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1.
Int J Mol Sci ; 25(9)2024 Apr 25.
Article in English | MEDLINE | ID: mdl-38731902

ABSTRACT

Investigation of chiroptical polymers in the solution phase is paramount for designing supramolecular architectures for photonic or biomedical devices. This work is devoted to the case study of poly(propylene oxide) (PPO) optical activity in several solvents: benzonitrile, carbon disulfide, chloroform, ethyl acetate, and p-dioxane. To attain information on the interactions in these systems, rheological testing was undertaken, showing distinct variations of the rheological parameters as a function of the solvent type. These aspects are also reflected in the refractive index dispersive behavior, from which linear and non-linear optical properties are extracted. To determine the circular birefringence and specific rotation of the PPO solutions, the alternative method of the channeled spectra was employed. The spectral data were correlated with the molecular modeling of the PPO structural unit in the selected solvents. Density functional theory (DFT) computational data indicated that the torsional potential energy-related to the O1-C2-C3-O4 dihedral angle from the polymer repeating unit-was hindered in solvation environments characterized by high polarity and the ability to interact via hydrogen bonding. This was in agreement with the optical characterization of the samples, which indicated a lower circular birefringence and specific rotation for the solutions of PPO in ethyl acetate and p-dioxane. Also, the shape of optical rotatory dispersion curves was slightly modified for PPO in these solvents compared with the other ones.


Subject(s)
Solvents , Solvents/chemistry , Propylene Glycols/chemistry , Polypropylenes/chemistry , Polymers/chemistry , Models, Molecular , Rotation , Hydrogen Bonding , Rheology
2.
Sensors (Basel) ; 23(9)2023 May 05.
Article in English | MEDLINE | ID: mdl-37177692

ABSTRACT

A series of polyimide supramolecular systems containing different amounts of azochromophore were tested as flexible supports that can be used in the fabrication of certain devices, such as sensors for monitoring the temperature changes, by coating them with conductive metals. That is why it is required to have good interfacial compatibility between the flexible substrate and the inorganic layer. The interface of the sensor elements must be designed in such a way as to improve the sensitivity, accuracy, and response time of the device. Laser irradiation is one of the commonly employed techniques used for surface adaptation by patterning polyimides to increase contact and enhance device reliability and signal transmission. In this context, this work highlights unreported aspects arising from the azo-polyimide morphology, local nanomechanical properties and wettability, which are impacting the compatibility with silver. The texture parameters indicate an improvement of the modulations' quality arising after laser irradiation through the phase mask, increasing the bearing capacity, fluid retention, and surface anisotropy when the amount of the azochromophore increases. The force curve spectroscopy and wettability studies indicated that the modification of the polymer morphology and surface chemistry lead to a better interfacial interaction with the metal lines when the azo component and the polyamidic acid are in equimolar quantities.

3.
Molecules ; 28(7)2023 Mar 26.
Article in English | MEDLINE | ID: mdl-37049717

ABSTRACT

Optical polymers are recognized for their high transparency, raised flexibility, low cost, and good film-forming ability; hence, they introduce a multitude of benefits in a wide range of devices, such as information storage, displays, optical communications, and filters. Among the optical properties, birefringence is an essential parameter in practical cases that demand the control of the state of polarization of light. This review is focused on describing some fundamental and applicative aspects concerning the optical birefringence of the polymer materials. First, elementary notions depicting the phenomenon of light double refraction in macromolecular media are provided. Furthermore, the most relevant optical techniques to determine birefringence are reviewed by highlighting the working principle and mathematical basis for computing this parameter. Then, a series of investigations of optically birefringent polymers are described, summarizing the most utilized approaches to induce light double refraction in such materials. The selected results are analyzed in relation to the pursued applications. In the end, the future of this scientific domain is briefly presented by establishing the research paths that need further exploration. Moreover, the novel directions that could be formulated and might contribute to certain considerable advancements in the materials employed in the modern optical technologies are mentioned.

4.
Int J Mol Sci ; 23(9)2022 Apr 25.
Article in English | MEDLINE | ID: mdl-35563112

ABSTRACT

Starting from the bactericidal properties of functionalized polysulfone (PSFQ) and due to its excellent biocompatibility, biodegradability, and performance in various field, cellulose acetate phthalate (CAP) and polyvinyl alcohol (PVA), as well as their blends (PSFQ/CAP and PSFQ/PVA), have been tested to evaluate their applicative potential in the biomedical field. In this context, because the polymer processing starts from the solution phase, in the first step, the rheological properties were followed in order to assess and control the structural parameters. The surface chemistry analysis, surface properties, and antimicrobial activity of the obtained materials were investigated in order to understand the relationship between the polymers' structure-surface properties and organization form of materials (fibers and/or films), as important indicators for their future applications. Using the appropriate organization form of the polymers, the surface morphology and performance, including wettability and water permeation, were improved and controlled-these being the desired and needed properties for applications in the biomedical field. Additionally, after antimicrobial activity testing against different bacteria strains, the control of the inhibition mechanism for the analyzed microorganisms was highlighted, making it possible to choose the most efficient polymers/blends and, consequently, the efficiency as biomaterials in targeted applications.


Subject(s)
Polymers , Polyvinyl Alcohol , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Polymers/chemistry , Polyvinyl Alcohol/chemistry , Sulfones/pharmacology
5.
Int J Mol Sci ; 23(23)2022 Dec 03.
Article in English | MEDLINE | ID: mdl-36499549

ABSTRACT

High-performance supramolecular polyimide systems were synthesized via a simple and innovative approach using two types of azo-chromophores, leading to concomitant special properties: high thermostability, the ability to be processed in the form of films with high flexibility, adequate morphological features, and good structuring capacity via phase mask ultraviolet (UV) laser irradiation, induced by the presence of the azo groups (-N=N-). The dimension and the anisotropy degree of the micro/nano patterns obtained on the surface of the flexible films (determined by atomic force microscopy) depend on the azo-dye type used in the supramolecular azopolyimide synthesis, which were higher when the azo-chromophore containing a -cyano group (-C≡N) was used. The molecular dynamics method, an excellent tool for an in-depth examination of the intermolecular interactions, was used to explain the morphological aspects. Energetic, dynamic and structural parameters were calculated for the two systems containing azo-chromophores, as well as for the pristine polymer system. It was highlighted that the van der Waals forces make a major contribution to the intermolecular interactions. The results from the combination of the dynamic analysis and the concentration profile explain the better mobility of the polyimide chains with a maximum content of azo groups in the cis configuration compared to the other systems. Taking all these data into account, the surfaces of the films can be tuned as required for the proposed applications, namely as substrates for flexible electronis.


Subject(s)
Azo Compounds , Light , Azo Compounds/chemistry , Microscopy, Atomic Force , Ultraviolet Rays , Polymers/chemistry
6.
Beilstein J Org Chem ; 10: 2145-56, 2014.
Article in English | MEDLINE | ID: mdl-25246973

ABSTRACT

We report on the synthesis as well as the optical, electrochemical and morphological properties of two polyrotaxanes (4a and 4b), which consist of electron-accepting 9,9-dicyanomethylenefluorene 1 as an inclusion complex in persilylated ß- or γ-cyclodextrin (TMS-ß-CD, TMS-γ-CD) (1a, 1b) and methyltriphenylamine as an electron-donating molecule. They are statistically distributed into the conjugated chains of 9,9-dioctylfluorene 3 and compared with those of the corresponding non-rotaxane 4 counterpart. Rotaxane formation results in improvements of the solubility, the thermal stability, and the photophysical properties. Polyrotaxanes 4a and 4b exhibited slightly red-shifted absorption bands with respect to the non-rotaxane 4 counterpart. The fluorescence lifetimes of polyrotaxanes follow a mono-exponential decay with a value of τ = 1.14 ns compared with the non-rotaxane, where a bi-exponential decay composed of a main component with a relative short time of τ1 = 0.88 (57.08%) and a minor component with a longer lifetime of τ2 = 1.56 ns (42.92%) were determined. The optical and electrochemical band gaps (ΔE g) as well as the ionization potential and electronic affinity characterized by smaller values compared to the values of any of the constituents. AFM reveals that the film surface of 4a and 4b displays a granular morphology with a lower dispersity supported by a smaller roughness exponent compared with the non-rotaxane counterpart.

7.
Carbohydr Polym ; 339: 122288, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-38823936

ABSTRACT

This paper reports on biofunctionalisation of a poly(lactic acid) (PLA) film by surface activation through cold plasma treatment followed by coating with a chitosan-gelatin xerogel. The UV cross-linking of the xerogel precursor was simultaneously performed with the fixation onto the PLA support. This has a strong effect on surface properties, in terms of wettability, surface free energy, morphology and micromechanical features. The hydrophilic - hydrophobic character of the surface, determined by contact angle measurements, was tuned along the process, passing from moderate hydrophobic PLA to enhanced hydrophilic plasma activated surface, which favors coating adhesion, then to moderate hydrophobic chitosan-gelatin coating. The coating has a Lewis amphoteric surface, with a porous xerogel-like morphology, as revealed by scanning electron microscopy images. By riboflavin mediated UV cross-linking the chitosan-gelatin coating becomes high adhesive and with a more pronounced plasticity, as shown by AFM force-distance spectroscopy. Thus prepared surface-coated PLA supports were successfully tested for growth of dermal fibroblasts, which are known for their induction potential of chondrogenic cells, which is very important in cartilage tissue engineering.


Subject(s)
Chitosan , Fibroblasts , Gelatin , Polyesters , Chitosan/chemistry , Gelatin/chemistry , Polyesters/chemistry , Fibroblasts/drug effects , Fibroblasts/cytology , Humans , Surface Properties , Gels/chemistry , Ultraviolet Rays , Plasma Gases/chemistry , Hydrophobic and Hydrophilic Interactions , Coated Materials, Biocompatible/chemistry , Cross-Linking Reagents/chemistry , Wettability
8.
Int J Biol Macromol ; 262(Pt 1): 130034, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38340942

ABSTRACT

The multiple uses of cellulose nanofibrils (CNFs) originate from their availability from renewable resources, and are due to their physico-chemical properties, biodegradability and biocompatibility. At the same time, reducing sensitivity to humidity, increasing interfacial adhesion and hydrophobic modification of the CNF surface to diversify applications and improve operation, are current targets pursued. This study focuses on the preparation of a novel gel structure using cellulose nanofibrils (CNFs) and poly(ethylene brassylate-co-squaric acid) (PEBSA50/50), a bio-based copolymacrolactone. The primary goal is to achieve the gel with reduced sensitivity to humidity and enhanced hydrophobic behaviour. The new system was characterized in comparison to its constituent components using various techniques, such as Fourier transform infrared spectroscopy, thermal analysis, X-ray diffraction, and NIR - chemical imaging. Rheological tests demonstrated the formation of the CNF_PEBSA50/50 gel as a result of physical interactions between the two polymeric partners and revealed self-healing abilities for the prepared gels. Determination of the contact angle, surface free energy, as well as dynamic measurements of the vapour sorption of the CNF_PEBSA50/50 system, confirmed the achievement of the study's aim. Furthermore, the CNF_PEBSA50/50 network was utilized to encapsulate citric acid, resulting in the creation of a new bioactive composite with both antioxidant and antimicrobial activity.


Subject(s)
Cellulose , Nanofibers , Cellulose/chemistry , Antioxidants/pharmacology , Polymers , Hydrophobic and Hydrophilic Interactions , Nanofibers/chemistry
9.
Materials (Basel) ; 16(14)2023 Jul 13.
Article in English | MEDLINE | ID: mdl-37512255

ABSTRACT

Azo-polyimide films with supramolecular structure were obtained by casting onto glass plates a mixture based on polyamidic acid and different quantities of azochromophore, followed by thermal treatment to realize the final azo-polyimide structure. The dielectric characteristics of the supramolecular structure of polymer films were investigated by broad-band dielectric spectroscopy measurements at different temperatures and frequencies. The free-standing films proved to be flexible and tough and maintained their integrity after repeated bending. The work of adhesion at the polymer/platinum interface was calculated after the evaluation of the surface energy parameters before and after plasma treatment. Atomic force microscopy was used to image the surface morphology, the evolution of the roughness parameters, and the adhesion force between the platinum-covered tip and the polymer surface, registered at the nanoscale with the quantity of the azo dye introduced in the system. The simulation of the columnar growth of a platinum layer was made to provide information about the deposition parameters that should be used for optimal results in the deposition of platinum electrodes for sensors.

10.
Polymers (Basel) ; 15(7)2023 Mar 24.
Article in English | MEDLINE | ID: mdl-37050239

ABSTRACT

The progress achieved in recent years in the biomedical field justifies the objective evaluation of new techniques and materials obtained by using silver in different forms as metallic silver, silver salts, and nanoparticles. Thus, the antibacterial, antiviral, antifungal, antioxidant, and anti-inflammatory activity of silver nanoparticles (AgNPs) confers to newly obtained materials characteristics that make them ideal candidates in a wide spectrum of applications. In the present study, the use of hydroxypropyl methyl cellulose (HPMC) in the new formulation, by embedding AgNPs with antibacterial activity, using poly(N-vinylpyrrolidone) (PVP) as a stabilizing agent was investigated. AgNPs were incorporated in HPMC solutions, by thermal reduction of silver ions to silver nanoparticles, using PVP as a stabilizer; a technique that ensures the efficiency and selectivity of the obtained materials. The rheological properties, morphology, in vitro antimicrobial activity, and stability/catching of Ag nanoparticles in resulting HPMC/PVP-AgNPs materials were evaluated. The obtained rheological parameters highlight the multifunctional roles of PVP, focusing on the stabilizing effect of new formulations but also the optimization of some properties of the studied materials. The silver amount was quantified using the spectroscopy techniques (energy-dispersive X-ray fluorescence (XRF), energy-dispersive X-ray spectroscopy (EDX)), while formation of the AgNPs was confirmed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and dynamic light scattering (DLS). Also, the morphological examination (Atomic Force Microscopy (AFM) and Scanning electron microscopy (SEM)) by means of the texture roughness parameters has evidenced favorable characteristics for targeted applications. Antibacterial activity was tested against Escherichia coli and Staphylococcus aureus and was found to be substantially improved was silver was added in the studied systems.

11.
Polymers (Basel) ; 15(4)2023 Feb 20.
Article in English | MEDLINE | ID: mdl-36850339

ABSTRACT

The progress of digital technologies demands more speed and larger storage capacity. Optical storage systems have the advantage of being cheap, fast and capacious. This article explores the potential use of polyimide-based films as a recording medium for optical storage devices. The materials were designed through a host-guest approach that involves a cyano-containing polyimide precursor and an azochromophore combined in the following ratios: 1:0.25, 1:0.5, 1:0.75 and 1:1. After thermal treatment up to 200 °C, polyimide systems were formed with supramolecular structures constructed via hydrogen bonding as shown by molecular modeling and FTIR at around 3350 cm-1. The aspects arising from the variation of the azo-dye content in the polyimide samples and their impact on the vitrification temperature, colorimetric features, refractive index, band gap, non-linear optical susceptibility and birefringence were investigated for the first time. The thermal analysis indicated a slight decrease in the vitrification temperature from 190.84 °C for the sample without azo dye to 163.91 °C for the film containing the highest leading of azo dye. The morphology images revealed the occurrence of periodic structures in azo-derived materials exposed to a UV laser, which is accentuated by the addition of more azo dye molecules. Optical tests allowed observation of the increase in the dominant wavelength, refractivity and optical conductivity of the samples, produced by the incorporation of azochromophore and laser irradiation. The photo-generated birefringence increased from 0.014 (sample with 1:0.25) to 0.036 (sample with 1:1), which in combination with the created regular topography pattern, is essential for the use of these materials as recording media in optical storage applications.

12.
Pharmaceutics ; 15(2)2023 Jan 21.
Article in English | MEDLINE | ID: mdl-36839694

ABSTRACT

Peptides and their related compounds can self-assemble into diverse nanostructures of different shapes and sizes in response to various stimuli such as pH, temperature or ionic strength. Here we report the synthesis and characterization of a lysozyme derived pentapeptide and its ability to build well-defined fibrillar structures. Lysozyme FESNF peptide fragment was synthesized by solid phase peptide synthesis using the Fmoc/t-Bu strategy, purified by analytical high-performance liquid chromatography (HPLC) and its molecular weight was confirmed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Spectroscopic features of this pentapeptide were investigated by UV-visible spectroscopy and fluorimetry showing the pattern of marginal phenylalanine residues within the peptide sequence. Self-assembling properties were determined using atomic force microscopy (AFM), aggregation index and thioflavin T assay (ThT). FESNF generating fibrillar structures observed by AFM and aggregation propensity were primarily influenced by pH conditions. Moreover, the experimental data were confirmed by molecular dynamics simulation studies. The obtained fibrils will be used next to explore their potential to act as support material for medical and cosmetic application.

13.
Gels ; 9(11)2023 Nov 09.
Article in English | MEDLINE | ID: mdl-37998976

ABSTRACT

Low-molecular-weight gelators (LMWGs) are compounds with an intrinsic tendency to self-assemble forming various supramolecular architectures via non-covalent interactions. Considering that the development of supramolecular assemblies through the synergy of molecules is not entirely understood at the molecular level, this study introduced a Fmoc-short peptide and four Fmoc-amino acids as building blocks for the self-assembly/co-assembly process. Hence, we investigated the formation of supramolecular gels starting from the molecular aggregation following two triggering approaches: solvent/co-solvent method and pH switch. The complex morphological analysis (POM, AFM, and STEM) offered an insight into the spontaneous formation of well-ordered nanoaggregates. Briefly, POM and AFM images demonstrated that self-assembled gels present various morphologies like dendrimer, spherulite, and vesicle, whereas all co-assembled supramolecular systems exhibit fibrillar morphologies as a result of the interaction between co-partners of each system. STEM study has confirmed that the molecules interact and join together, finally forming a fibrous network, an aspect seen in both self-assembled and co-assembled gels. XRD allowed the determination of the molecular arrangement. The study emphasized that the Fmoc motif protected the amino groups and facilitated gelation through additional π-π interactions.

14.
Pharmaceutics ; 15(12)2023 Dec 05.
Article in English | MEDLINE | ID: mdl-38140071

ABSTRACT

In light of the increasing resistance of pathogenic microorganisms to the action of antibiotics, essential oils extracted from plants with therapeutic activity provide a significant alternative to obtaining dressings for the treatment of skin wounds. The encapsulation of essential oils in an amphiphilic gel network allows better dispersion and preservation of hydrophobic bioactive substances while promoting their prolonged release. In this study, we focused on the development of a poly (vinyl alcohol) (PVA)/poly (ethylene brassylate-co-squaric acid) (PEBSA) platform embedded with thymol (Thy), and α-tocopherol (α-Tcp) as a co-drug structure with prospective use for the treatment and healing of skin wounds. The new complex bioactive system was prepared through repeated freeze-thaw processes. The influence of the composition on surface topography, hydrophilic/hydrophobic character, and in vitro interaction with simulated body fluids was evidenced. BALB/3T3 fibroblast cell culture demonstrated the cryogel scaffolds' cytocompatibility. Tests on Wistar rats confirmed their biocompatibility, integration with host tissue, and the absence of inflammatory processes. The bioactive compound significantly enhanced the healing process of full-thickness excision wounds in a rat model. Further investigations on in vivo infection models would assess the potential of the PVA/PEBSA platform with dual bioactive activity for clinical antimicrobial and wound healing therapy.

15.
Materials (Basel) ; 15(5)2022 Mar 04.
Article in English | MEDLINE | ID: mdl-35269150

ABSTRACT

This study aims to present the properties of the polymeric films after being subjected to DBD plasma treatment in atmospheric conditions. Three different commercial films of polyester (Xerox Inkjet transparencies and Autostat CUS5 Clear film) and polycarbonate (Lexan™ 8010 MC) have been considered for the tests. The surface wettability has been evaluated based on static water contact angle (WCA) for different treatment times varying between 0.2 s and 30 s, the results revealing a maximum WCA decrease compared to a pristine of up to 50% for Xerox films, 75% for Autostat and 70% for Lexan. The persistence of the hydrophilic effect induced by the plasma treatment has also been verified for up to 72 h of storage after treatment, the results indicating a degradation of the treatment effects starting with the first hours after the treatment. The WCA stabilizes to a value inferior to the one corresponding to pristine in the first 24 h after plasma treatment. The adhesion forces, as well as preliminary surface morphology evaluations have been determined for the considered films using atomic force microscopy (AFM). The adhesion forces are increased together with the prolongation of the plasma treatment application time, varying from initial values of 165 nN, 58 nN and 204 nN to around 390 nN, 160 nN and 375 nN for Xerox, Autostat and Lexan films, respectively, after 5 s of DBD treatment. For the considered materials, the results revealed that the plasma treatment determines morphological changes of the surfaces indicating an increase in surface roughness.

16.
Chempluschem ; 87(2): e202100462, 2022 02.
Article in English | MEDLINE | ID: mdl-35104052

ABSTRACT

Bioinspired peptides are attractive biomolecules which can improve our understanding of self-assembly processes for rational design of new peptide-based materials. Herein, a new amidated peptide FRSAPFIE (FRS), based on a sequence present in human collagen, was synthesized, characterized by mass spectrometry and subjected to self-assembling investigations. The optimal conditions for self-assembly were disclosed by dynamic light scattering at 32 °C and a peptide concentration of 0.51 %. In addition, AFM studies revealed ellipsoidal FRS shapes with an area between 0.8 and 3.1 µm2 . The ability of self-assembly was also proved using FAD dye as extrinsic fluorescence reporter. According to the theoretical analysis, the FRS peptide tends to form a bundle-type association, with a type of fibrillary tangles particle. Altogether, our findings address new challenges regarding the FRS peptide which can be used in further self-assembly studies to design biocompatible drug-delivery platforms.


Subject(s)
Biomimetics , Collagen , Collagen/chemistry , Drug Delivery Systems , Humans , Peptides/chemistry
17.
Polymers (Basel) ; 14(19)2022 Sep 27.
Article in English | MEDLINE | ID: mdl-36235997

ABSTRACT

The performance of photovoltaics with superstrate configuration is limited by the rigidity and low refractivity of a classical glass cover. In this work, two polyimides (PIs) and two copolyimides combined in the main chain cycloaliphatic moieties, aromatic sequences, chalcogen atoms, and having/lacking fluorine atoms, are proposed as shielding covers for solar cells. The samples containing small cycloaliphatic moieties displayed high transmittance above 80% at 550 nm. The refractive index values under changeable wavelengths and temperatures were shown to influence the magnitude of the reflection losses. At the sample interface with the transparent electrode, optical losses were reduced (~0.26%) in comparison to the classical glass (~0.97%). The samples with the best optical features were further subjected to a surface treatment to render the self-cleaning ability. For this, a new approach was used residing in irradiation with the diffuse coplanar surface barrier discharge (DCSBD), followed by spraying with a commercial substance. Scanning electron microscopy and atomic force microscopy scans show that the surface characteristics were changed after surface treatment, as indicated by the variations in root mean square roughness, surface area ratio, and surface bearing index values. The proposed PI covers diminish the optical losses caused by total internal reflection and soiling, owing to their adapted refractivity and superhydrophobic surfaces (contact angles > 150°), and open up new perspectives for modern photovoltaic technologies.

18.
Nanomaterials (Basel) ; 12(18)2022 Sep 19.
Article in English | MEDLINE | ID: mdl-36145037

ABSTRACT

The efficiency of photovoltaics (PVs) is related to cover material properties and light management in upper layers of the device. This article investigates new polyimide (PI) covers for PVs that enable light trapping through their induced surface texture. The latter is attained via a novel strategy that involves multi-directional rubbing followed by plasma exposure. Atomic force microscopy (AFM) is utilized to clarify the outcome of the proposed light-trapping approach. Since a deep clarification of either random or periodic surface morphology is responsible for the desired light capturing in solar cells, the elaborated texturing procedure generates a balance among both discussed aspects. Multidirectional surface abrasion with sand paper on pre-defined directions of the PI films reveals some relevant modifications regarding both surface morphology and the resulted degree of anisotropy. The illuminance experiments are performed to examine if the created surface texture is suitable for proper light propagation through the studied PI covers. The adhesion among the upper layers of the PV, namely the PI and transparent electrode, is evaluated. The correlation between the results of these analyses helps to identify not only adequate polymer shielding materials, but also to understand the chemical structure response to new design routes for light-trapping, which might significantly contribute to an enhanced conversion efficiency of the PV devices.

19.
Nanomaterials (Basel) ; 11(11)2021 Nov 18.
Article in English | MEDLINE | ID: mdl-34835871

ABSTRACT

The operability of liquid crystal displays is strongly impacted by the orientation aspects of nematics, which in turn are affected by the alignment layer surface features. In this work, two polyimide (PI) structures are obtained based on a cycloaliphatic dianhydride and aromatic or aliphatic diamines with distinct flexibility. The attained PI films have high transmittance (T) for visible radiations, i.e., at 550 nm T > 80%. Here, a novel strategy for creating surface anisotropy in the samples that combines rubbing with a cloth and stretching via pressing is reported. Birefringence and atomic force microscopy (AFM) scans reveal that the generated orientation of the chains is affected by the chemical structure of the polymer and order of the steps involved in the surface treatment. Molecular modeling computations and wettability tests show that the PI structure and produced surface topography are competitive factors, which are impacting the intensity of the interactions with the nematic liquid crystals. The achieved results are of great relevance for designing of reliable display devices with improved uniform orientation of liquid crystals.

20.
Nanomaterials (Basel) ; 11(3)2021 Mar 22.
Article in English | MEDLINE | ID: mdl-33809999

ABSTRACT

Aromatic polyimides containing side azo-naphthalene groups have been investigated regarding their capacity of generating surface relief gratings (SRGs) under pulsed UV laser irradiation through phase masks, using different fluencies and pulse numbers. The process of the material photo-fluidization and the supramolecular re-organization of the surface were investigated using atomic force microscopy (AFM). At first, an AFM nanoscale topographical analysis of the induced SRGs was performed in terms of morphology and tridimensional amplitude, spatial, hybrid, and functional parameters. Afterward, a nanomechanical characterization of SRGs using an advanced method, namely, AFM PinPoint mode, was performed, where the quantitative nanomechanical properties (i.e., modulus, adhesion, deformation) of the nanostructured azo-polyimide surfaces were acquired with a highly correlated topographic registration. This method proved to be very effective in understanding the formation mechanism of the surface modulations during pulsed UV laser irradiation. Additionally to AFM investigations, confocal Raman measurements and molecular simulations were performed to provide information about structured azo-polyimide chemical composition and macromolecular conformation induced by laser irradiation.

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