Vapor-Phase-Deposited Ag/Ir and Ag/Au Film Heterostructures for Implant Materials: Cytotoxic, Antibacterial and Histological Studies.

Using gas-phase deposition (Physical Vapor Deposition (PVD) and Metal Organic Chemical Vapor Deposition (MOCVD)) methods, modern implant samples (Ti alloy and CFR-PEEK polymer, 30% carbon fiber) were functionalized with film heterostructures consisting of an iridium or gold sublayer, on the surface of which an antibacterial component (silver) was deposited: Ag/Ir(Au)/Ti(CFR-PEEK). The biocidal effect of the heterostructures was investigated, the effect of the surface relief of the carrier and the metal sublayer on antibacterial activity was established, and the dynamics of silver dissolution was evaluated. It has been shown that the activity of Ag/Ir heterostructures was due to high Ag+ release rates, which led to rapid (2-4 h) inhibition of P. aeruginosa growth. In the case of Ag/Au type heterostructures, the inhibition of the growth of P. aeruginosa and S. aureus occurred more slowly (from 6 h), and the antibacterial activity appeared to be due to the contribution of two agents (Ag+ and Au+ ions). It was found, according to the in vitro cytotoxicity study, that heterostructures did not exhibit toxic effects (cell viability > 95-98%). An in vivo biocompatibility assessment based on the results of a morphohistological study showed that after implantation for a period of 30 days, the samples were characterized by the presence of a thin fibrous capsule without volume thickening and signs of inflammation.

Supermolecular Nanoentities of Vitamin B12 Derivative as a Link in the Evolution of the Parent Molecules During Self-Assembly at the Air-Water Interface.

Nanoarchitectures with promising properties have now been formed from many important biomolecules. However, the preparation of nanoparticles of vitamin B12 and its derivatives remains an ongoing research challenge. This paper describes the formation of supermolecular nanoentities (SMEs) of vitamin B12 derivatives, unique nanoparticles with strong noncovalent intermolecular interactions, emerging properties, and activity. These were created by a nanoarchitectonic approach using directed assembly of layers at the air-water interface as a link in the chain of evolution of the parent molecules under specially created conditions. Such layers can be represented as a nanocosm, where, at a critical density, the assemblies act as nanoreactors in which the transformation of the original material occurs. The discovered SMEs not only replicate the functioning of vitamin B12 assemblies with proteins in living organisms and act as vitamin B12-depended enzymes but also demonstrate important advantages over vitamin B12. They are more efficient in oxygen reduction/evolution reactions and in transformation into other forms. These SMEs, in performing advanced tasks, are an alternative to widely used materials based on noble metals for catalysis, medicine, and environment protection. Our findings open new perspectives both for the fabrication of novel SMEs of biomolecules and for a better understanding of the evolution of biomolecules in nature.

Biological Studies of New Implant Materials Based on Carbon and Polymer Carriers with Film Heterostructures Containing Noble Metals.

This paper presents pioneering results on the evaluation of noble metal film hetero-structures to improve some functional characteristics of carbon-based implant materials: carbon-composite material (CCM) and carbon-fiber-reinforced polyetheretherketone (CFR-PEEK). Metal-organic chemical vapor deposition (MOCVD) was successfully applied to the deposition of Ir, Pt, and PtIr films on these carriers. A noble metal layer as thin as 1 µm provided clear X-ray imaging of 1−2.5 mm thick CFR-PEEK samples. The coated and pristine CCM and CFR-PEEK samples were further surface-modified with Au and Ag nanoparticles (NPs) through MOCVD and physical vapor deposition (PVD) processes, respectively. The composition and microstructural features, the NPs sizes, and surface concentrations were determined. In vitro biological studies included tests for cytotoxicity and antibacterial properties. A series of samples were selected for subcutaneous implantation in rats (up to 3 months) and histological studies. The bimetallic PtIr-based heterostructures showed no cytotoxicity in vitro, but were less biocompatible due to a dense two-layered fibrous capsule. AuNP heterostructures on CFR-PEEK promoted cell proliferation in vitro and exhibited a strong inhibition of bacterial growth (p < 0.05) and high in vitro biocompatibility, especially Au/Ir structures. AgNP heterostructures showed a more pronounced antibacterial effect, while their in vivo biocompatibility was better than that of the pristine CFR-PEEK, but worse than that of AuNP heterostructures.

Electrochemical Sensor Based on Iron(II) Phthalocyanine and Gold Nanoparticles for Nitrite Detection in Meat Products.

Nitrites are widely used in the food industry, particularly for the preservation of meat products. Controlling the nitrate content in food is an important task to ensure people's health is not at risk; therefore, the search for, and research of, new materials that will modify the electrodes in the electrochemical sensors that detect and control the nitrate content in food products is an urgent task. In this paper, we describe the electrochemical behavior of a glass carbon electrode (GCE), modified with a Fe(II) tetra-tert-butyl phthalocyanine film (FePc(tBu)4/GCE), and decorated with gold nanoparticles (Au/FePc(tBu)4/GCE); this electrode was deposited using gas-phase methods. The composition and morphology of such electrodes were examined using spectroscopy and electron microscopy methods, whereas the main electrochemical characteristics were determined using cyclic voltammetry (CV) and amperometry (CA) methods in the linear ranges of CV 0.25-2.5 mM, CA 2-120 µM in 0.1 M phosphate buffer (pH = 6.8). The results showed that the modification of bare GCEs, with a Au/FePc(tBu)4 heterostructure, provided a high surface-to-volume ratio, thus ensuring its high sensitivity to nitrite ions of 0.46 µAµM-1. The sensor based on the Au/FePc(tBu)4/GCE has a low limit of nitrite detection at 0.35 µM, good repeatability, and stability. The interference study showed that the proposed Au/FePc(tBu)4/GCE exhibited a selective response in the presence of interfering anions, and the analytical capability of the sensor was demonstrated by determining nitrite ions in real samples of meat products.

Heterostructures Based on Cobalt Phthalocyanine Films Decorated with Gold Nanoparticles for the Detection of Low Concentrations of Ammonia and Nitric Oxide.

This work is aimed at the development of new heterostructures based on cobalt phthalocyanines (CoPc) and gold nanoparticles (AuNPs), and the evaluation of the prospects of their use to determine low concentrations of ammonia and nitric oxide. For this purpose, CoPc films were decorated with AuNPs by gas-phase methods (MOCVD and PVD) and drop-casting (DC), and their chemiresistive sensor response to low concentrations of NO (10-50 ppb) and NH3 (1-10 ppm) was investigated. A comparative analysis of the characteristics of heterostructures depending on the preparation methods was carried out. The composition, structure, and morphology of the resulting hybrid films were studied by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission (ICP-AES) spectroscopy, as well as electron microscopy methods to discuss the effect of these parameters on the sensor response of hybrid films to ammonia and nitric oxide. It was shown that regardless of the fabrication method, the response of Au/CoPc heterostructures to NH3 and NO gases increased with an increase in the concentration of gold. The sensor response of Au/CoPc heterostructures to NH3 increased 2-3.3 times compared to CoPc film, whereas in the case of NO it increased up to 16 times. The detection limits of the Au/CoPc heterostructure with a gold content of ca. 2.1 µg/cm2 for NH3 and NO were 0.1 ppm and 4 ppb, respectively. It was shown that Au/CoPc heterostructures can be used for the detection of NH3 in a gas mixture simulating exhaled air (N2-74%, O2-16%, H2O-6%, CO2-4%).

The Theoretical and Experimental Investigation of the Fluorinated Palladium ß-Diketonate Derivatives: Structure and Physicochemical Properties.

To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH3CXCHCO(R))2] with ß-diketone [tfa-1,1,1-trifluoro-2,4-pentanedionato (1); pfpa-5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba-5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and ß-iminoketone [i-tfa-1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa-5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70-80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd ß-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd ß-iminoketonates. The molecules 2-6 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 1-2, and C…F, F…F, NH…F contacts appeared in the structures of complexes 4-6. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd ß-iminoketonates and Pd ß-diketonates were minimized with the elongation of the fluorine chain in the ligands.

Noble Metals for Modern Implant Materials: MOCVD of Film Structures and Cytotoxical, Antibacterial, and Histological Studies.

This work is aimed at developing the modification of the surface of medical implants with film materials based on noble metals in order to improve their biological characteristics. Gas-phase transportation methods were proposed to obtain such materials. To determine the effect of the material of the bottom layer of heterometallic structures, Ir, Pt, and PtIr coatings with a thickness of 1.4-1.5 µm were deposited by metal-organic chemical vapor deposition (MOCVD) on Ti6Al4V alloy discs. Two types of antibacterial components, namely, gold nanoparticles (AuNPs) and discontinuous Ag coatings, were deposited on the surface of these coatings. AuNPs (11-14 nm) were deposited by a pulsed MOCVD method, while Ag films (35-40 nm in thickness) were obtained by physical vapor deposition (PVD). The cytotoxic (24 h and 48 h, toward peripheral blood mononuclear cells (PBMCs)) and antibacterial (24 h) properties of monophase (Ag, Ir, Pt, and PtIr) and heterophase (Ag/Pt, Ag/Ir, Ag/PtIr, Au/Pt, Au/Ir, and Au/PtIr) film materials deposited on Ti-alloy samples were studied in vitro and compared with those of uncoated Ti-alloy samples. Studies of the cytokine production by PBMCs in response to incubation of the samples for 24 and 48 h and histological studies at 1 and 3 months after subcutaneous implantation in rats were also performed. Despite the comparable thickness of the fibrous capsule after 3 months, a faster completion of the active phase of encapsulation was observed for the coated implants compared to the Ti alloy analogs. For the Ag-containing samples, growth inhibition of S. epidermidis, S. aureus, Str. pyogenes, P. aeruginosa, and Ent. faecium was observed.

The interface between chloroaluminum phthalocyanine and titanium dioxide: the influence of surface defects and substrate termination.

Interface properties of chloroaluminum(iii) phthalocyanine (AlClPc) on two different rutile titanium dioxide (TiO2) single crystal surfaces ((100) and (001)) have been studied using X-ray and ultraviolet photoemission spectroscopy (XPS and UPS). It is shown that the strength of the interaction clearly depends on the substrate termination and preparation. Generally, the (001) surface is more reactive compared to the (100) surface. The most important interaction channel involves the nitrogen atoms of the phthalocyanine macrocycle. An exposure to oxygen during the annealing steps of the preparation procedure allows diminishing the extent of interaction of nitrogen with titanium dioxide. The work function of AlClPc/TiO2 is rather independent of the substrate, indicating a pinning regime at all interfaces, where the HOMO of the molecule is aligned at the maximum of the defect states of the substrate.

Bimetallic Pt,Ir-containing coatings formed by MOCVD for medical applications.

Biocompatible PtxIr(1-x) layers combining high mechanical strength of the iridium component and outstanding corrosion resistance of the platinum component providing reversible charge transfer reactions in the living tissue are one of the important materials required for implantable medical electrodes. The modern trend to complicate the shape and reduce the electrode dimensions includes the challenge to develop precise methods to obtain such bimetallic coatings with enhanced surface area and advanced electrochemical characteristics. Herein, PtxIr(1-x) coatings were firstly obtained on cathode and anode pole tips of endocardial electrodes for pacemakers using chemical vapor deposition technique. To deposit PtxIr(1-x) coatings with a wide range of metal ratios (x = 0.5-0.9) the combination of acetylacetonate-based volatile precursors with compatible thermal characteristics was used for the first time. The expected metal ratio in the coatings was regulated by a partial pressure of the precursor vapors in the reaction zone and was in the good agreement with its real value measured by various methods, including energy-dispersive and wavelength dispersive spectroscopy, X-ray photoelectron spectroscopy. According to the X-ray powder diffraction analysis, PtxIr(1-x) coatings consisted of fcc-PtxIr(1-x) solid solution phases. The microscopy data confirmed the formation of PtxIr1-x coatings with the enhanced surface areas. The effect of electrochemical activation on the surface composition and morphology of the samples was studied. The electrochemical characteristics of samples were estimated from cyclic voltammetry and electrochemical impedance spectroscopy data. The charge storage capacity (CSC) values of activated samples were in the range of 19-108 mCcm-2 (phosphate buffer saline solution, 100 mV/s).

Electric field assisted effects on molecular orientation and surface morphology of thin titanyl(IV)phthalocyanine films.

Herein we present electric field assisted effects on the molecular orientation, the polymorphism, and the surface morphology of thin titanyl(IV)phthalocyanine (TiOPc) films. The ability of electric fields to affect the thin film structure of polar molecules is demonstrated using titanyl(IV)phthalocyanine as a model compound exhibiting both a permanent and an induced electric dipole moment. Thin films of TiOPc prepared by organic molecular beam deposition (OMBD) in the absence and in the presence of an electric field during the thin film growth are characterized using polarization dependent Raman spectroscopy and atomic force microscopy (AFM). The distinctive pattern of vibrational modes of the phthalocyanine skeleton indicates different molecular orientations in these thin films: Raman spectra of regions where an electric field is present during thin film growth reveal a preferential molecular orientation with an inclination angle of the molecular plane (pseudoplanar macrocycle) with respect to the substrate plane of nearly 90 degrees. Contrary to that, in regions where the electric field was absent, the molecules adopt predominantly a configuration with a smaller tilt angle (approximately 60 degrees). In addition, an electric field assisted change is apparent in AFM images: A large amount of well-formed steplike crystallites lying parallel to the substrate is observed when no electric field was present, whereas in the case when an electric field was applied during thin film growth the crystallites exhibit a tilt with respect to the substrate plane.