Fucoidan- and Ciprofloxacin-Doped Plasma-Activated Polymer Coatings on Biodegradable Zinc: Hemocompatibility and Drug Release.

Blood-contacting medical devices such as biodegradable metallic bone implant materials are expected to show excellent hemocompatibility both in vitro and in vivo. Different approaches are being studied and used to modify biomaterial surfaces for enhanced biocompatibility and hemocompatibility. However, the composition of degradable biomaterial must address several drawbacks at once. Iron-reinforced zinc material was used as a metallic substrate with improved mechanical properties when compared with those of pure zinc. Poly(lactic) acid (PLA) or polyethylenimine (PEI) was selected as a polymeric matrix for further doping with antibiotic ciprofloxacin (CPR) and marine-sourced polysaccharide fucoidan (FU), which are known for their antibacterial and potential anticoagulant properties, respectively. Radiofrequency air plasma was employed to induce metallic/polymer-coated surface activation before further modification with FU/CPR. Sample surface morphology and composition were studied and evaluated (contact angle measurements, AFM, SEM, and FT-IR) along with the hemolysis ratio and platelet adhesion test. Successful doping of the polymer layer by FU/CRP was confirmed. While PEI induced severe hemolysis over 12%, the PLA-coated samples exhibited even lower hemolysis (∼2%) than uncoated samples while the uncoated samples showed the lowest platelet adhesion. Moreover, gradual antibiotic release from PLA determined by the electrochemical methods using screen-printed carbon electrodes was observed after 24, 48, and 72 h, making the PLA-coated zinc-based material an attractive candidate for biodegradable material design.

Colloidal lithography as a novel approach for the development of Ni-nanocavity insulin sensor.

In this study, a highly sensitive, fast, and selective enzyme-free electrochemical sensor based on the deposition of Ni cavities on conductive glass was proposed for insulin detection. Considering the growing prevalence of diabetes mellitus, an electrochemical sensor for the determination of insulin was proposed for the effective diagnosis of the disease. Colloidal lithography enabled deposition of nanostructured layer (substrate) with homogeneous distribution of Ni cavities on the electrode surface with a large active surface area. The morphology and structure of conductive indium tin oxide glass modified with Ni cavities (Ni-c-ITO) were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The diameter of the resulting cavities was approximately 500 nm, while their depth was calculated at 190 ± 4 nm and 188 ± 18 nm using AFM and SEM, respectively. The insulin assay performance was evaluated by cyclic voltammetry. Ni-c-ITO exhibited excellent analytical characteristics, including high sensitivity (1.032 µA µmol-1 dm3), a low detection limit (156 µmol dm-3), and a wide dynamic range (500 nmol dm-3 to 10 µmol dm-3). Finally, the determination of insulin in buffer with interferents and in real blood serum samples revealed high specificity and demonstrated the practical potential of the method.

Interaction of thin polyethyleneimine layer with the iron surface and its effect on the electrochemical behavior.

Polymer-coated metals may act as biodegradable orthopedic implants with adjustable corrosion rates. Metallic surfaces represent a dynamic system with specific interactions occurring after the material is implanted into the human body. An additional layer, in the form of polymeric thin film, changes the nature of this metal-body fluids interface. Moreover, the interaction between polymer and metal itself can differ for various systems. Iron-based material modified with a thin layer of polyethyleneimine (PEI) coating was prepared and studied as potential absorbable implant. Computational methods were employed to study the interaction between the metallic surface and polymer functional monomer units at atomic levels. Various spectroscopical and optical methods (SEM, AFM, Confocal, and Raman spectroscopy) were also used to characterize prepared material. Electrochemical measurements have been chosen to study the polymer adsorption process onto the iron surface and corrosion behavior which is greatly influenced by the PEI presence. The adsorption mechanism of PEI onto iron was proposed alongside the evaluation of Fe and Fe-PEI degradation behavior studied using the impedance method. Bonding via amino -NH2 group of PEI onto Fe and enhanced corrosion rate of coated samples were observed and confirmed.

Microstructural, Mechanical and Corrosion Characteristics of Degradable PM Biomaterials Made from Copper-Coated Iron Powders.

Copper-containing iron-based materials have recently been recognized as potential biomaterials possessing antimicrobial ability. Since then, iron-copper systems have been prepared by different methods and investigated. This article is focused on PM materials made from composite powders. The powders, each particle of which consisted of an iron core and a copper shell, were prepared by electroplating. Test-pieces with copper contents of 0, 3.2, and 8 wt.% were fabricated by pressing and sintering from iron and composite powders. Some microstructural, mechanical, and corrosion characteristics of test-pieces were examined. Microstructures were composed of pores and iron grains with alloyed peripheral regions and copper-free cores. As the copper content in test-pieces was increased, their density and Young's modulus decreased, and macrohardness, corrosion potential and corrosion current density increased. Likely causes of density and Young's modulus reduction were higher porosity, low enough copper content, and compliant inclusions in stiff matrix. The increase in macrohardness was attributed to the precipitation hardening which prevailed over softening induced by pores. The increase in corrosion potential and corrosion current density was most likely due to the presence of more noble phase providing surfaces for a faster cathodic reaction.

Electrochemical behavior, biocompatibility and mechanical performance of biodegradable iron with PEI coating.

Coating of the biodegradable metals represents an effective way of modification of their properties. Insufficient biological, mechanical, or degradation performance of pure metals may be enhanced when the proper type of organic polymer coating is used. In our previous work, the significant effect of the polyethyleneimine (PEI) coating not only on the rate but also on the type of corrosion was discovered. To bring a comprehensive overview of the Fe-PEI system performance, iron-based biodegradable scaffolds with polyethyleneimine coating were studied and their cytocompatibility and hemocompatibility, and mechanical properties were evaluated and discussed in this work. Electrochemical impedance spectroscopy (EIS) measurements were conducted for further study of material behavior. Biological analyses (MTS assay, fluorescent imaging, hemocompatibility tests) showed better cell proliferation on the surface of Fe-PEI samples but not sufficient overall cytocompatibility. Good anti-platelet adhesion properties but higher hemolysis when compared to the pure iron was also observed for the coated samples. Mechanical properties of the prepared Fe-PEI material were enhanced after coating. These findings suggest that the Fe-PEI may be an interesting potential biomaterial after further composition optimization resulting in lower cytotoxicity and better hemocompatibility.

Corrosion Behavior of Zn, Fe and Fe-Zn Powder Materials Prepared via Uniaxial Compression.

Powder metallurgy is one of the most prevalent ways for metallic degradable materials preparation. Knowledge of the properties of initial powders used during this procedure is therefore of great importance. Two different metals, iron and zinc, were selected and studied in this paper due to their promising properties in the field of biodegradable implants. Raw powders were studied using scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDX). Powders (Fe, Zn and Fe-Zn in a weight ratio of 1:1) were then compressed at the pressure of 545 MPa to the form of pellets with a diameter of 1.7 cm. Surface morphology and degradation behavior in the Hanks´ solution were studied and evaluated. Electrochemical polarization tests along with the static immersion tests carried out for 21 days were employed for corrosion behavior characterization. The highest corrosion rate was observed for pure Zn powder followed by the Fe-Zn and Fe, respectively. A mixed Fe-Zn sample showed similar properties as pure zinc with no signs of iron degradation after 21 days due to the effect of galvanic protection secured by the zinc acting as a sacrificial anode.

NiO Nanoparticles for Electrochemical Insulin Detection.

Diabetes mellitus represents one of the most widespread diseases in civilization nowadays. Since the costs for treating and diagnosing of diabetes represent several billions of dollars per year, a cheap, fast, and simple sensor for diabetes diagnosis is needed. Electrochemical insulin sensors can be considered as a novel approach for diabetes diagnosis. In this study, carbon electrode with electrodeposited NiO nanoparticles was selected as a suitable electrode material for insulin determination. The morphology and surface composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). For a better understanding of insulin determination on NiO-modified electrodes, the mechanism of electrochemical reaction and the kinetic parameters were studied. They were calculated from both voltammetric and amperometric measurements. The modified carbon electrode displayed a wide linear range from 600 nM to 10 µM, a low limit of detection of 19.6 nM, and a high sensitivity of 7.06 µA/µM. The electrodes were stable for 30 cycles and were able to detect insulin even in bovine blood serum. Additionally, the temperature stability of this electrode and its storage conditions were studied with appropriate outcomes. The above results show the high promise of this electrode for detecting insulin in clinical samples.

Detection of organic dyes by surface-enhanced Raman spectroscopy using plasmonic NiAg nanocavity films.

This work presents the NiAg nanocavity film for the detection of organic dyes by surface-enhanced Raman spectroscopy (SERS). Nanocavity films were prepared by colloidal lithography using 518-nm polystyrene spheres combined with the electrochemical deposition of Ni supporting layer and Ag nanoparticles homogeneous SERS-active layer. The theoretical study was modelled by finite-difference time-domain (FDTD) simulation of electromagnetic field enhancement near the nanostructured surface and experimentally proven by SERS measurement of selected organic dyes (rhodamine 6G, crystal violet, methylene blue, and malachite green oxalate) in micromolar concentration. Furthermore, the concentration dependence was investigated to prove the suitability of NiAg nanocavity films to detect ultra-low concentrations of samples. The detection limit was 1.3 × 10-12, 1.5 × 10-10, 1.4 × 10-10, 7.5 × 10-11 mol·dm-3, and the standard deviation was 20.1%, 13.8%, 16.7%, and 19.3% for R6G, CV, MB, and MGO, respectively. The analytical enhancement factor was 3.4 × 105 using R6G as a probe molecule. The principal component analysis (PCA) was performed to extract the differences in complex spectra of the dyes where the first and second PCs carry 42.43% and 31.39% of the sample variation, respectively. The achieved results demonstrated the suitability of AgNi nanocavity films for the SERS-based detection of organic dyes, with a potential in other sensing applications.

Degradation Performance of Open-Cell Biomaterials from Phosphated Carbonyl Iron Powder with PEG Coating.

Advances in biomedicine and development of modern technologies in the last century have fostered the improvement in human longevity and well-being. This progress simultaneously initiated the need for novel biomaterials. Recently, degradable metallic biomaterials have attracted serious attention in scientific and clinical research owing to their utilization in some specific applications. This work investigates the effect of the polyethylene glycol (PEG) coating of open-cell iron and phosphorus/iron foams on their microstructure and corrosion properties. The addition of phosphorus causes a slight increase in pore size and the deposition of a polymer coating results in a smoothened surface and a moderate decrease in pore diameter. The PEG coating leads to an increase in corrosion rates in both foams and potentially a more desirable product.

In Vitro Corrosion Behavior of Biodegradable Iron Foams with Polymeric Coating.

Research in the field of biodegradable metallic scaffolds has advanced during the last decades. Resorbable implants based on iron have become an attractive alternative to the temporary devices made of inert metals. Overcoming an insufficient corrosion rate of pure iron, though, still remains a problem. In our work, we have prepared iron foams and coated them with three different concentrations of polyethyleneimine (PEI) to increase their corrosion rates. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), Fourier-transform infrared spectroscopy (FT-IR), and Raman spectroscopy were used for characterization of the polymer coating. The corrosion behavior of the powder-metallurgically prepared samples was evaluated electrochemically using an anodic polarization method. A 12 weeks long in vitro degradation study in Hanks' solution at 37 °C was also performed. Surface morphology, corrosion behavior, and degradation rates of the open-cell foams were studied and discussed. The use of PEI coating led to an increase in the corrosion rates of the cellular material. The sample with the highest concentration of PEI film showed the most rapid corrosion in the environment of simulated body fluids.

Influence of a polymer membrane on the electrochemical determination of insulin in nanomodified screen printed carbon electrodes.

Diabetes mellitus can be considered one of the most widespread diseases globally. Hence, the diabetes research is currently focused on developing an effective, low-cost sensor having high stability and suitable analytical characteristics. Screen printed carbon electrodes (SPCEs) embody ideal candidates for insulin determination due to the small area of the working electrode eliminating the solution volume required for the given purpose. Modification of SPCEs by using nanoparticles resulted in an increase of the working electrode surface area and formation of a higher number of active species. The aim of this paper is to examine the impact of a chitosan membrane on the electrochemical determination of insulin on NiO nanoparticles (NiONPs) and multi-walled nanotube (MWCNTs) modified SPCE (NiONPs/MWCNTs/SPCE). This study is primarily conceived to compare the analytical characteristics and stability of NiONPs/chitosan-MWCNTs/SPCE and NiONPs/MWCNTs/SPCE. An electrode modified with chitosan displays a wider linear range, one of 0.25 µM - 5 µM (R2 0.997); a lower limit of detection, 94 nM; a high sensitivity (0.021 µA/µM) and better stability than that of an electrode without chitosan. According to these characteristics, the polymer is considered a necessary compound of the electrochemical insulin sensor, improving the sensor's analytical characteristics.

Electrochemically deposited silver detection substrate for surface-enhanced Raman spectroscopy cancer diagnostics.

Surface-enhanced Raman spectroscopy (SERS) of blood plasma on an electrochemically prepared silver surface has been studied as a label-free, noninvasive diagnostic test for colorectal cancer. Indium tin oxide glass substrates were modified with 0.01 mol dm - 3 silver nitrate using the pulsed double-potentiostatic method. The prepared silver substrates were tested with Rhodamine 6G as a model analyte and the surface with the highest signal enhancement was selected. This silver dendritic surface was used as a diagnostic substrate for SERS measurements of human blood plasma. A group of oncological patients with declared colorectal carcinoma (n = 15) and the control group of healthy volunteers (n = 15) were compared. The biomolecular changes in chemical composition in the cancer samples were detected by statistical processing of the resulting SERS spectra. About 94% specificity and 100% sensitivity were achieved for the analysis by the ratio of the SERS peak intensity at 725 cm - 1 for adenine to the peak intensity at 638 cm - 1 for tyrosine and 100% specificity and sensitivity by using principal component analysis. This method of SERS diagnostics of colorectal cancer, which does not require the nanoparticle preparation, mixing, and incubation of plasma with a colloidal solution as in conventional tests, is a rapid, inexpensive method, which could be introduced as a primary diagnostic test.

A study of cytocompatibility and degradation of iron-based biodegradable materials.

Biodegradable metallic implants are of significant importance in the replacement of bones or the repair of bone defects. Iron-phosphate-coated carbonyl iron powder (Fe/P) was prepared by the phosphating method. Moreover, Fe/P-Mn alloy was produced by sintering the Fe/P powder mixed with manganese powder. Bare carbonyl iron samples and the Fe/P and Fe/P-Mn sintered samples were evaluated for their microstructure, cytotoxicity, and hemocompatibility. The microstructure of the sintered samples was examined using an optical microscope and scanning electron microscopic analysis. Corrosion behavior was evaluated by potentiodynamic polarization in Hank's solution. The in vitro biocompatibilities were investigated by cytotoxicity and hemolysis tests. The results obtained demonstrate that the addition of Mn resulted in higher surface inhomogeneity, porosity and roughness as well as in increased cytotoxicity. The phosphate coating has a moderately negative effect on the cytotoxicity. The corrosion rates determined from Tafel diagrams were ordered in the following sequence: Fe/P-Mn, Fe, Fe/P from high to low. The hemocompatibility of experimental samples was ordered in the following sequence: Fe/P, Fe/P-Mn, Fe from high to low. All samples were found to be hemocompatible.

Introduction to time-of-flight secondary ion mass spectrometry application in chromatographic analysis.

New on-line analytical system coupling thin layer chromatography (TLC) and high selective identification unit-time of flight secondary ion mass spectrometry (TOF-SIMS) is introduced in this article. Chromatographic mixture separation and analyte surface deposition followed with surface TOF-SIMS analysis on-line allows to identify the analytes at trace and ultratrace levels. The selected analytes with different detectability and identification possibility were analysed in this hyphenated unit (Methyl Red indicator, Terpinolen and Giberrelic acid). Here, the chromatographic thin layer plays a universal role: separation unit, analyte depositing surface and TOF-SIMS interface, finally. Two depositing substrates and TOF-SIMS compatible interfaces were tested in above-mentioned interfacing unit: modified aluminium backed chromatographic thin layer and monolithic silica thin layer. The sets of positive and negative ions TOF-SIMS spectra obtained from different SIMS modes of analysis were used for analyte identification purposes. SIMS enables analyte detection with high mass resolution at the concentration level that is not achieved by other methods.