Three-dimensional Polymeric Network Research Articles

Flexible Highly Thermally Conductive PCM Film Prepared by Centrifugal Electrospinning for Wearable Thermal Management

Personal thermal management materials integrated with phase-change materials have significant potential to satisfy human thermal comfort needs and save energy through the efficient storage and utilization of thermal energy. However, conventional organic phase-change materials in a solid state suffer from rigidity, low thermal conductivity, and leakage, making their application challenging. In this work, polyethylene glycol (PEG) was chosen as the phase-change material to provide the energy storage density, polyethylene oxide (PEO) was chosen to provide the backbone structure of the three-dimensional polymer network and cross-linked with the PEG to provide flexibility, and carbon nanotubes (CNTs) were used to improve the mechanical and thermal conductivity of the material. The thermal conductivity of the composite fiber membranes was boosted by 77.1% when CNTs were added at 4 wt%. Water-resistant modification of the composite fiber membranes was successfully performed using glutaraldehyde-saturated steam. The resulting composite fiber membranes had a reasonable range of phase transition temperatures, and the CC4PCF-55 membranes had melting and freezing latent heats of 66.71 J/g and 64.74 J/g, respectively. The results of this study prove that the green CC4PCF-55 composite fiber membranes have excellent flexibility, with good thermal energy storage capacity and thermal conductivity and, therefore, high potential in the field of flexible wearable thermal management textiles.

Rational Designing Microenvironment of Gas-Diffusion Electrodes via Microgel-Augmented CO2 Availability for High-Rate and Selective CO2 Electroreduction to Ethylene.

Efficient electrochemical CO2 reduction reaction (CO2RR) requires advanced gas-diffusion electrodes (GDEs) with tunned microenvironment to overcome low CO2 availability in the vicinity of catalyst layer. Herein, for the first time, pyridine-containing microgels-augmented CO2 availability is presented in Cu2O-based GDE for high-rate CO2 reduction to ethylene, owing to the presence of CO2-phil microgels with amine moieties. Microgels as three-dimensional polymer networks act as CO2 micro-reservoirs to engineer the GDE microenvironment and boost local CO2 availability. The superior ethylene production performance of the GDE modified by 4-vinyl pyridine microgels, as compared with the GDE with diethylaminoethyl methacrylate microgels, indicates the bifunctional effect of pyridine-based microgels to enhance CO2 availability, and electrocatalytic CO2 reduction. While the Faradaic efficiency (FE) of ethylene without microgels was capped at 43% at 300mAcm-2, GDE with the pyridine microgels showed 56% FE of ethylene at 700mAcm-2. A similar trend was observed in zero-gap design, and GDEs showed 58% FE of ethylene at -4.0 cell voltage (>350mAcm-2 current density), resulting in over 2-fold improvement in ethylene production. This study showcases the use of CO2-phil microgels for a higher rate of CO2RR-to-C2+, opening an avenue for several other microgels for more selective and efficient CO2 electrolysis.

Chitosan-derived activated carbon/chitosan composite beads for adsorptive removal of methylene blue and acid orange 7 dyes

In this study, a chitosan/activated carbon composite was developed for the sustainable removal of dye pollutants from activated carbon derived from chitosan. First, chitosan was converted into chitosan-derived activated carbon (C-AC) with a large Brunauer-Emmett-Teller (BET) surface area of 2428 m2/g through carbonization using a potassium hydroxide (KOH) chemical activator. To enable simple separation from contaminated water and sustainable use in the adsorption process, the generated C-AC was incorporated into a bead-type, stable three-dimensional chitosan polymer network structure. The prepared C-AC-incorporated chitosan beads showed excellent adsorption capacity for the anionic acid orange 7 (AO) (511.38 mg/g) and the cationic methylene blue (MB) (413.08 mg/g). In addition, it maintained structural stability even in various pH environments and could be easily separated from contaminated water. The C-AC-incorporated chitosan beads showed excellent reusability and durability, maintaining at least 82% and 86% removal efficiencies for AO and MB dyes even after five reuses. This study suggests the potential use of chitosan as an eco-friendly adsorbent that can be utilized simultaneously as an activated carbon precursor and as a matrix for robust bead-like polymer composites.

Ultrasensitive Surface-Enhanced Raman Scattering Platform for Protein Detection via Active Delivery to Nanogaps as a Hotspot.

Surface-enhanced Raman scattering (SERS) is an attractive technique in molecular detection with high sensitivity and label-free characteristics. However, its use in protein detection is limited by the large volume of proteins, hindering its approach to the narrow spaces of hotspots. In this study, we fabricated a Au nanoTriangle plate Array on Gel (AuTAG) as an SERS substrate by attaching a Au nanoTriangle plate (AuNT) arrangement on a thermoresponsive hydrogel surface. The AuTAG acts as an actively tunable plasmonic device, on which the interparticle distance is altered by controlling temperature via changes in hydrogel volume. Further, we designed a Gel Filter Trapping (GFT) method as an active protein delivery strategy based on the characteristics of hydrogels, which can absorb water and separate biopolymers through their three-dimensional (3D) polymer networks. On the AuTAGs, fabricated with AuNTs modified with charged surface ligands to prevent the nonspecific adsorption of analytes to particles, the GFT method helped the delivery of proteins to hotspot areas on the AuNT arrangement. This combination of a AuTAG substrate and the GFT method enables ultrahigh sensitivity for protein detection by SERS up to a single-molecule level as well as a wide quantification concentration range of 6 orders due to their geometric advantages.

Hydrogel in Drylands: A Review

Significant amounts of water and nutrients are held in reserve by hydrogels due to their three-dimensional polymeric network. The capacity of hydrogels to absorb water lowers the frequency of irrigation, which is beneficial for agricultural application. When applied to soil, it functions well as a nutrient mobilizer and a reservoir for water. Applying hydrogel will be a profitable and advantageous way to boost agricultural crop yield and sustainability in settings where moisture is scarce. Because of their three-dimensional polymeric network, hydrogels can store large amounts of water and nutrients. Because hydrogels can absorb water, less irrigation is required, which is advantageous for agricultural use. It works well as a water reservoir and nutrient mobilizer when added to soil. In environments where moisture is limited, applying hydrogel will be a profitable and beneficial strategy to increase agricultural crop productivity and sustainability.

Hydrogel-based Drug Delivery System in Diabetes Management.

It is estimated that there are over 200 million people living with diabetes mellitus (DM) all over the world. It is a metabolic condition caused by decreased insulin action or secretion. Diabetes Mellitus is also known as Type 2 Diabetes Mellitus. Type 1 diabetes mellitus and type 2 diabetes mellitus are the two most common types of DM. Treatment for type 1 diabetes often consists of insulin replacement therapy, while treatment for type 2 diabetes typically consists of oral hypoglycemics. Conventional dosing schedules for the vast majority of these medications come with a number of drawbacks, the most common of which are frequent dosing, a short half-life, and low bioavailability. Thus, innovative and regulated oral hypoglycemic medication delivery methods have been developed to reduce the limitations of standard dose forms. The studies and reviews published under the title were looked up in several databases (including PubMed, Elsevier, and Google Scholar). Hydrogels made from biopolymers are three-dimensional polymeric networks that can be physically or chemically crosslinked. These networks are based on natural polymers and have an inherent hydrophilic quality because of the functional groups they contain. They have a very high affinity for biological fluids in addition to a high water content, softness, flexibility, permeability, and biocompatibility. The fact that these features are similar to those of a wide variety of soft living tissues paves the way for several potentials in the field of biomedicine. In this sense, hydrogels offer excellent platforms for the transport of medications and the controlled release of those drugs. Additionally, biopolymer-based hydrogels can be put as coatings on medical implants in order to improve the biocompatibility of the implants and to prevent medical diseases. The current review focuses on the most recent advancements made in the field of using biopolymeric hydrogels that are physically and chemically crosslinked, in addition to hydrogel coatings, for the purpose of providing sustained drug release of oral hypoglycemics and avoiding problems that are associated with the traditional dosage forms of oral hypoglycemics.

Real-Space Visualization of Charged Polymer Network of Hydrogel by Double Network Strategy and Mineral Staining.

Hydrogels consist of three-dimensional (3D) and complicated polymer networks that determine their physical properties. Among the methods for structural analyses of hydrogels, the real-space imaging of a polymer network of hydrogels on a nanometer scale is one of the optimal methods; however, it is highly challenging. In this study, we propose a direct observation method for cationic polymer networks using transmission electron microscopy (TEM). By combining the double network strategy and the mineral staining technique, we overcame the challenges of polymer aggregation and the low electron density of the polymer. An objective cationic network was incorporated into a neutral skeleton network to suppress shrinkage during subsequent staining. Titania mineralization along the cationic polymer strands provided sufficient electron density for the objective polymer network for TEM observation. This observation method enables the visualization of local structures in real space and plays a complementary role to scattering methods for soft matter structure analysis.

Increasing the Economic Value of Hydrogel as an Alternative Planting Media at Madrasah Aliyah Swasta Muhammadiyah Sidomulyo

Hydrogel technology can be used as a solution for indoor growing media. Hydrogel is a three-dimensional polymer network with cross-linked hydrophilic polymers, which are capable of swelling or storing water and physiological solutions up to thousands of times their dry weight, and are not easily soluble. To increase knowledge about ornamental plant cultivation using hydrogel media, a service was carried out by using partners at the Madrasah Aliyah Swasta Muhammadiyah Sidomulyo. This service aims to provide solutions to partners in the form of alternative hydrogel-based planting media made from alginate that are environmentally friendly which can be used as moisture and nutrient control agents. This goal is achieved through outreach activities, training, and the application of alternative planting media on ornamental plants. The target of the results to be achieved is to increase the economic value of hydrogels and to foster the entrepreneurial spirit of the students of Madrasah Aliyah Swasta Muhammadiyah Sidomulyo.

Resilient 3D porous self-healable triple network hydrogels reinforced with graphene oxide for high-performance flexible supercapacitors

The application of gel polymer electrolyte (GPE) in flexible supercapacitor (FSC) has attracted much attention due to its excellent mechanical properties and chemical stability. However, traditional polymer substrates have high crystallinity, resulting in sluggish ion migration and low ionic conductivity. This study reports the successful fabrication of a resilient highly porous triple hydrogel network (TNH) comprising the natural polymer of sodium alginate and biocompatible components of polyvinyl alcohol and graphene oxide (GO), exhibiting remarkably high ionic conductivity and astonishing mechanical strength, self-healing, and flame retardant properties. The physical and electrochemical features of the GPEs were optimized by tuning the GO wt% within the polymeric matrix. Adding a low wt% of GO (0.8 wt%) led to remarkable improvements in ionic conductivity (83.33 mS cm−1), mechanical strength (2.21 MPa), and self-healing and flame-retardant properties of the resulting PVA/SA/GO GPE than the pristine GPE. This was attributed to the formation of a microporous three-dimensional polymeric network based on reversible non-covalent bonds. The carbon cloth-based symmetric SC prepared based on this GPE exhibited a long cycle life, high specific capacitance of 633.3 mF cm−2 at 0.5 mA cm−2, and an energy density of 84 mWh cm−2 at a high power density of 500.2 mW cm−2 (at 1 mA cm−2)), which surpassed the values reported in previous studies. The electrochemical performance of the FSC prepared based on PVA/SA/GO GPE remained constant when subjected to bending deformation, indicating the harmonious physical, chemical, and electrochemical properties of the developed GPE and its suitability for flexible energy storage devices, and wearable electronics

Revolutionizing medicine: Molecularly imprinted polymers as precision tools in cancer diagnosis and antibiotic detection.

Molecularly imprinted polymers (MIPs) are pivotal in medicine, mimicking biological receptors with enhanced specificity and affinity. Comprising templates, functional monomers, and cross-linkers, MIPs form stable three-dimensional polymer networks. Synthetic templates like glycan and aptamers improve efficiency, guiding the molecular imprinting process. Cross-linking determines MIPs' morphology and mechanical stability, with printable hydrogels offering biocompatibility and customizable properties, mimicking native extracellular matrix (ECM) microenvironments. Their versatility finds applications in tissue engineering, soft robotics, regenerative medicine, and wastewater treatment. In cancer research, MIPs excel in both detection and therapy. MIP-based detection systems exhibit superior sensitivity and selectivity for cancer biomarkers. They target nucleic acids, proteins, and exosomes, providing stability, sensitivity, and adaptability. In therapy, MIPs offer solutions to challenges like multidrug resistance, excelling in drug delivery, photodynamic therapy, photothermal therapy, and biological activity regulation. In microbiology, MIPs serve as adsorbents in solid-phase extraction (SPE), efficiently separating and enriching antibiotics during sample preparation. They contribute to bacterial identification, selectively capturing specific strains or species. MIPs aid in detecting antibiotic residues using fluorescent nanostructures and developing sensors for sulfadiazine detection in food samples. In summary, MIPs play a pivotal role in advancing medical technologies with enhanced sensitivity, selectivity, and versatility. Applications range from biomarker detection to innovative cancer therapies, making MIPs indispensable for the accurate determination and monitoring of diverse biological and environmental samples.

Stereoscopic Polymer Network for Developing Mechanically Robust Flexible Perovskite Solar Cells with an Efficiency Approaching 25.

Flexible perovskite solar cells (pero-SCs) have the potential to overturn the application scenario of silicon photovoltaic technology. However, their mechanical instability severely impedes their practical applicability, and the corresponding intrinsic degradation mechanism remains unclear. In this study, the degradation behavior of flexible pero-SCs is systematically analyzed under mechanical stress and it is observed that the structural failure first occurs in the polycrystal perovskite film, then extend to interfaces. To suppress the structural failure, pentaerythritol triacrylate, a crosslinked molecule with three stereoscopic crosslink sites, is employed to establish a 3D polymer network in both the interface and bulk perovskite. This network reduced the Young's modulus of the perovskite and simultaneously enhanced the interfacial toughness. As a result, the formation of cracks and delamination, which occur under a high mechanical stress, is significantly suppressed in the flexible pero-SC, which consequently retained 92% of its initial power conversion efficiency (PCE) after 20000 bending cycles. Notably, the flexible device also shows a record PCE of 24.9% (certified 24.48%).

Thermodynamic and network characteristics of optimized lysine-modified kutki (Panicum sumatrense) millet starch hydrogels.

Three-dimensional polymeric network of hydrogels avoids its dissolution into the aqueous region. Hydrogels must have strong structural integrity to be used for drug/nutraceutical delivery. A three factor-three-level Box-Behnken design was used to understand the effects of starch concentration, NaCl, and pH on the textural and structural integrity of Lysine modified kutki millet starch hydrogels. Various kinetic models were fitted to the time-course measurement of shrinkage behavior of both conventionally (CDHG) and freeze-dried (FDHG) hydrogel. Increasing the swelling temperature (5-50°C) showed values of higher molecular weight of polymer chains between neighboring crosslinks (g/mol) for FDHG (9539.59-56,769.72) than CDHG (1096.28-11,420.48). Similarly, mesh size (ξ) was more for FDHG (38.63-109.53 Ȧ) than CDHG (10.97-42.74 Ȧ). However, other network parameters such as polymer volume fraction ( ) was lower for FDHG (0.229-0.146) than CDHG (0.3882-0.222). These values suggest low swelling power of CDHG compared to FDHG. Thermodynamically, FDHG took less energy to swell than CDHG. The study showed that FDHG has better properties than CDHG and could be employed in nutraceutical delivery. The online version contains supplementary material available at 10.1007/s13197-024-05953-x.

Hydrogel-Based Therapy for Age-Related Macular Degeneration: Current Innovations, Impediments, and Future Perspectives.

Age-related macular degeneration (AMD) is an ocular disease that leads to progressive photoreceptor death and visual impairment. Currently, the most common therapeutic strategy is to deliver anti-vascular endothelial growth factor (anti-VEGF) agents into the eyes of patients with wet AMD. However, this treatment method requires repeated injections, which potentially results in surgical complications and unwanted side effects for patients. An effective therapeutic approach for dry AMD also remains elusive. Therefore, there is a surge of enthusiasm for the developing the biodegradable drug delivery systems with sustained release capability and develop a promising therapeutic strategy. Notably, the strides made in hydrogels which possess intricate three-dimensional polymer networks have profoundly facilitated the treatments of AMD. Researchers have established diverse hydrogel-based delivery systems with marvelous biocompatibility and efficacy. Advantageously, these hydrogel-based transplantation therapies provide promising opportunities for vision restoration. Herein, we provide an overview of the properties and potential of hydrogels for ocular delivery. We introduce recent advances in the utilization of hydrogels for the delivery of anti-VEGF and in cell implantation. Further refinements of these findings would lay the basis for developing more rational and curative therapies for AMD.

Biopolymer Packaging Materials in the Pharmaceutical Industry

Biopolymer packaging materials are gaining prominence in the pharmaceutical industry due to environmental concerns. Derived from renewable sources, these biopolymers offer biodegradability, biocompatibility, and non-toxicity, making them ideal for various pharmaceutical applications. In drug delivery, biopolymers play a crucial role in controlled release formulations, especially for personalized medicines and biopharmaceutical products. Hydrogels, three-dimensional polymer networks, are key in mimicking living tissues and facilitating stimuli-responsive drug release with minimal toxic effects. The formulation strategies involve diffusion-controlled, degradation-controlled, or environmentally triggered release. Biodegradable systems, using polymers like poly(lactic acid) and poly(glycolic acid), contribute to sustainable drug delivery by undergoing controlled degradation. Osmotic delivery systems leverage osmotic pressure for controlled drug release, while stimuli-responsive designs respond to environmental changes. Biopolymer integration in pharmaceutical packaging aligns with eco-friendly practices, addressing challenges posed by traditional petroleum-based materials. This shift signifies a sustainable and innovative approach to pharmaceutical packaging in harmony with environmental preservation.

In Situ Single-Cell Bacterial Imaging Provides Mechanistic Insight into the Photodynamic Action of Photosensitizer-Loaded Hydrogels.

Hydrogels, three-dimensional hydrophilic polymeric networks with high water retaining capacity, have gained prominence in wound management and drug delivery due to their tunability, softness, permeability, and biocompatibility. Electron-beam polymerized poly(ethylene glycol) diacrylate (PEGDA) hydrogels are particularly useful for phototherapies such as antimicrobial photodynamic therapy (aPDT) due to their excellent optical properties. This work takes advantage of the transparency of PEGDA hydrogels to investigate bacterial responses to aPDT at the single-cell level, in real-time and in situ. The photosensitizer methylene blue (MB) was loaded in PEGDA hydrogels by using two methods: reversible loading and irreversible immobilization within the 3D polymer network. MB release kinetics and singlet oxygen generation were studied, revealing the distinct behaviors of both hydrogels. Real-time imaging of Escherichia coli was conducted during aPDT in both hydrogel types, using the Min protein system to report changes in bacterial physiology. Min oscillation patterns provided mechanistic insights into bacterial photoinactivation, revealing a dependence on the hydrogel preparation method. This difference was attributed to the mobility of MB within the hydrogel, affecting its direct interaction with bacterial membranes. These findings shed light on the complex interplay between hydrogel properties and the bacterial response during aPDT, offering valuable insights for the development of antibacterial wound dressing materials. The study demonstrates the capability of real-time, single-cell fluorescence microscopy to unravel dynamic bacterial behaviors in the intricate environment of hydrogel surfaces during aPDT.

The evolution of artificial tears based on hyaluronic acid

In recent years, there has been growing interest in the use of tear substitutes, based on natural polysaccharides in the treatment of dry eye syndrome, the leader of which is hyaluronic acid (HA). It has sufficient biocompatibility, non-immunogenicity, high viscoelasticity, hydrophilic, mucus-adhesive and good moisturizing properties. At the same time, in order to improve artificial tear preparations, there is a need to improve the mechanical and rheological properties of HA, its hygroscopicity, swelling in an aqueous environment and reducing the rate of biodegradation. One of the ways to solve this problem was the chemical modification of HA, by cross-linking its chains with two or more covalent bonds, with the participation of various polyfunctional molecules: urea, HA-cysteine ethyl ester, polyfunctional diepoxides, glutaraldehyde, carbodiimide, and many others. At the same time, the rigidity of the three-dimensional polymer network increases, increasing its resistance to enzymatic decomposition at the site of burial. Cross-linked HA has a higher viscosity compared to native hyaluronic acid due to the binding of its chains, which determines longer retention on the corneal epithelium and naturally makes it possible to reduce the frequency of drug instillations. Convincing data were obtained on the effectiveness of the resulting cross-linked hydrogel with non-Newtonian properties in vitro – on cultures of corneal epithelial cells and in vivo – on models of mechanical trauma and chemical burns of the cornea, as well as in animals with torpid corneal ulcers. The clinical effectiveness of cross-linked hyaluronic acid in the treatment of patients with dry eye syndrome of varying severity, including those due to Sjögren’s syndrome, has also been established. The higher effectiveness of cross-linked HA compared to native HA preparations has been convincingly proven. Taking into account the available information, an official drug has been developed based on cross-linked 0.2% hyaluronic acid Ocutears® Hydro+ (Santen).

Mechanical properties and microstructure of waterborne polyurethane-modified cement composites as concrete repair mortar

With the increase in service life, the durability of a large number of concrete structures deteriorates year by year under the influence of the external environment, requiring urgent repair and reinforcement. Ordinary cement concrete materials have disadvantages such as high brittleness, low tensile strength, poor bonding ability, and insufficient durability, making it difficult to meet the repair needs of high-quality building structures. Therefore, self-synthesized anion WPU was used to study its effect on the mechanical properties of cement-based repair mortar. The research found that waterborne polyurethane (WPU)-modified cementitious composite repair materials exhibit better bonding strength with old concrete substrates compared to traditional cement-based materials. Additionally, the incorporation of WPU significantly reduces the brittleness of the repair material, ensuring enhanced efficiency in the repair process. However, according to the hydration heat test results, the addition of WPU delays the hydration process of the composite repair materials. In addition, the addition of WPU enhances the flexibility and bonding ability of the materials, with flexural strength and tensile strength at the age of 28 days reaching 13 MPa and 6 MPa, respectively. Through stress‒strain curve analysis, it was found that the maximum strain amplification of WPU cement mortar can reach 134 %. Combined with SEM testing, it was observed that cured WPU films were present in specimens aged 28 days with P/C ratios of 10 % and 15 %. WPU and cement hydration products permeate each other, forming a three-dimensional polymer network structure, improving the pore structure, and fully exerting the flexibility of WPU. This also validates the experimental results of increased ultimate tensile strain. WPU cement-based composite repair materials have higher bonding strength at a high P/C ratio (15 %), and WPU alone, used as an interface agent for pretreating the interface of old concrete, can improve the interface bonding strength, up to twice that of the group without the surface agent.

Investigating Solid-State Luminescent Properties of New Cadmium(II) and Lead(II) Oxamato-Based Coordination Polymers

Two novel coordination polymers were synthesized through the reaction of the Hpcpa2− ligand (H3pcpa = N-(4-carboxyphenyl)oxamic acid) with cadmium(II) and lead(II) metal ions, yielding [Cd2(Hpcpa)2(H2O)6]n⋅H2O (1) and [Pb(Hpcpa)(H2O)]n (2). Structural analysis by single-crystal X-ray diffraction revealed that 1 consists of one-dimensional zigzag polymeric chains, while 2 is a three-dimensional polymer network. Additionally, investigations of their optical properties were carried out in a comparative study involving the previously reported pcpa-based coordination polymers {[Zn(Hpcpa)(H2O)3]·0.5H2O}n and {[Gd2(Hpcpa)3(H2O)5]·H2O}n], called here as 3 and 4, respectively. Under 330 nm excitation wavelength, all compounds exhibited broad emission bands spanning from 350 to 650 nm. Particularly, 1 and 3 displayed notable external quantum yields of 15.4 and 12.8%, respectively, highlighting their potential in luminescent applications.

Pharmaceutical Hydrogels: A Comprehensive Review

Three-dimensional hydrophilic polymeric networks called hydrogels can absorb vast volumes of fluids present in the body or water. Among synthesized biomaterials they most nearly resemble natural living tissues because of their high-water content porosity and soft consistency. To customize hydrogels for particular purposes cellulose functionalization offers improved physical and chemical properties as well as control over biological interactions. Here we provide a critical evaluation of hydrogels utilized in biomedicine. Hydrogels encourage cell regeneration while providing the necessary mechanical qualities for tissue engineering scaffolds advantageous in treating wounds and repairing cartilage. Hydrogels have become a highly customizable platform for a variety of biomedical applications offering effective and sustainable solutions for the life sciences. In this review article an attempt was made to discuss the processes for developing hydrogels prepared from hydrophilic polymers of synthetic and natural origin with a focus on naturally occurring biopolymers that are water-soluble hydrocolloids and their proposed applications were also reviewed.

In Situ Thermal Cross-Linking of 9,9'-Spirobifluorene-Based Hole-Transporting Layer for Perovskite Solar Cells.

A novel 9,9'-spirobifluorene derivative bearing thermally cross-linkable vinyl groups (V1382) was developed as a hole-transporting material for perovskite solar cells (PSCs). After thermal cross-linking, a smooth and solvent-resistant three-dimensional (3D) polymeric network is formed such that orthogonal solvents are no longer needed to process subsequent layers. Copolymerizing V1382 with 4,4'-thiobisbenzenethiol (dithiol) lowers the cross-linking temperature to 103 °C via the facile thiol-ene "click" reaction. The effectiveness of the cross-linked V1382/dithiol was demonstrated both as a hole-transporting material in p-i-n and as an interlayer between the perovskite and the hole-transporting layer in n-i-p PSC devices. Both devices exhibit better power conversion efficiencies and operational stability than devices using conventional PTAA or Spiro-OMeTAD hole-transporting materials.