Long-Chain Hyperbranched Polymers: Synthesis, Properties, and Applications.

By combining the virtues of conventional linear and hyperbranched polymers, long-chain hyperbranched polymers (LCHBPs) have attracted great attention. Therefore, a comprehensive summary of the research progress of LCHBPs is presented, with a particular focus on their synthetic strategies, unique properties, and potential applications. The synthetic methodologies are rationalized into four main classes according to their construction process or mechanism, namely ABx (x ≥ 2), A2  + Bx (x ≥ 3), AB + ABx (x ≥ 2), and self-condensing vinyl polymerization. Some of their rheological properties, self-assembly behavior, and stimuli-response features are then discussed. Finally, the emergent applications including biomedicine, electrical conductivity, chemical sensing, and catalyst carrier, are outlined. It is anticipated that this review will stimulate more inspiration for advancing the development of this novel kind of LCHBP.

The hemostatic performance and mechanism of palygorskite with structural regulate by oxalic acid gradient leaching.

Palygorskite (Pal) is a naturally available one-dimensional clay mineral, featuring rod-shaped morphology, nanoporous structure, permanent negative charges as well as abundant surface hydroxyl groups, exhibiting promising potential as a natural hemostatic material. In this study, the hemostatic performance and mechanisms of Pal were systematically investigated based on the structural regulate induced by oxalic acid (OA) gradient leaching from perspectives of structure, surface attributes and ion release.In vitroandin vivohemostasis evaluation showed that Pal with OA leaching for 1 h exhibited a superior blood procoagulant effect compared with the raw Pal as well as the others leached for prolonging time. This phenomenon might be ascribed to the synergistic effect of the intact nanorod-like morphology, the increase in the surface negative charge, the release of metal ions (Fe3+and Mg2+), and the improved blood affinity, which promoted the intrinsic coagulation pathway, the fibrinogenesis and the adhesion of blood cells, thereby accelerating the formation of robust blood clots. This work is expected to provide experimental and theoretical basis for the construction of hemostatic biomaterials based on clay minerals.

Biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres for controlled drug release.

Well-defined biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres have been accomplished via the layer-by-layer (LbL) self-assembly technique. The hybrid shell was fabricated by the electrostatic interaction between the polyelectrolyte cation, chitosan (CS), and the hybrid anion, citrate modified ferroferric oxide nanoparticles (Fe3O4-CA), onto the uniform polystyrene sulfonate microsphere templates. Then the magnetic hybrid core/shell composite particles were modified with a linear, functional poly(ethylene glycol) (PEG) monoterminated with a biotargeting molecule (folic acid (FA)). Afterward the dual targeting hybrid hollow microspheres were obtained after etching the templates by dialysis. The dual targeting hybrid hollow microspheres exhibit exciting pH response and stability in high salt-concentration media. Their pH-dependent controlled release of the drug molecule (anticancer drug, doxorubicin (DOX)) was also investigated in different human body fluids. As expected, the cell viability of the HepG2 cells which decreased more rapidly was treated by the FA modified hybrid hollow microspheres rather than the unmodified one in the in vitro study. The dual-targeting hybrid hollow microspheres demonstrate selective killing of the tumor cells. The precise magnetic and molecular targeting properties and pH-dependent controlled release offers promise for cancer treatment.

Incorporation of clay minerals into magnesium phosphate bone cement for enhancing mechanical strength and bioactivity.

The poor mechanical strength and bioactivity of magnesium phosphate bone cements (MPCs) are the vital defects for bone reconstruction. Clay minerals have been widely used in biomedical field due to the good reinforcing property and cytocompatibility. Here, laponite, sepiolite or halloysite were incorporated to fabricate MPCs composite, and the composition, microstructure, setting time, compressive strength, thermal stability, degradation performance,in vitrobioactivity and cell viability of MPCs composite were investigated. The results suggested that the MPCs composite possessed appropriate setting time, high mechanical strength and good thermal stability. By contrast, MPCs composite containing 3.0 wt.% of sepiolite presented the highest compressive strength (33.45 ± 2.87 MPa) and the best thermal stability. The degradation ratio of MPCs composite was slightly slower than that of MPCs, and varied in simulated body fluid and phosphate buffer solution. Therefore, the obtained MPCs composite with excellent bioactivity and cell viability was expected to meet the clinical requirements for filling bone defect.

Progress and future prospects of hemostatic materials based on nanostructured clay minerals.

The occurrence of uncontrolled hemorrhage is a significant threat to human life and health. Although hemostatic materials have made remarkable advances in the biomaterials field, it remains a challenge to develop safe and effective hemostatic materials for global medical use. Natural clay minerals (CMs) have long been used as traditional inorganic hemostatic agents due to their good hemostatic capability, biocompatibility and easy availability. With the advancement of science, technology and ideology, CM-based hemostatic materials have undergone continuous innovations by integrating new inspirations with conventional concepts. This review systematically summarizes the hemostatic mechanisms of different natural CMs based on their nanostructures. Moreover, it also comprehensively reviews the latest research progress for CM-based hemostatic hybrid and nanocomposite materials, and discusses the challenges and developments in this field.

Incorporation of mixed-dimensional palygorskite clay into chitosan/polyvinylpyrrolidone nanocomposite films for enhancing hemostatic activity.

Clay mineral-based hemostatic materials have attracted much attention in recent years, but it is scarce to report the hemostatic nanocomposite films containing natural mixed-dimensional clay composed of natural one-dimensional and two-dimensional clay minerals. In this study, the high-performance hemostatic nanocomposite films were facilely prepared by incorporating the natural mixed-dimensional palygorskite clay leached by oxalic acid (O-MDPal) into chitosan/polyvinylpyrrolidone (CS/PVP) matrix. By contrast, the obtained nanocomposite films exhibited the higher tensile strength (27.92 MPa), lower water contact angel (75.40°), better degradation, thermal stability and biocompatibility after incorporation of 20 wt% of O-MDPal, suggesting that O-MDPal contributed to enhancing the mechanical performance and water holding capacity of the CS/PVP nanocomposite films. Compared with the medical gauze and CS/PVP matrix groups, the nanocomposite films also indicated excellent hemostatic performance evaluated by blood loss and hemostasis time indexes based on the mouse tail amputation model, which might be ascribed to the enriched hemostatic functional sites, and hydrophilic surface, robust physical barrier role of nanocomposite films. Therefore, the nanocomposite film exhibited a promising practical application in wound healing.

A structure-function relationship for the optical modulation of phenyl boronic acid-grafted, polyethylene glycol-wrapped single-walled carbon nanotubes.

Phenyl boronic acids (PBA) are important binding ligands to pendant diols useful for saccharide recognition. The aromatic ring can also function to anchor an otherwise hydrophilic polymer backbone to the surface of hydrophobic graphene or carbon nanotube. In this work, we demonstrate both functions using a homologous series of seven phenyl boronic acids conjugated to a polyethylene glycol, eight-membered, branched polymer (PPEG8) that allows aqueous dispersion of single-walled carbon nanotubes (SWNT) and quenching of the near-infrared fluorescence in response to saccharide binding. We compare the 2-carboxyphenylboronic acid (2CPBA); 3-carboxy- (3CPBA) and 4-carboxy- (4CPBA) phenylboronic acids; N-(4-phenylboronic)succinamic acid (4SCPBA); 5-bromo-3-carboxy- (5B3CPBA), 3-carboxy-5-fluoro- (5F3CPBA), and 3-carboxy-5-nitro- (5N3CPBA) phenylboronic acids, demonstrating a clear link between SWNT photoluminescence quantum yield and boronic acid structure. Surprisingly, quantum yield decreases systematically with both the location of the BA functionality and the inclusion of electron-withdrawing or -donating substituents on the phenyl ring. For three structural isomers (2CPBA, 3CPBA, and 4CPBA), the highest quantum yields were measured for para-substituted PBA (4CPBA), much higher than ortho- (2CPBA) and meta- (3CPBA) substituted PBA, indicating the first such dependence on molecular structure. Electron-withdrawing substituents such as nitro groups on the phenyl ring cause higher quantum yield, while electron-donating groups such as amides and alkyl groups cause a decrease. The solvatochromic shift of up to 10.3 meV was used for each case to estimate polymer surface coverage on an areal basis using a linear dielectric model. Saccharide recognition using the nIR photoluminescence of SWNT is demonstrated, including selectivity toward pentoses such as arabinose, ribose, and xylose to the exclusion of the expected fructose, which has a high selectivity on PBA due to the formation of a tridentate complex between fructose and PBA. This study is the first to conclusively link molecular structure of an adsorbed phase to SWNT optical properties and modulation in a systematic manner.

Structure and function of glucose binding protein-single walled carbon nanotube complexes.

Understanding the structure and function of glucose binding proteins (GBP) complexed with single walled carbon nanotubes (SWNTs) is important for the development of applications including fluorescent sensors and nanostructure particle tracking. Herein, circular dichroism (CD), thermal denaturation, photo-absorption spectroscopy and atomic force microscopy are used to study these nanostructures. The protein retains its glucose-binding activity after complexation and is thermally stable below 36 °C. However, the SWNT lowers the midpoint denaturation temperature (Tm) by 5 °C and 4 °C in the absence and presence of 10 mM glucose, respectively. This data highlights that using techniques such as CD and thermal denaturation may be necessary to fully characterize such protein-nanomaterial nanostructures.

Fabrication of flocculation-resistant pH/ionic strength/temperature multiresponsive hollow microspheres and their controlled release.

pH/ionic strength/temperature multiresponsive hollow microspheres were successfully prepared by the Ce(IV) initiated grafting polymerization of N-isopropylacrylamide (NIPAm) onto the multilayered polyelectrolyte shells encapsulating the polystyrene sulfonate (PSS) microsphere templates fabricated by the layer-by-layer assembly of chitosan (CS) and alginate (SAL), after etching the templates by dialysis. The hollow structure of the obtained multiresponsive hollow microspheres was characterized by transmission electron microscopy (TEM), which indicated that the inner diameter of the hollow microspheres was about 200 nm. The environmental responsive properties of the multiresponsive hollow microspheres were characterized with dynamic light scattering (DLS) in an aqueous system. The introduction of poly(N-isopropylacrylamide) (PNIPAm) brushes onto the pH/ionic strength dual-responsive hollow microspheres achieved temperature-responsive characteristics. It also could prevent flocculation among the obtained multiresponsive hollow microspheres in a solution with higher salt concentration. Their controlled release of drug molecules (a model hydrophobic drug, dipyridamole (DIP)) was also investigated.

Preparation of crosslinked polymeric nanocapsules by surface-initiated self-condensing vinyl polymerization on silica templates.

We developed a process to fabricate crosslinked polymeric nanocapsules with about 10-40 nm hollow cores. These crosslinked polymeric nanocapsules were fabricated via the surface-initiated self-condensing vinyl polymerization (SI-SCVP) of p-chloromethyl styrene (CMS) from initiator modified silica nanoparticles with atom transfer radical polymerization (ATRP) technique. The silica templates were removed by HF etching to produce the crosslinked polymeric nanocapsules after the grafted hyperbranched polymers had been crosslinked. Transmission electron microscopy (TEM) was used to characterize the products and to demonstrate that the polymeric nanospheres were hollow. FTIR spectroscopy showed that the silica templates were completely removed by etching.

Polymeric nanocapsules with controllable crosslinking degree via combination of surface-initiated atom transfer radical polymerisation and photocrosslinking techniques.

The crosslinked polystyrene nanocapsules with controllable crosslinking degree have been prepared by the ultraviolet (UV)-induced photocrosslinking of the polystyrene grafted silica nanoparticles (SN-PS), which was obtained by the surface-initiated atom transfer radical polymerisation of styrene from the modified silica nanoparticle templates, after the silica templates were etched with hydrofluoric acid. The effect of the UV-irradiating time on the inner diameter of the nanocapsules, and the degree of crosslinking and the thickness of the shells was investigated. The dynamic light scattering results showed that the degree of crosslinking of the obtained nanocapsules increased with the prolongation of the UV-irradiation time, therefore the inner diameter of the nanocapsules increased. However, the percentage of grafting of the crosslinked polymer shells decreased with increasing the UV-irradiation time because of the photodecomposition of the polystyrene grafted during the UV-irradiated crosslinking process, according to the thermogravimetric analysis.

Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes.

Understanding molecular recognition is of fundamental importance in applications such as therapeutics, chemical catalysis and sensor design. The most common recognition motifs involve biological macromolecules such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific molecule. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for specific molecules. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodynamic model of surface interactions in which the dissociation constants can be tuned by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.

Stimuli-responsive multilayer chitosan hollow microspheres via layer-by-layer assembly.

Novel stimuli-responsive multilayer chitosan hollow microspheres with chitosan as the unique component have been fabricated by the sequential layer-by-layer electrostatic assembly technique from the sacrificial templates (polystyrene sulfonate, PSS) with chitosan (CS) as the polycation and carboxymethyl chitosan (CMCS) as the polyanion, respectively. Their hollow structure was confirmed by the TEM analysis. The DLS analysis indicated that the multilayer chitosan microcapsules were pH and ionic strength dual-responsive. Due to the biocompatibility of the single component chitosan used, the multilayer chitosan microcapsules are expected to be used in the controlled release of drugs.

Disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules via covalent layer-by-layer assembly.

The disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules have been fabricated via the covalent layer-by-layer assembly between the amino groups of chitosan (CS) and the aldehyde groups of the oxidized sodium alginate (OSA) onto the sacrificial templates (polystyrene sulfonate, PSS) which was removed by dialysis subsequently. The covalent crosslinking bonds of the multilayer microcapsules were confirmed by FTIR analysis. The TEM analysis showed that the diameter of the multilayer microcapsules was <200nm. The diameter of the multilayer microcapsules decreased with the increasing of the pH values or the ionic strength. The pH and ionic strength dual-responsive multilayer microcapsules were stable in acidic and neutral media while they could disintegrate only at strong basic media.

Crosslinked polymeric nanocapsules from polymer brushes grafted silica nanoparticles via surface-initiated atom transfer radical polymerization.

The crosslinked polymeric nanocapsules with inner diameter of about 20-50nm were prepared successfully by the post-treatment of the poly(methyl acrylate) (PMA) brushes grafted silica nanoparticles (SN-PMA) produced with the surface-initiated atom transfer radical polymerization (SI-ATRP) technique. The PMA chains grafted were modified with amino groups by being treated with ethanediamine (EDA). Then the silica nanoparticles (SN) templates were removed by being etched with hydrofluoric acid (HF) to produce the crosslinked polymeric nanocapsules after the aminated poly(methyl acrylate) (APMA) chains on the SN templates were crosslinked with hexamethylene diisocyanate (HDI). Transmission electron microscopy (TEM) analyses were used to estimate the size of the polymeric nanocapsules.