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.

Thin Films of Chlorinated Vanadyl Phthalocyanines as Active Layers of Chemiresistive Sensors for the Detection of Ammonia.

Halogenated metal phthalocyanines are promising materials for the manufacture of active layers of chemiresistive sensors for the detection of various gases. Despite the high interest in such sensors, there are few systematic studies of the position of halogen substituents in phthalocyanine macroring on the chemiresistive response of their films to gases. In this work, we prepared and studied films of novel tetrachlorosubstituted vanadyl phthalocyanine derivatives with Cl substituents in the peripheral (VOPcCl4-p) and nonperipheral (VOPcCl4-np) positions of the phthalocyanine ring as active layers of chemiresistive sensors to reveal the effect of the position of substituents on their structure and sensor response to low concentrations of NH3. It was shown that the films of VOPcCl4-p exhibited a noticeably higher sensor response to NH3 than the VOPcCl4-np ones. The limit of detection of NH3 was 0.7 ppm. The sensing layers demonstrated a reversible sensor response at room temperature with fairly low response/recovery times. It was also demonstrated that NH3 can be detected in the presence of various interfering gases (CO2 and H2) and some volatile organic vapors, as well as in a mixture of gases with a composition close to exhaled air.

Cobalt and Iron Phthalocyanine Derivatives: Effect of Substituents on the Structure of Thin Films and Their Sensor Response to Nitric Oxide.

In this work, we study the effect of substituents in cobalt(II) and iron(II) phthalocyanines (CoPcR4 and FePcR4 with R = H, F, Cl, tBu) on the structural features of their films, and their chemi-resistive sensor response to a low concentration of nitric oxide. For the correct interpretation of diffractograms of phthalocyanine films, structures of CoPcCl4 and FePcCl4 single crystals were determined for the first time. Films were tested as active layers for the determination of low concentrations of NO (10-1000 ppb). It was found that the best sensor response to NO was observed for the films of chlorinated derivatives MPcCl4 (M = Co, Fe), while the lowest response was in the case of MPc(tBu)4 films. FePcCl4 films exhibited the maximal response to NO, with a calculated limit of detection (LOD) of 3 ppb; the response and recovery times determined at 30 ppb of NO were 30 s and 80 s, respectively. The LOD of a CoPcCl4 film was 7 ppb. However, iron phthalocyanine films had low stability and their sensitivity to NO decreased rapidly over time, while the response of cobalt phthalocyanine films remained stable for at least several months. In order to explain the obtained regularities, quantum chemical calculations of the binding parameters between NO and phthalocyanine molecules were carried out. It was shown that the binding of NO to the side atoms of phthalocyanines occurred through van der Waals forces, and the values of the binding energies were in direct correlation with the values of the sensor response to NO.

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.

Octafluoro-Substituted Phthalocyanines of Zinc, Cobalt, and Vanadyl: Single Crystal Structure, Spectral Study and Oriented Thin Films.

In this work, octafluoro-substituted phthalocyanines of zinc, vanadyl, and cobalt (MPcF8, M = Zn(II), Co(II), VO) were synthesized and studied. The structures of single crystals of the obtained phthalocyanines were determined. To visualize and compare intermolecular contacts in MPcF8, an analysis of Hirshfeld surfaces (HS) was performed. MPcF8 nanoscale thickness films were deposited by organic molecular beam deposition technique and their structure and orientation were studied using X-ray diffraction. Comparison of X-ray diffraction patterns of thin films with the calculated diffractograms showed that all three films consisted of a single crystal phase, which corresponded to a phase of single crystals. Only one strong diffraction peak corresponding to the plane (001) was observed on the diffraction pattern of each film, which indicated a strong preferred orientation with the vast majority of crystallites oriented with a (001) crystallographic plane parallel to the substrate surface. The effect of the central metals on the electronic absorption and vibrational spectra of the studied phthalocyanines as well as on the electrical conductivity of their films is also discussed.

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.

Recent Advances in Phthalocyanine and Porphyrin-Based Materials as Active Layers for Nitric Oxide Chemical Sensors.

Nitric oxide (NO) is a highly reactive toxic gas that forms as an intermediate compound during the oxidation of ammonia and is used for the manufacture of hydroxylamine in the chemical industry. Moreover, NO is a signaling molecule in many physiological and pathological processes in mammals, as well as a biomarker indicating the course of inflammatory processes in the respiratory tract. For this reason, the detection of NO both in the gas phase and in the aqueous media is an important task. This review analyzes the state of research over the past ten years in the field of applications of phthalocyanines, porphyrins and their hybrid materials as active layers of chemical sensors for the detection of NO, with a primary focus on chemiresistive and electrochemical ones. The first part of the review is devoted to the study of phthalocyanines and porphyrins, as well as their hybrids for the NO detection in aqueous solutions and biological media. The second part presents an analysis of works describing the latest achievements in the field of studied materials as active layers of sensors for the determination of gaseous NO. It is expected that this review will further increase the interest of researchers who are engaged in the current level of evaluation and selection of modern materials for use in the chemical sensing of nitric oxide.

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.

A Hybrid Nanomaterial Based on Single Walled Carbon Nanotubes Cross-Linked via Axially Substituted Silicon (IV) Phthalocyanine for Chemiresistive Sensors.

In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first example of a carbon-based nanomaterial in which an axially substituted phthalocyanine derivative is used as a linker. The prepared hybrid material was characterized by spectroscopic methods, thermogravimetry, scanning and transmission electron microscopies. The layers of the prepared hybrid were tested as sensors toward ammonia and hydrogen by a chemiresistive method at different temperatures and relative humidity as well as in the presence of interfering gases like carbon dioxide, hydrogen sulfide and volatile organic vapors. The hybrid layers exhibited the completely reversible sensor response to both gases at room temperature; the recovery time was 100-200 s for NH3 and 50-120 s in the case of H2 depending on the gas concentrations. At the relative humidity (RH) of 20%, the sensor response was almost the same as that measured at RH 5%, whereas the further increase of RH led to its 2-3 fold decrease. It was demonstrated that the SWCNT/SiPc layers can be successfully used for the detection of both NH3 and H2 in the presence of CO2. On the contrary, H2S was found to be an interfering gas for the NH3 detection.

Chlorosubstituted Copper Phthalocyanines: Spectral Study and Structure of Thin Films.

In this work, the tetra-, octa- and hexadecachloro-substituted copper phthalocyanines CuPcClx (where x can equal 4, 8 or 16) were investigated by the methods of vibrational (IR and Raman) spectroscopy and X-ray diffraction. The assignment of the most intense bands, both in IR and Raman spectra, was carried out on the basis of DFT calculations. The structure of a CuPcCl4 single crystal grown by sublimation in vacuum was refined for the first time. The effect of chloro-substitution on the structure of CuPcClx thin films deposited in a vacuum onto a glass substrate at 50 and 200 °C was studied. It was shown that CuPcCl4 formed polycrystalline films with the preferential orientation of the (100) crystallographic plane of crystallites parallel to the substrate surface when deposited on a substrate at 50 °C. Introduction of more Cl-substituents into the phthalocyanine macrocycle leads to the formation of amorphous films on the substrates at 50 °C. At the elevated substrate temperature, the growth of polycrystalline disordered films was observed for all three copper phthalocyanines.

Vanadyl Phthalocyanine Films and Their Hybrid Structures with Pd Nanoparticles: Structure and Sensing Properties.

In this work, thin films of vanadyl phthalocyanines (VOPc and VOPcF4) are studied as active layers for the detection of gaseous ammonia and hydrogen. The effect of F-substituents on the structural features of vanadyl phthalocyanine films and their sensor response toward ammonia (10-50 ppm) and hydrogen (100-500 ppm) is investigated by X-ray diffraction (XRD) and chemiresistive methods, respectively. It is shown that the sensor response of VOPcF4 films to ammonia is 2-3 times higher than that of VOPc films. By contrast, the sensor response to hydrogen is higher in the case of VOPc films. Apart from this, the hybrid structures of vanadyl phthalocyanine films with Pd nanoparticles deposited on their surface by a chemical vapor deposition method are also tested to reveal the effect of Pd nanoparticles on the sensitivity of VOPc films to hydrogen. Deposition of Pd nanoparticles on the surface of VOPc films leads to the noticeable increase of their sensitivity to hydrogen.

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).

Highly selective and ultra-sensitive electrochemical sensor behavior of 3D SWCNT-BODIPY hybrid material for eserine detection.

In this work, 4,4-difluoro-8-(4-hydroxyphenyl)- 2,6-diethynly-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) having double terminal ethynyl groups was synthesized. Three dimensional single walled carbon nanotube (SWCNT)-BODIPY hybrid material (3D SWCNT-BODIPY) was synthesized by the reaction of BODIPY bearing double terminal ethynyl groups with azido containing SWCNTs via "Click" reaction. The structural properties and electrochemical detection of eserine (a pesticide) on BODIPY functionalized SWCNTs as a three dimensional (3D) material were investigated. A glassy carbon electrode (GCE) was modified by 3D SWCNT-BODIPY hybrid material for the determination of eserine in the range of 0.25-2.25 µM. In the study by the square wave voltammetry (SWV), the bare GCE showed no response, while the new peak at - 0.6 V appeared in the case of the modified electrode. The detection limit and quantification were determined as 160 nM and 528 nM for eserine on the 3D SWCNT-BODIPY modified electrode, respectively. Eserine was also determined with a standard addition method in different brands of orange juices, and the recovery of eserine was obtained to be in the range of 102.09% and 103.22%. This study clearly indicates that the 3D SWCNT-BODIPY modified electrode tested as an electrochemical sensor was found to be highly selective and sensitive to eserine.

Synthesis and organic solar cell performance of BODIPY and coumarin functionalized SWCNTs or graphene oxide nanomaterials.

The synthesis and characterization of new hybrid materials based on reduced graphene oxide (rGO) or single walled carbon nanotubes (SWCNTs) covalently functionalized by 4,4'-difluoro-8-(4-propynyloxy)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) (2) or 7-(prop-2-yn-1-yloxy)-3-(3',4',5'-trimethoxyphenyl)-coumarin (4) as light harvesting groups have been described. The organic solar cell performances of these novel nanomaterials in P3HT:PCBM blends were investigated. These covalently bonded hybrid materials (reduced graphene oxide:BODIPY (GB), reduced graphene oxide:Coumarin (GC), SWCNTs:BODIPY (CB) and SWCNTs:Coumarin (CC)) were prepared by an azide-alkyne Huisgen cycloaddition (click) reaction between the azide bearing SWCNTs or rGO and terminal ethynyl functionalized BODIPY (2) or coumarin (4) derivatives. The formation of novel nanomaterials was confirmed by FT-IR, UV-Vis and Raman spectroscopies and thermogravimetric analysis. The best performance on P3HT:PCBM organic solar cells was produced by SWCNTs:Coumarin (CC) hybrids which were coated on an indium tin oxide coated polyethylene terephthalate film (ITO-PET). The reference device based on the P3HT:PCBM blend without CC showed a power conversion efficiency (PCE) of 1.16%, an FF of 35% and a short-circuit current density (Jsc) of 5.51 mA cm-2. The reference device with CC hybrids within the P3HT:PCBM blend increased the values significantly to 1.62% for PCE, 40% for FF and 6.8 mA cm-2 for Jsc.

Fluorinated Metal Phthalocyanines: Interplay between Fluorination Degree, Films Orientation, and Ammonia Sensing Properties.

In this work, the sensor response of MPcFx (M = Cu, Co, Zn; x = 0, 4, 16) films toward gaseous NH3 (10⁻50 ppm) was studied by a chemiresistive method and compared to that of unsubstituted MPc films to reveal the effects of central metals and F-substituents on the sensing properties. A combination of atomic force microscopy and X-ray diffraction techniques have been used to elucidate the structural features of thin MPcFx films deposited by organic molecular beam deposition. It has been shown that the sensor response of MPcF4 films to ammonia is noticeably higher than that of MPc films, which is in good correlation with the values of binding energy between the metal phthalocyanine and NH3 molecules, as calculated by the density functional theory (DFT) method. At the same time, in contrast to the DFT calculations, MPcF16 demonstrated the lesser sensor response compared with MPcF4, which appeared to be connected with the different structure and morphology of their films. The ZnPcF4 films were shown to exhibit a sensitivity to ammonia up to concentrations as low as 0.1 ppm, and can be used for the selective detection of ammonia in the presence of some reducing gases and volatile organic compounds. Moreover, the ZnPcF4 films can be used for the detection of NH3 in the gas mixture simulating exhaled air (N2 76%, O2 16%, H2O 5%, and CO2 3%).

Copper Phthalocyanine Functionalized Single-Walled Carbon Nanotubes: Thin Films for Optical Detection.

Thin films of non-covalently hybridized single-walled carbon nanotubes (SWCNT) and tetra-substituted copper phthalocyanine (CuPcR4) molecules have been produced from their solutions in dimethylformamide (DMF). FTIR spectra revealed the 7π-7π interaction between SWCNTs and CuPcR4 molecules. DC conductivity of films of acid-treated SWCNT/CuPcR4 hybrid has increased by more than three orders of.magnitude in comparison with conductivity of CuPcR4 films. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements have shown that films obtained from the acid-treated SWCNTs/CuPcR4 hybrids demonstrated more homogenous surface which is ascribed to the highly improved solubility of the hybrid powder in DMF Using total internal reflection ellipsometry spectroscopy (TIRE), thin films of the new hybrid have been examined as an optical sensing membrane for the detection of benzo[a]pyrene in water to demonstrate the sensing properties of the hybrid.