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1.
Sci Total Environ ; 916: 170320, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38278278

RESUMEN

In environmental analysis, the detection of water-soluble synthetic polymers (WSSP) presents considerable challenges. Thus, a precise and reproducible analytical method was developed using continuous-flow off-line pyrolysis with gas chromatography/mass spectrometry (GC/MS) to simultaneously identify multiple water-soluble polymers from a single environmental sample. WSSP are widely used in multiple industries as hydrogels due to their hydrophilic character and potential biocompatibility. This adaptability of hydrogels is reflected in their ability to provide customized formulations for specific needs, such as in the development of personal care products, medicine, and pharmaceuticals. Specifically, polyvinylpyrrolidone (PVP), poly(N-vinylcaprolactam) (PNVCL), and polyethyleneimine (PEI) were targeted for analysis in wastewater, employing unique pyrolysis products for identification. These polymers require careful assessment in wastewater to evaluate potential environmental risks associated with their release. PVP and PNVCL were identified through two pyrolysis products, while six pyrolysis products were utilized for the identification of PEI. The validated method demonstrated very good linearity and reproducibility, with correlation coefficients ranging from 0.94 to 0.99 and relative standard deviation (RSD) values between 3 % and 36 % for the targeted compounds. The limit of quantification (LOQ) for the three polymers ranged from 1 to 10 µg L-1. Moreover, the average recovery rates for these polymers, determined from artificial water samples, were approx. 85 %. Utilizing the validated method, water samples from seven wastewater treatment plants in Germany were successfully analyzed, confirming the presence of these polymers at elevated concentrations in the µg L-1 range. Notably, untreated influent waters exhibited higher polymer levels compared to treated influents and effluents, underscoring their significant contribution to overall polymer content. The developed analytical method provides an efficient tool for the simultaneous identification and quantification of PVP, PNVCL, and PEI in wastewater samples. The results highlighted the prevalent presence of PVP, PNVCL, and PEI in the tested wastewater samples, indicating their significant abundance.

2.
J Chromatogr A ; 1706: 464268, 2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37544237

RESUMEN

Poly(ethyleneimine) (PEI) modified silica spheres were used to graft butyric acid and octanoic acid onto their surfaces, forming two stationary phases named Sil-PEI-BAD and Sil-PEI-CAD, respectively. Characterized methods including fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA) and thermogravimetric analysis (TGA) were utilized to determine the successful synthesis of these two stationary phase materials. The chromatographic performance of these two stationary phases was analyzed with hydrophobic and hydrophilic compounds as analytes. Compared with Sil-PEI-CAD column, Sil-PEI-BAD column was more effective in separating hydrophilic compounds including nucleosides, alkaloids and vitamins. Hydrophobic substances including polycyclic aromatic hydrocarbons (PAHs) and alkylbenzenes obtained excellent separation results on Sil-PEI-CAD column than Sil-PEI-BAD column. Additionally, according to the separation of phenols, Sil-PEI-CAD column can be used in HILIC/RPLC mixed-mode. The results showed that the properties and retention mechanisms of the prepared stationary phases depended on the length of the alkyl chains bonded on the silica surface.


Asunto(s)
Cromatografía de Fase Inversa , Nucleósidos , Cromatografía de Fase Inversa/métodos , Interacciones Hidrofóbicas e Hidrofílicas , Nucleósidos/análisis , Dióxido de Silicio/química , Espectroscopía Infrarroja por Transformada de Fourier
3.
Nanomaterials (Basel) ; 13(12)2023 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-37368295

RESUMEN

Graphene oxide (GO)-branched poly(ethyleneimine) (BPEI) hydrated mixtures were studied by means of fully atomistic molecular dynamics simulations to assess the effects of the size of polymers and the composition on the morphology of the complexes, the energetics of the systems and the dynamics of water and ions within composites. The presence of cationic polymers of both generations hindered the formation of stacked GO conformations, leading to a disordered porous structure. The smaller polymer was found to be more efficient at separating the GO flakes due to its more efficient packing. The variation in the relative content of the polymeric and the GO moieties provided indications for the existence of an optimal composition in which interaction between the two components was more favorable, implying more stable structures. The large number of hydrogen-bonding donors afforded by the branched molecules resulted in a preferential association with water and hindered its access to the surface of the GO flakes, particularly in polymer-rich systems. The mapping of water translational dynamics revealed the existence of populations with distinctly different mobilities, depending upon the state of their association. The average rate of water transport was found to depend sensitively on the mobility of the freely to move molecules, which was varied strongly with composition. The rate of ionic transport was found to be very limited below a threshold in terms of polymer content. Both, water diffusivity and ionic transport were enhanced in the systems with the larger branched polymers, particularly with a lower polymer content, due to the higher availability of free volume for the respective moieties. The detail afforded in the present work provides a new insight for the fabrication of BPEI/GO composites with a controlled microstructure, enhanced stability and adjustable water transport and ionic mobility.

4.
Polymers (Basel) ; 15(8)2023 Apr 19.
Artículo en Inglés | MEDLINE | ID: mdl-37112095

RESUMEN

The modification of inorganic surfaces with weak cationic polyelectrolytes by direct deposition through precipitation is a fast approach to generating composites with high numbers of functional groups. The core/shell composites present very good sorption capacity for heavy metal ions and negatively charged organic molecules from aqueous media. The sorbed amount of lead ions, used as a model for priority pollutants such as heavy metals, and diclofenac sodium salt, as an organic contaminant model for emerging pollutants, depended strongly on the organic content of the composite and less on the nature of contaminants, due to the different retention mechanisms (complexation vs. electrostatics/hydrophobics). Two experimental approaches were considered: (i) simultaneous adsorption of the two pollutants from a binary mixture and (ii) the sequential retention of each pollutant from monocomponent solutions. The simultaneous adsorption also considered process optimization by using the central composite design methodology to study the univariate effects of contact time and initial solution acidity with the purpose of enabling further practical applications in water/wastewater treatment. Sorbent regeneration after multiple sorption-desorption cycles was also investigated to assess its feasibility. Based on different non-linear regressions, the fitting of four isotherms (Langmuir, Freundlich, Hill, and Redlich-Peterson models) and three kinetics models (pseudo-first order (PFO), pseudo-second order (PSO), and two-compartment first order (TC)) has been carried out. The best agreement with experiments was found for the Langmuir isotherm and the PFO kinetic model. Silica/polyelectrolytes with a high number of functional groups may be considered efficient and versatile sorbents that can be used in wastewater treatment processes.

5.
Artículo en Inglés | MEDLINE | ID: mdl-36749691

RESUMEN

The demand to improve the chlorine resistance of polyamide (PA) membranes is escalated with greater amounts of chlorine-containing disinfectant being used in global water treatment during the COVID-19 pandemic. In this work, we designed thiophene-functionalized poly(ethyleneimine) (TPEI) materials first and grafted them onto a conventional PA membrane to develop novel nanofiltration membranes (PEI-M, TPEI-1-M, TPEI-2-M). These membranes have dual-functionalized selective surfaces covered by hydrophilic amino groups and electron-rich thiophene moieties, which endow these membranes with superior chlorine resistance and improved separation performance. The modified membranes increase the rejection of MgCl2 from 86.5% of the nascent PA membrane (PA-M) to higher than 93.0% without sacrificing the membrane water permeability. More stable separation performance is achieved with all of the as-prepared membranes than PA-M after exposure to a 2000 ppm sodium hypochlorite solution. TPEI-2-M outperforms other membranes after being treated in a chlorination intensity of 16,000 ppm·h with the smallest flux loss and the highest MgCl2 rejection. This is mainly ascribed to the highest amount of amino and thiophene moieties on the TPEI-2-M surface. This study provides an effective protocol for developing novel PA-based nanofiltration membranes while demonstrating its superiority over current technologies with exceptional separation performance and antichlorine ability.

6.
Carbohydr Polym ; 298: 120060, 2022 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-36241262

RESUMEN

Engineering high mass electroactive materials into hydrogel scaffolds remains an enormous challenge in achieving flexible energy storage devices. Herein, carboxymethyl cellulose (CMC) assisted high mass polyaniline (PANI) into an interpenetrating double-network polyethyleneimine/polyacrylamide (PEI/PAAM) hydrogel was developed. With the optimum mass loading of PANI at 9.04 mg/cm2, the all-in-gel CMC-PANI0.8M/PEI/PAAM supercapacitor can deliver a high specific capacitance of 679 mF/cm2, a maximum energy density of 58.82 µWh/cm2 at a power density of 14.69 mW/cm2, and an enhanced capacitance retention of 98 % after 5000 cycles. Such device can withstand severely bending/compressing deformations and operate properly at extreme temperatures (-30-70 °C). The CMC-PANI0.8M/PEI/PAAM hydrogel exhibits high sensitivity and stable electrical performance for wearable strain sensors. By connecting the supercapacitor with the strain sensor, the fabricated self-powered sensing system is capable of monitoring human activities accurately. Therefore, the multifunctional performance of the CMC-PANI0.8M/PEI/PAAM hydrogel is competent in the field of flexible electronics.


Asunto(s)
Carboximetilcelulosa de Sodio , Hidrogeles , Compuestos de Anilina , Humanos , Polietileneimina
7.
ACS Appl Mater Interfaces ; 14(36): 40992-41002, 2022 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-36047596

RESUMEN

The rapidly increasing atmospheric CO2 concentration has driven research into the development of cost- and energy-efficient materials and processes for the direct air capture of CO2 (DAC). Solid-supported amine materials can give high CO2 uptakes and acceptable sorption kinetics, but they are generally prepared in powder forms that are likely not practically deployable in large-scale operations due to significant pressure drops associated with packed-bed gas-solid contactors. To this end, the development of effective gas-solid contactors for CO2 capture technologies is important to allow processing high flow rates of gas with low-pressure drops and high mass transfer rates. In this study, we demonstrate new laminate-supported amine CO2 sorbents based on the impregnation of low-molecular-weight, branched poly(ethyleneimine) (PEI) into an expanded poly(tetrafluoroethylene) (ePTFE) sheet matrix containing embedded silica particles to form free-standing sheets amenable to incorporation into structured gas-solid contactors. The free-standing sheets are functionalized with PEI using a highly scalable wet impregnation method. This method allowed controllable PEI distribution and enough porosity retained inside the sheets to enable practical CO2 capacities ranging from 0.4 to 1.6 mmol CO2/gsorbent under dry conditions. Reversible CO2 capacities are achieved under both dry and humid temperature swing cycles, indicating promising material stability. The specific thermal energy requirement for the regeneration based on the measured CO2 and water capacities is 287 kJ/mol CO2, where the molar ratio of water to CO2 of 3.1 is achieved using hydrophobic materials. This is the lowest molar ratio among published DAC sorbents. A larger laminate module is tested under conditions closer to larger-scale operations (linear velocities 0.03, 0.05, and 0.1 m/sec) and demonstrates a stable capacity of 0.80 CO2/gsorbent over five cycles of CO2 adsorption and steam regeneration. The PEI-impregnated ePTFE/silica composite sorbent/contactors demonstrate promising DAC performance derived from the amine-filled silica particles contained in hydrophobic ePTFE domains to reduce water sorption and its concomitant regeneration energy penalty.

8.
ACS Appl Bio Mater ; 4(12): 8466-8476, 2021 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-35005922

RESUMEN

Opportunistic skin pathogens and their resistance to pre-existing therapeutics are a challenge to normal physiological wound healing processes. Consistent development of antimicrobial agents is required to overcome the complications raised by antimicrobial resistance. An effective alternative proposed in recent research includes the use of antimicrobial nanoparticles or nanobiopolymers. Unfortunately, metallic nanoparticles that have been proven as antimicrobial agents also possess a certain level of toxicity. In this work, we demonstrate the use of a cationic polymer, branched polyethyleneimine (B-PEI), that has been electrospun to obtain a scaffold/fiber (B-PEI NF) mat resulting in a large surface area-to-volume ratio. SEM analysis revealed that the average diameter of the obtained fibers is 240 nm. The formation of nanoscaffold modulates the controlled release of the polymer from the matrix resulting in long-term effects. The antimicrobial and antibiofilm activity of the B-PEI nanofiber (B-PEI NF) was evaluated against ESKAPE pathogens (Pseudomonas aeruginosa and Staphylococcus aureus) and also against Candida albicans. Dose-dependent inhibition was observed for microbial growth and biofilm for all three test organisms, the minimum inhibitory concentration required for inhibiting P. aeruginosa, S. aureus, and C. albicans is 33.125, 26.5, and 19.875 µM, respectively, in 2 mL of bacterial/fungal broth. Crystal violet and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assays showed significant reduction in biomass and cell viability of sessile cells, respectively, within the biofilm after treatment using B-PEI NFs. A B-PEI NF matrix promotes cell migration and wound healing processes by mimicking the extracellular matrix. In vitro wound healing studies showed a fivefold increase in cell migration and wound healing by B-PEI NFs (97% wound coverage in 17 h) when compared to B-PEI (15% wound coverage in 17 h). The in vitro wound healing assays confirmed the biocompatibility and better wound healing activity of B-PEI NF mats.


Asunto(s)
Antiinfecciosos , Nanofibras , Antibacterianos/química , Antiinfecciosos/farmacología , Candida albicans , Nanofibras/uso terapéutico , Polietileneimina/farmacología , Staphylococcus aureus , Cicatrización de Heridas
9.
ACS Appl Mater Interfaces ; 12(42): 47245-47255, 2020 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-32955238

RESUMEN

In this work, nitrogen-doped carbon quantum dots from poly(ethyleneimine) (PQDs) were synthesized by a low-cost and facile one-step hydrothermal method without other reagents. A quantum yield (QY) of up to 23.2% with maximum emission at 460 nm under an excitation wavelength of 340 nm was ascribed to the high nitrogen doping (20.59%). The PQDs selectively form a blue complex with Cu2+ accompanied by strong quenching of the fluorescence emission. Meanwhile, the PQD-Cu2+ complex exhibited selective fluorescence recovery and color disappearance on exposure to l-cysteine (Cys). The electron transfer from amino or oxygen groups on the PQDs to Cu2+ leads to fluorescence quenching, and a chromogenic reaction of the cuprammonium complex results in a color change. The strong affinity between Cys and Cu2+ causes the detachment of Cu2+ from the surface of PQDs, so the color of the solution disappears and the fluorescence of PQDs recovers. Under the optimized condition, the proposed sensor was applied to detect Cu2+ in the linear range of 0-280 µM. A detection limit of 4.75 µM is achieved using fluorescence spectroscopy and 4.74 µM by monitoring the absorbance variation at 272 nm. For Cys detection, the linear range of 0-800 µM with detection limits of 28.11 µM (fluorescence determination) and 19.74 µM (peak shift determination at 272 nm) was obtained. Meanwhile, the PQD-Cu2+ system exhibits distinguishable responses to other biothiols such as l-glutathione (GSH) and dl-homocysteine (Hcy). Based on the multimode signals, an "AND" logic gate was constructed successfully. Interestingly, besides Cu2+, Fe3+ can also quench the fluorescence of PQDs and the PQD-Fe3+ system exhibits superior selectivity for Cys detection. Most importantly, the proposed assay is not only simple, cheap, and stable but also suitable for detecting Cu2+ and Cys in some real samples.


Asunto(s)
Cobre/análisis , Cisteína/análisis , Contaminantes Radiactivos del Agua/análisis , Carbono/química , Colorimetría , Fluorescencia , Lagos , Nitrógeno/química , Tamaño de la Partícula , Polietileneimina/química , Puntos Cuánticos/química , Propiedades de Superficie , Agua
10.
J Microencapsul ; 37(7): 467-480, 2020 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-32627670

RESUMEN

AIMS: This study was conducted to evaluate block copolymers containing two different poly(ethyleneimine) (PEI) amounts, as new pH-sensitive micellar delivery systems for doxorubicin. METHODS: Micelles were prepared with block copolymers consisting of poly(2-ethyl-2-oxazoline)-co-poly(ethyleneimine) (PEtOx-co-PEI) and poly(ε-caprolactone) (PCL) as hydrophilic and hydrophobic blocks, respectively. Doxorubicin loading, micelle size, pH-dependent drug release, and in vitro cytotoxicity on MCF-7 cells were investigated. RESULTS: The average size of drug-loaded micelles was under 100 nm and drug loading was between 10.7% and 48.3% (w/w). pH-sensitive drug release was more pronounced (84.7% and 68.9% (w/w) of drug was released at pH 5.0 and pH 7.4, respectively) for the micelles of the copolymer with the lowest PEI amount. The cell viability of doxorubicin-loaded micelles which were prepared by the copolymer with the lowest PEI amount was 28-33% at 72 h. CONCLUSIONS: PEtOx-co-PEI-b-PCL micelles of this copolymer were found to be stable and effective pH-sensitive nano-sized carriers for doxorubicin delivery.


Asunto(s)
Antibióticos Antineoplásicos/administración & dosificación , Preparaciones de Acción Retardada/química , Doxorrubicina/administración & dosificación , Poliaminas/química , Polietileneimina/química , Antibióticos Antineoplásicos/farmacología , Neoplasias de la Mama/tratamiento farmacológico , Doxorrubicina/farmacología , Portadores de Fármacos/química , Femenino , Humanos , Concentración de Iones de Hidrógeno , Células MCF-7 , Micelas
11.
ACS Appl Mater Interfaces ; 12(33): 37585-37596, 2020 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-32697568

RESUMEN

Composite solid surfaces with high content of functional groups (FGs) are useful materials in different types of applications requiring stimuli-responsive "hard/soft" architectures, their improved properties rising from the combination of organic-inorganic parts. Among different types of weak polyelectrolytes, poly(ethyleneimine) (PEI) is of great interest in the construction of composite systems with thin layer-by-layer (LbL) organic films due to the large number of amino groups per unit mass of polymer. Herein, the spherical silica microparticles were modified with linear (L) or branched (B) PEI chains using LbL deposition of a copper complex (PEIL-Cu2+ or PEIB-Cu2+) and poly(acrylic acid) (PAA), glutaraldehyde selective cross-linking, followed by copper and PAA extraction from the multilayer. The newly formed silica/(PEIL)10 and silica/(PEIB)10 composites were used in batch and column sorption/desorption experiments of four heavy metal ions (Cu2+, Ni2+, Co2+, and Cd2+). In noncompetitive conditions ([FG]/Σ[M2+] > 9), all heavy metal ions were retained on composites, demonstrating the potential application of the prepared functional microparticles in surface water treatment. However, in competitive conditions ([FG]/Σ[M2+] < 9), only Cu2+ is sorbed in high amount (∼2.5 mmol·g-1 PEI) on composites, with simultaneous displacement of already sorbed ions, demonstrating the solid-phase extraction and chromatographic properties of the synthesized silica/(PEIL)n and silica/(PEIB)n composites.

12.
Methods Mol Biol ; 2118: 99-110, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32152973

RESUMEN

Skewing the macrophage polarity to achieve a favorable phenotype is a recently investigated therapeutic strategy in multiple disease/dysfunctional conditions such as inflammation, tumors, autoimmune disorders, and tissue repairs. However, delivering the therapeutic agent specifically to the macrophages has been a challenge in this field. Here, we describe the synthesis of hyaluronic acid (HA)-based nanoparticles for targeting CD44 receptors on the macrophages. The HA backbone is modified with cationic polyethyleneimine (PEI) for efficient encapsulation of microRNA into the self-assembling nanoparticles for targeted delivery to macrophages.


Asunto(s)
Ácido Hialurónico/química , Macrófagos/citología , MicroARNs/genética , Transfección/métodos , Animales , Línea Celular , Receptores de Hialuranos/genética , Receptores de Hialuranos/metabolismo , Macrófagos/metabolismo , Ratones , MicroARNs/química , Nanopartículas , Polietileneimina/química
13.
ACS Appl Mater Interfaces ; 12(9): 10527-10534, 2020 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-32048829

RESUMEN

A semitransparent flexible metal halide perovskite (MHP) solar cells were demonstrated by reproducible dry stamping transfer of a poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS, PH1000) transparent flexible top electrode onto poly(ethylene terephthalate) (PET)/indium tin oxide (ITO)/PEDOT:PSS (AI4083)/MHP/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The reproducible transfer of the PEDOT:PSS top electrode was enabled by the modification of PEDOT:PSS with poly(ethylene imine) (PEI)/2-methoxyethanol (2-MEA) solution. In addition, the PEI/2-MEA modification to PEDOT:PSS resulted in improved conductivity and reduced work function of the top electrode. Therefore, we could fabricate highly efficient flexible semitransparent MHP solar cells with >13% (active area = 1 cm2) power conversion efficiency.

14.
J Chromatogr A ; 1611: 460586, 2020 Jan 25.
Artículo en Inglés | MEDLINE | ID: mdl-31606157

RESUMEN

It has been known that anion exchangers prepared by grafting poly(ethyleneimine) (PEI) onto Sepharose FF (PEI-Sepharose) at ionic capacities (IC) over 600 mmol/L show both high protein adsorption capacity and uptake kinetics, and charge reversal of PEI-Sepharose by modification with succinic anhydride can produce protein cation exchangers of high capacity and uptake rate. Previously, a Charge Reversal-then-Reduction procedure (route A) was studied for preparation of cation exchangers of different IC values from PEI-Sepharose. In this work, we proposed a new route, that is, Charge Reduction-then-Reversal route (route B), to develop cation exchangers of different IC values from PEI-Sepharose FF with an IC of 700 mmol/L (FF-PEI-L700) as the starting resin. The two kinds of cation exchangers (route A, PEI-L700-CRn; route B, PEI-Rm-Cn) are compared for lysozyme (Lys) adsorption and chromatography. The two modification routes result in the difference in the ligand structures that significantly affect protein adsorption equilibrium and kinetics. Route A introduces long electroneutral groups that hinder protein adsorption and reduce equilibrium capacity. Moreover, charge reversal by reaction with succinic anhydride could cause diamide formation, which reduces remaining carboxyl groups or the IC. In the charge-reduced FF-PEI-Rm resins of the lowest IC (394 mmol/L) prepared in route B, the diamide formation was little due to the lack of primary and secondary amine groups, so its charge reversal makes a higher-IC cation exchanger. This makes PEI-Rm-Cn show a higher IC (589 mmol/L) than PEI-L700-CRn (463 mmol/L) in which De/D0 jumps about four times. The differences in the adsorption equilibrium and kinetics make the two kinds of resins behave distinctly in dynamic adsorption and chromatography. Namely, PEI-Rm-Cn resins display obviously higher dynamic binding capacities than PEI-L700-CRn resins in the IC range studied. For instance, the DBC (at 10% breakthrough) of PEI-R590-C680 (192 mg/mL) is 33% higher than that of PEI-L700-CR680 (144 mg/mL). This is proved by the purification of Lys from chicken egg white solution, in which the PEI-R590-C680 column purified Lys with a recovery yield 14% higher than the PEI-L700-CR680 column. This research thus demonstrated that Charge Reduction-then-Reversal route is superior over Charge Reversal-then-Reduction route in fabricating a high-capacity cation exchanger from PEI-Sepharose.


Asunto(s)
Resinas de Intercambio de Catión/química , Cromatografía por Intercambio Iónico/métodos , Muramidasa/aislamiento & purificación , Polietileneimina/química , Sefarosa/química , Adsorción , Cromatografía por Intercambio Iónico/instrumentación , Cinética , Ligandos , Muramidasa/química
15.
Molecules ; 24(11)2019 Jun 06.
Artículo en Inglés | MEDLINE | ID: mdl-31174307

RESUMEN

The deposition and nanostructure of polyelectrolyte (PEL) multilayers (PEMs) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA) onto silicon substrates was studied in terms of the dependence of pH and the PEL concentration (cPEL) in the individual adsorption steps z. Both a commercial automatic dipping device and a homebuilt automatic stream coating device (flow cell) were used. Gravimetry, SFM, transmission (TRANS) and in situ attenuated total reflection (ATR) FTIR spectroscopy were used for the quantitative determination of the adsorbed amount, thickness, chemical composition and morphology of deposited PEMs, respectively. Firstly, the combination of pH = 10 for PEI and pH = 4 for PAA, where both PEL were predominantly in the neutral state, resulted in an extraordinarily high PEM deposition, while pH combinations, where one PEL component was charged, resulted in a significantly lower PEM deposition. This was attributed to both PEL conformation effects and acid/base interactions between basic PEI and acidic PAA. Secondly, for that pH combination an exponential relationship between PEM thickness and adsorption step z was found. Thirdly, based on the results of three independent methods, the course of the deposited amount of a PEM-10 (z = 10) versus cPEL in the range 0.001 to 0.015 M at pH = 10/4 was non-monotonous showing a pronounced maximum at cPEL = 0.005 M. Analogously, for cPEL = 0.005 M a maximum of roughness and structure size was found. Fourthly, related to that finding, in situ ATR-FTIR measurements gave evidence for the release of outermost located PEI upon PAA immersion (even step) and of outermost PAA upon PEI immersion (odd step) under formation of PEL complexes in solution. These studies help us to prepare PEL-based films with a defined thickness and morphology for interaction with biofluids in the biomedical and food fields.


Asunto(s)
Resinas Acrílicas/química , Nanoestructuras/química , Polielectrolitos/química , Polietileneimina/química , Conformación Molecular , Nanoestructuras/ultraestructura , Espectroscopía Infrarroja por Transformada de Fourier , Propiedades de Superficie
16.
Int J Pharm ; 554: 420-428, 2019 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-29933061

RESUMEN

UV and NIR-responsive monoolein cubic phase was prepared by including poly(ethyleneimine) (PEI)/cinnamic acid (CA) conjugate and gold nanoparticle (GNP) within its structure. UV irradiation elevated significantly the release % of Auramine O loaded in cubic phase containing PEI/CA, possibly because of the trans-to-cis isomerization of CA. NIR irradiation also increased significantly the release % of FITC-dextran loaded in cubic phase containing PEI/CA. The release % of the dye loaded in cubic phase containing PEI/CA and GNP was elevated more markedly by NIR irradiation, possibly due to the phase transition of cubic phase and the disassembling of PEI/CA assembly.


Asunto(s)
Cinamatos/química , Glicéridos/química , Nanopartículas del Metal , Polietileneimina/química , Benzofenoneido/administración & dosificación , Benzofenoneido/química , Dextranos/administración & dosificación , Dextranos/química , Liberación de Fármacos , Fluoresceína-5-Isotiocianato/administración & dosificación , Fluoresceína-5-Isotiocianato/análogos & derivados , Fluoresceína-5-Isotiocianato/química , Colorantes Fluorescentes/administración & dosificación , Oro , Rayos Infrarrojos , Rayos Ultravioleta
17.
Bioimpacts ; 8(4): 241-252, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-30397579

RESUMEN

Introduction: Sorafenib (SFB) is an FDA-approved chemotherapeutic agent with a high partition coefficient (log P = 4.34) for monotherapy of hepatocellular carcinoma (HCC). The oral bioavailability is low and variable, so it was aimed to study the application of the polymeric nanoassembly of cholesterol conjugates of branched polyethyleneimine (PEI) for micellar solubilization of SFB and to investigate the impact of the polymer PEGylation on the physicochemical and cellular characteristics of the lipopolymeric dispersions. Methods: Successful synthesis of cholesterol-PEI lipopolymers, either native or PEGylated, was confirmed by FTIR, 1H-NMR, pyrene assay methods. The nanoassemblies were also characterized in terms of morphology, particle size distribution and zeta-potential by TEM and dynamic light scattering (DLS). The SFB loading was optimized using general factorial design. Finally, the effect of particle characteristics on cellular uptake and specific cytotoxicity was investigated by flow cytometry and MTT assay in HepG2 cells. Results: Transmission electron microscopy (TEM) showed that PEGylation of the lipopolymers reduces the size and changes the morphology of the nanoassembly from rod-like to spherical shape. However, PEGylation of the lipopolymer increased critical micelle concentration (CMC) and reduced the drug loading. Moreover, the particle shape changes from large rods to small spheres promoted the cellular uptake and SFB-related cytotoxicity. Conclusion: The combinatory effects of enhanced cellular uptake and reduced general cytotoxicity can present PEGylated PEI-cholesterol conjugates as a potential carrier for delivery of poorly soluble chemotherapeutic agents such as SFB in HCC that certainly requires further investigations in vitro and in vivo.

18.
Anal Chim Acta ; 1042: 165-173, 2018 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-30428983

RESUMEN

A poly(ethyleneimine) embedded phenyl mixed-mode stationary phase was prepared through epoxide ring opening reaction. Elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) were used to characterize whether functional groups have been modified on the surface of silica successfully. The researches of chromatographic performance for designed column were divided to four parts. The retention behavior under reversed-phase mode was studied using polycyclic aromatic hydrocarbons (PAHs), positional isomers and alkylbenzenes. The retention characteristic under hydrophilic interaction mode was studied by nucleosides, nucleobases and flavonoids. The chromatographic performance of anion exchange mode was evaluated by benzoic acids and phenols. Due to a high content of amino and phenyl groups on the stationary phase, aromatic amines were chosen for the evaluation of retention mechanisms of benzene ring attraction and amino repulsion. The investigations about effects of mobile phase constitution and pH on retention demonstrated the mixed-mode retention mechanisms of the column. Furthermore, due to amino selectivity of the column, a method for the rapid separation and determination of phenylenediamines in hair dye was established. And both linear correlation coefficients of p-diaminobenzene and m-diaminobenzene in concentration range from 0.1 to 30 µg mL-1 were over 0.999. In conclude, the prepared mixed-mode stationary phase could realize various separation modes by adjusting chromatographic conditions, and it had the potential for the rapid separation and determination of aniline compounds in various complex samples.

19.
Biomolecules ; 8(3)2018 08 20.
Artículo en Inglés | MEDLINE | ID: mdl-30127319

RESUMEN

Donald A. Tomalia is one of the pioneers in the field of dendrimers, who is still active at the age of 80 years-old. The present contribution is a journey through his scientific contributions from the early beginning until his discovery of the poly(amidoamine), (PAMAM)-dendrimers.


Asunto(s)
Química/historia , Dendrímeros/química , Historia del Siglo XX , Historia del Siglo XXI
20.
Materials (Basel) ; 11(3)2018 Mar 09.
Artículo en Inglés | MEDLINE | ID: mdl-29522480

RESUMEN

Two different commercial hyperbranched poly(ethyleneimine)s (HBPEI), with molecular weights (MW) of 800 and 25,000 g/mol, and denoted as PEI800 and PEI25000, respectively, as well as the mixtures with a Diglycidyl Ether of Bisphenol-A (DGEBA) epoxy resin, have been studied using thermal analysis techniques (DSC, TGA), dielectric relaxation spectroscopy (DRS), and dynamic mechanical analysis (DMA). Only a single glass transition is observed in these mixtures by DSC. DRS of the HBPEIs shows three dipolar relaxations: γ, ß, and α. The average activation energy for the γ-relaxation is similar for all HBPEIs and is associated with the motion of the terminal groups. The ß-relaxation has the same average activation energy for both PEI800 and PEI25000; this relaxation is attributed to the mobility of the branches. The α-relaxation peak for all the HBPEIs is an asymmetric peak with a shoulder on the high temperature side. This shoulder suggests the existence of ionic charge trapped in the PEI. For the mixtures, the γ- and ß-relaxations follow the behaviour of the epoxy resin alone, indicating that the epoxy resin dominates the molecular mobility. The α-relaxation by DRS is observed only as a shoulder, as a consequence of an overlap with conductivity effects, whereas by DMA, it is a clear peak.

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