Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films

Polyelectrolyte multilayer films are a versatile functionalization method of surfaces and rely on the alternated adsorption of oppositely charged species. Among such species, charged dyes can also be alternated with oppositely charged polymers, which is challenging from a fundamental point of view, because polyelectrolytes require a minimal number of charges, whereas even monovalent dyes can be incorporated during the alternated adsorption process. We will not only focus on organic dyes but also on their inorganic counterparts and on metal complexes. Such films offer plenty of possible applications in dye sensitized solar cells. In addition, dyes are massively used in the textile industry and in histology to stain textile fibers or tissues. However, the excess of non bound dyes poses serious environmental problems. It is hence of the highest interest to design materials able to adsorb such dyes in an almost irreversible manner. Polyelectrolyte multilayer films, owing to their ion exchange behavior can be useful for such a task allowing for impressive overconcentration of dyes with respect to the dye in solution. The actual state of knowledge of the interactions between charged dyes and adsorbed polyelectrolytes is the focus of this review article.     

Synthesis,Characterization, DFT Study and Antifungal Activities of Some Novel 2-(Phenyldiazenyl)phenol Based Azo Dyes

In recent decades, there has been an increased interest in azo compounds with special optical and biological properties. In this work, we report the preparation of novel azo-compounds with two and three –N=N- double bonds, using the classical method of synthesis, diazotization and coupling. The compounds were characterized by ¹H-NMR, ¹³C-NMR, FTIR, UV-VIS and fluorescence spectra. DFT calculations were employed for determining the optical parameters, polarizability α, the total static dipole moment μ_tot, the quadrupole moment Q and the mean first polarizability β_tot. All azo derivatives show strong fluorescence emission in solutions. The antioxidant and antifungal activities were determined and the influence of the number of azo bonds was discussed. The synthesized compounds exhibit remarkable efficiency in the growth reduction of standard and clinical isolated Candida strains, suggesting future applications as novel antifungal.     

Novel Red Light-Absorbing Organic Dyes Based on Indolo[3,2-b]carbazole as the Donor Applied in Co-Sensitizer-Free Dye-Sensitized Solar Cells

Three novel organic dyes (D6, D7 and D8), based on indolo[3,2-b]carbazole as the donor and different types of electron-withdrawing groups as the acceptors, were synthesized and successfully applied in dye-sensitized solar cells (DSSCs). Their molecular structures were fully characterized by ¹H NMR, ¹³C NMR and mass spectroscopy. The density functional theory (DFT) calculations, electrochemical impedance spectroscopy analysis, UV–Vis absorption characterization and tests of the solar cells were used to investigate the photophysical/electrochemical properties as well as DSSCs’ performances based on the dyes. Dye D8 showed the broadest light-response range (300–770 nm) in the incident monochromatic photo-to-electron conversion efficiency (IPCE) curve, due to its narrow bandgap (1.95 eV). However, dye D6 exhibited the best device performance among the three dyes, with power conversion efficiency of 5.41%, J_sc of 12.55 mA cm⁻², V_oc of 745 mV and fill factor (FF) of 0.59. We also found that dye aggregation was efficiently suppressed by the introduction of alkylated indolo[3,2-b]carbazole, and, hence, better power conversion efficiencies were observed for all the three dyes, compared to the devices of co-sensitization with chenodeoxycholic acid (CDCA). It was unnecessary to add adsorbents to suppress the dye aggregation.     

Utilisation of Carp Skin Post-Production Waste in Binary Films Based on Furcellaran and Chitosan to Obtain Packaging Materials for Storing Blueberries

The aim of the study was to develop and characterise an innovative three-component biopolymer film based on chitosan (CHIT), furcellaran (FUR) and a gelatin hydrolysate from carp skins (Cyprinus carpio) (HGEL). The structure and morphology were characterised using the Fourier transform infrared spectroscopy (FT-IR) and atomic force microscopy (AFM). The FT-IR test showed no changes in the matrix after the addition of HGEL, which indicates that the film components were compatible. Based on the obtained AFM results, it was found that the addition of HGEL caused the formation of grooves and cracks on the surface of the film (reduction by ~21%). The addition of HGEL improved the antioxidant activity of the film (improvement by up to 2.318% and 444% of DPPH and FRAP power, respectively). Due to their properties, the tested films were used as active materials in the preservation of American blueberries. In the active films, the blueberries lost mass quickly compared to the synthetic film and were characterised by higher phenol content. The results obtained in this study create the opportunity to use the designed CHIT–FUR films in developing biodegradable packaging materials for food protection, but it is necessary to test their effectiveness on other food products.     

Macromonomers as a Novel Way to Investigate and Tailor Silicon-Oxycarbide-Based Materials Obtained from Polymeric Preceramic Precursors

It has been shown that bifunctional monomers (D units), which are used to increase the carbon content in silicon oxycarbide precursors, can form volatile oligomers, thus affecting the amount of carbon available during the transition into the final material in the annealing process. Additionally, an uneven distribution of carbon-rich mers may lead to the formation of a free-carbon phase, instead of the incorporation of carbon atoms into the silicon matrix. In this study, a novel two-step approach was utilized. Firstly, a macromonomer containing a number of structural units with precise structure was synthesized, which was later polycondensed into a ceramic precursor. Chlorodimethylsilane modified 2,4,6,8-tetramethylcyclotetrasiloxane was used as a silicon oxycarbide precursor monomer containing both T and D structural units (i.e., silicon atoms bonded to three and two oxygen atoms, respectively), with well-defined interconnections between structural units. Such a macromonomer prevents the formation of small siloxane rings, and has a very limited number of possible combinations of structural units neighboring each silicon atom. This, after investigation using IR, XRD, TG and elemental analysis, gave insight into the effect of “anchoring” silicon atoms bonded to two methyl groups, as well as the impact of their distribution in comparison to the materials obtained using simple monomers containing a single silicon atom (structural unit).     

Synthesis and Physicochemical Characterization of Novel Dicyclopropyl-Thiazole Compounds as Nontoxic and Promising Antifungals

There is a need to search for new antifungals, especially for the treatment of the invasive Candida infections, caused mainly by C. albicans. These infections are steadily increasing at an alarming rate, mostly among immunocompromised patients. The newly synthesized compounds (3a–3k) were characterized by physicochemical parameters and investigated for antimicrobial activity using the microdilution broth method to estimate minimal inhibitory concentration (MIC). Additionally, their antibiofilm activity and mode of action together with the effect on the membrane permeability in C. albicans were investigated. Biofilm biomass and its metabolic activity were quantitatively measured using crystal violet (CV) staining and tetrazolium salt (XTT) reduction assay. The cytotoxic effect on normal human lung fibroblasts and haemolytic effect were also evaluated. The results showed differential activity of the compounds against yeasts (MIC = 0.24–500 µg/mL) and bacteria (MIC = 125–1000 µg/mL). Most compounds possessed strong antifungal activity (MIC = 0.24–7.81 µg/mL). The compounds 3b, 3c and 3e, showed no inhibitory (at 1/2 × MIC) and eradication (at 8 × MIC) effect on C. albicans biofilm. Only slight decrease in the biofilm metabolic activity was observed for compound 3b. Moreover, the studied compounds increased the permeability of the membrane/cell wall of C. albicans and their mode of action may be related to action within the fungal cell wall structure and/or within the cell membrane. It is worth noting that the compounds had no cytotoxicity effect on pulmonary fibroblasts and erythrocytes at concentrations showing anticandidal activity. The present studies in vitro confirm that these derivatives appear to be a very promising group of antifungals for further preclinical studies.     

Adhesive Films Based on Benzoxazine Resins and the Photoreactive Epoxyacrylate Copolymer

UV-cross-linkable and thermally curable self-adhesive structural tapes (SATs) were compounded using solid commercial benzoxazine resins (Araldite MT 35700 and Araldite MT 35910) and a photoreactive epoxyacrylate copolymer (EAC). As initiators of benzoxazine resin polymerization and epoxy component cationic polymerization, two kinds of latent curing agents (LCAs) were tested, i.e., amine type and ionic liquid type. The influence of the benzoxazine resin and the LCA type on the UV-cross-linking process, the self-adhesive features and thermal curing behavior of UV-cross-linked tapes, as well as the shear strength of cured aluminum/SAT/aluminum joints and thermal stability of adhesives were investigated. It was found that the amine additive and the benzoxazine resin take part in the UV-cross-linking process of the EAC as hydrogen donors, which is confirmed by an increase in cohesion (+86%) and a decrease in adhesion (−25%) of SATs. The highest results of adhesion to steel (47 N/25 mm) and overlap shear strength (11.1 MPa) values were registered for SATs based on Araldite MT 35910 and contained 7.5 wt. parts of the amine-type hardener. The formation of a polyacrylate-benzoxazine network has a significant impact on the course of the thermal curing process and the thermomechanical properties of adhesive joints, which was also confirmed by the Cure Index calculation.     

Effects of the Chemical Treatment on the Physical-Chemical and Electrochemical Properties of the Commercial Nafion™ NR212 Membrane

Polymer Electrolyte Fuel Cells (PEFCs) are one of the most promising power generation systems. The main component of a PEFC is the proton exchange membrane (PEM), object of intense research to improve the efficiency of the cell. The most commonly and commercially successful used PEMs are Nafion™ perfluorosulfonic acid (PFSA) membranes, taken as a reference for the development of innovative and alternative membranes. Usually, these membranes undergo different pre-treatments to enhance their characteristics. With the aim of understanding the utility and the effects of such pre-treatments, in this study, a commercial Nafion™ NR212 membrane was subjected to two different chemical pre-treatments, before usage. HNO₃ or H₂O₂ were selected as chemical agents because the most widely used ones in the procedure protocols in order to prepare the membrane in a well-defined reference state. The pre-treated membranes properties were compared to an untreated membrane, used as-received. The investigation has showed that the pre-treatments enhance the hydrophilicity and increase the water molecules coordinated to the sulphonic groups in the membrane structure, on the other hand the swelling of the membranes also increases. As a consequence, the untreated membrane shows a better mechanical resistance, a good electrochemical performance and durability in fuel cell operations, orienting toward the use of the NR212 membrane without any chemical pre-treatment.     

Influence of organic films on the evaporation and condensation of water in aerosol

Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [C_nH_(2n+1)OH], with the value decreasing from 2.4 × 10⁻³ to 1.7 × 10⁻⁵ as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid.     

Development of the Composite Thermoluminescent Detectors Based on the Single Crystalline Films and Crystals of Perovskite Compounds

This work is dedicated to the development of new types of composite thermoluminescent detectors based on the single crystalline films of Ce-doped GdAlO₃ perovskite and Mn-doped YAlO₃ and (Lu_0.8Y_0.2)AlO₃:Mn perovskites as well as Ce and Pr-doped YAlO₃ single crystal substrates. These detectors were obtained using the Liquid Phase Epitaxy growth method from the melt solution based on the PbO-B₂O₃ fluxes. Such composite detectors can by applied for the simultaneous registration of different components of mixed ionization fluxes using the differences between the thermoluminescent glow curves, recorded from the film and crystal parts of epitaxial structures. For creation of the new composite detectors, we considered using, for the film and crystal components of epitaxial structures (i) the different perovskite matrixes doped with the same type of activator or (ii) the same perovskite host with various types of activators. The thermoluminescent properties of the different types of epitaxial structures based on the abovementioned films and crystal substrates were examined in the conditions of β-particles and X-ray excitation with aim of determination of the optimal combination of perovskites for composite detectors. It was shown that, among the structures with all the studied compositions, the best properties for the simultaneous thermoluminescent detection of α- and X-rays were the GdAlO₃:Ce film/YAlO₃:Ce crystal epitaxial structure.     

Electrospun PA66/Graphene Fiber Films and Application on Flexible Triboelectric Nanogenerators

Triboelectric nanogenerators (TENGs) are considered to be the most promising energy supply equipment for wearable devices, due to their excellent portability and good mechanical properties. Nevertheless, low power generation efficiency, high fabrication difficulty, and poor wearability hinder their application in the wearable field. In this work, PA66/graphene fiber films with 0, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt% graphene and PVDF films were prepared by electrospinning. Meanwhile, TENGs were prepared with PA66/graphene fiber films, PVDF films and plain weave conductive cloth, which were used as the positive friction layer, negative friction layer and the flexible substrate, respectively. The results demonstrated that TENGs prepared by PA66/graphene fiber films with 2 wt% grapheme showed the best performance, and that the maximum open circuit voltage and short circuit current of TENGs could reach 180 V and 7.8 μA, respectively, and that the power density was 2.67 W/m² when the external load was 113 MΩ. This is why the PA66/graphene film produced a more subtle secondary network with the addition of graphene, used as a charge capture site to increase its surface charge. Additionally, all the layered structures of TENGs were composed of breathable electrospun films and plain conductive cloth, with water vapor transmittance (WVT) of 9.6 Kgm⁻²d⁻¹, reflecting excellent wearing comfort. The study showed that TENGs, based on all electrospinning, have great potential in the field of wearable energy supply devices.     

Carbon-Silica Composite as Adsorbent for Removal of Hazardous C.I. Basic Yellow 2 and C.I. Basic Blue 3 Dyes

Treatment of wastewaters containing hazardous substances such as dyes from the textile, paper, plastic and food industries is of great importance. Efficient technique for the removal of highly toxic organic dyes is adsorption. In this paper, adsorptive properties of the carbon-silica composite (C/SiO₂) were evaluated for the cationic dyes C.I. Basic Blue 3 (BB3) and C.I. Basic Yellow 2 (BY2). The sorption capacities were determined as a function of temperature (924.6–1295.9 mg/g for BB3 and 716.3-733.2 mg/g for BY2 at 20–60 °C) using the batch method, and the Langmuir, Freundlich and Temkin isotherm models were applied for the equilibrium data evaluation using linear and non-linear regression. The rate of dye adsorption from the 100 mg/L solution was very fast, after 5 min. of phase contact time 98% of BB3 and 86% of BY2 was removed by C/SiO₂. Presence of the anionic (SDS), cationic (CTAB) and non-ionic (Triton X-100) surfactants in the amount of 0.25 g/L caused decrease in BB3 and BY2 uptake. The electrokinetic studies, including determination of the solid surface charge density and zeta potential of the composite suspensions in single and mixed adsorbate systems, were also performed. It was shown that presence of adsorption layers changes the structure of the electrical double layer formed on the solid surface, based on the evidence of changes in ionic composition of both surface layer and the slipping plane area. The greatest differences between suspension with and without adsorbates was obtained in the mixed dye + SDS systems; the main reason for this is the formation of dye-surfactant complexes in the solution and their adsorption at the interface.     

Annealing Effect on the Structural and Optical Properties of Sputter-Grown Bismuth Titanium Oxide Thin Films

The aim of this work is to assess the evolution of the structural and optical properties of Bi_xTi_yO_z films grown by rf magnetron sputtering upon post-deposition annealing treatments in order to obtain good quality films with large grain size, low defect density and high refractive index similar to that of single crystals. Films with thickness in the range of 220–250 nm have been successfully grown. After annealing treatment at 600 °C the films show excellent transparency and full crystallization. It is shown that to achieve larger crystallite sizes, up to 17 nm, it is better to carry the annealing under dry air than under oxygen atmosphere, probably because the nucleation rate is reduced. The refractive index of the films is similar under both atmospheres and it is very high (n =2.5 at 589 nm). However it is still slightly lower than that of the single crystal value due to the polycrystalline morphology of the thin films.     

A Thermodynamically Consistent Model of Quasibrittle Elastic Damaged Materials Based on a Novel Helmholtz Potential and Dissipation Function

In the paper, a thermodynamically consistent model of elastic damaged material in the framework of small strain theory is formulated, describing the process of deterioration in quasibrittle materials, concrete in particular. The main goal is to appropriately depict the distinction between material responses in tension and compression. A novel Helmholtz energy and a dissipation potential including three damage parameters are introduced. The Helmholtz function has a continuous first derivative with respect to strain tensor. Based on the assumed functions, the strain–stress relationship, the damage condition, the evolution laws, and the tangent stiffness tensor are derived. The model’s predictions for uniaxial tension, uniaxial compression, uniaxial cyclic compression–tension, and pure shear tests are calculated using Wolfram Mathematica in order to identify the main features of the model and to grasp the physical meaning of an isotropic damage parameter, a tensile damage parameter, and a compressive damage parameter. Their values can be directly bound to changes of secant stiffness and generalized Poisson’s ratio. An interpretation of damage parameters in association with three mechanisms of damage is given. The considered dissipation potential allows a flexible choice of a damage condition. The influence of material parameters included in dissipation function on damage mode interaction is discussed.     

A Novel Biodegradable Composite Polymer Material Based on PLGA and Silver Oxide Nanoparticles with Unique Physicochemical Properties and Biocompatibility with Mammalian Cells

A method for obtaining a stable colloidal solution of silver oxide nanoparticles has been developed using laser ablation. The method allows one to obtain nanoparticles with a monomodal size distribution and a concentration of more than 10⁸ nanoparticles per mL. On the basis of the obtained nanoparticles and the PLGA polymer, a nanocomposite material was manufactured. The manufacturing technology allows one to obtain a nanocomposite material without significant defects. Nanoparticles are not evenly distributed in the material and form domains in the composite. Reactive oxygen species (hydrogen peroxide and hydroxyl radical) are intensively generated on the surfaces of the nanocomposite. Additionally, on the surface of the composite material, an intensive formation of protein long-lived active forms is observed. The ELISA method was used to demonstrate the generation of 8-oxoguanine in DNA on the developed nanocomposite material. It was found that the multiplication of microorganisms on the developed nanocomposite material is significantly decreased. At the same time, the nanocomposite does not inhibit proliferation of mammalian cells. The developed nanocomposite material can be used as an affordable and non-toxic nanomaterial to create bacteriostatic coatings that are safe for humans.     

Interference Phenomena and Stimulated Emission in ZnO Films on Sapphire

We studied the texturing, roughness, and morphology features of ZnO films grown on the R (11¯02)-, M (101¯0)-, A (112¯0)-, and C (0001)-planes of sapphire, as well as their optical and luminescent properties. We showed that the growth conditions, substrate orientation, and the presence of a buffer layer significantly affected the structure and morphology of the growing films, which was reflected in their optical and radiative properties. In particular, films grown on the A- and M- planes of sapphire showed the highest UV radiation brightness values and exhibited stimulated emissions upon pulsed photoexcitation. The dependence of the topography of the film surface on the substrate orientation allowed the formation of a smooth continuous film with pronounced interference properties using the R- and M- planes of sapphire. A change in the crystallographic orientation, as well as a significant enhancement in crystallinity and luminescence, were observed for ZnO films grown on R-plane sapphire substrates with a gold buffer layer as compared to films grown on bare substrates. At the same time, the use of gold facilitates a significant smoothing of the film’s surface, retaining its interference properties. The sensitivity of interference and laser properties to changes in the external environment, as well as the ease of fabrication of such structures, create prospects for their application as key elements of optical converters, chemical and biological sensors, and sources of coherent radiation.     

Split Aptamers Immobilized on Polymer Brushes Integrated in a Lab-on-Chip System Based on an Array of Amorphous Silicon Photosensors: A Novel Sensor Assay

Innovative materials for the integration of aptamers in Lab-on-Chip systems are important for the development of miniaturized portable devices in the field of health-care and diagnostics. Herein we highlight a general method to tailor an aptamer sequence in two subunits that are randomly immobilized into a layer of polymer brushes grown on the internal surface of microfluidic channels, optically aligned with an array of amorphous silicon photosensors for the detection of fluorescence. Our approach relies on the use of split aptamer sequences maintaining their binding affinity to the target molecule. After binding the target molecule, the fragments, separately immobilized to the brush layer, form an assembled structure that in presence of a “light switching” complex [Ru(phen)₂(dppz)]²⁺, emit a fluorescent signal detected by the photosensors positioned underneath. The fluorescent intensity is proportional to the concentration of the target molecule. As proof of principle, we selected fragments derived from an aptamer sequence with binding affinity towards ATP. Using this assay, a limit of detection down to 0.9 µM ATP has been achieved. The sensitivity is compared with an assay where the original aptamer sequence is used. The possibility to re-use both the aptamer assays for several times is demonstrated.     

Nickel Oxide Films Deposited by Sol-Gel Method: Effect of Annealing Temperature on Structural,Optical, and Electrical Properties

In our study, transparent and conductive films of NiO_x were successfully deposited by sol-gel technology. NiO_x films were obtained by spin coating on glass and Si substrates. The vibrational, optical, and electrical properties were studied as a function of the annealing temperatures from 200 to 500 °C. X-ray Photoelectron (XPS) spectroscopy revealed that NiO was formed at the annealing temperature of 400 °C and showed the presence of Ni⁺ states. The optical transparency of the films reached 90% in the visible range for 200 °C treated samples, and it was reduced to 76–78% after high-temperature annealing at 500 °C. The optical band gap of NiOx films was decreased with thermal treatments and the values were in the range of 3.92–3.68 eV. NiO_x thin films have good p-type electrical conductivity with a specific resistivity of about 4.8 × 10⁻³ Ω·cm. This makes these layers suitable for use as wideband semiconductors and as a hole transport layer (HTL) in transparent solar cells.