic forms were also reported. PEI is produced on an industrial scale and finds many applications usually derived from its polycationic character.
Properties
The linear PEI is a semi-crystalline solid at
room temperature
Colloquially, "room temperature" is a range of air temperatures that most people prefer for indoor settings. It feels comfortable to a person when they are wearing typical indoor clothing. Human comfort can extend beyond this range depending on ...
while branched PEI is a fully amorphous polymer existing as a liquid at all molecular weights. Linear polyethyleneimine is soluble in hot water, at low pH, in
methanol
Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a ...
,
ethanol
Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an Alcohol (chemistry), alcohol with the chemical formula . Its formula can be also written as or (an ethyl ...
, or
chloroform
Chloroform, or trichloromethane, is an organic compound with chemical formula, formula Carbon, CHydrogen, HChlorine, Cl3 and a common organic solvent. It is a colorless, strong-smelling, dense liquid produced on a large scale as a precursor to ...
. It is insoluble in cold water,
benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
,
ethyl ether
Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...
, and
acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
. Linear polyethyleneimine has a
melting point
The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
of around 67 °C.
Both linear and branched polyethyleneimine can be stored at room temperature. Linear polyethyleneimine is able to form cryogels upon freezing and subsequent thawing of its aqueous solutions.
Synthesis
Branched PEI can be synthesized by the
ring opening polymerization
In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer (see figure). The reactive center can be radical, anion ...
of
aziridine
Aziridine is an organic compound consisting of the three-membered heterocycle . It is a colorless, toxic, volatile liquid that is of significant practical interest. Aziridine was discovered in 1888 by the chemist Siegmund Gabriel. Its derivati ...
. Depending on the reaction conditions different degree of branching can be achieved. Linear PEI is available by post-modification of other polymers like poly(2-oxazolines) or ''N''-substituted polyaziridines. Linear PEI was synthesised by the hydrolysis of poly(2-ethyl-2-oxazoline) and sold as jetPEI. The current generation in-vivo-jetPEI uses bespoke poly(2-ethyl-2-oxazoline) polymers as precursors.
Applications
Polyethyleneimine finds many applications in products like: detergents, adhesives, water treatment agents and cosmetics.
Owing to its ability to modify the surface of cellulose fibres, PEI is employed as a wet-strength agent in the
paper-making process. It is also used as flocculating agent with silica sols and as a chelating agent with the ability to complex metal ions such as zinc and zirconium. There are also other highly specialized PEI applications:
Biology
PEI has a number of uses in laboratory biology, especially
tissue culture
Tissue culture is the growth of tissues or cells in an artificial medium separate from the parent organism. This technique is also called micropropagation. This is typically facilitated via use of a liquid, semi-solid, or solid growth medium, su ...
, but is also toxic to cells if used in excess.
Toxicity is by two different mechanisms, the disruption of the cell membrane leading to necrotic cell death (immediate) and disruption of the mitochondrial membrane after internalisation leading to apoptosis (delayed).
Attachment promoter
Polyethyleneimines are used in the cell culture of weakly anchoring cells to increase attachment. PEI is a cationic polymer; the negatively charged outer surfaces of cells are attracted to dishes coated in PEI, facilitating stronger attachments between the cells and the plate.
Transfection reagent
Poly(ethylenimine) was the second polymeric transfection agent discovered, after poly-L-lysine. PEI condenses DNA into positively charged particles, which bind to anionic cell surface residues and are brought into the cell via
endocytosis
Endocytosis is a cellular process in which substances are brought into the cell. The material to be internalized is surrounded by an area of cell membrane, which then buds off inside the cell to form a vesicle containing the ingested material. E ...
. Once inside the cell, protonation of the amines results in an influx of counter-ions and a lowering of the osmotic potential. Osmotic swelling results and bursts the vesicle releasing the polymer-DNA complex (polyplex) into the cytoplasm. If the polyplex unpacks then the DNA is free to diffuse to the nucleus.
Permeabilization of gram negative bacteria
Poly(ethylenimine) is also an effective permeabilizer of the outer membrane of
Gram-negative bacteria
Gram-negative bacteria are bacteria that do not retain the crystal violet stain used in the Gram staining method of bacterial differentiation. They are characterized by their cell envelopes, which are composed of a thin peptidoglycan cell wall ...
.
CO2 capture
Both linear and branched polyethylenimine have been used for CO
2 capture, frequently impregnated over porous materials. First use of PEI polymer in CO
2 capture was devoted to improve the CO
2 removal in space craft applications, impregnated over a polymeric matrix. After that, the support was changed to MCM-41, an hexagonal mesostructured silica, and large amounts of PEI were retained in the so-called "molecular basket". MCM-41-PEI adsorbent materials led to higher CO
2 adsorption capacities than bulk PEI or MCM-41 material individually considered. The authors claim that, in this case, a synergic effect takes place due to the high PEI dispersion inside the pore structure of the material. As a result of this improvement, further works were developed to study more in depth the behaviour of these materials. Exhaustive works have been focused on the CO
2 adsorption capacity as well as the CO
2/O
2 and CO
2/N
2 adsorption selectivity of several MCM-41-PEI materials with PEI polymers. Also, PEI impregnation has been tested over different supports such as a glass fiber matrix and monoliths. However, for an appropriate performance under real conditions in post-combustion capture (mild temperatures between 45-75 °C and the presence of moisture) it is necessary to use thermally and hydrothermally stable silica materials, such as SBA-15, which also presents an hexagonal mesostructure. Moisture and real world conditions have also been tested when using PEI-impregnated materials to adsorb CO
2 from the air.
A detailed comparison among PEI and other amino-containing molecules showed an excellent performance of PEI-containing samples with cycles. Also, only a slight decrease was registered in their CO
2 uptake when increasing the temperature from 25 to 100 °C, demonstrating a high contribution of chemisorption to the adsorption capacity of these solids. For the same reason, the adsorption capacity under diluted CO
2 was up to 90% of the value under pure CO
2 and also, a high unwanted selectivity towards SO
2 was observed. Lately, many efforts have been made in order to improve PEI diffusion within the porous structure of the support used. A better dispersion of PEI and a higher CO
2 efficiency (CO
2/NH molar ratio) were achieved by impregnating a template-occluded PE-MCM-41 material rather than perfect cylindrical pores of a calcined material, following a previously described route. The combined use of organosilanes such as aminopropyl-trimethoxysilane, AP, and PEI has also been studied. The first approach used a combination of them to impregnate porous supports, achieving faster CO
2-adsorption kinetics and higher stability during reutilization cycles, but no higher efficiencies. A novel method is the so-called "double-functionalization". It is based on the impregnation of materials previously functionalized by grafting (covalent bonding of organosilanes). Amino groups incorporated by both paths have shown synergic effects, achieving high CO
2 uptakes up to 235 mg CO
2/g (5.34 mmol CO
2/g). CO
2 adsorption kinetics were also studied for these materials, showing similar adsorption rates as impregnated solids. This is an interesting finding, taking into account the smaller pore volume available in double-functionalized materials. Thus, it can be also concluded that their higher CO
2 uptake and efficiency compared to impregnated solids can be ascribed to a synergic effect of the amino groups incorporated by two methods (grafting and impregnation) rather than to a faster adsorption kinetics.
Low work function modifier for electronics
''Poly(ethylenimine) and poly(ethylenimine) ethoxylated'' (PEIE) have been shown as effective low-work function modifiers for organic electronics by Zhou and Kippelen et al. It could universally reduce the work function of metals, metal oxides, conducting polymers and graphene, and so on. It is very important that low-work function solution-processed conducting polymer could be produced by the PEI or PEIE modification. Based on this discovery, the polymers have been widely used for organic solar cells, organic light-emitting diodes, organic field-effect transistors, perovskite solar cells, perovskite light-emitting diodes, quantum-dot solar cells and light-emitting diodes etc.
Use in delivery of HIV-gene therapies
Polyethylenimine (PEI), a cationic polymer, has been widely studied and shown great promise as an efficient gene delivery vehicle. Likewise, the HIV-1 Tat peptide, a cell-permeable peptide, has been successfully used for intracellular gene delivery.
See also
*
Tetraethylenepentamine
Tetraethylenepentamine (TEPA) is an organic compound and is in the class of chemicals known as ethyleneamines. It is a slightly viscous liquid and is not colorless but, like many amines, has a yellow color. It is soluble in most polar solvents. Di ...
*
Ethylenediamine
Ethylenediamine (abbreviated as en when a ligand) is the organic compound with the formula C2H4(NH2)2. This colorless liquid with an ammonia-like odor is a basic amine. It is a widely used building block in chemical synthesis, with approximately ...
*
Polyetherimide
Polyetherimide (PEI) is an amorphous, amber-to-transparent thermoplastic with characteristics similar to the related plastic PEEK. When comparing PEI to PEEK, the former is cheaper but has lower impact strength and a tighter temperature range.
D ...
(Also goes by PEI)
References
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Polyelectrolytes
Polymers
Amines