Hyperbranched Poly Research Articles

Facile and efficient grafting of graphene oxide onto carbon fiber with hyperbranched poly(thioether-yne) via click chemistry to improve interface and mechanical properties of composite

For the purpose of simultaneously improving the interface and mechanical properties of carbon fiber (CF)/epoxy (EP) composite, we presented a more facile and efficient approach to graft graphene oxide (GO) onto CF using hyperbranched poly(thioether-yne) (HPTY) as a bridging agent through the thiol-alkyne click chemistry reaction. The characterization results of FTIR, XPS, Raman, TGA, SEM, and AFM verified successful synthesis of CF-HPTY-GO hybrid reinforcement. The simultaneous introduction of GO and HPTY changed the fiber surface topography, meanwhile enhancing wettability and surface energy of CF. Based on that, the composite with superior interface 0Notably, the value of interface shear strength (IFSS) for CF-HPTY-GO/EP composite was enhanced by 94.4 % compared with pristine CF/EP composite. Moreover, the tensile and bending strength for CF-HPTY-GO/EP composite were increased by 38.2 % and 49.1 % compared with pristine CF/EP composite because of the effective stress transfer through interface. Therefore, this work is expected to offer a promising technique for preparing advanced structural composites with outstanding interface and mechanical properties.

Multiple applications of synthesized hyperbranched poly(amidoamine)dendrimer and its ZnO nanohybrid: anti-microbial agents, anti-biofilms, biocides and corrosion inhibitors

Multiple applications of synthesized hyperbranched poly(amidoamine)dendrimer and its ZnO nanohybrid: anti-microbial agents, anti-biofilms, biocides and corrosion inhibitors

Self-reporting and Biodegradable Thermosetting Solid Polymer Electrolyte.

To date, significant efforts have been dedicated to improve their ionic conductivity, thermal stability, and mechanical strength of solid polymer electrolytes (SPEs). However, direct monitoring of physical and chemical changes in SPEs is still lacking. Moreover, existing thermosetting SPEs are hardly degradable. Herein, by overcoming the limitation predicted by Flory theory, self-reporting and biodegradable thermosetting hyperbranched poly(β-amino ester)-based SPEs (HPAE-SPEs) are reported. HPAE is successfully synthesized through a well-controlled "A2+B4" Michael addition strategy and then crosslinked it in situ to produce HPAE-SPEs. The multiple tertiary aliphatic amines at the branching sites confer multicolour luminescence to HPAE-SPEs, enabling direct observation of its physical and chemical damage. After use, HPAE-SPEs can be rapidly hydrolysed into non-hazardous β-amino acids and polyols via self-catalysis. Optimized HPAE-SPE exhibits an ionic conductivity of 1.3×10-4 S/cm at 60 °C, a Na+ transference number ( ) of 0.67, a highly stable sodium plating-stripping behaviour and a low overpotential of ≈190 mV. This study establishes a new paradigm for developing SPEs by engineering multifunctional polymers. The self-reporting and biodegradable properties would greatly expand the scope of applications for SPEs.

Self‐reporting and Biodegradable Thermosetting Solid Polymer Electrolyte

AbstractTo date, significant efforts have been dedicated to improve their ionic conductivity, thermal stability, and mechanical strength of solid polymer electrolytes (SPEs). However, direct monitoring of physical and chemical changes in SPEs is still lacking. Moreover, existing thermosetting SPEs are hardly degradable. Herein, by overcoming the limitation predicted by Flory theory, self‐reporting and biodegradable thermosetting hyperbranched poly(β‐amino ester)‐based SPEs (HPAE‐SPEs) are reported. HPAE is successfully synthesized through a well‐controlled “A2+B4” Michael addition strategy and then crosslinked it in situ to produce HPAE‐SPEs. The multiple tertiary aliphatic amines at the branching sites confer multicolour luminescence to HPAE‐SPEs, enabling direct observation of its physical and chemical damage. After use, HPAE‐SPEs can be rapidly hydrolysed into non‐hazardous β‐amino acids and polyols via self‐catalysis. Optimized HPAE‐SPE exhibits an ionic conductivity of 1.3×10−4 S/cm at 60 °C, a Na+ transference number ( ) of 0.67, a highly stable sodium plating‐stripping behaviour and a low overpotential of ≈190 mV. This study establishes a new paradigm for developing SPEs by engineering multifunctional polymers. The self‐reporting and biodegradable properties would greatly expand the scope of applications for SPEs.

Flexible and transparent humidity sensors based on hyperbranched poly(ionic liquid)s for wearable sensing

The rapid development of wearable electronics is driving the exploration of flexible and transparent humidity sensors. However, the limited humidity response and mechanical flexibility of sensitive materials hinder the normal operation of the device. In this research, flexible humidity sensors with a fast response time (1 s) were prepared using transparent imidazolium-based hyperbranched poly(ionic liquid)s (HPIL). The sensor performance was improved by regulating the counter anions with different hydrophobicity, such as trifluoromethanesulfonimide ion (TFSI-). The HPIL-TFSI sensor featured an improved response under low humidity condition (6%∼33% RH) with good linearity, excellent bending humidity response, mechanical stability, and long-term stability over a wide humidity range from 6% to 98% RH. Moreover, accurate sensing was achieved for respiratory monitoring, non-contact sensing, and detecting moisture on patched skin. The HPIL-TFSI sensor paves the way for the production of high-performance wearable sensor platforms.

Preparation and performance testing of novel bendable optically transparent fluorinated hyperbranched linear long chain segment poly(amide-imide) films

A series of fluorinated hyperbranched linear long-chain segment poly(amide-imide)s were prepared. Subsequently, a detailed comparative study of the optical properties of the hyperbranched PAI films with those of commercial films was carried out.

Ionic Hyperbranched Poly(amido-amine)-Incorporated Nanofiltration Membranes for High-Efficiency Dye Desalination.

High-efficiency dye desalination is crucial in the textile industry, considering its importance for human health, safe aquatic ecological systems, and resource recovery. In order to solve the problem of effective separation of univalent salt and ionic dye under the condition of high salt, ionic hyperbranched poly(amido-amine) (HBPs) were synthesized based on a simple and scalable one-step polycondensation method and then incorporated into the polyamide (PA) selective layers to construct charged nanochannels through interfacial polymerization (IP) on the surface of a polyvinyl chloride ultrafiltration (PVC-UF) hollow fiber membrane. Both the internal nanopores of HBPs (internal nanochannels) and the interfacial voids between HBPs and the PA matrix (external nanochannels) can be regarded as a fast water molecule transport pathway, while the terminal ionic groups of ionic HBPs endow the nanochannels with charge characteristics for improving ionic dye/salt selectivities. The permeate fluxes and dye/salt selectivities of HBP-TAC/PIP (57.3 L m-2 h-1 and rhodamine B (RB)/NaCl selectivity of 224.0) and HBP-PS/PIP (63.7 L m-2 h-1 and lemon yellow (LY)/NaCl selectivity of 664.0) membranes under 0.4 MPa operation pressure are much higher than PIP-only and HBP-NH2/PIP membranes. At the same time, this project also studied the membrane desalination process in a simulated high-salinity dye/salt mixture system to provide a theoretical basis and technical support for the actual dye desalination process.

Anionic Hyperbranched Amphiphilic Polyelectrolytes as Nanocarriers for Antimicrobial Proteins and Peptides.

This manuscript presents the synthesis of hyperbranched amphiphilic poly (lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), H-P(LMA-co-tBMA-co-MAA) copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization of tBMA and LMA, and their post-polymerization modification to anionic amphiphilic polyelectrolytes. The focus is on investigating whether the combination of the hydrophobic characters of LMA and tBMA segments, as well as the polyelectrolyte and hydrophilic properties of MAA segments, both distributed within a unique hyperbranched polymer chain topology, would result in intriguing, branched copolymers with the potential to be applied in nanomedicine. Therefore, we studied the self-assembly behavior of these copolymers in aqueous media, as well as their ability to form complexes with cationic proteins, namely lysozyme (LYZ) and polymyxin (PMX). Various physicochemical characterization techniques, including size exclusion chromatography (SEC) and proton nuclear magnetic resonance (1H-NMR), verified the molecular characteristics of these well-defined copolymers, whereas light scattering and fluorescence spectroscopy techniques revealed promising nanoparticle (NP) self- and co-assembly properties of the copolymers in aqueous media.

Multifunctional Injectable Hydrogel Microparticles Loaded with miR-29a Abundant BMSCs Derived Exosomes Enhanced Bone Regeneration by Regulating Osteogenesis and Angiogenesis.

The study investigated whether both the osteogenic and angiogenic potential of Exos (Exosomes) can be enhanced by overexpression of exosomal miRNA (microRNA) and to confirm whether Exos loaded in HMPs (Hydrogel microparticles) exert long-term effects during new bone formation. BMSCs and Exos are successfully obtained. In vitro and in vivo experiments confirmed that HDAC4 (Histone deacetylase 4) is inhibited by miR-29a overexpression accompanied by the upregulation of RUNX2 (Runt-related transcription factor 2) and VEGF (Vascular Endothelial Growth Factor), thereby enhancing osteogenic and angiogenic capabilities. The HMP@Exo system is synthesized from HB-PEGDA (Hyperbranched Poly Ethylene Glycol Diacrylate)- and SH-HA (Sulfhydryl-Modified Hyaluronic Acid)-containing Exos using a microfluidic technique. The HMP surface is modified with RGD (Arg-Gly-Asp) peptides to enhance cell adhesion. The system demonstrated good injectability, remarkable compatibility, outstanding cell adhesion properties, and slow degradation capacity, and the sustained release of Agomir-29a-Exos (Exosomes derived from Agomir-29a transfected BMSCs) from HMPs enhanced the proliferation and migration of BMSCs and HUVECs (Human Umbilical Vein Endothelial Cells) while promoting osteogenesis and angiogenesis. Overall, the findings demonstrate that the HMP@Exo system can effectively maintain the activity and half-life of Exos, accompanied by overexpression of miR-29a (microRNA-29a). The injectable system provides an innovative approach for accelerating fracture healing by coupling osteogenesis and angiogenesis.

Amino-terminated hyperbranched poly(phenylene oxide) as a novel antioxidant for nitrile-butadiene rubber

Amino-terminated hyperbranched poly(phenylene oxide) as a novel antioxidant for nitrile-butadiene rubber

Preparation of Novel Nitrogen-Rich Fluorinated Hyperbranched Poly(amide-imide) and Evaluation of Its Electrochromic Properties and Iodine Adsorption Behavior.

In this study, we successfully synthesized a novel triacid monomer by means of the thermal cyclization reaction. Subsequently, a series of nitrogen-rich (A3+B2)-type fluorinated hyperbranched poly(amide-imide)s (denoted as PAI-1 and -2, respectively) were prepared by means of a one-pot method using this triacid monomer and a diamine monomer with a triphenylamine-carbazole unit as precursors. The degree of support of the prepared hyperbranched PAIs was found to be about 60% via 1H NMR calculations. Through X-ray photoelectron spectroscopy (XPS), it was found that the binding energies of C-N (398.4 eV) and -NH (399.7 eV) became lower under a current, while the binding energy peak of N+ appeared at 402.9 eV. In addition, the PAIs have good solubility and thermal stability (Tgs: 256-261 °C, T10%: 564-608 °C). Cyclic voltammetry (CV) analysis shows that the hyperbranched PAI films have good redox properties, and a range of values for the HOMO (4.83 to 4.85 eV) versus LUMO (1.85 to 1.97 eV) energy levels are calculated. The PAI films have excellent electrochromic properties: PAI-1 on coloration efficiency (CE) and transmittance change (ΔT, 852 nm) are 257 cm2/C and 62%, respectively, and have long-lasting redox properties (100 cycles). In addition, we conduct iodine adsorption tests using the structural features of PAIs with electron-drawing units, and the results show that PAI-1 had a high adsorption capacity for iodine (633 mg/g).

Crosslinked poly(hydroxyurethane) films from biobased carbonates: Structure-properties relationships and the influence of moisture in the mechanical properties

In this work, crosslinked poly(hydroxyurethane) (PHU) films were prepared by the reaction of biobased cyclic carbonates (BisCC), with different chain lengths, with hyperbranched poly(ethyleneimine) (PEI) under amenable conditions and in the absence of catalysts. Fourier transform infrared (FTIR) spectroscopy revealed that the carbonate groups were completely consumed in the crosslinking reaction and the gel content of the films was about 99 %. It was shown that the thermal and mechanical properties of the PHU films depended on the length of the carbon chain of the BisCC. In the presence of moist environment, the PHU films absorbed moisture (6–8 %) which is ascribed to the presence of hydroxyl groups. This resulted in a deterioration of the mechanical properties, which were not completely recovered after drying. To counteract this effect, a simple procedure was used in which the hydroxyl groups on the surface were modified by stearate groups. Although FTIR and water contact angle measurements demonstrated that the films of PHU became more hydrophobic after modification, the water absorption capacity was similar to that of the unmodified PHU films. This suggests that the modification process may cause some degradation in the bulk of the material that opens spaces for water molecules penetration.In summary, this work has shed light for the first time on the effects of moisture on the mechanical properties of pure PHU films and has shown that surface modifications are not sufficient to prevent moisture absorption.

Synthesis and properties of highly thermally stable ultrathin films of fluorine‐containing hyperbranched polybenzoxazoles

AbstractIn this paper, we aimed to develop ultrathin films of hyperbranched polybenzoxazole with a thickness in the range between 1 and 100 nm. They are expected to have great potential for various applications as functional materials due to their high thermal stability, good chemical resistance and mechanical strength. The synthesis of various hyperbranched poly(o‐hydroxyamide)s as precursors of polybenzoxazole was examined by the polycondensation of 2,2‐bis(3‐amino‐4‐hydroxyphenyl)propane (AHP) and 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane (AHFP) with 1,3,5‐benzenetricarbonyl trichloride (BCC), yielding the corresponding hyperbranched poly(o‐hydroxyamide), poly(AHFPm‐co‐AHPn‐co‐BCC2.0), with Mn in the range between 12,870 and 22,210 in satisfactory yields. Poly(AHFP3.0‐co‐BCC2.0), poly(AHFP2.25‐co‐AHP0.75‐co‐BCC2.0), and poly(AHFP1.50‐co‐AHP1.50‐co‐BCC2.0) showed good solubility and film‐forming ability, and ultrathin films 8.9–88.6 nm thick were prepared on silicon wafers. Heating of the ultrathin films of poly(AHFPm‐co‐AHPn‐co‐BCC2.0) on a hot plate at 350 °C for 1 h afforded the corresponding ultrathin films of hyperbranched polybenzoxazole, poly(AHFPm‐cyclo‐AHPn‐cyclo‐BCC2.0), with a thickness of 5.3–82.4 nm. Double‐layer thin films consisting of resist materials on top of hyperbranched polybenzoxazole were also prepared.

On the mechanism of initiation steam cracking of C6 hydrocarbons by hyperbranched poly(amidoamine) (PAMAM) initiator

Initiators with low bond dissociation energy can initiate the cracking of hydrocarbons, but the initiation effect on hydrocarbons with different molecule structures remains ambiguous. In this study, the steam cracking of three C6 hydrocarbons, namely n-hexane, iso-hexane and methyl-cyclopentane (MCP), initiated by hyperbranched poly(amidoamine) (PAMAM) were investigated experimentally in a stainless-steel tubular reactor, and the detailed kinetic reaction models and reaction process simulations were conducted by Reaction Mechanism Generator and Chemkin-pro software packages. The results confirm that the addition of PAMAM can significantly promote the cracking conversion and reduce the initial cracking temperature of hydrocarbons because the decomposition of PAMAM at relatively low temperature produces high concentration of active NH2 and CH3 radicals, which significantly increases the rate of hydrogen abstraction. Importantly, the promotion efficiency of the initiator can be highly dependent on the cracking behaviour of hydrocarbons. The initiator will show higher promotion efficiency for hydrocarbon that is more prone to undergo sustained hydrogen abstraction after initiation. Therefore, the promotion efficiency of PAMAM follows the order of n-hexane > iso-hexane > MCP. This study is helpful for a better understanding of the initiation mechanism and will guide the design and screening of effective initiators for naphtha with different compositions.

Distribution and Transport of CO2 in Hyperbranched Poly(ethylenimine)-Loaded MCM-41: A Molecular Dynamics Simulation Approach.

Fossil fuel use is accelerating climate change, driving the need for efficient CO2 capture technologies. Solid adsorption-based direct air capture (DAC) of CO2 has emerged as a promising mode for CO2 removal from the atmosphere due to its potential for scalability. Sorbents based on porous supports incorporating oligomeric amines in their pore spaces are widely studied. In this study, we investigate the intermolecular interactions and adsorption of CO2 and H2O molecules in hyperbranched poly(ethylenimine) (HB-PEI) functionalized MCM-41 systems to understand the distribution and transport of CO2 and H2O molecules. Density Functional Theory (DFT) is employed to compute the binding energies of CO2 and H2O molecules with HB-PEI and MCM-41 and to develop force field parameters for molecular dynamics (MD) simulations. The MD simulations are performed to examine the distribution and transport of CO2 and H2O molecules as a function of the HB-PEI content. The study finds that an HB-PEI content of approximately 34 wt % is thermodynamically favorable, with an upper limit of HB-PEI loading between 45 and 50 wt %. The distribution of CO2 and H2O molecules is primarily determined by their adsorptive binding energies, for which H2O molecules dominate the occupation of binding sites due to their strong affinity with silanol groups on MCM-41 and amine groups of HB-PEI. The HB-PEI content has a considerable impact on the diffusion of CO2 and H2O molecules. Furthermore, a larger number of water molecules (higher relative humidity) reduces the correlation of CO2 with the MCM-41 pore surface while enhancing the correlation of CO2 with the amine groups of the HB-PEI. Overall, the presence of H2O molecules increases the CO2 correlation with the amine groups and also the CO2 transport within HB-PEI-loaded MCM-41, meaning that the presence of H2O enhances the CO2 capture in the HB-PEI-loaded MCM-41. These findings are consistent with experimental observations of the impact of increasing humidity on CO2 capture while providing new, molecular-level explanations for the macroscopic experimental findings.

Study of the temperature/HCO3- response mechanism of hyperbranched poly(bis-acrylamide)s

Study of the temperature/HCO3- response mechanism of hyperbranched poly(bis-acrylamide)s

Frontispiece: Amplified Chirality Transfer to Aromatic Molecules through Non‐specific Inclusion by Amorphous, Hyperbranched Poly(fluorenevinylene) Derivatives

Frontispiece: Amplified Chirality Transfer to Aromatic Molecules through Non‐specific Inclusion by Amorphous, Hyperbranched Poly(fluorenevinylene) Derivatives

Frontispiz: Amplified Chirality Transfer to Aromatic Molecules through Non‐specific Inclusion by Amorphous, Hyperbranched Poly(fluorenevinylene) Derivatives

Frontispiz: Amplified Chirality Transfer to Aromatic Molecules through Non‐specific Inclusion by Amorphous, Hyperbranched Poly(fluorenevinylene) Derivatives

Mixed Hyperbranched/Triblock Copolymer Micelle Assemblies: Physicochemical Properties and Potential for Drug Encapsulation

AbstractMixed micelles have numerous advantages while requiring little to no effort in preparation. This study aims to produce mixed micelle nanostructures from a linear triblock copolymer and a hyperbranched random copolymer, and is able to be loaded with the weakly water‐soluble drugs curcumin and indomethacin. Different preparation techniques are employed to produce mixed micelles comprised of Pluronic F127 block copolymer, and hyperbranched poly[(ethylene glycol) methyl ether methacrylate‐co‐lauryl methacrylate], H‐[P(OEGMA‐co‐LMA)], copolymer. Few studies have dabbled in these types of coassemblies, which provides insight into how structural differences of each copolymer can affect the formation of micelles. To determine the properties of the emerging nanostructures in aqueous environments, including their size, homogeneity, and surface charge, different physicochemical techniques are used, such as light scattering and spectroscopic methods. The results reveal that the copolymers combine, and spontaneously self‐assemble into mixed micelle‐like nanostructures in aqueous environments, whereas both systems of neat and drug‐loaded nanostructures exhibit desirable properties such as small average micelle hydrodynamic radii and low size polydispersity indices. The nanostructures that result from the effective encapsulation of curcumin exhibit outstanding stability over 169 days. The fluorescent qualities of curcumin persist after encapsulation, making the novel nanostructures excellent candidates for bioimaging applications.

UV-Assisted Hyperbranched Poly(β-amino ester) Modification of a Silica Membrane for Two-Step Microfluidic DNA Extraction from Blood.

Integrating nucleic acid extraction in amplification-based point-of-care diagnostics will be a significant feature for next-generation point-of-care virus detection devices. However, extracting DNA efficiently on a microfluidic chip poses many technological and commercialization challenges, including manual steps, multiple instruments, pretreatment processes, and the use of organic solvents (ethanol, IPA) that inhibit detection, which is not viable with routine testing such as viral load monitoring of transplant patients for post-operative care. This paper presents a microfluidic system capable of two-step DNA extraction from blood using a UV-assisted hyperbranched poly(β-amino ester) (HPAE)-modified silica membrane for cytomegalovirus (CMV) detection in a rapid and instrument-free manner without the presence of amplification inhibitors. HPAEs of varying branch ratios were synthesized, screened, and coated on a silica membrane and bonded between two layers of poly(methyl methacrylate) (PMMA) substrates. Our system could selectively extract DNA from blood with an efficiency of 94% and a lower limit viral load of 300 IU/mL in 20 min. The extracted DNA was used as the template for real-time loop-mediated isothermal amplification (LAMP)-based detection of CMV and was found to produce a fluorescent signal intensity that was comparable with commercially extracted templates. This system can be integrated easily with a nucleic acid amplification system and used for routine rapid testing of viral load in patient blood samples.