Polymer Hybrid Systems Research Articles

Titanium oxide hydrates as versatile polymer crosslinkers and molecular‐hybrid formers

AbstractMolecular hybrid materials based on widely available polymers crosslinked with an inorganic species have received increasing interest for their unique property sets outside of the usual range of commodity plastics and/or nanocomposites. Here, we provide a mini‐review on molecular hybrids based on metal oxide hydrates—compounds that readily react with, for example, hydroxylated polymers to form inorganic:organic materials systems with many desirable features and properties. Focusing on titanium oxide hydrates, we discuss here that such molecular hybrids can exhibit a broad refractive index range in addition to an increased glass transition temperature, mechanical stiffness and swelling resistance in comparison to the neat polymer, which illustrates that such hybrid systems offer a new, low‐cost, robust and versatile functional materials platform with great promise for, for example, solution‐processed photonics, catalysts and antimicrobial coatings. Generally, our mini‐review seeks to provide a concise and accessible overview of titanium oxide hydrate:polymer hybrid systems, focusing on their unique properties and processability as well as their broad and largely untapped potential as functional materials. © 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Construction of a dual colorimetric fluorescent imprinting polymer hybrid system for the detection of alpha-fetoprotein based on the multi-FRET effect and modeling of its color response mechanism

The hybrid ratiometric fluorescence sensors (GKHMIPs & RKHMIPs) encompass luminescent substances incorporated within a core-shell architecture. These sensors manifest a diverse array of hues in response to variations in the concentration of alpha-fetoprotein, accomplished through disparities in the quantum dots (QDs)-protein response. This study is devoted to comprehending the principles governing the alteration of fluorescence during the recognition process of the ratiometric fluorescence sensor. A compensation mechanism, rooted in the correlation between fluorescence and protein response, is postulated through a fluorescence interaction model (multi-FRET model). Multi-FRET model can be divided into FRET process and Fluorescence compensate process (FCP), FCP occurs when electron orbits are filled, hindering the fluorescence resonance energy transfer process and leading to the return of excited state electrons to the ground state by alternative pathways. Based on the multi-FRET model we demonstrate the Sherpa formular to calculating the fluorescence-target relation. To assess the visual impact, the CIE-Lab model is introduced to validate the rationale behind the multi-color colorimetric model. The influence of different mixing ratios on the visualization effect is elucidated using the concentration fluorescence response model, and the optimal relationship between wavelength combinations in the tricolor mixing model is proposed.

Polymeric Nanoparticles for Delivery of Natural Bioactive Agents: Recent Advances and Challenges.

In the last few decades, several natural bioactive agents have been widely utilized in the treatment and prevention of many diseases owing to their unique and versatile therapeutic effects, including antioxidant, anti-inflammatory, anticancer, and neuroprotective action. However, their poor aqueous solubility, poor bioavailability, low GIT stability, extensive metabolism as well as short duration of action are the most shortfalls hampering their biomedical/pharmaceutical applications. Different drug delivery platforms have developed in this regard, and a captivating tool of this has been the fabrication of nanocarriers. In particular, polymeric nanoparticles were reported to offer proficient delivery of various natural bioactive agents with good entrapment potential and stability, an efficiently controlled release, improved bioavailability, and fascinating therapeutic efficacy. In addition, surface decoration and polymer functionalization have opened the door to improving the characteristics of polymeric nanoparticles and alleviating the reported toxicity. Herein, a review of the state of knowledge on polymeric nanoparticles loaded with natural bioactive agents is presented. The review focuses on frequently used polymeric materials and their corresponding methods of fabrication, the needs of such systems for natural bioactive agents, polymeric nanoparticles loaded with natural bioactive agents in the literature, and the potential role of polymer functionalization, hybrid systems, and stimuli-responsive systems in overcoming most of the system drawbacks. This exploration may offer a thorough idea of viewing the polymeric nanoparticles as a potential candidate for the delivery of natural bioactive agents as well as the challenges and the combating tools used to overcome any hurdles.

Engineering network entanglement of functionalized graphene oxide/poly(acrylamide) nanocomposites for enhanced oil recovery

Hydroxyl-functionalized graphene oxide (OGO) was prepared from graphene oxide (GO) modified by diethanolamine (DEOA) to promote the interaction between nano sheets and polymer molecules. Three OGO samples with different GO to DEOA ratios, and an acrylamide-based polymer (PM) were synthesized. The nanoparticle and polymer hybrid systems were prepared using GO or OGO suspension into PM solution. The interaction strength investigation indicated that the hybrid system had two kinds of hydrogen bonds, one is between amide groups on polymer and the other is between amide groups on polymer and hydroxyl groups on nanosheets, and there was a competition for them. As a result, a proper surface hydroxyl density is critical to form a suitable molecular network for improving the hybrid property under harsh condition. The rheological properties of PM solution and these hybrid systems were studied, and the results showed that the introduction of OGO obviously improved the salt-resistance and temperature-tolerance of PM solution. The results from oil displacement experiments showed that the enhanced oil recovery ratio jumped to 20.9% for PM/OGO system, while it was only 13.8% for PM solution.

An illustrative understanding of strengthening the stability and efficiency of perovskite solar cells: utilization of the perovskite-constructed polymer hybrid system, PHQACl-CN

Integrating a proper amount of polymer hybrid of quaternary ammonium chloride functionalized graphitic carbon nitride (PHQACl-CN) in the perovskite leads to positive adjustments in the morphology of the treated perovskite films and boosts the PSC device performance.

NEW HIGH- CONDUCTING HYBRID CsH5(PO4)2-BUTVAR COMPOUNDS

Hybrid polymer compounds (1–x)CsH5(PO4)2-xButvar (polyvinyl butyral brand Butvar®) (x = 0–0.3, x - weight fraction), synthesized with ethanol and isopropanol as solvents, studied using the electrochemical impedance method, powder X-ray diffraction analysis (XRD hereinafter), differential scanning calorimetry, and electron microscopy. A more optimal synthesis method was determined and the fundamental possibility of creating new highly conductive thin polymer electrolytes based on CsH5(PO4)2 was shown. The crystal structure of the CsH5(PO4)2 (P21/c) salt remains unchanged in the polymer hybrid system, but dispersion and partial amorphization of salt were observed during synthesis. It was found that, to achieve the highest proton conductivity of (1–x)CsH5(PO4)2-xButvar, the most preferable method of synthesis is the precipitation of the salt, from the starting components, in the presence of a solvent common with the polymer. The most optimal is the method of salt precipitation from a polymer solution in ethanol as a common solvent with further tape casting. The thickness of polymer electrolytes is no more than 50–100 μm. Proton conductivity increases by 2 orders of magnitude relative to the initial salt and depends on composition, uniformity of salt distribution in the polymer volume, and the presence of residual humidity during electrolyte synthesis. The highest proton conductivity was 10-2 S/cm at 130 °C at low humidity conditions. Changes in the electrotransport characteristics of the system are caused by dispersion and partial amorphization of the salt, as well as by the presence of insignificant amounts of residual water molecules on the salt surface under the conditions of the synthesis of polymer compositions.

Design, characterization and evaluation of cucurbitacin B-loaded core–shell-type hybrid nano-sized particles using DoE approach

The main objective of this research was to design and optimize novel core–shell-type hybrid nano-sized systems of cucurbitacin B (CuB) based on the design of experiment (DoE) approach. The hybrid formulations consisting of polyethylene glycol (PEG)-conjugated phospholipid, lecithin and poly-lactic-co-glycolic acid (PLGA) were produced by employing self-assembly modified nanoprecipitation technique. A 32 factorial design was utilized to understand the effect of two input factors, namely PEG phospholipid/polymer ratio and total lipids/lecithin ratio, on entrapment efficiency and drug release percentage. The particle size and surface charge analyses, excipient interactions and thermal behavior, particle morphology, presence and thickness of lipid shell, and also storage stability studies were carried out through in vitro characterization. The entrapment efficiency of all nanoparticles of CuB ranged between 49.35 and 80.00%. The prepared lipid–polymer hybrid systems exhibited an average particle size from 94.5 to 127.2 nm with polydispersity in the range from 0.094 to 0.114, which inhibited a narrow size distribution. The nano-sized formulation at the center point of the design was selected as optimum formulation due to its excellent characteristics and the configuration determined using ANOVA and response surface methodology (RSM) approach.

Extraction of magnetic circular dichroism effects from blended mixture of magnetic linear dichroism signals in the cobalt/Scotch tape system

Circular dichroism (CD) signals revealed in some materials may arise from different origins during measurements. Magnetic field dependent CD (MCD) emanating from the spin-polarized band provides direct insight into the spin–spin interband transitions in magnetic materials. On the contrary, natural CD effects which are artefactual signals resulting from the linear polarization (LP) components during the polarization modulation with a photo-elastic modulator in anisotropic polymer systems were usually observed. There is no simple method to reliably distinguish MCD effect due to spin polarized band structures from natural CD effect, which limits our understanding of the magnetic material/polymer hybrid structures. This paper aims to introduce a general strategy of averaging out the magnetic linear dichroism (MLD) contributions due to the anisotropic structure and disentangling MCD signal(s) from natural MCD signal(s). We demonstrate the effectiveness of separating MCD from natural MCD using rotational MCD measurement and presented the results of a sample with Co thin film on polymer Scotch tape (unplasticized polyvinyl chloride) glued on a quartz substrate. We demonstrate that the proposed method can be used as an effective tool in disentangling MCD and natural MCD effects, and it opens prospects to study the magnetic material /polymer hybrid systems.

A genipin-crosslinked protein-polymer hybrid system for the intracellular delivery of ribonuclease A.

BackgroundTherapeutic proteins have been widely used in the treatment of various diseases, and effective carriers are highly required for achieving protein delivery to obtain favorable treatment potency.Materials and methodsA protein–polymer hybrid system was constructed through the genipin-mediated crosslinking of polyethyleneimine with a weight-average molecular weight of 25,000 g/mol (PEI25K) and ribonuclease A (RNase A), namely RGP.ResultsThe RGP nanoparticles were observed to be easily internationalized in HeLa cells owing to the introduction of positively charged PEI25K, thereby triggering the antiproliferative effects by cleaving RNA molecules in the tumor cells. Moreover, red fluorescence could be obviously visualized in the tumor cells after RGP delivery, which was attributed to the intrinsic characteristics of genipin.ConclusionThe protein–polymer hybrid system prepared via the genipin-mediated crosslinking has exhibited potential to be used as a theranostic platform for both in vivo imaging and delivering diverse therapeutic proteins.

Photocleavable Peptide-Poly(2-hydroxyethyl methacrylate) Hybrid Graft Copolymer via Postpolymerization Modification by Click Chemistry To Modulate the Cell Affinities of 2D and 3D Materials.

Controlling the surface properties of engineered materials to enhance or reduce their cellular affinities remains a significant challenge in the field of biomaterials. We describe a universal technique for modulating the cytocompatibilities of two-dimensional (2D) and three-dimensional (3D) materials using a novel photocleavable peptide-grafted poly(2-hydroxyethyl methacrylate) (PHEMA) hybrid. The reversible addition-fragmentation chain transfer copolymerization of HEMA and propargyl acrylate was successfully controlled. The resultant alkyne-containing PHEMA was then used to modify the azide-terminated oligopeptides [Arg-Gly-Asp-Ser (RGDS)] with a photolabile 3-amino-3-(2-nitrophenyl)propanoic acid moiety via the copper-catalyzed alkyne-azide click chemistry. This strategy was readily used to decorate the surfaces of both hydrophilic and hydrophobic materials with RGDS peptides due to the high film-forming abilities of the PHEMA unit. The resultant thin film acted as an effective scaffold for improving cell adhesion and growth of NIH/3T3 fibroblasts and MC3T3-E1 osteoblast-like cells in vitro. In addition, UV irradiation of the surface led to the detachment of cells from the material surface accompanied by the photocleavage of RGDS grafts and enabled the 2D-patterning of cells and cell sheet engineering. The applicability of this system to 3D materials was investigated, and the cell adhesion was remarkably enhanced on a 3D-printed poly(lactic acid) object. This facile, biocompatible, and photoprocessable peptide-vinyl polymer hybrid system is valuable for its ability to advance the fields of tissue engineering, cell chips, and regenerative medicine.

Photoactive Hybrid Film Photocatalyst of Polyethersulfone-ZnO for the Degradation of Methyl Orange Dye: Kinetic Study and Operational Parameters

A facile and effective technique to immobilize photocatalyst nanoparticles by incorporating zinc oxide (ZnO) into polyethersulfone polymeric films by means of a phase inversion technique is reported. The degradation study of methyl orange (MO) dye was performed using a series of ZnO-embedded polymer hybrid systems. The photoactivity of the films increased in parallel with increased ZnO loading up to 17 wt%. The photodegradation process followed a pseudo first-order kinetics with an achievement of almost 100% MO removal in original conditions. The PZ-17 film demonstrated an excellent and comparable degradation performance up to five cycles, signifying the reliability of the film photocatalyst against ultraviolet irradiation and degradation.

Reversible photochromic effect in the TiO2—polymer hybrid system

The photochromism of poly methyl methacrylate–TiO2 composites have been investigated in this research. Amorphous titanium oxide was synthesized by sol–gel using titanium isopropoxide. The titanium solution was mixed with a dissolved polymer. The composite shows photo-response under UV radiation by changing, generally, to a dark brown tonality. This effect was reversible in different time ranges according to the intensity and exposure time. The mechanism for this photochromic change was proposed as a reduction of TiOOH domains to Ti3+ and not directly from amorphous TiO2, which provide electron-hole pairs after absorbing UV. The backscattered electrons image shows the clusters or domains of titanium compounds as white dots, ranging from 0.1 to 1 μm. The electron spin resonance spectroscopy signals indicated a titanium valence change from Ti(IV) to Ti(III). The X-ray photoelectron spectroscopy peaks positions for Ti 2p1/2 and Ti 2p3/2 were assigned as Ti4+. The values were obtained for Ti 2p3/2 and the identified species were Ti4+ and Ti3+, that correspond to TiO2, Ti2O3, and Ti(OOH). Few and small crystalline domains were identified by Transmission Electron Microscope as orthorhombic TiO2.’

Effect of host-mobility dependent carrier scattering on thermoelectric power factors of polymer composites

The interfacial carrier scattering was thought to be ineffective in enhancing thermoelectric (TE) properties of polymer hybrids and there was also a lack of fundamental understanding of carrier scattering at polymer/polymer interfaces. Here we unravel the mechanism behind the role of polymer/polymer interfacial scattering on the TE properties through integration of computation and experiments. We discover that the effect of interfacial scattering at polymer/polymer interfaces on TE properties of polymer hybrids is strongly dependent on the carrier mobility of host polymers besides interfacial barriers. Only when the host carrier mobility is above a threshold, the effect of interfacial scattering on TE enhancement can be significant. Simulation suggests that the host mobility threshold is ~1cm2V−1s−1 for PEDOT-based polymers. The polymer hybrid system of poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires/PEDOT was successfully employed to verify the theoretical results. These findings offer groundbreaking knowledge on polymer/polymer interfacial carrier-transport and will advance the design and fabrication of high-efficiency organic thermoelectric materials.

Organic-inorganic hybrid material and multifunctional fibers

Organic-inorganic hybrid materials can achieve the multi-scale composites of organic polymers and inorganic materials in the nano or molecular level. On one hand, such hybrid materials can exert each components characteristics. On the other hand, they reflect the unique collaboration features, such as new performance and multifunction. This principle can also be implemented in organic-organic hybrid system. With the continuous development of industrial fiber materials, their applications continue to be expanded. The development of new polymer materials to achieve multifunctional fibers has become a hot topic. According to the requirement of multifunctional fibers development, researchers try to build hybrid functional materials at the molecular level, build hybrid functional materials system and fiber-forming polymer hybrid system using the methods of structural design and construct interface combining with the organic-inorganic hybrid mechanism. This paper takes the structural design and condensed control of fiber-forming polymers, the structure-controllable preparation of nano-fibers and low-dimensional nano-fibers for example, introducing the research progress of organic-inorganic hybrid principles in the aspect of multi-functional fibers. Finally, it prospects the development of multifunctional organic-inorganic hybrid fibers.

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Photovoltaic Performance of AgInSe2-Conjugated Polymer Hybrid Systems

Conduction mechanism of lithium bis(oxalato)borate–cellulose acetate polymer gel electrolytes

Polymer gel electrolytes (PGE) belonging to salt–solvent–polymer hybrid systems are prepared using a mixture of lithium bis(oxalato)borate (LiBOB), γ-butyrolactone (γ-BL), and cellulose acetate (CA). The increase in ionic conductivity of PGE is due to the dissociation of ion aggregates, as confirmed by Fourier transform infrared analysis. The highest conductivity attained by the PGE is 7.05 mS cm−1 at 2.4 wt.% CA. The plots of conductivity–temperature show a classical Arrhenius relationship. The electrical properties of the sample with the highest conductivity are analyzed using electrical permittivity and electric modulus formalism studies. Meanwhile, the frequency-dependent conductivity of the polymer gel electrolyte adheres to Jonscher’s power law. Conduction mechanism study also shows that the 2.4 wt.% CA PGE is in agreement with the small polaron hopping model.