Functionalized Polymer Nanoparticles Research Articles

Enhancement of insulation properties of LLDPE by PPy-functionalized PS-NPs

The strategy of functionalized PS-NPs via PPy (PPy@PS-NPs) forming heterogeneous interface composition is highly efficient in increasing the insulation properties of linear low-density polyethylene (LLDPE). The morphology results show that PPy@PS-NPs are monodispersed in the LLDPE matrix after melting blend, which exhibits unparalleled engineering application value. The electrical insulation results show that PPy@PS-NPs introduced into the LLDPE matrix can reduce its DC electrical conductivity, enhance DC breakdown strength, and inhibit space charge accumulation. When the PPy@PS-NPs concentration is 0.5 wt%, the DC breakdown strength is 35.3 % higher than that of LLDPE. Mechanism research indicates that the depths of carrier traps are decreased due to high electron affinity caused by the introduction of PPy@PS-NPs, but the trap density is increased. The reported strategy of using functionalized polymer nanoparticles to improve the polymer insulation property provides new insights for developing future high-insulation materials and other functional materials based on functionalized polymer nanofillers.

Targeting delivery of CRISPR systems into tumours to edit glutamine metabolism for cancer therapy by DPA-Zn-modified nanoparticles

Functional polymer nanoparticles deliver CRISPR-Cas9 into tumours to efficiently and simultaneously cut off two different genes to manipulate glutamine metabolism for fighting cancers.

Preparation of functionalized polymer nanomaterials and application in renal injury

Renal injury, which is a prevalent condition, significantly impacts the health of competitive wrestlers. However, there is a limited number of therapeutic methods and drugs available for its treatment. To tackle this issue, a renal targeted drug based on functionalized polymer nanoparticles (FPNPs) is being studied. The primary methods in the preparation of FPNPs involve utilizing the thin film hydration technique to create nanoparticles and encapsulating the drug TP within them as a treatment for renal injury, thus forming TP-FPNPs. Subsequently, the renal targeting of TP-FPNPs is analyzed using in vitro organ fluorescence imaging techniques. Furthermore, a renal IRI model is constructed to assess the pharmacokinetics of TP-FPNPs using the application method. The preparation results of TP-FPNPs reveal a hydrated particle size of approximately 90 nm, which remains in the renal region for over 48 hours. Additionally, the concentration content surpasses that of other organs by more than threefold after 12 hours. Moreover, in the application results, TP-FPNPs continue to possess a concentration of 302.5 ng/g even after 48 hours post-injection. Based on the aforementioned results, it can be concluded that TP-FPNPs exhibit specific targeting, biocompatibility, and an extended retention time. Thus, this study is expected to effectively achieve the effect of treating renal injury in martial arts athletes, establishing an experimental foundation for its clinical treatment.

Synergistic cytotoxicity of irinotecan combined with polysaccharide-based nanoparticles for colorectal carcinoma

Functional polymeric nanoparticles (NPs) with antitumor potential were combined with the topoisomerase I inhibitor, irinotecan (IRT), to enhance cytotoxicity against colorectal cancers. The negatively charged γ-polyglutamic acid (γ-PGA) or fucoidan (FCD) was complexed with the positively charged chitosan (CS) to encapsulate IRT. The size of the γ-PGA/CS/IRT NPs and FCD/CS/IRT NPs were 146.0 ± 8.0 nm and 230.8 ± 2.5 nm, respectively, with polydispersity index ≤0.3. The cellular uptake ability of FCD/CS-FITC NPs was better than that of γ-PGA/CS-FITC NPs, especially in p-selectin positive HCT116 colorectal cancer cells (4.8 ± 0.8 μg/mL vs 11.4 ± 2.2 μg/mL). The IC50 of FCD/CS/IRT NPs was 2.4 times lower than that of γ-PGA/CS/IRT NPs in HCT116 cells (4.8 ± 0.8 μg/mL vs 11.4 ± 2.2 μg/mL), indicating its superior antitumor potential. The combination of irinotecan and fucoidan-based NPs exhibited a synergistic effect (CI <1), resulting in better anticancer activity of FCD/CS/IRT NPs than irinotecan alone. The apoptosis-related proteins, caspase 3, caspase 9, and poly(ADP-ribose) polymerase (PARP), were prominently increased in FCD/CS/IRT NPs-treated HCT116 cells by 2.3 folds, 3.5 folds, and 6.3 folds, respectively. All results support that fucoidan-based irinotecan-loaded nanoparticles possess the ability to effectively enhance cellular uptake and induce synergistic apoptosis of colorectal cancer cells.

Patterning of Polymer-Functionalized Nanoparticles with Varied Surface Mobilities of Polymers.

The polymers can be either dynamically tethered to or permanently grafted to the nanoparticle to produce polymer-functionalized nanoparticles. The surface mobility of polymer ligands with one end anchored to the nanoparticle can affect the surface pattern, but the effect remains unclear. Here, we addressed the influence of lateral polymer mobility on surface patterns by performing self-consistent field theory calculations on a modeled polymer-functionalized nanoparticle consisting of immobile and mobile brushes. The results show that except for the radius of nanoparticles and grafting density, the fraction of mobile brushes substantially influences the surface patterning of polymer-functionalized nanoparticles, including striped patterns and patchy patterns with various patches. The number of patches on a nanoparticle increases as the fraction of mobile brushes decreases, favored by the entropy of immobile brushes. Critically, we found that broken symmetry usually occurs in patchy nanoparticles, associated with the balance of enthalpic and entropic effects. The present work provides a fundamental understanding of the dependence of surface patterning on lateral polymer mobility. The work could also guide the preparation of diversified nanopatterns, especially for the asymmetric patchy nanoparticles, enabling the fundamental investigation of the interaction between polymer-functionalized nanoparticles.

Adipocytolytic Polymer Nanoparticles for Localized Fat Reduction.

The demand for body fat reduction is increasing. However, conventional lipolytic approaches fail to control adipose tissue reduction and cause severe side effects in adjacent nonadipose tissues. A strategy to specifically reduce subcutaneous fat using adipocytolytic polymer nanoparticles in a minimally invasive manner is reported here. The polymer nanoparticles are designed to generate carbon dioxide gas when selectively absorbed by adipocytes. The carbon dioxide gas generated within late endosomes/lysosomes induces adipocytolysis, thereby reducing the number of cells. Localized injection of the adipocytolytic nanoparticles substantially reduces subcutaneous fat in a high-fat diet-induced obese mouse model, without significant changes in hematological or serum biochemical parameters. The adipocytolytic efficacy of the nanoparticles is also evaluated in a porcine model. This strategy addresses the need to develop safe and effective adipocytolytic agents using functional polymer nanoparticles.

Polymer-functionalized nanoparticles as agents for the in situ remediation of oil-contaminated soils

In-situ flushing of chemicals, such as nanoparticle (NP) suspensions, and NP-based Pickering emulsions, is a well-promising method for the remediation of soils and aquifers contaminated with non-aqueous phase liquids (NAPLs) and the enhanced oil recovery from reservoir rocks. Linear and comb-type copolymers were synthesized by combining (i) hydrophilic, anionic monomers like 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) and acrylic acid (AA) with (ii) hydrophobic monomers like dodecyl methacrylate (DMA). Moreover, polymer-coated nanoparticles (PNPs) was prepared by post-grafting and surface initiated free radical polymerization (FRP) on commercial silica nanoparticles. Dilute dispersions of polymers and PNPs were mixed with salts (NaCl, CaCl2), their dynamic surface and oil/water interfacial tensions were measured by the pendant drop method, and the wettability of all fluid systems to glass surface was quantified by measuring the contact angle. Oil-in-water Pickering emulsions were prepared by dispersing n-dodecane in polymers and n-decane in PNP-colloid with ultrasound probe, and their stability was evaluated by tracking the phase separation and changes of rheological properties, as functions of time. Furthermore, the most stable polymers and PNP-based dispersions and emulsions were chosen and tested as chemicals for the removal of residual oil from a transparent glass-etched pore network.

Metal-free and ecofriendly photoluminescent nanoparticles for visualization of latent fingerprints, anticounterfeiting, and information encryption

Visualization of latent fingerprints (LFPs) on different substrates is a significant challenge for security forces in crime scene, which the highly fluorescent materials with maximum brightness and contrast for rapid detection by simple instruments are essential for this propose. In this study, the multi-color photoluminescent functional polymer nanoparticles based on oxazolidine (as fluorescent dye with concentration of 1 wt%) and a copolymer of methyl methacrylate (MMA)/2-(dimethylamino)ethyl methacrylate (DMAEMA) as matrix were synthesized by emulsion copolymerization and physical post-polymerization modification methods. After investigation of physicochemical and optical properties, the multi-color photoluminescent polymer powders were used for printing of security tags and visualization of LFPs by means of powder dusting strategy. The printed encoded security tags as quick responsive (QR) codes are highly fluorescent with maximum brightness and resolution in different colors. The photoluminescent polymer powders were used for fast and facile visualization of LFPs by powder dusting and fluorescence imaging using of smart phone camera under UV irradiation (365 nm). Results of fluorescence imaging indicated that the unique and personal details of fingerprints patterns are detectable by naked eye. Therefore, developed highly photoluminescent polymer powders for powder dusting and fluorescence imaging can provide reliable evidence to recognition of individual identity in a short time and by the least facilities.

Preparation of AIE Functional Single-Chain Polymer Nanoparticles and Their Application in H2 O2 Detection through Intermolecular Heavy-Atom Effect.

Single-chain polymer nanoparticles (SCNPs) are soft matter constructed by intrachain crosslinks, with promising prospects in detection and catalysis. Herein, a fluorescent core (SCNPs) with aggregation-induced emission (AIE) is prepared, applying for H2 O2 detection through intermolecular heavy-atom effect. In detail, the SCNPs precursors are synthesized by ring-opening copolymerization. Then the SCNPs are prepared by intramolecularly cross-linking via olefin metathesis. Imitating the structure of AIE dots, SCNPs are encapsulated by H2 O2 -responsive polymers. Probably due to the stable secondary structure of SCNPs, the obtained micelles show stable fluorescence performance. Furthermore, as the heavy-atom, tellurium is introduced into the carriers to construct the heavy-atom effect. In this micelle-based system, the SCNPs act as the fluorescent core, and the stimuli-responsive polymer acts as the carrier and the fluorescent switch. The hydrophilicity of the tellurium-containing segment is affected by the concentration of H2 O2 , resulting in a change in the distance from the SCNPs, which ultimately leads to a change in the fluorescence intensity. Furthermore, tellurium is particularly sensitive to H2 O2 , which can detect low concentrations of H2 O2 . The SCNPs are merged with AIE materials, with the hope of exploring new probe designs.

Visualized uranium rapid monitoring system based on self-enhanced electrochemiluminescence-imaging of amidoxime functionalized polymer nanoparticles

The development of uranyl ion detection technology has exhibited its significance in public security and environmental fields for the radioactivity and chemical toxicity of uranyl ion. The WHO standard of uranyl ion makes it necessary to develop highly sensitive uranyl rapid warning system in drinking water monitoring. Herein, a visualized rapid warning system for trace uranyl ion is carried out based on electrochemiluminescence (ECL) imaging technology to give an ultra-low limit of detection (LOD) and high selectivity. Amidoxime, a bi-functional group with both uranyl ion capturing and co-reactive functions, is modified on a conjugated polymer backbone with strong ECL signal to be prepared into three-in-one polymer nanoparticles (PNPs) with self-enhanced ECL property. The captured uranyl ion can enhance the ECL signal of PNPs via resonance energy transfer process to give the LOD as 0.5 ng/L, which is much lower than the known luminescent uranyl sensors. Furthermore, ECL imaging technology is introduced into realizing visualized uranyl rapid warning, and can be successfully applied on natural water samples. This study provides a novel strategy for uranyl rapid warning, and shows its potential meaning in public security and environmental fields.

A ROS-responsive fluorescent probe detecting experimental colitis by functional polymeric nanoparticles

Current evidence shows that oxidative stress plays an essential role in the pathogenesis and progression of inflammatory bowel disease (IBD). TotalROX (λabs/λem = 425/525 nm) is a ratiometric probe with high detection sensitivity and a superior capacity to monitor total cellular oxidative capacity. Herein, we investigated the potential of combining totalROX with an oral nanoparticle delivery system to detect the degree of colitis. This detection system also featured pH-responsive Eudragit S100, hyaluronic acid with high affinity to the CD44 receptor, and chitosan, and demonstrated improved loading efficiency and stability. An experimental mouse model of experimental colitis was induced by dextran sodium sulfate do that we could investigate the ability of our nanoparticles to target the colon and determine the degree of inflammation. We also determined and validated the positive correlation between the fluorescence intensity of the detection product (Ox670, λabs/λem = 650/675 nm) and myeloperoxidase activity (R2 = 0.97) and the histopathological score (R2 = 0.98). TotalROX had significant ability to measure reactive oxygen species (ROS) produced by cells under inflammatory conditions, as confirmed by in vitro experiments with Caco-2 cells. Collectively, the data generated demonstrate that when loaded with totalROX, these functional nanoparticles are promising tools for cellular imaging after oral administration. This is the first description of a ROS-responsive fluorescent probe to evaluate the degree of colitis in experimental animal models and provides a promising approach for the diagnosis of inflammation in IBD with fluorescence-guided colonoscopy.

Polymer nanolatexes for dyeing of soybean fabric

AbstractIn this study, functionalized polymer nanolatexes based on P(MMA‐co‐BA‐co‐MAA) are synthesized by semicontinuous emulsion polymerization. An evaluation of the effect of reaction parameters such as monomer composition and initiators type on the latex properties is performed. Consideration of these effects allows the synthesis of low surfactant concentration‐high functionalized polymer nanoparticles as small as 29 nm. Then, a functionalized nanolatex is used as a binder in dyeing process of soybean protein fabric (SBF) using the cationic dye, Basic Red 46. Colorimetric tests show that the previous functionalization of soybean fibers with the nanolatex improves the efficiency of dyeing process by up to 13%. In addition, washing and rubbing fastness tests revealed that dyed functionalized fabrics had better performance than the one without nanolatex.

How the Reactive End Group of Macro-RAFT Agent Affects RAFT-Mediated Emulsion Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly via reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization is an emerging method in which macro-RAFT agents are chain extended with hydrophobic monomers in water to form block copolymer nano-objects. However, almost all RAFT-mediated emulsion polymerizations are limited to AB diblock copolymers by using monofunctional macro-RAFT agents with non-reactive end groups. In this study, the first investigation on how the reactive end group of macro-RAFT agent affects RAFT-mediated emulsion polymerization is reported. Three macro-RAFT agents with different end groups are synthesized and employed in RAFT-mediated emulsion polymerization. Effects of end groups on morphologies of block copolymer nano-objects and polymerization process are studied. Block copolymer nano-objects prepared by using an asymmetric difunctional macro-RAFT agent can be functionalized by further chain extension on the surface. It is expected that the current study will not only expand the scope of RAFT-mediated emulsion polymerization, but also provide a novel strategy to prepare functional polymer nanoparticles.

Functional Nanocarriers for Delivering Itraconazole Against Fungal Intracellular Infections.

Infectious diseases caused by intracellular microorganisms represent a significant challenge in medical care due to interactions among drugs during coinfections and the development of resistance in microorganisms, limiting existing therapies. This work reports on itraconazole (ITZ) encapsulated into functional polymeric nanoparticles for their targeted and controlled release into macrophages to fight intracellular infections. NPs are based on poly (lactic acid-co-glycolic acid) (PLGA) polymers of different compositions, molecular weights, and lactic acid–to–glycolic acid ratios. They were self-assembled using the high-energy nanoemulsion method and characterized by transmission electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and differential scanning calorimetry. It was studied how the polymer-to-drug ratio, changes in the aqueous phase pH, and type and concentration of surfactant affected nanocarriers’ formation, drug-loading capacity, and encapsulation efficiency. Results showed that drug-loading capacity and encapsulation efficiency reached 6.7 and 80%, respectively, by lowering the pH to 5.0 and using a mixture of surfactants. Optimized formulation showed an initial immediate ITZ release, followed by a prolonged release phase that fitted better with a Fickian diffusion kinetic model and high stability at 4 and 37°C. NPs functionalized by using the adsorption and carbodiimide methods had different efficiencies, the carbodiimide approach being more efficient, stable, and reproducible. Furthermore, linking F4/80 and mannose to the NPs was demonstrated to increase J774A.1 macrophages’ uptake. Overall, in vitro assays showed the nanosystem’s efficacy to eliminate the Histoplasma capsulatum fungus and pave the way to design highly efficient nanocarriers for drug delivery against intracellular infections.

Surface-Initiated Ring-Opening Metathesis Polymerization: A Method for Synthesizing Polymer-Functionalized Nanoparticles Exhibiting Semicrystalline Properties and Diverse Macromolecular Architectures

Polymer-grafted nanoparticles are effective for designing hybrid materials with optimal component dispersion and enhanced material properties. The olefin chemistry accessible through ring-opening m...

100th Anniversary of Macromolecular Science Viewpoint: Biological Stimuli-Sensitive Polymer Prodrugs and Nanoparticles for Tumor-Specific Drug Delivery.

The development of smart polymer vehicles to carry and release cytotoxic drugs to tumor tissues and cells while reducing the exposure of drugs in the blood and healthy organs is a highly challenging task with continuously growing interest from multiple fields, including polymer science, pharmaceutical science, nanotechnology, and clinical oncology. Inspired by the unique tumor microenvironment, such as mild acidity and overexpressed enzymes, functional polymer prodrugs and nanoparticles with reversible charge, detachable PEG shell, activatable ligand, and switchable size have been designed to enhance tumor deposition, tumor penetration, tumor cell uptake, and tumoral drug release. Utilizing biological signals inside tumor cells, such as acidic endo/lysosomal pH, elevated glutathione levels, and reactive oxygen species, responsive polymer prodrugs and nanoparticles with good extracellular stability but fast intracellular disintegration have been engineered for specific intracellular drug release. These biological stimuli-sensitive polymer prodrugs and nanoparticles have shown superior specificity and therapeutic efficacy to nonsensitive counterparts and, in certain cases, even clinically approved systems in varying tumor models. In this Viewpoint, design strategies and recent advances of biological stimuli-responsive polymer prodrugs and nanoparticles for tumor-specific drug delivery will be highlighted, and their challenges and future perspectives will be discussed.

Low-Temperature Miniemulsion-Based Routes for Synthesis of Metal Oxides.

The use of miniemulsions containing chemical precursors in the disperse phase is a versatile method to produce nanoparticles and nanostructures of different chemical nature, including not only polymers, but also a variety of inorganic materials. This Minireview focuses on materials in which nanostructures of metal oxides are synthesized in processes that involve the miniemulsion technique in any of the steps. This includes in the first place those approaches in which the spaces provided by nanodroplets are directly used to confine precipitation reactions that lead eventually to oxides. On the other hand, miniemulsions can also be used to form functionalized polymer nanoparticles that can serve either as supports or as controlling agents for the synthesis of metal oxides. Herein, the description of essential aspects of the methods is combined with the most representative examples reported in the last years for each strategy.

Encryption and authentication of security patterns by ecofriendly multi-color photoluminescent inks containing oxazolidine-functionalized nanoparticles

Counterfeiting of confidential documents has been a costly challenge for banks, companies, and customers. Encryption of invisible security marks, such as barcodes, quick response codes, and logos, in national or international confidential documents by high-security anticounterfeiting inks is the most significant solution for counterfeiting problems. Ecofriendly multi-color photoluminescent anticounterfeiting inks based on highly-fluorescent polymer nanoparticles functionalized with new oxazolidine derivatives were developed for the fast and facile encryption of security labels on cellulosic documents, such as paper currency, passport, and certificate. Depending on the polarity of functionalized polymer nanoparticles, a wide range of colors and fluorescence emissions were observed as a result of polar-polar interactions between the oxazolidine molecules and surface functional groups of the nanoparticles. The fluorescent polymer nanoparticles showed spherical, vesicular, and cauliflower-like morphologies resulted from different surface functional groups. Functional polymer nanoparticles displayed high stability and printability on cellulosic substrates due to hydrogen bonding interactions. The highly-fluorescent polymer nanoparticles were also used to prepare anticounterfeiting inks with different colors and fluorescence emissions. All the ecofriendly polymeric anticounterfeiting inks were loaded to stamps with specific marks, and then applied to different confidential documents. Printed labels displayed highly intense fluorescence emission in different colors (green, orange, pink, and purple depending on the matrix polarity) under UV irradiation (365 nm). These water-based multi-color fluorescent anticounterfeiting inks with highly intense, bright, and sensitive fluorescence emission have potential applications in encryption and authentication of security patterns.

Production of New Functionalized Polymer Nanoparticles and Use for Manufacture of Novel Nanobiocatalysts

AbstractNew nanoparticles are synthesized through emulsion polymerization, using distinct comonomers (styrene, divinylbenzene, glycidyl methacrylate and pentafluorostyrene). Then, for the first time, two strategies are adopted to functionalize such nanoparticles using benzylamine and thiophenol: (i) after the manufacture of the nanoparticles; and (ii) in situ during the polymerization reaction. Afterwards, the functionalized nanoparticles are used as nanosupports for immobilization of lipase B from Candida antarctica and the performance of the novel nanobiocatalysts are evaluated. It is shown that the nanoparticles exhibit different properties (specific areas ranging from 34 m2 g−1 to 324 m2 g−1; and contact angles ranging from 29° to 126°), indicating that both procedures can be used to adjust the properties of the polymer supports. Moreover, the nanobiocatalysts are applied successfully in hydrolysis and esterification reactions, exhibiting higher activities than the non‐functionalized biocatalysts. It is also observed that more hydrophilic supports result in more active biocatalysts in hydrolysis (27 ± 1 U g−1) and intermediate hydrophobic matrices conduct to more active biocatalysts in esterification reactions (1564 ± 50 U g−1). It is shown that highly hydrophobic surfaces may cause a significant decrease in the activity of such biocatalysts, probably due to distortions on the enzyme active center and to more intense chemical partitioning effects.

Self-stabilized precipitation polymerization: principle, method and application

A novel heterogeneous polymerization technique, termed as self-stabilized precipitation (2SP) polymerization, was developed beyond emulsion/dispersion/suspension. Through quiescent polymerization, self-nucleation and surface deposition process, a stable colloid composed of uniform polymer particles and reaction medium was formed without the use of any stabilizers. More importantly, the polymer particles can be easily separated from the solvent and the supernatant liquid can be recycled, making this strategy a truly “green” polymerization process. This technique leads to several revolutionary advances: (1) one of the most simple, efficient and green strategies to produce uniform, size-tunable and functional polymer nanoparticles; (2) the polymerization reactivity of α-olefin is highly enhanced through copolymerization with maleic anhydride; (3) generation of functional copolymer particles directly from single olefinic monomer or complex olefinic mixtures (including C4/C5/C9 fractions) without any further purification, which provides a new way to transform huge amount of olefinic compounds in C4/C5/C9 fractions into valuable functional polymers.