Dental silicate ceramics surface modification by nonthermal plasma: A systematic review.

OBJECTIVES: Nonthermal atmospheric or low-pressure plasma (NTP) can improve the surface characteristics of dental materials without affecting their bulk properties. This study aimed to systematically review the available scientific evidence on the effectiveness of using NTP for the surface treatment of etchable, silica-based dental ceramics before cementation, and elucidate its potential to replace the hazardous and technically demanding protocol of hydrofluoric acid (HF) etching. METHODS: A valid search query was developed with the help of PubMed's Medical Subject Headings (MeSH) vocabulary thesaurus and translated to three electronic databases: PubMed, Web of Science, and Scopus. The methodological quality of the studies was assessed according to an adapted version of the Methodological Index for Non-Randomized Studies (MINORS). RESULTS: Thirteen in vitro study reports published between 2008 and 2023 were selected for the qualitative and quantitative data synthesis. The implemented methodologies were diverse, comprising 19 different plasma treatment protocols with various device settings. Argon, helium, oxygen, or atmospheric air plasma may significantly increase the wettability and roughness of silicate ceramics by plasma cleaning, etching, and activation, but the treatment generally results in inferior bond strength values after cementation compared to those achieved with HF etching. The technically demanding protocol of plasma-enhanced chemical vapor deposition was employed more commonly, in which the surface deposition of hexamethyl disiloxane with subsequent oxygen plasma activation proved the most promising, yielding bond strengths comparable to those of the positive control. Lack of power analysis, missing adequate control, absence of examiner blinding, and non-performance of specimen aging were common methodological frailties that contributed most to the increase in bias risk (mean MINORS score 15.3 ± 1.1). SIGNIFICANCE: NTP can potentially improve the adhesive surface characteristics of dental silicate ceramics in laboratory conditions, but the conventional protocol of HF etching still performs better in terms of the resin-ceramic bond strength and longevity. More preclinical research is needed to determine the optimal NTP treatment settings and assess the aging of plasma-treated ceramic surfaces in atmospheric conditions.

Fine-Tuning the Nanostructured Titanium Oxide Surface for Selective Biological Response.

Cardiovascular diseases are a pre-eminent global cause of mortality in the modern world. Typically, surgical intervention with implantable medical devices such as cardiovascular stents is deployed to reinstate unobstructed blood flow. Unfortunately, existing stent materials frequently induce restenosis and thrombosis, necessitating the development of superior biomaterials. These biomaterials should inhibit platelet adhesion (mitigating stent-induced thrombosis) and smooth muscle cell proliferation (minimizing restenosis) while enhancing endothelial cell proliferation at the same time. To optimize the surface properties of Ti6Al4V medical implants, we investigated two surface treatment procedures: gaseous plasma treatment and hydrothermal treatment. We analyzed these modified surfaces through scanning electron microscopy (SEM), water contact angle analysis (WCA), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) analysis. Additionally, we assessed in vitro biological responses, including platelet adhesion and activation, as well as endothelial and smooth muscle cell proliferation. Herein, we report the influence of pre/post oxygen plasma treatment on titanium oxide layer formation via a hydrothermal technique. Our results indicate that alterations in the titanium oxide layer and surface nanotopography significantly influence cell interactions. This work offers promising insights into designing multifunctional biomaterial surfaces that selectively promote specific cell types' proliferation─which is a crucial advancement in next-generation vascular implants.

Fabrication of Antibacterial TiO2 Nanostructured Surfaces Using the Hydrothermal Method.

Implant-associated infections (IAI) are a common cause for implant failure, increased medical costs, and critical for patient healthcare. Infections are a result of bacterial colonization, which leads to biofilm formation on the implant surface. Nanostructured surfaces have been shown to have the potential to inhibit bacterial adhesion mainly due to antibacterial efficacy of their unique surface nanotopography. The change in topography affects the physicochemical properties of their surface such as surface chemistry, morphology, wettability, surface charge, and even electric field which influences the biological response. In this study, a conventional and cost-effective hydrothermal method was used to fabricate nanoscale protrusions of various dimensions on the surface of Ti, Ti6Al4V, and NiTi materials, commonly used in biomedical applications. The morphology, surface chemistry, and wettability were analyzed using scanning electron microscopy (SEM), X-ray photoemission spectroscopy (XPS), and water contact angle analysis. The antibacterial efficacy of the synthesized nanostructures was analyzed by the use of Escherichia coli bacterial strain. XPS analysis revealed that the concentration of oxygen and titanium increased on Ti and Ti6Al4V, which indicates that TiO2 is formed on the surface. The concentration of oxygen and titanium however decreased on the NiTi surface after hydrothermal treatment, and also a small amount of Ni was detected. SEM analysis showed that by hydrothermal treatment alterations in the surface topography of the TiO2 layer could be achieved. The oxide layer on the NiTi prepared by the hydrothermal method contains a low amount of Ni (2.8 atom %), which is especially important for implantable materials. The results revealed that nanostructured surfaces significantly reduced bacterial adhesion on the Ti, Ti6Al4V, and NiTi surface compared to the untreated surfaces used as a control. Furthermore, two sterilization techniques were also studied to evaluate the stability of the nanostructure and its influence on the antibacterial activity. Sterilization with UV light seems to more efficiently inhibit bacterial growth on the hydrothermally modified Ti6Al4V surface, which was further reduced for hydrothermally treated Ti and NiTi. The developed nanostructured surfaces of Ti and its alloys can pave a way for the fabrication of antibacterial surfaces that reduce the likelihood of IAI.

Nanoporous Stainless Steel Materials for Body Implants-Review of Synthesizing Procedures.

Despite the inadequate biocompatibility, medical-grade stainless steel materials have been used as body implants for decades. The desired biological response of surfaces to specific applications in the body is a highly challenging task, and usually not all the requirements of a biomaterial can be achieved. In recent years, nanostructured surfaces have shown intriguing results as cell selectivity can be achieved by specific surface nanofeatures. Nanoporous structures can be fabricated by anodic oxidation, which has been widely studied for titanium and its alloys, while no systematic studies are so far available for stainless steel (SS) materials. This paper reviews the current state of the art in the anodisation of SS; correlations between the parameters of anodic oxidation and the surface morphology are drawn. The results reported by various authors are scattered because of a variety of experimental configurations. A linear correlation between the pores' diameter anodisation voltage was deduced, while no correlation with other processing parameters was found obvious. The analyses of available data indicated a lack of systematic experiments, which are recommended to understand the kinetics of pore formation and develop techniques for optimal biocompatibility of stainless steel.

Bio-Performance of Hydrothermally and Plasma-Treated Titanium: The New Generation of Vascular Stents.

The research presented herein follows an urgent global need for the development of novel surface engineering techniques that would allow the fabrication of next-generation cardiovascular stents, which would drastically reduce cardiovascular diseases (CVD). The combination of hydrothermal treatment (HT) and treatment with highly reactive oxygen plasma (P) allowed for the formation of an oxygen-rich nanostructured surface. The morphology, surface roughness, chemical composition and wettability of the newly prepared oxide layer on the Ti substrate were characterized by scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA) analysis. The alteration of surface characteristics influenced the material's bio-performance; platelet aggregation and activation was reduced on surfaces treated by hydrothermal treatment, as well as after plasma treatment. Moreover, it was shown that surfaces treated by both treatment procedures (HT and P) promoted the adhesion and proliferation of vascular endothelial cells, while at the same time inhibiting the adhesion and proliferation of vascular smooth muscle cells. The combination of both techniques presents a novel approach for the fabrication of vascular implants, with superior characteristics.

Mechanical and Electrical Interaction of Biological Membranes with Nanoparticles and Nanostructured Surfaces.

In this review paper, we theoretically explain the origin of electrostatic interactions between lipid bilayers and charged solid surfaces using a statistical mechanics approach, where the orientational degree of freedom of lipid head groups and the orientational ordering of the water dipoles are considered. Within the modified Langevin Poisson-Boltzmann model of an electric double layer, we derived an analytical expression for the osmotic pressure between the planar zwitterionic lipid bilayer and charged solid planar surface. We also show that the electrostatic interaction between the zwitterionic lipid head groups of the proximal leaflet and the negatively charged solid surface is accompanied with a more perpendicular average orientation of the lipid head-groups. We further highlight the important role of the surfaces' nanostructured topography in their interactions with biological material. As an example of nanostructured surfaces, we describe the synthesis of TiO2 nanotubular and octahedral surfaces by using the electrochemical anodization method and hydrothermal method, respectively. The physical and chemical properties of these nanostructured surfaces are described in order to elucidate the influence of the surface topography and other physical properties on the behavior of human cells adhered to TiO2 nanostructured surfaces. In the last part of the paper, we theoretically explain the interplay of elastic and adhesive contributions to the adsorption of lipid vesicles on the solid surfaces. We show the numerically predicted shapes of adhered lipid vesicles corresponding to the minimum of the membrane free energy to describe the influence of the vesicle size, bending modulus, and adhesion strength on the adhesion of lipid vesicles on solid charged surfaces.

Use of Plasma Technologies for Antibacterial Surface Properties of Metals.

Bacterial infections of medical devices present severe problems connected with long-term antibiotic treatment, implant failure, and high hospital costs. Therefore, there are enormous demands for innovative techniques which would improve the surface properties of implantable materials. Plasma technologies present one of the compelling ways to improve metal's antibacterial activity; plasma treatment can significantly alter metal surfaces' physicochemical properties, such as surface chemistry, roughness, wettability, surface charge, and crystallinity, which all play an important role in the biological response of medical materials. Herein, the most common plasma treatment techniques like plasma spraying, plasma immersion ion implantation, plasma vapor deposition, and plasma electrolytic oxidation as well as novel approaches based on gaseous plasma treatment of surfaces are gathered and presented. The latest results of different surface modification approaches and their influence on metals' antibacterial surface properties are presented and critically discussed. The mechanisms involved in bactericidal effects of plasma-treated surfaces are discussed and novel results of surface modification of metal materials by highly reactive oxygen plasma are presented.

Strategies for improving antimicrobial properties of stainless steel.

In this review, strategies for improving the antimicrobial properties of stainless steel (SS) are presented. The main focus given is to present current strategies for surface modification of SS, which alter surface characteristics in terms of surface chemistry, topography and wettability/surface charge, without influencing the bulk attributes of the material. As SS exhibits excellent mechanical properties and satisfactory biocompatibility, it is one of the most frequently used materials in medical applications. It is widely used as a material for fabricating orthopedic prosthesis, cardiovascular stents/valves and recently also for three dimensional (3D) printing of custom made implants. Despite its good mechanical properties, SS lacks desired biofunctionality, which makes it prone to bacterial adhesion and biofilm formation. Due to increased resistance of bacteria to antibiotics, it is imperative to achieve antibacterial properties of implants. Thus, many different approaches were proposed and are discussed herein. Emphasis is given on novel approaches based on treatment with highly reactive plasma, which may alter SS topography, chemistry and wettability under appropriate treatment conditions. This review aims to present and critically discuss different approaches and propose novel possibilities for surface modification of SS by using highly reactive gaseous plasma in order to obtain a desired biological response.

Crystallized TiO2 Nanosurfaces in Biomedical Applications.

Crystallization alters the characteristics of TiO2 nanosurfaces, which consequently influences their bio-performance. In various biomedical applications, the anatase or rutile crystal phase is preferred over amorphous TiO2. The most common crystallization technique is annealing in a conventional furnace. Methods such as hydrothermal or room temperature crystallization, as well as plasma electrolytic oxidation (PEO) and other plasma-induced crystallization techniques, present more feasible and rapid alternatives for crystal phase initiation or transition between anatase and rutile phases. With oxygen plasma treatment, it is possible to achieve an anatase or rutile crystal phase in a few seconds, depending on the plasma conditions. This review article aims to address different crystallization techniques on nanostructured TiO2 surfaces and the influence of crystal phase on biological response. The emphasis is given to electrochemically anodized nanotube arrays and their interaction with the biological environment. A short overview of the most commonly employed medical devices made of titanium and its alloys is presented and discussed.

Titanium Dioxide Nanotube Arrays for Cardiovascular Stent Applications.

Efficient stent implantation among others depends on avoiding the aggregation of platelets in the blood vessels and appropriate proliferation of endothelial cells and controlled proliferation of smooth muscle cells, which reduces the development of pathology, such as neointimal hyperplasia, thrombosis, and restenosis. The current article provides an elegant solution for prevention of platelet and smooth muscle cell adhesion and activation on stent surfaces while obtaining surface conditions to support the growth of human coronary artery endothelial cells. This was achieved by surface nanostructuring and chemical activation of the surface. Specific nanotopographies of titanium were obtained by electrochemical anodization, while appropriate chemical properties were attained by treatment of titanium oxide nanotubes by highly reactive oxygen plasma. Surface properties were studied by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Wettability was evaluated by measuring the water contact angle. The influence of nanostructured morphology and plasma modification on in vitro biological response with human coronary artery endothelia and smooth muscle cells as well as whole blood was studied. Our results show that a combination of nanostructuring and plasma modification of the surfaces is an effective way to achieve desired biological responses necessary for implantable materials such as stents.

Plasma-Induced Crystallization of TiO2 Nanotubes.

Facile crystallization of titanium oxide (TiO2) nanotubes (NTs), synthesized by electrochemical anodization, with low pressure non-thermal oxygen plasma is reported. The influence of plasma processing conditions on TiO2 NTs crystal structure and morphology was examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). For the first time we report the transition of amorphous TiO2 NTs to anatase and rutile crystal structures upon treatment with highly reactive oxygen plasma. This crystallization process has a strong advantage over the conventional heat treatments as it enables rapid crystallization of the surface. Thus the crystalline structure of NTs is obtained in a few seconds of treatment and it does not disrupt the NTs' morphology. Such a crystallization approach is especially suitable for medical applications in which stable crystallized nanotubular morphology is desired. The last part of the study thus deals with in vitro biological response of whole blood to the TiO2 NTs. The results indicate that application of such surfaces for blood connecting devices is prospective, as practically no platelet adhesion or activation on crystallized TiO2 NTs surfaces was observed.

Visible-light photoactivity of Bi-pyrochlores with high Fe contents.

Three Bi-pyrochlores with different Fe contents (Bi(2)Ti(2)O(7), Bi(1.65)Nb(1.12)Fe(1.16)O(7) and Bi(1.9)Te(0.58)Fe(1.52)O(6.87)) were synthesized in the form of nanopowders with similar morphological characteristics. All three nanopowders show an intensive visible-light photocatalytic activity. The analysis of their band gap and absorption characteristics has shown a strong correlation with the Fe-content indicating that a significant band gap reduction can be obtained by Fe incorporation. The photocatalytic activity has not followed this trend. The initial increase in the Fe-content has resulted in a significant enhancement of the photoactivity while with the further increase the photoactivity has slowly decreased. The reason for this behaviour has been proposed to be in an opposing influence of the increased exciton density and recombination rate.

Intensive visible-light photoactivity of Bi- and Fe-containing pyrochlore nanoparticles.

Bi-Fe-Nb-O pyrochlore nanoparticles were synthesized by a facile coprecipitation reaction. They exhibit intense visible-light absorption due to a narrow band gap and high visible-light photocatalytic activity for degradation of methyl orange.

Ba4Ta2O9 oxide prepared from an oxalate-based molecular precursor-characterization and properties.

A novel heterometallic oxalate-based compound, {Ba2(H2O)5[TaO(C2O4)3]HC2O4}·H2O (1), was obtained by using an (oxalato)tantalate(V) aqueous solution as a source of the complex anion and characterized by X-ray single-crystal diffraction, IR spectroscopy, and thermal analysis. Compound 1 is a three-dimensional (3D) coordination polymer with the Ta atom connected to eight neighboring Ba atoms through the oxalate ligands and the oxo oxygen group. Thermal treatment of 1 up to 1200 °C leads to molecular precursor-to-material conversion that yields the mixed-metal γ-Ba4Ta2O9 phase. This high-temperature γ-Ba4Ta2O9 polymorph has the 6H-perovskite structure (space group P6(3)/m), in which the Ta2O9 face-sharing octahedral dimers are interconnected via corners to the regular BaO6 octahedra. To date, γ-Ba4Ta2O9 has never been obtained at room temperature, because of the reduction of symmetry (P6(3)/m → P2(1)/c) that usually occurs during the cooling. Spectroscopic, optical, photocatalytic, and electrical properties of the obtained γ-Ba4Ta2O9 phase were investigated. In addition to the experimental data, an absorption spectrum and band structure of the γ-Ba4Ta2O9 polymorph were calculated using density functional theory.