Synthesis and Characterization of Chelating Hyperbranched Polyester Nanoparticles for Cd(II) Ion Removal from Water.

Chelating hyperbranched polyester (CHPE) nanoparticles have become an attractive new material family for developing high-capacity nanoscale chelating agents with highly branched structures and many functional groups in the main chains and end groups that can be used to remove heavy metals from water. In this study, a hyperbranched polyester with a particle size of 180-643 nm was synthesized with A2+B3 interfacial polymerization, using dimethylmalonyl chloride as the difunctional monomer (A2) and 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) as the trifunctional monomer (B3). FTIR and NMR were used to characterize the CHPE and confirm the structure. The CHPE nanoparticles were generally considered hydrophilic, with an observed swelling capacity of 160.70%. The thermal properties of the CHPE nanoparticles were studied by thermal gravimetric analysis (TGA) with 1% mass loss at temperatures above 185 °C. The XRD of the CHPE nanoparticles showed a semi-crystalline pattern, as evident from the presence of peaks at positions ~18° and 20°. The nature of the surface of the CHPE was examined using SEM. Batch equilibrium was used to investigate the removal properties of the CHPE nanoparticles towards Cd(II) ions as a function of temperature, contact time, and Cd(II) concentration. The Cd(II) ion thermodynamics, kinetics, and desorption data on the CHPE nanoparticles were also studied.

Magnetic solid-phase extraction of benzoylurea insecticides in tea samples with Fe3 O4 -hyperbranched polyester magnetic composite as sorbent.

In this work, a method for the analysis of benzoylurea insecticides, including hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron, in tea samples by high-performance liquid chromatography with Fe3 O4 -hyperbranched polyester nanocomposite as the adsorbent for magnetic solid-phase extraction was developed. The magnetic nanocomposite was prepared and characterized by infrared spectroscopy, vibrating sample magnetometry, and scanning electron microscopy. The as-prepared nanocomposite was used as a sorbent for the extraction and preconcentration of pesticide residues in tea samples. The extraction and desorption conditions, including mass ratios of raw materials, amount of sorbent, pH value, extraction time, and desorption time, were investigated. Under the final conditions chosen for the analysis, good linearity was obtained for all the tested compounds, with R2 values of at least 0.9979. The limits of detection were determined in the range of 0.15-0.3 µg/L. The recovery obtained from the analysis of tea samples with various spiked concentrations was between 90.7 and 98.4%, with relative standard deviations (n = 4) lower than 4.1%. Furthermore, the present approach was successfully applied to the quantitative determination of residues of benzoylurea insecticides in real samples.

Stable nanoscale sea-island structure of biobased polyamide 56/poly (butylene adipate-co-terephthalate) blends compatibilized by interfacial hyperbranched structure: Toward biobased polymer blends with ultrahigh toughness.

Developing biobased materials is a considerably effective approach to save fossil resources and reduce emissions. Biobased polyamide 56 (PA56) is an excellent engineering material, but it has low toughness. Herein, to enhance the toughness of PA56, an ultra-tough biodegradable material, i.e., poly (butylene adipate-co-terephthalate) (PBAT) was introduced into PA56. Moreover, a self-synthesized epoxy-terminated hyperbranched polyester (EHBP) was used to improve the compatibility of the blended materials. The results of differential scanning calorimetry and Fourier-transform infrared spectroscopy indicated that the epoxide group of EHBP could react with PA56 and PBAT to form a block-like polymer structure and limit the crystallization behavior of the blends. The scanning electron microscopy results show that the addition of EHBP considerably reduced the dispersed-phase size in the blends, forming a nanoscale island structure. Moreover, the hydrogen bonds formed between EHBP and PA56/PBAT enhanced the intermolecular interaction between the two materials. Thus, PA56 blends with ultrahigh toughness were successfully prepared. The prepared PA56/PBAT/EHBP blend exhibited a notch impact strength of 20.71 kJ/m2 and a breaking elongation of 38.3 %, which represent increases of 427.3 % and 252.8 %, respectively, compared with those of pure PA56. Thus, the proposed method is suitable for toughening PA56 and broadening its applications.

Influence of carboxy-terminated hyperbranched polyester and polyethylene glycol on the mechanical and thermal properties of polylactic acid/straw flour composites.

Polylactic acid (PLA) wood-plastic composites have a significant advantage over traditional petroleum-based plastics due to their biodegradability. However, PLA has several shortcomings, including high brittleness, low heat resistance, slow crystallization, and poor compatibility with biomass materials, which have limited its potential applications. In this paper, we investigated the effects of carboxy-terminated hyperbranched polyester (CHBP) on the mechanical, crystalline, and thermal properties of PLA/straw flour (SF) blends through extrusion injection molding. Additionally, we added the traditional plasticizer polyethylene glycol (PEG) to synergize with CHBP to enhance the toughness of PLA/SF composites. Our results showed that the appropriate addition of CHBP effectively improved the interfacial bonding between PLA and straw flour. The incorporation of CHBP also improved the tensile strength, bending strength, impact strength, elongation at break, thermal stability, and crystallization rate of the composites. Furthermore, the addition of both CHBP and PEG significantly improved the impact strength of the composites compared to using PEG alone. This method also improved the heat resistance of the material and reduced the migration of plasticizers. Our study demonstrates the feasibility of using hyperbranched polymers and plasticizers to enhance the toughness, thermal stability, and crystalline properties of PLA wood-plastic composites, providing a new approach to improving the properties of these composites.

Polyvinylidene Fluoride/Aromatic Hyperbranched Polyester of Third-Generation-Based Electrospun Nanofiber as a Self-Powered Triboelectric Nanogenerator for Wearable Energy Harvesting and Health Monitoring Applications.

Flexible pressure sensors have played an increasingly important role in the Internet of Things and human-machine interaction systems. For a sensor device to be commercially viable, it is essential to fabricate a sensor with higher sensitivity and lower power consumption. Polyvinylidene fluoride (PVDF)-based triboelectric nanogenerators (TENGs) prepared by electrospinning are widely used in self-powered electronics owing to their exceptional voltage generation performance and flexible nature. In the present study, aromatic hyperbranched polyester of the third generation (Ar.HBP-3) was added into PVDF as a filler (0, 10, 20, 30 and 40 wt.% w.r.t. PVDF content) to prepare nanofibers by electrospinning. The triboelectric performances (open-circuit voltage and short-circuit current) of PVDF-Ar.HBP-3/polyurethane (PU)-based TENG shows better performance than a PVDF/PU pair. Among the various wt.% of Ar.HBP-3, a 10 wt.% sample shows maximum output performances of 107 V which is almost 10 times that of neat PVDF (12 V); whereas, the current slightly increases from 0.5 µA to 1.3 µA. The self-powered TENG is also effective in measuring human motion. Overall, we have reported a simpler technique for producing high-performance TENG using morphological alteration of PVDF, which has the potential for use as mechanical energy harvesters and as effective power sources for wearable and portable electronic devices.

Synthesis of DOPO-Based Phosphorus-Nitrogen Containing Hyperbranched Flame Retardant and Its Effective Application for Poly(ethylene terephthalate) via Synergistic Effect.

To obtain industrialized poly(ethylene terephthalate) (PET) composites with highly efficient flame retardancy, a phosphorus-nitrogen (P-N) containing hyperbranched flame retardant additive was synthesized by 9,10-dihydro-9-oxa-10-phospho-phenanthrene-butyric acid (DDP) and tris(2-hydroxyethyl) isocyanurate (THEIC) through high temperature esterification known as hyperbranched DDP-THEIC (hbDT). The chemical structure of the synthesized hbDT was determined by FTIR, 1H NMR, 13C NMR, and GPC, etc. Subsequently, hbDT/PET composites were prepared by co-blending, and the effects of hbDT on the thermal stability, flame retardancy, combustion performance, and thermal degradation behavior of PET were explored to deeply analyze its flame retardant mechanism. The test results showed that hbDT was successfully synthesized, and that hbDT maintained thermal stability well with the required processing conditions of PET as retardant additives. The flame retardant efficiency of PET was clearly improved by the addition of hbDT via the synergistic flame-retardant effect of P and N elements. When the mass fraction of flame retardant was 5%, the LOI of the hbDT/PET composite increased to 30.2%, and the vertical combustion grade reached UL-94 V-0. Compared with pure PET, great decreased total heat release (decreased by 16.3%) and peak heat release rate (decreased by 54.9%) were exhibited. Finally, the flame retardant mechanism of hbDT/PET was supposed, and it was confirmed that retardant effect happened in both the gas phase and condensed phase. This study is expected to provide a new idea for the development of low toxic, environment-friendly and highly efficient flame retardant additive for polyesters in an industry scale.

The Hyperbranched Polyester Reinforced Unsaturated Polyester Resin.

We report a method of reinforcing and toughening unsaturated polyester resin (UPR) with a kind of hyperbranched polyester (HBP-1). Polyethylene glycol with different molecular weight was used as the core molecule of the preparation reaction, and the reaction product of phthalic anhydride and glycerol was used as the branching unit. The esterification reaction of polycondensation occurred, and then the hydroxyl-terminated hyperbranched polyester was prepared. The reaction product of maleic anhydride and isooctanol was added to the prepared hydroxyl-terminated hyperbranched polyester for esterification reaction. Both ends of the hyperbranched polyester had unsaturated double bond to obtain the hyperbranched polyester (HBP-1). The effects of this treatment on the morphology, mechanical properties and thermal properties of the composites were studied in detail. The HBP-1 was investigated by Fourier Transform Infrared Spectroscopy (FT-IR). The HBP-1/UPR composites were investigated by Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA), mechanical properties analysis and Scanning Electron Microscope (SEM). The results showed that HBP-1 enhanced the thermostability and mechanical properties of UPR. However, DMA indicated that the addition of HBP-1 cannot effectively improve the thermodynamic properties of UPR due to the flexible chain in HBP-1 structure. The HBP-1 improves tensile strength, bending strength and impact strength compared to neat UPR.

Hyperbranched Polyester Polyfumaratomaleate Doped with Gd(III) and Dy(III) Ions: Synthesis, Structure and Properties.

For the first time, metal-polymer complexes have been synthesized using hyperbranched polyester polyfumaratomaleate as a matrix, the structure of which has been established by 1H NMR, IR, electron spectroscopy, and elemental analysis methods. The formation of complexes with Gd(III) and Dy(III) ions involving fumarate and maleate groups of the polyester was proved by IR and electron spectroscopy methods. It was established that the structure of the coordination units has the form of a square antiprism. The compositions and conditional logarithms of the stability constants of the complexes were determined. It was established that complexation with lanthanide ions promotes emission enhancement in the ligand.

Antibiotic-Loaded Hyperbranched Polyester Embedded into Peptide-Enriched Silk Fibroin for the Treatment of Orthopedic or Dental Infections.

The development of innovative osteoconductive matrices, which are enriched with antibiotic delivery nanosystems, has the invaluable potential to achieve both local contaminant eradication and the osseointegration of implanted devices. With the aim of producing safe, bioactive materials that have osteoconductive and antibacterial properties, novel, antibiotic-loaded, functionalized nanoparticles (AFN)-based on carboxylic acid functionalized hyperbranched aliphatic polyester (CHAP) that can be integrated into peptide-enriched silk fibroin (PSF) matrices with osteoconductive properties-were successfully synthesized. The obtained AFNPSF sponges were first physico-chemically characterized and then tested in vitro against eukaryotic cells and bacteria involved in orthopedic or oral infections. The biocompatibility and microbiological tests confirmed the promising characteristics of the AFN-PSF products for both orthopedic and dental applications. These preliminary results encourage the establishment of AFN-PSF-based preventative strategies in the fight against implant-related infections.

Effect of Terminal Groups on Thermomechanical and Dielectric Properties of Silica-Epoxy Composite Modified by Hyperbranched Polyester.

To study the effect of hyperbranched polyester with different kinds of terminal groups on the thermomechanical and dielectric properties of silica-epoxy resin composite, a molecular dynamics simulation method was utilized. Pure epoxy resin and four groups of silica-epoxy resin composites were established, where the silica surface was hydrogenated, grafted with silane coupling agents, and grafted with hyperbranched polyester with terminal carboxyl and terminal hydroxyl, respectively. Then the thermal conductivity, glass transition temperature, elastic modulus, dielectric constant, free volume fraction, mean square displacement, hydrogen bonds, and binding energy of the five models were calculated. The results showed that the hyperbranched polyester significantly improved the thermomechanical and dielectric properties of the silica-epoxy composites compared with other surface treatments, and the terminal groups had an obvious effect on the enhancement effect. Among them, epoxy composite modified by the hyperbranched polyester with terminal carboxy exhibited the best thermomechanical properties and lowest dielectric constant. Our analysis of the microstructure found that the two systems grafted with hyperbranched polyester had a smaller free volume fraction (FFV) and mean square displacement (MSD), and the larger number of hydrogen bonds and greater binding energy, indicating that weaker strength of molecular segments motion and stronger interfacial bonding between silica and epoxy resin matrix were the reasons for the enhancement of the thermomechanical and dielectric properties.

Structure and Properties of PSf Hollow Fiber Membranes with Different Molecular Weight Hyperbranched Polyester Using Pentaerythritol as Core.

A homologous series of hyperbranched polyesters (HBPEs) was successfully synthesized via an esterification reaction of 2,2-bis(methylol)propionic acid (bis-MPA) with pentaerythritol. The molecular weights of the HBPEs were 2160, 2660, 4150 and 5840 g/mol, respectively. These HBPEs were used as additives to prepare polysulfone (PSf) hollow fiber membranes via non-solvent induced phase separation. The characteristic behaviors of the casting solution were investigated, as well as the morphologies, hydrophilicity and mechanical properties of the PSf membranes. The results showed that the initial viscosities of the casting solutions were increased, and the shear-thinning phenomenon became increasingly obvious. The demixing rate first increased and then decreased when increasing the HBPE molecular weight, and the turning point was 2660 g/mol. The PSf hollow fiber membranes with different molecular weights of HBPEs had a co-existing morphology of double finger-like and sponge-like structures. The starting pure water contact angle decreased obviously, and the mechanical properties improved.

Preparation of a flame-retardant coating based on solvent-free synthesis with high efficiency and durability on cotton fabric.

A novel formaldehyde-free and halogen-free flame retardant (FR), HBPOPN, was synthesized under solvent-free conditions and applied on cotton fabric to improve its durability. The reactive groups of HBPOPN could react with cellulose to form covalent bonds. The limit oxygen index (LOI) value of 160 g/L HBPOPN-treated cotton was 42.0 % and the LOI value was still 29.3 % after 50 laundering cycles (LCs). The entire vertical flammability test showed no after-flame or after-glow time. Moreover, the cone calorimetry results suggested that the peak heat release rate (PHRR) and the total heat release (THR) of the HBPOPN-treated samples were dramatically lower than those of the untreated samples. Scanning electron microscopy (SEM) images and X-ray diffraction (XRD) patterns indicated that HBPOPN hardly affected the structure of cellulose. Thermogravimetric data from thermogravimetric analysis (TGA) with an infrared spectrometer implied that HBPOPN changed the thermal decomposition mechanism of cotton. The mechanical properties of the treated cotton fabrics were well maintained. These results indicate that the HBPOPN-treated samples had highly efficient flame retardancy and superior durability.

Amphiphilic hyperbranched polyester coated rod mesoporous silica nanoparticles for pH-responsive doxorubicin delivery.

Rod-like mesoporous silica nanoparticles with pH-responsive amphiphilic hyperbranched polyester shells were prepared for doxorubicin (DOX) delivery. First, rod-shaped mesoporous silica nanoparticles (MSNs) were obtained, then hydrophobic hyperbranched polyester Boltorn H40 (H40) was grafted on their surface. The H40 coated MSNs were next treated with amine-functionalized polyethylene glycol (PEG) to achieve the hydrophilic and pH-responsive material denoted as PEG-H40-MSNs. The experimental results showed that PEG-H40-MSNs were successfully synthesized. BET analysis showed that rod MSNs exhibits a type IV standard isotherm. TEM revealed that the thin gray polymer layer was formed around the SBA-15 particle with a diameter of around 150 nm. DOX was effectively loaded, which can be released according to the ambient pH inside the cell as follow: at pH 7.4, only 9.7% of the DOX was released after 48 h; as the pH decreased to 5.5, the cumulative release reached to 49% at the same time. PEG-H40-MSNs showed less than 1.6% of hemolytic activity and a slight effect on the liver and kidney of treated mice were observed at a high disposal dosage implying negligible toxicities were caused by PEG-H40-MSNs in both in vitro hemolysis analysis and in vivo biochemical in mice. However, the in vitro cytotoxicity evaluation of the DOX-PEG-H40-MSNs showed that the cell cytotoxicity of both pure DOX and DOX-loaded PEG-H40-MSNs generally enhanced by increasing the concentration of DOX. Graphical abstract Schematic of cellular uptake and DOX release of PEG-H40-MSNs nanoparticle.

Poly(Glycerol Succinate) as an Eco-Friendly Component of PLLA and PLCL Fibres towards Medical Applications.

This study was conducted as a first step in obtaining eco-friendly fibres for medical applications using a synthesised oligomer poly(glycerol succinate) (PGSu) as an additive for synthetic poly(L-lactic acid) (PLLA) and poly (L-lactide-co-caprolactone) (PLCL). The effects of the oligomer on the structure formation, morphology, crystallisation behaviour, and mechanical properties of electrospun bicomponent fibres were investigated. Nonwovens were investigated by means of scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and mechanical testing. The molecular structure of PLLA fibres is influenced by the presence of PGSu mainly acting as an enhancer of molecular orientation. In the case of semicrystalline PLCL, chain mobility was enhanced by the presence of PGSu molecules, and the crystallinity of bicomponent fibres increased in relation to that of pure PLCL. The mechanical properties of bicomponent fibres were influenced by the level of PGSu present and the extent of crystal formation of the main component. An in vitro study conducted using L929 cells confirmed the biocompatible character of all bicomponent fibres.

Hyperbranch-Crosslinked S-SEBS Block Copolymer Membranes for Desalination by Pervaporation.

Sulfonated aromatic polymer (SAP) featuring hydrophilic nanochannels for water transport is a promising membrane material for desalination. SAPs with a high sulfonation degree favor water transport but suffer from reduced mechanical strength and membrane swelling. In this work, a hyperbranched polyester, H302, was introduced to crosslink a sulfonated styrene-ethylene/butylene-styrene (S-SEBS) copolymer membrane. The effects of crosslinking temperature and amount of H302 on the microstructure, and the pervaporation desalination performance of the membrane, were investigated. H302/S-SEBS copolymer membranes with different crosslinking conditions were characterized by various techniques including FTIR, DSC, EA, SEM, TEM and SAXS, and tensile strength, water sorption and contact angle measurements. The results indicate that the introduction of hyperbranched polyester enlarged the hydrophilic microdomain of the S-SEBS membrane. Crosslinking with hyperbranched polyester with heat treatment effectively enhanced the mechanical strength of the S-SEBS membrane, with the tensile strength being increased by 140-200% and the swelling ratio reduced by 45-70%, while reasonable water flux was maintained. When treating 5 wt% hypersaline water at 65 °C, the optimized crosslinked membrane containing 15 wt% H302 and heated at 100 °C reached a water flux of 9.3 kg·m-2·h-1 and a salt rejection of 99.9%. The results indicate that the hyperbranched-S-SEBS membrane is promising for use in PV desalination.

Investigation on the Effect of Hyperbranched Polyester Grafted Graphene Oxide on the Crystallization Behaviors of ß-Nucleated Isotactic Polypropylene.

In this article, hyperbranched polyester grafted graphene oxide (GO) was successfully prepared. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were performed for its characterizations. On the other hand, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were also performed to study its influences on non-isothermal crystallization behaviors of ß-nucleated isotactic polypropylene (ß-iPP). The grafting ratios of hyperbranched polyester with different supermolecular structures were calculated to be 19.8-24.0 wt %, which increase with the degree of branching. The results showed that the grafting of hyperbranched polyester was advantageous in increasing the crystallization peak temperature Tp and decreasing the crystallization activation energy ΔE of ß-iPP/GO composites, which contributed to the iPP's crystallization process. Moreover, under all cooling rates (2, 5, 10, 20, 40 °C/min), crystallinities of ß-iPP/GO were greatly improved after being grafted with hyperbranched polyester, because of the increase of the relative contents of α-phase αc and the average α-crystal sizes.

A novel organic-inorganic hybrid K-HBPE@APP performing excellent flame retardancy and smoke suppression for polypropylene.

To overcome the flammability and severe dripping of polypropylene (PP), a novel organic-inorganic hybrid K-HBPE@APP (microencapsulated APP by a hyperbranched polyester (HBPE) via silane coupling agent (KH-550)) was obtained and used as a high-efficient flame retardant and smoke suppressant. Herein, HBPE acted as the charring agent for APP. 20 wt% of K-HBPE@APP imparted PP excellent flame retardancy, V-0 rating (UL-94 test) and 82.6% decrease in the peak of heat release rate (PHRR). However, PP with 25 wt% of mechanically mixed APP and HBPE achieved V-1 rating (UL-94 test) and 77.3% decrease in PHRR. That is because the direct contact and sufficient interaction between APP and HBPE gives full play to their synergy. Besides, K-HBPE@APP accelerated the formation of cross-linked POC/SiOSi/SiOC/SiOP/POΦ structures, leading to a strong and compact char layer with a result of dramatic reduction in heat release rate and smoke production. Furthermore, K-HBPE@APP was highly water-resistant and has good compatibility with PP matrix. In particular, the flame-retarded PP had similar tensile strength to pure PP and enhanced impact strength.

Robust Hyperbranched Polyester-Based Anti-Smudge Coatings for Self-Cleaning, Anti-Graffiti, and Chemical Shielding.

In this work, a novel anti-smudge coating system was developed by using hydroxyl-terminated hyperbranched polyester as a coating precursor, mono-hydroxyl-terminated poly(dimethylsiloxane) (PDMS) as an anti-smudge agent, and hexamethylene diisocyanate trimer as a curing agent. The resultant coatings with 0.5 wt % PDMS content incorporated are highly transparent and liquid repellent. They exhibit striking repellency against various liquids and display remarkable self-cleaning performance. Water, hexadecane, salt solution, strong alkali solution, strong acid solution, pump oil, and crude oil could slide off the coated surface without leaving any traces, and the dirt on the coated surface could be readily removed by water or oil. Besides, these coatings show potential application for anti-fingerprint and anti-graffiti due to the exceptional repellency of coated surface against artificial fingerprint liquid, oil-based ink, paint, and water-based smudge. Furthermore, they also possess superb chemical shielding ability and thus endow substrates with remarkable protection against exposure to harsh chemical conditions. Moreover, these coatings are mechanically robust against extensive abrasion, impact, and bending without compromising anti-smudge properties, and they also exhibit excellent adhesion to various substrates. Therefore, these newly developed coatings have tremendous potential for widespread applications.

Influences of Hyperbranched Polyester Modification on the Crystallization Kinetics of Isotactic Polypropylene/Graphene Oxide Composites.

In this study, the hyperbranched polyester grafted graphene oxide (GO-H202) was synthesized, and the isotactic polypropylene/graphene oxide (iPP/GO) composites were prepared. Results of X-ray photoelectron spectra (XPS), Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) revealed the successful synthesis of GO-H202, while thermogravimetric analysis (TGA) indicated that the weight ratio of grafting was about 35 wt %. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) were carried out to investigate the role of GO and GO-H202 on the crystallization kinetics of the composites. Results suggested that the addition of GO enhanced the nucleation rate and crystallizability of the composites, while GO-H202 exhibited a higher crystallization acceleration effect compared to neat GO; results of isothermal crystallization kinetics and self-nucleation isothermal crystallization kinetics showed that both the overall crystallization rate and crystal growth rate increase after the addition of GO and GO-H202, and the crystallization acceleration of GO-H202 became evidently stronger compared to GO. Moreover, the variation trends of Avrami exponent n with the isothermal crystallization temperature TcISO changed significantly after the addition of GO or GO-H202, which might imply that the addition of GO and GO-H202 lead to different crystallization dimensionalities during the isothermal crystallization of the composites. The related mechanism was also discussed.

Hyperbranched polymeric nanomaterials impair the freshwater crustacean Daphnia magna.

Hyperbranched polymers are nanomaterials belonging to the class of dendritic architectures with increasing applications in many diverse fields. We studied the toxicity of two hyperbranched polymers to the freshwater crustacean Daphnia magna. A hyperbranched hydroxyl-terminated polyester and a commercial hyperbranched polyamidoamine, Helux-3316 were tested for the acute immobilization of daphnids, the overproduction of reactive oxygen species and the activity of the antioxidant enzymes catalase and glutathione S-transferase. The effect for D. magna immobilization was higher for the hyperbranched polyamidoamine Helux-3316, which was attributed to the presence of primary amino groups on its surface. Following exposure to both hyperbranched polymers, a clear overproduction of reactive oxygen species took place accompanied by concentration-dependent enzymatic antioxidant response. Our results showed that the overproduction of reactive oxygen species activated antioxidant defence mechanisms and was responsible for the immobilization of daphnids exposed to both hyperbranched polymers. We showed evidence of the uptake of fluorescently labelled Helux-3316 that accumulated into the gastrointestinal tract of D. magna, and its removal via excretion within fecal pellets. This is the first work reporting the internalization of hyperbranched polymers in aquatic organisms.