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1.
Int J Biol Macromol ; 273(Pt 2): 133173, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38880441

RESUMO

Sodium alginate (SA) and chito oligosaccharide (COS) are widely used food additives in the food industry, and exploring their interaction to form polyelectrolyte complexes (PECs) may provide insights into food development. In the present study, the effects of viscosity-average molecular weight (Mv) and relative amounts of SA on the formation of sodium alginate/chito oligosaccharide polyelectrolyte (SCP) complexes were investigated. The results showed that the electrostatic interaction between -COOH and -NH2 and the hydrogen bonding between OH, were attributed to the formation of the SCP complexes. Then the formation and properties of SCP complexes were greatly dependent on the Mv and the relative amount of SA. SA with Mv of ≥2.16 × 106 Da could form spherical SCP complexes, while the SA/COS ratio (w/w) ≥ 0.8 was not conducive to the formation of SCP complexes. Moreover, the SCP complexes were more stable in the gastric environment than in the intestinal condition. In addition, 1.73 × 107 Da was the optimal Mv of SA for SCP complexes formation. This study contributed to a comprehensive understanding of the interaction between SA and COS, and shed light on the potential application of SA and COS formulation to develop new food products.


Assuntos
Alginatos , Quitina , Polieletrólitos , Polieletrólitos/síntese química , Alginatos/química , Quitina/química
2.
AAPS PharmSciTech ; 22(5): 195, 2021 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-34184117

RESUMO

Microbial keratitis (MK) is a vision-threatening disease and the fourth leading cause of blindness worldwide. In this work, we aim to develop moxifloxacin (MXN)-loaded chitosan-based cationic mucoadhesive polyelectrolyte nanocapsules (PENs) for the effective treatment of MK. PENs were formulated by polyelectrolyte complex coacervation method and characterized for their particle size, surface charge, morphology, mucoadhesive property, in-vitro and ex-vivo release, ocular tolerance, and antimicrobial efficacy studies. The pharmacodynamic study was conducted on rabbit eye model of induced keratitis and it is compared with marketed formulation (MF). Developed PENs showed the size range from 230.7 ± 0.64 to 249.0 ± 0.49 nm and positive surface charge, spherical shape along with appropriate physico-chemical parameters. Both in-vitro and ex-vivo examination concludes that PENs having more efficiency in sustained release of MXN compared to MF. Ocular irritation studies demonstrated that no corneal damage or ocular irritation. The in-vivo study proved that the anti-bacterial efficacy of PENs was improved when compared with MF. These results suggested that PENs are a feasible choice for MK therapy because of their ability to enhance ocular retention of loaded MXN through interaction with the corneal surface of the mucous membrane.


Assuntos
Desenvolvimento de Medicamentos/métodos , Ceratite/tratamento farmacológico , Moxifloxacina/síntese química , Nanocápsulas/química , Polieletrólitos/síntese química , Animais , Antibacterianos/administração & dosagem , Antibacterianos/síntese química , Antibacterianos/farmacocinética , Embrião de Galinha , Córnea/efeitos dos fármacos , Córnea/metabolismo , Córnea/microbiologia , Cabras , Ceratite/metabolismo , Ceratite/microbiologia , Moxifloxacina/administração & dosagem , Moxifloxacina/farmacocinética , Nanocápsulas/administração & dosagem , Polieletrólitos/administração & dosagem , Polieletrólitos/farmacocinética , Coelhos
3.
Angew Chem Int Ed Engl ; 60(35): 19222-19231, 2021 08 23.
Artigo em Inglês | MEDLINE | ID: mdl-33991002

RESUMO

We reported an efficient multicomponent polyannulation for in situ generation of heteroaromatic hyperbranched polyelectrolytes by using readily accessible internal diynes and low-cost, commercially available arylnitriles, NaSbF6 , and H2 O/AcOH. The polymers were obtained in excellent yields (up to 99 %) with extraordinary high molecular weights (Mw up to 1.011×106 ) and low polydispersity indices. The resulting polymers showed good processibility and high quantum yields with tunable emission in the solid state, making them ideal materials for highly ordered fluorescent photopatterning. These hyperbranched polyelectrolytes also possessed strong ability to generate reactive oxygen species, which allowed their applications in efficient bacterial killing and customizable photodynamic patterning of living organisms in a simple and cost-effective way.


Assuntos
Antibacterianos/farmacologia , Bactérias/efeitos dos fármacos , Compostos Heterocíclicos/farmacologia , Hidrocarbonetos Aromáticos/farmacologia , Polieletrólitos/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Bactérias/metabolismo , Compostos Heterocíclicos/química , Hidrocarbonetos Aromáticos/química , Estrutura Molecular , Peso Molecular , Polieletrólitos/síntese química , Polieletrólitos/química , Espécies Reativas de Oxigênio/metabolismo
4.
ChemMedChem ; 16(17): 2727-2730, 2021 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-33908695

RESUMO

Polyoxometalates (POMs), molecular metal oxide anions, are inorganic clusters with promising antiviral activity. Herein we report increased anti-HIV-1 activity of a POM when electrostatically combined with organic counter-cations. To this end, Keggin-type cerium tungstate POMs have been combined with organic methyl-caffeinium (Caf) cations, and their cytotoxicity, antiviral activity and mode of action have been studied. The novel compound, Caf4 K[ß2 -CeSiW11 O39 ]×H2 O, exhibits sub-nanomolar antiviral activity and inhibits HIV-1 infectivity by acting on an early step of the viral infection cycle. This work demonstrates that combination of POM anions and organic bioactive cations can be a powerful new strategy to increase antiviral activity of these inorganic compounds.


Assuntos
Ânions/farmacologia , Fármacos Anti-HIV/farmacologia , Cafeína/farmacologia , HIV/efeitos dos fármacos , Polieletrólitos/farmacologia , Ânions/síntese química , Ânions/química , Fármacos Anti-HIV/síntese química , Fármacos Anti-HIV/química , Cafeína/química , Relação Dose-Resposta a Droga , Testes de Sensibilidade Microbiana , Polieletrólitos/síntese química , Polieletrólitos/química
5.
Carbohydr Res ; 499: 108194, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33234262

RESUMO

Strategies for incorporating water-insoluble photosensitisers (PS) in drug delivery systems have been extensively studied. In this work, we evaluate the formation, characterisation, drug sorption studies, and cytotoxicity of chitosan (CHT)/chondroitin sulphate (CS) polyelectrolyte complexes (PECs) coated with polystyrene-block-poly(acrylic acid) (PS-b-PAA) nanoparticles (NPs) loaded with chloroaluminum phthalocyanine (AlClPc). The PECs were characterised by infrared spectroscopy (FTIR), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The PS-b-PAA NPs on the PEC surface was confirmed by scanning electron microscopy (SEM). Additionally, optical images distinguished the PEC structures containing PS-b-PAA or PS-b-PAA/AlClPc from the unloaded PEC. Kinetic and equilibrium studies investigate the sorption capacity of the PEC/PS-b-PAA toward AlClPc. The encapsulation efficiency reached 95% at 190 µg mL-1 AlClPc after only 15 min. The Brunauer-Emmett-Teller (BET) isotherm and pseudo-second-order kinetic fitted well to the experimental data. The PS-b-PAA NPs on the PEC surfaces increase the AlClPc bioavailability and the PEC structure stabilizes the PS-b-PAA/AlClPc nanostructures. The materials were cytocompatible upon healthy VERO (kidney epithelial cells), and cytotoxic against colorectal cancerous cells (HT-29 cells). For the first time, we associate PS-b-PAA/AlClPc with a hydrophilic and cytocompatible polysaccharide matrix. We suggest the use of these materials in strategies to treat cancer by using photodynamic therapy.


Assuntos
Antineoplásicos/farmacologia , Materiais Biocompatíveis/farmacologia , Neoplasias Colorretais/tratamento farmacológico , Polieletrólitos/farmacologia , Polissacarídeos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Configuração de Carboidratos , Linhagem Celular , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Neoplasias Colorretais/patologia , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Tamanho da Partícula , Polieletrólitos/síntese química , Polieletrólitos/química , Polissacarídeos/síntese química , Polissacarídeos/química
6.
ACS Appl Mater Interfaces ; 12(44): 49346-49361, 2020 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-33089982

RESUMO

Cationic, π-conjugated oligo-/polyelectrolytes (CCOEs/CCPEs) have shown great potential as antimicrobial materials to fight against antibiotic resistance. In this work, we treated wild-type and ampicillin-resistant (amp-resistant) Escherichia coli (E. coli) with a promising cationic, π-conjugated polyelectrolyte (P1) with a phenylene-based backbone and investigated the resulting morphological, mechanical, and compositional changes of the outer membrane of bacteria in great detail. The cationic quaternary amine groups of P1 led to electrostatic interactions with negatively charged moieties within the outer membrane of bacteria. Using atomic force microscopy (AFM), high-resolution transmission electron microscopy (TEM), we showed that due to this treatment, the bacterial outer membrane became rougher, decreased in stiffness/elastic modulus (AFM nanoindentation), formed blebs, and released vesicles near the cells. These evidences, in addition to increased staining of the P1-treated cell membrane by lipophilic dye Nile Red (confocal laser scanning microscopy (CLSM)), suggested loosening/disruption of packing of the outer cell envelope and release and exposure of lipid-based components. Lipidomics and fatty acid analysis confirmed a significant loss of phosphate-based outer membrane lipids and fatty acids, some of which are critically needed to maintain cell wall integrity and mechanical strength. Lipidomics and UV-vis analysis also confirmed that the extracellular vesicles released upon treatment (AFM) are composed of lipids and cationic P1. Such surface alterations (vesicle/bleb formation) and release of lipids/fatty acids upon treatment were effective enough to inhibit further growth of E. coli cells without completely disintegrating the cells and have been known as a defense mechanism of the cells against cationic antimicrobial agents.


Assuntos
Antibacterianos/farmacologia , Módulo de Elasticidade/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , Lipídeos/química , Polieletrólitos/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Cátions/síntese química , Cátions/química , Cátions/farmacologia , Escherichia coli/citologia , Ácidos Graxos/análise , Lipidômica , Testes de Sensibilidade Microbiana , Microscopia de Força Atômica , Estrutura Molecular , Tamanho da Partícula , Polieletrólitos/síntese química , Polieletrólitos/química , Propriedades de Superfície
7.
Dalton Trans ; 49(32): 11226-11237, 2020 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-32756631

RESUMO

There are still some key problems in the process of the flame retardant treatment of poly vinyl alcohol (PVA): poor compatibility, deteriorating mechanical properties and potential toxicity to human health and environment. To solve these issues, a green and eco-friendly bio-based polyelectrolyte complex (PEC) formed by chitosan and phytic acid was designed to enhance the flame retardant and mechanical properties of PVA by a facile ultrasonic-assisted solution blending method. Moreover, the mechanical and flame retardant properties could be regulated by varying the ratio of each component in the PEC. Thermogravimetric analysis (TGA) indicated that after the introduction of PEC, PVA/PEC composites maintained better thermal stability and char formation ability. Besides, when the addition of PEC reached 20 wt%, the limited oxygen index (LOI) value of cured PVA increased from 18% to 25.9%, 30.8% and 35.6% for PVA/20(2 : 1) PEC, PVA/20(1 : 2) PEC and PVA/20(1 : 8) PEC, respectively. Moreover, UL-94 V-0 rating was achieved except for the PVA/20(2 : 1) PEC. Compared with pure PVA, the peak heat release rate (pHRR) and the total heat release (THR) of PVA/20(1 : 8) PEC demonstrated a sharp decrease by 69.9% and 45.5%, respectively, in the microscale combustion calorimeter measurements (MCC). These results indicate that PEC can endow PVA with excellent flame retardancy. Furthermore, the microscopic investigations on char residues of all samples by scanning electron microscopy, Fourier transform infrared spectra and Raman spectroscopy revealed the possible flame retardant mechanisms in condensed and gaseous phases. In addition, PVA/PEC composites have better mechanical properties owing to their harder backbones of chitosan, formation of phosphonate bonds and the PVA molecular chain movement blocked by PEC. As a result, the facile processing technology and eco-friendly flame retardants are expected to be applied in practice.


Assuntos
Quitosana/química , Ácido Fítico/química , Polieletrólitos/síntese química , Álcool de Polivinil/síntese química , Calorimetria , Estrutura Molecular , Tamanho da Partícula , Polieletrólitos/química , Álcool de Polivinil/química , Espectroscopia de Infravermelho com Transformada de Fourier
8.
J Colloid Interface Sci ; 575: 286-297, 2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32380320

RESUMO

Antimicrobial surfaces are important in medical, clinical, and industrial applications, where bacterial infection and biofouling may constitute a serious threat to human health. Conventional approaches against bacteria involve coating the surface with antibiotics, cytotoxic polymers, or metal particles. However, these types of functionalization have a limited lifetime and pose concerns in terms of leaching and degradation of the coating. Thus, there is a great interest in developing long-lasting and non-leaching bactericidal surfaces. To obtain a bactericidal surface, we combine micro and nanoscale patterning of borosilicate glass surfaces by ultrashort pulsed laser irradiation and a non-leaching layer-by-layer polyelectrolyte modification of the surface. The combination of surface structure and surface charge results in an enhanced bactericidal effect against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria. The laser patterning and the layer-by-layer modification are environmentally friendly processes that are applicable to a wide variety of materials, which makes this method uniquely suited for fundamental studies of bacteria-surface interactions and paves the way for its applications in a variety of fields, such as in hygiene products and medical devices.


Assuntos
Antibacterianos/farmacologia , Materiais Revestidos Biocompatíveis/farmacologia , Escherichia coli/efeitos dos fármacos , Lasers , Polieletrólitos/farmacologia , Staphylococcus aureus/efeitos dos fármacos , Antibacterianos/síntese química , Antibacterianos/química , Materiais Revestidos Biocompatíveis/síntese química , Materiais Revestidos Biocompatíveis/química , Testes de Sensibilidade Microbiana , Tamanho da Partícula , Polieletrólitos/síntese química , Polieletrólitos/química , Propriedades de Superfície , Fatores de Tempo
9.
J Colloid Interface Sci ; 567: 316-327, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32065906

RESUMO

HYPOTHESIS: Flocculation performance using polyelectrolytes is influenced by critical design parameters including molecular weight, amount and sign of the ionic charge, and polymer architecture. It is expected that systematic variation of these characteristics will impact not only flocculation efficiency (FE) achieved but that charge density and architecture, specifically, can alter the flocculation mechanism. Therefore, it should be possible to tune these design parameters for a desired flocculation application. EXPERIMENTS: Cationic-neutral and polyampholytic copolymers, exhibiting a range of molecular weights (103-106 g/mol), varying charge levels (0-100% cationic, neutral and anionic), and random or block copolymer architecture, were applied to dilute suspensions of silica microparticles (control) and Chlorella vulgaris. FE and zeta potential values were determined over a range of flocculant doses to evaluate effectiveness and mechanism achieved. FINDINGS: These different classes of copolymers provide specific benefits for flocculation, with many achieving >95% flocculation. Block copolymer flocculants exhibit a proposed, dominant bridging mechanism, therefore reducing flocculant dosage required for effective flocculation when compared to analogous random copolymer flocculants. Polyampholytic copolymers applied to C. vulgaris generally exhibited a bridging mechanism and increased FE compared to equivalent cationic-neutral copolymers, indicating a benefit of the anionic component on a more, complex, diversely charged suspension.


Assuntos
Chlorella vulgaris/química , Polieletrólitos/síntese química , Polímeros/síntese química , Dióxido de Silício/síntese química , Chlorella vulgaris/crescimento & desenvolvimento , Floculação , Tamanho da Partícula , Polieletrólitos/química , Polímeros/química , Dióxido de Silício/química , Propriedades de Superfície
10.
Carbohydr Polym ; 234: 115920, 2020 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-32070539

RESUMO

Vitamin C (VC) is an indispensable nutrient for human health. However, poor chemical stability in gastric environment restricts its full assimilation by intestine. It is important to construct a safe carrier that can protect VC from the gastric fluid and sustainably release it in intestine. Herein, we designed a novel polyelectrolyte complex (PEC) hydrogel through self-assembly of salecan and chitosan. PEC structure formed by electrostatic interactions was confirmed by FT-IR, XRD, XPS and TGA. Their swelling, morphology, rheology, cytocompatibility and biodegradation were well investigated. In particular, VC released in a controlled and pH-dependent manner. The release amount in simulated intestinal fluid (SIF) was significantly higher than simulated gastric fluid (SGF), and can be maintained at high level in blood after 6 h. Release mechanism agreed well with Ritger-Peppas model. The purpose of this study was to develop a smart nutrient delivery platform for targeted release of VC in intestinal condition.


Assuntos
Ácido Ascórbico/química , Ácido Ascórbico/metabolismo , Quitosana/química , Hidrogéis/química , Polieletrólitos/química , beta-Glucanas/química , Células 3T3-L1 , Animais , Sobrevivência Celular , Células Cultivadas , Preparações de Ação Retardada , Liberação Controlada de Fármacos , Hidrogéis/síntese química , Cinética , Masculino , Camundongos , Estrutura Molecular , Tamanho da Partícula , Polieletrólitos/síntese química , Reologia , Propriedades de Superfície
11.
Molecules ; 25(2)2020 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-31941140

RESUMO

Polymer-based CO2 selective membranes offer an energy efficient method to separate CO2 from flue gas. `Top-down' polyelectrolytes represent a particularly interesting class of polymer materials based on their vast synthetic flexibility, tuneable interaction with gas molecules, ease of processability into thin films, and commercial availability of precursors. Recent developments in their synthesis and processing are reviewed herein. The four main groups of post-synthetically modified polyelectrolytes discern ionised neutral polymers, cation and anion functionalised polymers, and methacrylate-derived polyelectrolytes. These polyelectrolytes differentiate according to the origin and chemical structure of the precursor polymer. Polyelectrolytes are mostly processed into thin-film composite (TFC) membranes using physical and chemical layer deposition techniques such as solvent-casting, Langmuir-Blodgett, Layer-by-Layer, and chemical grafting. While solvent-casting allows manufacturing commercially competitive TFC membranes, other methods should still mature to become cost-efficient for large-scale application. Many post-synthetically modified polyelectrolytes exhibit outstanding selectivity for CO2 and some overcome the Robeson plot for CO2/N2 separation. However, their CO2 permeance remain low with only grafted and solvent-casted films being able to approach the industrially relevant performance parameters. The development of polyelectrolyte-based membranes for CO2 separation should direct further efforts at promoting the CO2 transport rates while maintaining high selectivities with additional emphasis on environmentally sourced precursor polymers.


Assuntos
Dióxido de Carbono/química , Membranas Artificiais , Polieletrólitos , Polieletrólitos/síntese química , Polieletrólitos/química
12.
Biomater Sci ; 8(5): 1394-1404, 2020 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-31922160

RESUMO

Injectable shear-thinning hydrogels can be prepared by the non-covalent interactions between hydrophilic polymers. Although electrostatic force is a typical non-covalent interaction, direct mixing of two oppositely charged polyelectrolytes usually leads to a complex coacervate rather than an injectable hydrogel. Herein, a facile approach is proposed to prepare a shear-thinning hydrogel by nanoengineering of polyelectrolytes. Nanosized cationic micelles with electroneutral shells were prepared by mixing methoxyl poly(ethylene glycol)-block-poly(ε-caprolactone) and poly(ε-caprolactone)-block-poly(hexamethylene guanidine) hydrochloride-block-poly(ε-caprolactone) in an aqueous solution. When sodium carboxymethyl cellulose was added into the micellar solution, the outer poly(ethylene glycol) shell of mixed micelles prevented the instant electrostatic interaction between poly(hexamethylene guanidine) hydrochloride segments and sodium carboxymethyl cellulose, resulting in a homogenous shear-thinning electrostatic (STES) hydrogel. Because of the cationic poly(hexamethylene guanidine) hydrochloride segments, this hydrogel exhibits strong antibacterial activity against both Gram-positive and Gram-negative bacteria. Furthermore, the poly(ε-caprolactone) core of the mixed micelles can efficiently encapsulate a hydrophobic drug. In this work, curcumin-loaded STES hydrogel prepared by this method was used as wound dressing material that can promote wound healing even in infected wounds by further reducing bacterial infection via releasing curcumin. The present study provides a facile strategy to prepare shear-thinning antibacterial hydrogels from polyelectrolytes, which has great potential in biomedical application.


Assuntos
Antibacterianos/farmacologia , Hidrogéis/farmacologia , Nanotecnologia , Polieletrólitos/farmacologia , Animais , Antibacterianos/síntese química , Antibacterianos/química , Linhagem Celular , Curcumina/química , Escherichia coli/efeitos dos fármacos , Voluntários Saudáveis , Humanos , Hidrogéis/síntese química , Hidrogéis/química , Masculino , Camundongos , Micelas , Osteoblastos/efeitos dos fármacos , Osteoblastos/patologia , Polieletrólitos/síntese química , Polieletrólitos/química , Ratos , Ratos Sprague-Dawley , Staphylococcus aureus/efeitos dos fármacos , Eletricidade Estática , Cicatrização/efeitos dos fármacos
13.
J Colloid Interface Sci ; 565: 555-566, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31982722

RESUMO

Polyelectrolyte multilayers composed of pharmaceutical grade fucoidan and chitosan have been assembled and studied in terms of their response to physiological solution conditions and the presence of lysozyme. The influence of phosphate buffered saline (PBS) solution on the multilayer was interrogated using attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM). The combination of the techniques reveal that the polyelectrolyte multilayers swell when exposed to PBS after build-up and may include a small degree of mass loss as the film swells. The degree of swelling was influenced by the terminating layer of the multilayer. Upon exposure to lysozyme, it was observed that some deswelling occurred, as the enzyme adsorbed onto and permeated into the multilayer. The behaviour of the multilayer as a potential reservoir for lysozyme contrasts with the interaction with bovine serum albumin, which did not penetrate into the multilayer, indicating either exclusion by size or due to the overall net negative charge of the film.


Assuntos
Quitosana/metabolismo , Muramidase/metabolismo , Polieletrólitos/metabolismo , Polissacarídeos/metabolismo , Quitosana/química , Muramidase/química , Tamanho da Partícula , Polieletrólitos/síntese química , Polieletrólitos/química , Polissacarídeos/química , Propriedades de Superfície
14.
ACS Appl Mater Interfaces ; 12(19): 21242-21253, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-31825196

RESUMO

A functional monomer carrying a carboxylate and a protected primary ammonium group is synthesized from itaconic acid. When copolymerized with dimethyl acrylamide and 4-methacryloyloxybenzophenone, cross-linkable polyzwitterions are obtained. These are converted to surface-attached polyzwitterion networks by simultaneous UV-triggered C,H insertion reactions. The resulting polyzwitterion-coated substrates were studied by surface plasmon resonance spectroscopy measurements, ζ potential and various biological assays. They were (expectedly) protein repellent, yet at the same time (and unexpectedly) cell-adhesive and antimicrobially active. This was attributed to stimulus-responsiveness of the polyzwitterion (confirmed by the ζ potential measurements), which enables charge adjustment at different pH values. When protonated, the polyzwitterions become amphiphilic polycations and, in this state, kill bacteria upon contact like their parent structures (polymer-based synthetic mimics of antimicrobial peptides, SMAMPs).


Assuntos
Antibacterianos/farmacologia , Fibrinogênio/química , Polieletrólitos/farmacologia , Ácidos Polimetacrílicos/farmacologia , Succinatos/farmacologia , Tensoativos/farmacologia , Acrilamidas/química , Adsorção/efeitos dos fármacos , Antibacterianos/síntese química , Antibacterianos/toxicidade , Escherichia coli/efeitos dos fármacos , Queratinócitos/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Polieletrólitos/síntese química , Polieletrólitos/toxicidade , Ácidos Polimetacrílicos/síntese química , Ácidos Polimetacrílicos/toxicidade , Staphylococcus aureus/efeitos dos fármacos , Succinatos/síntese química , Succinatos/toxicidade , Tensoativos/síntese química , Tensoativos/toxicidade
15.
Int J Biol Macromol ; 147: 809-820, 2020 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-31751709

RESUMO

Polyelectrolyte multilayer (PEC) films of sodium alginate (Na-Alg) and poly(4-vinylpyridine) (P4VP) were prepared and were loaded with an antibacterial agent, ciprofloxacin HCl (CIP.HCl) aiming to design new hydrophilic films with controlled physicochemical properties and drug release behaviour that may find application as components of transdermal drug delivery systems. The PEC films were characterized by SEM, XRD, TGA, AFM and FTIR spectroscopy. The hydrophilicity of the PEC films was examined by using contact angle measurement. The number of layers and the nature of the outer layer affect the physicochemical characteristics, CIP.HCl loading and release behaviour of the films. The three layer film PEC-3, which is composed of Na-Alg outer layer deposited on a P4VP/Na-Alg double layer, is characterized by the lowest roughness (Rq = 16.3 nm) and the most hydrophilic surface with a contact angle value of 38.1° among all other films. Its crystallinity index is 0.36, and starts to degrade at 195 °C. It exhibits 130-135% equilibrium swelling capacity in acid buffer and water respectively. PEC-3 is the film with the highest drug loading capacity and drug loading efficiency values of 3.51% and 87% respectively. A cumulative drug release of 65% is obtained from PEC-3 within 24 h in pH = 1.2 buffer solution.


Assuntos
Alginatos , Ciprofloxacina , Membranas Artificiais , Polivinil , Alginatos/química , Alginatos/farmacocinética , Alginatos/farmacologia , Ciprofloxacina/química , Ciprofloxacina/farmacocinética , Preparações de Ação Retardada/síntese química , Preparações de Ação Retardada/química , Preparações de Ação Retardada/farmacocinética , Preparações de Ação Retardada/farmacologia , Polieletrólitos/síntese química , Polieletrólitos/química , Polieletrólitos/farmacocinética , Polieletrólitos/farmacologia , Polivinil/química , Polivinil/farmacocinética , Polivinil/farmacologia
16.
Int J Mol Sci ; 20(23)2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31810352

RESUMO

To overcome the high relapse rate of multiple myeloma (MM), a drug delivery coating for functionalization of bone substitution materials (BSM) is reported based on adhesive, catechol-containing and stimuli-responsive polyelectrolyte complexes (PECs). This system is designed to deliver the MM drug bortezomib (BZM) directly to the anatomical site of action. To establish a gradual BZM release, the naturally occurring caffeic acid (CA) is coupled oxidatively to form poly(caffeic acid) (PCA), which is used as a polyanion for complexation. The catechol functionalities within the PCA are particularly suitable to form esters with the boronic acid group of the BZM, which are then cleaved in the body fluid to administer the drug. To achieve a more thorough control of the release, the thermoresponsive poly(N-isoproplyacrylamide-co-dimethylaminoethylmethacrylate) (P(NIPAM-co-DMAEMA)) was used as a polycation. Using turbidity measurements, it was proven that the lower critical solution temperature (LCST) character of this polymer was transferred to the PECs. Further special temperature dependent attenuated total reflection infrared spectroscopy (ATR-FTIR) showed that coatings formed by PEC immobilization exhibit a similar thermoresponsive performance. By loading the coatings with BZM and studying the release in a model system, via UV/Vis it was observed, that both aims, the retardation and the stimuli control of the release, were achieved.


Assuntos
Bortezomib/farmacologia , Ácidos Cafeicos/química , Sistemas de Liberação de Medicamentos , Mieloma Múltiplo/tratamento farmacológico , Bortezomib/química , Ácidos Cafeicos/síntese química , Catecóis/química , Catecóis/farmacologia , Materiais Revestidos Biocompatíveis/síntese química , Materiais Revestidos Biocompatíveis/química , Preparações de Ação Retardada/química , Preparações de Ação Retardada/farmacologia , Humanos , Metacrilatos/síntese química , Metacrilatos/química , Metacrilatos/farmacologia , Mieloma Múltiplo/patologia , Polieletrólitos/síntese química , Polieletrólitos/química , Polieletrólitos/farmacologia , Polímeros/síntese química , Polímeros/química , Polímeros/farmacologia
17.
Biomacromolecules ; 20(9): 3524-3534, 2019 09 09.
Artigo em Inglês | MEDLINE | ID: mdl-31381318

RESUMO

This work presents a salt-responsive interpenetrating network (IPN) hydrogel with effective antimicrobial properties and surface regeneration. The hydrogels were engineered using the double network strategy to form loosely cross-linked zwitterionic poly(sulfobetaine vinylimidazole) (pSBVI) networks into the highly cross-linked cationic poly((trimethylamino)ethyl methacrylate chloride) (pTMAEMA) framework via photopolymerization. The pTMAEMA/pSBVI hydrogel has strong mechanical properties, with a fracture stress 120× higher than single network pTMAEMA hydrogel. In addition, there is inverse correlation between elastic modulus and elastic strain of pTMAEMA/pSBVI hydrogels as a function of ionic strength. The cationic pTMAEMA and zwitterionic pSBVI show opposite swelling behaviors in salt solutions due to the polyelectrolyte effect and antipolyelectrolyte effect. Therefore, the pTMAEMA/pSBVI hydrogel elicits a significant interfacial transition in solutions with different ionic strengths. The IPN hydrogels have switchable lubrication and optical transmittance between deionized water and 1.0 M NaCl solution. The protein adsorption tests further confirmed the switchable interface of salt-responsive IPN hydrogels. In addition, bacterial attachment test on pTMAEMA/pSBVI hydrogels with Staphylococcus epidermidis (S. epidermidis) and Escherichia coli (E. coli) show bacterial killing rates of the IPN hydrogel over 80% for S. epidermidis and 90% for E. coli after incubating the hydrogels in the bacterial solutions for 24 h. The bacterial release rate from the IPN hydrogel reached 96% after washing with 1.0 M NaCl solution. Furthermore, the excellent reusability of the pTMAEMA/pSBVI hydrogels was demonstrated by the high bacterial killing and bacterial release rates after five kill/release cycles. The work presents a new stimuli-responsive IPN hydrogel with structural modulation, tunable antimicrobial properties, and surface regeneration by ionic strength. Integrating two salt-responsive polymers with mutually independent actions into a single material provides a new direction for smart materials with potential medical and industrial applications.


Assuntos
Anti-Infecciosos/farmacologia , Materiais Biocompatíveis/farmacologia , Hidrogéis/farmacologia , Polieletrólitos/farmacologia , Anti-Infecciosos/síntese química , Anti-Infecciosos/química , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Escherichia coli/efeitos dos fármacos , Hidrogéis/síntese química , Hidrogéis/química , Metacrilatos/síntese química , Metacrilatos/química , Metacrilatos/farmacologia , Polieletrólitos/síntese química , Polieletrólitos/química , Polímeros/síntese química , Polímeros/química , Polímeros/farmacologia , Sais/química , Cloreto de Sódio/química , Staphylococcus epidermidis/efeitos dos fármacos , Água/química
18.
J Am Chem Soc ; 141(28): 11259-11268, 2019 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-31264856

RESUMO

Polyelectrolytes play an important role in both natural biological systems and human society, and their synthesis, functional exploration, and profound application are thus essential for biomimicry and creating new materials. In this study, we developed an efficient synthetic methodology for in situ generation of azonia-containing polyelectrolytes in a one-pot manner by using readily accessible nonionic reactant in the presence of commercially available cheap ionic species. The resulting polyelectrolytes are emissive in the solid state and can readily form luminescent photopatterns with different colors. The azonia-containing polyelectrolytes possess extraordinary potency of reactive oxygen species (ROS) generation, enabling them to impressively kill methicillin-resistant Staphylococcus aureus (MRSA), a drug resistant superbug, both in vitro and in vivo.


Assuntos
Amidas/farmacologia , Antibacterianos/farmacologia , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Polieletrólitos/farmacologia , Amidas/química , Antibacterianos/síntese química , Antibacterianos/química , Luminescência , Staphylococcus aureus Resistente à Meticilina/metabolismo , Testes de Sensibilidade Microbiana , Estrutura Molecular , Processos Fotoquímicos , Polieletrólitos/síntese química , Polieletrólitos/química , Espécies Reativas de Oxigênio/metabolismo
19.
Molecules ; 24(5)2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30823653

RESUMO

Polyelectrolyte complexation is a versatile platform for the design of self-assembled materials. Here we use rational design to create ionic hydrophobically-patterned peptides that allow us to precisely explore the role of hydrophobicity on electrostatic self-assembly. Polycations and polyanions were designed and synthesized with an alternating sequence of d- and l-chiral patterns of lysine or glutamic acid with either glycine, alanine or leucine due to their increasing hydrophobicity index, respectively. Two motifs were considered for the oppositely charged patterned peptides; one with equal residues of charged and uncharged amino acids and the other with increased charge density. Mass spectroscopy, circular dichroism, H- and F-NMR spectroscopy were used to characterize the polypeptides. Polyelectrolyte complexes (PECs) formed using the sequences were characterized using turbidity measurements, optical microscopy and infrared spectroscopy. Our results show that the critical salt concentration, a key measure of PEC stability, increased with both increasing charge density as well as hydrophobicity. Furthermore, by increasing the hydrophobicity, the amount of PEC formed increased with temperature, contrary to purely ionic PECs. Lastly, we assessed the encapsulation behavior of these materials using a hydrophobic dye. Concluding that encapsulation efficiency increased with hydrophobic content of the complexes providing insight for future work on the application of these materials for drug delivery.


Assuntos
Sistemas de Liberação de Medicamentos , Peptídeos/química , Polieletrólitos/química , Engenharia de Proteínas , Dicroísmo Circular , Ácido Glutâmico/química , Humanos , Interações Hidrofóbicas e Hidrofílicas , Lisina/química , Espectrometria de Massas , Peptídeos/síntese química , Peptídeos/farmacologia , Poliaminas/síntese química , Poliaminas/química , Polieletrólitos/síntese química , Polieletrólitos/farmacologia , Polímeros/síntese química , Polímeros/química , Eletricidade Estática
20.
J Mater Chem B ; 7(13): 2102-2122, 2019 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32073569

RESUMO

Polyelectrolytes (PELs) - polymers with charged repeat units - have emerged as a useful class of polymers for biomedical applications due to their high aqueous solubility, low aggregation propensity and the opportunity they afford for polyvalent interactions with surfaces. Biodegradability and biocompatibility of PELs are important prerequisites for their utilization in in vivo applications. PELs that can be chemically functionalized with ease prove advantageous for creating diverse biomaterials. Polyaspartic acid (PASA) is a modular and biocompatible synthetic PEL that has all these features. It also shows many positive biomedical attributes such as bone-tissue targeting, muco-adhesive behavior and extended blood circulation time. Cationic PELs derived from PASA are rapidly internalized by mammalian and bacterial cells, and hence have immense utility in therapeutic delivery applications. Polyelectrolyte complexes (PECs) and multilayers (PEMs) formed from PASA PELs have further expanded their biomedical utility. This mini-review highlights some recent literature examples of unique biomedical applications of PELs, PECs and PEMs prepared through the molecular engineering of PASA. It discusses biomineralization modulators, anti-mycobacterial agents, underwater adhesives, mucoadhesive drug and gene delivery agents, and cell encapsulants fabricated using PASA derived PELs.


Assuntos
Materiais Biocompatíveis/farmacologia , Plásticos Biodegradáveis/farmacologia , Peptídeos/farmacologia , Polieletrólitos/farmacologia , Animais , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Plásticos Biodegradáveis/síntese química , Plásticos Biodegradáveis/química , Incrustação Biológica/prevenção & controle , Humanos , Peptídeos/síntese química , Peptídeos/química , Polieletrólitos/síntese química , Polieletrólitos/química , Alicerces Teciduais/química
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