Poly(ethylene imine)-controlled calcium phosphate mineralization

The current paper shows that poly(ethylene imine) (PEI) is an efficient template for the fabrication of spherical calcium phosphate (CaP)/polymer hybrid particles at pH values above 8. The polymer forms spherical entities, which contain one or a few CaP particles with diameters of ca. 6 nm. The samples contain up to 20 wt % polymer, which appears to be wrapped around the small CaP particles. The particles form via a mineralization-trapping pathway, where at the beginning of the precipitation small CaP particles form. Further particle growth is then prevented by precipitation of the PEI onto these particles at pH values of ca. 8. Stabilization of the particles is provided by the re-protonation of the PEI, which is adsorbed on the CaP particles, during the remainder of the mineralization process. At low pH, much larger particles form. They most likely grow via heterogeneous nucleation and growth on existing, polymer-modified CaP surfaces.     

Maghemite nanoparticles protectively coated with poly(ethylene imine) and poly(ethylene oxide)-block-poly(glutamic acid)

Superparamagnetic iron oxide particles (SPIO) of maghemite were prepared in aqueous solution and subsequently stabilized with polymers in two layer-by-layer deposition steps. The first layer around the maghemite core is formed by poly(ethylene imine) (PEI), and the second one is formed by poly(ethylene oxide)-block-poly(glutamic acid) (PEO-PGA). The hydrodynamic diameter of the particles increases stepwise from D(h) = 25 nm (parent) via 35 nm (PEI) to 46 nm (PEI plus PEO-PGA) due to stabilization. This is accompanied by a switching of their zeta-potentials from moderately positive (+28 mV) to highly positive (+50 mV) and finally slightly negative (-3 mV). By contrast, the polydispersity indexes of the particles remain constant (ca. 0.15). M?ssbauer spectroscopy revealed that the iron oxide, which forms the core of the particles, is only present as Fe(III) in the form of superparamagnetic maghemite nanocrystals. The magnetic domains and the maghemite crystallites were found to be identical with a size of 12.0 +/- 0.5 nm. The coated maghemite nanoparticles were tested to be stable in water and in physiological salt solution for longer than 6 months. In contrast to novel methods for magnetic nanoparticle production, where organic solvents are necessary, the procedure proposed here can dispense with organic solvents. Magnetic resonance imaging (MRI) experiments on living rats indicate that the nanoparticles are useful as an MRI contrast agent.     

Transition metal compatibilization of poly(vinylamine) and poly(ethylene imine)

Poly(vinylamine), PVA, complexes with cobalt chloride hexahydrate exhibit a 45 °C enhancement in the glass‐transition temperature per mol % of the d‐block metal cation. Poly(ethylene imine), PEI, complexes with CoCl₂(H₂O)₆ exhibit a 20 °C enhancement in T_g per mol % Co²⁺. Since the basicities of primary and secondary amines are comparable (i.e., pK_b,PVA ≈ 3.34 vs. pK_b,PEI ≈ 3.27) and the rates at which each polymeric ligand displaces waters of hydration in the coordination sphere of Co²⁺ are similar, transition metal compatibilization is operative in blends of both polymers with CoCl₂(H₂O)₆. These two polymers are immiscible in the absence of the inorganic component. Infrared spectroscopy suggests that nitrogen lone pairs in PVA and PEI coordinate to Co²⁺. The stress–strain response of a 75/25 blend of PVA and PEI with 2 mol % Co²⁺ reveals a decrease in elastic modulus from 4.4 × 10⁹ N/m² to 5.7 × 10⁷ N/m², a decrease in fracture stress from 3.7 × 10⁷ N/m² to 2.0 × 10⁶ N/m², and an increase in ultimate strain from 1.3 to 12% relative to the 75/25 immiscible polymer–polymer blend. A plausible explanation for this effect is based on the fact that cobalt chloride hexahydrate compatibilizes both polymers by forming a coordination bridge between nitrogen lone pairs in dissimilar chains. Hence, poly(ethylene imine), which is very weak with a T_g near −40 °C, is integrated into a homogeneous structure with poly(vinylamine) and the mechanical properties of the individual polymers are averaged in the compatibilized ternary complex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 552–561, 2000     

聚乙烯亚胺交联壳聚糖微球的研制

交联壳聚糖(CLC)因有良好的耐酸性,对金属离子有极强的螯合能力,可用作含金属离子污水的吸附剂,已受到人们的广泛关注。但交联壳聚糖因交联反应往往发生在活性较高、具有螯合能力的-NH2上,致使-NH2含量降低;同时-NH2上其它基团的加入增加了氮同金属离子配位的空间位阻,因此吸附性能大大降低。     

Branched and linear poly(ethylene imine)-based conjugates: synthetic modification, characterization, and application

Poly(ethylene imine)s (PEIs) are widely used in different applications, but most extensively investigated as non-viral vector systems. The high ability of cationic PEIs to complex and condense negatively charged DNA and RNA combined with their inherent proton sponge behavior accounts for the excellent efficiency in gene delivery. Further chemical modifications of the polymer expand the application potential, primarily aiming at increased transfection efficiency, cell selectivity and reduced cytotoxicity. Improvements in the synthesis of tailor-made PEIs in combination with new in-depth analytical techniques offer the possibility to produce highly purified polymers with defined structures. The contemporary strategies towards linear and branched poly(ethylene imine)s with modified surface characteristics, PEI-based copolymers as well as conjugates with bioactive molecules will be discussed. In this regard, the versatile branched PEIs have been successfully modified in a statistical manner, whereas the linear counterparts open avenues to design and synthesize well-defined architectures, in order to exploit their high potential in gene delivery.     

Charging and stability of anionic latex particles in the presence of linear poly(ethylene imine)

Charging properties and colloidal stability of negatively charged polystyrene latex particles were investigated in the presence of linear poly(ethylene imine) (LPEI) of different molecular masses by electrophoresis and dynamic light scattering (DLS). Electrophoretic mobility measurements illustrate that LPEI strongly adsorbs on these particles leading to charge neutralization at isoelectric point (IEP) and charge reversal. Time-resolved DLS experiments indicate that the aggregation of the latex particles is rapid near the IEP and slows down away from this point. Surprisingly, the colloidal stability does not depend on the molecular mass, which indicates that the adsorbed LPEI layer is rather homogeneous.     

Multiarm star nanocarriers containing a poly(ethylene imine) core and polylactide arms

Star polymers (SPs) containing a hyperbranched poly(ethylene imine) (PEI; number‐average molecular weight = 10,000) core and polylactide arms were synthesized via the ring‐opening polymerization of lactide. PEI was used as a multifunctional macroinitiator for the ring‐opening polymerization of lactide. Different lactide monomer/amino‐functional group (LA/NH_n; n = 1 or 2) ratios were used for preparing SPs with different molecular weights. SPs were able to encapsulate small guest molecules such as Rose Bengal; they also transported small, hydrophilic molecules from water to the organic phase. The transport capacity of all the nanocarriers depended on the LA/NH_n ratio used for synthesizing the SPs. Nanocarriers with a higher LA/NH_n ratio had higher transport capacities. The size of all the nanocarriers depended on the type of solvent. In chloroform, these nanoparticles had several sizes that were related to the self‐assembly of these nanocarriers, but in acetone, they were monodisperse, and their size was smaller than that in chloroform. Also, the transport of polar dyes from water to the chloroform phase was possible. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5740–5749, 2006     

Tripolyphosphate-sensitive egg phosphatidylcholine liposomes incorporating hydrophobically modified poly(ethylene imine)

Liposomes, which release their contents in answer to tripolyphosphate (TPP, a penta-anion), were prepared by immobilizing hydrophobically modified poly(ethylene imine) (HmPEI) on the surface of egg phosphatidylcholine (egg PC) liposome. HmPEI was prepared by covalently attaching decanoyl chloride to PEI through a condensation reaction. According to the ¹H NMR spectrum, the number of decanoyl chloride per one molecule of PEI was about 21, and HmPEI was air/water interface-active. HmPEI could readily complex with TPP in HEPES buffer (30 mM, pH 7.0), confirmed by Fourier transformed infrared spectrophotometer spectroscopy. The complexation increased with increasing the concentration of HmPEI and TPP, investigated through the measurement of optical density and light scattering intensity. Liposomes incorporating HmPEI were prepared by a film hydration and sonication method. The liposomes were multi-lamellar vesicles, observed on transmission electron microscope. Liposomes free of HmPEI did not release calcien when they were mixed with TPP. Liposomes whose egg PC/HmPEI was relatively low (e.g., 20:1 and 20:2) released calcein but not extensively (less than 10%) when mixed with TPP. Liposomes whose egg PC/HmPEI was relatively high (e.g., 20:4 and 20:20) released calcein extensively. For example, when the liposomes with lager amount of HmPEI were mixed with TPP so that HmPEI/TPP weight ratio was 8:1, the release degree in 60 sec was more than 70%. HmPEI can complex with TPP through electrostatic interaction and the complexation was thought to cause perturbation in the liposomal membranes and trigger the release.     

Optimized preparation of pDNA/poly(ethylene imine) polyplexes using a microfluidic system

Poly(ethylene imine) (PEI) is an established non-viral vector system for the delivery of various nucleic acids in gene therapy applications. Polyelectrolyte complexes between both compounds, so called polyplexes, are formed by electrostatic interactions of oppositely charged macromolecules and are thought to facilitate uptake into cells. Such complexes form spontaneously and on lab scale they are usually prepared by mixing solutions through pipetting. Hence, an optimized preparation procedure allowing the scale-up of well-defined polyplexes would be of general interest. We developed a new method for microfluidic polyplex preparation on a chip. The mixing behaviour within the microfluidic channels was evaluated. Polyplexes with PEI and plasmid DNA were prepared using this method, in comparison to the standard pipetting procedure. Sizes and polydispersity indices of these complexes were examined. The influence of various parameters on the polyplex characteristics and the suitability of this production procedure for other PEI-based complexes were also evaluated. It was shown that polyplexes could easily be prepared by microfluidics. The ratio of PEI to DNA was most important for the formation of small polyplexes, whereas other parameters had minor influence. The size of polyplexes prepared with this new method was observed to be relatively constant between 140 nm and 160 nm over a wide range of complex concentrations. In comparison, the size of polyplexes prepared by pipetting (approximately 90 nm to 160 nm) varied considerably. The versatility of this system was demonstrated with different (targeted) PEI-based vectors for the formation of complexes with pDNA and siRNA. In conclusion, polyplex preparation using microfluidics could be a promising alternative to the standard pipetting method due to its suitability for preparation of well-defined complexes with different compositions over a wide range of concentrations.     

Interaction forces and molecular adhesion between pre-adsorbed poly(ethylene imine) layers

Interaction forces between pre-adsorbed layers of branched poly(ethylene imine) (PEI) of different molecular mass were studied with the colloidal probe technique, which is based on atomic force microscopy (AFM). During approach, the long-ranged forces between the surfaces are repulsive due to overlap of diffuse layers down to distances of a few nanometers, whereby regulation of the surface charge is observed. The ionic strength dependence of the observed diffuse layer potentials can be rationalized with a surface charge of 2.3 mC/m2. The forces remain repulsive down to contact, likely due to electro-steric interactions between the PEI layers. These electro-steric forces have a range of a few nanometers and appear to be superposed to the force originating from the overlap of diffuse layers. During retraction of the surfaces, erratic attractive forces are observed due to molecular adhesion events (i.e., bridging adhesion). The frequency of the molecular adhesion events increases with increasing the ionic strength. The force response of the PEI segments is dominated by rubber-like extension profiles. Strong adhesion forces are observed for low molecular mass PEI at short distances directly after separation, while for high molecular mass weaker adhesion forces at larger distances are more common. The work of adhesion was estimated by integrating the retraction force profiles, and it was found to increase with the ionic strength.     

Anisotropic molecular structure in dip-coated films of linear poly(ethylene imine) studied by infrared multiple-angle incidence resolution spectrometry

Molecular structure in dip-coated films of linear poly(ethylene imine) (LPEI) on a germanium (Ge) substrate in dried and hydrated conditions have been analyzed by infrared multiple-angle incidence resolution spectrometry (IR MAIRS). The MAIRS-IP (in-plane) and -OP (out-of-plane) spectra of the dried film exhibited largely different patterns from each other, which indicated that LPEI molecules had an apparent molecular orientation with respect to the substrate surface. Although the film exhibited no peak in X-ray diffraction patterns, the low-crystallinity film has been found to have highly oriented molecular structure. Many key bands indicated that the molecules were involved in the double-stranded helix structure, which is specific to the anhydrate crystal of LPEI, with nearly perpendicular orientation. The Davydov splitting of the NH stretching vibration mode was readily captured by the IR MAIRS spectra, which also supported the helix standing model. When the film was stored in a humid condition, on the other hand, IR MAIRS spectra revealed that the helix was resolved to be straight chains, but the perpendicular orientation was kept unchanged. In addition, the MAIRS spectra also revealed molecular orientation of the water molecules of crystallization. The unique molecular arrangements are understandable by considering that the stabilization energy in the polymer monolayer directly attached on the substrate surface is minimized by the standing-molecule arrangements.     

Poly(ether imide) membranes modified with poly(ethylene imine) as potential carriers for epidermal substitutes

Poly(ether imide) (PEI) membranes were modified with a linear low-molecular weight (PETIM_0.6) and a branched high-molecular weight poly(ethylene imine) (PETIM_60). The membrane surfaces became more hydrophilic and the zeta potentials were shifted from negative to positive zeta values after immobilisation of both PETIM. These measurements also indicated the presence of a swollen surface layer in the case of PETIM_60, while a regular structuring of the surface was observed with scanning force microscopy for PETIM_0.6. A human keratinocyte cell line HaCaT was cultured on the different membranes. It was found that HaCaT cell growth was stimulated by PETIM_0.6. Cells reached earlier confluence on this substratum, while their growth was inhibited on a PEI membrane modified with PETIM_60, which makes PEI membranes modified with PETIM_0.6 a promising material for in vitro culture of epidermal transplants.     

Hollow nanoparticles via stepwise complexation and selective decomplexation of poly(ethylene imine)

The preparation of hollow nanoparticles with amino groups on the inner side via the stepwise complexation and selective decomplexation of poly(ethylene imine) is presented.     

Water-soluble pH-responsive dendritic core-shell nanocarriers for polar dyes based on poly(ethylene imine)

A simple general synthetic concept to build dendritic core-shell architectures with pH-labile linkers based on hyperbranched PEI cores and biocompatible PEG shells is presented. Using these dendritic core-shell architectures as nanocarriers, the encapsulation and transport of polar dyes of different sizes is studied. The results show that the acid-labile nanocarriers exhibit much higher transport capacities for dyes than unfunctionalized hyperbranched PEI. The cleavage of imine bonds and controlled release of the polar dyes revealed that weak acidic condition (pH approximately 5.0) could cleave the imine bonds linker and release the dyes up to five times faster than neutral conditions (pH = 7.4).     

Calcium/poly(9,9-dioctylfluorene) interaction: a theoretical study

The geometric and electronic structures of poly(9,9-dioctylfluorene) (PFO) oligomer interacting with Ca atoms were studied using M?ller-Plesset perturbation theory. A weak interaction with little charge transfer and with a relatively long Ca-C distance (about 4.0 Angstrom) was found when only one Ca atom was attached to a PFO unit. However, when two Ca atoms were adsorbed at a PFO unit, a strong interaction with a shorter Ca-C distance (about 2.67 Angstrom) took place with considerable charge transfer from the Ca atom to the PFO, resulting in significant deformation in the backbone of the PFO oligomer. In the latter case, the frontier orbitals of the PFO were modified. However, the deformed PFO and its modified frontier orbitals could be recovered when oxygen was added, which is in good agreement with experimental observation.     

Synthesis of a triblock copolymer: Poly(ethylene glycol)‐poly(alkylene phosphate)‐poly(ethylene glycol) as a modifier of CaCO3 crystallization

Triblock copolymer poly(ethylene glycol)‐poly(alkylene phosphate)‐poly(ethylene glycol) was prepared by first reacting hexamethylene glycol with dimethyl‐H‐phosphonate at conditions of transesterification and then replacing the CH₃OP(O)(H)O‐… end‐groups by monomethyl ether of poly(ethylene glycol). The course of reaction was studied by ³¹P NMR indicating complete conversion. After oxidation the poly(alkylene H‐phosphonate was converted into the final triblock polyphosphate. This triblock copolymer was used as a modifier of CaCO₃ crystallization. Unusual semi open empty spheres resulted, composed of small crystallites of the size (diameter) equal to 40–90 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 650–657, 2005     

Mesophase structures in poly(ethylene terephthalate), poly(ethylene naphthalate) and poly(ethylene naphthalate bibenzoate)

Films of poly(ethylene naphthalate) (PEN) and poly(ethylene naphthalate bibenzoate) (PENBB) have been drawn under a variety of conditions of temperature and strain rate to determine the conditions under which a nematic-like mesophase structure can be produced. In PEN the combination of low temperature and high-strain rate encourages mesophase formation, while in PENBB the mesophase was formed under all conditions where it proved possible to draw the material at all. A molecular modelling study of the mesophase in PEN and in poly(ethylene terephthalate) (PET) offers possible structures for the mesophase and showed that the mesophase structure could be stable once formed © 1997 John Wiley & Sons, Ltd.     

Complexation of linear and poly(ethylene oxide)‐grafted poly(methacryl oxyethyl trimethylammonium chloride) with poly(ethylene oxide‐block‐sodium methacrylate)

The interactions between oppositely charged polyelectrolytes were studied in saline aqueous solutions as functions of the temperature and the salt and polymer concentrations. The polyanion was a diblock copolymer composed of a poly(ethylene oxide) block and a poly(sodium methacrylate) block. Two polycations were used, the homopolymer poly(methacryl oxyethyl trimethylammonium chloride) and its poly(ethylene oxide)‐grafted analogue. By dynamic light scattering and turbidity measurements, it was observed that the salt concentration, temperature, and counterion size had a significant effect on the formation of the polymer complexes in aqueous solutions. At a fixed salt concentration and a fixed temperature, it was possible to form completely soluble complexes of an ionic polymer in aqueous solutions between poly(ethylene oxide)‐grafted poly(methacryl oxyethyl trimethylammonium chloride)and the polyanion with a poly(ethylene oxide) block at a 1:1 anion/cation ratio. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1904–1914, 2003     

Complex forming properties of crosslinked poly (ethylene oxide). I. Interaction of linear and crosslinked poly(ethylene oxide) with molybdenum(vi) salts

Evidence was found of donor–acceptor complexation of molybdenum(VI) compounds by linear and crosslinked PEO. The interaction was studied by optical and NMR spectroscopy and conductivity measurements in organic medium. PEO networks were capable of binding molybdenum salts even in aqueous solution. The character of the interaction is considered to be essentially different from complex formation with alkali metal salts. This is manifested in the relatively low values of the stability constants of complexes with linear PEO. A remarkable effect of crosslinking on the binding capacity of PEO is registered resulting in an increase of complexation constants in chloroform by two orders of magnitude.     

Poly(ethylene imine)s as Antimicrobial Agents with Selective Activity

We report the structure–activity relationship in the antimicrobial activity of linear and branched poly(ethylene imine)s (L‐ and B‐PEIs) with a range of molecular weights (MWs) (500–12 000). Both L‐ and B‐PEIs displayed enhanced activity against Staphylococcus aureus over Escherichia coli. Both B‐ and L‐PEIs did not cause any significant permeabilization of E. coli cytoplasmic membrane. L‐PEIs induced depolarization of S. aureus membrane although B‐PEIs did not. The low MW B‐PEIs caused little or no hemolysis while L‐PEIs are hemolytic. The low MW B‐PEIs are less cytotoxic to human HEp‐2 cells than other PEIs. However, they induced significant cell viability reduction after 24 h incubation. The results presented here highlight the interplay between polymer size and structure on activity.