Introduction to the RSC Advances themed collection on nano and microscale modifications of biomaterials.

Andrzej Zielinski and Beata Majkowska-Marzec introduce the RSC Advances themed collection on nano and microscale modifications of biomaterials.

Cytocompatibility, antibacterial, and corrosion properties of chitosan/polymethacrylates and chitosan/poly(4-vinylpyridine) smart coatings, electrophoretically deposited on nanosilver-decorated titania nanotubes.

The development of novel implants subjected to surface modification to achieve high osteointegration properties at simultaneous antimicrobial activity is a highly current problem. This study involved different surface treatments of titanium surface, mainly by electrochemical oxidation to produce a nanotubular oxide layer (TNTs), a subsequent electrochemical reduction of silver nitrate and decoration of a nanotubular surface with silver nanoparticles (AgNPs), and finally electrophoretic deposition (EPD) of a composite of chitosan (CS) and either polymethacrylate-based copolymer Eudragit E 100 (EE100) or poly(4-vinylpyridine) (P4VP) coating. The effects of each stage of this multi-step modification were examined in terms of morphology, roughness, wettability, corrosion resistance, coating-substrate adhesion, antibacterial properties, and osteoblast cell adhesion and proliferation. The results showed that the titanium surface formed nanotubes (inner diameter of 97 ± 12 nm, length of 342 ± 36 nm) subsequently covered with silver nanoparticles (with a diameter of 88 ± 8 nm). Further, the silver-decorated nanotubes were tightly coated with biopolymer films. Most of the applied modifications increased both the roughness and the surface contact angle of the samples. The deposition of biopolymer coatings resulted in reduced burst release of silver. The coated samples revealed potent antimicrobial activity against both Gram-positive and Gram-negative bacteria. Total elimination (99.9%) of E. coli was recorded for a sample with CS/P4VP coating. Cytotoxicity results using hFOB 1.19, a human osteoblast cell line, showed that after 3 days the tested modifications did not affect the cellular growth according to the titanium control. The proposed innovative multilayer antibacterial coatings can be successful for titanium implants as effective postoperative anti-inflammation protection.

Trajectories of primary health care utilization: a 10-year follow-up after the Swedish Patient Choice Reform of primary health care.

BACKGROUND: In January 2010, the choice reform was instituted in Swedish primary health care establishing free entry for private primary health care providers and enabling patients to choose freely among primary health care centers. The motivation behind the reform was to improve access to primary care and responsiveness to patient expectations. Reform effects on health care utilization have previously been investigated by using subgroup analyses assuming a pattern of homogeneous subgroups of the population. By using a different methodological approach, the aim of this study was to, from an equity perspective, investigate long term trends of primary health care utilization following the choice reform. METHOD: A closed cohort was created based on register data from Region Skåne, the third most populated region in Sweden, describing individuals' health care utilization between 2007-2017. Using a novel approach, utilization data, measured as primary health care visits, was matched with socioeconomic and geographic determinants, and analyzed using logistic regression models. RESULTS: A total of 659,298 individuals were included in the cohort. Sex differences in utilization were recorded to decrease in the older age group and to increase in the younger age group. Multivariable logistic regression showed increasing utilization in older men to be associated with higher socioeconomic position, while in women it was associated with lower socioeconomic position. Furthermore, groups of becoming high utilizers were all associated with lower socioeconomic position and with residence in urban areas. CONCLUSION: The impact of demographic, socioeconomic and geographic determinants on primary health care utilization varies in magnitude and direction between groups of the population. As a result, the increase in utilization as observed in the general population following the choice reform is unevenly distributed between different population groups.

Evaluation of adhesion strength, corrosion, and biological properties of the MWCNT/TiO2 coating intended for medical applications.

Multi-wall carbon nanotube (MWCNT) coatings are gaining increasing interest because of their special properties used in many science fields. The titania coatings are known for their improvement of osteoblast adhesion, thus changing the surface architecture. Bi-layer coatings comprising 0.25 wt% of the MWCNTs and 0.30 wt% of titania (anatase structure) were synthesized in a two-stage procedure using the electrophoretic deposition method (EPD). The MWCNT and TiO2 coatings were deposited with voltage and time parameters, respectively, of 20 V and 0.5 min, and 50 V and 4 min. EDS, AFM, SEM, Raman spectroscopy, nano-scratch test, potentiodynamic corrosion tests, wettability studies, and cytotoxicity determined with MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test on human dermal fibroblasts (HDF) and mouse osteoblast precursors (MC3T3), and lactate dehydrogenase (LDH) activity test were carried out on examined surfaces. The prepared MWCNT/TiO2 coating is uniformly distributed by MWCNTs and agglomerated by TiO2 particles of size ranging from 0.1 to 3 µm. Raman spectroscopy confirmed the anatase structure of the TiO2 addition and showed typical peaks of the MWCNTs. The MWCNT/TiO2 coating had higher roughness, higher adhesion strength, and improved corrosion resistance compared to the MWCNT basic coating. The results of biological tests proved that physicochemical properties of the surface, such as high porosity and wettability of MWCNT/TiO2-coated material, would support cell adhesion, but toxic species could be released to the culture medium, thus resulting in a decrease in proliferation.

Mechanical Properties and Wear Susceptibility Determined by Nanoindentation Technique of Ti13Nb13Zr Titanium Alloy after "Direct Laser Writing".

Laser treatment has often been applied to rebuild the surface layer of titanium and its alloys destined for long-term implants. Such treatment has always been associated with forming melted and re-solidified thin surface layers. The process parameters of such laser treatment can be different, including the patterning of a surface by so-called direct writing. In this research, pulse laser treatment was performed on the Ti13Nb13Zr alloy surface, with the distance between adjacent laser paths ranging between 20 and 50 µm. The obtained periodic structures were tested to examine the effects of the scan distance on the microstructure using SEM, the roughness and chemical and phase composition using EDS and XRD, and the mechanical properties using the nanoindentation technique. After direct laser writing, the thickness of the melted layers was between 547 and 123 µm, and the surface roughness varied between 1.74 and 0.69 µm. An increase in hardness was observed after laser treatment. The highest hardness, 5.44 GPa, was obtained for the sample modified with a laser beam spacing of 50 µm. The value of the distance has been shown to be important for several properties and related to a complex microstructure of the thin surface layer close to and far from the laser path.

Osteoblast and bacterial cell response on RGD peptide-functionalized chitosan coatings electrophoretically deposited from different suspensions on Ti13Nb13Zr alloy.

Metallic materials for long-term load-bearing implants still do not provide high antimicrobial activity while maintaining strong compatibility with bone cells. This study aimed to modify the surface of Ti13Nb13Zr alloy by electrophoretic deposition of a chitosan coating with a covalently attached Arg-Gly-Asp (RGD) peptide. The suspensions for coating deposition were prepared in two different ways either using hydroxyacetic acid or a carbon dioxide saturation process. The coatings were deposited using a voltage of 10 V for 1 min. The prepared coatings were examined using SEM, EDS, FTIR, and XPS techniques. In addition, the wettability of these surfaces, corrosion resistance, adhesion of the coatings to the metallic substrate, and their antimicrobial activity (E. coli, S. aureus) and cytocompatibility properties using the MTT and LDH assays were studied. The coatings produced tightly covered the metallic substrate. Spectroscopic studies confirmed that the peptide did not detach from the chitosan chain during electrophoretic deposition. All tested samples showed high corrosion resistance (corrosion current density measured in nA/cm2 ). The deposited coatings contributed to a significant increase in the antimicrobial activity of the samples against Gram-positive and Gram-negative bacteria (reduction in bacterial counts from 99% to, for CS-RGD-Acid and the S. aureus strain, total killing capacity). MTT and LDH results showed high compatibility with bone cells of the modified surfaces compared to the bare substrate (survival rates above 75% under indirect contact conditions and above 100% under direct contact conditions). However, the adhesion of the coatings was considered weak.

Influence of Surface Modification of Titanium and Its Alloys for Medical Implants on Their Corrosion Behavior.

Titanium and its alloys are often used for long-term implants after their surface treatment. Such surface modification is usually performed to improve biological properties but seldom to increase corrosion resistance. This paper presents research results performed on such metallic materials modified by a variety of techniques: direct voltage anodic oxidation in the presence of fluorides, micro-arc oxidation (MAO), pulse laser treatment, deposition of chitosan, biodegradable Eudragit 100 and poly(4-vinylpyridine (P4VP), carbon nanotubes, nanoparticles of TiO2, and chitosan with Pt (nano Pt) and polymeric dispersant. The open circuit potential, corrosion current density, and potential values were determined by potentiodynamic technique, and microstructures of the surface layers and coatings were characterized by scanning electron microscopy. The results show that despite the applied modifications, the corrosion current density still appears in the region of very low values of some nA/cm2. However, almost all surface modifications, designed principally for the improvement of biological properties, negatively influence corrosion resistance. The reasons for observed effects can vary, such as imperfections and permeability of some coatings or accelerated degradation of biodegradable deposits in simulated body fluids during electrochemical testing. Despite that, all coatings can be accepted for biological applications, and such corrosion testing results are presumed not to be of major importance for their applications in medicine.

Antibacterial properties of laser-encapsulated titanium oxide nanotubes decorated with nanosilver and covered with chitosan/Eudragit polymers.

To provide antibacterial properties, the titanium samples were subjected to electrochemical oxidation in the fluoride-containing diethylene glycol-based electrolyte to create a titanium oxide nanotubular surface. Afterward, the surface was covered by sputtering with silver 5 nm film, and the tops of the nanotubes were capped using laser treatment, resulting in an appearance of silver nanoparticles (AgNPs) of around 30 nm in diameter on such a modified surface. To ensure a controlled release of the bactericidal substance, the samples were additionally coated with a pH-sensitive chitosan/Eudragit 100 coating, also exhibiting bactericidal properties. The modified titanium samples were characterized using SEM, EDS, AFM, Raman, and XPS techniques. The wettability, corrosion properties, adhesion of the coating to the substrate, the release of AgNPs into solutions simulating body fluids at different pH, and antibacterial properties were further investigated. The obtained composite coatings were hydrophilic, adjacent to the surface, and corrosion-resistant. An increase in the amount of silver released as ions or metallic particles into a simulated body fluid solution at acidic pH was observed for modified samples with the biopolymer coating after three days of exposure avoiding burst effect. The proposed modification was effective against both Gram-positive and Gram-negative bacteria.

Influence of Different Nanometals Implemented in PMMA Bone Cement on Biological and Mechanical Properties.

Cemented arthroplasty is a common process to fix prostheses when a patient becomes older and his/her bone quality deteriorates. The applied cements are biocompatible, can transfer loads, and dampen vibrations, but do not provide antibacterial protection. The present work is aimed at the development of cement with antibacterial effectivity achieved with the implementation of nanoparticles of different metals. The powders of Ag, Cu with particles size in a range of 10-30 nm (Cu10) and 70-100 nm (Cu70), AgCu, and Ni were added to PMMA cement. Their influence on compression strength, wettability, and antibacterial properties of cement was assessed. The surface topography of samples was examined with biological and scanning electron microscopy. The mechanical properties were determined by compression tests. A contact angle was observed with a goniometer. The biological tests included an assessment of cytotoxicity (XTT test on human cells Saos-2 line) and bacteria viability exposure (6 months). The cements with Ag and Cu nanopowders were free of bacteria. For AgCu and Ni nanoparticles, the bacterial solution became denser over time and, after 6 months, the bacteria clustered into conglomerates, creating a biofilm. All metal powders in their native form in direct contact reduce the number of eukaryotic cells. Cell viability is the least limited by Ag and Cu particles of smaller size. All samples demonstrated hydrophobic nature in the wettability test. The mechanical strength was not significantly affected by the additions of metal powders. The nanometal particles incorporated in PMMA-based bone cement can introduce long-term resistance against bacteria, not resulting in any serious deterioration of compression strength.

Manipulation of light spectrum can improve the performance of photosynthetic apparatus of strawberry plants growing under salt and alkalinity stress.

Strawberry is one of the plants sensitive to salt and alkalinity stress. Light quality affects plant growth and metabolic activities. However, there is no clear answer in the literature on how light can improve the performance of the photosynthetic apparatus of this species under salt and alkalinity stress. The aim of this work was to investigate the effects of different spectra of supplemental light on strawberry (cv. Camarosa) under salt and alkalinity stress conditions. Light spectra of blue (with peak 460 nm), red (with peak 660 nm), blue/red (1:3), white/yellow (1:1) (400-700 nm) and ambient light were used as control. There were three stress treatments: control (no stress), alkalinity (40 mM NaHCO3), and salinity (80 mM NaCl). Under stress conditions, red and red/blue light had a positive effect on CO2 assimilation. In addition, blue/red light increased intrinsic water use efficiency (WUEi) under both stress conditions. Salinity and alkalinity stress decreased OJIP curves compared to the control treatment. Blue light caused an increase in its in plants under salinity stress, and red and blue/red light caused an increase in its in plants under alkalinity. Both salt and alkalinity stress caused a significant reduction in photosystem II (PSII) performance indices and quantum yield parameters. Adjustment of light spectra, especially red light, increased these parameters. It can be concluded that the adverse effects of salt and alkalinity stress on photosynthesis can be partially alleviated by changing the light spectra.

Mechanical Properties and Residual Stress Measurements of Grade IV Titanium and Ti-6Al-4V and Ti-13Nb-13Zr Titanium Alloys after Laser Treatment.

Nowadays, surface engineering focuses on research into materials for medical applications. Titanium and its alloys are prominent, especially Ti-6Al-4V and Ti-13Nb-13Zr. Samples made of pure grade IV titanium and the titanium alloys Ti-6Al-4V and Ti-13Nb-13Zr were modified via laser treatment with laser beam frequency f = 25 Hz and laser beam power P = 1000 W during a laser pulse with duration t = 1 ms. Subsequently, to analyze the properties of the obtained surface layers, the following tests were performed: scanning electron microscopy, chemical and phase composition analysis, wetting angle tests and roughness tests. The assessment of the impact of the laser modification on the internal stresses of the investigated materials was carried out by comparing the values of the stresses of the laser-modified samples to those of the reference samples. The obtained results showed increased values of tensile stresses after laser modification: the highest value was found for the Ti-6Al-4V alloy at 6.7434 GPa and the lowest for pure grade IV titanium at 3.742 GPa. After laser and heat treatment, a reduction in the stress was observed, together with a significant increase in the hardness of the tested materials, with the highest value for Ti-6Al-4V alloy at 27.723 GPa. This can provide better abrasion resistance and lower long-term toxicity, both of which are desirable when using Ti-6Al-4V and Ti-13Nb-13Zr alloys for implant materials.

Electrophoretically Deposited Chitosan/Eudragit E 100/AgNPs Composite Coatings on Titanium Substrate as a Silver Release System.

Due to the possibility of bacterial infections occurring around peri-implant tissues, it is necessary to provide implant coatings that release antibacterial substances. The scientific goal of this paper was to produce by electrophoretic deposition (EPD) a smart, chitosan/Eudragit E 100/silver nanoparticles (chit/EE100/AgNPs) composite coating on the surface of titanium grade 2 using different deposition parameters, such as the content of AgNPs, applied voltage, and time of deposition. The morphology, surface roughness, thickness, chemical and phase composition, wettability, mechanical properties, electrochemical properties, and silver release rate at different pH were investigated. Using lower values of deposition parameters, coatings with more homogeneous morphology were obtained. The prepared coatings were sensitive to the reduced pH environment.

Mechanical Behavior of Bi-Layer and Dispersion Coatings Composed of Several Nanostructures on Ti13Nb13Zr Alloy.

Titanium implants are commonly used because of several advantages, but their surface modification is necessary to enhance bioactivity. Recently, their surface coatings were developed to induce local antibacterial properties. The aim of this research was to investigate and compare mechanical properties of three coatings: multi-wall carbon nanotubes (MWCNTs), bi-layer composed of an inner MWCNTs layer and an outer TiO2 layer, and dispersion coatings comprised of simultaneously deposited MWCNTs and nanoCu, each electrophoretically deposited on the Ti13Nb13Zr alloy. Optical microscopy, scanning electron microscopy, X-ray electron diffraction spectroscopy, and nanoindentation technique were applied to study topography, chemical composition, hardness, plastic and elastic properties. The results demonstrate that the addition of nanocopper or titanium dioxide to MWCNTs coating increases hardness, lowers Young's modulus, improves plastic and elastic properties, wear resistance under deflection, and plastic deformation resistance. The results can be attributed to different properties, structure and geometry of applied particles, various deposition techniques, and the possible appearance of porous structures. These innovative coatings of simultaneously high strength and elasticity are promising to apply for deposition on long-term titanium implants.

The Chemical and Biological Properties of Nanohydroxyapatite Coatings with Antibacterial Nanometals, Obtained in the Electrophoretic Process on the Ti13Zr13Nb Alloy.

The risk of an early inflammation after implantation surgery of titanium implants has caused the development of different antimicrobial measures. The present research is aimed at characterizing the effects of nanosilver and nanocopper dispersed in the nanohydroxyapatite coatings, deposited on the Ti13Zr13Nb alloy, and on the chemical and biological properties of the coatings. The one-stage deposition process was performed by the electrophoretic method at different contents of nanomaterials in suspension. The surface topography of the coatings was examined with scanning electron microscopy. The wettability was expressed as the water contact angle. The corrosion behavior was characterized by the potentiodynamic technique. The release rate of copper and silver into the simulated body fluid was investigated by atomic absorption spectrometry. The antibacterial efficiency was evaluated as the survivability and adhesion of the bacteria and the growth of the biofilm. The cytotoxicity was assessed for osteoblasts. The results demonstrate that silver and copper increase the corrosion resistance and hydrophilicity. Both elements together effectively kill bacteria and inhibit biofilm growth but appear to be toxic for osteoblasts. The obtained results show that the nanohydroxyapatite coatings doped with nanosilver and nanocopper in a one-stage electrophoretic process can be valuable for antibacterial coatings.

The Influence of Nanometals, Dispersed in the Electrophoretic Nanohydroxyapatite Coatings on the Ti13Zr13Nb Alloy, on Their Morphology and Mechanical Properties.

In this work, nanohydroxyapatite coatings with nanosilver and nanocopper have been fabricated and studied. The presented results concern coatings with a chemical composition that has never been proposed before. The present research aims to characterize the effects of nanosilver and nanocopper, dispersed in nanohydroxyapatite coatings and deposited on a new, non-toxic Ti13Zr13Nb alloy, on the physical and mechanical properties of coatings. The coatings were obtained by a one-stage electrophoretic process. The surface topography, and the chemical and phase compositions of coatings were examined with scanning electron microscopy, atomic force microscopy, X-ray diffractometry, glow discharge optical emission spectroscopy, and energy-dispersive X-ray spectroscopy. The mechanical properties of coatings were determined by nanoindentation tests, while coatings adhesion was determined by nanoscratch tests. The results demonstrate that copper addition increases the hardness and adhesion. The presence of nanosilver has no significant influence on the adhesion of coatings.

Structural and Material Determinants Influencing the Behavior of Porous Ti and Its Alloys Made by Additive Manufacturing Techniques for Biomedical Applications.

One of the biggest challenges in tissue engineering is the manufacturing of porous structures that are customized in size and shape and that mimic natural bone structure. Additive manufacturing is known as a sufficient method to produce 3D porous structures used as bone substitutes in large segmental bone defects. The literature indicates that the mechanical and biological properties of scaffolds highly depend on geometrical features of structure (pore size, pore shape, porosity), surface morphology, and chemistry. The objective of this review is to present the latest advances and trends in the development of titanium scaffolds concerning the relationships between applied materials, manufacturing methods, and interior architecture determined by porosity, pore shape, and size, and the mechanical, biological, chemical, and physical properties. Such a review is assumed to show the real achievements and, on the other side, shortages in so far research.

Infectious diseases in Poland in 2019.

OBJECTIVE OF THE WORK: The article reviews the main problems of the epidemiology of infectious diseases in Poland. It is an introduction to the Epidemiological Chronicle presented annually in the Epidemiological Review. MATERIAL AND METHODS: The data contained in this article come from the reports of the State Sanitary Inspectorate collected as part of routine epidemiological surveillance. Information on deaths comes from the reports from Statics Poland. RESULTS AND THEIR DISCUSSION: Based on the basic materials, this text presents data on infectious diseases of particular importance due to high incidence, such as influenza and other respiratory infections, or due to increasing trends, such as C. difficile infections, and Lyme disease. Particular attention was paid to diseases against which vaccinations are used and to non-endemic diseases imported from abroad. In the epidemiological characteristics of individual diseases, reference was made mainly to the data on the number of cases, incidence and deaths included in Table 1.

Hydrogen Embrittlement and Oxide Layer Effect in the Cathodically Charged Zircaloy-2.

The present paper is aimed at determining the less investigated effects of hydrogen uptake on the microstructure and the mechanical behavior of the oxidized Zircaloy-2 alloy. The specimens were oxidized and charged with hydrogen. The different oxidation temperatures and cathodic current densities were applied. The scanning electron microscopy, X-ray electron diffraction spectroscopy, hydrogen absorption assessment, tensile, and nanoindentation tests were performed. At low oxidation temperatures, an appearance of numerous hydrides and cracks, and a slight change of mechanical properties were noticed. At high-temperature oxidation, the oxide layer prevented the hydrogen deterioration of the alloy. For nonoxidized samples, charged at different current density, nanoindentation tests showed that both hardness and Young's modulus revealed the minims at specific current value and the stepwise decrease in hardness during hydrogen desorption. The obtained results are explained by the barrier effect of the oxide layer against hydrogen uptake, softening due to the interaction of hydrogen and dislocations nucleated by indentation test, and hardening caused by the decomposition of hydrides. The last phenomena may appear together and result in hydrogen embrittlement in forms of simultaneous hydrogen-enhanced localized plasticity and delayed hydride cracking.

Infectious diseases in Poland in 2018.

OBJECTIVE OF THE ARTICLE: The introductory text to the Epidemiological Chronicle (EC) of the Epidemiological Review contains data on the incidence of infectious and parasitic diseases in Poland in 2018 compared to 2017 data and medians from 2012-2016. It is a general overview of the epidemiological situation of infectious and parasitic diseases in Poland. With regard to selected diseases, widening and deepening picture is in the content of remaining articles of the epidemiological chronicle. MATERIAL AND METHODS: The source data for this article are mainly individual reports submitted by doctors to the County Sanitary/Epidemiological Stations. The basic material of this study is the data published in the bulletins "Infectious diseases and poisoning in Poland in 2018" and "Immunization in Poland in 2018", as well as data published in the reports "Influenza and suspected influenza in Poland in 2018". Data on deaths due to infectious diseases come from the summaries of the Demographic Research Department of the Central Statistical Office. RESULTS AND THE DISCUSSION: As in previous years, the highest incidence was recorded in the category of upper respiratory tract infections and, but to a much lesser extent, gastrointestinal infections. For at least two decades, there has been a shift in the profile of gastrointestinal infections characterized by an increase in viral infections compared to bacterial infections. Regarding healthcare associated infections, rotavirus infections predominate among children and C. difficile infections among adults. The later creates a serious, growing problem, largely related to the use of antibiotics, but also to fecal-oral transmission. Among infectious diseases, C. difficile caused the highest number of deaths in 2018. Viral infection of the liver continues to be an important problem. Apart from hepatitis B and C, this also applies to hepatitis A, which took the form of an epidemic in 2017. In 2018, the incidence decreased by more than a half, but still the number of cases was about thirty times higher than for the median from 2012-2016. Despite declining tendency for many years, the incidence of tuberculosis still remains above the numbers recorded in the developed countries of Western Europe. In other disease groups, there was no marked increase in risk compared to previous years.