RESUMO
Biobased porous hydrogels enriched with phytocompounds-rich herbal extracts have aroused great interest in recent years, especially in healthcare. In this study, new macroporous hybrid cryogel constructs comprising thiourea-containing chitosan (CSTU) derivative and a Hypericum perforatum L. extract (HYPE), commonly known as St John's wort, were prepared by a facile one-pot ice-templating strategy. Benefiting from the strong interactions between the functional groups of the CSTU matrix and those of polyphenols in HYPE, the hybrid cryogels possess excellent liquid absorption capacity, mechanical resilience, antioxidant performance, and a broad spectrum of antibacterial activity simultaneously. Thus, owing to their design, the hybrid constructs exhibit an interconnected porous architecture with the ability to absorb over 33 and 136 times their dry weight, respectively, when contacted with a phosphate buffer solution (pH 7.4) and an acidic aqueous solution (pH 2). These cryogel constructs have extremely high compressive strengths ranging from 839 to 1045 kPa and withstand elevated strains of over 70% without developing fractures. Moreover, the water-swollen hybrid cryogels with the highest HYPE content revealed a complete and instant shape recovery after uniaxial compression. The incorporation of HYPE into CSTU cryogels enabled substantial improvement in scavenging reactive oxygen species and an expanded antibacterial spectrum toward multiple pathogens, including Gram-positive bacteria (Staphylococcus aureus and Staphylococcus epidermidis), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), and fungi (Candida albicans). Cell viability experiments demonstrated the cytocompatibility of the 3D cryogel constructs, which did not induce changes in the fibroblast morphology. This work showcases a simple and effective strategy to immobilize HYPE extracts on CSTU 3D networks, allowing the development of novel multifunctional platforms with promising potential in hemostasis, wound dressing, and dermal regeneration scaffolds.
Assuntos
Antibacterianos , Materiais Biocompatíveis , Quitosana , Criogéis , Hypericum , Extratos Vegetais , Quitosana/química , Quitosana/farmacologia , Hypericum/química , Criogéis/química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Extratos Vegetais/química , Extratos Vegetais/farmacologia , Antibacterianos/farmacologia , Antibacterianos/química , Animais , Camundongos , Porosidade , Staphylococcus aureus/efeitos dos fármacos , Força Compressiva , Antioxidantes/farmacologia , Antioxidantes/química , Escherichia coli/efeitos dos fármacos , Escherichia coli/crescimento & desenvolvimentoRESUMO
The need for bone substitutes is a major challenge as the incidence of serious bone disorders is massively increasing, mainly attributed to modern world problems, such as obesity, aging of the global population, and cancer incidence. Bone cancer represents one of the most significant causes of bone defects, with reserved prognosis regarding the effectiveness of treatments and survival rate. Modern therapies, such as hyperthermia, immunotherapy, targeted therapy, and magnetic therapy, seem to bring hope for cancer treatment in general, and bone cancer in particular. Mimicking the composition of bone to create advanced scaffolds, such as bone substitutes, proved to be insufficient for successful bone regeneration, and a special attention should be given to control the changes in the bone tissue micro-environment. The magnetic manipulation by an external field can be a promising technique to control this micro-environment, and to sustain the proliferation and differentiation of osteoblasts, promoting the expression of some growth factors, and, finally, accelerating new bone formation. By incorporating stimuli responsive nanocarriers in the scaffold's architecture, such as magnetic nanoparticles functionalized with bioactive molecules, their behavior can be rigorously controlled under external magnetic driving, and stimulates the bone tissue formation.
Assuntos
Neoplasias Ósseas , Substitutos Ósseos , Humanos , Alicerces Teciduais , Neoplasias Ósseas/terapia , Osteogênese , Regeneração Óssea , Fenômenos Magnéticos , Engenharia Tecidual/métodos , Impressão Tridimensional , Microambiente TumoralRESUMO
Drug delivery to the anterior or posterior segments of the eye is a major challenge due to the protection barriers and removal mechanisms associated with the unique anatomical and physiological nature of the ocular system. The paper presents the preparation and characterization of drug-loaded polymeric particulated systems based on pre-emulsion coated with biodegradable polymers. Low molecular weight biopolymers (chitosan, sodium hyaluronate and heparin sodium) were selected due to their ability to attach polymer chains to the surface of the growing system. The particulated systems with dimensions of 190-270 nm and a zeta potential varying from -37 mV to +24 mV depending on the biopolymer charges have been obtained. Current studies show that particles release drugs (dexamethasone/pilocarpine/bevacizumab) in a safe and effective manner, maintaining therapeutic concentration for a longer period of time. An extensive modeling study was performed in order to evaluate the drug release profile from the prepared systems. In a multifractal paradigm of motion, nonlinear behaviors of a drug delivery system are analyzed in the fractal theory of motion, in order to correlate the drug structure with polymer. Then, the functionality of a SL(2R) type "hidden symmetry" implies, through a Riccati type gauge, different "synchronization modes" (period doubling, damped oscillations, quasi-periodicity and intermittency) during the drug release process. Among these, a special mode of Kink type, better reflects the empirical data. The fractal study indicated more complex interactions between the angiogenesis inhibitor Bevacizumab and polymeric structure.
Assuntos
Quitosana , Nanopartículas , Bevacizumab , Quitosana/química , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos/métodos , Liberação Controlada de Fármacos , Emulsões , Nanopartículas/química , Tamanho da Partícula , Polímeros/químicaRESUMO
A considerable interest in cancer research is represented by the development of magnetic nanoparticles based on biofunctionalized polymers for controlled-release systems of hydrophobic chemotherapeutic drugs targeted only to the tumor sites, without affecting normal cells. The objective of the paper is to present the synthesis and in vitro evaluation of the nanocomposites that include a magnetic core able to direct the systems to the target, a polymeric surface shell that provides stabilization and multi-functionality, a chemotherapeutic agent, Paclitaxel (PTX), and a biotin tumor recognition layer. To our best knowledge, there are no studies concerning development of magnetic nanoparticles obtained by partial oxidation, based on biotinylated N-palmitoyl chitosan loaded with PTX. The structure, external morphology, size distribution, colloidal and magnetic properties analyses confirmed the formation of well-defined crystalline magnetite conjugates, with broad distribution, relatively high saturation magnetization and irregular shape. Even if the ability of the nanoparticles to release the drug in 72 h was demonstrated, further complex in vitro and in vivo studies will be performed in order to validate the magnetic nanoparticles as PTX delivery system.
Assuntos
Antineoplásicos Fitogênicos/química , Biotina/química , Quitosana/análogos & derivados , Nanopartículas de Magnetita/química , Paclitaxel/química , Linhagem Celular Tumoral , Quitosana/química , Coloides/química , Preparações de Ação Retardada/química , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos/métodos , Humanos , Interações Hidrofóbicas e Hidrofílicas/efeitos dos fármacos , Células MCF-7 , Polímeros/químicaRESUMO
Background and objectives: Cancer is the second leading cause of death globally, an alarming but expected increase. In comparison to other types of cancer, malignant bone tumors are unusual and their treatment is a real challenge. This paper's main purpose is the study of the potential application of composite scaffolds based on biopolymers and calcium phosphates with the inclusion of magnetic nanoparticles in combination therapy for malignant bone tumors. Materials and Methods: The first step was to investigate if X-rays could modify the scaffolds' properties. In vitro degradation of the scaffolds exposed to X-rays was analyzed, as well as their interaction with phosphate buffer solutions and cells. The second step was to load an anti-tumoral drug (doxorubicin) and to study in vitro drug release and its interaction with cells. The chemical structure of the scaffolds and their morphology were studied. Results: Analyses showed that X-ray irradiation did not influence the scaffolds' features. Doxorubicin release was gradual and its interaction with cells showed cytotoxic effects on cells after 72 h of direct contact. Conclusions: The obtained scaffolds could be considered in further studies regarding combination therapy for malignant bone tumors.
Assuntos
Biopolímeros/uso terapêutico , Neoplasias Ósseas/terapia , Fosfatos de Cálcio/uso terapêutico , Quimiorradioterapia/métodos , Alicerces Teciduais , Biopolímeros/administração & dosagem , Fosfatos de Cálcio/administração & dosagem , Quimiorradioterapia/normas , Humanos , Nanopartículas de Magnetita/administração & dosagem , Nanopartículas de Magnetita/uso terapêuticoRESUMO
Natural proteins have been extensively studied as matrices for tissue engineering, due to their excellent biocompatibility and biological properties associated with increasing cell proliferation. By generating complex materials, cell and tissue functions can be tailored to obtain a specific direction, according to the medical needs. The aim of this paper was to obtain scaffolds based on collagen, hyaluronan and sericin, with morphology and physical-chemical properties adequate for controlled drug delivery systems. In this aim various tests were performed: in vitro swelling and degradation studies, Fourier Transform Infrared spectroscopy (FT-IR), Scanning Electronic Microscopy (SEM) and thermogravimetric analysis. Loading and releasing of ibuprofen is also discussed. The results indicate that scaffolds based on collagen, hyaluronan and sericin have a porous structure, strength and stability adequate for skin tissue engineering. The obtained scaffolds swell, degrade and have controlled drug release properties in simulated biological fluids.
Assuntos
Sistemas de Liberação de Medicamentos , Ácido Hialurônico , Sericinas , Engenharia Tecidual , Materiais Biocompatíveis , Colágeno , Microscopia Eletrônica de Varredura , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Alicerces TeciduaisRESUMO
The bacterial nanocellulose (BnC) membranes were produced extracellularly by a novel aerobic acetic acid bacterium Komagataeibacter melomenusus. The BnC was modified in situ by adding carboxymethyl cellulose (CMC) into the culture media, obtaining a BnC-CMC product with denser fibril arrangement, improved rehydration ratio and elasticity in comparison to BnC. The proteolytic enzyme bromelain (Br) and antimicrobial peptide nisin (N) were immobilized to BnC matrix by ex situ covalent binding and/or adsorption. The optimal Br immobilization conditions towards the maximized specific proteolytic activity were investigated by response surface methodology as factor variables. At optimal conditions, i.e., 8.8 mg/mL CMC and 10 mg/mL Br, hyperactivation of the enzyme was achieved, leading to the specific proteolytic activity of 2.3 U/mg and immobilization efficiency of 39.1 %. The antimicrobial activity was observed against Gram-positive bacteria (S. epidermidis, S. aureus and E. faecalis) for membranes with immobilized N and was superior when in situ modified BnC membranes were used. N immobilized on the BnC or BnC-CMC membranes was cytocompatible and did not cause changes in normal human dermal fibroblast cell morphology. BnC membranes perform as an efficient carrier for Br or N immobilization, holding promise in wound debridement and providing antimicrobial action against Gram-positive bacteria, respectively.
Assuntos
Acetobacteraceae , Bromelaínas , Celulose , Nisina , Nisina/farmacologia , Nisina/química , Bromelaínas/química , Bromelaínas/farmacologia , Celulose/química , Celulose/farmacologia , Acetobacteraceae/química , Humanos , Antibacterianos/farmacologia , Antibacterianos/química , Cicatrização/efeitos dos fármacos , Enzimas Imobilizadas/química , Enzimas Imobilizadas/farmacologia , Nanoestruturas/química , Testes de Sensibilidade MicrobianaRESUMO
This research focuses on the synthesis of hydrogels exhibiting enhanced antioxidant properties derived from hyaluronic acid (HA) and poly(ethylene brassylate-co-squaric acid) (PEBSA), a copolymacrolactone that have the ability to be used in drug delivery applications. Quercetin (Q), a bioflavonoid with strong antioxidant properties, is employed as a bioactive compound. The biomolecule is encapsulated in the polymeric network using different entrapment techniques, including the initial formation of a complex between PEBSA and Q, which is demonstrated through the dynamic light scattering technique. Fourier transform infrared spectroscopy (FT-IR) and rheological studies confirm the formation of the hydrogels, revealing the occurrence of physical interactions between the synthetic polymer and the polysaccharide. Moreover, the hydrogels demonstrate biocompatible properties after direct contact with the HDFa cell line and antioxidant properties, as revealed by DPPH tests.
Assuntos
Antioxidantes , Ácido Hialurônico , Hidrogéis , Cicatrização , Ácido Hialurônico/química , Ácido Hialurônico/farmacologia , Hidrogéis/química , Hidrogéis/farmacologia , Hidrogéis/síntese química , Antioxidantes/farmacologia , Antioxidantes/química , Cicatrização/efeitos dos fármacos , Humanos , Quercetina/farmacologia , Quercetina/química , Linhagem Celular , Espectroscopia de Infravermelho com Transformada de Fourier , Reologia , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologiaRESUMO
Several newly obtained titanium alloys were characterized in order to evaluate the biocompatibility and their possible application as implants. For improvement of the performances of the TiMo alloys compared to other alloys, silicon was added, targeting good mechanical and technological properties, avoiding the toxic effects for human body. Titanium is very used in medical applications, due to their extremely low toxicity and good chemical stability in different body fluids. Four Ti15MoxSi (where x = 0, 0.5, 0.75, 1.0 wt %), alloys were developed and investigated regarding microstructure, mechanical, chemical and biological behavior (in vitro and in vivo evaluation). By increasing the Si content from 0 to 1% wt., the mechanical properties of the Ti15Mo alloys were significantly improved. By increasing the Si content from 0 to 1% wt., the mechanical properties of the Ti15Mo alloys were significantly improved (about 50%) from 44.50 GPa to 19.81 GPa modulus of elasticity and the hardness values 361.28 to 188.52 HV. The cytocompatibility assessment on human line osteoblasts indicated good cell-material interactions and in vivo tests indicated a successful osseointegration, the surrounding newly bone being formed without any significant inflammatory reaction. Expression of osteopontin in the peri-implant area highlights the presence of osteogenesis and bone mineralization. Metalloproteinase-2 (gelatinase A) and metallopeptidase-9 (gelatinase B) overexpression in osteoblasts, osteoclasts and osteocytes represent the markers of normal bone remodeling. All these results suggest that the TiMoSi alloys are promising materials for orthopedics devices, since mechanical properties and biocompatibility offer conditions for applying them as biomaterial.
Assuntos
Metaloproteinase 2 da Matriz , Titânio , Ligas , Materiais Biocompatíveis , Humanos , Teste de Materiais , Próteses e ImplantesRESUMO
Composites based on combination of biopolymers (chitosan, hyaluronic acid and bovine serum albumin or gelatin), calcium phosphates (CP) and magnetic nanoparticles have been prepared by a biomimetic co-precipitation method. The biomimetic strategy is inspired by natural mineralization processes, where the synthesized minerals are usually combined with proteins, polysaccharides or other mineral forms to form composite, in physiological conditions of temperature and pH. The morphology of the magnetic composites, studied using scanning electron microscopy (SEM) indicated a macroporous structure, which influenced the retention of simulated biological fluids. Fourier transformed infrared spectroscopy and X-ray diffraction and Energy-dispersive X-ray spectroscopy (EDX) confirmed the composition of the scaffolds and the formation of various types of calcium phosphates with amorphous nature. The in vitro degradation studies showed a slow degradation process for magnetic composites that confirmed the tightly connection of the polymeric matrix with calcium phosphates, which limits the enzyme access to the degradable components and material disintegration. The magnetic scaffolds exhibited no negative effect on osteoblasts cell, emphasizing a good biocompatibility. Considering the scaffolds properties, some compositions based on calcium phosphates, chitosan, Hya/Bsa and more than 3% of MNPs are recommended for further optimization and in vivo tests.
Assuntos
Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Biopolímeros/química , Osso e Ossos/efeitos dos fármacos , Fosfatos de Cálcio/química , Nanopartículas de Magnetita/química , Células 3T3 , Animais , Materiais Biomiméticos/química , Linhagem Celular , Quitosana/química , Humanos , Ácido Hialurônico/química , Teste de Materiais/métodos , Camundongos , Osteoblastos/efeitos dos fármacos , Soroalbumina Bovina/química , Engenharia Tecidual , Alicerces TeciduaisRESUMO
Cost-effective water cleaning approaches using improved treatment technologies, for instance based on catalytic processes with high activity catalysts, are urgently needed. The aim of our study was to synthesize efficient Fenton-like photo-catalysts for rapid degradation of persistent organic micropollutants in aqueous medium. Iron-based nanomaterials were chemically synthesized through simple procedures by immobilization of either iron(II) oxalate (FeO) or iron(III) citrate (FeC) on magnetite (M) nanoparticles stabilized with polyethylene glycol (PEG). Various investigation techniques were performed in order to characterize the freshly prepared catalysts. By applying advanced oxidation processes, the effect of catalyst dosage, hydrogen peroxide concentration and UV-A light exposure were examined for Bisphenol A (BPA) conversion, at laboratory scale, in mild conditions. The obtained results revealed that BPA degradation was rapidly enhanced in the presence of low-concentration H2O2, as well as under UV-A light, and is highly dependent on the surface characteristics of the catalyst. Complete photo-degradation of BPA was achieved over the M/PEG/FeO catalyst in less than 15 minutes. Based on the catalytic performance, a hierarchy of the tested catalysts was established: M/PEG/FeO > M/PEG/FeC > M/PEG. The results of cytotoxicity assay using MCF-7 cells indicated that the aqueous samples after treatment are less cytotoxic.
Assuntos
Magnetismo , Nanopartículas Metálicas/química , Nanopartículas Metálicas/toxicidade , Animais , Catálise , Embrião não Mamífero/efeitos dos fármacos , Compostos Férricos/química , Óxido Ferroso-Férrico/química , Peróxido de Hidrogênio/química , Cinética , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Ácido Oxálico/química , Polietilenoglicóis/química , Espectrometria por Raios X , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X , Peixe-Zebra/embriologiaRESUMO
A series of hybrid polymeric hydrogels, prepared by the reaction of acrylic acid-functionalized chitosan with either N-isopropylacrylamide or 2-hydroxyethyl methacrylate monomers, were synthesized, pressed into minitablets, and investigated for their ability to act as controlled release vehicles for ophthalmic drug delivery. For comparison, interpolymeric complex analogues synthesized using the same monomers and pure, unfunctionalized chitosan were examined by means of an identical characterization protocol. The effects of network structure and composition upon the swelling properties, adhesion behavior, and drug release characteristics were investigated. Comparative in vitro studies employing chloramphenicol, atropine, norfloxacin, or pilocarpine informed the selection of drug-specific carrier compositions for the controlled delivery of these compounds. In addition, in vivo (rabbit model) experiments involving the delivery of pilocarpine indicated that chitosan-based hybrid polymer networks containing 2-hydroxyethyl methacrylate are useful carriers for the delivery of this therapeutic agent.
Assuntos
Acrilamidas , Materiais Biocompatíveis , Quitosana , Sistemas de Liberação de Medicamentos , Olho , Metacrilatos , Animais , Antibacterianos/farmacocinética , Materiais Biocompatíveis/síntese química , Antagonistas Colinérgicos/farmacocinética , Masculino , CoelhosRESUMO
The elaboration of chemically crosslinked hydrogels based on collagen (C), hyaluronanic acid (HA) and sericin (S) with different polymer ratios was investigated by in-situ rheology. This reaction was performed via amide or ester bond reaction activated by carbodiimide, in pure water. Prior to molecule crosslinking, the rheological behaviour of the biopolymers (alone or in mixture) was characterized in a semi-dilute concentration regime. Both flow and dynamic measurements showed that uncrosslinked collagen alone appears to be rather elastic with yield stress properties, whereas uncrosslinked HA alone appears to be rather shear thinning and viscoelastic in agreement with entangled polymer behaviour. Sericin exhibited Newtonian low viscosity behaviour according to its very low molar mass. Before crosslinking, HA exhibited viscoelastic behaviour at concentrations above the critical entangled concentration (C*) in the mixtures, thus HA shows promise as a matrix for future crosslinked networks, whereas sericin did not significantly modify the rheology. During the reaction, followed by rheology, the kinetics were slower for pure HA systems compared with the mixtures (i.e., with added collagen and/or to a lesser extent sericin). At the same time, the final network of hydrogels (i.e., the elastic modulus) was more structured in the mixture based systems. This result is explained by ester bonds (the only possibility for pure HA systems), which are less favourable and reactive than amide bonds (possible with sericin and collagen). The presence of collagen in the HA matrix reinforced the hydrogel network. SEM studies confirmed the structure of the hydrogels, and in vitro degradability was globally consistent with the effect of the selected enzyme according to the hydrogel composition. All the elaborated hydrogels were non-cytotoxic in vitro.
Assuntos
Colágeno/química , Ácido Hialurônico/química , Hidrogéis/química , Sericinas/química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Humanos , Microscopia Eletrônica de Varredura , Reologia , Viscosidade , Água/químicaRESUMO
Zero-length crosslinked hydrogels have been synthesized by covalent linking of three natural polymers (collagen, hyaluronic acid and sericin), in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide. The hydrogels have been investigated by FT-IR spectroscopy, microcalorimetry, in vitro swelling, enzymatic degradation, and in vitro cell viability studies. The obtained crosslinked hydrogels showed a macroporous structure, high swelling degree and in vitro enzymatic resistance compared to uncrosslinked collagen. The in vitro cell viability studies performed on normal human dermal fibroblasts assessed the sericin proliferation properties indicating a potential use of the hydrogels based on collagen, hyaluronic acid and sericin in skin tissue engineering.
Assuntos
Materiais Biocompatíveis/química , Hidrogéis/química , Pele , Engenharia Tecidual , Adsorção , Colágeno/química , Reagentes de Ligações Cruzadas/química , Regeneração Tecidual Guiada , Ácido Hialurônico/química , Sericinas/química , Espectroscopia de Infravermelho com Transformada de Fourier , Alicerces Teciduais/químicaRESUMO
The synthesis and characterisation of semi-interpenetrating polymeric networks obtained by the radical-induced polymerisation of N-isopropylacrylamide in the presence of chitosan using tetraethyleneglycoldiacrylate as the crosslinker is described. The influence of the degree of crosslinking and that of the ratio of chitosan to poly(N-isopropylacrylamide) on the "pH/temperature induced" phase transition behaviour and swelling characteristics of the hydrogel system are investigated. The ability of the same system to act as a controlled release vehicle for pilocarpine hydrochloride is evaluated.
Assuntos
Resinas Acrílicas/química , Quitina/análogos & derivados , Quitina/química , Reagentes de Ligações Cruzadas/química , Hidrogéis/química , Fenômenos Químicos , Físico-Química , Quitosana , Preparações de Ação Retardada , Composição de Medicamentos , Concentração de Íons de Hidrogênio , Soluções Farmacêuticas , Pilocarpina/administração & dosagem , Pilocarpina/química , Temperatura , Fatores de TempoRESUMO
Poly(acrylic acid) (PAA) and poly(ethylene glycol) (PEG), four-arm, amine-terminated particles with nanometer size and spherical shape were obtained by the polymers cross-linking, via activation with 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide hydrochloride, in a w/o emulsion. The morphology and surface charge of the final particles are strongly dependent on the molar ratio of PAA-PEG and the PAA concentration. The physicochemical characteristics correlated with the drug-loading capacity, in vitro and ex vivo release kinetics of pilocarpine hydrochloride and biocompatibility results indicate that these nanoparticles exhibit the prerequisite behavior for use as carriers of ophthalmic drugs.
Assuntos
Resinas Acrílicas/química , Soluções Oftálmicas/química , Polietilenoglicóis/química , Algoritmos , Animais , Varredura Diferencial de Calorimetria , Sobrevivência Celular/efeitos dos fármacos , Células Cultivadas , Córnea/citologia , Córnea/efeitos dos fármacos , Córnea/metabolismo , Difusão , Portadores de Fármacos , Sistemas de Liberação de Medicamentos , Eletroquímica , Células Endoteliais/efeitos dos fármacos , Humanos , Técnicas In Vitro , Cinética , Microscopia Eletrônica de Varredura , Nanopartículas , Tamanho da Partícula , Coelhos , Solubilidade , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
A novel biomimetic technique for obtaining chitosan-calcium phosphates (Cs-CP) scaffolds are presented: calcium phosphates are precipitated from its precursors, CaCl(2) and NaH(2) PO(4) on the Cs matrix, under physiological conditions (human body temperature and body fluid pH; 37°C and pH = 7.2, respectively). Materials composition and structure have been confirmed by various techniques: elemental analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). FTIR and SEM data have shown the arrangement of the calcium phosphates-hydroxyapatite (CP-Hap) onto Cs matrix. In this case the polymer is acting as glue, bonding the calcium phosphates crystals. Behavior in biological simulated fluids (phosphate buffer solution-PBS and PBS-albumin) revealed an important contribution of the chelation between -NH3(+) and Ca(2+) on the scaffold interaction with aqueous mediums; increased quantities of chitosan in composites permit the interaction with human albumin and improve the retention of fluid. The composites are slightly degraded by the lysozyme which facilitates an in vivo degradation control of bone substitutes. Modulus of elasticity is strongly dependent of the ratio chitosan/calcium phosphates and recommends the obtained biomimetic composites as promising materials for a prospective bone application.
Assuntos
Materiais Biomiméticos/química , Substitutos Ósseos/química , Fosfatos de Cálcio/química , Quitosana/química , Teste de Materiais , Alicerces Teciduais/química , Albuminas/química , Temperatura Alta , Humanos , Concentração de Íons de Hidrogênio , Microscopia Eletrônica de Varredura , Muramidase/química , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios XRESUMO
The study presents the preparation of a semi-synthetic hydrogel based on poly(N-isopropyl acrylamide-co-diethylene glycol diacrylate) inserted onto the collagen porous membrane. The synthesis of the hydrogels was performed through radical copolymerization of N-isopropyl acrylamide (NIPAM) with diethylene glycol diacrylate (DEGDA) also as crosslinking agent, using ammonium persulfate as initiator and N,N,N',N'-tetramethylethylene diamine as activator, and it was achieved in the presence of the collagen matrix. The prepared hydrogels were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. The swelling behaviour of the semi-interpenetrated polymer network related on the hydrogel composition, it was also evaluated. The pore sizes of the synthesized hydrogels, much larger than the typical mesh size of a conventional hydrogel, allow to consider the hybrid hydrogel based on the inserted poly(NIPAM-co-DEGDA) onto collagen fibrils as a super-porous hydrogel.
Assuntos
Materiais Biocompatíveis/síntese química , Colágeno/química , Portadores de Fármacos/síntese química , Hidrogéis/síntese química , Acrilamidas/química , Acrilatos/química , Materiais Biocompatíveis/análise , Colágeno/análise , Colágeno/ultraestrutura , Portadores de Fármacos/análise , Etilenoglicol/química , Humanos , Hidrogéis/análise , Microscopia Eletrônica de Varredura , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , CicatrizaçãoRESUMO
UNLABELLED: The paper presents synthesis, swelling properties and in vitro degradation tests of collagen-hydroxyapatite composites, in the order to obtain new bone substitutes. Also, by using a 3D analysis with finite element the tension distribution at bone--synthesised substitute interface and in bone by comparing to bone substitute was determined. MATERIALS AND METHOD: Collagen type I from tendon bovine source, provided from Sigma-Aldrich, has been used for materials synthesis. Composite materials have been obtained by hydroxyapatite (HA) precipitation from its precursors (aqueous solutions of CaCl2 and NaH2PO4), in the presence of NH4OH and process finalising at 37 degrees C. Three types of materials have been prepared: 75% collagen--25% HA(w/w)--Coll75-HA; 50% collagen--50% HA(w/w)--Coll50-HA; 25% collagen--75% HA(w/ w)--Coll25-HA. Swelling properties of the composite materials were evaluated gravimetrically and in vitro degradation in buffered collagenase was studied. The elasticity modulus was calculated from the dependence force versus material's strain. The 3D analysis with finite element at bone--synthesised substitute interface was performed for a right osteosynthesised fracture from femur. RESULTS AND DISCUSSION: Materials swelling in simulated body fluids revealed higher equilibrium swelling degree for HA-collagen composites with increased content of collagen. Materials are degraded by collagenase, the degradation rate being strongly dependent by composition; a higher content of collagen makes the composites more sensitive to the specific enzyme. SEM data have shown the forming of hydroxyapatite crystals onto collagen fibers. The mechanical characterisation has shown a limited elasticity at an increased value of the applied force for Coll25-HA. Over these forces the plasticity was observed. By using the 3D analysis with finite element at bone--synthesised substitute interface a higher strength was determined in the bone by comparison to bone substitute. CONCLUSIONS: The superior elasticity properties of the synthesised collagen-HA by comparison to physiological biomechanical limits indicate a good behaviour as resistance bone substitute with applications in the extensive bones reconstruction (endoprosthesis revision, bone infections etc.).
Assuntos
Materiais Biocompatíveis/química , Substitutos Ósseos , Colágeno/química , Durapatita/química , Animais , Substitutos Ósseos/síntese química , Osso e Ossos , Bovinos , Força Compressiva , Fraturas do Fêmur/terapia , Humanos , Técnicas In Vitro , Teste de Materiais/métodos , Computação Matemática , Modelos Anatômicos , Estresse MecânicoRESUMO
UNLABELLED: Porous scaffolds based on collagen and chitosan have been obtained from mixed bio-polymeric solutions and mixture freeze-drying method in the purpose of using them as materials for post-burns tissue regeneration. MATERIAL AND METHOD: Soluble collagen from bovine leather was obtained by acid-base extraction (isoelectric pH = 4.82). Two types of chitosan (CS I, M(w) = 755.900, de-acetylating degree of 79.2% and CS II, M(w) = 309.900, de-acetylating degree of 79.7%), were provided by Vascon Co., Canada. Various compositions were prepared and then structurally and morphologically characterized. In vitro degradation studies were performed in buffered collagenase or chitosan solutions, respectively, and the kinetic data were analysed. Materials effect on the tissue regeneration was tested on heat-induced burns in Wistar rats by covering the damaged tissue with collagen-chitosan scaffolds for a period of 28 days. Materials were changed every 7 days. At the end of the follow-up period skin tissue samples were harvested for histological investigation. RESULTS: By freeze-drying of collagen-chitosan solutions porous scaffolds were obtained with a lamellar morphology and porosity closer to chitosan than to collagen. In vitro degradation tests in simulated body fluid with collagenase revealed a decrease of the degradation rate of the collagen by mixing with chitosan. By using chitosan with lower molecular weight the degradation rate of the materials was decreased too, and the influence of the proportion of chitosan in composition diminished; stronger interactions between polymers hinder the enzyme diffusion to the following amino-acids groups: glycine - leucine (Gly-Leu), glycine - isoleucine (Gly-Ile), alanine-proline-glycine/leucine (-Ala-Pro-Gly-/-Leu-). In vivo tests and histological examination revealed a differentiated repair process of the post-combustion wounds in accordance with the scaffold-type influence. CONCLUSION: Scaffolds based on collagen and chitosan are biocompatible materials with promising results for tissue regeneration of the wounds.