Lignin (LIG) is a natural biopolymer with well-known antioxidant capabilities. Accordingly, in the present work, a method to combine LIG with poly(lactic acid) (PLA) for fused filament fabrication ...applications (FFF) is proposed. For this purpose, PLA pellets were successfully coated with LIG powder and a biocompatible oil (castor oil). The resulting pellets were placed into an extruder at 200 °C. The resulting PLA filaments contained LIG loadings ranging from 0% to 3% (
/
). The obtained filaments were successfully used for FFF applications. The LIG content affected the mechanical and surface properties of the overall material. The inclusion of LIG yielded materials with lower resistance to fracture and higher wettabilities. Moreover, the resulting 3D printed materials showed antioxidant capabilities. By using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) method, the materials were capable of reducing the concentration of this compound up to ca. 80% in 5 h. This radical scavenging activity could be potentially beneficial for healthcare applications, especially for wound care. Accordingly, PLA/LIG were used to design meshes with different designs for wound dressing purposes. A wound healing model compound, curcumin (CUR), was applied in the surface of the mesh and its diffusion was studied. It was observed that the dimensions of the meshes affected the permeation rate of CUR. Accordingly, the design of the mesh could be modified according to the patient's needs.
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•A single step solid state crosslinking reaction has been developed to obtain hyaluronic acid hydrogels.•The use of microwave radiation reduces significantly the crosslinking ...time.•The synthesized materials allowed sustained release of a model molecule (methylene blue) for a period of up to 2days.•The material can be used to prepare micro-engineered devices such as microneedles through a micromoulding process.•The resulting hydrogels showed anti-infective and bacteriostatic properties.
Hyaluronic acid (HA) is a natural linear polysaccharide that has been used extensively in the biomedical field as it is a biocompatible, biodegradable, nontoxic and non-immunogenic polymer with high water affinity. Besides, the presence of multiple acid and hydroxyl groups in the HA molecule makes it an ideal candidate for chemical modification. The present paper describes the synthesis and characterization of HA-based hydrogels. For this purpose, aqueous mixtures containing 5% (w/w) of HA and different concentrations of Gantrez S97 (GAN) (1, 3 and 5% w/w) were used to prepare HA-based hydrogels. The mixtures were dried and the hydrogels were obtained after heating the solid material at 80°C for 24h. GAN is the acid form of an methylvinylether and maleic anhydride copolymer and contains multiple acid groups that can form ester bonds when reacting with the multiple hydroxyl groups present in HA chains. The method described here present potential to be applied for the preparation of HA-based biomaterials with a defined form as the crosslinking reaction between HA and the crosslinker takes place in solid phase. Besides, the method can be considered an environmental-friendly process as no organic solvents or potentially toxic substances were used. The esterification reaction was confirmed by infrared spectroscopy and dynamic scanning calorimetry measurements. The loading and release capabilities of the hydrogels were evaluating by using methylene blue (MB) as a model molecule. The hydrogels showed a high affinity for MB showing loadings up to 0.35mg MB per mg of hydrogel. Moreover, the hydrogels were capable of sustaining the MB release over two days. The use of microwave radiation was evaluated to reduce the crosslinking time from 24h to 1h, but this procedure needs to be optimized in future studies. As the crosslinking procedure takes place in solid state, the HA/GAN hydrogels were used to prepare micro-engineered device, microneedle arrays. Finally, the antimicrobial properties of the hydrogels were evaluated. The results showed that the hydrogels presented anti-infective properties.
Lignin (LIG) is a renewable biopolymer with well-known antimicrobial and antioxidant properties. In the present work LIG was combined with poly(butylene succinate) (PBS), a ...biocompatible/biodegradable polymer, to obtain composites with antimicrobial and antioxidant properties. Hot melt extrusion was used to prepare composites containing up to 15% (w/w) of LIG. Water contact angle measurements suggested that the incorporation of LIG did not alter the wettability of the material. The material density increased slightly when LIG was incorporated (<1%). Moreover, the melt flow index test showed an increase in the fluidity of the material (from 6.9 to 27.7 g/10 min) by increasing the LIG content. The Young's modulus and the tensile deformation of the material were practically unaffected when LIG was added. Infrared spectroscopy and differential scanning calorimeter confirmed that there were interactions between LIG and PBS. The DPPH assay was used to evaluate the antioxidant properties of the materials. The results suggested that all the materials were capable of reducing the DPPH concentrations up to 80% in <5 h. Finally, LIG-containing composites showed resistance to adherence of the common nosocomial pathogen, Staphylococcus aureus. All tested materials showed ca. 90% less bacterial adherence than PBS.
•Lignin/Poly(butylene succinate) composites were prepared using hot melt extrusion.•The composites containing up to 15% of lignin.•The presence of lignin in the composite did not alter significantly their mechanical properties.•Lignin-containing composites showed antioxidant activity.•Lignin-containing composites showed resistance to Staphylococcus aureus adherence.
The crystallization of magnesium ammonium phosphate hexahydrate (struvite) often occurs under conditions of fluid flow, yet the dynamics of struvite growth under these relevant environments has not ...been previously reported. In this study, we use a microfluidic device to evaluate the anisotropic growth of struvite crystals at variable flow rates and solution supersaturation. We show that bulk crystallization under quiescent conditions yields irreproducible data owing to the propensity of struvite to adopt defects in its crystal lattice, as well as fluctuations in pH that markedly impact crystal growth rates. Studies in microfluidic channels allow for time‐resolved analysis of seeded growth along all three principle crystallographic directions and under highly controlled environments. After having first identified flow rates that differentiate diffusion and reaction limited growth regimes, we operated solely in the latter regime to extract the kinetic rates of struvite growth along the 100, 010, and 001 directions. In situ atomic force microscopy was used to obtain molecular level details of surface growth mechanisms. Our findings reveal a classical pathway of crystallization by monomer addition with the expected transition from growth by screw dislocations at low supersaturation to that of two‐dimensional layer generation and spreading at high supersaturation. Collectively, these studies present a platform for assessing struvite crystallization under flow conditions and demonstrate how this approach is superior to measurements under quiescent conditions.
Going with the flow: A microfluidics platform for assessing crystal growth under flow conditions is used to characterize struvite crystallization over a range of synthesis conditions. A combination of in situ microfluidic assays and atomic force microscopy measurements reveal that struvite predominantly grows by a classical pathway involving layered surface growth through the addition of solute ions/molecules (see figure; the image of the encrusted catheter has been reprinted by permission from Springer Nature and Elsevier).
We describe, for the first time, stimulus-responsive hydrogel-forming microneedle (MN) arrays that enable delivery of a clinically relevant model drug (ibuprofen) upon application of light. MN arrays ...were prepared using a polymer prepared from 2-hydroxyethyl methacrylate (HEMA) and ethylene glycol dimethacrylate (EGDMA) by micromolding. The obtained MN arrays showed good mechanical properties. The system was loaded with up to 5% (w/w) ibuprofen included in a light-responsive 3,5-dimethoxybenzoin conjugate. Raman spectroscopy confirmed the presence of the conjugate inside the polymeric MN matrix. In vitro, this system was able to deliver up to three doses of 50 mg of ibuprofen upon application of an optical trigger over a prolonged period of time (up to 160 h). This makes the system appealing as a controlled release device for prolonged periods of time. We believe that this technology has potential for use in "on-demand" delivery of a wide range of drugs in a variety of applications relevant to enhanced patient care.
Infectious disease outbreaks within healthcare facilities can exacerbate patient illness and, in some cases, can be fatal. Contaminated surfaces and medical devices can act as a reservoir for ...transmission of pathogens and have been linked to the rising incidence of healthcare-acquired infections. Antimicrobial surfaces can reduce microbial contamination and transmission and have emerged as a crucial component in healthcare infection control in recent years. The aim of this study was to manufacture antimicrobial polymer surfaces containing the photosensitiser, toluidine blue O (TBO), using hot-melt extrusion (HME). Several concentrations of TBO were combined with a range of medically relevant polymers via HME. TBO-polymer extrudates displayed no significant differences in thermal properties and surface wettability relative to non-loaded polymers. Minimal leaching of TBO from the surface was confirmed through in vitro release studies. Antibacterial activity was observed to vary according to the polymer and concentration of incorporated TBO, with PEBAX® polymers modified with 0.1% w/w TBO demonstrating promising reductions of >99.9% in viable bacterial adherence of a range of common nosocomial pathogens, including Staphylococcus aureus, Staphylococcus epidermidis, Acinetobacter baumannii and Escherichia coli. This study demonstrates the use of HME as a facile alternative method to common encapsulation strategies for the production of light-activated antimicrobial polymer surfaces. This method can be easily translated to large-scale manufacture and, in addition, the polymers constitute promising antimicrobial base materials for the rapidly growing additive manufacturing industries.
•TBO-loaded polymers were formulated by hot-melt extrusion without TBO degradation.•Loading of TBO up to 0.1% w/w caused no adverse effects on thermal and wetting properties.•TBO-loaded polymers eradicated both Gram-positive and -negative bacteria.•Antibacterial efficacy may be linked to polymer surface swelling properties.
Long-term catheterised individuals are at significant risk of developing catheter-associated urinary tract infections (CAUTIs), with up to 50% of patients experiencing recurrent episodes of catheter ...encrustation and blockage. Catheter blockage is a result of accumulation of carbonate apatite and struvite formed upon precipitation of ions within urine due to an infection-induced rise in pH. The aim of this study was to investigate the antimicrobial and anti-encrustation activities of tetrasodium ethylenediaminetetraacetic acid (tEDTA) to evaluate its potential efficacy in preventing CAUTIs and catheter blockages. The antimicrobial activity of tEDTA against uropathogens was assessed using time kill assays performed in artificial urine (AU). Crystallisation studies and
in vitro
bladder model assays were conducted to investigate the effect of tEDTA on struvite crystallisation and catheter blockage. tEDTA displayed bacteriostatic activity against
Proteus mirabilis
and prevented precipitation of ions in the AU. Crystallisation studies confirmed tEDTA inhibits struvite nucleation and growth
via
Mg
2+
chelation with 7.63 mM tEDTA, equimolar to the concentration of divalent cations in AU, preventing the formation of crystalline deposits and blockage of Foley catheters for ≥168 h. The promising chelating abilities of low tEDTA concentrations could be exploited to inhibit encrustation and blockage of indwelling catheters. The fundamental research presented will inform our future development of an effective tEDTA-eluting catheter coating aimed at preventing catheter encrustation.
Tetrasodium EDTA is an effective chelating agent that prevents struvite crystallisation in
P. mirabilis
-infected artificial urine, allowing catheters exposed to low tEDTA concentrations to remain unblocked after 168 h.
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Medical device-associated infections present a leading global healthcare challenge, and effective strategies to prevent infections are urgently required. Herein, we present an ...innovative anti-adherent hydrogel copolymer as a candidate catheter coating with complementary hydrophobic drug-carrying and eluting capacities. The amphiphilic block copolymer, Poloxamer 188, was chemically-derivatized with methacryloyl moieties and copolymerized with the hydrogel monomer, 2-hydroxyethyl methacrylate. Performance of the synthesized copolymers was evaluated in terms of equilibrium swelling, surface water wettability, mechanical integrity, resistance to encrustation and bacterial adherence, and ability to control release of the loaded fluoroquinolone antibiotic, ofloxacin. The developed matrices were able to provide significant protection from fouling, with observed reductions of over 90% in both adherence of the common urinary pathogen Escherichia coli and encrusting crystalline deposits of calcium and magnesium salts relative to the commonly employed hydrogel, poly (hydroxyethyl methacrylate). Additionally, the release kinetics of a loaded hydrophobic drug could be readily tuned through facile manipulation of polymer composition. This combinatorial approach shows significant promise in the development of suitable systems for prevention of catheter-associated infections.
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•PVC was herein surface functionalized with 4-aminothiophenol.•A variety of reaction conditions were systematically investigated.•Degrees of modification approximating 150μgcm−3 were ...obtained under optimal conditions.•This optimized method will facilitate an array of property-enhancing modifications.
The efficient covalent functionalization of poly(vinyl chloride) (PVC), which is widely used in medical device manufacture, allows an array of potential property-enhancing surface modifications to be made. To demonstrate a general method of functionalization via substituted (functional) thiols, we describe a systematic approach to the optimization of PVC surface modification by nucleophilic substitution with 4-aminothiophenol through control of reaction conditions: solvent composition, sonication, reaction time and presence of base and/or phase transfer catalyst (PTC). Efficient thiol attachment was confirmed using solid-state NMR and Raman spectroscopies, and the extent of surface modification was quantified using ATR-FTIR spectroscopy. Sonicated samples exhibited a lower degree of modification than their statically immersed counterparts (21.7vs 99.6μgcm−3), and mechanical integrity was compromised. In DMSO/H2O systems with a PTC, resultant degrees of PVC surface modification were up to 12.5% higher when caesium carbonate was employed as the base than in corresponding systems with potassium carbonate.
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