Polyethylenimine Functionalized with Dopamine: Characterization and Electrocatalytic Properties

We report the chemical modification of polyethylenimine (PEI) by functionalization with dopamine (Do) using glutaraldehyde (Glu) as a linker (PEI‐Glu‐Do). The new polymer was characterized by FT‐IR spectroscopy, by derivative UV‐vis spectroscopy, and Cyclic Voltammetry. The PEI‐Glu‐Do demonstrated to have an important electrocatalytic activity allowing an important decrease in the overvoltages for the oxidation of NADH and a significant increase in its oxidation peaks currents. Different ratios of PEI:Do were assayed and the best response was obtained using PEI : Glu : Do 1 : 2 : 1. The new polymer represents an interesting and promising alternative for the electrochemical quantification of NADH and other analytes of clinical interest, as well as for the development of new electrochemical (bio)sensors.     

一种新型聚乙烯亚胺(PEI)载体的制备及表征

设计一种新型的用于传输小干扰核糖核酸(siRNA)聚乙烯亚胺-聚类丙交酯功能聚合物。首先合成一类含功能基团羧基的丙交酯衍生物,对其进行了1 H NMR、GPC、DSC表征,功能基团的密度可以通过与丙交酯共聚的单体的物质的量来调控,利用羧基与聚乙烯亚胺(PEI)分子上的氨基偶合,将小分子量PEI通过共价键连接到可生物降解的高分子主链骨架上,这种方法提供了一条途径来解决分子量与细胞毒性以及转染效率之间相互矛盾的关系。本文进一步研究了此体系在负载siRNA前后粒径及zeta电位的变化,颗粒粒径分布在50~500nm之间,Zeta电位在-9~-35mV之间。     

Tetraphenylethene End-capped Polyethylenimine Fluorescent Nanoparticles for Cell Imaging

Water soluble tetraphenylethene-based（TPE） aggregation-induced emission fluorescent organic nanoparticles（FONs） were facilely prepared via Schiff base condensation with polyethylenimine（PEI） and subsequent reduction. The obtained TPE-PEI FONs were characterized by a series of techniques including 1H-NMR, 13C-NMR, gel permeation chromatography, UV absorption spectra, fluorescence spectra, Fourier transform infrared spectroscopy, size distribution and zeta potential measurement, and transmission electron microscopy. Biocompatibility evaluation and cell imaging of TPE-PEI FONs were further explored. We demonstrated that such FONs showed intense fluorescence, spherical morphology and excellent biocompatibility, making them very suitable for cell imaging application.     

Spectroscopic Studies of Polyethylenimine with Pyrimidine or Purine Grafts

Hypochromic effects of 2-(thymin-1-yl)propionyl graft polyethylenimine (P-T) and its related monomer (M-T) and dimer model (D-T), and 2-(adenin-9-yl)propionyl graft polyethylenimine (P-A) and its monomer (M-A) and dimer model (D-A) have been systematically investigated, and the base-stacked conformation in comparison with corresponding polynucleotides and dinucleotides has been discussed. The results suggest that the graft polymers and even their dimer models may have a particular preference for a stacked conformation compared with the corresponding poly- and dinucleotides. A study of solvent effect on the NMR spectra of the dimer model suggests the existence of a preferred base-stacked conformation. Base pairing effects between the complementary bases have also been studied for various combinations among the model systems. Only the combination P-T/P-A showed a considerable hypochromic effect.     

聚乙烯亚胺介导siRNA和顺铂协同抗肿瘤治疗

用聚乙烯亚胺(PEI)为载体,介导siRNA(siSurvivin)沉默肿瘤细胞抗凋亡基因survivin,并与抗癌药物(顺铂)进行协同抗肿瘤治疗.凝胶阻滞电泳实验显示,PEI能够对siRNA进行有效复合,在PEI/siRNA质量比为0.4时实现完全阻滞.细胞耐药性实验证明了耐顺铂细胞(A549DDP细胞)的survivin基因过度表达且耐顺铂能力是顺铂敏感细胞(A549细胞)的8倍.RT-PCR实验验证了PEI担载siSurvivin后对survivin基因实现了有效沉默,与顺铂药物共同作用后不影响基因沉默效果.细胞凋亡实验验证了基因与药物协同作用后细胞的凋亡率达到60.9％,而单独药物或PEI/siSurvivin复合物分别作用后的细胞凋亡率仅分别为30.2％和19.8％.细胞增殖实验进一步验证了PEI介导siSurvivin与顺铂联合治疗能够实现有效地协同抗肿瘤效果.     

Self‐Assembled Multilayers of Polyethylenimine and DNA: Spectrophotometric and Electrochemical Characterization and Application for the Determination of Acridine Orange Interaction

This work deals with the study of the interaction between acridine orange (AO) and calf‐thymus double stranded DNA (dsDNA) present in supramolecular architectures built on gold electrodes modified with mercapto‐1‐propanesulfonic acid (MPS) by self‐assembling of polyethylenimine and dsDNA. The optimal conditions for building the supramolecular architecture were obtained from UV‐vis spectrophotometric experiments. The electrochemical studies were performed by adsorptive transfer square wave voltammetry from the evaluation of the oxidation signal of AO accumulated within the multistructure. The effect of the number of PEI‐dsDNA bilayers (Au/MPS/(PEI‐dsDNA)_n) on the accumulation and electrooxidation of AO is also discussed.     

Thermosensitive Nanoparticles Based on Polyethylenimine as Promising Materials for Biomedical Applications

Russian Journal of General Chemistry - Thermosensitive nanoparticles were synthesized by acylation of branched polyethyleneimine with isobutyroyl chloride and cross-linking by 1,6-hexamethylene...     

Reducible Polyethylenimine Nanoparticles for Efficient siRNA Delivery in Corneal Neovascularization Therapy

The aim of this study is to establish the safe and effective ocular delivery system of therapeutic small interfering RNA (siRNA) in corneal neovascularization therapy. The major hurdle present in siRNA‐based corneal neovascularization (CNV) therapy is severe cytotoxicity caused by repetitive drug treatment. A reducible branched polyethylenimine (rBPEI)‐based nanoparticle (NP) system is utilized as a new siRNA carrier as a hope for CNV therapy. The thiolated BPEI is readily self‐crosslinked in mild conditions to make high molecular weight rBPEI thus allowing the creation of stable siRNA/rBPEI nanoparticles (siRNA‐rBPEI‐NPs). In the therapeutic region, the rBPEI polymeric matrix is effectively degraded into nontoxic LMW BPEI inside the reductive cytosol causing the rapid release of the encapsulated siRNA into the cytosol to carry out its function. The fluorescent‐labeled siRNA‐rBPEI‐NPs can release siRNA into the entire corneal region after subconjuctival injection into the eye of Sprague Dawley rats thus confirming the proof of concept of this system.

     

Enhanced Survivin siRNA Delivery Using Cationic Liposome Incorporating Fatty Acid-modified Polyethylenimine

We described a novel approach for survivin siRNA cellular delivery via a cationic liposome incorporating fatty acid-modified polyethylenimine. A linoleic acid derivative of branched polyethylenimine(PEI, M_w=25 kDa), PEI-LA, was synthesized and incorporated into the liposome. The properties of the liposome, cytotoxicity, cellular uptake of cancer cells for survivin siRNA, survivin protein downregulation levels were investigated. PEI-modified liposome showed a lower cytotoxicity and delivered survivin siRNA into HeLa cells and A549 cells efficiently compared with PEI-25kDa.     

Effect of Chain Topology of Polyethylenimine on Physisorption and Chemisorption of Carbon Dioxide

Polyethylenimine (PEI) is a promising candidate for CO₂ capture. In this work, the physisorption and chemisorption of CO₂ on various low‐molecular‐weight PEIs are investigated to identify the effect of chain architecture on sorption. The reliability of theoretical calculations are partially supported by our experimental measurements. Physisorption is calculated independently by the reference interaction‐site model integral equation theory; chemisorption is distinguished from the total sorption given by the quantum density functional theory. It is shown that, as the chain length increases, both chemisorption and physisorption drop off nonlinearly, but the decay amplitude of chemisorption is more apparent. Conversely, as the amine group approaches the central triamine unit of each oligomer, the sorption capacity decreases, affecting the sorption equilibrium in a complex way. This arises from the cooperative contribution of an increased steric effect and renormalized electronic distribution.     

Metal-Chelate Immobilization of Lipase onto Polyethylenimine Coated MCM-41 for Apple Flavor Synthesis

An enzyme immobilized on a mesoporous silica nanoparticle can serve as a multiple catalyst for the synthesis of industrially useful chemicals. In this work, MCM-41 nanoparticles were coated with polyethylenimine (MCM-41@PEI) and further modified by chelation of divalent metal ions (M = Co²⁺, Cu²⁺, or Pd²⁺) to produce metal-chelated silica nanoparticles (MCM-41@PEI-M). Thermomyces lanuginosa lipase (TLL) was immobilized onto MCM-41, MCM-41@PEI, and MCM-41@PEI-M by physical adsorption. Maximum immobilization yield and efficiency of 75 ± 3.5 and 65 ± 2.7% were obtained for MCM@PEI-Co, respectively. The highest biocatalytic activity at extremely acidic and basic pH (pH = 3 and 10) values were achieved for MCM-PEI-Co and MCM-PEI-Cu, respectively. Optimum enzymatic activity was observed for MCM-41@PEI-Co at 75 °C, while immobilized lipase on the Co-chelated support retained 70% of its initial activity after 14 days of storage at room temperature. Due to its efficient catalytic performance, MCM-41@PEI-Co was selected for the synthesis of ethyl valerate in the presence of valeric acid and ethanol. The enzymatic esterification yield for immobilized lipase onto MCM-41@PEI-Co was 60 and 53%, respectively, after 24 h of incubation in n-hexane and dimethyl sulfoxide media.

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Graphical Abstract Divalent metal chelated polyethylenimine coated MCM-41 (MCM-41@PEI-M) was used for immobilization of Thermomyces lanuginosa lipase catalyzing green apple flavor preparation

     

Polyethylenimine catalysts containing an isolated apolar binding site: Solovolysis of p-nitrophenyl esters

The preparation dodecane-block-poly[ethylenimine-graft-4(5)-methylimidazole] copolymers and related model compounds has been described and such polymers have been described and such polymers have been demonstrated to be efficient catalysts for the hydrolysis of activated phenyl esters in aqueous solutions. Polymeric catalysts that contain isolated apolar blocks exhibited enhanced catalytic activity for the hydrolysis of the p-nitrophenyl esters of acetate and butyrate compared with polymer model compounds. This rate enhancement was atributed to the apolar binding of substrate within the apolar polymer regime. Twenty-to 100-fold increases in the second-order rate constants were observed for the hydrolysis of the longer-chain p-nitrophenyl esters. This is indicative of a significant hydrophobic interaction. The contribution of the apolar block to the hydrophobic interaction was masked in the hydrolysis of the p-nitrophenyl caproate and p-nitrophenyl laurate substrates. In both instances the dominant contribution to the hydrophobic interactions was ascribed to a substrate-imidazole intermediate rather than the apolar block of the catalyst. The pH-rate profiles for the hydrolysis of p-nitrophenyl esters by the various catalysts indicated an absence of any cooperative interactions between imidazole residues or amine groups.     

基于低分子量聚乙烯亚胺和油酸的负电性基因载体

构建负电性的基因载体、发展基于低分子量聚乙烯亚胺(PEI)的基因载体对基因传递研究具有重要意义. 本文基于低分子量聚乙烯亚胺(2 kDa)和油酸构建了负电性的基因载体. 它通过混合聚乙烯亚胺(2 kDa)、dsDNA和油酸胶束而自发形成. 该基因载体在血清中很稳定,细胞毒性非常低,可包封80%以上DNA. 通过1,2-二硬脂酰-sn-甘油-3-磷酸乙醇胺-N-[甲氧基(聚乙二醇2000)]铵盐(DSPE-PEG)对其表面进行修饰,发现多达90%的基因可被细胞摄取.     

Electrochemical Sensing of Uric Acid Using Glassy Carbon Modified with Multiwall Carbon Nanotubes Dispersed in Polyethylenimine

This work reports the advantages of using glassy carbon electrodes modified with multiwall carbon nanotubes (MWCNT) dispersed in polyethylenimine (PEI). The presence of MWCNTs wrapped by PEI largely facilitated the strong adsorption of uric acid (UA) and allowed its highly sensitive and selective quantification even in the presence of high excess of ascorbic acid. The selected conditions for the electrochemical sensing were 5 s accumulation at ?0.300 V under stirring and quantification in a 0.050 M phosphate buffer solution pH 7.40 by differential pulse voltammetry adsorptive‐stripping after medium exchange. The platform allowed the successful application in the quantification of UA in urine.     

Polyethylenimine Functionalized Multi‐walled Carbon Nanotubes for Electrochemical Detection of Chromium(VI)

Multi‐walled carbon nanotubes (MWCNTs) functionalized with polyethylenimine (PEI) were synthesized and characterized by dispersibility, field‐emission scanning electron microscope (FE‐SEM), FT‐IR and thermogravimetric Analyzer (TGA). The glassy carbon electrodes modified by MWCNT‐PEI composite were used for sensitive and selective detection of chromium (VI). A linear response was obtained over a wide range of Cr(VI) concentrations (0.002–20 µmol L^?1) with the detection limit of 0.0006 µmol L^?1 (S/N=3). The proposed electrodes were used successfully for Cr(VI) detection in three real water samples.     

Pluronic/Polyethylenimine Shell Crosslinked Nanocapsules with Embedded Magnetite Nanocrystals for Magnetically Triggered Delivery of siRNA

Pluronic/polyethylenimine shell crosslinked nanocapsules with embedded magnetite nanocrystals (PPMCs) were developed for magnetically triggered delivery of siRNA. The positively charged PPMCs formed stable nanosized polyelectrolyte complexes via electrostatic interactions with negatively charged siRNA‐polyethylene glycol conjugate (siRNA‐s‐s‐PEG) that was linked via a cleavable disulfide linkage. PPMC/siRNA‐s‐s‐PEG polyelectrolyte complexes were efficiently taken up by cancer cells upon exposure to a magnet, thereby enhancing intracellular uptake and silencing effect of siRNA. The present study suggests that these novel nanomaterials could be potentially utilized for magnetically triggered delivery of various nucleic acid‐based therapeutic agents.

     

Composite Zn(II) Ferrocyanide/Polyethylenimine Cryogels for Point-of-Use Selective Removal of Cs-137 Radionuclides

The feasibility of several approaches to the fabrication of monolith composite cryogels containing transition-metal ferrocyanides for Cs⁺ ion uptake has been evaluated. Although in the series of investigated metal ion precursors (Cu(II), Zn(II), Ni(II), and Co(II)), in situ formation of the sorption active phase in polyethyleneimine (PEI) cryogel was feasible only in the case of Zn(II) ferrocyanide, this approach has shown significant advantages over the immobilization of ex situ synthesized ferrocyanide nanoparticles. Nanoparticles of the mixed ferrocyanide Zn_1.85K_0.33[Fe(CN)₆] formed in situ had an average size of 516 ± 146 nm and were homogeneously distributed in the monolith located at the polymer surface rather than embedded in the matrix. The Young modulus of the PEI cryogel increased after modification from 25 to 57 kPa, but composites maintained high permeability to the flow. Sorption of Cs⁺ ions has been investigated at superficial velocity up to 8 m/h. Steep breakthrough profiles and uptake efficiency of >99.5% until breakthrough point confirmed that a supermacroporous structure of the monolith composite assured good mass transfer, so that intraparticle diffusion was not the limiting stage of sorption kinetics. Application of the rate-constant distribution model (RCD model) to analyze the breakthrough curves of Cs⁺ sorption allowed the identification of two types of sorption sites with a difference in sorption rate constants of ~1 log unit. Most likely, sorption on “fast” sorption sites was governed by ion exchange between Cs⁺ ions in solution and K⁺ ions in the ferrocyanide lattice. Cs-137 radionuclide removal was investigated using the monolith composite columns of various geometries at superficial velocity up to the 6.6 m/h; specific gamma activity was reduced from 265 kBq/L to the background level, showing high potential of these materials for POU application.