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Sample records for amphiphilic hyperbranched polyglycerol

  1. Adsorption of amphiphilic hyperbranched polyglycerol derivatives onto human red blood cells.

    PubMed

    Liu, Zonghua; Janzen, Johan; Brooks, Donald E

    2010-04-01

    Hydrophobically derivatized hyperbranched polyglycerol (HPG)-polyethylene glycol (PEG) polymers bearing stearoyl chains (HPG-C18-PEG) were originally developed as human serum albumin substitutes and further as a unimolecular drug delivery system. In view of these in vivo applications and the potential for membrane interaction by these materials due to their amphiphilic structure, determining the adsorption of the polymers to human red blood cells (RBCs) is an important issue. This paper reports on the in vitro adsorption to RBCs of tritium-radiolabeled HPG-C18-PEG polymers. The morphological changes of RBCs associated with the adsorption were also examined by light and scanning electron microscopy (SEM). Laser scanning confocal microscopy (LSCM) suggests that the binding site of the polymers on RBCs is the cell membrane. Adsorption experiments show that, in the medium of either saline or plasma, the binding amount of the polymers to RBCs increases with increased polymer concentration in a manner which implies simple Langmurian behavior. The binding amount in saline is of the order of 10(5) molecules/cell at an equilibrium concentration of 1 mg/mL of HPG-C18-PEG polymer. The RBC morphology depends on the adsorbed amount; the cells become crenated in high concentrations (5 and 10 mg/mL) of the polymer solutions in the absence of plasma proteins. Interestingly, a large amount of polymers remain bound to RBCs even after washes with plasma (of the order of 10(4) molecules/cell). Thus, the bound polymers might have an extended circulating time by "hitchhiking" on RBCs in the bloodstream. These results provide significant information and insight for related studies of the interaction of amphiphilic molecules with cell membranes and for in vivo applications of biopolymers as drug delivery systems.

  2. Synthesis and physicochemical characterization of a novel amphiphilic polylactic acid-hyperbranched polyglycerol conjugate for protein delivery.

    PubMed

    Gao, Xiujun; Zhang, Xinge; Wu, Zhongming; Zhang, Xuejiao; Wang, Zhen; Li, Chaoxing

    2009-12-03

    Amphiphilic copolymers with polylactic acid (PLA) chains grafted onto hyperbranched polyglycerol (HPG) have been synthesized and characterized. The copolymer nanoparticles with corona and core structure were formed by self-assembly in aqueous solution. The loading capacity and association efficiency were up to 23% and 86%, respectively. Protein release profiles with different copolymer compositions and BSA concentrations all showed a burst effect followed by a continuous release phase. The released BSA from the copolymer nanoparticles remained in its original structure over a period of 4 days, as testified by circular dichroism spectroscopy. Furthermore, cell viability research suggested good biocompatibility of the copolymer nanoparticles, which have a promising potential for protein delivery system.

  3. One-pot synthesis of linear-hyperbranched amphiphilic block copolymers based on polyglycerol derivatives and their micelles.

    PubMed

    Oikawa, Yurie; Lee, Sueun; Kim, Do Hyung; Kang, Dae Hwan; Kim, Byeong-Su; Saito, Kyohei; Sasaki, Shigeko; Oishi, Yoshiyuki; Shibasaki, Yuji

    2013-07-08

    This paper describes the one-pot synthesis of a polyglycidol (PG)-based polymer, poly(ethoxyethyl glycidyl ether) (PEEGE)-b-[hyperbranched polyglycerol (hbPG)-co-PEEGE]x/y, its micelle formulation, and the ability to encapsulate a model therapeutic molecule. Amphiphilic block copolymers were prepared by the sequential addition of ethoxyethyl glycidyl ether (EEGE) to glycidol. The composition of the block copolymers varied from 62:38 to 92:8. Block copolymers with composition x:y≥66:34 were soluble only in organic solvents. Micelles were formulated by injection of deionized water into a tetrahydrofuran block copolymer solution with or without pyrene as a model hydrophobic molecule. The critical micelle concentration was 18.2-30.9 mg/L, and the micelle size was 100-250 nm. The pyrene-containing micelle rapidly collapsed on acidic exposure, allowing conversion of hydrophobic PEEGE to hydrophilic PG, thus, facilitating the release of the encapsulated pyrene. Cytotoxicity data showed high biocompatibility of PG-based block copolymers, suggesting their potential as a drug delivery carrier.

  4. Star-Shaped Amphiphilic Hyperbranched Polyglycerol Conjugated with Dendritic Poly(l-lysine) for the Codelivery of Docetaxel and MMP-9 siRNA in Cancer Therapy.

    PubMed

    Zhou, Xiaoyan; Zheng, Qianqian; Wang, Changyong; Xu, Jiake; Wu, Jian-Ping; Kirk, Thomas Brett; Ma, Dong; Xue, Wei

    2016-05-25

    The drug/gene codelivery is a promising strategy for cancer treatment. Herein, to realize the codelivery of docetaxel and MMP-9 siRNA plasmid efficiently into tumor cells, a star-shaped amphiphilic copolymer consisting of hyperbranched polyglycerol derivative (HPG-C18) and dendritic poly(l-lysine) (PLLD) was synthesized by the click reaction between azido-modified HPG-C18 and propargyl focal point PLLD. The obtained HPG-C18-PLLD could form the nanocomplexes with docetaxel and MMP-9, and the complexes showed good gene delivery ability in vitro by inducing an obvious decrease in MMP-9 protein expression in MCF-7 cells. The apoptosis assay showed that the complex could induce a more significant apoptosis to breast cancer cells than that of docetaxel or MMP-9 used alone. In vivo assay indicated that the codelivery strategy displayed a better effect on tumor inhibition. Moreover, HPG-C18-PLLD displayed lower toxicity as well as better blood compatibility compared to polyethylenimine PEI-25k, which may be the result of that HPG-C18-PLLD showed the comparative MMP-9 delivery ability in vivo compared with PEI-25k even if it showed the slight lower transfection efficiency in vitro. Therefore, HPG-C18-PLLD is a safe and effective carrier for the codelivery of drug/gene, which should be encouraged in tumor therapy.

  5. Hyperbranched polyglycerols at the biointerface

    NASA Astrophysics Data System (ADS)

    Moore, Eli; Thissen, Helmut; Voelcker, Nicolas H.

    2013-08-01

    The control over biointerfacial interactions is the key to a broad range of biomedical applications, ranging from implantable devices to drug delivery and nanomedicine. In many of these applications, coatings are required that reduce or prevent non-specific interactions with the biological environment, while at the same time presenting specific bioactive signals. Whilst surface coatings based on polymers such as poly(ethylene glycol) (PEG) have been used successfully, many limitations persist in regard to the biocompatibility, stability and functionality of state-of-the-art polymer coatings. Most of these limitations are related to the fact that, typically, linear polymers are used with associated limited chemical functionality. Here, we examine the development of hyperbranched polyglycerols (HPGs) as promising candidates for the replacement of traditional linear polymers, such as the chemically analogous PEG, for the control of biointerfacial interactions. HPGs are highly branched globular molecules that exhibit a high valency, allow easy access to a variety of functionalities and can present biologically active signals. In this review, a comprehensive overview is provided with respect to the history, synthetic strategies, modifications and applications of HPGs.

  6. Hyperbranched polyglycerol hydrogels prepared through biomimetic mineralization.

    PubMed

    Postnova, Irina; Silant'ev, Vladimir; Kim, Min Hee; Song, Ga Young; Kim, Il; Ha, Chang-Sik; Shchipunov, Yury

    2013-03-01

    Hyperbranched polyglycerols find increasing usage in biomedicine owing to their excellent biocompatibility like polysaccharides. To prepare hydrogels, they are cross-linked mainly by treating with toxic epoxy reagents. Here we suggest a one-stage nontoxic procedure for the jellification of aqueous solutions that was previously developed for nongelable polysaccharides. It was carried out via the biomimicking mineralization. As the silica precursor, tetrakis(2-hydroxyethyl)orthosilicate containing ethylene glycol residues was employed. It could mineralize directly hydroxyl-containing macromolecules passing a stage of the sol formation. Jellification was performed in one stage in the neutral pH region at the ambient conditions. An organic solvent was not needed because of high hydrophilicity of both the precursor and polyglycerols. An as-prepared hydrogel is ready for applications because of the absence of toxic products. Its structure and mechanical properties were characterized by scanning and transmission electron microscopy as well as dynamic rheology. It was demonstrated that hyperbranched polyglycerols were encased into silica matrix that formed three-dimensional mesoporous network. A study of initial solutions of hyperbranched polyglycerols by the dynamic light scattering revealed their aggregation. This important result was confirmed by direct observations of aggregated macromolecules with high resolution scanning electron microscopy. Entrapped aggregates were also found in the silica matrix.

  7. Biodegradable hyperbranched polyglycerol with ester linkages for drug delivery.

    PubMed

    Hu, Mei; Chen, Mingsheng; Li, Guolin; Pang, Yan; Wang, Dali; Wu, Jieli; Qiu, Feng; Zhu, Xinyuan; Sun, Jian

    2012-11-12

    Biodegradable hyperbranched polyglycerols (dHPGs) were synthesized through oxyanionic initiating hybrid polymerization of glycerol and glycidyl methacrylate. Due to the introduction of ester linkages into the hyperbranched polyglycerol backbone, dHPGs showed good biodegradability and low cytotoxicity. Benefiting from the existence of terminal hydroxyls and methacryloyl groups, both the anticancer drug methotrexate (MTX) and fluorescent probe Rhodamine-123 could be conjugated onto the surface of dHPGs easily. The resultant MTX-conjugated polymers (dHPG-MTXs) exhibited an amphiphilic character, resulting in the formation of micelles in an aqueous solution. The release of MTX from micelles was significantly faster at mildly acidic pH of 5.0 compared to physiological pH of 7.4. dHPG-MTX micelles could be efficiently internalized by cancer cells. MTT assay against cancer cells showed dHPG-MTXs micelles had high anticancer efficacy. On the basis of their good biodegradability and low cytotoxicity, dHPGs provide an opportunity to design excellent drug delivery systems.

  8. Hyperbranched polyglycerols on the nanometer and micrometer scale.

    PubMed

    Steinhilber, Dirk; Seiffert, Sebastian; Heyman, John A; Paulus, Florian; Weitz, David A; Haag, Rainer

    2011-02-01

    We report the preparation of polyglycerol particles on different length scales by extending the size of hyperbranched polyglycerols (3 nm) to nanogels (32 nm) and microgels (140 and 220 μm). We use miniemulsion templating for the preparation of nanogels and microfluidic templating for the preparation of microgels, which we obtain through a free-radical polymerization of hyperbranched polyglycerol decaacrylate and polyethylene glycol-diacrylate. The use of mild polymerization conditions allows yeast cells to be encapsulated into the resultant microgels with cell viabilities of approximately 30%.

  9. Controlled crystallization of CaCO(3) on hyperbranched polyglycerol adsorbed to self-assembled monolayers.

    PubMed

    Balz, Mathias; Barriau, Emilie; Istratov, Vladislav; Frey, Holger; Tremel, Wolfgang

    2005-04-26

    The formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that only account for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, namely, a self-assembled monolayer (SAM), and a soluble component, hyperbranched polyglycerol. The model mineral calcium carbonate displays diverse polymorphism. It could be demonstrated that the phase selection of calcium carbonate is controlled by the cooperative interaction of the SAM and hyperbranched polyglycerol of different molecular weights (M(n) = 500-6000 g/mol) adsorbed to the SAM. Our studies showed that hyperbranched polyglycerol is adsorbed to polar as well as to nonpolar SAMs. This effect can be related to its highly flexible structure and its amphiphilic character. The adsorption of hyperbranched polyglycerol to the SAMs with different surface polarities resulted in the formation of aragonite for alkyl-terminated SAMs and no phase selection for carboxylate-terminated SAMs.

  10. Synthesis and characterization of hyperbranched polyglycerol hydrogels.

    PubMed

    Oudshoorn, Marion H M; Rissmann, Robert; Bouwstra, Joke A; Hennink, Wim E

    2006-11-01

    Hyperbranched polyglycerol (HyPG; M(n) 2000g/mol) was derivatized with glycidyl methacrylate (GMA) in dimethyl sulfoxide using 4-(N,N-dimethylamino)pyridine as a catalyst to obtain methacrylated HyPG (HyPG-MA). The degree of substitution (DS, the percentage of derivatized hydroxyl groups), established by NMR and RP-HPLC, was fully controlled in the range of 0.7-70 by varying the molar ratio of GMA to HyPG in the reaction mixture. This indicates that for e.g. a DS of 28, 9 out of the 32 hydroxyl groups of a HyPG molecule were esterified with methacryloyl groups. Under the selected conditions, the reaction reached an equilibrium within 4h. Furthermore, it was demonstrated that under the applied conditions the reaction was reversible. Hydrogels were obtained by crosslinking HyPG-MA in aqueous solutions using potassium peroxodisulfate (KPS) and N,N,N',N'-tetramethylethylenediamine (TEMED) as initiator and catalyst, respectively. Within 10min, 99% of the methacryloyl groups were polymerized. Rheological analysis showed that the storage modulus of these gels could be tailored by varying the concentration of HyPG-MA in the aqueous solution as well as by the DS. Moreover, the obtained hydrogels have a limited swelling capacity indicating that rather dimensionally stable networks were obtained. As an alternative for radical polymerization with KPS and TEMED, the HyPG-MA could also be crosslinked by photopolymerization using Irgacure 2959 as photoinitiator. A methacrylate conversion of 99% was obtained within 3min of illumination. As for the gels prepared with KPS and TEMED, networks formed by photopolymerization also had a high shear storage modulus and showed limited swelling. Hydrogels based on HyPG have great potential as drug delivery matrices and for tissue engineering purposes.

  11. Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

    PubMed Central

    Krysiak, Stefanie; Wei, Qiang; Rischka, Klaus; Hartwig, Andreas; Haag, Rainer

    2015-01-01

    Summary Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings. PMID:26150898

  12. Functionalization of graphene with hyperbranched polyglycerol for stable aqueous dispersion

    NASA Astrophysics Data System (ADS)

    Cai, Ning; Hou, Dajun; Shen, Liang; Luo, Xiaogang; Xue, Yanan; Yu, Faquan

    2015-07-01

    The application of graphene for some particular fields including biomedical engineering was hindered by its poor aqueous dispersivity and hydrophobic property. In this study, the strategy of the functionalization of graphene with hyperbranched polyglycerol (HPG) by a facile procedure was proposed. By the epoxy ring-opening hyperbranched polymerization of glycidol, graphene surface was grafted with HPG layer with rich hydroxyl groups. The content of polyglycerol on HPG functionalized graphene (HPG-G) was determined to be 55%. The results of fourier transform infrared (FTIR), X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and UV-Vis demonstrated that HPG was successfully grafted onto graphene sheets (GSs), and the aromatic and crystalline structure of graphene was maintained after HPG functionalization. The obtained HPG-G composites possess high hydrophilicity and can be dispersed well in water. Furthermore, no discernable precipitation was found in HPG-G aqueous solution even after three months of storage.

  13. In vitro biological evaluation of high molecular weight hyperbranched polyglycerols.

    PubMed

    Kainthan, Rajesh Kumar; Hester, Samuel R; Levin, Elena; Devine, Dana V; Brooks, Donald Elliott

    2007-11-01

    Low molecular weight hyperbranched polyglycerols are highly water soluble and biocompatible polyether polyols, which can be synthesized in a controlled manner with narrow polydispersity. Recently we reported the synthesis and characterization of very high molecular weight (Mn up to 700,000) and narrowly polydispersed polyglycerols which could be potentially used as alternatives to high generation dendrimers which are difficult to make. A detailed biocompatibility testing of these polymers conducted in vitro is reported here. The in vitro studies include hemocompatibility testing for effects on coagulation (prothrombin time (PT), activated partial thromboplastin time (APTT), plasma recalcification time (PRT), thrombelastograph parameters (TEG)), complement activation, platelet activation, red blood cell aggregation and cytotoxicity. Results from these studies show that these high molecular weight polyglycerols are highly biocompatible and are potential candidates for various applications in nanobiotechnology and in nanomedicine. Moreover these polymers are thermally and oxidatively stable.

  14. Hyperbranched amphiphilic polymer with folate mediated targeting property.

    PubMed

    Zhang, Lei; Hu, Chao-Hua; Cheng, Si-Xue; Zhuo, Ren-Xi

    2010-09-01

    Hyperbranched amphiphilic polymer PG6-PLA-PEG was synthesized through grafting hydrophobic poly(D,L-lactide) (PLA) segments and hydrophilic poly(ethylene glycol) (PEG) blocks to hydrophilic hyperbranched polyglycerol core (PG6), subsequently. To achieve cell targeting property, folic acid (FA) was further incorporated to the hyperbranched polymer to obtain PG6-PLA-PEG-FA. The polymers were characterized by (1)H NMR, UV-vis spectroscopy and combined size-exclusion chromatography and multiangle laser light scattering (SEC-MALLS) analysis. Due to the amphiphilicity, PG6-PLA-PEG and PG6-PLA-PEG-FA could self-assemble to form nanoparticles in aqueous solutions. Antineoplastic drug, paclitaxel (PTX), was encapsulated into the nanoparticles. The nanoparticles were observed by transmission electron microscopy (TEM). The targeting property of PG6-PLA-PEG-FA was evaluated in vitro. The results showed that the PTX loaded PG6-PLA-PEG-FA nanoparticles exhibited enhanced inhibition on folate receptor positive tumor cells due to the folate mediated targeting.

  15. Patterning and biofunctionalization of antifouling hyperbranched polyglycerol coatings.

    PubMed

    Moore, Eli; Delalat, Bahman; Vasani, Roshan; Thissen, Helmut; Voelcker, Nicolas H

    2014-07-14

    We demonstrate the patterned biofunctionalization of antifouling hyperbranched polyglycerol (HPG) coatings on silicon and glass substrates. The ultralow fouling HPG coatings afforded straightforward chemical handles for rapid bioconjugation of amine containing biomolecular species. This was achieved by sodium periodate oxidation of terminal HPG diols to yield reactive aldehyde groups. Patterned microprinting of sodium periodate and cell adhesion mediating cyclic peptides containing the RGD sequence resulted in an array of covalently immobilized bioactive signals. When incubated with mouse fibroblasts, the HPG background resisted cell attachment whereas high density cell attachment was observed on the peptide spots, resulting in high-contrast cell microarrays. We also demonstrated single-step, in situ functionalization of the HPG coatings by printing periodate and peptide concurrently. Our results demonstrate the effectiveness of antifouling and functionalized HPG graft polymer coatings and establish their use in microarray applications for the first time.

  16. Light-responsive micelles of spiropyran initiated hyperbranched polyglycerol for smart drug delivery.

    PubMed

    Son, Suhyun; Shin, Eeseul; Kim, Byeong-Su

    2014-02-10

    Light-responsive polymeric micelles have emerged as site-specific and time-controlled systems for advanced drug delivery. Spiropyran (SP), a well-known photochromic molecule, was used to initiate the ring-opening multibranching polymerization of glycidol to afford a series of hyperbranched polyglycerols (SP-hb-PG). The micelle assembly and disassembly were induced by an external light source owing to the reversible photoisomerization of hydrophobic SP to hydrophilic merocyanine (MC). Transmission electron microscopy, atomic force microscopy, UV/vis spectroscopy, and dynamic light scattering demonstrated the successful assembly and disassembly of SP-hb-PG micelles. In addition, the critical micelle concentration (CMC) was determined through the fluorescence analysis of pyrene to confirm the amphiphilicity of respective SP-hb-PGn (n = 15, 29, and 36) micelles, with CMC values ranging from 13 to 20 mg/L, which is correlated to the length of the polar polyglycerol backbone. Moreover, the superior biocompatibility of the prepared SP-hb-PG was evaluated using WI-38 cells and HeLa cells, suggesting the prospective applicability of the micelles in smart drug delivery systems.

  17. Hydrophobically derivatized hyperbranched polyglycerol as a human serum albumin substitute.

    PubMed

    Kainthan, Rajesh K; Janzen, Johan; Kizhakkedathu, Jayachandran N; Devine, Dana V; Brooks, Donald E

    2008-04-01

    There is a huge clinical demand for Human Serum Albumin (HSA), with a world market of approximately $1.5B/year. Concern over prion and viral transmission in the blood supply has led to a need for safer substitutes and offers the opportunity for development of materials with enhanced properties over the presently available plasma expanders. We report here the synthesis and testing of a new synthetic plasma expander that can replace not only the osmotic and volume expansion properties of HSA but, uniquely, its binding and transport properties. We have synthesized several hyperbranched polyglycerols derivatized with hydrophobic groups and short poly(ethylene glycol) (PEG) chains. The hydrophobic groups provide regions for binding fatty acids and other hydrophobic materials while PEG imparts the necessary protection from host defense systems and enhances circulation longevity. These polymers, being hyperbranched, have only a small effect on plasma viscosity. We have shown in vitro that our materials bind 2-3 moles palmitic acid per mole, do not activate the platelet, coagulation or complement systems and do not cause red cell aggregation. In mice these materials are non-toxic with circulation half-lives as high as 34h, controllable by manipulating the molecular weight and the degree of PEG derivatization.

  18. Controllable Nonspecific Protein Adsorption by Charged Hyperbranched Polyglycerol Thin Films.

    PubMed

    Yu, Yaming; Frey, Holger

    2015-12-08

    Antifouling thin films derived from charged hyperbranched polyglycerol (hbPG) layers were fabricated and evaluated. The anionic hbPG (a-hbPG) monolayers and cationic hbPG/anionic hbPG (c/a-hbPG) bilayers were adsorbed on the underlying self-assembled monolayers (SAMs) of cysteamine and 3-mercaptopropionic acid (3-MPA) by electrostatic interaction, respectively, and their procession was monitored by surface plasmon resonance spectroscopy (SPR). The adsorption of bovine serum albumin (BSA) and fibrinogen on the premade a-hbPG and c/a-hbPG thin films was measured and the capability of these thin films to resist nonspecific protein adsorption was evaluated by SPR as well. It is observed that the c/a-hbPG bilayer films possessed good antifouling properties. With c/a-hbPG bilayers consisting of higher molecular weight a-hbPG, the adsorption of BSA and fibrinogen were as low as 0.015 ng/mm(-2) and 0.0076 ng/mm(-2), respectively, comparable to the traditionally ultralow antifouling surfaces (<0.05 ng/mm(-2) of nonspecific protein adsorption). This work proved that the charged hbPG thin films can strongly reduce the nonspecific protein adsorption and have the promise for the antifouling coatings with improved performance.

  19. One-pot synthesis of doxorubicin-loaded multiresponsive nanogels based on hyperbranched polyglycerol.

    PubMed

    Sousa-Herves, Ana; Wedepohl, Stefanie; Calderón, Marcelo

    2015-03-28

    Doxorubicin-loaded nanogels with multiresponsive properties are prepared using hyperbranched polyglycerol as a biocompatible scaffold. The nanogels are synthesized in a single step combining free-radical polymerization and a mild nanoprecipitation technique. The nanogels respond to different biological stimuli such as low pH and reductive environments, resulting in a more efficient cell proliferation inhibition in A549 cells.

  20. Hyperbranched polyglycerol as a colloid in cold organ preservation solutions.

    PubMed

    Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E; Nguan, Christopher Y C; Kizhakkedathu, Jayachandran N; Du, Caigan

    2015-01-01

    Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in

  1. Hyperbranched Polyglycerol as a Colloid in Cold Organ Preservation Solutions

    PubMed Central

    Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E.; Nguan, Christopher Y. C.; Kizhakkedathu, Jayachandran N.; Du, Caigan

    2015-01-01

    Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in

  2. Hyperbranched polyglycerol electrospun nanofibers for wound dressing applications.

    PubMed

    Vargas, E A Torres; do Vale Baracho, N C; de Brito, J; de Queiroz, A A A

    2010-03-01

    This study reports on the performance of electrospun hyperbranched polyglycerol nanofibers capable of providing an active agent delivery for wound dressing applications. The aim of this work was to prepare electrospun HPGL nanofibers containing Calendula officinalis as a wound-healing and anti-inflammatory agent. The morphology of the electrospun HPGL-C. officinalis nanofibers was analyzed using a scanning electron microscope. The results showed that the diameters of the fibers were in nanoscales. The release of C. officinalis from the electrospun HPGL fibers was determined by HPLC at a physiological temperature (37 degrees C). Rapid release of the C. officinalis from the electrospun HPGL-C. officinalis nanofibers was exhibited as result of the high swelling ability as well as the high porosity of the electrospun HPGL-C. officinalis membranes. The degree of swelling, and the mechanical and biocompatible properties of the electrospun HPGL fibers were determined. The results showed that, in physiological conditions, the water absorption into the HPGL electrospun fibers slowed down, governed by the rate at which the electrospun HPGL-C. officinalis membranes interacted with the physiological fluid. The rate of release of C. officinalis seemed to depend on the C. officinalis content in the HPGL nanofibers. From the elastic modulus, it could be seen that elastic electrospun HPGL fibers were obtained with increments of C. officinalis content in the HPGL-C. officinalis membranes. The results of in vivo experiments in rats suggested that HPGL-C. officinalis might be an interesting bioactive wound dressing material for clinical applications.

  3. Perfluoroalkyl-Functionalized Hyperbranched Polyglycerol as Pore Forming Agents and Supramolecular Hosts in Polymer Microspheres

    PubMed Central

    Wagner, Olaf; Zieringer, Maximilian; Duncanson, Wynter J.; Weitz, David A.; Haag, Rainer

    2015-01-01

    Perfluoroalkyl-functionalized, hyperbranched polyglycerols that produce stable microbubbles are integrated into a microfluidic emulsion to create porous microspheres. In a previously-presented work a dendrimer with a perfluorinated shell was used. By replacing this dendrimer core with a hyperbranched core and evaluating different core sizes and degrees of fluorinated shell functionalization, we optimized the process to a more convenient synthesis and higher porosities. The new hyperbranched polyglycerol porogens produced more pores and can be used to prepare microspheres with porosity up to 12% (v/v). The presented preparation forms pores with a perfluoroalkyl-functionalized surface that enables the resulting microspheres to act as supramolecular host systems. The microspheres can incorporate gases into the pores and actives in the polymer matrix, while the perfluoroalkylated pore surface can be used to immobilize perfluoro-tagged molecules onto the pores by fluorous-fluorous interaction. PMID:26343631

  4. Perfluoroalkyl-Functionalized Hyperbranched Polyglycerol as Pore Forming Agents and Supramolecular Hosts in Polymer Microspheres.

    PubMed

    Wagner, Olaf; Zieringer, Maximilian; Duncanson, Wynter J; Weitz, David A; Haag, Rainer

    2015-08-26

    Perfluoroalkyl-functionalized, hyperbranched polyglycerols that produce stable microbubbles are integrated into a microfluidic emulsion to create porous microspheres. In a previously-presented work a dendrimer with a perfluorinated shell was used. By replacing this dendrimer core with a hyperbranched core and evaluating different core sizes and degrees of fluorinated shell functionalization, we optimized the process to a more convenient synthesis and higher porosities. The new hyperbranched polyglycerol porogens produced more pores and can be used to prepare microspheres with porosity up to 12% (v/v). The presented preparation forms pores with a perfluoroalkyl-functionalized surface that enables the resulting microspheres to act as supramolecular host systems. The microspheres can incorporate gases into the pores and actives in the polymer matrix, while the perfluoroalkylated pore surface can be used to immobilize perfluoro-tagged molecules onto the pores by fluorous-fluorous interaction.

  5. Secondary and primary relaxations in hyperbranched polyglycerol: A comparative study in the frequency and time domains

    NASA Astrophysics Data System (ADS)

    Garcia-Bernabé, Abel; Dominguez-Espinosa, Gustavo; Diaz-Calleja, Ricardo; Riande, Evaristo; Haag, Rainer

    2007-09-01

    The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency β and γ processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the β absorption is swallowed by the α in the glass-liquid transition, the γ absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the α absorption vanishes appearing the αγ relaxation. Two characteristics of α absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the αγ process. Williams' ansatz seems to hold for these topologically complex macromolecules.

  6. Secondary and primary relaxations in hyperbranched polyglycerol: a comparative study in the frequency and time domains.

    PubMed

    Garcia-Bernabé, Abel; Dominguez-Espinosa, Gustavo; Diaz-Calleja, Ricardo; Riande, Evaristo; Haag, Rainer

    2007-09-28

    The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency beta and gamma processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the beta absorption is swallowed by the alpha in the glass-liquid transition, the gamma absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the alpha absorption vanishes appearing the alphagamma relaxation. Two characteristics of alpha absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the alphagamma process. Williams' ansatz seems to hold for these topologically complex macromolecules.

  7. Succinate Functionalization of Hyperbranched Polyglycerol-Coated Magnetic Nanoparticles as a Draw Solute During Forward Osmosis.

    PubMed

    Yang, Hee-Man; Choi, Hye Min; Jang, Sung-Chan; Han, Myeong Jin; Seo, Bum-Kyoung; Moon, Jei-Kwon; Lee, Kune-Woo

    2015-10-01

    Hyperbranched polyglycerol-coated magnetic nanoparticles (SHPG-MNPs) were functionalized with succinate groups to form a draw solute for use in a forward osmosis (FO). After the one-step synthesis of hyperbranched polyglycerol-coated magnetic nanoparticles (HPG-MNPs), the polyglycerol groups on the surfaces of the HPG-MNPs were functionalized with succinic anhydride moieties. The resulting SHPG-MNPs showed no change of size and magnetic property compared with HPG-MNPs and displayed excellent dispersibility in water up to the concentration of 400 g/L. SHPG-MNPs solution showed higher osmotic pressure than that of HPG-MNPs solution due to the presence of surface carboxyl groups in SHPG-MNPs and could draw water from a feed solution across an FO membrane without any reverse draw solute leakage during FO process. Moreover, the water flux remained nearly constant over several SHPG-MNP darw solute regeneration cycles applied to the ultrafiltration (UF) process. The SHPG-MNPs demonstrate strong potential for use as a draw solute in FO processes.

  8. Enzymatically cross-linked hyperbranched polyglycerol hydrogels as scaffolds for living cells.

    PubMed

    Wu, Changzhu; Strehmel, Christine; Achazi, Katharina; Chiappisi, Leonardo; Dernedde, Jens; Lensen, Marga C; Gradzielski, Michael; Ansorge-Schumacher, Marion B; Haag, Rainer

    2014-11-10

    Although several strategies are now available to enzymatically cross-link linear polymers to hydrogels for biomedical use, little progress has been reported on the use of dendritic polymers for the same purpose. Herein, we demonstrate that horseradish peroxidase (HRP) successfully catalyzes the oxidative cross-linking of a hyperbranched polyglycerol (hPG) functionalized with phenol groups to hydrogels. The tunable cross-linking results in adjustable hydrogel properties. Because the obtained materials are cytocompatible, they have great potential for encapsulating living cells for regenerative therapy. The gel formation can be triggered by glucose and controlled well under various environmental conditions.

  9. Structurally Enhanced Self-Plasticization of Poly(vinyl chloride) via Click Grafting of Hyperbranched Polyglycerol.

    PubMed

    Lee, Kyu Won; Chung, Jae Woo; Kwak, Seung-Yeop

    2016-12-01

    A highly self-plasticized poly(vinyl chloride) (PVC) is demonstrated for the first time via click grafting of hyperbranched polyglycerol (HPG). The plasticizing effect of the grafted HPG on PVC is systematically investigated by various analytical methods. The amorphous and bulky dendritic structure of HPG efficiently increases the free volume of the grafted PVC, which leads to a remarkably lower glass transition temperature comparable to that of the conventional plasticized PVC. Viscoelastic analysis reveals that HPG considerably improves the softness of the grafted PVC at room temperature and promotes the segmental motion in the system. The HPG-grafted PVC films exhibit an exceptional stretchability unlike the mixture of PVC and HPG because the covalent attachment of HPG to PVC allows it to maintain its homogeneous and well-organized architecture under tensile stretching. The work provides valuable insights into the design of highly flexible and stretchable polymeric materials by means of introducing hyperbranched side chains.

  10. Xylanase Immobilized on Novel Multifunctional Hyperbranched Polyglycerol-Grafted Magnetic Nanoparticles: An Efficient and Robust Biocatalyst.

    PubMed

    Landarani-Isfahani, Amir; Taheri-Kafrani, Asghar; Amini, Mina; Mirkhani, Valiollah; Moghadam, Majid; Soozanipour, Asieh; Razmjou, Amir

    2015-08-25

    Although several strategies are now available for immobilization of enzymes to magnetic nanoparticles for bioapplications, little progresses have been reported on the use of dendritic or hyperbranched polymers for the same purpose. Herein, we demonstrated synthesis of magnetic nanoparticles supported hyperbranched polyglycerol (MNP/HPG) and a derivative conjugated with citric acid (MNP/HPG-CA) as unique and convenient nanoplatforms for immobilization of enzymes. Then, an important industrial enzyme, xylanase, was immobilized on the nanocarriers to produce robust biocatalysts. A variety of analytical tools were used to study the morphological, structural, and chemical properties of the biocatalysts. Additionally, the results of biocatalyst systems exhibited the substantial improvement of reactivity, reusability, and stability of xylanase due to this strategy, which might confer them a wider range of applications.

  11. Synthesis and supramolecular association of immobilized NCN-pincer platinum(II) complexes on hyperbranched polyglycerol supports.

    PubMed

    Stiriba, Salah-Eddine; Slagt, Martijn Q; Kautz, Holger; Klein Gebbink, Robertus J M; Thomann, Ralf; Frey, Holger; van Koten, Gerard

    2004-03-05

    Pertosylation of hyperbranched polyglycerol (M(n)=2000; M(w)/M(n)=1.3) followed by partial displacement of the tosyl groups with carboxylic acid functionalized NCN-pincer platinum(II) complexes [PtI-2,6-(NMe(2)CH(2))(2)C(6)H(2)-4-COOH], resulted in covalent attachment of the NCN-pincer complexes to the polyglycerol. These functionalized hyperbranched macromolecules have been characterized by (1)H, (13)C, and (195)Pt NMR, UV-visible, and IR spectroscopy. The presence of Pt and I atoms renders them directly visible by transmission electron microscopy (TEM) without staining procedures, which offers images of associated hyperbranched macromolecules. TEM micrographs show disk-shaped structures with a small size-distribution (15-20 nm), and characteristic core-shell ring structures. The thickness of the corona observed in TEM could be correlated with the substitution degree with pincer platinum moieties.

  12. Hyperbranched polyglycerols: from the controlled synthesis of biocompatible polyether polyols to multipurpose applications.

    PubMed

    Wilms, Daniel; Stiriba, Salah-Eddine; Frey, Holger

    2010-01-19

    Dendritic macromolecules with random branch-on-branch topology, termed hyperbranched polymers in the late 1980s, have a decided advantage over symmetrical dendrimers by virtue of typically being accessible in a one-step synthesis. Saving this synthetic effort once had an unfortunate consequence, though: hyperbranching polymerization used to result in a broad distribution of molecular weights (that is, very high polydispersities, often M(w)/M(n) > 5). By contrast, a typical dendrimer synthesis yields a single molecule (in other words, M(w)/M(n) = 1.0), albeit by a labor-intensive, multistep process. But 10 years ago, Sunder and colleagues reported the controlled synthesis of well-defined hyperbranched polyglycerol (PG) via ring-opening multibranching polymerization (ROMBP) of glycidol. Since then, hyperbranched and polyfunctional polyethers with controlled molar mass and low polydispersities (M(w)/M(n) = 1.2-1.9) have been prepared, through various monomer addition protocols, by ROMBP. In this Account, we review the progress in the preparation and application of these uniquely versatile polyether polyols over the past decade. Hyperbranched PGs combine several remarkable features, including a highly flexible aliphatic polyether backbone, multiple hydrophilic groups, and excellent biocompatibility. Within the past decade, intense efforts have been directed at the optimization of synthetic procedures affording PG homo- and copolymers with different molecular weight characteristics and topology. Fundamental parameters of hyperbranched polymers include molar mass, polydispersity, degree of branching, and end-group functionality. Selected approaches for optimizing and tailoring these characteristics are presented and classified with respect to their application potential. Specific functionalization in the core and at the periphery of hyperbranched PG has been pursued to meet the growing demand for novel specialty materials in academia and industry. A variety of

  13. Molecular dynamics simulation studies of hyperbranched polyglycerols and their encapsulation behaviors of small drug molecules.

    PubMed

    Yu, Chunyang; Ma, Li; Li, Ke; Li, Shanlong; Liu, Yannan; Zhou, Yongfeng; Yan, Deyue

    2016-08-10

    Hyperbranched polyglycerol (HPG) is one of the most important hyperbranched polymers (HBPs) due to its interesting properties and applications. Herein, the conformation of HPGs depending on the degree of polymerization (DP) and the degree of branching (DB) is investigated explicitly by molecular dynamics simulations. This study shows that the radius of gyration (Rg) scales as Rg ∼ DP(1/3), which is in close agreement with the result of the SANS experiment. For HPGs with the same DP, the radius of gyration, asphericities and solvent accessible surface area all monotonically decrease with the increase of DB; while for HPGs with the same DB, the molecular anisotropy decreases with the increase of DP. The radial density investigation discloses that the cavities are randomly distributed in the interior of the HPG core to support the "dendritic box effect", which can be used to encapsulate the guest molecules. Interestingly, the terminal groups of HPGs with a high Wiener index (WI) are more favorable to fold back into the interiors than those with the low WI when in water. For the hyperbranched multi-arm copolymer with a HPG core and many polyethylene glycol (PEG) arms, drug encapsulation studies show that the PEG caps can not only effectively prevent tamoxifen from leaving the HPG core, but also encapsulate tamoxifen inside the PEG chains. These simulation results have provided more details for understanding the structure-property relationships of HPGs in water.

  14. Hyperbranched polyglycerol-based lipids via oxyanionic polymerization: toward multifunctional stealth liposomes.

    PubMed

    Hofmann, Anna Maria; Wurm, Frederik; Hühn, Eva; Nawroth, Thomas; Langguth, Peter; Frey, Holger

    2010-03-08

    We describe the synthesis of linear-hyperbranched lipids for liposome preparation based on linear poly(ethylene glycol) (PEG) and hyperbranched polyglycerol (PG). Molecular weights were adjusted to values around 3000 g/mol with varying degrees of polymerization of the linear and the branched segments in analogy to PEG-based stealth lipids; polydispersities were generally low and below 1.3. The hydrophobic anchors were introduced into the lipid structures as initiators for the anionic polymerization of ethylene oxide and are either based on cholesterol or on different aliphatic glyceryl ethers. Complete incorporation of the apolar initiators was evidenced by MALDI-ToF analysis at all stages of the reaction. The linear-hyperbranched polyether lipid is incorporated as the polyfunctional shell in liposome formulations together with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The resulting liposomes were subsequently characterized via dynamic light scattering (DLS) and small angle neutron scattering (SANS) as well as transmission electron microscopy (TEM), demonstrating the formation of unilamellar liposomes in the size range of 40 to 50 nm.

  15. Highly colloidally stable hyperbranched polyglycerol grafted red fluorescent silicon nanoparticle as bioimaging probe.

    PubMed

    Das, Pradip; Jana, Nikhil R

    2014-03-26

    Here we report a surface modification approach for fluorescent silicon nanoparticle that transforms hydrophobic nanoparticle into water-soluble nanoparticle of high colloidal stability. The approach involves ring-opening polymerization of glycidol at the hydroxyl-terminated nanoparticle surface that results in a hyperbranched polyglycerol grafted silicon nanoparticle (Si-HPG). The resultant Si-HPG has 25 nm hydrodynamic diameter, low surface charge, and broad emission in the range of 450-700 nm with a fluorescence quantum yield of 6-9%. The Si-HPG has been transformed into cyclic RGD peptide functionalized nanoprobe using the conventional bioconjugation chemistry and used for specific targeting to αvβ3 integrin overexpressed cervical cancer cells and glioblastoma cells. Result shows that a silicon nanoparticle-based red fluorescent nanoprobe can be developed for in vitro/in vivo bioimaging applications.

  16. Controlled release of DNA from photoresponsive hyperbranched polyglycerols with oligoamine shells.

    PubMed

    Fischer, Wiebke; Quadir, Mohiuddin A; Barnard, Anna; Smith, David K; Haag, Rainer

    2011-12-08

    Two photo-responsive core/shell nanoparticles based on hyperbranched polyglycerol (hPG) are synthesized for controlled release of DNA. The shell is composed either of bis-(3-aminopropyl)methylamine (AMPA) or pentaethylenehexamine (PEHA) derivatives and is attached to the hPG core with a photo-responsive o-nitrobenzyl linker. Ethidium bromide displacement assay, gel electrophoresis, DLS, and ζ-potential measurements are performed with these nanoparticles. Photo-responsive changes within the carrier scaffold are investigated by irradiating the polymer solution with 350 nm monochromatic light. Fully covered APMA-shelled carriers are found to complex the DNA at an N/P ratio of 10 with an average size ranging from 54 to 78 nm depending on the degree of functionalization of the core.

  17. A hydrotropic β-cyclodextrin grafted hyperbranched polyglycerol co-polymer for hydrophobic drug delivery.

    PubMed

    Zhang, Xuejiao; Zhang, Xinge; Wu, Zhongming; Gao, Xiujun; Cheng, Cui; Wang, Zhen; Li, Chaoxing

    2011-02-01

    The development of successful formulations for poorly water soluble drugs remains a longstanding, critical, and challenging issue in cancer therapy. A β-cyclodextrin (CD) functionalized hyperbranched polyglycerol (HPG) has been prepared as a potential water insoluble drug carrier. The HPG-g-CD molecules could self-assemble into multimolecular spherical micelles in water, the size of which ranged from 200 to 300 nm, with good dispersity. A high loading capacity and high encapsulation efficiency of paclitaxel, as a model, were obtained. The release profiles of different co-polymer compositions showed a burst release followed by continuous extended release. Furthermore, MTT analysis showed that HPG-g-CD had good biocompatibility, indicating that HPG-g-CD may be considered a promising hydrophobic drug delivery system.

  18. Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols.

    PubMed

    Alizadeh Noghani, M; Brooks, D E

    2016-03-07

    Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.

  19. Negatively charged hyperbranched polyglycerol grafted membranes for osmotic power generation from municipal wastewater.

    PubMed

    Li, Xue; Cai, Tao; Chen, Chunyan; Chung, Tai-Shung

    2016-02-01

    Osmotic power holds great promise as a clean, sustainable and largely unexploited energy resource. Recent membrane development for pressure-retarded osmosis (PRO) is making the osmotic power generation more and more realistic. However, severe performance declines have been observed because the porous layer of PRO membranes is fouled by the feed stream. To overcome it, a negatively charged antifouling PRO hollow fiber membrane has been designed and studied in this work. An antifouling polymer, derived from hyperbranched polyglycerol and functionalized by α-lipoic acid and succinic anhydride, was synthesized and grafted onto the polydopamine (PDA) modified poly(ether sulfone) (PES) hollow fiber membranes. In comparison to unmodified membranes, the charged hyperbranched polyglycerol (CHPG) grafted membrane is much less affected by organic deposition, such as bovine serum albumin (BSA) adsorption, and highly resistant to microbial growths, demonstrated by Escherichia coli adhesion and Staphylococcus aureus attachment. CHPG-g-TFC was also examined in PRO tests using a concentrated wastewater as the feed. Comparing to the plain PES-TFC and non-charged HPG-g-TFC, the newly developed membrane exhibits not only the smallest decline in water flux but also the highest recovery rate. When using 0.81 M NaCl and wastewater as the feed pair in PRO tests at 15 bar, the average power density remains at 5.6 W/m(2) in comparison to an average value of 3.6 W/m(2) for unmodified membranes after four PRO runs. In summary, osmotic power generation may be sustained by properly designing and anchoring the functional polymers to PRO membranes.

  20. Multivalent presentation of mannose on hyperbranched polyglycerol and their interaction with concanavalin A lectin.

    PubMed

    Papp, Ilona; Dernedde, Jens; Enders, Sven; Riese, Sebastian B; Shiao, Tze Chieh; Roy, René; Haag, Rainer

    2011-05-02

    We describe the synthesis of multivalent mannose derivatives by using hyperbranched polyglycerols (hPG) as a scaffold with different linker structures. Grafting of protected mannose (Man) units is achieved by using Cu(I) -catalyzed Huisgen click chemistry with either an anomeric azide or propargyl ether onto complementarily functionalized alkyne or azido polymer surfaces. NMR spectroscopy, dynamic light scattering (DLS), IR spectroscopy, size-exclusion chromatography (SEC), and elemental analysis have been used to characterize the hPG-Man compounds. The surface availability and bioactivity of Man-modified polymers were evaluated by using a competitive surface plasmon resonance (SPR)-based binding assay by interactions of the glycopolymers with concanavalin A (Con A), a lectin that binds mannose containing molecules. The results indicated that the novel glycoarchitectures presented in this work are efficient inhibitors of Con A-mannose recognition and resulted in inhibitor concentrations (mean IC(50)) from the micro- to the nanomolar range, whereas the corresponding monovalent mannoside (methyl-Man) requires millimolar concentrations. The results provide an interesting structure-activity relationship for libraries of materials that differ in the linkage of the sugar moiety presented on a biocompatible polyglycerol scaffold.

  1. Antigens protected functional red blood cells by the membrane grafting of compact hyperbranched polyglycerols.

    PubMed

    Chapanian, Rafi; Constantinescu, Iren; Brooks, Donald E; Scott, Mark D; Kizhakkedathu, Jayachandran

    2013-01-02

    Red blood cell (RBC) transfusion is vital for the treatment of a number of acute and chronic medical problems such as thalassemia major and sickle cell anemia. Due to the presence of multitude of antigens on the RBC surface (~308 known antigens), patients in the chronic blood transfusion therapy develop alloantibodies due to the miss match of minor antigens on transfused RBCs. Grafting of hydrophilic polymers such as polyethylene glycol (PEG) and hyperbranched polyglycerol (HPG) forms an exclusion layer on RBC membrane that prevents the interaction of antibodies with surface antigens without affecting the passage of small molecules such as oxygen, glucose, and ions. At present no method is available for the generation of universal red blood donor cells in part because of the daunting challenge presented by the presence of large number of antigens (protein and carbohydrate based) on the RBC surface and the development of such methods will significantly improve transfusion safety, and dramatically improve the availability and use of RBCs. In this report, the experiments that are used to develop antigen protected functional RBCs by the membrane grafting of HPG and their characterization are presented. HPGs are highly biocompatible compact polymers, and are expected to be located within the cell glycocalyx that surrounds the lipid membrane and mask RBC surface antigens.

  2. Multivalent anchored and crosslinked hyperbranched polyglycerol monolayers as antifouling coating for titanium oxide surfaces.

    PubMed

    Wei, Qiang; Krysiak, Stefanie; Achazi, Katharina; Becherer, Tobias; Noeske, Paul-Ludwig Michael; Paulus, Florian; Liebe, Hendrik; Grunwald, Ingo; Dernedde, Jens; Hartwig, Andreas; Hugel, Thorsten; Haag, Rainer

    2014-10-01

    A set of new catecholic monolayer coatings was developed to improve the antifouling performance of TiO2 surfaces. To solve the problem of the weak charge-transfer interaction between a single catechol anchor and TiO2, multiple catechol groups were combined with hyperbranched polyglycerol (hPG) which is a distinct dendritic scaffold that exposes its multivalent anchor groups on the surface. Thus, multivalent catecholic hPGs can be easily prepared for surface modification. The immobilization of the compounds was monitored by quartz crystal microbalance with dissipation monitoring. Surface properties of the coatings were analyzed by water contact angle, X-ray photoelectron spectroscopy, and atomic force microscopy. The antifouling ability and stability were investigated by protein adsorption and cell adhesion. By increasing the number of catechol groups on the hPG scaffold, the stability and surface coverage could be significantly enhanced. Moreover, the inner-layer crosslinking of the coatings by grafting and initiating vinyl groups clearly improved their long-term stability. As a result, hPG with a catecholic functional degree of 10% (hPG-Cat10) and hPG with both catecholic and vinylic functional degree of 5% (hPG-Cat5-V5) were identified as the best catecholic hPGs to prepare bioinert and stable monolayer coatings on TiO2.

  3. The Effect of Hyperbranched Polyglycerol Coatings on Drug Delivery Using Degradable Polymer Nanoparticles

    PubMed Central

    Deng, Yang; Saucier-Sawyer, Jennifer; Hoimes, Christopher; Zhang, Junwei; Seo, Young-Eun; Andrejecsk, Jillian W.; Saltzman, W. Mark

    2014-01-01

    A key attribute for nanoparticles (NPs) that are used in medicine is the ability to avoid rapid uptake by phagocytic cells in the liver and other tissues. Poly(ethylene glycol) (PEG) coatings has been the gold standard in this regard for several decades. Here, we examined hyperbranched polyglycerols (HPG) as an alternate coating on NPs. In earlier work, HPG was modified with amines and subsequently conjugated to poly(lactic acid) (PLA), but that approach compromised the ability of HPG to resist non-specific adsorptions of biomolecules. Instead, we synthesized a copolymer of PLA-HPG by a one-step esterification. NPs were produced from a single emulsion using PLA-HPG: fluorescent dye or the anti-tumor agent camptothecin (CPT) were encapsulated at high efficiency in the NPs. PLA-HPG NPs were quantitatively compared to PLA-PEG NPs, produced using approaches that have been extensively optimized for drug delivery in humans. Despite being similar in size, drug release profile and in vitro cytotoxicity, the PLA-HPG NPs showed significantly longer blood circulation and significantly less liver accumulation than PLA-PEG. CPT-loaded PLA-HPG NPs showed higher stability in suspension and better therapeutic effectiveness against tumors in vivo than CPT-loaded PLA-PEG NPs. Our results suggest that HPG is superior to PEG as a surface coating for NPs in drug delivery. PMID:24816286

  4. Reversible hemostatic properties of sulfabetaine/quaternary ammonium modified hyperbranched polyglycerol.

    PubMed

    Wen, Jiying; Weinhart, Marie; Lai, Benjamin; Kizhakkedathu, Jayachandran; Brooks, Donald E

    2016-04-01

    A library of hyperbranched polyglycerols (HPGs) functionalized with different mole fractions of zwitterionic sulfabetaine and cationic quaternary ammonium ligands was synthesized and characterized. A post-polymerization method was employed that utilized double bond moieties on the dendritic HPG for the coupling of thiol-terminated ligands via UV initiated thiol-ene "click" chemistry. The proportions of different ligands were precisely controlled by varying the ligand concentration during the irradiation process. The effect of the polymer library on hemostasis was investigated using whole human blood. It was found that polymer with ≥40% of alkenes converted to positive charges and the remainder to sulfabetaines caused hemagglutination at ≥1 mg/mL, without causing red blood cell lysis. The quaternary ammonium groups can interact with the negative charged sites on the membranes of erythrocytes, which provides the bioadhesion. The zwitterionic sulfabetaine evidently provides a hydration layer to partially mask the adverse effects that are likely to be caused by cationic moieties. The polymer was also found able to enhance platelet aggregation and activation in a concentration and positive charge density-dependent manner, which would contribute to initiating hemostasis. In a variety of other assays the material was found to be largely biocompatible. The polymer-induced hemostasis is obtained by a process independent of the normal blood clotting cascade but dependent on red blood cell agglutination, where the polymers promote hemostasis by linking erythrocytes together to form a lattice to entrap the cells.

  5. PEI grafted hyperbranched polymers with polyglycerol as a core for gene delivery.

    PubMed

    Zhang, Lei; Hu, Chao-Hua; Cheng, Si-Xue; Zhuo, Ren-Xi

    2010-04-01

    Hyperbranched polymers, PG6-PEI25k and PG6-PEI800, were synthesized through grafting branched polyethylenimines (PEIs) with molecular weights of 25 kDa and 800 Da to a polyglycerol core (PG6), respectively. The structure of the polymers was characterized by 1H NMR and FTIR. Through agarose gel electrophoresis retardation assay, PG6-PEI25k and PG6-PEI800 were demonstrated to have capability for DNA binding. PG6-PEI/DNA complexes with different weight ratios were characterized by TEM and particle size analysis. The activity of PG6-PEIs to mediate transfection of reporter plasmids pEGFP-C1 and pGL3-Luc was evaluated on 293T and HeLa cell lines. PG6-PEI25k and PG6-PEI800 showed enhanced levels in transgene expression and decreased cytotoxicities as compared with PEI25k and PEI800, respectively. The results indicated potential applications of PG6-PEIs for efficient gene delivery.

  6. In vitro biocompatibility evaluations of hyperbranched polyglycerol hybrid nanostructure as a candidate for nanomedicine applications.

    PubMed

    Zarrabi, Ali; Shokrgozar, Mohammad Ali; Vossoughi, Manouchehr; Farokhi, Mehdi

    2014-02-01

    In the present study, a detailed biocompatibility testing of a novel class of hybrid nanostructure based on hyperbranched polyglycerol and β-cyclodextrin is conducted. This highly water soluble nanostructure with size of less than 10 nm, polydispersity of less than 1.3, chemical tenability and highly branched architecture with the control over branching structure could be potentially used as a carrier in drug delivery systems. To this end, extensive studies in vitro and in vivo conditions have to be demonstrated. The in vitro studies include in vitro cytotoxicity tests; MTT and Neutral Red assay as an indicator of mitochondrial and lysosomal function, and blood biocompatibility tests such as effects on coagulation cascade, and complement activation. The results show that these hybrid nanostructures, which can be prepared in a simple reaction, are considerably biocompatible. The in vivo studies showed that the hybrid nanostructure is well tolerated by rats even in high doses of 10 mg ml(-1). After autopsy, the normal structure of liver tissue was observed; which divulges high biocompatibility and their potential applications as drug delivery and nanomedicine.

  7. The effect of hyperbranched polyglycerol coatings on drug delivery using degradable polymer nanoparticles.

    PubMed

    Deng, Yang; Saucier-Sawyer, Jennifer K; Hoimes, Christopher J; Zhang, Junwei; Seo, Young-Eun; Andrejecsk, Jillian W; Saltzman, W Mark

    2014-08-01

    A key attribute for nanoparticles (NPs) that are used in medicine is the ability to avoid rapid uptake by phagocytic cells in the liver and other tissues. Poly(ethylene glycol) (PEG) coatings has been the gold standard in this regard for several decades. Here, we examined hyperbranched polyglycerols (HPG) as an alternate coating on NPs. In earlier work, HPG was modified with amines and subsequently conjugated to poly(lactic acid) (PLA), but that approach compromised the ability of HPG to resist non-specific adsorption of biomolecules. Instead, we synthesized a copolymer of PLA-HPG by a one-step esterification. NPs were produced from a single emulsion using PLA-HPG: fluorescent dye or the anti-tumor agent camptothecin (CPT) were encapsulated at high efficiency in the NPs. PLA-HPG NPs were quantitatively compared to PLA-PEG NPs, produced using approaches that have been extensively optimized for drug delivery in humans. Despite being similar in size, drug release profile and in vitro cytotoxicity, the PLA-HPG NPs showed significantly longer blood circulation and significantly less liver accumulation than PLA-PEG. CPT-loaded PLA-HPG NPs showed higher stability in suspension and better therapeutic effectiveness against tumors in vivo than CPT-loaded PLA-PEG NPs. Our results suggest that HPG is superior to PEG as a surface coating for NPs in drug delivery.

  8. A Highly Photostable Hyperbranched Polyglycerol-Based NIR Fluorescence Nanoplatform for Mitochondria-Specific Cell Imaging.

    PubMed

    Dong, Chunhong; Liu, Zhongyun; Liu, Junqing; Wu, Changzhu; Neumann, Falko; Wang, Hanjie; Schäfer-Korting, Monika; Kleuser, Burkhard; Chang, Jin; Li, Wenzhong; Ma, Nan; Haag, Rainer

    2016-09-01

    Considering the critical role of mitochondria in the life and death of cells, non-invasive long-term tracking of mitochondria has attracted considerable interest. However, a high-performance mitochondria-specific labeling probe with high photostability is still lacking. Herein a highly photostable hyperbranched polyglycerol (hPG)-based near-infrared (NIR) quantum dots (QDs) nanoplatform is reported for mitochondria-specific cell imaging. Comprising NIR Zn-Cu-In-S/ZnS QDs as extremely photostable fluorescent labels and alkyl chain (C12 )/triphenylphosphonium (TPP)-functionalized hPG derivatives as protective shell, the tailored QDs@hPG-C12 /TPP nanoprobe with a hydrodynamic diameter of about 65 nm exhibits NIR fluorescence, excellent biocompatibility, good stability, and mitochondria-targeted ability. Cell uptake experiments demonstrate that QDs@hPG-C12 /TPP displays a significantly enhanced uptake in HeLa cells compared to nontargeted QDs@hPG-C12 . Further co-localization study indicates that the probe selectively targets mitochondria. Importantly, compared with commercial deep-red mitochondria dyes, QDs@hPG-C12 /TPP possesses superior photostability under continuous laser irradiation, indicating great potential for long-term mitochondria labeling and tracking. Moreover, drug-loaded QDs@hPG-C12 /TPP display an enhanced tumor cell killing efficacy compared to nontargeted drugs. This work could open the door to the construction of organelle-targeted multifunctional nanoplatforms for precise diagnosis and high-efficient tumor therapy.

  9. Hyperbranched Polyglycerol-Induced Porous Silica Nanoparticles as Drug Carriers for Cancer Therapy In Vitro and In Vivo.

    PubMed

    Yang, Yang; Wang, Anhe; Wei, Qiang; Schlesener, Cathleen; Haag, Rainer; Li, Qi; Li, Junbai

    2017-02-01

    Mesoporous silica-based nanoparticles are generally accepted as a potential platform for drug loading with a lot of advantages, except for their complex purification procedures and structures that are difficult to decompose. In this work, biocompatible hyperbranched polyglycerol is introduced to synthesize mesoporous silica nanoparticles (MSNs). The materials possess good biocompatibility, controlled release, and biodegradability. They also show passive targeting capability through the enhanced permeability and retention effect and can be excreted from the biological system. The method avoids the needs to employ traditional surfactants and complicated purified procedures, which make these MSNs an efficient delivery system for cancer therapy.

  10. Leukocyte-mimicking stem cell delivery via in situ coating of cells with a bioactive hyperbranched polyglycerol.

    PubMed

    Jeong, Jae Hyun; Schmidt, John J; Kohman, Richie E; Zill, Andrew T; DeVolder, Ross J; Smith, Cartney E; Lai, Mei-Hsiu; Shkumatov, Artem; Jensen, Tor W; Schook, Lawrence G; Zimmerman, Steven C; Kong, Hyunjoon

    2013-06-19

    Since stem cells emerged as a new generation of medicine, there are increasing efforts to deliver stem cells to a target tissue via intravascular injection. However, the therapeutic stem cells lack the capacity to detect and adhere to the target tissue. Therefore, this study presents synthesis of a bioactive hyperbranched polyglycerol (HPG) that can noninvasively associate with stem cells and further guide them to target sites, such as inflamed endothelium. The overall process is analogous to the way in which leukocytes are mobilized to the injured endothelium.

  11. Hyperbranched double hydrophilic block copolymer micelles of poly(ethylene oxide) and polyglycerol for pH-responsive drug delivery.

    PubMed

    Lee, Sueun; Saito, Kyohei; Lee, Hye-Ra; Lee, Min Jae; Shibasaki, Yuji; Oishi, Yoshiyuki; Kim, Byeong-Su

    2012-04-09

    We report the synthesis of a well-defined hyperbranched double hydrophilic block copolymer of poly(ethylene oxide)-hyperbranched-polyglycerol (PEO-hb-PG) to develop an efficient drug delivery system. In specific, we demonstrate the hyperbranched PEO-hb-PG can form a self-assembled micellar structure on conjugation with the hydrophobic anticancer agent doxorubicin, which is linked to the polymer by pH-sensitive hydrazone bonds, resulting in a pH-responsive controlled release of doxorubicin. Dynamic light scattering, atomic force microscopy, and transmission electron microscopy demonstrated successful formation of the spherical core-shell type micelles with an average size of about 200 nm. Moreover, the pH-responsive release of doxorubicin and in vitro cytotoxicity studies revealed the controlled stimuli-responsive drug delivery system desirable for enhanced efficiency. Benefiting from many desirable features of hyperbranched double hydrophilic block copolymers such as enhanced biocompatibility, increased water solubility, and drug loading efficiency as well as improved clearance of the polymer after drug release, we believe that double hydrophilic block copolymer will provide a versatile platform to develop excellent drug delivery systems for effective treatment of cancer.

  12. Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols

    NASA Astrophysics Data System (ADS)

    Alizadeh Noghani, M.; Brooks, D. E.

    2016-02-01

    Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The

  13. The size-dependent efficacy and biocompatibility of hyperbranched polyglycerol in peritoneal dialysis.

    PubMed

    Du, Caigan; Mendelson, Asher A; Guan, Qiunong; Chapanian, Rafi; Chafeeva, Irina; da Roza, Gerald; Kizhakkedathu, Jayachandran N

    2014-02-01

    Glucose is a common osmotic agent for peritoneal dialysis (PD), but has many adverse side effects for patients with end-stage renal disease. Recently, hyperbranched polyglycerol (HPG) has been tested as an alternative osmotic agent for PD. This study was designed to further examine the efficacy and biocompatibility of HPG over a range of different molecular weights. HPGs of varying molecular weights (0.5 kDa, 1 kDa, 3 kDa) were evaluated in a preclinical rodent model of PD. HPG PD solutions were standardized for osmolality and compared directly to conventional glucose-based Physioneal™ PD solution (PYS). The efficacy of HPG solutions was measured by their ultrafiltration (UF) capacity, solute removal, and free water transport; biocompatibility was determined in vivo by the histological analysis of the peritoneal membrane and the cell count of detached peritoneal mesothelial cells (PMCs) and neutrophils, and in vitro cytotoxicity to cultured human PMCs. All the different sized HPGs induced higher UF and sodium removal over a sustained period of time (up to 8 h) compared to PYS. Urea removal was significantly higher for 1-3 kDa than PYS, and was similar for 0.5 kDa. Our analyses indicated that the peritoneal membrane exhibited more tolerance to the HPG solutions compared to PYS, evidenced by less submesothelial injury and neutrophil infiltration in vivo, and less cell death in cultured human peritoneal mesothelial cells. Free water transport analysis of HPG indicated that these molecules function as colloids and induce osmosis mainly through capillary small pores. We attribute the differences in the biocompatibility and osmotic activity of different sized HPGs to the differences in the polymer bound water measured by differential scanning calorimetry. These preclinical data indicate that compared to PYS, low MW HPGs (0.5-3 kDa) produces superior fluid and waste removal with better biocompatibility profile, suggesting that they are promising osmotic agents for PD.

  14. Design Considerations for Developing Hyperbranched Polyglycerol Nanoparticles as Systemic Drug Carriers.

    PubMed

    Wong, Nelson K Y; Misri, Ripen; Shenoi, Rajesh A; Chafeeva, Irina; Kizhakkedathu, Jayachandran N; Khan, Mohamed K

    2016-05-01

    PEGylation is commonly used to increase the plasma residence time of anticancer drug nanocarriers. However, PEGylation may trigger antibody production and lead to accelerated blood clearance in subsequent administrations. Moreover, the presence of PEG shells on nanocarriers may also hamper endosomal escape and decrease drug payload release. To avoid these shortcomings, we synthesized and evaluated a non-PEGylated, hyperbranched polyglycerol nanoparticle (HPG NP) with a hydrophobic core and a hydrophilic HPG shell, HPG-C10-HPG, as a candidate for systemic delivery of anticancer drug. In vitro studies with primary human cell lines revealed that HPG-C10-HPG possesses low cytotoxicity. The presence of long chain alkyl groups (C1o) in the core as the hydrophobic pocket in the NP enabled the binding and sustained release of the hydrophobic drug docetaxel. Remarkably, the docetaxel-loaded HPG-C10-HPG formulation also confers preferential protection to primary cells, when compared to cancer cells, potentially widening the therapeutic index. HPG-C10-HPG, however, accumulated at higher levels in the liver and spleen when administered intravenously in mice. Comparing the biodistribution patterns of HPG-C10-HPG, PEGylated HPG-C10-PEG, and unmodified HPG in a xenograft model reveals that the accumulation pattern of HPG-C10-HPG was attributed to insufficient shielding of the hydrophobic groups by the HPG shell. Our results revealed the influence of the nature of the hydrophilic shell and the presence of hydrophobic groups on the tumor-to-tissue accumulation specificities of these HPG NP variants. Therefore, the present study provides insights into the structural considerations of future HPG NP designs for systemic drug delivery.

  15. Hydrotropic polymeric mixed micelles based on functional hyperbranched polyglycerol copolymers as hepatoma-targeting drug delivery system.

    PubMed

    Zhang, Xuejiao; Zhang, Xinge; Yu, Peien; Han, Yucai; Li, Yangguang; Li, Chaoxing

    2013-01-01

    Mixed copolymer nanoparticles (NPs) self-assembled from β-cyclodextrin-grafted hyperbranched polyglycerol (HPG-g-CD) and lactobionic acid (LA)-grafted hyperbranched polyglycerol (HPG-g-LA) were applied as carriers for a hydrophobic antitumor drug, paclitaxel (PTX), achieving hepatocellular carcinoma-targeted delivery. The resulting NPs exhibited high drug loading capacity and substantial stability in aqueous solution. In vitro drug release studies demonstrated a controlled drug release profile with increased release at acidic pH. Remarkably, tumor proliferation assays showed that PTX-loaded mixed copolymer NPs inhibited asialoglycoprotein (ASGP) receptor positive HepG2 cell proliferation in a concentration-dependent manner in comparison with ASGP receptor negative BGC-823 cells. Moreover, the competition assay demonstrated that the small molecular LA inhibited the cellular uptake of the PTX-loaded mixed copolymer NPs, indicating the ASGP receptor-mediated endocytosis in HepG2 cells. In addition, the intracellular uptake tests by confocal laser scanning microscopy showed that the mixed copolymer NPs were more efficiently taken up by HepG2 cells compared with HPG-g-CD NPs. These results suggest a feasible application of the mixed copolymer NPs as nanocarriers for hepatoma-targeted delivery of potent antitumor drugs.

  16. Preparation and characterization of structured hydrogel microparticles based on cross-linked hyperbranched polyglycerol.

    PubMed

    Oudshoorn, Marion H M; Penterman, Roel; Rissmann, Robert; Bouwstra, Joke A; Broer, Dirk J; Hennink, Wim E

    2007-11-06

    The aim of this work was to obtain well-defined HyPG-MA (methacrylated hyperbranched polyglycerol) microparticles with uniform sizes. Therefore, three different preparation methods were evaluated. First, we assessed a micromolding technique using rigid SU-8 (a photoresist based on epoxies) grids. Independent of the surface treatment of the SU-8 grid or the type of polymer used, approximately 50% of the microgels remained attached to the SU-8 grid or broke into smaller particles during the release process in which drying of the gels was followed by a sonication process. Although 90% methacrylate conversion could be obtained, this method has some additional drawbacks as the obtained dried microgels did not rehydrate completely after the drying step. Second, a soft micromolding technique was evaluated using elastomeric PDMS (poly(dimethyl siloxane)) grids. The use of these flexible grids resulted in a high yield (80-90% yield; >90% methacrylate conversion) of microgels with a well-defined size and shape (squares 100 microm x 100 microm x 50 microm or hexagons with Ø 30 microm and a thickness of 20 microm) without the occurrence of water evaporation. However, a number of particles showed a less-defined shape as not all grids could be filled well. The microgels showed restricted swelling, implying that these gels are dimensionally stable. Third, an alternative method referred to as photolithography was evaluated. This method was suitable to tailor accurately the size and shape of HyPG-MA microgels and additionally gained 100% yield. Well-defined HyPG-MA microgels in the size range of 200-1400 microm (thickness of 6, 20, or 50 microm), with a methacrylate conversion of >90%, could easily be prepared by adding an inhibitor (e.g., 1% (w/v) of vitamin C) to the polymer solution to inhibit dark polymerization. Microgels in the size range of 30-100 microm (>90% conversion) could only be obtained when applying the photomask in direct contact with the polymer solution and

  17. One-pot reaction for the large-scale synthesis of hyperbranched polyglycerol-grafted Fe3O4 nanoparticles.

    PubMed

    Wang, Liang; Su, Dan; Zeng, Lintao; Liu, Ning; Jiang, Lai; Feng, Xuequan; Neoh, K G; Kang, E T

    2013-10-07

    Fe3O4 nanoparticles with surface hydroxyl groups (MNP-OH), prepared by the thermal decomposition of ferric oxalate pentahydrate in triethylene glycol, were grafted in situ with polyglycerol through the ring-opening polymerization of glycidol. By this method, hyperbranched polyglycerol-grafted Fe3O4 nanoparticles (HPG-grafted MNPs) can be obtained on an ultra-large scale of 50 g in a single reaction under laboratory conditions, and it is anticipated that the production of the HPG-grafted MNPs could be scaled up with the use of larger reaction vessels. The successful grafting of HPG onto the nanoparticles was confirmed by (1)H NMR and XPS analyses. The as-synthesized nanoparticles can be tuned from 8 to 24 nm in diameter by varying the reaction conditions. The size, morphology, and surface component of the nanoparticles were characterized by TEM, XPS, and XRD. The HPG-grafted MNPs are highly dispersible in aqueous media such as cell culture medium and serum. Since these magnetic nanoparticles possess desirable magnetic properties, controllable size, and can be produced by a facile inexpensive method, they can be potentially applied as a novel contrast agent for enhancing a MRI signal.

  18. OX26 modified hyperbranched polyglycerol-conjugated poly(lactic-co-glycolic acid) nanoparticles: synthesis, characterization and evaluation of its brain delivery ability.

    PubMed

    Bao, Hanmei; Jin, Xu; Li, Ling; Lv, Feng; Liu, Tianjun

    2012-08-01

    A novel nanoparticles-based brain drug delivery system made of hyperbranched polyglycerol-conjugated poly(lactic-co-glycolic acid) which was surface functionalized with transferrin antibody (OX26) was prepared. Hyperbranched polyglycerol-conjugated poly(lactic-co-glycolic acid) was synthesized, characterized and applied to prepare nanoparticles by means of double emulsion solvent evaporation technique. Transmission electron micrograph and dynamic light scattering showed that nanoparticles had a round and regular shape with a mean diameter of 170 ± 20 nm. Surface chemical composition was detected by X-ray photoelectron spectroscopy. Endomorphins, as a model drug, was encapsulated in the nanoparticles. In vitro drug release study showed that endomorphins was released continuously for 72 h. Cellular uptake study showed that the uptake of nanoparticles by the brain microvascular endothelial cells was both time- and concentration-dependant. Further uptake inhibition study indicated that the uptake of nanoparticles was via a caveolae-mediated endocytic pathway. In vivo endomorphins brain delivery ability was evaluated based upon the rat model of chronic constriction injury of sciatic nerve. OX26 modified nanoparticles had achieved better analgesic effects, compared with other groups. Thus, OX26 modified hyperbranched polyglycerol-conjugated poly(lactic-co-glycolic acid) nanoparticles may be a promising brain drug delivery carrier.

  19. Blood compatibility of novel water soluble hyperbranched polyglycerol-based multivalent cationic polymers and their interaction with DNA.

    PubMed

    Kainthan, Rajesh Kumar; Gnanamani, Muthiah; Ganguli, Munia; Ghosh, Tanay; Brooks, Donald E; Maiti, Souvik; Kizhakkedathu, Jayachandran N

    2006-11-01

    A novel class of hyperbranched polymers based on polyglycerol (PG) and poly(ethylene glycol) (PEG) are synthesized by multibranching anionic ring opening polymerization. Multivalent cationic sites are added to these polymers by a post-amination and quarternization reactions. Blood compatibility studies using these polymers at different concentrations showed insignificant effects on complement activation, platelet activation, coagulation, erythrocyte aggregation and hemolysis compared to branched cationic polyethyleneimine (PEI). The degree of quarternization does not have large influence on the blood compatibility of the new polymers. Cytotoxicity of these polymers is significantly lower than that of PEI and is a function of quarternized nitrogen present in the polymer. Also, these polymers bind DNA in the nanomolar range and are able to condense DNA to highly compact, stable, water soluble nanoparticles in the range of 60-80 nm. Gel electrophoresis studies showed that they form electroneutral complexes with DNA around N/P ratio 1 irrespective of the percentage of quarternization under the conditions studied.

  20. Methotrexate-conjugated and hyperbranched polyglycerol-grafted Fe₃O₄ magnetic nanoparticles for targeted anticancer effects.

    PubMed

    Li, Min; Neoh, Koon-Gee; Wang, Rong; Zong, Bao-Yu; Tan, Jia Yong; Kang, En-Tang

    2013-01-23

    Superparamagnetic nanoparticles grafted with hyperbranched polyglycerol (HPG) and conjugated with methotrexate (MTX) (MNP-g-HPG-MTX) were synthesized via a sol-gel reaction followed by thiol-ene click chemistry and esterification reaction. The successful grafting of MTX and HPG onto the nanoparticles was confirmed by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, and UV-visible spectroscopy. The HPG-graft layer confers the magnetic nanoparticles with good dispersibility and stability in aqueous medium and macrophage-evasive property while the MTX acts as a chemotherapeutic drug as well as a tumor targeting ligand. The dose-dependent targeting and anticancer effect of the MNP-g-HPG-MTX nanoparticles were evaluated, and the results showed that depending on the amount of conjugated MTX and the concentration of the incubated nanoparticles, the uptake of MNP-g-HPG-MTX nanoparticles by human head and neck cancer (KB) cells can be eight times or more higher than those by 3T3 fibroblasts and RAW macrophages. As a result, the MNP-g-HPG-MTX nanoparticles are capable of killing ∼50% of the KB cells while at the same time exhibiting low cytotoxicity towards 3T3 fibroblasts and RAW macrophages. Thus, such nanoparticles can potentially be used as active targeting anticancer agents.

  1. Surface-initiated hyperbranched polyglycerol as an ultralow-fouling coating on glass, silicon, and porous silicon substrates.

    PubMed

    Moore, Eli; Delalat, Bahman; Vasani, Roshan; McPhee, Gordon; Thissen, Helmut; Voelcker, Nicolas H

    2014-09-10

    Anionic ring-opening polymerization of glycidol was initiated from activated glass, silicon, and porous silicon substrates to yield thin, ultralow-fouling hyperbranched polyglycerol (HPG) graft polymer coatings. Substrates were activated by deprotonation of surface-bound silanol functionalities. HPG polymerization was initiated upon the addition of freshly distilled glycidol to yield films in the nanometer thickness range. X-ray photoelectron spectroscopy, contact angle measurements, and ellipsometry were used to characterize the resulting coatings. The antifouling properties of HPG-coated surfaces were evaluated in terms of protein adsorption and the attachment of mammalian cells. The adsorption of bovine serum albumin and collagen type I was found to be reduced by as much as 97 and 91%, respectively, in comparison to untreated surfaces. Human glioblastoma and mouse fibroblast attachment was reduced by 99 and 98%, respectively. HPG-grafted substrates outperformed polyethylene glycol (PEG) grafted substrates of comparable thickness under the same incubation conditions. Our results demonstrate the effectiveness of antifouling HPG graft polymer coatings on a selected range of substrate materials and open the door for their use in biomedical applications.

  2. Solution-Stable Colloidal Gold Nanoparticles via Surfactant-Free, Hyperbranched Polyglycerol-b-polystyrene Unimolecular Templates.

    PubMed

    Iocozzia, James; Lin, Zhiqun

    2016-07-19

    Hyperbranched polyglycerol-block-polystyrene copolymers, denoted HPG-b-PS, are synthesized and employed as a new and effective unimolecular template for synthesizing colloidal gold (Au) nanoparticles. The coordination of noble metal precursors with polyether within the inner HPG core and subsequent in situ reduction enables the formation of well-dispersed and stable PS-capped Au nanoparticles. The inner HPG core is produced via ring opening multibranching polymerization (ROMBP) and subsequently converted into atom transfer radical polymerization (ATRP) macroinitiators for the controlled growth of polystyrene (PS) arms possessing low polydispersity (PDI < 1.31). An initial investigation into the templating parameters of HPG-b-PS was undertaken by producing templates with different arm numbers (98 and 117) and different PS chain lengths (i.e., molecular weight = 3500-13400 g/mol). It was found that the PS chain length and solvent conditions affect the quality of the resulting PS-capped colloidal Au nanoparticles. This work demonstrates, for the first time, a simple, lower-cost approach for templating nonpolar solvent-soluble PS-capped Au nanoparticles on the order of 10-30 nm in diameter.

  3. Robust Fe3O4/SiO2-Pt/Au/Pd magnetic nanocatalysts with multifunctional hyperbranched polyglycerol amplifiers.

    PubMed

    Zhou, Li; Gao, Chao; Xu, Weijian

    2010-07-06

    Here we report a facile approach to prepare multicarboxylic hyperbranched polyglycerol (HPG)-grafted SiO(2)-coated iron oxide (Fe(3)O(4)/SiO(2)) magnetic hybrid support. This support combined the both features of Fe(3)O(4) and HPG, facile magnetic separation, and favorable molecular structure with numerous functional groups. With the use of the grafted-HPGs as templates, various noble metal nanocatalysts such as Pt, Au, and Pd were directly grown on the surfaces of magnetic support with ultrasmall and nearly monodisperse sizes (e.g., the average sizes of Pt, Au, and Pd are 4.8 +/- 0.5, 6.0 +/- 0.6, and 4.0 +/- 0.4 nm, respectively) and high coverage densities. Because of the amplification effect of HPG, high loading capacities of the nanocatalysts, around 0.296, 0.243, and 0.268 mmol/g for Pt, Au, and Pd, respectively, were achieved. Representative catalytic reactions including reduction of 4-nitrophenol, alcohol oxidation, and Heck reaction demonstrated the high catalytic activity of the noble metal nanocatalysts. Because of the stabilization of HPG templates, the nanocatalysts can be readily recycled by a magnet and reused for the next reactions with high efficiencies. The robust multifunctional magnetic hybrids will find important applications in catalysis and other fields such as drug delivery and bioseparations.

  4. Investigation on the interactions between fullerene and β-CD-g-hyperbranched polyglycerol to produce water-soluble fullerene

    NASA Astrophysics Data System (ADS)

    Eskandari, Mohammad; Najdian, Atena; Soleyman, Rouhollah

    2016-06-01

    Developing a successful way to solubilize C60 in water is a longstanding, critical, and challenging issue in nanotechnology, biological, and medicine applications because of the great potential of fullerene derivatives in anti-viral therapy. In the current study, an efficient strategy for the preparing of water-soluble C60 at room temperature has been developed by complexion of C60 with hyperbranched polyglycerol linked to the β-cyclodextrin core (β-CD-g-HPG). The interactions between C60 and β-CD-g-HPG were investigated using a range of analytical techniques such as FTIR, NMR, UV-vis spectroscopy as well as visual techniques including SEM and AFM images. The particle size for a 1:2 (C60: β-CD-g-HPG) complex was also determined to be monodisperse ∼60 nm from DLS, and it was appropriately matched with the size obtained from SEM pictures. The results show our synthesized hybrid nanomaterials will hopefully find interesting applications in biomedicine.

  5. Anti-fouling behavior of hyperbranched polyglycerol-grafted poly(ether sulfone) hollow fiber membranes for osmotic power generation.

    PubMed

    Li, Xue; Cai, Tao; Chung, Tai-Shung

    2014-08-19

    To sustain high performance of osmotic power generation by pressure-retarded osmosis (PRO) processes, fouling on PRO membranes must be mitigated. This is especially true for the porous support of PRO membranes because its porous structure is very prone to fouling by feeding river water. For the first time, we have successfully designed antifouling PRO thin-film composite (TFC) membranes by synthesizing a dendritic hydrophilic polymer with well-controlled grafting sites, hyperbranched polyglycerol (HPG), and then grafting it on poly(ether sulfone) (PES) hollow fiber membrane supports. Compared to the pristine PES membranes, polydopamine modified membranes, and conventional poly(ethylene glycol) (PEG)-grafted membranes, the HPG grafted membranes show much superior fouling resistance against bovine serum albumin (BSA) adsorption, E. coli adhesion, and S. aureus attachment. In high-pressure PRO tests, the PES TFC membranes are badly fouled by model protein foulants, causing a water flux decline of 31%. In comparison, the PES TFC membrane grafted by HPG not only has an inherently higher water flux and a higher power density but also exhibits better flux recovery up to 94% after cleaning and hydraulic pressure impulsion. Clearly, by grafting the properly designed dendritic polymers to the membrane support, one may substantially sustain PRO hollow fiber membranes for power generation.

  6. Hyperbranched polyglycerol-grafted titanium oxide nanoparticles: synthesis, derivatization, characterization, size separation, and toxicology

    NASA Astrophysics Data System (ADS)

    Qin, Hongmei; Maruyama, Kyouhei; Amano, Tsukuru; Murakami, Takashi; Komatsu, Naoki

    2016-10-01

    We have been developing surface functionalization of various nanoparticles including nanodiamond and iron oxide nanoparticles in view of biomedical applications. In this context, TiO2 nanoparticles (TiO2 NP) are functionalized with polyglycerol (PG) to provide water-dispersible TiO2-PG, which is further derivatized through multi-step organic transformations. The resulting TiO2-PG and its derivatives are fully characterized by various analyses including solution-phase 1H and 13C NMR. TiO2-PG was size-tuned with centrifugation by changing the acceleration and duration. At last, no cytotoxicity of TiO2 NP, TiO2-PG, and TiO2-PG functionalized with RGD peptide was observed under dark conditions.

  7. Tissue uptake of docetaxel loaded hydrophobically derivatized hyperbranched polyglycerols and their effects on the morphology of the bladder urothelium.

    PubMed

    Mugabe, Clement; Raven, Peter A; Fazli, Ladan; Baker, Jennifer H E; Jackson, John K; Liggins, Richard T; So, Alan I; Gleave, Martin E; Minchinton, Andrew I; Brooks, Donald E; Burt, Helen M

    2012-01-01

    Recently, we have reported that docetaxel (DTX) loaded, amine terminated hyperbranched polyglycerol (HPG-C(8/10)-MePEG-NH(2)) nanoparticles significantly increased drug uptake in mouse bladder tissues and was the most effective formulation to significantly inhibit tumor growth in an orthotopic model of bladder cancer. The objective of this study was to investigate the effects of HPG-C(8/10)-MePEG-NH(2) nanoparticles on bladder urothelial morphology and integrity, DTX uptake and permeability in bladder tissue and the extent of bladder urothelial recovery following exposure to, and then washout of, HPG-C(8/10)-MePEG-NH(2) nanoparticles. HPG-C(8/10)-MePEG-NH(2) nanoparticles significantly increased the uptake of DTX in both isolated pig bladder as well as in live mouse bladder tissues. Furthermore, HPG-C(8/10)-MePEG-NH(2) nanoparticles were demonstrated to increase the permeability of the urinary bladder wall by causing changes to the urothelial barrier function and morphology through opening of tight junctions and exfoliation of the superficial umbrella cells. These data suggest that exfoliation may be triggered by an apoptosis mechanism, which was followed by a rapid recovery of the urothelium within 24 h post-instillation of HPG-C(8/10)-MePEG-NH(2) nanoparticles. HPG-C(8/10)-MePEG-NH(2) nanoparticles cause significant but rapidly recoverable changes in the bladder urothelial morphology, which we believe may make them suitable for increasing drug permeability of bladder tissue and intravesical drug delivery.

  8. Multicarboxylic hyperbranched polyglycerol modified SBA-15 for the adsorption of cationic dyes and copper ions from aqueous media

    NASA Astrophysics Data System (ADS)

    Chen, Zhengji; Zhou, Li; Zhang, Faai; Yu, Chuanbai; Wei, Zhibo

    2012-04-01

    The aim of the present work was to investigate the potential of multicarboxylic hyperbranched polyglycerol (HPG) modified mesoporous SBA-15 (SBA/HPG-COOH) as adsorbent for the removal of cationic dyes or/and heavy metal ions from aqueous media. The SBA/HPG-COOH adsorbents can be facilely synthesized through two steps: in situ anionic ring-opening polymerization of glycidol and further modification of hydroxyl groups by succinic anhydride. The resulting SBA/HPG-COOH was characterized by means of FTIR, TGA, XRD, SEM and nitrogen adsorption-desorption isotherms. The results demonstrate that the SBA/HPG-COOH was successfully synthesized and the density of carboxylic groups on the SBA/HPG-COOH is calculated to be as high as 1.5 mmol/g, posing a powerful base for adsorbing cationic adsorbates. Four kinds of dyes and copper ions were chosen as representatives to investigate the adsorption ability of SBA/HPG-COOH. The SBA/HPG-COOH adsorbent showed quick adsorption rate, high adsorption capacity (e.g., its saturated adsorption capacity for methylene blue (MB) can reach 0.50 mmol/g, while for unmodified SBA-15 is lower than 0.05 mmol/g), and high selectivity for cationic adsorbates. The fitness of Langmuir adsorption model and pseudo second-order kinetics on describing the adsorption isotherm and kinetics of SBA/HPG-COOH for MB dye was examined, respectively. It is believed that this robust SBA/HPG-COOH adsorbent will find important application in removal of cationic adsorbates from aqueous solution.

  9. Mannose-Functionalized Hyperbranched Polyglycerol Loaded with Zinc Porphyrin: Investigation of the Multivalency Effect in Antibacterial Photodynamic Therapy.

    PubMed

    Staegemann, Michael H; Gitter, Burkhard; Dernedde, Jens; Kuehne, Christian; Haag, Rainer; Wiehe, Arno

    2017-03-17

    The antibacterial photodynamic activity of hyperbranched polyglycerol (hPG) loaded with zinc porphyrin photosensitizers and mannose units was investigated. hPG, with a MW of 19.5 kDa, was functionalized with about 15 molecules of the photosensitizer {5,10,15-tris(3-hydroxyphenyl)-20-[4-(prop-2-yn-1-ylamino)tetrafluorophenyl]porphyrinato}-zinc(II) by using copper(I)-catalyzed 1,3-dipolar cycloaddition (CuAAC). These nanoparticle conjugates were functionalized systematically with increasing loadings of mannose in the range of approximately 20 to 110 groups. With higher mannose loadings (ca. 58-110 groups) the water-insoluble zinc porphyrin photosensitizer could thus be transferred into a water-soluble form. Targeting of the conjugates was proven in binding studies to the mannose-specific lectin concanavalin A (Con A) by using surface plasmon resonance (SPR). The antibacterial phototoxicity of the conjugates on Staphylococcus aureus (as a typical Gram-positive germ) was investigated in phosphate-buffered saline (PBS). It was shown that conjugates with approximately 70-110 mannose units exhibit significant antibacterial activity, whereas conjugates with approximately 20-60 units did not induce bacterial killing at all. These results give an insight into the multivalency effect in combination with photodynamic therapy (PDT). On addition of serum to the bacterial cultures, a quenching of this antibacterial phototoxicity was observed. In fluorescence studies with the conjugates in the presence of increasing bovine serum albumin (BSA) concentrations, protein-conjugate associations could be identified as a plausible cause for this quenching.

  10. Cold preservation with hyperbranched polyglycerol-based solution improves kidney functional recovery with less injury at reperfusion in rats

    PubMed Central

    Li, Shadan; Liu, Bin; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E; Nguan, Christopher YC; Kizhakkedathu, Jayachandran N; Du, Caigan

    2017-01-01

    Minimizing donor organ injury during cold preservation (including cold perfusion and storage) is the first step to prevent transplant failure. We recently reported the advantages of hyperbranched polyglycerol (HPG) as a novel substitute for hydroxyethyl starch in UW solution for both cold heart preservation and cold kidney perfusion. This study evaluated the functional recovery of the kidney at reperfusion after cold preservation with HPG solution. The impact of HPG solution compared to conventional UW and HTK solutions on tissue weight and cell survival at 4°C was examined using rat kidney tissues and cultured human umbilical vein endothelial cells (HUVECs), respectively. The kidney protection by HPG solution was tested in a rat model of cold kidney ischemia-reperfusion injury, and was evaluated by histology and kidney function. Here, we showed that preservation with HPG solution prevented cell death in cultured HUVECs and edema formation in kidney tissues at 4°C similar to UW solution, whereas HTK solution was less effective. In rat model of cold ischemia-reperfusion injury, the kidneys perfused and subsequently stored 1-hour with cold HPG solution showed less leukocyte infiltration, less tubular damage and better kidney function (lower levels of serum creatinine and blood urea nitrogen) at 48 h of reperfusion than those treated with UW or HTK solution. In conclusion, our data show the superiority of HPG solution to UW or HTK solution in the cold perfusion and storage of rat kidneys, suggesting that the HPG solution may be a promising candidate for improved donor kidney preservation prior to transplantation. PMID:28337272

  11. Hyperbranched polyglycerol/graphene oxide nanocomposite reinforced hollow fiber solid/liquid phase microextraction for measurement of ibuprofen and naproxen in hair and waste water samples.

    PubMed

    Rezaeifar, Zohreh; Es'haghi, Zarrin; Rounaghi, Gholam Hossein; Chamsaz, Mahmoud

    2016-09-01

    A new design of hyperbranched polyglycerol/graphene oxide nanocomposite reinforced hollow fiber solid/liquid phase microextraction (HBP/GO -HF-SLPME) coupled with high performance liquid chromatography used for extraction and determination of ibuprofen and naproxen in hair and waste water samples. The graphene oxide first synthesized from graphite powders by using modified Hummers approach. The surface of graphene oxide was modified using hyperbranched polyglycerol, through direct polycondensation with thionyl chloride. The ready nanocomposite later wetted by a few microliter of an organic solvent (1-octanol), and then applied to extract the target analytes in direct immersion sampling mode.After the extraction process, the analytes were desorbed with methanol, and then detected via high performance liquid chromatography (HPLC). The experimental setup is very simple and highly affordable. The main factors influencing extraction such as; feed pH, extraction time, aqueous feed volume, agitation speed, the amount of functionalized graphene oxide and the desorption conditions have been examined in detail. Under the optimized experimental conditions, linearity was observed in the range of 5-30,000ngmL(-1) for ibuprofen and 2-10,000ngmL(-1) for naproxen with correlation coefficients of 0.9968 and 0.9925, respectively. The limits of detection were 2.95ngmL(-1) for ibuprofen and 1.51ngmL(-1) for naproxen. The relative standard deviations (RSDs) were found to be less than 5% (n=5).

  12. Hyperbranched Polyglycerol Is an Efficacious and Biocompatible Novel Osmotic Agent in a Rodent Model of Peritoneal Dialysis

    PubMed Central

    Mendelson, Asher A.; Guan, Qiunong; Chafeeva, Irina; da Roza, Gerald A.; Kizhakkedathu, Jayachandran N.; Du, Caigan

    2013-01-01

    ♦ Objectives: To enhance the effectiveness of peritoneal dialysis (PD), new biocompatible PD solutions may be needed. The present study was designed to test the efficacy and biocompatibility of hyperbranched polyglycerol (HPG)—a nontoxic, nonimmunogenic water-soluble polyether polymer—in PD. ♦ Methods: Adult Sprague-Dawley rats were instilled with 30 mL HPG solution (molecular weight 3 kDa; 2.5% - 15%) or control glucose PD solution (2.5% Dianeal: Baxter Healthcare Corporation, Deerfield, IL, USA), and intraperitoneal fluid was recovered after 4 hours. Peritoneal injury and cellular infiltration were determined by histologic and flow cytometric analysis. Human peritoneal mesothelial cells were assessed for viability in vitro after 3 hours of PD fluid exposure. ♦ Results: The 15% HPG solution achieved a 4-hour dose-related ultrafiltration up to 43.33 ± 5.24 mL and a dose-related urea clearance up to 39.17 ± 5.21 mL, results that were superior to those with control PD solution (p < 0.05). The dialysate-to-plasma (D/P) ratios of urea with 7.5% and 15% HPG solution were not statistically different from those with control PD solution. Compared with fluid recovered from the control group, fluid recovered from the HPG group contained proportionally fewer neutrophils (3.63% ± 0.87% vs 9.31% ± 2.89%, p < 0.0001). Detachment of mesothelial cells positive for human bone marrow endothelial protein 1 did not increase in the HPG group compared with the stain control (p = 0.1832), but it was elevated in the control PD solution group (1.62% ± 0.68% vs 0.41% ± 0.31%, p = 0.0031). Peritoneal biopsies from animals in the HPG PD group, compared with those from control PD animals, demonstrated less neutrophilic infiltration and reduced thickness. Human peritoneal mesothelial cell survival after HPG exposure was superior in vitro (p < 0.0001, 7.5% HPG vs control; p < 0.01, 15% HPG vs control). Exposure to glucose PD solution induced cytoplasmic vacuolation and caspase 3

  13. Highly elastomeric poly(glycerol sebacate)-co-poly(ethylene glycol) amphiphilic block copolymers.

    PubMed

    Patel, Alpesh; Gaharwar, Akhilesh K; Iviglia, Giorgio; Zhang, Hongbin; Mukundan, Shilpaa; Mihaila, Silvia M; Demarchi, Danilo; Khademhosseini, Ali

    2013-05-01

    Poly(glycerol sebacate) (PGS), a tough elastomer, has been proposed for tissue engineering applications due to its desired mechanical properties, biocompatibility and controlled degradation. Despite interesting physical and chemical properties, PGS shows limited water uptake capacity (∼2%), thus constraining its utility for soft tissue engineering. Therefore, a modification of PGS that would mimic the water uptake and water retention characteristics of natural extracellular matrix is beneficial for enhancing its utility for biomedical applications. Here, we report the synthesis and characterization of highly elastomeric poly(glycerol sebacate)-co-polyethylene glycol (PGS-co-PEG) block copolymers with controlled water uptake characteristics. By tailoring the water uptake property, it is possible to engineer scaffolds with customized degradation and mechanical properties. The addition of PEG results in almost 15-fold increase in water uptake capacity of PGS, and improves its mechanical stability under dynamic loading conditions. PGS-co-PEG polymers show elastomeric properties and can be subjected to serve deformation such as bending and stretching. The Young's modulus of PGS-co-PEG can be tuned from 13 kPa to 2.2 MPa by altering the amount of PEG within the copolymer network. Compared to PGS, more than six-fold increase in elongation was observed upon PEG incorporation. In addition, the rate of degradation increases with an increase in PEG concentration, indicating that degradation rate of PGS can be regulated. PGS-co-PEG polymers also support cell proliferation, and thus can be used for a range of tissue engineering applications.

  14. Multi-modal magnetic resonance imaging and histology of vascular function in xenografts using macromolecular contrast agent hyperbranched polyglycerol (HPG-GdF).

    PubMed

    Baker, Jennifer H E; McPhee, Kelly C; Moosvi, Firas; Saatchi, Katayoun; Häfeli, Urs O; Minchinton, Andrew I; Reinsberg, Stefan A

    2016-01-01

    Macromolecular gadolinium (Gd)-based contrast agents are in development as blood pool markers for MRI. HPG-GdF is a 583 kDa hyperbranched polyglycerol doubly tagged with Gd and Alexa 647 nm dye, making it both MR and histologically visible. In this study we examined the location of HPG-GdF in whole-tumor xenograft sections matched to in vivo DCE-MR images of both HPG-GdF and Gadovist. Despite its large size, we have shown that HPG-GdF extravasates from some tumor vessels and accumulates over time, but does not distribute beyond a few cell diameters from vessels. Fractional plasma volume (fPV) and apparent permeability-surface area product (aPS) parameters were derived from the MR concentration-time curves of HPG-GdF. Non-viable necrotic tumor tissue was excluded from the analysis by applying a novel bolus arrival time (BAT) algorithm to all voxels. aPS derived from HPG-GdF was the only MR parameter to identify a difference in vascular function between HCT116 and HT29 colorectal tumors. This study is the first to relate low and high molecular weight contrast agents with matched whole-tumor histological sections. These detailed comparisons identified tumor regions that appear distinct from each other using the HPG-GdF biomarkers related to perfusion and vessel leakiness, while Gadovist-imaged parameter measures in the same regions were unable to detect variation in vascular function. We have established HPG-GdF as a biocompatible multi-modal high molecular weight contrast agent with application for examining vascular function in both MR and histological modalities.

  15. Supramolecular aggregates of water soluble dendritic polyglycerol architectures for the solubilization of hydrophobic compounds.

    PubMed

    Kurniasih, Indah N; Liang, Hua; Rabe, Jürgen P; Haag, Rainer

    2010-09-01

    Dendritic core-shell architectures which are based on hyperbranched polyglycerol for the solubilization of hydrophobic drugs have been synthesized and characterized. The core of hyperbranched polyglycerol has been modified with hydrophobic biphenyl groups or perfluorinated chains to increase the core hydrophobicity of the macromolecules. These amphiphilic core-shell type architectures were then used to solubilize pyrene, nile red, and a perfluoro tagged diazo dye, as well as the drug nimodipine in water. Specific host-guest interactions such as fluorous-fluorous interactions could be tailored by this flexible core design and determined by UV spectroscopy. The transport capacity increased 450-fold for nile red, 47-fold for nimodipine, and 37-fold for pyrene at a polymer concentration of only 0.1 wt.-%. Surface tension measurements and scanning force microscopy (SFM) were used to reveal the aggregation properties of these complexes. The formation of supramolecular aggregates with diameters of ≈20 nm and critical aggregate concentrations of 2 × 10(-6)  mol · L(-1) have been observed. This indicates the controlled self-assembly of the presented amphiphilic dendritic core-shell type architectures.

  16. Dendronized multifunctional amphiphilic polymers as efficient nanocarriers for biomedical applications.

    PubMed

    Kumari, Meena; Gupta, Shilpi; Achazi, Katharina; Böttcher, Christoph; Khandare, Jayant; Sharma, Sunil K; Haag, Rainer

    2015-01-01

    To gain insight into the factors that affect stability and transport efficiency under dilution conditions, dendronized and hyperbranched multifunctional amphiphilic polymers are synthesized by following the "grafting to" approach using varied amounts of propargylated alkyl chain with perfect and hyperbranched polyglycerol dendrons on the base copolymer of PEG (Mn: 1000 g mol(-1)) diethylester and 2-azidopropane-1,3-diol following the "bio-catalytic method" and "click approach". The dendronized and hyperbranched polymeric systems form supramolecular aggregates and exhibit an efficient transport potential for the model dye "Nile red" in the low μm range in the core-shell-type architecture provided with distinct amphiphilicity as required for encapsulation. Cytotoxicity studies show the polymeric systems to be non-toxic over a wide concentration range. The cellular internalization of Nile-red-encapsulated supramolecular micellar structures is also studied using cellular fluorescence micro-scopy and fluorescence-activated cell sorting (FACS) measurements. A comparison of the data for the dendronized polymers (PEG Mn: 600/1000 g mol(-1)) with the respective low-molecular-weight amphiphile reveal that these polymeric systems are excellent nanotransporters.

  17. Randomly Hyperbranched Polymers

    NASA Astrophysics Data System (ADS)

    Konkolewicz, Dominik; Gilbert, Robert G.; Gray-Weale, Angus

    2007-06-01

    We describe a model for the structures of randomly hyperbranched polymers in solution, and find a logarithmic growth of radius with polymer mass. We include segmental overcrowding, which puts an upper limit on the density. The model is tested against simulations, against data on amylopectin, a major component of starch, on glycogen, and on polyglycerols. For samples of synthetic polyglycerol and glycogen, our model holds well for all the available data. The model reveals higher-level scaling structure in glycogen, related to the β particles seen in electron microscopy.

  18. Randomly hyperbranched polymers.

    PubMed

    Konkolewicz, Dominik; Gilbert, Robert G; Gray-Weale, Angus

    2007-06-08

    We describe a model for the structures of randomly hyperbranched polymers in solution, and find a logarithmic growth of radius with polymer mass. We include segmental overcrowding, which puts an upper limit on the density. The model is tested against simulations, against data on amylopectin, a major component of starch, on glycogen, and on polyglycerols. For samples of synthetic polyglycerol and glycogen, our model holds well for all the available data. The model reveals higher-level scaling structure in glycogen, related to the beta particles seen in electron microscopy.

  19. Biodegradable hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol), poly(ethylene glycol), and polycaprolactone as in situ thermogels.

    PubMed

    Li, Zibiao; Zhang, Zhongxing; Liu, Kerh Li; Ni, Xiping; Li, Jun

    2012-12-10

    This paper reports the synthesis and characterization of new hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), and polycaprolactone (PCL) segments as in situ thermogels. The hyperbranched poly(PPG/PEG/PCL urethane)s, termed as HBPEC copolymers, were synthesized from PPG-diol, PEG-diol, and PCL-triol by using 1,6-hexamethylene diisocyanate (HMDI) as a coupling agent. The compositions and structures of HBPEC copolymers were determined by GPC and 1H NMR spectroscopy. We carried out comparative studies of the new hyperbranched copolymers with their linear counterparts, the linear poly(PPG/PEG/PCL urethane) (LPEC) copolymer and Pluronic F127 PEG-PPG-PEG block copolymer, in terms of their self-assembly and aggregation behaviors and thermoresponsive properties. HBPEC copolymers were found to show thermoresponsive micelle formation and aggregation behaviors. Particularly, the lower critical solution temperature (LCST) of the copolymers was significantly affected by the copolymer architecture. HBPEC copolymers showed much lower LCST than LPEC, the linear counterpart. Our studies revealed that the effect of hyperbranch architecture was more prominent in the gelation of the copolymers. The aqueous solutions of HBPEC copolymers exhibited thermogelling behaviors at critical gelation concentrations (CGCs) ranging from 4.3 to 7.4 wt %. These values are much lower than those reported on other PCL-contained linear thermogelling copolymers and Pluronic F127 copolymer. In addition, the CGC of HBPEC copolymers is much lower than the control LPEC copolymer. More interestingly, at high temperatures, while LPEC and other linear thermogelling copolymers formed turbid sol, HBPEC formed a dehydrated gel. Our data suggest that these phenomena are caused by the hyperbranched structure of HBPEC copolymers, which could increase the interaction of copolymer branches and enhance the chain association through

  20. The effect of polyglycerol sulfate branching on inflammatory processes.

    PubMed

    Paulus, Florian; Schulze, Ronny; Steinhilber, Dirk; Zieringer, Maximilian; Steinke, Ingo; Welker, Pia; Licha, Kai; Wedepohl, Stefanie; Dernedde, Jens; Haag, Rainer

    2014-05-01

    In this study, the extent to which the scaffold architecture of polyglycerol sulfates affects inflammatory processes and hemocompatibility is investigated. Competitive L-selectin binding assays, cellular uptake studies, and blood compatibility readouts are done to evaluate distinct biological properties. Fully glycerol based hyperbranched polyglycerol architectures are obtained by either homopolymerization of glycidol (60% branching) or a new copolymerization strategy of glycidol with ethoxyethyl glycidyl ether. Two polyglycerols with 24 and 42% degree of branching (DB) are synthesized by using different monomer feed ratios. A perfectly branched polyglycerol dendrimer is synthesized according to an iterative two-step protocol based on allylation of the alcohol and subsequent catalytic dihydroxylation. All the polyglycerol sulfates are synthesized with a comparable molecular weight and degree of sulfation. The DB make the different polymer conjugates perform different ways. The optimal DB is 60% in all biological assays.

  1. A supramolecular Janus hyperbranched polymer and its photoresponsive self-assembly of vesicles with narrow size distribution.

    PubMed

    Liu, Yong; Yu, Chunyang; Jin, Haibao; Jiang, Binbin; Zhu, Xinyuan; Zhou, Yongfeng; Lu, Zhongyuan; Yan, Deyue

    2013-03-27

    Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation.

  2. Dissipative particle dynamics simulation study on self-assembly of amphiphilic hyperbranched multiarm copolymers with different degrees of branching.

    PubMed

    Tan, Haina; Wang, Wei; Yu, Chunyang; Zhou, Yongfeng; Lu, Zhongyuan; Yan, Deyue

    2015-11-21

    Hyperbranched multiarm copolymers (HMCs) have shown great potential to be excellent precursors in self-assembly to form various supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the self-assembly of HMCs, especially the self-assembly dynamics and mechanisms, have been greatly lagging behind the experimental progress. Herein, we investigate the effect of degree of branching (DB) on the self-assembly structures of HMCs by dissipative particle dynamics (DPD) simulation. Our simulation results demonstrate that the self-assembly morphologies of HMCs can be changed from spherical micelles, wormlike micelles, to vesicles with the increase of DBs, which are qualitatively consistent with the experimental observations. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these three aggregates have been systematically disclosed through the simulations. These self-assembly details are difficult to be shown by experiments and are very useful to fully understand the self-assembly behaviors of HMCs.

  3. Dynamic Relaxational Behaviour of Hyperbranched Polyether Polyols

    NASA Astrophysics Data System (ADS)

    Navarro-Gorris, A.; Garcia-Bernabé, A.; Stiriba, S.-E.

    2008-08-01

    Hyperbranched polymers are highly cascade branched polymers easily accessible via one-pot procedure from ABm type monomers. A key property of hyperbranched polymers is their molecular architecture, which allows core-shell morphology to be manipulated for further specific applications in material and medical sciences. Since the discovery of hyperbranched polymer materials, an increasing number of reports have been published describing synthetic procedures and technological applications of such materials, but their physical properties have remained less studied until the last decade. In the present work, different esterified hyperbranched polyglycerols have been prepared starting from polyglycerol precursors in presence of acetic acid, thus generating functionalization degree with range from 0 to 94%. Thermal analysis of the obtained samples has been studied by Differential Scanning Calorimetry (DSC). Dielectric Spectroscopy measurements have been analyzed by combining loss spectra deconvolution with the modulus formalism. In this regard, all acetylated polyglycerols exhibited a main relaxation related to the glass transition (α process) and two sub-glassy relaxations (β and γ processes) which vanish at high functionalization degrees.

  4. Synthesis and noncovalent protein conjugation of linear-hyperbranched PEG-poly(glycerol) alpha,omega(n)-telechelics.

    PubMed

    Wurm, Frederik; Klos, Johannes; Räder, Hans Joachim; Frey, Holger

    2009-06-17

    Linear-hyperbranched, heterobifunctional alpha,omega(n) telechelic block copolymers consisting of a linear poly(ethylene glycol) (PEG) chain and a hyperbranched polyglycerol (PG) block have been prepared in five steps, using a protected amino-functional initiator. The polyfunctionality omega(n) (OH groups) can be adjusted by the degree of polymerization (DP(n)) of the polyglycerol block. Subsequent introduction of a single biotin unit by amidation in alpha-position permitted noncovalent bioconjugation with avidin.

  5. Polyglycerol coatings of glass vials for protein resistance.

    PubMed

    Höger, Kerstin; Becherer, Tobias; Qiang, Wei; Haag, Rainer; Friess, Wolfgang; Küchler, Sarah

    2013-11-01

    Proteins are surface active molecules which undergo non-specific adsorption when getting in contact with surfaces such as the primary packaging material. This process is critical as it may cause a loss of protein content or protein aggregation. To prevent unspecific adsorption, protein repellent coatings are of high interest. We describe the coating of industrial relevant borosilicate glass vials with linear methoxylated polyglycerol, hyperbranched polyglycerol, and hyperbranched methoxylated polyglycerol. All coatings provide excellent protein repellent effects. The hyperbranched, non-methoxylated coating performed best. The protein repellent properties were maintained also after applying industrial relevant sterilization methods (≥200 °C). Marginal differences in antibody stability between formulations stored in bare glass vials and coated vials were detected after 3 months storage; the protein repellent effect remained largely stable. Here, we describe a new material suitable for the coating of primary packaging material of proteins which significantly reduces the protein adsorption and thus could present an interesting new possibility for biomedical applications.

  6. Size-dependant cellular uptake of dendritic polyglycerol.

    PubMed

    Reichert, Stephanie; Welker, Pia; Calderón, Marcelo; Khandare, Jayant; Mangoldt, Dorothea; Licha, Kai; Kainthan, Rajesh K; Brooks, Donald E; Haag, Rainer

    2011-03-21

    To study the mechanism of cellular internalization, hyperbranched polyether derivatives consisting of amino-bearing hyperbranched polyglycerols (HPGs) of varied molecular mass and size range are designed and synthesized. HPGs were further fluorescently labelled by conjugating maleimido indocarbocyanine dye (ICC-mal). The conjugates are characterized by UV-vis spectroscopy, fluorescence profile, zeta potential, and dynamic light scattering. The uptake mechanism is studied by fluorescence-activated cell sorting (FACS) analysis, fluorescence spectroscopy, and confocal microscopy with human lung cancer cells A549, human epidermoid carcinoma cells A431, and human umbilical vein endothelial cells (HUVEC) cells. For the first time, the results suggest that the higher-molecular-weight HPGs (40-870 kDa) predominantly accumulate in the cytoplasm much better than their low-molecular-weight counterparts (2-20 kDa). The HPG nanocarriers discussed here have many biomedical implications, particularly for delivering drugs to the targeted site.

  7. Beyond poly(ethylene glycol): linear polyglycerol as a multifunctional polyether for biomedical and pharmaceutical applications.

    PubMed

    Thomas, Anja; Müller, Sophie S; Frey, Holger

    2014-06-09

    Polyglycerols (sometimes also called "polyglycidols") represent a class of highly biocompatible and multihydroxy-functional polymers that may be considered as a multifunctional analogue of poly(ethylene glycol) (PEG). Various architectures based on a polyglycerol scaffold are feasible depending on the monomer employed. While polymerization of glycidol leads to hyperbranched polyglycerols, the precisely defined linear analogue is obtained by using suitably protected glycidol as a monomer, followed by removal of the protective group in a postpolymerization step. This review summarizes the properties and synthetic approaches toward linear polyglycerols (linPG), which are at present mainly based on the application of ethoxyethyl glycidyl ether (EEGE) as an acetal-protected glycidol derivative. Particular emphasis is placed on the manifold functionalization strategies including, e.g., the synthesis of end-functional linPGs or multiheterofunctional modifications at the polyether backbone. Potential applications like bioconjugation and utilization as a component in degradable biomaterials or for diagnostics, in which polyglycerol acts as a promising PEG substitute are discussed. In the last section, the important role of linear polyglycerol as a macroinitiator or as a highly hydrophilic segment in block co- or terpolymers is highlighted.

  8. Bacteria-repulsive polyglycerol surfaces by grafting polymerization onto aminopropylated surfaces.

    PubMed

    Weber, Theresa; Gies, Yasmin; Terfort, Andreas

    2012-11-13

    The formation of hydrogels on surfaces is a frequently used strategy to render these surfaces biorepulsive. Hyperbranched polyglycerol layers are a promising alternative to the frequently used polyethyleneglycol layers. Here, we present a strategy to covalently graft polyglycerol layers onto surfaces by first depositing an aminopropylsiloxane layer, which then acts as initiator layer for the ring-opening polymerization of 2-(hydroxymethyl)oxirane (glycidol). For silicon surfaces, the resulting polyglycerol layers start being biorepulsive for E. coli at a thickness of 2 nm and reach their highest bacterial repulsion (98%) at thicknesses of 7 nm or larger. This deposition strategy promises general applicability because the formation of aminopropylsiloxane layers has already been described for many materials.

  9. Phase behavior of hyperbranched polymer systems: experiments and application of the perturbed-chain polar SAFT equation of state.

    PubMed

    Kozłowska, Marta K; Jürgens, Bas F; Schacht, Christian S; Gross, Joachim; de Loos, Theo W

    2009-01-29

    Vapor-liquid equilibrium data for systems of hyperbranched polymer (HBP) and carbon dioxide are reported for temperatures of 285-455 K and pressures up to 13 MPa. The bubble-point pressures of (CO2 + hyperbranched polyester) and of (CO2 + hyperbranched polyglycerol + CH3OH) samples with fixed compositions were measured using a Cailletet apparatus. The system (CO2 + polyglycerol + CH3OH) also exhibits a liquid-liquid phase split characterized by lower critical solution temperatures. For this system cloud point curves and vapor-liquid-liquid bubble-point curves were also measured. Moreover, a thermodynamic model has been developed for HBP mixtures in the framework of the perturbed-chain polar statistical association fluid theory (PCP-SAFT) equation of state accounting for branching effects. There is no additional binary interaction parameter introduced along with the branching contributions to the model. Although the miscibility gap in the system (CO2 + polyglycerol + CH3OH) is not predicted by the model, PCP-SAFT including branching effects gives a good representation of the bubble-point curves of this system at temperatures lower than the lower solution temperature (LST).

  10. Biocompatible or biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications.

    PubMed

    Jin, Haibao; Huang, Wei; Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue

    2012-09-21

    Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes. The primary self-assemblies can be further assembled into more complex structures through hierachical self-assembly processes. Besides, the hyperbranched polymer vesicles have demonstrated great potential to be used as model membranes to mimic cellular behaviors, such as fusion, fission and cell aggregation. Other biomedical applications of HBPs as well as their self-assemblies are also briefly summarized.

  11. Synthesis and self-assembly behavior of POSS-embedded hyperbranched polymers.

    PubMed

    Li, Dawei; Niu, Yuguang; Yang, Yanyu; Wang, Xing; Yang, Fei; Shen, Hong; Wu, Decheng

    2015-05-14

    Here we demonstrate a simple and straightforward approach to prepare POSS-embedded hyperbranched (HB-POSS) polymers with customized molecular weights and sizes just by controlling the polymerization time. The polymers can be further used for building amphiphilic polymers, presenting morphological transition from micelle to vesicle in aqueous solution.

  12. High molecular weight polyglycerol-based multivalent mannose conjugates.

    PubMed

    Kizhakkedathu, Jayachandran N; Creagh, A Louise; Shenoi, Rajesh A; Rossi, Nicholas A A; Brooks, Donald E; Chan, Timmy; Lam, Jonathan; Dandepally, Srinivasa R; Haynes, Charles A

    2010-10-11

    We report the synthesis and characterization of multivalent mannose conjugates based on high molecular weight hyperbranched polyglycerols (HPG). A range of glycoconjugates were synthesized from high molecular weight HPGs (up to 493 kDa) and varying mannose units (22-303 per HPG). Hemagglutination assays using fresh human red blood cells and concanavalin A (Con A) showed that HPG-mannose conjugates exhibited a large enhancement in the relative potency of conjugates (as high as 40000) along with a significant increment in relative activity per sugar (up to 255). The size of the HPG scaffold and the number of mannose residues per HPG were all shown to influence the enhancement of binding interactions with Con A. Isothermal titration calorimetry (ITC) experiments confirmed the enhanced binding affinity and showed that both molecular size and ligand density play important roles. The enhancement in Con A binding to the high molecular weight HPG-mannose conjugates is due to a combination of inter- and intramolecular mannose binding. A few fold increments in the binding constant were obtained over mannose upon covalent attachment to HPG. The binding enhancement is due to the highly favorable entropic contribution to the multiple interactions of Con A to mannose residues on HPG. The high molecular weight HPG-mannose conjugates showed positive cooperativity in binding to Con A. Although carbohydrate density has less of an effect on functional valency of the conjugate compared to the molecular size, it determines the binding affinity.

  13. A fully synthetic glycopeptide antitumor vaccine based on multiple antigen presentation on a hyperbranched polymer.

    PubMed

    Glaffig, Markus; Palitzsch, Björn; Hartmann, Sebastian; Schüll, Christoph; Nuhn, Lutz; Gerlitzki, Bastian; Schmitt, Edgar; Frey, Holger; Kunz, Horst

    2014-04-07

    For antitumor vaccines both the selected tumor-associated antigen, as well as the mode of its presentation, affect the immune response. According to the principle of multiple antigen presentation, a tumor-associated MUC1 glycopeptide combined with the immunostimulating T-cell epitope P2 from tetanus toxoid was coupled to a multi-functionalized hyperbranched polyglycerol by "click chemistry". This globular polymeric carrier has a flexible dendrimer-like structure, which allows optimal antigen presentation to the immune system. The resulting fully synthetic vaccine induced strong immune responses in mice and IgG antibodies recognizing human breast-cancer cells.

  14. Enhanced immunogenicity of multivalent MUC1 glycopeptide antitumour vaccines based on hyperbranched polymers.

    PubMed

    Glaffig, M; Palitzsch, B; Stergiou, N; Schüll, C; Strassburger, D; Schmitt, E; Frey, H; Kunz, H

    2015-10-28

    Enhancing the immunogenicity of an antitumour vaccine still poses a major challenge. It depends upon the selected antigen and the mode of its presentation. We here describe a fully synthetic antitumour vaccine, which addresses both aspects. For the antigen, a tumour-associated MUC1 glycopeptide as B-cell epitope was synthesised and linked to the immunostimulating T-cell epitope P2 derived from tetanus toxoid. The MUC1-P2 conjugate is presented multivalently on a hyperbranched polyglycerol to the immune system. In comparison to a related vaccine of lower multivalency, this vaccine exposing more antigen structures on the hyperbranched polymer induced significantly stronger immune responses in mice and elicited IgG antibodies of distinctly higher affinity to epithelial tumour cells.

  15. Multivalent polyglycerol supported imidazolidin-4-one organocatalysts for enantioselective Friedel–Crafts alkylations

    PubMed Central

    Pecchioli, Tommaso; Muthyala, Manoj Kumar

    2015-01-01

    Summary The first immobilization of a MacMillan’s first generation organocatalyst onto dendritic support is described. A modified tyrosine-based imidazolidin-4-one was grafted to a soluble high-loading hyperbranched polyglycerol via a copper-catalyzed alkyne–azide cycloaddition (CuAAC) reaction and readily purified by dialysis. The efficiency of differently functionalized multivalent organocatalysts 4a–c was tested in the asymmetric Friedel–Crafts alkylation of N-methylpyrrole with α,β-unsaturated aldehydes. A variety of substituted enals was investigated to explore the activity of the catalytic system which was also compared with monovalent analogues. The catalyst 4b showed excellent turnover rates and no loss of activity due to immobilization, albeit moderate enantioselectivities were observed. Moreover, easy recovery by selective precipitation allowed the reuse of the catalyst for three cycles. PMID:26150897

  16. Multivalent polyglycerol supported imidazolidin-4-one organocatalysts for enantioselective Friedel-Crafts alkylations.

    PubMed

    Pecchioli, Tommaso; Muthyala, Manoj Kumar; Haag, Rainer; Christmann, Mathias

    2015-01-01

    The first immobilization of a MacMillan's first generation organocatalyst onto dendritic support is described. A modified tyrosine-based imidazolidin-4-one was grafted to a soluble high-loading hyperbranched polyglycerol via a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction and readily purified by dialysis. The efficiency of differently functionalized multivalent organocatalysts 4a-c was tested in the asymmetric Friedel-Crafts alkylation of N-methylpyrrole with α,β-unsaturated aldehydes. A variety of substituted enals was investigated to explore the activity of the catalytic system which was also compared with monovalent analogues. The catalyst 4b showed excellent turnover rates and no loss of activity due to immobilization, albeit moderate enantioselectivities were observed. Moreover, easy recovery by selective precipitation allowed the reuse of the catalyst for three cycles.

  17. Direct grafting of anti-fouling polyglycerol layers to steel and other technically relevant materials.

    PubMed

    Weber, Theresa; Bechthold, Maren; Winkler, Tobias; Dauselt, John; Terfort, Andreas

    2013-11-01

    Direct grafting of hyperbranched polyglycerol (PG) layers onto the oxide surfaces of steel, aluminum, and silicon has been achieved through surface-initiated polymerization of 2-hydroxymethyloxirane (glycidol). Optimization of the deposition conditions led to a protocol that employed N-methyl-2-pyrrolidone (NMP) as the solvent and temperatures of 100 and 140 °C, depending on the substrate material. In all cases, a linear growth of the PG layers could be attained, which allows for control of film thickness by altering the reaction time. At layer thicknesses >5 nm, the PG layers completely suppressed the adhesion of albumin, fibrinogen, and globulin. These layers were also at least 90% bio-repulsive for two bacteria strains, E. coli and Acinetobacter baylyi, with further improvement being observed when the PG film thickness was increased to 17 nm (up to 99.9% bio-repulsivity on silicon).

  18. Multifunctional polyglycerol-grafted Fe₃O₄@SiO₂ nanoparticles for targeting ovarian cancer cells.

    PubMed

    Wang, Liang; Neoh, Koon Gee; Kang, En-Tang; Shuter, Borys

    2011-03-01

    Ligand-mediated magnetic resonance (MR) contrast agents would be highly desirable for cancer diagnosis. In the present study, nanoparticles of Fe₃O₄ core with fluorescent SiO₂ shell were synthesized and grafted with hyperbranched polyglycerol (HPG-grafted Fe₃O₄@SiO₂ nanoparticles). These nanoparticles have a hydrodynamic diameter of 47.0 ± 4.0 nm, and are very stable in aqueous solution as well as in cell culture medium. Numerous surface hydroxyl groups of these nanoparticles were conjugated with folic acid by a thiol 'click' reaction. The successful covalent attachment of folic acid on the nanoparticles was confirmed by FTIR and XPS analyses. Both MR imaging and fluorescence microscopy show significant preferential uptake of the folic acid-conjugated polyglycerol-grafted Fe₃O₄@SiO₂ (FA-HPG-grafted Fe₃O₄@SiO₂) nanoparticles by human ovarian carcinoma cells (SKOV-3) as compared to macrophages and fibroblasts. Such nanoparticles can potentially be used to provide real-time imaging in ovarian cancer resection.

  19. Imidazole and dimethyl aminopropyl-functionalized hyperbranched polymers for nucleic acid transfection.

    PubMed

    Germershaus, Oliver; Pickaert, Guillaume; Konrad, Juliane; Krüger, Ute; Kissel, Thomas; Haag, Rainer

    2010-09-09

    In order to mimic the histidine binding motives of naturally occurring histones as DNA complexing proteins, hyperbranched poly(ethylene imine) and polyglycerol were functionalized with imidazole or 3-dimethylamino propyl groups. These new polycationic polymers were tested for interaction with dye-labelled oligonucleotide and DNA using UV and fluorescence spectroscopy and gel electrophoresis. Formation of stable complexes was observed above N/P ratios of 4 for unfunctionalized and 8 for functionalized PEIs. No stable complexes were formed with polyglycerol-based polyamines up to N/P 16. Cytotoxicity determined by MTT assay of all functionalized PEI polymers was found to be significantly lower than for unfunctionalized PEI. PG-based polymers showed no toxicity in the tested concentration range. Dynamic light scattering showed that only for PEI(21)-Imidaz polyplexes hydrodynamic diameters below 250 nm could be reached.The influence of functionalization and polymer type on transfection efficiency was evaluated in L929, NIH/3T3 and HeLa cells. Only imidazole-functionalized PEIs reached similar transfection efficiencies as unfunctionalized PEIs, while 3-dimethylamino propyl modification resulted in lower transfection efficiencies. We also demonstrated that the polymer plays an important role for transfection properties since, regardless of the modifications of polyglycerol, only low transfection efficiencies were observed at functionalization levels below 50%.

  20. Hyperbranched Polyglycerol‐Induced Porous Silica Nanoparticles as Drug Carriers for Cancer Therapy In Vitro and In Vivo

    PubMed Central

    Yang, Yang; Wang, Anhe; Wei, Qiang; Schlesener, Cathleen; Haag, Rainer; Li, Qi

    2016-01-01

    Abstract Mesoporous silica‐based nanoparticles are generally accepted as a potential platform for drug loading with a lot of advantages, except for their complex purification procedures and structures that are difficult to decompose. In this work, biocompatible hyperbranched polyglycerol is introduced to synthesize mesoporous silica nanoparticles (MSNs). The materials possess good biocompatibility, controlled release, and biodegradability. They also show passive targeting capability through the enhanced permeability and retention effect and can be excreted from the biological system. The method avoids the needs to employ traditional surfactants and complicated purified procedures, which make these MSNs an efficient delivery system for cancer therapy. PMID:28168161

  1. Directing the self-assembly of semiconducting copolymers: the consequences of grafting linear or hyperbranched polyether side chains.

    PubMed

    zur Borg, Lisa; Schüll, Christoph; Frey, Holger; Zentel, Rudolf

    2013-08-01

    The synthesis and self-assembly of novel semiconducting rod-coil type graft block copolymers based on poly(para-phenylene vinylene) (PPV) copolymers is presented, focusing on the ordering effect of linear versus hyperbranched side chains. Using an additional reactive ester block, highly polar, linear poly(ethylene glycol), and hyperbranched polyglycerol side chains are attached in a grafting-to approach. Remarkably, the resulting novel semiconducting graft copolymers with polyether side chains show different solubility and side-chain directed self-assembly behavior in various solvents, e.g., cylindrical or spherical superstructures in the size range of 10 to 120 nm, as shown by TEM. By adjusting the molecular weight and the topology of the polyether segments, self-assembly into defined superstructures can be achieved, which is important for the efficient charge transport in potential electronic applications.

  2. Monofunctional hyperbranched ethylene oligomers.

    PubMed

    Wiedemann, Thomas; Voit, Gregor; Tchernook, Alexandra; Roesle, Philipp; Göttker-Schnetmann, Inigo; Mecking, Stefan

    2014-02-05

    The neutral κ(2)N,O-salicylaldiminato Ni(II) complexes [κ(2)N,O-{(2,6-(3',5'-R2C6H3)2C6H3-N═C(H)-(3,5-I2-2-O-C6H2)}]NiCH3(pyridine)] (1a-pyr, R = Me; 1b-pyr, R = Et; 1c-pyr, R = iPr) convert ethylene to hyperbranched low-molecular-weight oligomers (Mn ca. 1000 g mol(-1)) with high productivities. While all three catalysts are capable of generating hyperbranched structures, branching densities decrease significantly with the nature of the remote substituent along Me > Et > iPr and oligomer molecular weights increase. Consequently, only 1a-pyr forms hyperbranched structures over a wide range of reaction conditions (ethylene pressure 5-30 atm and 20-70 °C). An in situ catalyst system achieves similar activities and identical highly branched oligomer microstructures, eliminating the bottleneck given by the preparation and isolation of Ni-Me catalyst precursor species. Selective introduction of one primary carboxylic acid ester functional group per highly branched oligoethylene molecule was achieved by isomerizing ethoxycarbonylation and alternatively cross metathesis with ethyl acrylate followed by hydrogenation. The latter approach results in complete functionalization and no essential loss of branched oligomer material and molecular weight, as the reacting double bonds are close to a chain end. Reduction yielded a monoalcohol-functionalized oligomer. Introduction of one reactive epoxide group per branched oligomer occurs completely and selectively under mild conditions. All reaction steps involved in oligomerization and monofunctionalization are efficient and readily scalable.

  3. Click modification of multifunctional liposomes bearing hyperbranched polyether chains.

    PubMed

    Fritz, Thomas; Hirsch, Markus; Richter, Felix C; Müller, Sophie S; Hofmann, Anna M; Rusitzka, Kristiane A K; Markl, Jürgen; Massing, Ulrich; Frey, Holger; Helm, Mark

    2014-07-14

    Aiming at controlled modification of liposomal surface structures, we describe a postpreparational approach for surface derivatization of a new type of multifunctional, sterically stabilized liposomes. Application of dual centrifugation (DC) resulted in high encapsulation efficiencies above 50% at very small batch sizes with a total volume of 150 μL, which were conductive to fast and efficient optimization of variegated surface modification reactions. Cholesterol-polymer amphiphiles, including complex hyperbranched polyether structures bearing 1-4 terminal alkynes, were used in DC formulations to provide steric stabilization. The alkyne moieties were explored as anchors for the conjugation of small molecules to the liposomal surface via click chemistry, binding 350-450 fluorophores per liposome as examples for surface active molecules. Using Förster resonance energy transfer (FRET) spectroscopy, the conjugation reaction as well as the uptake of FRET-labeled liposomes by RBE4 cells was monitored, and the distribution of the fluorescent lipids among cellular structures and membranes could be studied. Thus, the combination of clickable hyperbranched amphiphiles and dual centrifugation provides access to well-defined liposomal formulations with a variety of surface moieties.

  4. Polyglycerol-grafted superparamagnetic iron oxide nanoparticles: highly efficient MRI contrast agent for liver and kidney imaging and potential scaffold for cellular and molecular imaging.

    PubMed

    Arsalani, Nasser; Fattahi, Hassan; Laurent, Sophie; Burtea, Carmen; Vander Elst, Luce; Muller, Robert N

    2012-01-01

    Polyglycerol as a water-soluble and biocompatible hyperbranched polymer was covalently grafted on the surface of superparamagnetic iron oxide nanoparticles. With this aim, superparamagnetic magnetite nanoparticles were prepared by coprecipitation in aqueous media, then the surface of nanoparticles was modified to introduce the reactive groups on the surface of nanoparticles. After that, polyglycerol was grafted on the surface of nanoparticles by ring-opening anionic polymerization of glycidol using n-bulyllithium as initiator. The magnetometry, relaxometry and phantom MRI experiments of this highly stable ferrofluid showed its high potential as a negative MRI contrast agent. Calculated r(1) and r(2) relaxivities at different magnetic fields were higher than the values reported for commercially available iron oxide contrast agents. The in vivo MRI studies showed that, after intravenous injection into mice, the particles produced a strong negative contrast in liver and kidneys, which persisted for 80 min (in liver) to 110 min (in kidneys). The negative contrast of the liver and kidneys weakened over the time, suggesting that polyglycerol coating renders the nanoparticles stealth and possibly optimal for renal excretion.

  5. Influence of architecture of high molecular weight linear and branched polyglycerols on their biocompatibility and biodistribution.

    PubMed

    Imran ul-haq, Muhammad; Lai, Benjamin F L; Chapanian, Rafi; Kizhakkedathu, Jayachandran N

    2012-12-01

    The availability of long circulating, multifunctional polymers is critical to the development of drug delivery systems and bioconjugates. The ease of synthesis and functionalization make linear polymers attractive but their rapid clearance from circulation compared to their branched or cyclic counterparts, and their high solution viscosities restrict their applications in certain settings. Herein, we report the unusual compact nature of high molecular weight (HMW) linear polyglycerols (LPGs) (LPG - 100; M(n) - 104 kg mol(-1), M(w)/M(n) - 1.15) in aqueous solutions and its impact on its solution properties, blood compatibility, cell compatibility, in vivo circulation, biodistribution and renal clearance. The properties of LPG have been compared with hyperbranched polyglycerol (HPG) (HPG-100), linear polyethylene glycol (PEG) with similar MWs. The hydrodynamic size and the intrinsic viscosity of LPG-100 in water were considerably lower compared to PEG. The Mark-Houwink parameter of LPG was almost 10-fold lower than that of PEG. LPG and HPG demonstrated excellent blood and cell compatibilities. Unlike LPG and HPG, HMW PEG showed dose dependent activation of blood coagulation, platelets and complement system, severe red blood cell aggregation and hemolysis, and cell toxicity. The long blood circulation of LPG-100 (t(1/2β,) 31.8 ± 4 h) was demonstrated in mice; however, it was shorter compared to HPG-100 (t(1/2β,) 39.2 ± 8 h). The shorter circulation half life of LPG-100 was correlated with its higher renal clearance and deformability. Relatively lower organ accumulation was observed for LPG-100 and HPG-100 with some influence of on the architecture of the polymers. Since LPG showed better biocompatibility profiles, longer in vivo circulation time compared to PEG and other linear drug carrier polymers, and has multiple functionalities for conjugation, makes it a potential candidate for developing long circulating multifunctional drug delivery systems similar to HPG.

  6. Hyperbranched-hyperbranched polymeric nanoassembly to mediate controllable co-delivery of siRNA and drug for synergistic tumor therapy.

    PubMed

    Jia, Hui-Zhen; Zhang, Wei; Zhu, Jun-Yi; Yang, Bin; Chen, Si; Chen, Gang; Zhao, Yi-Fang; Feng, Jun; Zhang, Xian-Zheng

    2015-10-28

    This study reported a flexible nanoplatform constructed on the pH-dependent self-assembly of two kinds of hyperbranched polymers, and then validated its potency as the controllable siRNA/drug co-delivery vehicle for the combination of chemotherapy with RNA interfering (RNAi) therapy. By virtue of pH-reversible phenylboronate linking, phenylboronic acid-tethered hyperbranched oligoethylenimine (OEI600-PBA) and 1,3-diol-rich hyperbranched polyglycerol (HBPO) can be spontaneously interlinked together into a core-corona nanoconstruction. The special buildup of compactly clustering OEI600-PBA units around hydrophobic HBPO aggregate offered significant advantages over parent OEI600-PBA, including strengthened affinity to siRNA, ability of further loading anticancer drug, easier cellular transport, and acidity-responsive release of payloads. To evaluate the co-delivery capability, Beclin1 siRNA and antitumor DOX were used as the therapeutic models in order to suppress the post-chemotherapy survival of tumor cells caused by drug-induced autophagy. The nanoassembly-mediated single delivery of DOX displayed even better anticancer effects than free DOX, demonstrating the superiority of our pH-responsive nano-design. The nanoassembly-mediated co-delivery of siRNA together with DOX can effectively silence Beclin1 gene, suppress DOX-induced autophagy, and consequently provide strong synergism with a significant enhancement of cell-killing effects in cultured cancerous cells. The in vivo combinational treatment was shown to make the tumor more sensitive to DOX chemotherapy while displaying substantially improved safety as compared with the monochemotherapy.

  7. Self-assembly of hyperbranched polymers and its biomedical applications.

    PubMed

    Zhou, Yongfeng; Huang, Wei; Liu, Jinyao; Zhu, Xinyuan; Yan, Deyue

    2010-11-02

    Hyperbranched polymers (HBPs) are highly branched macromolecules with a three-dimensional dendritic architecture. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. In this paper, the recent developments in HBP self-assembly and their biomedical applications have been comprehensively reviewed. Many delicate supramolecular structures from zero-dimension (0D) to three-dimension (3D), such as micelles, fibers, tubes, vesicles, membranes, large compound vesicles and physical gels, have been prepared through the solution or interfacial self-assembly of amphiphilic HBPs. In addition, these supramolecular structures have shown promising applications in the biomedical areas including drug delivery, protein purification/detection/delivery, gene transfection, antibacterial/antifouling materials and cytomimetic chemistry. Such developments promote the interdiscipline researches among surpramolecular chemistry, biomedical chemistry, nano-technology and functional materials.

  8. Self-assembly of amido-ended hyperbranched polyester films with a highly ordered dendritic structure.

    PubMed

    Zhang, Daohong; Xu, Zhicai; Li, Junna; Chen, Sufang; Cheng, Juan; Zhang, Aiqing; Chen, Shenghui; Miao, Menghe

    2014-09-24

    Self-assemblies fabricated from dendrimers and amphiphilic polymers have demonstrated remarkable performances and a wide range of applications. Direct self-assembly of hyperbranched polymers into highly ordered macrostructures with heat-resistance remains a big challenge due to the weak amphiphilicity of the polymers. Here, we report the self-assembly of amphiphilic amido-ended hyperbranched polyester (HTDA-2) into millimeter-size dendritic films using combined hydrogen bond interaction and solvent induction. The self-assembly process and mechanism have been studied. Hydrogen bond interaction between amido-ended groups assists the aggregation of inner and outer chains of the HTDA-2, resulting in phase separation and micelle formation. Some micelles attach to and grow on the glass substrate like seedlings. Other micelles move to the seedlings and connect with their branches via solvent induction and hydrogen bond interaction, leading to the fabrication of highly ordered crystalline dendritic films that show high heat-resistance. HTDA-2 can further self-assemble into sheet crystals on the dendritic films.

  9. Biocompatible hyperbranched polyglycerol modified β-cyclodextrin derivatives for docetaxel delivery.

    PubMed

    Xu, Zejun; Zhang, Yi; Hu, Qian; Tang, Qiao; Xu, Jiake; Wu, Jianping; Kirk, Thomas Brett; Ma, Dong; Xue, Wei

    2017-02-01

    The development of biocompatible vector for hydrophobic drug delivery remains a longstanding issue in cancer therapy. We design and synthesis a drug delivery system based on HPG modified β-CD (β-CD-HPG) by conjugating HPG branches onto β-CD core and its structure was confirmed by NMR, FTIR, GPC and solubility. In vitro biocompatibility tests showed that HPG modification significantly improved red blood cells morphology alteration and hemolysis cause by β-CD and β-CD-HPG displayed cell safety apparently in a wide range of 0.01-1mg/mL. An anti-cancer drug, docetaxel, was effectively encapsulated into β-CD-HPG which was confirmed by DSC analysis. This copolymer could form nanoparticles with small size (<200nm) and exhibited better DTX loading capacity and controlled release kinetics without initial burst release behavior compared with β-CD. Furthermore, antitumor assay in vitro show that β-CD-HPG/DTX effectively inhibited proliferation of human breast adenocarcinoma cells. Therefore, β-CD-HPG/DTX exhibit great potential for cancer chemotherapy.

  10. Polyglycerol-Based Copper Chelators for the Transport and Release of Copper Ions in Biological Environments.

    PubMed

    Albrecht, Ralf; Fehse, Susanne; Pant, Kritee; Nowag, Sabrina; Stephan, Holger; Haag, Rainer; Tzschucke, Carl Christoph

    2016-03-01

    Here, the synthesis and characterization of three improved nanosystems is presented based on amino functionalized hyperbranched polyglycerol (hPG; M(w) = 16.8 kDa) as potential copper(II) chelators. The ligands, N-methyl-N-picolylglycine amide, 2,6-pyridine dicarboxylic acid monoamide, and cyclam tetraacetic acid (TETA) monoamide, are covalently attached to the polymer with amide bonds. In this paper, the Cu(II) loading capacity, the stability of the Cu(II)-loaded carriers at different pHs, with competing ligands and in human serum, as well as the transport of Cu(II) in biological systems are investigated. For the first time, a different cytotoxicity of functionalized polymer nanoparticles with and without Cu(II) is observed. The cyclam-based carrier combines the highest loading capacity (29 Cu ions/nanoparticle), best stability with respect to pH and EDTA (45% remaining Cu after 24 h), lowest cytotoxicity (IC50 > 100 × 10(-6) M (unloaded), 1500 × 10(-6) M Cu(II); Cu:carrier 29:1), and the highest stability in human serum.

  11. Highly efficient hyperbranched CNT surfactants: influence of molar mass and functionalization.

    PubMed

    Bertels, Ellen; Bruyninckx, Kevin; Kurttepeli, Mert; Smet, Mario; Bals, Sara; Goderis, Bart

    2014-10-21

    End-group-functionalized hyperbranched polymers were synthesized to act as a carbon nanotube (CNT) surfactant in aqueous solutions. Variation of the percentage of triphenylmethyl (trityl) functionalization and of the molar mass of the hyperbranched polyglycerol (PG) core resulted in the highest measured surfactant efficiency for a 5000 g/mol PG with 5.6% of the available hydroxyl end-groups replaced by trityl functions, as shown by UV-vis measurements. Semiempirical model calculations suggest an even higher efficiency for PG5000 with 2.5% functionalization and maximal molecule specific efficiency in general at low degrees of functionalization. Addition of trityl groups increases the surfactant-nanotube interactions in comparison to unfunctionalized PG because of π-π stacking interactions. However, at higher functionalization degrees mutual interactions between trityl groups come into play, decreasing the surfactant efficiency, while lack of water solubility becomes an issue at very high functionalization degrees. Low molar mass surfactants are less efficient compared to higher molar mass species most likely because the higher bulkiness of the latter allows for a better CNT separation and stabilization. The most efficient surfactant studied allowed dispersing 2.85 mg of CNT in 20 mL with as little as 1 mg of surfactant. These dispersions, remaining stable for at least 2 months, were mainly composed of individual CNTs as revealed by electron microscopy.

  12. Hyperbranched PEG-based supramolecular nanoparticles for acid-responsive targeted drug delivery.

    PubMed

    Chen, Xiaofei; Yao, Xuemei; Wang, Chunran; Chen, Li; Chen, Xuesi

    2015-06-01

    Herein, hyperbranched poly(ethylene glycol)-based supramolecular nanoparticles with pH-sensitive properties were designed and used for targeted drug delivery. Via host-guest recognition between benzimidazole anchored poly(ethylene glycol)-hyperbranched polyglycerol (PEG-HPG-BM) and folic acid modified CD (FA-CD), targeted supramolecular nanoparticles (TSNs) were fabricated. At neutral aqueous conditions TSNs could load the model drug DOX. While under intracellular acidic conditions the loaded-drug would be released due to the protonation of BM. This protonation allowed the supramolecular nanoparticles to expand or even disassemble, which showes the pH-dependent property. The introduction of the active targeting FA molecule and the specific interactions with the receptor of HeLa cells means that DOX-loaded TSNs show a significantly improved anticancer efficacy. In vitro drug release assays and intracellular experiments confirmed that TSNs had an obvious pH-sensitive property and remarkably improved anticancer effects, which hold great potential for further biomedical applications such as anticancer drug delivery.

  13. 21 CFR 172.854 - Polyglycerol esters of fatty acids.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ..., lard, palm oil from fruit, peanut oil, safflower oil, sesame oil, soybean oil, and tallow and the fatty... physical or technical effect. (c) Polyglycerol esters of a mixture of stearic, oleic, and coconut...

  14. 21 CFR 172.854 - Polyglycerol esters of fatty acids.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... conditions: (a) They are prepared from corn oil, cottonseed oil, lard, palm oil from fruit, peanut oil...) Polyglycerol esters of a mixture of stearic, oleic, and coconut fatty acids are used as a cloud inhibitor...

  15. 21 CFR 172.854 - Polyglycerol esters of fatty acids.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ..., lard, palm oil from fruit, peanut oil, safflower oil, sesame oil, soybean oil, and tallow and the fatty... physical or technical effect. (c) Polyglycerol esters of a mixture of stearic, oleic, and coconut...

  16. 21 CFR 172.854 - Polyglycerol esters of fatty acids.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ..., lard, palm oil from fruit, peanut oil, safflower oil, sesame oil, soybean oil, and tallow and the fatty... physical or technical effect. (c) Polyglycerol esters of a mixture of stearic, oleic, and coconut...

  17. 21 CFR 172.854 - Polyglycerol esters of fatty acids.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ..., lard, palm oil from fruit, peanut oil, safflower oil, sesame oil, soybean oil, and tallow and the fatty... physical or technical effect. (c) Polyglycerol esters of a mixture of stearic, oleic, and coconut...

  18. Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications.

    PubMed

    Jiang, Wenfeng; Zhou, Yongfeng; Yan, Deyue

    2015-06-21

    Vesicles, including lipid vesicles, surfactant vesicles, as well as polymer vesicles, have been extensively investigated over the past fifty years. Among them, polymer vesicles have attracted more and more attention because of their low permeability, superior stability and toughness, in addition to the numerous possibilities for tailoring physical, chemical and biological properties. Polymer vesicles are generally fabricated through the self-assembly of amphiphilic polymers with a linear architecture. Recently, as representative polymers with a highly branched three-dimensional architecture, hyperbranched polymers have also exhibited great potential for preparing vesicles. The resultant hyperbranched polymer vesicles, defined as branched-polymersomes (BPs), have shown unique properties, such as giant and easily tuned vesicle sizes, facile functionalization, a special formation mechanism, and appealing solution behaviours. In this tutorial review, ten years of advances in BPs have been summarized since their first discovery in the year 2004, including the syntheses of vesicle-forming hyperbranched polymers, self-assembly methods, self-assembly mechanisms, as well as the special properties. In addition, the cytomimetic, biomedical and other initiatory applications of BPs are also included.

  19. Squaric acid mediated synthesis and biological activity of a library of linear and hyperbranched poly(glycerol)-protein conjugates.

    PubMed

    Wurm, Frederik; Dingels, Carsten; Frey, Holger; Klok, Harm-Anton

    2012-04-09

    Polymer-protein conjugates generated from side chain functional synthetic polymers are attractive because they can be easily further modified with, for example, labeling groups or targeting ligands. The residue specific modification of proteins with side chain functional synthetic polymers using the traditional coupling strategies may be compromised due to the nonorthogonality of the side-chain and chain-end functional groups of the synthetic polymer, which may lead to side reactions. This study explores the feasibility of the squaric acid diethyl ester mediated coupling as an amine selective, hydroxyl tolerant, and hydrolysis insensitive route for the preparation of side-chain functional, hydroxyl-containing, polymer-protein conjugates. The hydroxyl side chain functional polymers selected for this study are a library of amine end-functional, linear, midfunctional, hyperbranched, and linear-block-hyperbranched polyglycerol (PG) copolymers. These synthetic polymers have been used to prepare a diverse library of BSA and lysozyme polymer conjugates. In addition to exploring the scope and limitations of the squaric acid diethylester-mediated coupling strategy, the use of the library of polyglycerol copolymers also allows to systematically study the influence of molecular weight and architecture of the synthetic polymer on the biological activity of the protein. Comparison of the activity of PG-lysozyme conjugates generated from relatively low molecular weight PG copolymers did not reveal any obvious structure-activity relationships. Evaluation of the activity of conjugates composed of PG copolymers with molecular weights of 10000 or 20000 g/mol, however, indicated significantly higher activities of conjugates prepared from midfunctional synthetic polymers as compared to linear polymers of similar molecular weight.

  20. Polymeric assembly of hyperbranched building blocks to establish tunable nanoplatforms for lysosome acidity-responsive gene/drug co-delivery.

    PubMed

    Jia, Hui-Zhen; Zhang, Wei; Wang, Xu-Li; Yang, Bin; Chen, Wei-Hai; Chen, Si; Chen, Gang; Zhao, Yi-Fang; Zhuo, Ren-Xi; Feng, Jun; Zhang, Xian-Zheng

    2015-07-01

    This study plans to develop a nanoparticle technology that can assemble different polymeric "building blocks" with various desired functionalities into one nanosystem in a pH-dependent manner. For this purpose, polymeric building blocks were specifically designed with hyperbranched architectures, and orthogonal pH-reversible phenylboronic acid-diols were taken as "joints" to integrate them together. To verify the idea, a corona-core dual-polymer nanoassembly was prepared as the vehicle for lysosomotropic gene/drug co-delivery. Phenylboronic acid modified hyperbranched oligoethylenimine (OEI-PBA) was arranged to cluster around the hydrophobic core composed of hyperbranched polyglycerol, just by mixing two polymers in an appropriate ratio at neutral conditions. Compared with the parent OEI-PBA, this nanoassembly demonstrated better capture of plasmid DNA, highly enhanced activity for cellular transport and gene transfection (up to 100 fold), the ability to further load hydrophobic drugs, lysosome acidity-targeting pH-dependent release of both carried cargoes, and improved cell-biocompatibility. To evaluate its potential for combinational gene/drug therapy, in vitro experiments using the therapeutic p53 gene and antitumor doxorubicin as models were carried out. This intracellular co-delivery led to apparently synergetic anti-cancer effects in cultured cancer cells. This dynamic paradigm shows interesting features including easy manipulation, reversible conjugation, lysosome-targeting pH-responsiveness, high co-delivery efficiency, and functional expandability by further accommodating other building blocks.

  1. In vivo circulation, clearance, and biodistribution of polyglycerol grafted functional red blood cells.

    PubMed

    Chapanian, Rafi; Constantinescu, Iren; Brooks, Donald E; Scott, Mark D; Kizhakkedathu, Jayachandran N

    2012-04-01

    The in vivo circulation of hyperbranched polyglycerol (HPG) grafted red blood cells (RBCs) was investigated in mice. The number of HPG molecules grafted per RBC was measured using tritium labeled HPGs ((3)H-HPG) of different molecular weights; the values ranged from 1 × 10(5) to 2 × 10(6) molecules per RBC. HPG-grafted RBCs were characterized in vitro by measuring the electrophoretic mobility, complement mediated lysis, and osmotic fragility. Our results show that RBCs grafted with 1.5 × 10(5) HPG molecules per RBC having molecular weights 20 and 60 kDa have similar characteristics as that of control RBCs. The in vivo circulation of HPG-grafted RBCs was measured by a tail vain injection of (3)H-HPG60K-RBC in mice. The radioactivity of isolated RBCs, whole blood, plasma, different organs, urine and feces was evaluated at different time intervals. The portion of (3)H-HPG60K-RBC that survived the first day in mice (52%) remained in circulation for 50 days. Minimal accumulation radioactivity in organs other than liver and spleen was observed suggesting the normal clearance mechanism of modified RBCs. Animals gained normal weights and no abnormalities observed in necropsy analysis. The stability of the ester-amide linker between the RBC and HPG was evaluated by comparing the clearance rate of (3)H-HPG60K-RBC and PKH-26 lipid fluorescent membrane marker labeled HPG60K-RBCs. HPG modified RBCs combine the many advantages of a dendritic polymer and RBCs, and hold great promise in systemic drug delivery and other applications of functional RBC.

  2. Biodegradable polyglycerols with randomly distributed ketal groups as multi-functional drug delivery systems.

    PubMed

    Shenoi, Rajesh A; Lai, Benjamin F L; Imran ul-haq, Muhammad; Brooks, Donald E; Kizhakkedathu, Jayachandran N

    2013-08-01

    Biodegradable multi-functional polymeric nanostructures that undergo controlled degradation in response to physiological cues are important in numerous biomedical applications including drug delivery, bio-conjugation and tissue engineering. In this paper, we report the development of a new class of water soluble multi-functional branched biodegradable polymer with high molecular weight and biocompatibility which demonstrates good correlation of in vivo biodegradation and in vitro hydrolysis. Main chain degradable hyperbranched polyglycerols (HPG) (20-100 kDa) were synthesized by the introduction of acid labile groups within the polymer structure by an anionic ring opening copolymerization of glycidol with ketal-containing epoxide monomers with different ketal structures. The water soluble biodegradable HPGs with randomly distributed ketal groups (RBHPGs) showed controlled degradation profiles in vitro depending on the pH of solution, temperature and the structure of incorporated ketal groups, and resulted in non-toxic degradation products. NMR studies demonstrated the branched nature of RBHPGs which is correlating with their smaller hydrodynamic radii. The RBHPGs and their degradation products exhibited excellent blood compatibility and tissue compatibility based on various analyses methods, independent of their molecular weight and ketal group structure. When administered intravenously in mice, tritium labeled RBHPG of molecular weight 100 kDa with dimethyl ketal group showed a circulation half life of 2.7 ± 0.3 h, correlating well with the in vitro polymer degradation half life (4.3 h) and changes in the molecular weight profile during the degradation (as measured by gel permeation chromatography) in buffer conditions at 37 °C. The RBHPG degraded into low molecular weight fragments that were cleared from circulation rapidly. The biodistribution and excretion studies demonstrated that RBHPG exhibited significantly lower tissue accumulation and enhanced urinary

  3. Degradation behavior of poly(glycerol sebacate).

    PubMed

    Pomerantseva, Irina; Krebs, Nicholas; Hart, Alison; Neville, Craig M; Huang, Albert Y; Sundback, Cathryn A

    2009-12-15

    Poly(glycerol sebacate) (PGS), a promising scaffold material for soft tissue engineering applications, is a soft, tough elastomer with excellent biocompatibility. However, the rapid in vivo degradation rate of PGS limits its use as a scaffold material. To determine the impact of crosslink density on degradation rate, a family of PGS materials was synthesized by incrementally increasing the curing time from 42 to 144 h, at 120 degrees C and 10 mTorr vacuum. As expected, PGS became a stiffer, tougher, and stronger elastomer with increasing curing time. PGS disks were subcutaneously implanted into rats and periodically harvested; only mild tissue responses were observed and the biocompatibility remained excellent. Regardless of crosslink density, surface erosion degradation was observed. The sample dimensions linearly decreased with implantation time, and the mass loss rates were constant after 1-week implantation. As surface erosion degradation frequently correlates with enzymatic digestion, parallel in vitro digestion studies were conducted in lipase solutions which hydrolyze ester bonds. Enzymatic digestion played a significant role in degrading PGS, and the mass loss rates were not a function of curing time. Alternative chemistry approaches will be required to decrease the enzymatic hydrolysis rate of the ester bonds in PGS polymers.

  4. Synthesis, characterization and application of polyglycerol coated Fe3O4 nanoparticles as a nano-theranostics agent

    NASA Astrophysics Data System (ADS)

    Jahandar, Marzieh; Zarrabi, Ali; Shokrgozar, Mohammad Ali; Mousavi, Hajar

    2015-12-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) with an average size of 10 nm have been successfully synthesized by the polyol method. Then, hyperbranched polyglycerol (HPG) branches have been introduced on the surface of SPIONs through ring opening polymerization of glycidol as a biocompatible surface modifier with a more hydrophilic nature than other biomedical polymers. The as-synthesized SPION-HPGs were analyzed by FT-IR, CHNS and TGA analysis which all exhibited the successful HPG grafting onto the SPION surface. The anticancer herbal drug, curcumin, was loaded on the resultant nanocarrier. The MTT assay demonstrated the non-cytotoxicity effect of SPION-HPGs and the low cytotoxicity effect of curcumin at low concentrations on L929 and MCF-7 cell lines as normal and cancerous cells, respectively. Moreover, these nanoparticles exhibited an improved effect as a contrast agent in magnetic resonance imaging. Thus, it is concluded that SPION-HPG has the potential to be used in theranostics applications due to its simultaneous drug delivery and imaging capabilities.

  5. Systematic adjustment of charge densities and size of polyglycerol amines reduces cytotoxic effects and enhances cellular uptake.

    PubMed

    Hellmund, Markus; Achazi, Katharina; Neumann, Falko; Thota, Bala N S; Ma, Nan; Haag, Rainer

    2015-11-01

    Excessive cationic charge density of polyplexes during cellular uptake is still a major hurdle in the field of non-viral gene delivery. The most efficient cationic vectors such as polyethylene imine (PEI) or polyamidoamine (PAMAM) can be highly toxic and may induce strong side effects due to their high cationic charge densities. Alternatives like polyethylene glycol (PEG) are used to 'shield' these charges and thus to reduce the cytotoxic effects known for PEI/PEG-core-shell architectures. In this study, we compared the ability of hyperbranched polyglycerol amines (hPG amines) with different amine densities and molecular weights as non-viral cationic vectors for DNA delivery. By adjusting the hydroxyl to amine group ratio on varying molecular weights, we were able to perform a systematic study on the cytotoxic effects caused by the effective charge density in correlation to size. We could demonstrate that carriers with moderate charge density have a higher potential for effective DNA delivery as compared to high/low charged ones independent of their size, but the final efficiency can be optimized by the molecular weight. We analyzed the physicochemical properties and cellular uptake capacity as well as the cytotoxicity and transfection efficiency of these new vector systems.

  6. Marginally compact hyperbranched polymer trees.

    PubMed

    Dolgushev, M; Wittmer, J P; Johner, A; Benzerara, O; Meyer, H; Baschnagel, J

    2017-03-29

    Assuming Gaussian chain statistics along the chain contour, we generate by means of a proper fractal generator hyperbranched polymer trees which are marginally compact. Static and dynamical properties, such as the radial intrachain pair density distribution ρpair(r) or the shear-stress relaxation modulus G(t), are investigated theoretically and by means of computer simulations. We emphasize that albeit the self-contact density diverges logarithmically with the total mass N, this effect becomes rapidly irrelevant with increasing spacer length S. In addition to this it is seen that the standard Rouse analysis must necessarily become inappropriate for compact objects for which the relaxation time τp of mode p must scale as τp ∼ (N/p)(5/3) rather than the usual square power law for linear chains.

  7. Hyperbranched polymer mediated fabrication of water soluble carbon nanotube-metal nanoparticle hybrids

    NASA Astrophysics Data System (ADS)

    Li, Haiqing; Cooper-White, Justin J.

    2013-03-01

    1-Pyrenemethanol initiated hyperbranched polyglycerol (PiHP) has been synthesized and utilized to non-covalently functionalize pristine multi-walled carbon nanotubes (CNTs) through π-π stacking interactions. Mediated with the PiHP coating, a variety of metal nanoparticles (Au, Ag, Pd and Pt) were in situ generated and randomly tethered on the CNT sidewalls, producing various water-soluble CNT/PiHP/metal hybrids. Particularly, the resulting CNT/PiHP/Pt hybrids possess improved metal coverage in comparison to the reported CNT/Pt nanohybrids obtained by the use of conventional non-covalent CNT surface-modifiers. Depending on the using concentration of Pt2+ precursor, Pt coverage in CNT/PiHP/Pt hybrids can be effectively controlled. In the meanwhile, Pt component on the CNT sidewalls can be either well isolated nanoparticles or loose ``nanoclusters''. To test the promising catalytic application of these obtained CNT/PiHP/Pt hybrids, a systematic investigation on their catalytic performance towards the reduction of 4-nitrophenol to produce 4-aminophenol was performed. Surprisingly, these hybrids exhibited significantly enhanced catalytic activity compared with the conventionally utilized Au and Ag nanoparticles. Moreover, they can be easily recovered and reused without significant loss in catalytic activity after running 6 circles.

  8. Development of biodegradable hyperbranched core-multishell nanocarriers for efficient topical drug delivery.

    PubMed

    Du, Fang; Hönzke, Stefan; Neumann, Falko; Keilitz, Juliane; Chen, Wei; Ma, Nan; Hedtrich, Sarah; Haag, Rainer

    2016-11-28

    The topical application of drugs allows for a local application in skin disease and can reduce side effects. Here we present biodegradable core-multishell (CMS) nanocarriers which are composed of a hyperbranched polyglycerol core functionalized with diblock copolymers consisting of polycaprolactone (PCL) and poly(ethylene glycol) (mPEG) as the outer shell. The anti-inflammatory drug Dexamethasone (Dexa) was loaded into these CMS nanocarriers. DLS results suggested that Dexa loaded nanoparticles mostly act as a unimolecular carrier system. With longer PCL segments, a better transport capacity is observed. In vitro skin permeation studies showed that CMS nanocarriers could improve the Nile red penetration through the skin by up to 7 times, compared to a conventional cream formulation. Interestingly, covalently FITC-labeled CMS nanocarriers remain in the stratum corneum layer. This suggests the enhancement is due to the release of cargo after being transported into the stratum corneum by the CMS nanocarriers. In addition, the hPG-PCL-mPEG CMS nanocarriers exhibited good stability, low cytotoxicity, and their production can easily be scaled up, which makes them promising nanocarriers for topical drug delivery.

  9. The role of amphiphiles.

    PubMed

    Hoekstra, Folkert A; Golovina, Elena A

    2002-03-01

    This paper reviews our work on the partitioning of amphiphilic compounds from the cytoplasm into membranes during drying of plant systems, and discusses how relevant this phenomenon might be for anhydrobiosis. Amphiphilic guest molecules do partition into membranes and oil bodies, as demonstrated by the results of in vivo electron paramagnetic resonance spectroscopy on incorporated spin probes. Arguments for the likelihood of endogenous cytoplasmic amphiphiles behaving similarly during dehydration and rehydration of plant systems are presented. Negative and positive aspects of the partitioning are summarized. Positive aspects are the automatic insertion of amphiphilic antioxidants into membranes of the dehydrating organism, and the control of membrane fluidity and the phase transition temperature. A negative aspect is the perturbation of membrane structure, leading to increased permeability and loss of function. The finding that after an initial fluidization during dehydration, the membrane surface becomes immobilized in desiccation-tolerant systems and not in desiccation-sensitive systems, is discussed in the light of a strict control of the effect of partitioning. The adaptive significance of amphiphile partitioning into the membranes of anhydrobiotes is discussed.

  10. Antifungal Amphiphilic Aminoglycosides

    PubMed Central

    Chang, C.-W. T.; Takemoto, J.Y.

    2014-01-01

    The attachment of alkyl and other hydrophobic groups to traditional antibacterial kanamycins and neomycins creates amphiphilic aminoglycosides with altered antimicrobial properties. In this review, we summarize the discovery of amphiphilic kanamycins that are antifungal, but not antibacterial, and that inhibit the growth of fungi by perturbation of plasma membrane functions. With low toxicities against plant and mammalian cells, they appear to specifically target the fungal plasma membrane. These new antifungal agents offer new options for fighting fungal pathogens and are examples of reviving old drugs to confront new therapeutic challenges. PMID:25110571

  11. Self-assembly of phospholipid-analogous hyperbranched polymers nanomicelles for drug delivery.

    PubMed

    Liu, Jinyao; Pang, Yan; Huang, Wei; Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue

    2010-02-01

    A drug nanocarrier has been constructed through self-assembly of phospholipid analogous hyperbranched polymers (HPHEEP-alkyls) which contain a polar hyperbranched polyphosphate headgroup and many aliphatic tails. HPHEEP-alkyls were synthesized by self-condensing ring-opening polymerization of 2-(2-hydroxyethoxy)ethoxy-2-oxo-1,3,2-dioxaphospholane and then capped with palmitoyl chloride. Benefiting from the amphiphilic structure with the hydrophilic core and many hydrophobic tails, HPHEEP-alkyls were able to self-assemble into nanomicelles in aqueous media. Importantly, the size of the nanomicelles could be controlled conveniently from 98 to 215 nm by adjusting the capped fraction of the hydroxyl groups with hydrophobic palmityls. The excellent biocompatibility of these nanomicelles was confirmed by methyl tetrazolium assay and acridine orange/ethidium bromide double staining against COS-7 cells. Confocal laser scanning microscopy and flow cytometry analysis demonstrated their good cell permeability, i.e. these nanomicelles were easily internalized by vivid cells and mainly located in the cytoplasm rather than nucleolus. Chlorambucil-loaded nanomicelles were investigated for proliferation inhibition of a MCF-7 breast cancer cell line in vitro, and the chlorambucil dose required for 50% cellular growth inhibition was found to be 5 microg/mL. All of these results indicate that HPHEEP-alkyls nanomicelles can be used as safe and promising drug nanocarriers.

  12. Spiropyran-based hyperbranched star copolymer: synthesis, phototropy, FRET, and bioapplication.

    PubMed

    Wang, Ying; Hong, Chun-Yan; Pan, Cai-Yuan

    2012-08-13

    Photo- and pH-responsive amphiphilic hyperbranched star copolymers, poly(6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-d-galactopyranose)[poly(2-(N,N-dimethylaminoethyl) methacrylate)-co-poly(1'-(2-methacryloxyethyl)-3',3'-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2'-indoline))](n)s [HPMAlpGP(PDMAEMA-co-PSPMA)(n)], were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of the DMAEMA and the SPMA using hyperbranched PMAlpGP as a macro RAFT agent. In aqueous solution, the copolymers self-assembled to form core-shell micelles with HPMAlpGP core and PDMAEMA-co-PSPMA shell. The hydrophobic fluorescent dye nitrobenzoxadiazolyl derivative (NBD) was loaded into the spiropyran-containing micelles. The obtained micelles not only have the photochromic properties, but also modulate the fluorescence of NBD through fluorescence resonance energy transfer (FRET), which was also observed in living cells. Slight fluorescence intensity decrease of the spiropyran in merocyanine (ME) form was observed after five UV-visible light irradiation cycles. The cytotoxicity of the HPMAlpGP(PDMAEMA-co-PSPMA)(n) micelles was lower than that of 25k PEI. All the results revealed that these photoresponsive nanoparticles are a good candidate for cell imaging and may find broad applications in biological areas such as biological diagnosis, imaging, and detection.

  13. RHEOLOGY OF CONCENTRATED SOLUTIONS OF HYPERBRANCHED POLYESTERS

    EPA Science Inventory

    The solution rheology of different generations of hyperbranched polyesters in N-methyl-2- pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amido...

  14. Preparation of water-soluble hyperbranched polyester nanoparticles with sulfonic acid functional groups and their micelles behavior, anticoagulant effect and cytotoxicity.

    PubMed

    Han, Qiaorong; Chen, Xiaohan; Niu, Yanlian; Zhao, Bo; Wang, Bingxiang; Mao, Chun; Chen, Libin; Shen, Jian

    2013-07-02

    Biocompatibility of nanoparticles has been attracting great interest in the development of nanoscience and nanotechnology. Herein, the aliphatic water-soluble hyperbranched polyester nanoparticles with sulfonic acid functional groups (HBPE-SO3 NPs) were synthesized and characterized. They are amphiphilic polymeric nanoparticles with hydrophobic hyperbranched polyester (HBPE) core and hydrophilic sulfonic acid terminal groups. Based on our observations, we believe there are two forms of HBPE-SO3 NPs in water under different conditions: unimolecular micelles and large multimolecular micelles. The biocompatibility and anticoagulant effect of the HBPE-SO3 NPs were investigated using coagulation tests, hemolysis assay, morphological changes of red blood cells (RBCs), complement and platelet activation detection, and cytotoxicity (MTT). The results confirmed that the sulfonic acid terminal groups can substantially enhance the anticoagulant property of HBPE, and the HBPE-SO3 NPs have the potential to be used in nanomedicine due to their good bioproperties.

  15. Stimuli Responsive Amphiphilic Assemblies

    DTIC Science & Technology

    2013-11-18

    Enzyme- Sensitive, Amphiphilic- Dendrimer -Based Nanoparticles through Photochemical Crosslinking, Chemistry - A European Journal, (10 2011): 0. doi...17, 2012 (Organizers: R. P. Singh) 8th International Dendrimer Symposium (IDS-8), Madrid, Spain, June 23-27, 2013 (Organizers: Dr. M’Angeles

  16. Polyglycerol-coated nanodiamond as a macrophage-evading platform for selective drug delivery in cancer cells.

    PubMed

    Zhao, Li; Xu, Yong-Hong; Akasaka, Tsukasa; Abe, Shigeaki; Komatsu, Naoki; Watari, Fumio; Chen, Xiao

    2014-07-01

    A successful targeted drug delivery device for cancer chemotherapy should ideally be able to avoid non-specific uptake by nonmalignant cells, particularly the scavenging monocyte-macrophage system as well as targeting efficacy to bring the drug preferentially into tumor cells. To this purpose, we developed a platform based on detonation nanodiamond (dND) with hyperbranched polyglycerol (PG) coating (dND-PG). dND-PG was first demonstrated to evade non-specific cell uptake, particularly by macrophages (U937). RGD targeting peptide was then conjugated to dND-PG through multistep organic transformations to yield dND-PG-RGD that still evaded macrophage uptake but was preferentially taken up by targeted A549 cancer cells (expressing RGD peptide receptors). dND-PG and dND-PG-RGD showed good aqueous solubility and cytocompatibitlity. Subsequently, the anticancer agent doxorubicin (DOX) was loaded through acid-labile hydrazone linkage to yield dND-PG-DOX and dND-PG-RGD-DOX. Their cellular uptake and cytotoxicity were compared against DOX in A549 cells and U937 macrophages. It was found that dND-PG-DOX uptake was substantially reduced, displaying little toxicity in either type of cells by virtue of PG coating, whereas dND-PG-RGD-DOX exerted selective toxicity to A549 cells over U937 macrophages that are otherwise highly sensitive to DOX. Finally, dND-PG was demonstrated to have little influence on U937 macrophage cell functions, except for a slight increase of TNF-α production in resting U937 macrophages. dND-PG is a promising drug carrier for realization of highly selective drug delivery in tumor cells through specific uptake mechanisms, with minimum uptake in and influence on macrophages.

  17. Clickable Amphiphilic Triblock Copolymers.

    PubMed

    Isaacman, Michael J; Barron, Kathryn A; Theogarajan, Luke S

    2012-06-15

    Amphiphilic polymers have recently garnered much attention due to their potential use in drug-delivery and other biomedical applications. A modular synthesis of these polymers is extremely desirable since it offers precise individual block characterization and increased yields. We present here for the first time a modular synthesis of poly(oxazoline)-poly(siloxane)-poly(oxazoline) block copolymers that have been clicked together using the copper-catalyzed azide-alkyne cycloaddition reaction. Various click methodologies for the synthesis of these polymers have been carefully evaluated and optimized. The approach using copper nanoparticles was found to be the most optimal among the methods evaluated. Furthermore, these results were extended to allow for a reactive Si-H group-based siloxane middle block to be successfully clicked. This enables the design of more complex amphiphilic block copolymers that have additional functionality, such as stimuli responsiveness, to be synthesized via a simple hydrosilylation reaction.

  18. Anti-tumor activity of paclitaxel through dual-targeting carrier of cyclic RGD and transferrin conjugated hyperbranched copolymer nanoparticles.

    PubMed

    Xu, Qing; Liu, Yuexian; Su, Shishuai; Li, Wei; Chen, Chunying; Wu, Yan

    2012-02-01

    Targeted delivery strategies are becoming increasingly important. Herein, a novel hyperbranched amphiphilic poly[(amine-ester)-co-(D,L-lactide)]/1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine copolymer (HPAE-co-PLA/DPPE) with RGD peptide (cRGDfK) and transferrin (Tf) on the periphery was synthesized and used to prepare paclitaxel-loaded nanoparticles (NPs) for dual-targeting chemotherapy. These NPs show satisfactory size distribution, high encapsulated efficiency and a pH-dependent release profile. The intrinsic fluorescence of the hyperbranched copolymer renders the detection and tracking of NPs in vitro and in vivo conveniently. In vitro cytotoxicity studies proved that the presence of cRGDfK enhanced the cytotoxic efficiency by 10 folds in α(ν)β(3) integrin over-expressed human umbilical vein endothelial cells, while Tf improved cytotoxicity by 2 folds in Tf receptor over-expressed human cervical carcinoma cells. The drug-loaded NPs can be efficiently transported into the vascular endothelial cells and the target tumor cells. These results indicate that the cRGDfK and Tf decorated HPAE-co-PLA/DPPE could deliver chemotherapies specifically inside the cell via receptor-mediated endocytosis with greater efficacy. Therefore, such a fluorescent nanocarrier prepared from non-cytotoxic and biodegradable polymers is promising for drug delivery in tumor therapy.

  19. Acid-Cleavable Unimolecular Micelles from Amphiphilic Star Copolymers for Triggered Release of Anticancer Drugs.

    PubMed

    Zhang, Shan; Xu, Jianbin; Chen, Heng; Song, Zhangfa; Wu, Yalan; Dai, Xingyi; Kong, Jie

    2017-03-01

    In this contribution, amphiphilic star copolymers (H40-star-PCL-a-PEG) with an H40 hyperbranched polyester core and poly(ε-caprolactone)-a-poly(ethylene glycol) copolymer arms linked with acetal groups are synthesized using ring-opening polymerization and a copper (I)-catalyzed alkyne-azide cycloaddition click reaction. The acid-cleavable acetal groups between the hydrophilic and hydrophobic segments of the arms endow the amphiphilic star copolymers with pH responsiveness. In aqueous solution, unimolecular micelles can be formed with good stability and a unique acid degradability, as is desirable for anticancer drug carriers. For the model drug of doxorubicin, the in vitro release behavior, intracellular release, and inhibition of proliferation of HeLa cells show that the acid-cleavable unimolecular micelles with anticancer activity can be dissociated in an acidic environment and efficiently internalized by HeLa cells. Due to the acid-cleavable and biodegradable nature, unimolecular micelles from amphiphilic star copolymers are promising for applications in intracellular drug delivery for cancer chemotherapy.

  20. SOLUTION RHEOLOGY OF HYPERBRANCHED POLYESTERS AND THEIR BLENDS WITH LINEAR POLYMERS

    EPA Science Inventory

    In this study, the rheological properties of different generations of hyperbranched polyesters in 1-methyl-2-pyrrolidinone solvent and their blends with poly(2-hydroxyethyl methacrylate) have ben investigated. All the hyperbranched polyester solutions exhibited Newtonian behavior...

  1. Amphiphilic polysaccharide nanoballs: a new building block for nanogel biomedical engineering and artificial chaperones.

    PubMed

    Takahashi, Haruko; Sawada, Shin-Ichi; Akiyoshi, Kazunari

    2011-01-25

    Enzymatically synthesized glycogen (ESG), a highly branched (1→4)(1→6)-linked α-glucan, is a new monodisperse spherical hyperbranched nanoparticle (molecular weight, 10(6)-10(7); diameter, 20-30 nm), polysaccharide nanoball. Amphiphilic ESG nanoballs were synthesized by introducing a cholesterol group to enzymatically synthesized glycogen (CHESG). CHESG assembled into a structure containing a few molecules to form cluster nanogels (approximately 35 nm in diameter) in water. The cluster nanogels were dissociated by the addition of cyclodextrin (CD) to form a supramolecular CHESG-CD nanocomplex due to complexation with the cholesterol group and CD. The CHESG nanogel showed high capacity for complexation with proteins, and the CHESG-CD nanocomplex showed high chaperone-like activity for thermal stabilization of enzymes. CHESG has great potential to become a new building block for nanogel biomedical engineering and to act as an artificial chaperone for protein engineering.

  2. Structure-triboproperty in biobased amphiphiles

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable oils and their derivatives are amphiphilic and display a number of properties critical to their application in tribological processes. Among such properties are: viscosity, viscosity index, oxidation stability, cold flow, boundary friction, etc. The properties of these biobased amphiphiles...

  3. Amphiphiles for protein solubilization and stabilization

    DOEpatents

    Gellman, Samuel Helmer; Chae, Pil Seok; Laible, Philip D.; Wander, Marc J.

    2012-09-11

    The invention provides amphiphiles for manipulating membrane proteins. The amphiphiles can feature carbohydrate-derived hydrophilic groups and branchpoints in the hydrophilic moiety and/or in a lipophilic moiety. Such amphiphiles are useful as detergents for solubilization and stabilization of membrane proteins, including photosynthetic protein superassemblies obtained from bacterial membranes.

  4. Amphiphiles for protein solubilization and stabilization

    DOEpatents

    Gellman, Samuel Helmer; Chae, Pil Seok; Laible, Phillip D; Wander, Marc J

    2014-11-04

    The invention provides amphiphiles for manipulating membrane proteins. The amphiphiles can feature carbohydrate-derived hydrophilic groups and branchpoints in the hydrophilic moiety and/or in a lipophilic moiety. Such amphiphiles are useful as detergents for solubilization and stabilization of membrane proteins, including photosynthetic protein superassemblies obtained from bacterial membranes.

  5. Self-assembling amphiphilic peptides†

    PubMed Central

    Dehsorkhi, Ashkan; Castelletto, Valeria; Hamley, Ian W

    2014-01-01

    The self-assembly of several classes of amphiphilic peptides is reviewed, and selected applications are discussed. We discuss recent work on the self-assembly of lipopeptides, surfactant-like peptides and amyloid peptides derived from the amyloid-β peptide. The influence of environmental variables such as pH and temperature on aggregate nanostructure is discussed. Enzyme-induced remodelling due to peptide cleavage and nanostructure control through photocleavage or photo-cross-linking are also considered. Lastly, selected applications of amphiphilic peptides in biomedicine and materials science are outlined. © 2014 The Authors. Journal of Peptide Science published by European Peptide Society and John Wiley & Sons, Ltd. PMID:24729276

  6. 3D printing of photocurable poly(glycerol sebacate) elastomers.

    PubMed

    Yeh, Yi-Cheun; Highley, Christopher B; Ouyang, Liliang; Burdick, Jason A

    2016-10-07

    Three-dimensional (3D) printed scaffolds have great potential in biomedicine; however, it is important that we are able to design such scaffolds with a range of diverse properties towards specific applications. Here, we report the extrusion-based 3D printing of biodegradable and photocurable acrylated polyglycerol sebacate (Acr-PGS) to fabricate scaffolds with elastic properties. Two Acr-PGS macromers were synthesized with varied molecular weights and viscosity, which were then blended to obtain photocurable macromer inks with a range of viscosities. The quality of extruded and photocured scaffolds was dependent on the initial ink viscosity, with flow of printed material resulting in a loss of structural resolution or sample breaking observed with too low or too high viscosity inks, respectively. However, scaffolds with high print resolution and up to ten layers were fabricated with an optimal ink viscosity. The mechanical properties of printed scaffolds were dependent on printing density, where the scaffolds with lower printing density possessed lower moduli and failure properties than higher density scaffolds. The 3D printed scaffolds supported the culture of 3T3 fibroblasts and both spreading and proliferation were observed, indicating that 3D printed Acr-PGS scaffolds are cytocompatible. These results demonstrate that Acr-PGS is a promising material for the fabrication of elastomeric scaffolds for biomedical applications.

  7. Biopolymers for Medical Applications: Polyglycerol Sebacate (PGS) doped Hydroxyapatite (HA)

    NASA Astrophysics Data System (ADS)

    Teruel, Maria; Kuthirummal, Narayanan; Levi, Nicole; Wake College Team

    2011-04-01

    In the investigation to engineer the ideal scaffolding device for cleft palate repair, polyglycerol sebacate (PGS) doped with hydroxyapatite (HA) were chosen for their elastomeric and biodegradable properties, as well as their cost-effective synthesis. Hydroxyapatite was integrated into the PGS to form a composite with high porosity and improved mechanical properties yielding a good substrate for cell attachment during the repair process. FT-IR scans were performed to characterize the composite polymer. Differential Scanning Calorimetry (DSC) was utilized to identify an acceptable glass transition temperature (Tg), between -18 and - 21°C. At this Tg, it was determined that the material was sufficiently polymerized to a point where it was durable yet pliable enough to use for cleft palate devices. In the synthesis of PGS 3% and 5% HA, a Tg of - 20.10°C and - 21.72°C, respectively, was achieved and further analytical tests were then performed on the polymers. Methods of analysis included X-Ray Diffraction and Tensile Strength Testing. Acknowledgements to the Research Department of Plastic and Reconstructive Surgery, Wake Forest University and College of Charleston.

  8. Foams stabilized by multilamellar polyglycerol ester self-assemblies.

    PubMed

    Curschellas, Corina; Kohlbrecher, Joachim; Geue, Thomas; Fischer, Peter; Schmitt, Bertrand; Rouvet, Martine; Windhab, Erich J; Limbach, Hans Jörg

    2013-01-08

    The importance of surfactant self-assemblies in foam stabilization is well-known. The aim of the current study was to investigate the self-assemblies of the nonionic surfactant polyglycerol ester (PGE) in bulk solutions, at the interface and within foams, using a combined approach of small-angle neutron scattering, neutron reflectivity, and electron microscopy. PGE bulk solutions contain vesicles as well as open lamellar structures. Upon heating of the solutions the lamellar spacing increases, with significant differences in the presence of NaCl or CaCl(2) as compared to the standard solution. The adsorption of the multilamellar structures present in the bulk solutions lead to a multilayered film at the air-water interface. The ordering within this film was increased as a result of a 20% area compression mimicking a coalescence event. Finally, PGE foams were shown to be stabilized not only by strong interfacial films but also by agglomerated self-assemblies within the interstitial areas of the foams.

  9. Structure and Dynamics in Hyperbranched Nanohybrids

    NASA Astrophysics Data System (ADS)

    Chrissopoulou, K.; Fotiadou, S.; Anastasiadis, S. H.; Frick, B.

    2012-02-01

    The structure and dynamics of a hyperbranched polyester-amide (Hybrane^ 1200, Mn=1200, Tg=45^oC) polymer and its nanocomposites with natural montmorillonite (Na^+-MMT) are investigated to offer a detailed picture of its behavior in bulk and under confinement and reveal its potential use for various applications. The static properties were studied utilizing X-ray diffraction (XRD), while the dynamics using energy-resolved elastic and quasi-elastic neutron scattering (QENS). XRD reveals that the polymer chains reside within the galleries of the Na^+-MMT producing an intercalated nanocomposite. The elastically scattered intensity for the polymer exhibits two distinct relaxation steps, which are attributed to the methyl group rotation and to the segmental motion. The intensity for the nanocomposite shows the first step broader than the respective of the pure polymer indicating restricted local motion whereas it indicates frozen dynamics under confinement at temperatures higher than the bulk polymer glass transition temperature, Tg. The QENS spectra measured at temperatures covering the regimes below and above Tg are in agreement with the elastic measurements. Sponsored by the Greek GSRT (σYNEP γA σIA; 09σYN-42-580) and by the EU (CP-IP 246095-2).

  10. Synthesis, characterization and nanocomposite formation of poly(glycerol succinate-co-maleate) with cellulose nanowhiskers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with cellulose nanowhiskers. This glycerol-based polymer is thermally stable as...

  11. Patterning of hyperbranched resist materials by e-beam

    NASA Astrophysics Data System (ADS)

    Trimble, Alexander R.; Tully, David C.; Frechet, Jean M. J.; Medeiros, David R.; Angelopoulos, Marie

    2000-06-01

    The application of a hyperbranched polymer with its globular architecture as a chemically amplified resist system is demonstrated. These hyperbranched poly(esters) based on 3,5- dihydroxybenzoic acid and 4,4-bis(4-hydroxyphenyl)valeric acid and obtained by a polycondensation process at high temperatures. Once obtained, the hyperbranched polymers are functionalized with acid and thermally labile t-BOC groups by reaction of their phenolic groups with di-t-butyl dicarbonate in the presence of a catalytic amount of potassium t-butoxide. These globular materials have number average molecular weights (Mn) in the range of 5,000 - 20,000 with polydispersities of 1.5 - 2. Exposure of the hyperbranched resist material formulated with a photoacid generator was carried out using a direct-write electron-beam (e-beam) tool operating at 50 keV with doses of 15 - 40 (mu) C/cm2. Development of these resist materials can be accomplished in either aqueous base developer or organic solvent, thereby allowing access to both the positive and negative tone images. Feature sizes of 100 nm are readily obtained from these unoptimized materials.

  12. Surfactant free preparation of biodegradable dendritic polyglycerol nanogels by inverse nanoprecipitation for encapsulation and release of pharmaceutical biomacromolecules.

    PubMed

    Steinhilber, Dirk; Witting, Madeleine; Zhang, Xuejiao; Staegemann, Michael; Paulus, Florian; Friess, Wolfgang; Küchler, Sarah; Haag, Rainer

    2013-08-10

    In this paper we report a novel approach to generate biodegradable polyglycerol nanogels on different length scales. We developed a mild, surfactant free inverse nanoprecipitation process to template hydrophilic polyglycerol nanoparticles. In situ crosslinking of the precipitated nanoparticles by bioorthogonal copper catalyzed click chemistry allows us to obtain size defined polyglycerol nanogels (100-1000nm). Biodegradability was achieved by the introduction of benzacetal bonds into the net points of the nanogel. Interestingly, the polyglycerol nanogels quickly degraded into low molecular weight fragments at acidic pH values, which are present in inflamed and tumor tissues as well as intracellular organelles, and they remained stable at physiological pH values for a long time. This mild approach to biodegradable polyglycerol nanogels allows us to encapsulate labile biomacromolecules such as proteins, including the therapeutic relevant enzyme asparaginase, into the protein resistant polyglycerol network. Enzymes were encapsulated with an efficacy of 100% and after drug release, full enzyme activity and structural integrity were retained. This new inverse nanoprecipitation procedure allows the efficient encapsulation and release of various biomacromolecules including proteins and could find many applications in polymer therapeutics and nanomedicine.

  13. Biocompatible fluorinated polyglycerols for droplet microfluidics as an alternative to PEG-based copolymer surfactants.

    PubMed

    Wagner, Olaf; Thiele, Julian; Weinhart, Marie; Mazutis, Linas; Weitz, David A; Huck, Wilhelm T S; Haag, Rainer

    2016-01-07

    In droplet-based microfluidics, non-ionic, high-molecular weight surfactants are required to stabilize droplet interfaces. One of the most common structures that imparts stability as well as biocompatibility to water-in-oil droplets is a triblock copolymer surfactant composed of perfluoropolyether (PFPE) and polyethylene glycol (PEG) blocks. However, the fast growing applications of microdroplets in biology would benefit from a larger choice of specialized surfactants. PEG as a hydrophilic moiety, however, is a very limited tool in surfactant modification as one can only vary the molecular weight and chain-end functionalization. In contrast, linear polyglycerol offers further side-chain functionalization to create custom-tailored, biocompatible droplet interfaces. Herein, we describe the synthesis and characterization of polyglycerol-based triblock surfactants with tailored side-chain composition, and exemplify their application in cell encapsulation and in vitro gene expression studies in droplet-based microfluidics.

  14. Modification of polylactide bioplastic using hyperbranched polymer based nanostructures

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Rahul

    Polylactide (PLA) is the most well known renewable resource based biodegradable polymer. The inherent brittleness and poor processability of PLA pose considerable technical challenges and limit its range of commercial applications. The broad objective of this research was to investigate novel pathways for polylactide modification to enhance its mechanical and rheological properties. The focus of this work was to tailor the architecture of a dendritic hyperbranched polymer (HBP) and study its influence on the mechanical and rheological properties of PLA bioplastic. The hyperbranched polymers under consideration are biodegradable aliphatic hydroxyl-functional hyperbranched polyesters having nanoscale dimensions, unique physical properties and high peripheral functionalities. This work relates to identifying a new and industrially relevant research methodology to develop PLA based nanoblends having outstanding stiffness-toughness balance. In this approach, a hydroxyl functional hyperbranched polymer was crosslinked in-situ with a polyanhydride (PA) in the PLA matrix during melt processing, leading to the generation of new nanoscale hyperbranched polymer based domains in the PLA matrix. Transmission electron microscopy and atomic force microscopy revealed the "sea-island" morphology of PLA-crosslinked HBP blends. The domain size of a large portion of the crosslinked HBP particles in PLA matrix was less than 100 nm. The presence of crosslinked hyperbranched polymers exhibited more than 500% and 800% improvement in the tensile toughness and elongation at break values of PLA, respectively, with a minimal sacrifice of tensile strength and modulus as compared to unmodified PLA. The toughening mechanism of PLA in the presence of crosslinked HBP particles was comprised of shear yielding and crazing. The volume fraction of crosslinked HBP particles and matrix ligament thickness (inter-particle distance) were found to be the critical parameters for the toughening of PLA. The

  15. Hyperbranched polymers with controlled degree of branching from 0 to 100%.

    PubMed

    Segawa, Yukari; Higashihara, Tomoya; Ueda, Mitsuru

    2010-08-18

    A linear polymer, hyperbranched polymers with various degrees of branching, and 100% hyperbranched polymers were successfully synthesized by self-polycondensation of 2,2,2-trifluoro-1-[4-(4-phenoxyphenoxy)phenyl]ethanone by using different amounts of trifluoromethanesulfonic acid from the same AB(2) monomer.

  16. Amphiphilic Soft Janus Particles as Interfacial Stabilizers

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Niu, Sunny; Sosa, Chris; Prud'Homme, Robert; Priestley, Rodney; Priestley Polymer Group Team; Prud'homme Research Group Team

    Janus particles, which incorporate two or more ``faces'' with different chemical functionality, have attracted great attention in scientific research. Amphiphilic Janus particles have two faces with distinctly different hydrophobicity. This can be thought of as colloidal surfactants. Theoretical studies on the stabilization of emulsions using Janus particles have confirmed higher efficiency. Herein we synthesize the narrow distributed amphiphilic polymeric Janus particles via Precipitation-Induced Self-Assembly (PISA). The efficiency of the amphiphilic Janus particles are tested on different oil/water systems. Biocompatible polymers can also be used on this strategy and may potentially have wide application for food emulsion, cosmetics and personal products.

  17. Amphiphilic NO-donor antioxidants.

    PubMed

    Chegaev, Konstantin; Lazzarato, Loretta; Rolando, Barbara; Marini, Elisabetta; Lopez, Gloria V; Bertinaria, Massimo; Di Stilo, Antonella; Fruttero, Roberta; Gasco, Alberto

    2007-02-01

    Models of amphiphilic NO-donor antioxidants 24-26 were designed and synthesized. The products were obtained by linking a lipophilic tail (C(6), C(8), C(10)) with a polar head constituted by the 2,6-dimethoxyphenol antioxidant joined to the NO-donor 3-furoxancarboxamide substructure through a bridge containing a quaternary ammonium group. Compound 23, containing the shortest C(2)-alkyl chain, was also studied as a reference. The antioxidant properties (TBARS and LDL oxidation assays) and the vasodilator properties of the compounds were studied in vitro. The ability of these products to interact with phospholipid vesicles was also investigated by NMR techniques. The results indicate that both activities are modulated by the ability of the compounds to accumulate on phospholipid layers.

  18. Use of hybrid composite particles prepared using alkoxysilane-functionalized amphiphilic polymer precursors for simultaneous removal of various pollutants from water.

    PubMed

    Cho, Seulki; Kim, Nahae; Lee, Soonjae; Lee, Hoseok; Lee, Sang-Hyup; Kim, Juyoung; Choi, Jae-Woo

    2016-08-01

    In this study, we present new inorganic-organic hybrid particles and their possible application as an adsorbent for simultaneous removal of hydrophobic and hydrophilic pollutants from water. These hybrid particles were prepared using tailor-made alkoxysilane-functionalized amphiphilic polymer precursors (M-APAS), which have amphiphilic polymers and reactive alkoxysilane groups attached to the same backbone. Through a single conventional sol-gel process, the polymerization of M-APAS and the chemical conjugation of M-APAS onto silica nanoparticles was simultaneous, resulting in the formation of hybrid particles (M-APAS-SiO2) comprised of hyperbranch-like amphiphilic polymers bonded onto silica nanoparticles with a relatively high grafting efficiency. A test for the adsorption of water-soluble dye (organe-16) and water insoluble dye (solvent blue-35) onto the hybrid particles was performed to evaluate the possibility of adsorbing hydrophilic and hydrophobic compound within the same particle. The hybrid particle was also evaluated as an adsorbent for the removal of contaminated water containing various pollutants by wastewater treatment test. The hybrid particle could remove phenolic compounds from wastewater and the azo dye reactive orange-16 from aqueous solutions, and it was easily separated from the treated wastewater because of the different densities involved. These results demonstrate that the hybrid particles are a promising sorbent for hydrophilic and/or hydrophobic pollutants in water.

  19. Frame-Guided Assembly of Amphiphiles.

    PubMed

    Dong, Yuanchen; Liu, Dongsheng

    2015-12-07

    Frame-guided assembly, a recently discovered strategy for amphiphilic assembly, is discussed as a strategy for constructing vesicle assemblies with programmed geometries and dimensions under identical surrounding conditions. The strategy is inspired by the cytoskeletal-membrane protein-lipid bilayer structure and shows great potential in the understanding and controlling of the amphiphilic assembly process. Both the principles and basic requirements are discussed, along with recently reported examples. The prospects and potential investigations of frame-guided assembly are also proposed.

  20. Improving of Mechanical and Shape-Memory Properties in Hyperbranched Epoxy Shape-Memory Polymers

    NASA Astrophysics Data System (ADS)

    Santiago, David; Fabregat-Sanjuan, Albert; Ferrando, Francesc; De la Flor, Silvia

    2016-09-01

    A series of shape-memory epoxy polymers were synthesized using an aliphatic amine and two different commercial hyperbranched poly(ethyleneimine)s with different molecular weights as crosslinking agents. Thermal, mechanical, and shape-memory properties in materials modified with different hyperbranched polymers were analyzed and compared in order to establish the effect of the structure and the molecular weight of the hyperbranched polymers used. The presence of hyperbranched polymers led to more heterogeneous networks, and the crosslinking densities of which increase as the hyperbranched polymer content increases. The transition temperatures can be tailored from 56 to 117 °C depending on the molecular weight and content of the hyperbranched polymer. The mechanical properties showed excellent values in all formulations at room temperature and, specially, at T_{{g}}^{{E^' with stress at break as high as 15 MPa and strain at break as high as 60 %. The shape-memory performances revealed recovery ratios around 95 %, fixity ratios around 97 %, and shape-recovery velocities as high as 22 %/min. The results obtained in this study reveal that hyperbranched polymers with different molecular weights can be used to enhance the thermal and mechanical properties of epoxy-based SMPs while keeping excellent shape-memory properties.

  1. Design and synthesis of novel polyglycerol hybrid nanomaterials for potential applications in drug delivery systems.

    PubMed

    Zarrabi, Ali; Adeli, Mohsen; Vossoughi, Manouchehr; Shokrgozar, Mohammad Ali

    2011-03-10

    The synthesis of a new drug delivery system based on hybrid nanomaterials containing a β-CD core and hyperbranched PG is described. Conjugating PG branches onto β-CD not only increases its water solubility but also affects its host/guest properties deeply. It can form molecular inclusion complexes with small hydrophobic guest molecules such as ferrocene or FITC with reasonable release. In addition, the achievable payloads are significantly higher as for carriers such as hyperbranched PGs. Short-term in vitro cytotoxicity and hemocompatibility tests on L929 cell lines show that the hybrid nanomaterial is highly biocompatible. Due to their outstanding properties, β-CD-g-PG hybrid nanomaterials are introduced as promising materials for nanomedicine, e.g., for drug delivery issues.

  2. Using hyperbranched oligomer functionalized glass fillers to reduce shrinkage stress

    PubMed Central

    Ye, Sheng; Azarnoush, Setareh; Smith, Ian R.; Cramer, Neil B.; Stansbury, Jeffrey W.; Bowman, Christopher N

    2012-01-01

    Objective Fillers are widely utilized to enhance the mechanical properties of polymer resins. However, polymerization stress has the potential to increase due to the higher elastic modulus achieved upon filler addition. Here, we demonstrate a hyperbranched oligomer functionalized glass filler UV curable resin composite which is able to reduce the shrinkage stress without sacrificing mechanical properties. Methods A 16-functional alkene-terminated hyperbranched oligomer is synthesized by thiol-acrylate and thiol-yne reactions and the product structure is analyzed by 1H-NMR, mass spectroscopy, and gel permeation chromatography. Surface functionalization of the glass filler is measured by thermogravimetric analysis. Reaction kinetics, mechanical properties and shrinkage stress are studied via Fourier transform infrared spectroscopy, dynamic mechanical analysis and a tensometer, respectively. Results Silica nanoparticles are functionalized with a flexible 16-functional alkene-terminated hyperbranched oligomer which is synthesized by multistage thiol-ene/yne reactions. 93% of the particle surface was covered by this oligomer and an interfacial layer ranging from 0.7 – 4.5 nm thickness is generated. A composite system with these functionalized silica nanoparticles incorporated into the thiol-yne-methacrylate resin demonstrates 30% reduction of shrinkage stress (from 0.9 MPa to 0.6 MPa) without sacrificing the modulus (3100 ± 300 MPa) or glass transition temperature (62 ± 3 °C). Moreover, the shrinkage stress of the composite system builds up at much later stages of the polymerization as compared to the control system. Significance Due to the capability of reducing shrinkage stress without sacrificing mechanical properties, this composite system will be a great candidate for dental composite applications. PMID:22717296

  3. The influence of surface charge on serum protein interaction and cellular uptake: studies with dendritic polyglycerols and dendritic polyglycerol-coated gold nanoparticles.

    PubMed

    Bewersdorff, Tony; Vonnemann, Jonathan; Kanik, Asiye; Haag, Rainer; Haase, Andrea

    2017-01-01

    Nanoparticles (NPs) have gained huge interest in the medical field, in particular for drug delivery purposes. However, binding of proteins often leads to fast NP uptake and rapid clearance, thereby hampering medical applications. Thus, it is essential to determine and control the bio-nano interface. This study investigated the serum protein interactions of dendritic polyglycerols (dPGs), which are promising drug delivery candidates by means of two dimensional gel electrophoresis (2DE) in combination with mass spectrometry. In order to investigate the influence of surface charge, sulfated (sulfated dendritic polyglycerol [dPGS]) and non-sulfated (dPGOH) surfaces were applied, which were synthesized on a gold core allowing for easier separation from unbound biomolecules through centrifugation. Furthermore, two different sizes for dPGS were included. Although size had only a minor influence, considerable differences were detected in protein affinity for dPGS versus dPGOH surfaces, with dPGOH binding much less proteins. Cellular uptake into human CD14(+) monocytes was analyzed by flow cytometry, and dPGOH was taken up to a much lower extent compared to dPGS. By using a pull-down approach, possible cellular interaction partners of serum pre-incubated dPGS-Au20 NPs from the membrane fraction of THP-1 cells could be identified such as for instance the transferrin receptor or an integrin. Clathrin-mediated endocytosis was further investigated using chlorpromazine as an inhibitor, which resulted in a 50% decrease of the cellular uptake of dPGS. This study could confirm the influence of surface charge on protein interactions and cellular uptake of dPGS. Furthermore, the approach allowed for the identification of possible uptake receptors and insights into the uptake mechanism.

  4. The influence of surface charge on serum protein interaction and cellular uptake: studies with dendritic polyglycerols and dendritic polyglycerol-coated gold nanoparticles

    PubMed Central

    Bewersdorff, Tony; Vonnemann, Jonathan; Kanik, Asiye; Haag, Rainer; Haase, Andrea

    2017-01-01

    Nanoparticles (NPs) have gained huge interest in the medical field, in particular for drug delivery purposes. However, binding of proteins often leads to fast NP uptake and rapid clearance, thereby hampering medical applications. Thus, it is essential to determine and control the bio–nano interface. This study investigated the serum protein interactions of dendritic polyglycerols (dPGs), which are promising drug delivery candidates by means of two dimensional gel electrophoresis (2DE) in combination with mass spectrometry. In order to investigate the influence of surface charge, sulfated (sulfated dendritic polyglycerol [dPGS]) and non-sulfated (dPGOH) surfaces were applied, which were synthesized on a gold core allowing for easier separation from unbound biomolecules through centrifugation. Furthermore, two different sizes for dPGS were included. Although size had only a minor influence, considerable differences were detected in protein affinity for dPGS versus dPGOH surfaces, with dPGOH binding much less proteins. Cellular uptake into human CD14+ monocytes was analyzed by flow cytometry, and dPGOH was taken up to a much lower extent compared to dPGS. By using a pull-down approach, possible cellular interaction partners of serum pre-incubated dPGS-Au20 NPs from the membrane fraction of THP-1 cells could be identified such as for instance the transferrin receptor or an integrin. Clathrin-mediated endocytosis was further investigated using chlorpromazine as an inhibitor, which resulted in a 50% decrease of the cellular uptake of dPGS. This study could confirm the influence of surface charge on protein interactions and cellular uptake of dPGS. Furthermore, the approach allowed for the identification of possible uptake receptors and insights into the uptake mechanism. PMID:28352171

  5. New methodologies for construction of hyperbranched organic and organometallic polymers

    NASA Astrophysics Data System (ADS)

    Xu, Kaitian

    2000-10-01

    A series of completely soluble hyperbranched polymers were synthesized by polycyclotrimerization of diynes for the first time. TaCl5-Ph 4Sn was found to be the effective catalyst and toluene to be the efficient solvent. A possible polycyclotrimerization mechanism via tantalacyclopentadiene intermediates is proposed. The polymerization processes including initiation, propagation and termination are analyzed. The unique backbiting reaction was found to be a plausible way to terminate the propagation chain. Conformations of the diynes greatly affect the occurrence of backbiting reaction and affect the solubility of resultant polymers to certain extent. Diynes with short spacers such as 1,5-hexadiyne (21 ); 1,6-heptadiyne (22); 1,7-octadiyne (23); and 1,8-nonadiyne (17); possess a conformation in which the two triple bonds locate closely. Such a conformation makes the backbiting termination to occur easily. Thus, soluble polymers are readily formed from these diynes. For the diynes of long spacers, a conformation with two far-separating triple bonds dramatically reduces the chance of backbiting reaction. Consequently, only partially soluble or insoluble polymers could be prepared. In the polycyclotrimerization of internal diynes, hexasubstituted benzene rings were formed. The steric effect of the terminal substituents plays an important role in the polymerization reaction. Internal diynes with bulky substituents such as 1,9-bis(trimethylsilyl)-1,8-nonadiyne (74), 1,6-bis(dimethylphenylsilyl)-1,5-hexadiyne (75), 1,8-bis(dimethylphenylsilyl)-1,7-octadiyne (76) gave little amount of polymers. Internal diynes with less bulky substituents and short spacers [e.g. 3,9-dodecadiyne (78) and 2,9-undecadiyne (79)] offered soluble polymers. In the study on hyperbranched organometallic polymers, a new methodology for the preparation of hyperbranched polysilynes was developed. Ceramization of the hyperbranched polymers produced mesoporous magnetoceramic materials. The compositions

  6. Dendritic polyglycerol sulfate as a novel platform for paclitaxel delivery: pitfalls of ester linkage

    NASA Astrophysics Data System (ADS)

    Sousa-Herves, Ana; Würfel, Patrick; Wegner, Nicole; Khandare, Jayant; Licha, Kai; Haag, Rainer; Welker, Pia; Calderón, Marcelo

    2015-02-01

    In this study, dendritic polyglycerol sulfate (dPGS) is evaluated as a delivery platform for the anticancer, tubulin-binding drug paclitaxel (PTX). The conjugation of PTX to dPGS is conducted via a labile ester linkage. A non-sulfated dendritic polyglycerol (dPG) is used as a control, and the labeling with an indocarbocyanine dye (ICC) renders multifunctional conjugates that can be monitored by fluorescence microscopy. The conjugates are characterized by 1H NMR, UV-vis measurements, and RP-HPLC. In vitro cytotoxicity of PTX and dendritic conjugates is evaluated using A549 and A431 cell lines, showing a reduced cytotoxic efficacy of the conjugates compared to PTX. The study of uptake kinetics reveals a linear, non saturable uptake in tumor cells for dPGS-PTX-ICC, while dPG-PTX-ICC is hardly taken up. Despite the marginal uptake of dPG-PTX-ICC, it prompts tubulin polymerization to a comparable extent as PTX. These observations suggest a fast ester hydrolysis and premature drug release, as confirmed by HPLC measurements in the presence of plasma enzymes.In this study, dendritic polyglycerol sulfate (dPGS) is evaluated as a delivery platform for the anticancer, tubulin-binding drug paclitaxel (PTX). The conjugation of PTX to dPGS is conducted via a labile ester linkage. A non-sulfated dendritic polyglycerol (dPG) is used as a control, and the labeling with an indocarbocyanine dye (ICC) renders multifunctional conjugates that can be monitored by fluorescence microscopy. The conjugates are characterized by 1H NMR, UV-vis measurements, and RP-HPLC. In vitro cytotoxicity of PTX and dendritic conjugates is evaluated using A549 and A431 cell lines, showing a reduced cytotoxic efficacy of the conjugates compared to PTX. The study of uptake kinetics reveals a linear, non saturable uptake in tumor cells for dPGS-PTX-ICC, while dPG-PTX-ICC is hardly taken up. Despite the marginal uptake of dPG-PTX-ICC, it prompts tubulin polymerization to a comparable extent as PTX. These

  7. Hyperbranched polymers with a degree of branching of 100% prepared by catalyst transfer Suzuki-Miyaura polycondensation.

    PubMed

    Huang, Weiguo; Su, Linjie; Bo, Zhishan

    2009-08-05

    Hyperbranched polymers with a degree of branching of 100% were prepared by catalyst transfer Suzuki-Miyaura polymerization of AB(2) monomers carrying one boronic acid and two aromatic bromo functional groups; in contrast, Suzuki-Miyaura polymerization of the same AB(2) monomers using a traditional catalyst afforded hyperbranched polymers with a branching degree of only approximately 56%. This is a nice example of controlling the topology of hyperbranched polymers via the catalyst.

  8. Dendritic polyglycerol sulfate as a novel platform for paclitaxel delivery: pitfalls of ester linkage.

    PubMed

    Sousa-Herves, Ana; Würfel, Patrick; Wegner, Nicole; Khandare, Jayant; Licha, Kai; Haag, Rainer; Welker, Pia; Calderón, Marcelo

    2015-03-07

    In this study, dendritic polyglycerol sulfate (dPGS) is evaluated as a delivery platform for the anticancer, tubulin-binding drug paclitaxel (PTX). The conjugation of PTX to dPGS is conducted via a labile ester linkage. A non-sulfated dendritic polyglycerol (dPG) is used as a control, and the labeling with an indocarbocyanine dye (ICC) renders multifunctional conjugates that can be monitored by fluorescence microscopy. The conjugates are characterized by (1)H NMR, UV-vis measurements, and RP-HPLC. In vitro cytotoxicity of PTX and dendritic conjugates is evaluated using A549 and A431 cell lines, showing a reduced cytotoxic efficacy of the conjugates compared to PTX. The study of uptake kinetics reveals a linear, non saturable uptake in tumor cells for dPGS-PTX-ICC, while dPG-PTX-ICC is hardly taken up. Despite the marginal uptake of dPG-PTX-ICC, it prompts tubulin polymerization to a comparable extent as PTX. These observations suggest a fast ester hydrolysis and premature drug release, as confirmed by HPLC measurements in the presence of plasma enzymes.

  9. Lithium modified zeolite synthesis for conversion of biodiesel-derived glycerol to polyglycerol

    SciTech Connect

    Ayoub, Muhammad; Abdullah, Ahmad Zuhairi; Inayat, Abrar

    2014-10-24

    Basic zeolite has received significant attention in the catalysis community. These zeolites modified with alkaline are the potential replacement for existing zeolite catalysts due to its unique features with added advantages. The present paper covers the preparation of lithium modified zeolite Y (Li-ZeY) and its activity for solvent free conversion of biodiesel-derived glycerol to polyglycerol via etherification process. The modified zeolite was well characterized by X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and Nitrogen Adsorption. The SEM images showed that there was no change in morphology of modified zeolite structure after lithium modification. XRD patterns showed that the structure of zeolite was sustained after lithium modification. The surface properties of parent and modified zeolite was also observed N{sub 2} adsortion-desorption technique and found some changes in surface area and pore size. In addition, the basic strength of prepared materials was measured by Hammet indicators and found that basic strength of Li-ZeY was highly improved. This modified zeolite was found highly thermal stable and active heterogamous basic catalyst for conversion of solvent free glycerol to polyglycerol. This reaction was conducted at different temperatures and 260 °C was found most active temperature for this process for reaction time from 6 to 12 h over this basic catalyst in the absence of solvent.

  10. Synthesis of a pH-independent bifurcated amphiphile

    PubMed Central

    Willham, Kaitlin A.; Laurent, Boyd A.; Grayson, Scott M.

    2008-01-01

    An efficient synthetic method for preparing bifurcated amphiphiles has been developed such that the functionality for attachment is located at the interface between the lipophilic and hydrophilic side chains. Attachment of the amphiphile to the repeat units of polymeric substrates enables the rapid preparation of amphiphilic homopolymers. PMID:19325700

  11. Nanostructured assemblies from amphiphilic ABC multiblock polymers

    NASA Astrophysics Data System (ADS)

    Hillmyer, Marc A.

    2012-02-01

    Amphiphilic AB diblock copolymers containing a water compatible segment can self-assemble in aqueous media to give supramolecular structures that include simple spherical micelles and macromolecular vesicles termed polymersomes. Amphiphilic ABA triblocks with hydrophobic end blocks can adopt analogous structures but can also form gels at high polymer concentrations. The structural and chemical diversity demonstrated in block copolymer micelles and gels makes them attractive for applications ranging from drug delivery to personal care products to nanoreactors. The inclusion of a third block in amphiphilic ABC triblock systems can lead to a much wider array of self-assembled structures that depend not only on composition but also on block sequence, architecture and incompatibility considerations. I will present our recent efforts on tuning micelle and gel structure and behavior using controlled architecture ABC triblocks. The combination of diverse polymer segments into a single macromolecule is a powerful method for development of self-assembled structures with both new form and new function.

  12. Supramolecular Nanofibers of Peptide Amphiphiles for Medicine

    PubMed Central

    Webber, Matthew J.; Berns, Eric J.; Stupp, Samuel I.

    2014-01-01

    Peptide nanostructures are an exciting class of supramolecular systems that can be designed for novel therapies with great potential in advanced medicine. This paper reviews progress on nanostructures based on peptide amphiphiles capable of forming one-dimensional assemblies that emulate in structure the nanofibers present in extracellular matrices. These systems are highly tunable using supramolecular chemistry, and can be designed to signal cells directly with bioactive peptides. Peptide amphiphile nanofibers can also be used to multiplex functions through co-assembly and designed to deliver proteins, nucleic acids, drugs, or cells. We illustrate here the functionality of these systems describing their use in regenerative medicine of bone, cartilage, the nervous system, the cardiovascular system, and other tissues. In addition, we highlight recent work on the use of peptide amphiphile assemblies to create hierarchical biomimetic structures with order beyond the nanoscale, and also discuss the future prospects of these supramolecular systems. PMID:24532851

  13. Stainless steel grafting of hyperbranched polymer brushes with an antibacterial activity: synthesis, characterization, and properties.

    PubMed

    Ignatova, Milena; Voccia, Samule; Gabriel, Sabine; Gilbert, Bernard; Cossement, Damien; Jerome, Robert; Jerome, Christine

    2009-01-20

    Two strategies were used for the preparation of hyperbranched polymer brushes with a high density of functional groups: (a) the cathodic electrografting of stainless steel by poly[2-(2-chloropropionate)ethyl acrylate] [poly(cPEA)], which was used as a macroinitiator for the atom transfer radical polymerization of an inimer, 2-(2-bromopropionate)ethyl acrylate in the presence or absence of heptadecafluorodecyl acrylate, (b) the grafting of preformed hyperbranched poly(ethyleneimine) onto poly(N-succinimidyl acrylate) previously electrografted onto stainless steel. The hyperbranched polymer, which contained either bromides or amines, was quaternized because the accordingly formed quaternary ammonium or pyridinium groups are known for antibacterial properties. The structure, chemical composition, and morphology of the quaternized and nonquaternized hyperbranched polymer brushes were characterized by ATR-FTIR reflectance, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The peeling test confirmed that the grafted hyperbranched polymer films adhered much more strongly to stainless steel than the nongrafted solvent-cast films. The quaternized hyperbranched polymer brushes were more effective in preventing both protein adsorption and bacterial adhesion than quaternary ammonium containing poly(cPEA) primary films, more likely because of the higher hydrophilicity and density of cationic groups.

  14. Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties.

    PubMed

    Schwieger, Christian; Achilles, Anja; Scholz, Sven; Rüger, Jan; Bacia, Kirsten; Saalwaechter, Kay; Kressler, Jörg; Blume, Alfred

    2014-09-07

    A novel class of symmetric amphi- and triphilic (hydrophilic, lipophilic, fluorophilic) block copolymers has been investigated with respect to their interactions with lipid membranes. The amphiphilic triblock copolymer has the structure PGMA(20)-PPO(34)-PGMA(20) (GP) and it becomes triphilic after attaching perfluoroalkyl moieties (F9) to either end which leads to F(9)-PGMA(20)-PPO(34)-PGMA(20)-F(9) (F-GP). The hydrophobic poly(propylene oxide) (PPO) block is sufficiently long to span a lipid bilayer. The poly(glycerol monomethacrylate) (PGMA) blocks have a high propensity for hydrogen bonding. The hydrophobic and lipophobic perfluoroalkyl moieties have the tendency to phase segregate in aqueous as well as in hydrocarbon environments. We performed differential scanning calorimetry (DSC) measurements on polymer bound lipid vesicles under systematic variation of the bilayer thickness, the nature of the lipid headgroup, and the polymer concentration. The vesicles were composed of phosphatidylcholines (DMPC, DPPC, DAPC, DSPC) or phosphatidylethanolamines (DMPE, DPPE, POPE). We showed that GP as well as F-GP binding have membrane stabilizing and destabilizing components. PPO and F9 blocks insert into the hydrophobic part of the membrane concomitantly with PGMA block adsorption to the lipid headgroup layer. The F9 chains act as additional membrane anchors. The insertion of the PPO blocks of both GP and F-GP could be proven by 2D-NOESY NMR spectroscopy. By fluorescence microscopy we show that F-GP binding increases the porosity of POPC giant unilamellar vesicles (GUVs), allowing the influx of water soluble dyes as well as the translocation of the complete triphilic polymer and its accumulation at the GUV surface. These results open a new route for the rational design of membrane systems with specific properties.

  15. Perfluorinated Moieties Increase the Interaction of Amphiphilic Block Copolymers with Lipid Monolayers.

    PubMed

    Schwieger, Christian; Blaffert, Jacob; Li, Zheng; Kressler, Jörg; Blume, Alfred

    2016-08-16

    The interaction of amphiphilic and triphilic block copolymers with lipid monolayers has been studied. Amphiphilic triblock copolymer PGMA20-PPO34-PGMA20 (GP) is composed of a hydrophobic poly(propylene oxide) (PPO) middle block that is flanked by two hydrophilic poly(glycerol monomethacrylate) (PGMA) side blocks. The attachment of a perfluoro-n-nonyl residue (F9) to either end of GP yields a triphilic polymer with the sequence F9-PGMA20-PPO34-PGMA20-F9 (F-GP). The F9 chains are fluorophilic, i.e., they have a tendency to demix in hydrophilic as well as in lipophilic environments. We investigated (i) the adsorption of both polymers to differently composed lipid monolayers and (ii) the compression behavior of mixed polymer/lipid monolayers. The lipid monolayers are composed of phospholipids with PC or PE headgroups and acyl chains of different length and saturation. Both polymers interact with lipid monolayers by inserting their hydrophobic moieties (PPO, F9). The interaction is markedly enhanced in the presence of F9 chains, which act as membrane anchors. GP inserts into lipid monolayers up to a surface pressure of 30 mN/m, whereas F-GP inserts into monolayers at up to 45 mN/m, suggesting that F-GP also inserts into lipid bilayer membranes. The adsorption of both polymers to lipid monolayers with short acyl chains is favored. Upon compression, a two-step squeeze-out of F-GP occurs, with PPO blocks being released into the aqueous subphase at 28 mN/m and the F9 chains being squeezed out at 48 mN/m. GP is squeezed out in one step at 28 mN/m because of the lack of F9 anchor groups. The liquid expanded (LE) to liquid condensed (LC) phase transition of DPPC and DMPE is maintained in the presence of the polymers, indicating that the polymers can be accommodated in LE- and LC-phase monolayers. These results show how fluorinated moieties can be included in the rational design of membrane-binding polymers.

  16. Behavior of atypical amphiphilic molecules

    NASA Astrophysics Data System (ADS)

    Ko, John

    1997-08-01

    The physical behavior of several atypical amphiphilic molecules was studied in various environments including micelles, model bilayer membranes, and emulsions. The molecules under investigation were nor-chenodeoxycholic acid (nor-CDCA), ursodeoxycholic acid (UDCA), sphingosine (Sp), sphingosine hydrochloride (SpċHCl), and tetrahydrolipstatin (THL). The bile acids, nor-CDCA and UDCA, were studied using 13C-Nuclear Magnetic Resonance ([13C) -NMR) in micelles of taurocholate and in bilayers of phosphatidylcholine. The pK a values of the bile acids in each environment were determined by [13C) -NMR and are as follows: 6.08 ±.03 for nor-CDCA and 6.27 ±.01 for UDCA in micelles, and 7.04 ± 12 for nor-CDCA and 6.89 ±.05 for UDCA in vesicles. Using line shape analysis, the transbilayer movement rate at 36oC for nor-CDCA and UDCA was calculated to be 580 sec--1 and 409 sec-1, respectively. [13C) -NMR titration of Sp gave pK a values of 9.09 ±.02 in micelles and 9.69 ±.21 in bilayers. Differential scanning calorimetry (DSC) and X-ray diffraction were used to establish the Spċwater and SpċHClċwater phase diagrams. Anhydrous and hydrated samples ranging from 5- 90% water were analyzed. The DSC thermograms traced out the transition temperatures of each molecule while the X- ray diffraction patterns revealed their chain and crystalline lattice packing structures. In general, sphingosine exists as a hydrated crystal with β packing phase below 43oC and melts into an Lα phase. Sphingosine hydrochloride, however, exists as a gel phase (L_beta or /beta/sp') below 42oC that swells to 61% hydration. At low water concentrations (0-64%), a lamellar liquid crystal phase (L_alpha) is formed above the chain melting transition of 42oC. At medium concentration (65%), a Hexagonal I phase is present, and at high water concentrations (66-90%), a micellar phase is present. THL, a specific inhibitor of lipases, was analyzed with [ 13C) -NMR to study its behavior in various environments

  17. Hyperbranched polymer films and dendrimers: Their chemistry and applications

    NASA Astrophysics Data System (ADS)

    Zhao, Mingqi

    The research in this dissertation examines the chemistry and applications of dendritic polymers; specifically, hyperbranched polymer thin films and dendrimers. We examined hyperbranched, fluorinated and unfluorinated poly(acrylic acid) (PAA) films on gold substrates, poly(amidoamine) (PAMAM) dendrimer monolayers and dendrimer-alkanethiol mixed monolayers on gold substrates, PAMAM dendrimer/poly(anhydride) and poly(iminopropane-1,3-diyl) (Cascade) dendrimer/poly(anhydride) multilayer films on silicon, gold, and aluminum substrates, PAMAM dendrimer/metal-ion composites, and PAMAM dendrimer-encapsulated metal nanoclusters in solution and on electrode surfaces. Hyperbranched PAA films have pH-dependent blocking abilities: at low pH PAA films effectively passivate Au electrodes while at high pH they are open and permeable. Fluorinated PAA films are far less permeable at any pH. Dendrimers ranging from generation 4 to 8 (G4--G8) can form highly stable and nearly close-packed monolayers and mixed monolayers with hexadecanethiol (C16SH) on surfaces. Moreover, dendrimers embedded within C16SH can act as gates of molecular dimension that control intradendrimer mass transfer of ions. Dendrimer/poly(anhydride) multilayers on surfaces were synthesized and their permeability was investigated. These composite membranes exhibit fully reversible, pH-switchable permselectivity for both cationic and anionic probe molecules because of their pH-dependent electrostatic properties. After heating, such films become highly blocking over the pH range studied due to thermally induced interdendrimer imidization, and other reactions. Finally, we show that PAMAM dendrimers can act first as templates for the preparation of transition-metal nanoclusters, and subsequently as stabilizers. Dendrimers quantitatively complex many transition-metal ions, including Cu 2+, Pt2+, Pd2+, Ru3+, and Ni2+, within their interiors. Chemical reduction of such nanocomposites results in formation of dendrimer

  18. Peptide Amphiphiles in Corneal Tissue Engineering

    PubMed Central

    Miotto, Martina; Gouveia, Ricardo M.; Connon, Che J.

    2015-01-01

    The increasing interest in effort towards creating alternative therapies have led to exciting breakthroughs in the attempt to bio-fabricate and engineer live tissues. This has been particularly evident in the development of new approaches applied to reconstruct corneal tissue. The need for tissue-engineered corneas is largely a response to the shortage of donor tissue and the lack of suitable alternative biological scaffolds preventing the treatment of millions of blind people worldwide. This review is focused on recent developments in corneal tissue engineering, specifically on the use of self-assembling peptide amphiphiles for this purpose. Recently, peptide amphiphiles have generated great interest as therapeutic molecules, both in vitro and in vivo. Here we introduce this rapidly developing field, and examine innovative applications of peptide amphiphiles to create natural bio-prosthetic corneal tissue in vitro. The advantages of peptide amphiphiles over other biomaterials, namely their wide range of functions and applications, versatility, and transferability are also discussed to better understand how these fascinating molecules can help solve current challenges in corneal regeneration. PMID:26258796

  19. Preparation and post-functionalization of hyperbranched polyurea coatings.

    PubMed

    Xiang, Fei; Asri, Lia; Ivashenko, Oleksii; Rudolf, Petra; Loontjens, Ton

    2015-03-10

    Postfunctionalizable hyperbranched polyurea coatings were prepared by the bulk polycondensation of AB2 monomers on preactivated silicon substrates. As previously shown, AB2 monomers were prepared, comprising a secondary amino group (A) and two blocked isocyanates (B) connected by hexyl spacers, in a single step and in quantitative yields. Covalent anchoring of the coatings on substrates was accomplished by reacting the secondary amino group in the focal point of the polymers with the blocked isocyanates (BIs) of the covalently attached coupling agent. The BIs in the top layer of the coatings were storage-stable under ambient conditions but well-modifiable with amino- or hydroxyl-functional compounds on heating. Attachment of polyethylene glycol or perfluoro-1-decanol afforded hydrophilic or hydrophobic surfaces. Immobilization and quaternization of polyethylenimines yielded highly charged surfaces. The coatings were extensively characterized by a number of techniques, such as Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, ellipsometry, and contact -angle measurements.

  20. Thermal and photochemical crosslinking of hyperbranched polyphenylene with organic azides.

    PubMed

    Pötzsch, Robert; Voit, Brigitte

    2012-04-23

    Here, we report on the first example of crosslinking (CL) hyperbranched polyphenylene (hb-PPh) with a small molecule crosslinker 1,3,5-tris(azidomethyl)benzene (TAMB). It was successfully shown that CL of the hb-PPh/TAMB (9:1) film is possible either thermally or photochemically making use of fundamentally different reaction mechanisms. Starting from a model reaction to prove the feasibility of the thermal CL reaction, we went on to check both the thermal and the photochemical crosslinkability of micrometer thick films. IR spectroscopy was furthermore used to confirm the CL process. Finally, the thin film morphology of the films before and after CL was investigated by AFM, revealing that the surface morphology was unaffected by the CL processes.

  1. Synthesis of functionalized CNTs/hyperbranched polyester nanocomposites

    NASA Astrophysics Data System (ADS)

    Pan, Yufeng; Cui, Xiaokun; Zhang, Yue

    2017-01-01

    Carbon nanotubes (CNTs) were unzipped using the modified Hummer method to prepare the CNTs-GO microstructure (see Fig. 1). A new type of CNTs-GO-H20 nanocomposite has been synthesized by grafting hyperbranched (HB) polyester (Boltorn H20) brushes on the CNTs-GO by coupling agent (KH560). The morphology of CNTs-GO-H20 was characterized by FTIR, TEM, XPS and TGA. The FT-IR data and XPS data evidenced that CNTs-GO-H20 nanocomposites were synthesized successfully. The addition of CNTs improved the thermal stability of the nanocomposites. The TEM data showed that the CNTs-GO microstructure was also prepared. These electrochemical measurements results indicated that coatings provided greater protection against corrosion behavior. Moreover, the nanocomposite material improved corrosion resistance of the coating.

  2. Poly(glycerol sebacate urethane)-cellulose nanocomposites with water-active shape-memory effects.

    PubMed

    Wu, Tongfei; Frydrych, Martin; O'Kelly, Kevin; Chen, Biqiong

    2014-07-14

    Biodegradable and biocompatible materials with shape-memory effects (SMEs) are attractive for use as minimally invasive medical devices. Nanocomposites with SMEs were prepared from biodegradable poly(glycerol sebacate urethane) (PGSU) and renewable cellulose nanocrystals (CNCs). The effects of CNC content on the structure, water absorption, and mechanical properties of the PGSU were studied. The water-responsive mechanically adaptive properties and shape-memory performance of PGSU-CNC nanocomposites were observed, which are dependent on the content of CNCs. The PGSU-CNC nanocomposite containing 23.2 vol % CNCs exhibited the best SMEs among the nanocomposites investigated, with the stable shape fixing and shape recovery ratios being 98 and 99%, respectively, attributable to the formation of a hydrophilic, yet strong, CNC network in the elastomeric matrix. In vitro degradation profiles of the nanocomposites were assessed with and without the presence of an enzyme.

  3. Poly(glycerol sebacate) elastomer: a novel material for mechanically loaded bone regeneration.

    PubMed

    Zaky, Samer Helal; Lee, Kee-Won; Gao, Jin; Jensen, Adrianna; Close, John; Wang, Yadong; Almarza, Alejandro J; Sfeir, Charles

    2014-01-01

    The selection criteria for potential bone engineering scaffolds are based chiefly on their relative mechanical comparability to mature bone. In this study, we challenge this notion by obtaining full regeneration of a rabbit ulna critical size defect by employing the elastomeric polymer, poly(glycerol sebacate) (PGS). We tested the regeneration facilitated by PGS alone, PGS in combination with hydroxyapatite particles, or PGS seeded with bone marrow stromal cells. We investigated the quantity and quality of the regenerated bone histologically, by microcomputed tomography and by four-point bending flexural mechanical testing at 8 weeks postimplantation. We conclude that the relatively lower stiffness of this biocompatible elastomer allows a load-transducing milieu in which osteogenesis, matrix deposition, and eventual bone maturation can take place. This study's results suggest that PGS elastomer is an auspicious osteoconductive material for the regeneration of bony defects. These results call for an innovative reassessment of the current art of selection for novel bone scaffold materials.

  4. Poly(glycerol methacrylate)-based degradable nanoparticles for delivery of small interfering RNA.

    PubMed

    Morsi, Noha G; Ali, Shimaa M; Elsonbaty, Sherouk S; Afifi, Ahmed A; Hamad, Mostafa A; Gao, Hui; Elsabahy, Mahmoud

    2017-04-07

    Nucleic acids therapeutic efficiency is generally limited by their low stability and intracellular bioavailability, and by the toxicity of the carriers used to deliver them to the target sites. Aminated poly(glycerol methacrylate) polymers are biodegradable and pH-sensitive polymers that have been used previously to deliver antisense oligonucleotide and show high transfection efficiency. The purpose of this study is to compare the efficiency and toxicity of aminated linear poly(glycerol methacrylate) (ALT) biodegradable polymer to the most commonly used cationic degradable (i.e. chitosan) and non-degradable (i.e. polyethylenimine (PEI)) polymers for delivery of short interfering RNA (siRNA). ALT, PEI and chitosan polymers were able to form nanosized particles with siRNA. Size, size-distribution and zeta-potential were measured over a wide range of nitrogen-to-phosphate (N/P) ratios, and the stability of the formed nanoparticles in saline and upon freeze-drying was also assessed. No significant cytotoxicity at the range of the tested concentrations of ALT and chitosan nanoparticles was observed, whereas the non-degradable PEI showed significant toxicity in huh-7 hepatocyte-derived carcinoma cell line. The safety profiles of the degradable polymers (ALT and chitosan) over non-degradable PEI were demonstrated in vitro and in vivo. In addition, ALT nanoparticles were able to deliver siRNA in vivo with significantly higher efficiency than chitosan nanoparticles. The results in the present study give evidence of the great implications of ALT nanoparticles in biomedical applications due to their biocompatibility, low cytotoxicity, high stability and simple preparation method.

  5. Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents.

    PubMed

    Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

    2014-08-21

    Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 ± 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.

  6. [Research process of the preparation of electrostatic spinning of poly-glycerol sebacate and the application in tissue engineering].

    PubMed

    Zhang, Xiaoming; Li, Wenho

    2015-10-01

    Poly-glycerol sebacate (PGS) is a novel biodegradable elastomer, it has been widely applied in the biomedical fields of heart, blood vessel and cartilage owing to its excellent biological performance, mechanical property and degradability. Electrostatic spinning is a preparation method of tissue engineering scaffolds with the characteristics of convenience, processing controllability and cost efficiency. In this paper, the author reviewed the research process of electrostatic spinning preparation and the application in the field of tissue engineering.

  7. A Peptide Amphiphile Organogelator of Polar Organic Solvents

    PubMed Central

    Rouse, Charlotte K.; Martin, Adam D.; Easton, Christopher J.; Thordarson, Pall

    2017-01-01

    A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents. PMID:28255169

  8. A Peptide Amphiphile Organogelator of Polar Organic Solvents

    NASA Astrophysics Data System (ADS)

    Rouse, Charlotte K.; Martin, Adam D.; Easton, Christopher J.; Thordarson, Pall

    2017-03-01

    A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents.

  9. A Peptide Amphiphile Organogelator of Polar Organic Solvents.

    PubMed

    Rouse, Charlotte K; Martin, Adam D; Easton, Christopher J; Thordarson, Pall

    2017-03-03

    A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents.

  10. Liposomal Formulation of Amphiphilic Fullerene Antioxidants

    PubMed Central

    Zhou, Zhiguo; Lenk, Robert P.; Dellinger, Anthony; Wilson, Stephen R.; Sadler, Robert; Kepley, Christopher L.

    2010-01-01

    Novel amphiphilic fullerene[70] derivatives that are rationally designed to intercalate in lipid bilayers are reported, as well as its vesicular formulation with surprisingly high loading capacity up to 65% by weight. The amphiphilic C70 bisadduct forms uniform and dimensionally stable liposomes with auxiliary natural phospholipids as demonstrated by buoyant density test, particle size distribution and 31P NMR. The antioxidant property of fullerenes is retained in the bipolarly functionalized C70 derivative, Amphiphilic Liposomal Malonylfullerene[70] (ALM) as well as in its liposomal formulations, as shown by both electron paramagnetic resonance (EPR) studies and in vitro reactive oxygen species (ROS) inhibition experiments. The liposomally formulated ALM efficiently quenched hydroxyl radicals and superoxide radicals. In addition, the fullerene liposome inhibited radical-induced lipid peroxidation and maintained the integrity of the lipid bilayer structure. This new class of liposomally formulated, amphipathic fullerene compounds represents a novel drug delivery system for fullerenes and provides a promising pathway to treat oxidative stress-related diseases. PMID:20839887

  11. Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

    PubMed Central

    Caldera, Fabrizio; Cavalli, Roberta; Mele, Andrea; Punta, Carlo; Melone, Lucio; Castiglione, Franca; Rossi, Barbara; Ferro, Monica; Crupi, Vincenza; Majolino, Domenico; Venuti, Valentina

    2014-01-01

    Summary A new hyper-branched water-soluble polymer was synthesized by reacting β-cyclodextrin with pyromellitic dianhydride beyond the critical conditions that allow the phenomenon of gelation to occur. The molar ratio between the monomers is a crucial parameter that rules the gelation process. Nevertheless, the concentration of monomers in the solvent phase plays a key role as well. Hyper-branched β-cyclodextrin-based polymers were obtained performing the syntheses with excess of solvent and cross-linking agent, and the conditions for critical dilution were determined experimentally. A hyper-branched polymer with very high water solubility was obtained and fully characterized both as for its chemical structure and for its capability to encapsulate substances. Fluorescein was used as probe molecule to test the complexation properties of the new material. PMID:25550720

  12. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 1. Effect of the chemical structure of amphiphiles on asphaltene stabilization

    SciTech Connect

    Chang, C.L.; Fogler, H.S. )

    1994-06-01

    Stabilization of crude oil asphaltenes in apolar alkane solvents was investigated using a series of alkylbenzene-derived amphiphiles as the asphaltene stabilizers. In this paper (i.e., part I), we present the study on the influences of the chemical structure of these amphiphiles on the effectiveness of asphaltene solubilization and on the strength of asphaltene-amphiphile interaction using both UV/vis and FTIR spectroscopies. The results showed that the amphiphile's effectiveness of asphaltene stabilization was primarily controlled by the polarity of the amphiphile's head group and the length of the amphiphile's alkyl tail. Increasing the acidity of the amphiphile's head group could promote the amphiphile's ability to stabilize asphaltenes by increasing the acid-base attraction between asphaltenes and amphiphiles. On the other hand, although decreasing the amphiphile's tail length increased the asphaltene-amphiphile attraction slightly, it still required a minimum tail length (six carbons for p-alkylphenol amphiphiles) for amphiphiles to form stable steric layers around asphaltenes. We also found additional acidic side groups of amphiphiles could further improve the amphiphile's ability to stabilize asphaltenes. The effect of the molecular weight of alkane solvents on the amphiphile's ability to stabilize asphaltenes was also studied. 18 refs., 12 figs., 3 tabs.

  13. Hyperbranched Polymers by Type II Photoinitiated Self-Condensing Vinyl Polymerization.

    PubMed

    Aydogan, Cansu; Ciftci, Mustafa; Yagci, Yusuf

    2016-04-01

    Type II photoinitiated self-condensing vinyl polymerization for the preparation of hyperbranched polymers is explored using 2-hydroxyethyl methacrylate (HEMA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA), and methyl methacrylate as hydrogen donating inimers and comonomer, respectively, in the presence of benzophenone and camphorquinone under UV and visible light. Upon irradiation at the corresponding wavelength, the excited photoinitiator abstracts hydrogen from HEMA or DMAEMA leading to the formation of initiating radicals. Depending on the concentration of inimers, type of the photoinitiator, and irradiation time, hyperbranched polymers with different branching densities and cross-linked polymers are formed.

  14. Enhanced dispersion of carbon nanotubes in hyperbranched polyurethane and properties of nanocomposites

    NASA Astrophysics Data System (ADS)

    Rana, Sravendra; Karak, Niranjan; Cho, Jae Whan; Kim, Young Ho

    2008-12-01

    Hyperbranched polyurethane (HBPU) nanocomposites with multi-walled carbon nanotubes (MWNTs) were prepared by in situ polymerization on the basis of poly(ɛ-caprolactone)diol as the soft segment, 4,4'-methylene bis(phenylisocyanate) as the hard segment, and castor oil as the multifunctional group for the hyperbranched structure. A dominant improvement in the dispersion of MWNTs in the HBPU matrix was found, and good solubility of HBPU-MWNT nanocomposites in organic solvents was shown. Due to the well-dispersed MWNTs, the nanocomposites resulted in achieving excellent shape memory properties as well as enhanced mechanical properties compared to pure HBPU.

  15. Communication: Density-functional theory for inhomogeneous hyperbranched polymeric fluids: polydisperse effect of degree of branching.

    PubMed

    Xu, Xiaofei; Cao, Dapeng

    2010-09-28

    We developed a new density-functional theory (DFT) for inhomogeneous hyperbranched polymers that is able to describe the polydisperse degree of branching quantitatively. The topological contributions of the polymer chains to the Helmholtz free energy take into account the effect of triple connections that are absent in previous DFT investigations. One key advantage of the new theory is that the computational cost shows only a linear relationship with the molecular weight (rather than an exponential relationship). The practical utility of the new DFT is illustrated by investigating colloidal stability in the presence of monodisperse and polydisperse hyperbranched polymers.

  16. Cellular recognition of synthetic peptide amphiphiles in supported bioartificial membranes

    NASA Astrophysics Data System (ADS)

    Pakalns, Teika

    The goal of this study was to demonstrate that lipidated cell adhesion peptides could form well-ordered biomimetic surfaces that were capable of influencing cellular behavior in a controlled and specific manner. The first step taken was to covalently link synthetic dialkyl tails to the amino-termini of the collagen-derived peptide IV-H1 (amino acid sequence GVKGDKGNPGWPGAP) and the well-known tripeptide Arg-Gly-Asp (RGD) to produce amino-coupled peptide amphiphiles. Other spatial orientations of RGD were also generated by coupling tails to the carboxyl-terminus to give carboxyl-coupled RGD amphiphiles and to both the amino- and carboxyl-termini to give looped RGD amphiphiles. The next step taken was to let the peptide amphiphile self-assemble along with methyl ester-capped dialkyl tails into mixed films. It was found that all the peptide amphiphiles formed stable monolayers at the air-water interface in a Langmuir trough. IV-H1 amphiphiles and carboxyl-coupled and looped RGD amphiphiles deposited well as Langmuir-Blodgett mixed films on solid surfaces at all peptide concentrations, but aminocoupled RGD amphiphiles did not deposit well at high RGD concentrations. FT-IR studies of films containing RGD amphiphiles showed that amino-coupled RGD head groups formed the strongest lateral hydrogen bonds. The final step was to study cellular response to mixed films containing IV-H1 or RGD amphiphiles. The spreading of melanoma cells was influenced by both the molar concentration and spatial orientation of the amphiphilic peptides. Cells spread on IV-H1 and looped RGD films in a concentration-dependent manner, but spread indiscriminately on carboxyl-coupled RGD films and did not spread at all on well-deposited amino-coupled RGD films. The specificity of the cellular response to looped RGD amphiphiles was investigated. Control films of looped Arg-Gly-Glu (RGE) amphiphiles inhibited the adhesion and spreading of melanoma and endothelial cells, and antibody inhibition of the

  17. Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation

    PubMed Central

    Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y. Eugene; Ma, Peter X.

    2015-01-01

    Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. PMID:26335860

  18. Prebiotic Alternatives to Proteins: Structure and Function of Hyperbranched Polyesters

    NASA Astrophysics Data System (ADS)

    Mamajanov, Irena; Callahan, Michael P.; Dworkin, Jason P.; Cody, George D.

    2015-06-01

    Proteins are responsible multiple biological functions, such as ligand binding, catalysis, and ion channeling. This functionality is enabled by proteins' three-dimensional structures that require long polypeptides. Since plausibly prebiotic synthesis of functional polypeptides has proven challenging in the laboratory, we propose that these functions may have been initially performed by alternative macromolecular constructs, namely hyperbranched polymers (HBPs), during early stages of chemical evolution. HBPs can be straightforwardly synthesized in one-pot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand binding and catalytic properties. Our initial study focuses on glycerol-citric acid HBPs synthesized via moderate heating in the dry state. The polymerization products consisted of a mixture of isomeric structures of varying molar mass as evidenced by NMR, mass spectrometry and size-exclusion chromatography. Addition of divalent cations during polymerization resulted in increased incorporation of citric acid into the HBPs and the possible formation of cation-oligomer complexes. The chelating properties of citric acid govern the makeup of the resulting polymer, turning the polymerization system into a rudimentary smart material.

  19. Improvement of antibody immobilization using hyperbranched polymer and protein A.

    PubMed

    Shen, Guangyu; Cai, Chenbo; Wang, Kun; Lu, Jilin

    2011-02-01

    For the construction of a well-defined antibody surface, protein A was used as a binding material to immobilize antibodies onto gold-derivatized transducers. The traditional method tends to assemble protein A directly onto the gold-derivatized transducers. In this paper, we tried to indirectly bind protein A onto sensors through hyperbranched polymer (HBP) which was synthesized from p-phenylenediamine and trimesic acid. The three-dimensional structure of HBP and the characteristics including orientation control and biocompatibility of protein A led to highly efficient immunoreactions and enhanced detection system performance. With this strategy, cysteamine monolayer was first assembled onto Au electrodes associated with the piezoelectric quartz crystal; secondly, the cysteamine-modified gold electrode was further modified by the activated HBP; thirdly, protein A was immobilized onto the HBP film; and finally, antibodies were immobilized onto the surface of protein A film for detecting the corresponding antigen. The quartz crystal microbalance immunosensor thus fabricated was applied to detect hepatitis B surface antigen in solutions that ranged from 0.71 to 300 μg mL(-1). The detection limit was estimated to be 0.53 μg mL(-1). The immunosensor holds good selectivity, sensitivity, and repeatability.

  20. [Amphiphilic cyclodextrins and their applications. Preparation of nanoparticles based on amphiphilic cyclodextrins for biomedical applications].

    PubMed

    Parrot-Lopez, H; Perret, F; Bertino-Ghera, B

    2010-01-01

    Solubilization of hydrophobic drugs at the molecular level as inclusion complexes inside cyclodextrins (CDs) offers a good alternative for improving their stability, solubility and bioavailability, and for preventing against their possible toxicity or controlling secondary effects. Therefore CDs are widely used as solubilizing excipients. However since dissociation takes place too readily upon dilution, inclusion complexes inside simple water-soluble CD appears ineffective for drug delivery applications. Chemical modifications of CDs allow them to self-organize as larger assemblies useful for resolving this lability issue. Depending on the position, the number and the nature of these groups, amphiphilic CDs can form assemblies such as vesicles, solid-lipid nanoparticles, nanospheres, liquid crystals, or micellar systems. This review deals with the synthesis of amphiphilic cyclodextrins leading to supramolecular assemblies and the physical properties of these assemblies. From the first sulfonated amphiphilic cyclodextrins isolated in our laboratory in 2003, to the latest ones being regioselectively functionalized by two or four fluoroalkyl chains, through the persubstituted fluorinated cyclodextrines, all these amphiphilic cyclodextrins have shown good abilities for encapsulation. Complexation of bioactive molecules (acyclovir) by these modified alpha-cyclodextrin derivatives, the encapsulation efficiency and release profile were measured as an assessment of the properties of such nanoparticles regarding drug delivery applications.

  1. Kinetic study of asphaltene dissolution in amphiphile/alkane solutions

    SciTech Connect

    Permsukarome, P.; Chang, C.; Fogler, H.S.

    1997-09-01

    The kinetics of dissolution of pentane-insoluble solid asphaltene precipitates by amphiphile/alkane solutions were investigated using a differential reactor flow system. Two amphiphiles, dodecylbenzenesulfonic acid and nonylphenol, and five alkane solvents, ranging from hexane to hexadecane, were used. Results showed that the rate of asphaltene dissolution in amphiphile/alkane fluids could be approximated with a first-order kinetics with respect to the undissolved asphaltene mass in solution. The specific dissolution rate constant, k, varied with the concentration of amphiphiles, the type of alkane solvents, the temperature, and the fluid flow rate. The rate of asphaltene dissolution displayed a Langmuir-Hinshelwood kinetics with respect to the concentration of amphiphiles. Increasing the temperature of amphiphile/alkane fluids also enhanced the rate of asphaltene dissolution. The apparent activation energy for asphaltene dissolution was approximated to be 4--7 kcal/mol. The rate of asphaltene dissolution was also greater in amphiphile solutions containing lighter alkanes, such as hexane, with lower viscosities. These trends suggest that both surface reaction and mass transfer processes are important to the rate of asphaltene dissolution in amphiphile/alkane fluids.

  2. Configurations of the amphiphilic molecules in micelles

    SciTech Connect

    Dill, K.A.

    1982-04-29

    Several theoretic models aim to account for the properties of micelles in terms of the configurations of the constituent amphiphilic chain molecules. Recent /sup 13/C NMR measurement of one property of the configuration distribution of the the hydrocarbon chain segments allows critical evaluation of these theories. It is concluded that the interphase and singly-bent chain theories, which fully account for chain continuity and for intermolecular constraints imposed by hydrophobic and steric forces, give a more satisfactory description of micellar molecular organization than models in which chains are ordered and radially aligned, or in which they have the complete disorder characteristic of an amorphous hydrocarbon liquid.

  3. Ionic liquids as amphiphile self-assembly media.

    PubMed

    Greaves, Tamar L; Drummond, Calum J

    2008-08-01

    In recent years, the number of non-aqueous solvents which mediate hydrocarbon-solvent interactions and promote the self-assembly of amphiphiles has been markedly increased by the reporting of over 30 ionic liquids which possess this previously unusual solvent characteristic. This new situation allows a different exploration of the molecular "solvophobic effect" and tests the current understanding of amphiphile self-assembly. Interestingly, both protic and aprotic ionic liquids support amphiphile self-assembly, indicating that it is not required for the solvents to be able to form a hydrogen bonded network. Here, the use of ionic liquids as amphiphile self-assembly media is reviewed, including micelle and liquid crystalline mesophase formation, their use as a solvent phase in microemulsions and emulsions, and the emerging field of nanostructured inorganic materials synthesis. Surfactants, lipids and block co-polymers are the focus amphiphile classes in this critical review (174 references).

  4. Mimicking of Chondrocyte Microenvironment Using In Situ Forming Dendritic Polyglycerol Sulfate-Based Synthetic Polyanionic Hydrogels.

    PubMed

    Dey, Pradip; Schneider, Tobias; Chiappisi, Leonardo; Gradzielski, Michael; Schulze-Tanzil, Gundula; Haag, Rainer

    2016-04-01

    A stable polymeric network that mimics the highly polyanionic extracellular cartilage matrix still remains a great challenge. The main aim of this study is to present the synthesis of dendritic polyglycerol sulfate (dPGS)-based in situ forming hydrogels using strain promoted azide-alkyne cycloaddition reactions. A real time rheological study has been used to characterize the hydrogel properties. The viability of encapsulated human chondrocytes in the different hydrogels are monitored using live-dead staining. Furthermore, type I and II collagen gene have been analyzed. Hydrogels with elastic moduli ranging from 1 to 5 kPa have been prepared by varying the dPGS amount. The chondrocyte viability in dPGS hydrogels is found to be higher than in pure PEG and alginate-based hydrogels after 21 d. The higher cell viability in the dPGS engineered hydrogels can be explained by the fact that dPGS can interact with different proteins responsible for cell growth and proliferation.

  5. Minimally invasive injectable short nanofibers of poly(glycerol sebacate) for cardiac tissue engineering

    NASA Astrophysics Data System (ADS)

    Ravichandran, Rajeswari; Reddy Venugopal, Jayarama; Sundarrajan, Subramanian; Mukherjee, Shayanti; Sridhar, Radhakrishnan; Ramakrishna, Seeram

    2012-09-01

    Myocardial tissue lacks the ability to appreciably regenerate itself following myocardial infarction (MI) which ultimately results in heart failure. Current therapies can only retard the progression of disease and hence tissue engineering strategies are required to facilitate the engineering of a suitable biomaterial to repair MI. The aim of this study was to investigate the in vitro properties of an injectable biomaterial for the regeneration of infarcted myocardium. Fabrication of core/shell fibers was by co-axial electrospinning, with poly(glycerol sebacate) (PGS) as core material and poly-l-lactic acid (PLLA) as shell material. The PLLA was removed by treatment of the PGS/PLLA core/shell fibers with DCM:hexane (2:1) to obtain PGS short fibers. These PGS short fibers offer the advantage of providing a minimally invasive injectable technique for the regeneration of infarcted myocardium. The scaffolds were characterized by SEM, FTIR and contact angle and cell-scaffold interactions using cardiomyocytes. The results showed that the cardiac marker proteins actinin, troponin, myosin heavy chain and connexin 43 were expressed more on short PGS fibers compared to PLLA nanofibers. We hypothesized that the injection of cells along with short PGS fibers would increase cell transplant retention and survival within the infarct, compared to the standard cell injection system.

  6. Highly Elastic and Suturable Electrospun Poly(Glycerol Sebacate) Fibrous Scaffolds

    PubMed Central

    Jeffries, Eric M.; Allen, Robert A.; Gao, Jin; Pesce, Matt; Wang, Yadong

    2015-01-01

    Poly(glycerol sebacate) (PGS) is a thermally-crosslinked elastomer suitable for tissue regeneration due to its elasticity, degradability, and pro-regenerative inflammatory response. Pores in PGS scaffolds are typically introduced by porogen leaching, which compromises strength. Methods for producing fibrous PGS scaffolds are very limited. Electrospinning is the most widely used method for laboratory scale production of fibrous scaffolds. Electrospinning PGS by itself is challenging, necessitating a carrier polymer which can affect material properties if not removed. We report a simple electrospinning method to produce distinct PGS fibers while maintaining the desired mechanical and cytocompatibility properties of thermally crosslinked PGS. Fibrous PGS demonstrated 5 times higher tensile strength and increased suture retention compared to porous PGS foams. Additionally, similar modulus and elastic recovery were observed. A final advantage of fibrous PGS sheets is the ability to create multi-laminate constructs due to fiber bonding that occurs during thermal crosslinking. Taken together, these highly elastic fibrous PGS scaffolds will enable new approaches in tissue engineering and regenerative medicine. PMID:25686558

  7. Highly elastic and suturable electrospun poly(glycerol sebacate) fibrous scaffolds.

    PubMed

    Jeffries, Eric M; Allen, Robert A; Gao, Jin; Pesce, Matt; Wang, Yadong

    2015-05-01

    Poly(glycerol sebacate) (PGS) is a thermally-crosslinked elastomer suitable for tissue regeneration due to its elasticity, degradability, and pro-regenerative inflammatory response. Pores in PGS scaffolds are typically introduced by porogen leaching, which compromises strength. Methods for producing fibrous PGS scaffolds are very limited. Electrospinning is the most widely used method for laboratory scale production of fibrous scaffolds. Electrospinning PGS by itself is challenging, necessitating a carrier polymer which can affect material properties if not removed. We report a simple electrospinning method to produce distinct PGS fibers while maintaining the desired mechanical and cytocompatibility properties of thermally crosslinked PGS. Fibrous PGS demonstrated 5 times higher tensile strength and increased suture retention compared to porous PGS foams. Additionally, similar modulus and elastic recovery were observed. A final advantage of fibrous PGS sheets is the ability to create multi-laminate constructs due to fiber bonding that occurs during thermal crosslinking. Taken together, these highly elastic fibrous PGS scaffolds will enable new approaches in tissue engineering and regenerative medicine.

  8. Elastomeric and mechanically stiff nanocomposites from poly(glycerol sebacate) and bioactive nanosilicates.

    PubMed

    Kerativitayanan, Punyavee; Gaharwar, Akhilesh K

    2015-10-01

    Poly(glycerol sebacate) (PGS) has been proposed for tissue engineering applications owing to its tough elastomeric mechanical properties, biocompatibility and controllable degradation. However, PGS shows limited bioactivity and thus constraining its utilization for musculoskeletal tissue engineering. To address this issue, we developed bioactive, highly elastomeric, and mechanically stiff nanocomposites by covalently reinforcing PGS network with two-dimensional (2D) nanosilicates. Nanosilicates are ultrathin nanomaterials and can induce osteogenic differentiation of human stem cells in the absence of any osteogenic factors such as dexamethasone or bone morphogenetic proteins-2 (BMP2). The addition of nanosilicate to PGS matrix significantly enhances the mechanical stiffness without affecting the elastomeric properties. Moreover, nanocomposites with higher amount of nanosilicates have higher in vitro stability as determined by degradation kinetics. The increase in mechanical stiffness and in vitro stability is mainly attributed to enhanced interactions between nanosilicates and PGS. We evaluated the in vitro bioactivity of nanocomposite using preosteoblast cells. The addition of nanosilicates significantly enhances the cell adhesion, support cell proliferation, upregulate alkaline phosphates and mineralized matrix production. Overall, the combination of high mechanically stiffness and elastomericity, tailorable degradation profile, and the ability to promote osteogenic differentiation of PGS-nanosilicate can be used for regeneration of bone.

  9. Elastomeric nanocomposite scaffolds made from poly(glycerol sebacate) chemically crosslinked with carbon nanotubes.

    PubMed

    Gaharwar, Akhilesh K; Patel, Alpesh; Dolatshahi-Pirouz, Alireza; Zhang, Hongbin; Rangarajan, Kaushik; Iviglia, Giorgio; Shin, Su-Ryon; Hussain, Mohammad Asif; Khademhosseini, Ali

    2015-01-01

    Carbon nanotube (CNT)-based nanocomposites often possess properties such as high stiffness, electrical conductivity, and thermal stability and have been studied for various biomedical and biotechnological applications. However, the current design approaches utilize CNTs as physical fillers, and thus, the true potential of CNT-based nanocomposites has not been realized. Here, we introduce a general approach to fabricating stiff, elastomeric nanocomposites from poly(glycerol sebacate) (PGS) and CNTs. The covalent crosslinking between the nanotubes and polymer chains resulted in novel property combinations that are not observed in conventional nanocomposites. The addition of 1% CNTs resulted in a five-fold increase in the tensile modulus and a six-fold increase in compression modulus compared with PGS alone, which is far superior to the previously reported studies for CNT-based nanocomposites. Despite a significant increase in mechanical stiffness, the elasticity of the network was not compromised and the resulting nanocomposites showed more than 94% recovery. This study demonstrates that the chemical conjugation of CNTs to a PGS backbone results in stiff and elastomeric nanocomposites. Additionally, in vitro studies using human mesenchymal stem cells (hMSCs) indicated that the incorporation of CNTs into the PGS network significantly enhanced the differentiation potential of the seeded hMSCs, rendering them potentially suitable for applications ranging from scaffolding in musculoskeletal tissue engineering to biosensors in biomedical devices.

  10. Biodegradable and elastomeric poly(glycerol sebacate) as a coating material for nitinol bare stent.

    PubMed

    Kim, Min Ji; Hwang, Moon Young; Kim, JiHeung; Chung, Dong June

    2014-01-01

    We synthesized and evaluated biodegradable and elastomeric polyesters (poly(glycerol sebacate) (PGS)) using polycondensation between glycerol and sebacic acid to form a cross-linked network structure without using exogenous catalysts. Synthesized materials possess good mechanical properties, elasticity, and surface erosion biodegradation behavior. The tensile strength of the PGS was as high as 0.28 ± 0.004 MPa, and Young's modulus was 0.122 ± 0.0003 MPa. Elongation was as high as 237.8 ± 0.64%, and repeated elongation behavior was also observed to at least three times the original length without rupture. The water-in-air contact angles of the PGS surfaces were about 60°. We also analyzed the properties of an electrospray coating of biodegradable PGS on a nitinol stent for the purpose of enhancing long-term patency for the therapeutic treatment of varicose veins disease. The surface morphology and thickness of coating layer could be controlled by adjusting the electrospraying conditions and solution parameters.

  11. Biomimetic poly(glycerol sebacate) (PGS) membranes for cardiac patch application.

    PubMed

    Rai, Ranjana; Tallawi, Marwa; Barbani, Niccoletta; Frati, Caterina; Madeddu, Denise; Cavalli, Stefano; Graiani, Gallia; Quaini, Federico; Roether, Judith A; Schubert, Dirk W; Rosellini, Elisabetta; Boccaccini, Aldo R

    2013-10-01

    In this study biomimetic poly(glycerol sebacate) PGS matrix was developed for cardiac patch application. The rationale was that such matrices would provide conducive environment for the seeded cells at the interphase with PGS. From the microstructural standpoint, PGS was fabricated into dense films and porous PGS scaffolds. From the biological aspect, biomimetic PGS membranes were developed via covalently binding peptides Tyr-Ile-Gly-Ser-Arg (YIGSR) and Gly-Arg-Gly-Asp-Ser-Pro (GRGDSP), corresponding to the epitope sequences of laminin and fibronectin, respectively onto the surface. To improve and enhance homogenous binding of peptides onto the PGS surface, chemical modification of its surface was carried out. A sequential regime of alkaline hydrolysis with 0.01 M NaOH for 5 min and acidification with 0.01 M HCl for 25s was optimal. More COOH chemical group was exposed without causing deleterious effect on the bulk properties of the polymer as revealed by the physicochemical analysis carried out. HPLC analysis, chemical imaging and ToF-SIMS were able to establish the successful homogenous functionalization of PGS membranes with the peptides. Finally, the developed biomimetic membranes supported the adhesion and growth of rat and human cardiac progenitor cells.

  12. Laser microfabricated poly(glycerol sebacate) scaffolds for heart valve tissue engineering.

    PubMed

    Masoumi, Nafiseh; Jean, Aurélie; Zugates, Jeffrey T; Johnson, Katherine L; Engelmayr, George C

    2013-01-01

    Microfabricated poly(glycerol sebacate) (PGS) scaffolds may be applicable to tissue engineering heart valve leaflets by virtue of their controllable microstructure, stiffness, and elasticity. In this study, PGS scaffolds were computationally designed and microfabricated by laser ablation to match the anisotropy and peak tangent moduli of native bovine aortic heart valve leaflets. Finite element simulations predicted PGS curing conditions, scaffold pore shape, and strut width capable of matching the scaffold effective stiffnesses to the leaflet peak tangent moduli. On the basis of simulation predicted effective stiffnesses of 1.041 and 0.208 MPa for the scaffold preferred (PD) and orthogonal, cross-preferred (XD) material directions, scaffolds with diamond-shaped pores were microfabricated by laser ablation of PGS cured 12 h at 160°C. Effective stiffnesses measured for the scaffold PD (0.83 ± 0.13 MPa) and XD (0.21 ± 0.03 MPa) were similar to both predicted values and peak tangent moduli measured for bovine aortic valve leaflets in the circumferential (1.00 ± 0.16 MPa) and radial (0.26 ± 0.03 MPa) directions. Scaffolds cultivated with fibroblasts for 3 weeks accumulated collagen (736 ± 193 μg/g wet weight) and DNA (17 ± 4 μg/g wet weight). This study provides a basis for the computational design of biomimetic microfabricated PGS scaffolds for tissue-engineered heart valves.

  13. Polyglycerol-functionalized nanodiamond as a platform for gene delivery: Derivatization, characterization, and hybridization with DNA

    PubMed Central

    Zhao, Li; Nakae, Yuki; Qin, Hongmei; Ito, Tadamasa; Kimura, Takahide; Kojima, Hideto; Chan, Lawrence

    2014-01-01

    Summary A gene vector consisting of nanodiamond, polyglycerol, and basic polypeptide (ND-PG-BPP) has been designed, synthesized, and characterized. The ND-PG-BPP was synthesized by PG functionalization of ND through ring-opening polymerization of glycidol on the ND surface, multistep organic transformations (–OH → –OTs (tosylate) → –N3) in the PG layer, and click conjugation of the basic polypeptides (Arg8, Lys8 or His8) terminated with propargyl glycine. The ND-PG-BPP exhibited good dispersibility in water (>1.0 mg/mL) and positive zeta potential ranging from +14.2 mV to +44.1 mV at neutral pH in Milli-Q water. It was confirmed by gel retardation assay that ND-PG-Arg8 and ND-PG-Lys8 with higher zeta potential hybridized with plasmid DNA (pDNA) through electrostatic attraction, making them promising as nonviral vectors for gene delivery. PMID:24778723

  14. Glycolic acid modulates the mechanical property and degradation of poly(glycerol, sebacate, glycolic acid).

    PubMed

    Sun, Zhi-Jie; Wu, Lan; Huang, Wei; Chen, Chang; Chen, Yan; Lu, Xi-Li; Zhang, Xiao-Lan; Yang, Bao-Feng; Dong, De-Li

    2010-01-01

    The development of biodegradable materials with controllable degradation properties is beneficial for a variety of applications. Poly(glycerol-sebacate) (PGS) is a promising candidate of biomaterials; so we synthesize a series of poly(glycerol, sebacate, glycolic acid) (PGSG) with 1:2:0, 1:2:0.2, 1:2:0.4, 1:2:0.6, 1:2:1 mole ratio of glycerol, sebacate, and glycolic acid to elucidate the relation of doped glycolic acid to the degradation rate and mechanical properties. The microstructures of the polymers with different doping of glycolic acid were dissimilar. PGSG with glycolic acid in the ratio of 0.2 displayed an integral degree of ordering, different to those with glycolic acid in the ratio of 0, 0.4, 0.6, and 1, which showed mild phase separation structure. The number, DeltaH(m), and temperature of the PGSG melting peaks tended to decrease with the increasing ratio of doped glycolic acid. In vitro and in vivo degradation tests showed that the degradation rate of PGSG with glycolic acid in the ratio of 0.2 was slowest, but in the ratio range of 0, 0.4, and 0.6, the degradation rate increased with the increase of glycolic acid. All PGSG samples displayed good tissue response and anticoagulant effects. Our data suggest that doping glycolic acid can modulate the microstructure and degree of crosslinking of PGS, thereby control the degradation rate of PGS.

  15. Degree of branching in hyperbranched poly(glycerol-co-diacid)s synthesized in toluene

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hyperbranched polymers were synthesized by using a Lewis acid (dibutyltin(IV)oxide) to catalyze the polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutaric acid (n=3) or azelaic acid (n=7) in toluene. These are the first examples of diacid-glycerol hyperbranc...

  16. The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

  17. Preparation of hyperbranched polymer via single electron transfer living radical polymerization

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Chen, X. H.; Li, J.; Cao, X. X.; Cheng, C. J.

    2015-07-01

    α-Trichloromethyl benzyl alcohol is converted to α-trichloromethyl benzyl methacrylate in 62% yield under esterification conditions. The ester proves to be a good inimer to prepare hyperbranched polymer by utilizing SET-LRP approach. The monomer conversion is about 72% at 60°C for 6 h.

  18. Synthesis and Characterization of Degradable Bioconjugated Hydrogels with Hyperbranched Multifunctional Crosslinkers

    PubMed Central

    Pedrón, Sara; Peinado, Carmen; Bosch, Paula; S.Anseth, Kristi

    2010-01-01

    Hyperbranched poly(ester amide) polymer (Hybrane™ S1200; Mn 1200 g/mol) was functionalized with maleic anhydride (MA) and propylene sulfide, to obtain multifunctional crosslinkers with fumaric and thiol-end groups, S1200MA and S1200SH, respectively. The degree of substitution of maleic acid groups (DS) was controlled by varying the molar ratio of MA to S1200 in the reaction mixture. Hydrogels were obtained by UV crosslinking of functionalized S1200 and poly(ethyleneglycol) diacrylate (PEGDA) in aqueous solutions. Compressive modulus increased with decreasing the S1200/PEG ratio and also depended on the DS of the multifunctional crosslinker (S1200). Also, heparin-based macromonomers together with functionalized hyperbranched polymers were used to construct novel functional hydrogels. The multivalent hyperbranched polymers allowed high crosslinking densities in heparin modified gels while introducing biodegradation sites. Both heparin presence and acrylate/thiol ratio have an impact on degradation profiles and morphologies. Hyperbranched crosslinked hydrogels showed no evidence of cell toxicity. Overall, the multifunctional crosslinkers afford hydrogels with promising properties that suggest that these may be suitable for tissue engineering applications. PMID:20561601

  19. Hyperbranched-polymer dispersed nanocomposite volume gratings for holography and diffractive optics

    NASA Astrophysics Data System (ADS)

    Tomita, Yasuo; Takeuchi, Shinsuke; Oyaizu, Satoko; Urano, Hiroshi; Fukamizu, Taka-aki; Nishimura, Naoya; Odoi, Keisuke

    2016-10-01

    We review our experimental investigations of photopolymerizable nanoparticle-polymer composites (NPCs) for holography and diffractive optics. Various types of hyperbranched polymer (HBP) were systhesized and used as transporting organic nanoparticles. These HBPs include hyperbranched poly(ethyl methacrylate) (HPEMA), hyperbranched polystyrene (HPS) and hyperbranched triazine/aromatic polymer units (HTA) whose refractive indices are 1.51, 1.61 and 1.82, respectively. Each HBP was dispersed in (meth)acrylate monomer whose refractive index was so chosen that a refractive index difference between HBP and the formed polymer was large. Such monomer-HBP syrup was mixed with a titanocene photoinitiator for volume holographic recording in the green. We used a two-beam interference setup to write an unslanted transmission volume grating at grating spacing of 1 μm and at a wavelength of 532 nm. It is shown that NPC volume gratings with the saturated refractive index modulation amplitudes as large as 0.008, 0.004 and 0.02 can be recorded in NPCs incorporated with HPEMA, HPS and HTA at their optimum concentrations of 34, 34 and 25 vol.%, respectively. We show the usefulness of HBP-dispersed NPC volume gratings for holographic applications such as holographic data storage and diffractive optical devices.

  20. Construction of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

    PubMed

    Tian, Yu-Kui; Yang, Zhi-Shuai; Lv, Xiao-Qin; Yao, Ri-Sheng; Wang, Feng

    2014-08-28

    A bis-alkynylplatinum(II) terpyridine tweezer-alkynylgold(III) diphenylpyridine guest is shown to maintain the specific complexation in the presence of a B21C7-secondary ammonium salt recognition motif, which facilitates the formation of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

  1. Hydrophobicity/hydrophilicity tunable hyperbranched polystyrenes as novel supports for transition-metal nanoparticles.

    PubMed

    Kojima, Keisuke; Chikama, Katsumi; Ishikawa, Makoto; Tanaka, Akihiro; Nishikata, Takashi; Tsutsumi, Hironori; Igawa, Kazunobu; Nagashima, Hideo

    2012-11-07

    Development of a new preparative procedure for hyperbranched polystyrene having Cl end groups (HPS-Cl) enables to prepare HPS-NR(3)(+)Cl(-), for which the hydrophobicity/hydrophilicity is tunable by the R groups. The resulting ammonium salts behave as a good support of platinum nanoparticles, which is useful for catalytic biphasic hydrogenation of alkenes.

  2. Valvular interstitial cell seeded poly(glycerol sebacate) scaffolds: toward a biomimetic in vitro model for heart valve tissue engineering.

    PubMed

    Masoumi, Nafiseh; Johnson, Katherine L; Howell, M Christian; Engelmayr, George C

    2013-04-01

    Tissue engineered replacement heart valves may be capable of overcoming the lack of growth potential intrinsic to current non-viable prosthetics, and thus could potentially serve as permanent replacements in the surgical repair of pediatric valvular lesions. However, the evaluation of candidate combinations of cells and scaffolds lacks a biomimetic in vitro model with broadly tunable, anisotropic and elastomeric structural-mechanical properties. Toward establishing such an in vitro model, in the current study, porcine aortic and pulmonary valvular interstitial cells (i.e. biomimetic cells) were cultivated on anisotropic, micromolded poly(glycerol sebacate) scaffolds (i.e. biomimetic scaffolds). Following 14 and 28 days of static culture, cell-seeded scaffolds and unseeded controls were assessed for their mechanical properties, and cell-seeded scaffolds were further characterized by confocal fluorescence and scanning electron microscopy, and by collagen and DNA assays. Poly(glycerol sebacate) micromolding yielded scaffolds with anisotropic stiffnesses resembling those of native valvular tissues in the low stress-strain ranges characteristic of physiologic valvular function. Scaffold anisotropy was largely retained upon cultivation with valvular interstitial cells; while the mechanical properties of unseeded scaffolds progressively diminished, cell-seeded scaffolds either retained or exceeded initial mechanical properties. Retention of mechanical properties in cell-seeded scaffolds paralleled the accretion of collagen, which increased significantly from 14 to 28 days. This study demonstrates that valvular interstitial cells can be cultivated on anisotropic poly(glycerol sebacate) scaffolds to yield biomimetic in vitro models with which clinically relevant cells and future scaffold designs can be evaluated.

  3. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation.

    PubMed

    Uppu, Divakara S S M; Haldar, Jayanta

    2016-03-14

    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

  4. Biodegradable fibrous scaffolds with tunable properties formed from photo-cross-linkable poly(glycerol sebacate).

    PubMed

    Ifkovits, Jamie L; Devlin, Jeffrey J; Eng, George; Martens, Timothy P; Vunjak-Novakovic, Gordana; Burdick, Jason A

    2009-09-01

    It is becoming increasingly apparent that the architecture and mechanical properties of scaffolds, particularly with respect to mimicking features of natural tissues, are important for tissue engineering applications. Acrylated poly(glycerol sebacate) (Acr-PGS) is a material that can be cross-linked upon exposure to ultraviolet light, leading to networks with tunable mechanical and degradation properties through simple changes during Acr-PGS synthesis. For example, the number of acrylate functional groups on the macromer dictates the concentration of cross-links formed in the resulting network. Three macromers were synthesized that form networks that vary dramatically with respect to their tensile modulus ( approximately 30 kPa to 6.6 MPa) and degradation behavior ( approximately 20-100% mass loss at 12 weeks) based on the extent of acrylation ( approximately 1-24%). These macromers were processed into biodegradable fibrous scaffolds using electrospinning, with gelatin as a carrier polymer to facilitate fiber formation and cell adhesion. The resulting scaffolds were also diverse with respect to their mechanics (tensile modulus ranging from approximately 60 kPa to 1 MPa) and degradation ( approximately 45-70% mass loss by 12 weeks). Mesenchymal stem cell adhesion and proliferation on all fibrous scaffolds was indistinguishable from those of controls. The scaffolds showed similar diversity when implanted on the surface of hearts in a rat model of acute myocardial infarction and demonstrated a dependence on the scaffold thickness and chemistry in the host response. In summary, these diverse scaffolds with tailorable chemical, structural, mechanical, and degradation properties are potentially useful for the engineering of a wide range of soft tissues.

  5. Biomimetic poly(glycerol sebacate)/poly(l-lactic acid) blend scaffolds for adipose tissue engineering.

    PubMed

    Frydrych, Martin; Román, Sabiniano; MacNeil, Sheila; Chen, Biqiong

    2015-05-01

    Large three-dimensional poly(glycerol sebacate) (PGS)/poly(l-lactic acid) (PLLA) scaffolds with similar bulk mechanical properties to native low and high stress adapted adipose tissue were fabricated via a freeze-drying and a subsequent curing process. PGS/PLLA scaffolds containing 73vol.% PGS were prepared using two different organic solvents, resulting in highly interconnected open-pore structures with porosities and pore sizes in the range of 91-92% and 109-141μm, respectively. Scanning electron microscopic analysis indicated that the scaffolds featured different microstructure characteristics, depending on the organic solvent in use. The PGS/PLLA scaffolds had a tensile Young's modulus of 0.030MPa, tensile strength of 0.007MPa, elongation at the maximum stress of 25% and full shape recovery capability upon release of the compressive load. In vitro degradation tests presented mass losses of 11-16% and 54-55% without and with the presence of lipase enzyme in 31days, respectively. In vitro cell tests exhibited clear evidence that the PGS/PLLA scaffolds prepared with 1,4-dioxane as the solvent are suitable for culture of adipose derived stem cells. Compared to pristine PLLA scaffolds prepared with the same procedure, these scaffolds provided favourable porous microstructures, good hydrophilic characteristics, and appropriate mechanical properties for soft tissue applications, as well as enhanced scaffold cell penetration and tissue in-growth characteristics. This work demonstrates that the PGS/PLLA scaffolds have potential for applications in adipose tissue engineering.

  6. In vitro human chondrocyte culture on plasma-treated poly(glycerol sebacate) scaffolds.

    PubMed

    Theerathanagorn, Tharinee; Klangjorhor, Jeerawan; Sakulsombat, Morakot; Pothacharoen, Peraphan; Pruksakorn, Dumnoensun; Kongtawelert, Prachya; Janvikul, Wanida

    2015-01-01

    Porous poly(glycerol sebacate) (PGS) scaffolds were prepared using a salt leaching technique and subsequently surface modified by a low oxygen plasma treatment prior to the use in the in vitro culture of human chondrocytes. Condensation polymerization of glycerol and sebacic acid used at various mole ratios, i.e. 1:1, 1:1.25, and 1:1.5, was initially conducted to prepare PGS prepolymers. Porous elastomeric PGS scaffolds were directly fabricated from the mixtures of each prepolymer and 90% (w/w) NaCl particles and then subjected to the plasma treatment to enhance the surface hydrophilicity of the materials. The properties of both untreated and plasma-treated PGS scaffolds were comparatively evaluated, in terms of surface morphology, surface chemical composition, porosity, and storage modulus using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy, micro-computed tomography, and dynamic mechanical analysis, respectively. The responses of chondrocytes cultured on individual PGS scaffolds were assessed, in terms of cell proliferation and ECM production. The results revealed that average pore sizes and porosity of the scaffolds were increased with an increasing sebacic acid concentration used. The storage moduli of the scaffolds were raised after the plasma treatment, possibly due to the further crosslinking of PGS upon treatment. Moreover, the scaffold prepared with a higher sebacic acid content demonstrated a greater capability of promoting cell infiltration, proliferation, and ECM production, especially when it was plasma-treated; the greatest HA, sGAG, uronic acid, and collagen contents were detected in matrix of this scaffold. The H & E and safranin O staining results also strongly supported this finding. The storage modulus of the scaffold was intensified after incubation with the chondrocytes for 21 days, indicating the accretion and retention of matrix ECM on the cell-cultured scaffold.

  7. The mechanical characteristics and in vitro biocompatibility of poly(glycerol sebacate)-bioglass elastomeric composites.

    PubMed

    Liang, Shu-Ling; Cook, Wayne D; Thouas, George A; Chen, Qi-Zhi

    2010-11-01

    Biodegradable elastomeric materials have gained much recent attention in the field of soft tissue engineering. Poly(glycerol sebacate) (PGS) is one of a new family of elastomers which are promising candidates used for soft tissue engineering. However, PGS has a limited range of mechanical properties and has drawbacks, such as cytotoxicity caused by the acidic degradation products of very soft PGS and degradation kinetics that are too fast in vivo to provide sufficient mechanical support to the tissue. However, the development of PGS/based elastomeric composites containing alkaline bioactive fillers could be a method for addressing these drawbacks and thus may pave the way towards wide clinical applications. In this study, we synthesized a new PGS composite system consisting of a micron-sized Bioglass filler. In addition to much improved cytocompatibility, the PGS/Bioglass composites demonstrated three remarkable mechanical properties. First, contrary to previous reports, the addition of microsized Bioglass increases the elongation at break from 160 to 550%, while enhancing the Young's modulus of the composites by up to a factor of four. Second, the modulus of the PGS/Bioglass composites drops abruptly in a physiological environment (culture medium), and the level of drop can be tuned such that the addition of Bioglass does not harden the composite in vivo and thus the desired compliance required for soft tissue engineering are maintained. Third, after the abrupt drop in modulus, the composites exhibited mechanical stability over an extended period. This latter observation is an important feature of the new composites, because they can provide reliable mechanical support to damaged tissues during the lag phase of the healing process. These mechanical properties, together with improved biocompatibility, make this family of composites better candidates than plastic and related composite biomaterials for the applications of tissue engineering.

  8. Drug incorporation and release of water soluble drugs from novel functionalized poly(glycerol adipate) nanoparticles.

    PubMed

    Puri, Sanyogita; Kallinteri, Paraskevi; Higgins, Sean; Hutcheon, Gillian A; Garnett, Martin C

    2008-01-04

    We have previously demonstrated the ability of poly(glycerol adipate) backbone (PGA) and PGA polymer backbone substituted with varying amounts of pendant C(18) chain length acyl groups to yield Dexamethasone phosphate DXMP loaded nanoparticles. The aim of this study was to obtain a deeper understanding of the underlying principles responsible for good drug incorporation and controlled release of drugs from poly (glycerol adipate) (PGA) nanoparticles. We compared the incorporation of the water soluble drugs DXMP and Cytosine arabinoside (CYT-ARA) in both unmodified and substituted PGA polymers. We investigated the effect of change in acyl group chain length and the degree of substitution on the physicochemical properties, drug loading and release of DXMP and CYT-ARA. Nanoparticles were prepared by the interfacial deposition technique and the simultaneous emulsification method. Amongst the nanoparticles prepared using acylated polymers with varying chain lengths (C(2) to C(10)) for DXMP incorporation, polymers with acyl group chain lengths containing 8 carbon atoms (C(8)) showed maximum drug incorporation. Amongst the C(8) series, polymers with 100% acylation provided both good drug incorporation and a controlled release for DXMP while for CYT-ARA it was the unsubstituted polymer backbone that had maximum drug loading and slower release. A number of inter-related factors are responsible for producing particles with particular size, zeta potential, drug loading and release characteristics. Drug loading and release from nanoparticles are primarily influenced by the nature of interactions between the drug and polymers which in turn depend upon the type of drug used and the physical chemistry of the polymer.

  9. Detecting and Quantifying Biomolecular Interactions of a Dendritic Polyglycerol Sulfate Nanoparticle Using Fluorescence Lifetime Measurements.

    PubMed

    Boreham, Alexander; Pikkemaat, Jens; Volz, Pierre; Brodwolf, Robert; Kuehne, Christian; Licha, Kai; Haag, Rainer; Dernedde, Jens; Alexiev, Ulrike

    2015-12-24

    Interactions of nanoparticles with biomaterials determine the biological activity that is key for the physiological response. Dendritic polyglycerol sulfates (dPGS) were found recently to act as an inhibitor of inflammation by blocking selectins. Systemic application of dPGS would present this nanoparticle to various biological molecules that rapidly adsorb to the nanoparticle surface or lead to adsorption of the nanoparticle to cellular structures such as lipid membranes. In the past, fluorescence lifetime measurements of fluorescently tagged nanoparticles at a molecular and cellular/tissue level have been proven to reveal valuable information on the local nanoparticle environment via characteristic fluorescent lifetime signatures of the nanoparticle bound dye. Here, we established fluorescence lifetime measurements as a tool to determine the binding affinity to fluorescently tagged dPGS (dPGS-ICC; ICC: indocarbocyanine). The binding to a cell adhesion molecule (L-selectin) and a human complement protein (C1q) to dPGS-ICC was evaluated by the concentration dependent change in the unique fluorescence lifetime signature of dPGS-ICC. The apparent binding affinity was found to be in the nanomolar range for both proteins (L-selectin: 87 ± 4 nM and C1q: 42 ± 12 nM). Furthermore, the effect of human serum on the unique fluorescence lifetime signature of dPGS-ICC was measured and found to be different from the interactions with the two proteins and lipid membranes. A comparison between the unique lifetime signatures of dPGS-ICC in different biological environments shows that fluorescence lifetime measurements of unique dPGS-ICC fluorescence lifetime signatures are a versatile tool to probe the microenvironment of dPGS in cells and tissue.

  10. Criteria for Quick and Consistent Synthesis of Poly(glycerol sebacate) for Tailored Mechanical Properties.

    PubMed

    Li, Xinda; Hong, Albert T-L; Naskar, Nilanjon; Chung, Hyun-Joong

    2015-05-11

    Poly(glycerol sebacate) (PGS) and its derivatives make up an attractive class of biomaterial owing to their tunable mechanical properties with programmable biodegradability. In practice, however, the application of PGS is often hampered by frequent inconsistency in reproducing process conditions. The inconsistency stems from the volatile nature of glycerol during the esterification process. In this study, we suggest that the degree of esterification (DE) can be used to predict precisely the physical status, the mechanical properties, and the degradation of the PGS materials. Young's modulus is shown to linearly increase with DE, which is in agreement with an entropic spring theory of rubbers. To provide a processing guideline for researchers, we also provide a physical status map as a function of curing temperature and time. The amount of glycerol loss, obtainable by monitoring the evolution of the total mass loss and the DE during synthesis, is shown to make the predictions even more precise. We expect that these strategies can be applicable to different categories of polymers that involve condensation polymerization with the volatility of the reactants. In addition, we demonstrate that microwave-assisted prepolymerization is a time- and energy-efficient pathway to obtain PGS. For example, 15 min of microwave time is shown to be as efficient as prepolymerization in nitrogen atmosphere for 6 h at 130 °C. The quick synthesis method, however, causes a severe evaporation of glycerol, resulting in a large distortion in the monomer ratio between glycerol and sebacic acid. Consequently, more rigid PGS is produced under a similar curing condition compared to the conventional prepolymerization method. Finally, we demonstrate that the addition of molecularly rigid cross-linking agents and network-structured inorganic nanoparticles are also effective in enhancing the mechanical properties of the PGS-derived materials.

  11. Hyperbranched hydrocarbon surfactants give fluorocarbon-like low surface energies.

    PubMed

    Sagisaka, Masanobu; Narumi, Tsuyoshi; Niwase, Misaki; Narita, Shioki; Ohata, Atsushi; James, Craig; Yoshizawa, Atsushi; Taffin de Givenchy, Elisabeth; Guittard, Frédéric; Alexander, Shirin; Eastoe, Julian

    2014-06-03

    Two series of Aerosol-OT-analogue surfactants (sulfosuccinate-type di-BCnSS and sulfoglutarate-type di-BCnSG) with hyperbranched alkyl double tails (so-called "hedgehog" groups, carbon number n = 6, 9, 12, and 18) have been synthesized and shown to demonstrate interfacial properties comparable to those seen for related fluorocarbon (FC) systems. Critical micelle concentration (CMC), surface tension at the CMC (γCMC), and minimum area per molecule (Amin) were obtained from surface tension measurements of aqueous surfactant solutions. The results were examined for relationships between the structure of the hedgehog group and packing density at the interface. To evaluate A and B values in the Klevens equation for these hedgehog surfactants, log(CMC) was plotted as a function of the total carbon number in the surfactant double tail. A linear relationship was observed, producing B values of 0.20-0.25 for di-BCnSS and di-BCnSG, compared to a value of 0.31 for standard double-straight-tail sulfosuccinate surfactants. The lower B values of these hedgehog surfactants highlight their lower hydrophobicity compared to double-straight-tail surfactants. To clarify how hydrocarbon density in the surfactant-tail layer (ρ(layer)) affects γCMC, the ρ(layer) of each double-tail surfactant was calculated and the relationship between γCMC and ρ(layer) examined. As expected for the design of low surface energy surfactant layers, ρ(layer) was identified as an important property for controlling γCMC with higher ρ(layer), leading to a lower γCMC. Interestingly, surfactants with BC9 and BC12 tails achieved much lower γCMC, even at low ρ(layer) values of <0.55 g cm(-3). The lowest surface energy surfactant studied here was di-BC6SS, which had a γCMC of only 23.8 mN m(-1). Such a low γCMC is comparable to those obtained with short FC-tail surfactants (e.g., 22.0 mN m(-1) for the sulfosuccinate-type FC-surfactant with R = F(CF2)6CH2CH2-).

  12. Phase behavior of an amphiphilic fluid.

    PubMed

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H L

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995)]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  13. Phase behavior of an amphiphilic fluid

    NASA Astrophysics Data System (ADS)

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H. L.

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995), 10.1103/PhysRevE.52.1915]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  14. Revealing Amphiphilic Nanodornains of Anti-Biofouling Polymer Coatings

    SciTech Connect

    Amadei, CA; Yang, R; Chiesa, M; Gleason, KK; Santos, S

    2014-04-09

    Undesired bacterial adhesion and biofilm formation on wetted surfaces leads to significant economic and environmental costs in various industries. Amphiphilic coatings with molecular hydrophilic and hydrophobic patches can mitigate such biofouling effectively in an environmentally friendly manner. The coatings are synthesized by copolymerizing (Hydroxyethyl)methacrylate and perfluorodecylacrylate via initiated chemical vapor deposition (iCVD). In previous studies, the size of the patches was estimated to be similar to 1.4-1.75 nm by fitting protein adsorption data to a theoretical model. However, no direct observations of the molecular heterogeneity exist and therefore the origin of the fouling resistance of amphiphilic coatings remains unclear. Here, the amphiphilic nature is investigated by amplitude modulation atomic force microscopy (AM-AFM). High-resolution images obtained by penetrating and oscillating the AFM tip under the naturally present water layer with sub-nanometer amplitudes reveal, for the first time, the existence of amphiphilic nanodomains (1-2 nm(2)). Compositional heterogeneity at the nanoscale is further corroborated by a statistical analysis on the data obtained with dynamic AM-AFM force spectroscopy. Variations in the long range attractive forces, responsible for water affinity, are also identified. These nanoscopic results on the polymers wettability are also confirmed by contact angle measurements (i.e., static and dynamic). The unprecedented ability to visualize the amphiphilic nanodomains as well as sub-nanometer crystalline structures provides strong evidence for the existence of previously postulated nanostructures, and sheds light on the underlying antifouling mechanism of amphiphilic chemistry.

  15. Hyperbranched polymers and dendrimers as templates for organic/inorganic hybrid nanomaterials.

    PubMed

    Huang, Xinhua; Zheng, Sudan; Kim, Il

    2014-02-01

    This paper reviews the recent research and development of hyperbranched polymers (HPs) and dendrimers, and their use as templates for organic-inorganic hybrid nanomaterials. Hyperbranched polymers (HPs) are highly branched macromolecules with three-dimensional globular structures featuring unique properties such as low viscosity, high solubility, and a large number of terminal functional groups compared to their linear analogs. They are easily prepared by (1) condensation polymerization, (2) self-condensing vinyl copolymerization (SCVCP), and (3) ring-opening multibranch polymerization methods. Organic-inorganic hybrid nanomaterials are synthesized by a template approach using HPs/dendrimers. Monometallic, bimetallic (alloy and core/shell), semiconductor, and metal oxide nanoparticles have been prepared by this route. The dendrimer component of these composites serves not only as a template for preparing the nanoparticles but also as a stabilizer for the nanoparticles.

  16. Facile synthesis of dendritic gold nanostructures with hyperbranched architectures and their electrocatalytic activity toward ethanol oxidation.

    PubMed

    Huang, Jianshe; Han, Xinyi; Wang, Dawei; Liu, Dong; You, Tianyan

    2013-09-25

    Gold dendritic nanostructures with hyperbranched architectures were synthesized by the galvanic replacement reaction between nickel wire and HAuCl4 in aqueous solution. The study revealed that the morphology of the obtained nanostructures strongly depended on experimental parameters such as the HAuCl4 solution concentration, reaction temperature, and time, as well as stirring or not. According to the investigation of the growth process, it was proposed that gold nanoparticles with rough surfaces were first deposited on the nickel substrate and that subsequent growth preferentially occurred on the preformed gold nanoparticles, finally leading to the formation of hyperbranched gold dendrites via a self-organization process under nonequilibrium conditions. The electrochemical experiment results demonstrated that the as-obtained gold dendrites exhibited high catalytic activity toward ethanol electrooxidation in alkaline solution, indicating that this nanomaterial may be a potential catalyst for direct ethanol fuel cells.

  17. Hyperbranched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits.

    PubMed

    Bi, Sai; Chen, Min; Jia, Xiaoqiang; Dong, Ying; Wang, Zonghua

    2015-07-06

    A hyper-branched hybridization chain reaction (HB-HCR) is presented herein, which consists of only six species that can metastably coexist until the introduction of an initiator DNA to trigger a cascade of hybridization events, leading to the self-sustained assembly of hyper-branched and nicked double-stranded DNA structures. The system can readily achieve ultrasensitive detection of target DNA. Moreover, the HB-HCR principle is successfully applied to construct three-input concatenated logic circuits with excellent specificity and extended to design a security-mimicking keypad lock system. Significantly, the HB-HCR-based keypad lock can alarm immediately if the "password" is incorrect. Overall, the proposed HB-HCR with high amplification efficiency is simple, homogeneous, fast, robust, and low-cost, and holds great promise in the development of biosensing, in the programmable assembly of DNA architectures, and in molecular logic operations.

  18. Rheology of Hyperbranched Poly(triglyceride)-Based Thermoplastic Elastomers via RAFT polymerization

    NASA Astrophysics Data System (ADS)

    Yan, Mengguo; Cochran, Eric

    2014-03-01

    In this contribution we discuss how melt- and solid-state properties are influenced by the degree of branching and molecular weight in a family of hyperbranched thermoplastics derived from soybean oil. Acrylated epoxidized triglycerides from soybean oils have been polymerized to hyperbranched thermoplastic elastomers using reversible addition-fragmentation chain transfer (RAFT) polymerization. With the proper choice of chain transfer agent, both homopolymer and block copolymer can be synthesized. By changing the number of acrylic groups per triglycerides, the chain architectures can range from nearly linear to highly branched. We show how the fundamental viscoelastic properties (e.g. entanglement molecular weight, plateau modulus, etc.) are influenced by chain architecture and molecular weight.

  19. Layer-by-layer deposition of rhenium-containing hyperbranched polymers and fabrication of photovoltaic cells.

    PubMed

    Tse, Chui Wan; Man, Ka Yan Kitty; Cheng, Kai Wing; Mak, Chris S K; Chan, Wai Kin; Yip, Cho Tung; Liu, Zheng Tong; Djurisić, Aleksandra B

    2007-01-01

    Multilayer thin films were prepared by the layer-by-layer (LBL) deposition method using a rhenium-containing hyperbranched polymer and poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (PTEBS). The radii of gyration of the hyperbranched polymer in solutions with different salt concentrations were measured by laser light scattering. A significant decrease in molecular size was observed when sodium trifluoromethanesulfonate was used as the electrolyte. The conditions of preparing the multilayer thin films by LBL deposition were studied. The growth of the multilayer films was monitored by absorption spectroscopy and spectroscopic ellipsometry, and the surface morphologies of the resulting films were studied by atomic force microscopy. When the pH of a PTEBS solution was kept at 6 and in the presence of salt, polymer films with maximum thickness were obtained. The multilayer films were also fabricated into photovoltaic cells and their photocurrent responses were measured upon irradiation with simulated air mass (AM) 1.5 solar light. The open-circuit voltage, short-circuit current, fill factor, and power conversion efficiency of the devices were 1.2 V, 27.1 mu A cm(-2), 0.19, and 6.1x10(-3) %, respectively. The high open-circuit voltage was attributed to the difference in the HOMO level of the PTEBS donor and the LUMO level of the hyperbranched polymer acceptor. A plot of incident photon-to-electron conversion efficiency versus wavelength also suggests that the PTEBS/hyperbranched polymer junction is involved in the photosensitization process, in which a maximum was observed at approximately 420 nm. The relatively high capacitance, determined from the measured photocurrent rise and decay profiles, can be attributed to the presence of large counter anions in the polymer film.

  20. Broadband optical limiting and nonlinear optical absorption properties of a novel hyperbranched conjugated polymer

    NASA Astrophysics Data System (ADS)

    Li, Chao; Liu, Chunling; Li, Quanshui; Gong, Qihuang

    2004-12-01

    The nonlinear transmittance of a novel hyperbranched conjugated polymer named DMA-HPV has been measured in CHCl 3 solution using a nanosecond optical parametric oscillator. DMA-HPV shows excellent optical limiting performance in the visible region from 490 to 610 nm. An explanation based on the combination of two-photon absorption and reverse saturable absorption was proposed for its huge and broadband nonlinear optical absorption.

  1. The effect of molecular weight, compositions and lectin type on the properties of hyperbranched glycopolymers as non-viral gene delivery systems.

    PubMed

    Ahmed, Marya; Narain, Ravin

    2012-05-01

    The architectures of gene delivery vectors, in addition to their molecular weights and compositions, can play a critical role in DNA condensation and hence on their gene expression. In general, branched polymers are superior gene delivery vectors as compared to their linear analogs. This study reports the efficacy of cationic hyperbranched glycopolymers for DNA condensation and gene expression. Hyperbranched glycopolymers of varying molecular weights and compositions are synthesized via reversible addition fragmentation chain transfer (RAFT) process and are further explored for their gene expression in vitro. Galactose-based hyperbranched polymers are compared to glucose-derived hyperbranched polymers for their cellular uptake, toxicity and gene expression. It is found that molecular weight of hyperbranched polymers, and carbohydrate content of copolymers are critical factors in determining the gene expression as well as in imparting the specificity to these novel gene delivery vectors. The galactose-based hyperbranched glycopolymer of ~30 kDa or lower show improved gene expression at varying polymer/plasmid ratios. The incubation of hyperbranched polyplexes in the presence of serum protein show the presence of stable particles and gene expression of these hyperbranched polyplexes is unaffected in the presence of serum proteins. Furthermore, the cellular uptake and gene expression are studied in two different cell lines in the presence of lectins. It is found that polyplexes-lectin conjugates show enhanced cellular uptake in vitro, however their gene expression is cell line and lectin type dependent.

  2. Synthesis of Cu-Ag@Ag particles using hyperbranched polyester as template

    NASA Astrophysics Data System (ADS)

    Han, Wen-Song

    2015-07-01

    In this manuscript, the third-generation hyperbranched polyester was synthesized with 2, 2-dimethylol propionic acid as AB2 monomer and pentaerythrite as core molecule by using step by step polymerization process at first. Then, the Cu-Ag particles were prepared by co-reduction of silver nitrate and copper nitrate with ascorbic acid in the aqueous solution using hyperbranched polyester as template. Finally, the Cu-Ag@Ag particles were prepared by coating silver on the surface of Cu-Ag particles by reduction of silver nitrate. The synthesized hyperbranched polyester and Cu-Ag@Ag particles were characterized by Fourier transform infrared (FT-IR) spectroscopy, UV-vis spectra, x-ray diffraction, Laser light scattering, thermogravimetric analysis (TGA) and SEM. UV-vis spectra results showed that the Cu-Ag@Ag particles had a strong absorption band at around 420 nm. Laser light scattering and SEM studies confirmed that the most frequent particle sizes of Cu-Ag@Ag particles were 1.2 um. TGA results indicated that the Cu-Ag@Ag particles had good thermal stability. [Figure not available: see fulltext.

  3. Bioorthogonal layer-by-layer encapsulation of pancreatic islets via hyperbranched polymers.

    PubMed

    Gattás-Asfura, Kerim M; Stabler, Cherie L

    2013-10-23

    Encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over the capsule properties. Herein, we report the development of a hyperbranched polymer-based, ultrathin capsule architecture expressing bioorthogonal functionality and tailored physiochemical properties. Random carbodiimide-based condensation of 3,5-dicarboxyphenyl glycineamide on alginate yielded a highly branched polysaccharide with multiple, spatially restricted, and readily functionalizable terminal carboxylate moieties. Poly(ethylene glycol) (PEG) was utilized to link azido end groups to the structured alginate. Together with a phosphine-functionalized poly(amidoamine) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized, ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs.

  4. Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

    DOEpatents

    Sen, Ayusman; Kim, Jang Sub; Pawlow, James H.; Murtuza, Shahid; Kacker, Smita; Wojcinski, III, Louis M.

    2001-01-01

    Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

  5. Stability and permeability of amphiphile bilayers.

    PubMed

    Exerowa, D; Kashchiev, D; Platikanov, D

    1992-05-30

    In this review the rupture and permeability of bilayers are considered on the basis of a mechanism of the formation of microscopic holes as fluctuations in the bilayers. The hole formation is treated as a nucleation process of a new phase in a two-dimensional system with short-range intermolecular forces. Free rupture and deliberate rupture (by alpha-particles) of foam bilayers (Newtonian black films) are discussed. A comparison is made between the rupture of foam and emulsion bilayers. Experimental methods for obtaining foam and emulsion bilayers from thin liquid films are considered. Methods for investigating the stability and permeability of foam bilayers, which are based on a microscopic model allowing the use of amphiphile solutions with very low concentrations, are described. Experimental dependences of the lifetime of bilayers, the probability of observing the foam bilayer in a foam film, the gas permeability of bilayers, etc. on the concentration of amphiphile molecules in the solution are reported. The influence of temperature and external impact (e.g. alpha-particle irradiation) have also been experimentally studied. A good agreement between theory and experiment is established, allowing determination of several characteristics of foam and emulsion bilayers obtained from ionics or non-ionics: the specific edge energy of bilayer holes, equilibrium surfactant concentration below which the bilayer is thermodynamically metastable, work for the formation of a nucleus hole, number of vacancies in the nucleus hole, coefficient of gas diffusion through the bilayer, etc. On the basis of the effect of temperature on the rupture of foam bilayers the binding energy of a surfactant molecule in the bilayer is determined. The adsorption isotherm of surfactant vacancies in the foam bilayer is obtained which shows a first-order phase transition. Some applications to scientific, technological and medical problems are considered. The foam bilayer is used as a model for

  6. Characterization of novel cationic amphiphiles for gene delivery

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoxiang

    Gene therapy has drawn vast interest for treating, preventing, or controlling a myriad of diseases. The two most common methods for gene delivery use either synthetic or viral vectors. Viral vectors (infection) are by far the most effective and efficient means of DNA delivery, but their use is tempered by safety and immunogenicity concerns. Consequently, there has been a significant effort to develop and evaluate non- viral vectors, which include cationic amphiphiles and polymers, and more recently anionic amphiphiles. Non-viral vectors have the advantages of ease of production, better stability and low immunogenicity. At the same time, they also have a number of limitations, including low in vitro and in vivo transfection efficiencies, and cytotoxicity in many instances. My research project has been focused on design, development and characterizations of novel amphiphilic lipids for gene delivery. Through rational design and characterization of the amphiphile structures, it not only yielded vectors showing high transfection activities, but also provided information of the structure-activity relationship. These results provide us with a better understanding on the transfection process and future directions to further optimize the amphiphile structures. More specifically, my dissertation research included the following three parts: (i) characterization of novel lipopeptides possessing di- or tri- peptide head groups; (ii) determination of the effect of spacer (between the cationic domain and the hydrophobic domain of charge-reversal amphiphiles) length, rigidity and hydrophilicity on gene delivery; (iii) identification of the cellular uptake pathway and the transfection mechanism of a known enzyme-sensitive charge-reversal amphiphile.

  7. Silica Ouzo Effect: Amphiphilic Drugs Facilitate Nanoprecipitation of Polycondensed Mercaptosilanes.

    PubMed

    Chiu, Shih-Jiuan; Lin, Chien-Yu; Chou, Hung-Chang; Hu, Teh-Min

    2016-01-12

    Amphiphilic drugs are therapeutic agents whose molecular structures contain both hydrophobic and hydrophilic portions. Here we report a systematic study on how amphiphilic drugs can assist in silica nanoprecipitation. 3-Mercaptopropyltrimethoxysilane (MPTMS) was used as the sole silica material and 12 amphiphilic drugs spanning a wide spectrum of therapeutic categories were included. MPTMS polycondensation was conducted in a DMSO-based organic phase. After a sufficient time, particle formation was induced by injecting a small amount of the organic phase into a water solution containing various amphiphiles. The results show that all amphiphilic drugs studied exerted concentration-dependent facilitating effect on nanoparticle formation. Under certain preparation conditions, the particle solution showed physical stability over a long period and the formed particles could be as small as 100 nm. By systematically varying drug concentrations and injection volumes, the ability of each amphiphile to promote nanoprecipitation can be quantified and compared, based on two novel indices: the area under the critical volume-concentration curve (AUC) and the critical stabilization concentration (CSC). We demonstrate that both ability indices significantly correlated with the drug's log P and critical micelle concentrations (CMC). Furthermore, we have optimized the aging and particle purification condition and extensively characterized our system through comprehensive TEM and zeta-potential measurements, as well as determinations for drug entrapment and release. In conclusion, we have established a quantitative structure-activity relationship for amphiphilic small-molecular drugs in their ability to interact with poly(mercaptopropyl)silsesquioxane species and form nanoparticles via solvent shifting. We speculate that both hydrophobic and electrostatic interactions play important roles in the formation and stabilization of nanoparticles.

  8. HBP Builder: A Tool to Generate Hyperbranched Polymers and Hyperbranched Multi-Arm Copolymers for Coarse-grained and Fully Atomistic Molecular Simulations

    PubMed Central

    Yu, Chunyang; Ma, Li; Li, Shanlong; Tan, Haina; Zhou, Yongfeng; Yan, Deyue

    2016-01-01

    Computer simulation has been becoming a versatile tool that can investigate detailed information from the microscopic scale to the mesoscopic scale. However, the crucial first step of molecular simulation is model building, particularly for hyperbranched polymers (HBPs) and hyperbranched multi-arm copolymers (HBMCs) with complex and various topological structures. Unlike well-defined polymers, not only the molar weight of HBPs/HBMCs with polydispersity, but the HBPs/HBMCs with the same degree of polymerization (DP) and degree of branching (DB) also have many possible topological structures, thus making difficulties for user to build model in molecular simulation. In order to build a bridge between model building and molecular simulation of HBPs and HBMCs, we developed HBP Builder, a C language open source HBPs/HBMCs building toolkit. HBP Builder implements an automated protocol to build various coarse-grained and fully atomistic structures of HBPs/HBMCs according to user’s specific requirements. Meanwhile, coarse-grained and fully atomistic output structures can be directly employed in popular simulation packages, including HOOMD, Tinker and Gromacs. Moreover, HBP Builder has an easy-to-use graphical user interface and the modular architecture, making it easy to extend and reuse it as a part of other program. PMID:27188541

  9. HBP Builder: A Tool to Generate Hyperbranched Polymers and Hyperbranched Multi-Arm Copolymers for Coarse-grained and Fully Atomistic Molecular Simulations

    NASA Astrophysics Data System (ADS)

    Yu, Chunyang; Ma, Li; Li, Shanlong; Tan, Haina; Zhou, Yongfeng; Yan, Deyue

    2016-05-01

    Computer simulation has been becoming a versatile tool that can investigate detailed information from the microscopic scale to the mesoscopic scale. However, the crucial first step of molecular simulation is model building, particularly for hyperbranched polymers (HBPs) and hyperbranched multi-arm copolymers (HBMCs) with complex and various topological structures. Unlike well-defined polymers, not only the molar weight of HBPs/HBMCs with polydispersity, but the HBPs/HBMCs with the same degree of polymerization (DP) and degree of branching (DB) also have many possible topological structures, thus making difficulties for user to build model in molecular simulation. In order to build a bridge between model building and molecular simulation of HBPs and HBMCs, we developed HBP Builder, a C language open source HBPs/HBMCs building toolkit. HBP Builder implements an automated protocol to build various coarse-grained and fully atomistic structures of HBPs/HBMCs according to user’s specific requirements. Meanwhile, coarse-grained and fully atomistic output structures can be directly employed in popular simulation packages, including HOOMD, Tinker and Gromacs. Moreover, HBP Builder has an easy-to-use graphical user interface and the modular architecture, making it easy to extend and reuse it as a part of other program.

  10. Interfacial adsorption and aggregation of amphiphilic proteins

    NASA Astrophysics Data System (ADS)

    Cheung, David

    2012-02-01

    The adsorption and aggregation on liquid interfaces of proteins is important in many biological contexts, such as the formation of aerial structures, immune response, and catalysis. Likewise the adsorption of proteins onto interfaces has applications in food technology, drug delivery, and in personal care products. As such there has been much interest in the study of a wide range of biomolecules at liquid interfaces. One class of proteins that has attracted particular attention are hydrophobins, small, fungal proteins with a distinct, amphiphilic surface structure. This makes these proteins highly surface active and they recently attracted much interest. In order to understand their potential applications a microscopic description of their interfacial and self-assembly is necessary and molecular simulation provides a powerful tool for providing this. In this presentation I will describe some recent work using coarse-grained molecular dynamics simulations to study the interfacial and aggregation behaviour of hydrophobins. Specifically this will present the calculation of their adsorption strength at oil-water and air-water interfaces, investigate the stability of hydrophobin aggregates in solution and their interaction with surfactants.

  11. Selective peptide binding using facially amphiphilic dendrimers.

    PubMed

    Gomez-Escudero, Andrea; Azagarsamy, Malar A; Theddu, Naresh; Vachet, Richard W; Thayumanavan, S

    2008-08-20

    Amphiphilic dendrimers, which contain both hydrophobic and hydrophilic groups in every repeat unit, exhibit environment-dependent assemblies both in hydrophilic solvent, water, and in lipophilic solvent, toluene. Upon investigating the status of these assemblies in a mixture of immiscible solvents, these dendrimers were found to be kinetically trapped in the solvent in which they are initially assembled. This property has been exploited to selectively extract peptides from aqueous solution into an organic phase, where the peptides bind to the interior functionalities of the dendritic inverse micelles. While the corresponding small molecule surfactant does not exhibit any selective binding toward peptides, all dendrons (G1-G3) are capable of this selective binding. We show that the inverse micelle-type assembly itself is crucial for the binding event and that the assembly formed by the G1 dendron has a greater capability for binding compared to the G2 or G3 dendrons. We have also shown that the average apparent pKa of the carboxylic acid functionalities varies with generation, and this could be the reason for the observed differences in binding capacity.

  12. Selection of Prebiotic Molecules in Amphiphilic Environments

    PubMed Central

    Mayer, Christian; Schreiber, Ulrich; Dávila, María J.

    2017-01-01

    A basic problem in all postulated pathways of prebiotic chemistry is the low concentration which generally is expected for interesting reactants in fluid environments. Even though compounds, like nucleobases, sugars or peptides, principally may form spontaneously under environmental conditions, they will always be rapidly diluted in an aqueous environment. In addition, any such reaction leads to side products which often exceed the desired compound and generally hamper the first steps of a subsequent molecular evolution. Therefore, a mechanism of selection and accumulation of relevant prebiotic compounds seems to be crucial for molecular evolution. A very efficient environment for selection and accumulation can be found in the fluid continuum circulating in tectonic fault zones. Vesicles which form spontaneously at a depth of approximately 1 km present a selective trap for amphiphilic molecules, especially for peptides composed of hydrophilic and hydrophobic amino acids in a suitable sequence. The accumulation effect is shown in a numeric simulation on a simplified model. Further, possible mechanisms of a molecular evolution in vesicle membranes are discussed. Altogether, the proposed scenario can be seen as an ideal environment for constant, undisturbed molecular evolution in and on cell-like compartments. PMID:28067845

  13. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers.

    PubMed

    Wang, Hui; Shi, Xuefeng; Yu, Danfeng; Zhang, Jian; Yang, Guang; Cui, Yingxian; Sun, Keji; Wang, Jinben; Yan, Haike

    2015-12-22

    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance.

  14. Highly regioselective synthesis of amino-functionalized dendritic polyglycerols by a one-pot hydroformylation/reductive amination sequence.

    PubMed

    Koç, Fikret; Wyszogrodzka, Monika; Eilbracht, Peter; Haag, Rainer

    2005-03-18

    [reaction: see text] Dendritic architectures with neutral core structures and amines groups in the shell are a synthetic challenge, and there is a need for an efficient access. In this paper, highly selective Rh-catalysts are used for sequential hydroformylation/reductive amination of dendritic perallylated polyglycerols 1 with various amines in a one-pot procedure to give dendritic polyamines 3a-e in high yields (73-99%). In all cases, complete conversion of the allyl ether and aldehyde intermediate has been observed. Furthermore, the use of protected amines provides reactive core-shell-type architectures after deprotection. These soluble but membrane filterable multifunctional dendritic polyamines are of high interest as reagents in synthesis or as supports in homogeneous catalysis as well as nonviral vectors for DNA-transfection.

  15. Ionization of amphiphilic acidic block copolymers.

    PubMed

    Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

    2012-06-28

    The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

  16. Multiwalled nanotubes formed by catanionic mixtures of drug amphiphiles.

    PubMed

    Lin, Yi-An; Cheetham, Andrew G; Zhang, Pengcheng; Ou, Yu-Chuan; Li, Yuguo; Liu, Guanshu; Hermida-Merino, Daniel; Hamley, Ian W; Cui, Honggang

    2014-12-23

    Mixing of oppositely charged amphiphilic molecules (catanionic mixing) offers an attractive strategy to produce morphologies different from those formed by individual molecules. We report here on the use of catanionic mixing of anticancer drug amphiphiles to construct multiwalled nanotubes containing a fixed and high drug loading. We found that the molecular mixing ratio, the solvent composition, the overall drug concentrations, as well as the molecular design of the studied amphiphiles are all important experimental parameters contributing to the tubular morphology. We believe these results demonstrate the remarkable potential that anticancer drugs could offer to self-assemble into discrete nanostructures and also provide important insight into the formation mechanism of nanotubes by catanionic mixtures. Our preliminary animal studies reveal that the CPT nanotubes show significantly prolonged retention time in the tumor site after intratumoral injection.

  17. Synthesis of silver nanoparticles in melts of amphiphilic polyesters

    NASA Astrophysics Data System (ADS)

    Vasylyev, S.; Damm, C.; Segets, D.; Hanisch, M.; Taccardi, N.; Wasserscheid, P.; Peukert, W.

    2013-03-01

    The current work presents a one-step procedure for the synthesis of amphiphilic silver nanoparticles suitable for production of silver-filled polymeric materials. This solvent free synthesis via reduction of Tollens’ reagent as silver precursor in melts of amphiphilic polyesters consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic alkyl chains allows the production of silver nanoparticles without any by-product formation. This makes them especially interesting for the production of medical devices with antimicrobial properties. In this article the influences of the chain length of the hydrophobic block in the amphiphilic polyesters and the process temperature on the particle size distribution (PSD) and the stability of the particles against agglomeration are discussed. According to the results of spectroscopic and viscosimetric investigations the silver precursor is reduced to elemental silver nanoparticles by a single electron transfer process from the poly(ethylene glycol) chain to the silver ion.

  18. Amphiphilic poly-N-vinylpyrrolidone nanocarriers with incorporated model proteins

    NASA Astrophysics Data System (ADS)

    Kuskov, A. N.; Villemson, A. L.; Shtilman, M. I.; Larionova, N. I.; Tsatsakis, A. M.; Tsikalas, I.; Rizos, A. K.

    2007-05-01

    New nanoscaled polymeric carriers have been prepared on the basis of different amphiphilic water-soluble derivatives of poly-N-vinylpyrrolidone (PVP). The polymer self-assembly and interaction with model proteins (Bowman-Birk soybean proteinase inhibitor (BBI) and its hydrophobized derivatives) were studied in aqueous media. The possibility of inclusion of both BBI and hydrophobized oleic acid derivatives of BBI in amphiphilic PVP aggregates was investigated. It was ascertained that polymeric particles of size 50-80 nm were formed in certain concentrations of amphiphilic PVP and poorly soluble dioleic acid derivatives of BBI. Such polymeric aggregates are capable of solubilization of dioleoyl BBI with a concomitant prevention of its inactivation at low pH values.

  19. Multiwalled Nanotubes Formed by Catanionic Mixtures of Drug Amphiphiles

    PubMed Central

    2015-01-01

    Mixing of oppositely charged amphiphilic molecules (catanionic mixing) offers an attractive strategy to produce morphologies different from those formed by individual molecules. We report here on the use of catanionic mixing of anticancer drug amphiphiles to construct multiwalled nanotubes containing a fixed and high drug loading. We found that the molecular mixing ratio, the solvent composition, the overall drug concentrations, as well as the molecular design of the studied amphiphiles are all important experimental parameters contributing to the tubular morphology. We believe these results demonstrate the remarkable potential that anticancer drugs could offer to self-assemble into discrete nanostructures and also provide important insight into the formation mechanism of nanotubes by catanionic mixtures. Our preliminary animal studies reveal that the CPT nanotubes show significantly prolonged retention time in the tumor site after intratumoral injection. PMID:25415538

  20. Competitive Binding of Natural Amphiphiles with Graphene Derivatives

    PubMed Central

    Radic, Slaven; Geitner, Nicholas K.; Podila, Ramakrishna; Käkinen, Aleksandr; Chen, Pengyu; Ke, Pu Chun; Ding, Feng

    2013-01-01

    Understanding the transformation of graphene derivatives by natural amphiphiles is essential for elucidating the biological and environmental implications of this emerging class of engineered nanomaterials. Using rapid discrete-molecular-dynamics simulations, we examined the binding of graphene and graphene oxide with peptides, fatty acids, and cellulose, and complemented our simulations by experimental studies of Raman spectroscopy, FTIR, and UV-Vis spectrophotometry. Specifically, we established a connection between the differential binding and the conformational flexibility, molecular geometry, and hydrocarbon content of the amphiphiles. Importantly, our dynamics simulations revealed a Vroman-like competitive binding of the amphiphiles for the graphene oxide substrate. This study provides a mechanistic basis for addressing the transformation, evolution, transport, biocompatibility, and toxicity of graphene derivatives in living systems and the natural environment. PMID:23881402

  1. Phase behavior and formation of o/w nano-emulsion in vegetable oil/ mixture of polyglycerol polyricinoleate and polyglycerin fatty acid ester/water systems.

    PubMed

    Wakisaka, Satoshi; Nakanishi, Masami; Gohtani, Shoichi

    2014-01-01

    It is reported that mixing polyglycerol polyricinoleate (PGPR) and polyglycerol laurilester has a great emulsifying capacity, and consequently fine oil-in-water (o/w) emulsions can be formed. However, the role of PGPR is not clear. The objective of this research is to investigate the phase behavior of vegetable oil/mixture of PGPR and polyglycerol fatty acid ester/water systems, and to clarify the role of PGPR in making a fine emulsion. Phase diagrams were constructed to elucidate the optimal process for preparing fine emulsions. In all the systems examined in this study, the phases, including the liquid crystal phase (L(c)) and sponge phase (L(3)), spread widely in the phase diagrams. We examined droplet size of the emulsions prepared from each phase and found that o/w nano-emulsions with droplet sizes as small as 50 nm were formed by emulsifying either from a single L(3) phase or a two-phase region, L(c) + L(3). These results indicate that a sponge phase L(3) or liquid crystal phase L(c) or both is necessary to form an o/w nano-emulsion whose average droplet diameter is less than 50 nm for PGPR and polyglycerin fatty acid ester mixtures used as surfactant.

  2. Amphiphile Meets Amphiphile: Beyond the Polar-Apolar Dualism in Ionic Liquid/Alcohol Mixtures.

    PubMed

    Russina, Olga; Sferrazza, Alessio; Caminiti, Ruggero; Triolo, Alessandro

    2014-05-15

    The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes.

  3. Aqueous phase behavior of polyelectrolytes with amphiphilic counterions modulated by cyclodextrin: the role of polyion flexibility.

    PubMed

    Carlstedt, Jonas; Bilalov, Azat; Olsson, Ulf

    2012-07-21

    Polyelectrolytes with amphiphilic counterions, PEACs, are water insoluble because the amphiphiles self-assemble into highly charged micelles that strongly associate with the equally highly charged polyions. However, in the presence of water soluble cyclodextrins (CDs) that form inclusion complexes with the amphiphiles and prevent micellization, PEACs become soluble as the dispersed amphiphiles behave essentially as simple monovalent counterions. In this paper, we illustrate, by example, how strongly the ternary phase behavior of PEAC:CD:water depends on the polyion flexibility; for a highly flexible polyion (polyacrylate) the amphiphilic aggregates dictate the phase behavior, whereas a much stiffer polyion (DNA) itself dictates liquid crystalline ordering.

  4. An efficient nonviral gene-delivery vector based on hyperbranched cationic glycogen derivatives

    PubMed Central

    Liang, Xuan; Ren, Xianyue; Liu, Zhenzhen; Liu, Yingliang; Wang, Jue; Wang, Jingnan; Zhang, Li-Ming; Deng, David YB; Quan, Daping; Yang, Liqun

    2014-01-01

    Background The purpose of this study was to synthesize and evaluate hyperbranched cationic glycogen derivatives as an efficient nonviral gene-delivery vector. Methods A series of hyperbranched cationic glycogen derivatives conjugated with 3-(dimethylamino)-1-propylamine (DMAPA-Glyp) and 1-(2-aminoethyl) piperazine (AEPZ-Glyp) residues were synthesized and characterized by Fourier-transform infrared and hydrogen-1 nuclear magnetic resonance spectroscopy. Their buffer capacity was assessed by acid–base titration in aqueous NaCl solution. Plasmid deoxyribonucleic acid (pDNA) condensation ability and protection against DNase I degradation of the glycogen derivatives were assessed using agarose gel electrophoresis. The zeta potentials and particle sizes of the glycogen derivative/pDNA complexes were measured, and the images of the complexes were observed using atomic force microscopy. Blood compatibility and cytotoxicity were evaluated by hemolysis assay and MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay, respectively. pDNA transfection efficiency mediated by the cationic glycogen derivatives was evaluated by flow cytometry and fluorescence microscopy in the 293T (human embryonic kidney) and the CNE2 (human nasopharyngeal carcinoma) cell lines. In vivo delivery of pDNA in model animals (Sprague Dawley rats) was evaluated to identify the safety and transfection efficiency. Results The hyperbranched cationic glycogen derivatives conjugated with DMAPA and AEPZ residues were synthesized. They exhibited better blood compatibility and lower cytotoxicity when compared to branched polyethyleneimine (bPEI). They were able to bind and condense pDNA to form the complexes of 100–250 nm in size. The transfection efficiency of the DMAPA-Glyp/pDNA complexes was higher than those of the AEPZ-Glyp/pDNA complexes in both the 293T and CNE2 cells, and almost equal to those of bPEI. Furthermore, pDNA could be more safely delivered to the blood vessels in brain

  5. Hyperbranched chelating polymers for the polymer-assisted ultrafiltration of boric acid

    SciTech Connect

    Smith, B.M.; Todd, P.; Bowman, C.N.

    1999-07-01

    Two hyperbranched chelating polymers, glucoheptonamide derivatives of dendrimetric poly(amido amine) and poly(ethylene imine), were employed in polymer-assisted ultrafiltration and concentration of boron from aqueous feed streams. For feeds containing approximately 1 mM B (10 ppm), volume reduction factors of 20 were observed in cyclic adsorption-desorption. The concentrations of both polymers declined due to permeation through an ultrafiltration membrane with pore sizes which should have retained them. Acid-catalyzed hydrolysis of the amide linkages between the polymer backbone and the chelating side groups is implicated in this loss of polymer mass and effectiveness.

  6. Drug release from hydrazone-containing peptide amphiphiles

    SciTech Connect

    Matson, John B.; Stupp, Samuel I.

    2012-03-15

    Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for release of the drug nabumetone from nanofiber gels. On-resin addition of the novel compound tri-Boc-hydrazido adipic acid to a lysine E-amine allowed for precise placement of a hydrazide in a peptide sequence.

  7. Bio-based amphiphilic materials development and applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Farm-based raw materials are increasingly used in the development of amphiphilic materials that have potential applications in the production of a variety of consumer and industrial products, including lubricants. Raw materials of interest include: starches, proteins, fats, oils, and sugars. These ...

  8. Pulmonary and generalized lysosomal storage induced by amphiphilic drugs.

    PubMed Central

    Hruban, Z

    1984-01-01

    Administration of amphiphilic drugs to experimental animals causes formation of myelinoid bodies in many cell types, accumulation of foamy macrophages in pulmonary alveoli and pulmonary alveolar proteinosis. These changes are the result of an interaction between the drugs and phospholipids which leads to an alteration in physicochemical properties of the phospholipids. Impairment of the digestion of altered pulmonary secretions in phagosomes of macrophages results in accumulation of foam cells in pulmonary alveoli. Impairment of the metabolism of altered phospholipids removed by autophagy induces an accumulation of myelinoid bodies. The administration of amphiphilic compounds thus causes pulmonary intra-alveolar histiocytosis which is a part of a drug-induced lysosomal storage or generalized lipidosis. The accumulation of drug-lipid complexes in myelinoid bodies and in pulmonary foam cells may lead to alteration of cellular functioning and to clinical disease. Currently over 50 amphiphilic drugs are known. Unique pharmacological properties necessitate clinical use of some of these drugs. The occurrence and severity of potential clinical side effects depend on the nature of each drug, dosage and duration of treatment, simultaneous administration of other drugs and foods, individual metabolic pattern of the patient and other factors. Further studies on factors preventing and potentiating adverse effects of amphiphilic drugs are indicated. Images FIGURE 1. FIGURE 2. FIGURE 3. FIGURE 4. FIGURE 5. FIGURE 6. FIGURE 7. FIGURE 8. FIGURE 9. FIGURE 10. PMID:6376111

  9. Reinforcement of latex rubber by the incorporation of amphiphilic nanoparticles

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Latex rubbers are fabricated from latex suspensions. During the fabrication process, latex particles are bound together while water is removed from the suspension. This report shows the mechanical properties of latex rubbers can be improved by incorporating a small amount of amphiphilic nanoparticle...

  10. Biobased oil structure on amphiphilic and tribological properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biobased oils are those derived from farm-based renewable raw materials. Most are vegetable oils (such as soybean, canola, corn, etc.) or chemical modifications of vegetable oils. They have a number of interesting structural features that impact their amphiphilic and lubrication properties. The basi...

  11. Vesicular self-assembly of colloidal amphiphiles in microfluidics.

    PubMed

    He, Jie; Wang, Lei; Wei, Zengjiang; Yang, Yunlong; Wang, Chaoyang; Han, Xiaojun; Nie, Zhihong

    2013-10-09

    Hydrodynamic flow in a microfluidic (MF) device offers a high-throughput platform for the continuous and controllable self-assembly of amphiphiles. However, the role of hydrodynamics on the assembly of colloidal amphiphiles (CAMs) is still not well understood. This Article reports a systematic study of the assembly of CAMs, which consist of Au nanoparticles (AuNPs) grafted with amphiphilic block copolymers, into vesicles with a monolayer of CAMs in the membranes using laminar flows in MF flow-focusing devices. Our experimental and simulation studies indicate that the transverse diffusion of solvents and colloids across the boundary of neighboring lamellar flows plays a critical role in the assembly of CAMs into vesicles. The dimension of the vesicles can be controlled in the range of 100-600 nm by tuning the hydrodynamic conditions of the flows. In addition, the diffusion coefficient of CAMs was also critical for their assembly. Under the same flow conditions, larger CAMs generated larger assemblies as a result of the reduced diffusion rate of large amphiphiles. This work could provide fundamental guidance for the preparation of nanoparticle vesicles with applications in bioimaging, drug delivery, and nano- and microreactors.

  12. Effects of perfluorinated amphiphiles on backward swimming in Paramecium caudatum

    SciTech Connect

    Matsubara, Eriko; Harada, Kouji; Inoue, Kayoko; Koizumi, Akio . E-mail: koizumi@pbh.med.kyoto-u.ac.jp

    2006-01-13

    PFOS and PFOA are ubiquitous contaminants in the environment. We investigated the effects of fluorochemicals on calcium currents in Paramecium caudatum using its behavioral changes. Negatively charged amphiphiles prolonged backward swimming (BWS) of Paramecium. PFOS significantly prolonged BWS, while PFOA was less potent (EC{sub 5}: 29.8 {+-} 4.1 and 424.1 {+-} 124.0 {mu}M, respectively). The BWS prolongation was blocked by cadmium, indicating that the cellular calcium conductance had been modified. The positively charged amphiphile FOSAPrTMA shortened BWS (EC{sub 5}: 19.1 {+-} 17.3). Nonionic amphiphiles did not affect BWS. The longer-chain perfluorinated carboxylates PFNA and PFDA were more potent than PFOA (EC{sub 5}: 98.7 {+-} 20.1 and 60.4 {+-} 10.1 {mu}M, respectively). However, 1,8-perfluorooctanedioic acid and 1,10-perfluorodecanedioic acid did not prolong BWS. The critical micelle concentration (CMC) and BWS prolongation for negatively charged amphiphiles showed a clear correlation (r {sup 2} = 0.8008, p < 0.001). In summary, several perfluorochemicals and PFOS and PFOA had similar effects in Paramecium, while chain length, CMC, and electric charge were major determinants of BWS duration.

  13. Hydrophobicity and thermodynamic response for aqueous solutions of amphiphiles

    NASA Astrophysics Data System (ADS)

    Zemánková, Katerina; Troncoso, Jacobo; Cerdeiriña, Claudio A.; Romaní, Luis; Anisimov, Mikhail A.

    2016-06-01

    The anomalous behavior of aqueous solutions of amphiphiles in the water-rich region is analyzed via a phenomenological approach that utilizes the isobaric heat capacity Cp as an experimental probe. We report extensive data for solutions of 14 amphiphiles as a function of temperature at atmospheric pressure. Beyond that, Cp data but also isobaric thermal expansivities and isothermal compressibilities for three solutions of tert-butanol as a function of both temperature and pressure are presented. Results rule out the possibility that the observed phenomenology is associated with the anomalous thermodynamics of pure water. Indeed, our Cp data, quantitatively consistent with recent spectroscopic analyses, suggest that water-mediated interactions between the nonpolar parts of amphiphiles are at the origin of anomalies, with the effects of such "hydrophobic aggregation" being observed at mole fractions as small as 0.01. Physicochemical details like the size, the electronic charge distribution and the geometry of amphiphile molecules as well as third-order derivatives of the Gibbs energy and the associated Koga lines support the above claims while they further contribute to characterizing the role of hydrophobicity in these phenomena. Progress with a view to gain a deeper, more concrete understanding remains.

  14. Elastohydrodynamics of farm-based blends comprising amphiphilic oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable oils contain non-polar hydrocarbon chains and polar ester groups (and possibly also other functional groups such as hydroxyl groups in castor oil). The presence of polar and non-polar groups within the same molecule gives vegetable oil amphiphilic character. The density, refractive index, ...

  15. Anion exchangers with negatively charged functionalities in hyperbranched ion-exchange layers for ion chromatography.

    PubMed

    Uzhel, Anna S; Zatirakha, Alexandra V; Smirnov, Konstantin N; Smolenkov, Alexandr D; Shpigun, Oleg A

    2017-01-27

    Novel pellicular poly(styrene-divinylbenzene)-based (PS-DVB) anion exchangers with covalently-bonded hyperbranched functional ion-exchange layers containing negatively charged functionalities are obtained and examined. The hyperbranched coating is created on the surface of aminated PS-DVB substrate by repeating the modification cycles including alkylation with 1,4-butanediol diglycidyl ether (1,4-BDDGE), and amination of the terminal epoxide rings with methylamine (MA) or glycine (Gly). The influence of the position and the number of the layers with glycine, as well as of the total number of the layers of amine in the coating on the chromatographic properties of the obtained stationary phases is investigated. Chromatographic performance of the obtained stationary phases is evaluated using the model mixtures of inorganic and organic anions with hydroxide eluent. It is shown that the best selectivity toward weakly retained organic acids and oxyhalides is possessed by the anion exchanger obtained after 5 modification cycles, with glycine being used in the first one. Such anion exchanger packed in 25-cm long column is capable of separating 22 anions in 58min including 7 standard anions, mono-, di- and trivalent organic acids, oxyhalides, and some other double- and triple-charged anions.

  16. Hard and flexible nanocomposite coatings using nanoclay-filled hyperbranched polymers.

    PubMed

    Fogelström, Linda; Malmström, Eva; Johansson, Mats; Hult, Anders

    2010-06-01

    The combination of hardness, scratch resistance, and flexibility is a highly desired feature in many coating applications. The aim of this study is to achieve this through the introduction of an unmodified nanoclay, montmorillonite (Na(+)MMT), in a polymer resin based on the hyperbranched polyester Boltorn H30. Smooth and transparent films were prepared from both the neat and the nanoparticle-filled hyperbranched resins. X-ray diffraction (XRD) and transmission electron microscopy (TEM) corroborated a mainly exfoliated structure in the nanocomposite films, which was also supported by results from dynamic mechanical analysis (DMA). Furthermore, DMA measurements showed a 9-16 degrees C increase in Tg and a higher storage modulus-above and below the T(g)-both indications of a more cross-linked network, for the clay-containing film. Thermogravimetric analysis (TGA) demonstrated the influence of the nanofiller on the thermal properties of the nanocomposites, where a shift upward of the decomposition temperature in oxygen atmosphere is attributed to the improved barrier properties of the nanoparticle-filled materials. Conventional coating characterization methods demonstrated an increase in the surface hardness, scratch resistance and flexibility, with the introduction of clay, and all coatings exhibited excellent chemical resistance and adhesion.

  17. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    PubMed Central

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-01

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach. PMID:26727881

  18. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    SciTech Connect

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-05

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.

  19. Controlled synthesis of hyper-branched inorganic nanocrystals withrich three-dimensional structures

    SciTech Connect

    Kanaras, Antonios G.; Sonnichsen, Carsten; Liu, Haitao; Alivisatos, A. Paul

    2005-07-27

    Studies of crystal growth kinetics are tightly integrated with advances in the creation of new nanoscale inorganic building blocks and their functional assemblies 1-11. Recent examples include the development of semiconductor nanorods which have potential uses in solar cells 12-17, and the discovery of a light driven process to create noble metal particles with sharp corners that can be used in plasmonics 18,19. In the course of studying basic crystal growth kinetics we developed a process for preparing branched semiconductor nanocrystals such as tetrapods and inorganic dendrimers of precisely controlled generation 20,21. Here we report the discovery of a crystal growth kinetics regime in which a new class of hyper-branched nanocrystals are formed. The shapes range from 'thorny balls', to tree-like ramified structures, to delicate 'spider net'-like particles. These intricate shapes depend crucially on a delicate balance of branching and extension. The multitudes of resulting shapes recall the diverse shapes of snowflakes 22.The three dimensional nature of the branch points here, however, lead to even more complex arrangements than the two dimensionally branched structures observed in ice. These hyper-branched particles not only extend the available three-dimensional shapes in nanoparticle synthesis ,but also provide a tool to study growth kinetics by carefully observing and modeling particle morphology.

  20. Hyperbranched epoxy/MWCNT-CuO-nystatin nanocomposite as a high performance, biocompatible, antimicrobial material

    NASA Astrophysics Data System (ADS)

    Barua, Shaswat; Chattopadhyay, Pronobesh; Phukan, Mayur M.; Konwar, Bolin K.; Karak, Niranjan

    2014-12-01

    Hyperbranched epoxy MWCNT-CuO-nystatin nanocomposite has been presented here as an advanced antimicrobial high performance material. The material showed significant improvement of mechanical properties (tensile strength from 38 to 63 MPa) over the pristine matrix without effecting elongation. MWCNT was modified by a non-ionic surfactant, triton X-100, wherein copper oxide nanoparticles were anchored in situ by a ‘green’ method. Further, sonochemical immobilization of nystatin enhanced the stability of the system. The immobilized nanohybrid system was incorporated into the hyperbranched matrix in 1, 2 and 3 wt%. The resultant system proved its ability to prevent bacterial, fungal and microalgal fouling against the tested strains, Staphylococcus aureus, Candida albicans and Chlorella sp. Additionally, this system is quite compatible with rat heart cells. Furthermore, in vivo assessment showed that this could be utilized as an implantable antimicrobial biomaterial. Thus, the overall study pointed out that the prepared material may have immense utility in marine industry as well as in biomedical domain to address microbial fouling, without inducing any toxicity to higher organisms.

  1. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    NASA Astrophysics Data System (ADS)

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-01

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

  2. A hyperbranched β-d-glucan with compact coil conformation from Lignosus rhinocerotis sclerotia.

    PubMed

    Hu, Ting; Huang, Qilin; Wong, Kahing; Yang, Hong; Gan, Jingsi; Li, Yanru

    2017-06-15

    An alkali-soluble polysaccharide was extracted from Lignosus rhinocerotis sclerotia (LRP). Its structural characteristics were determined by GC-MS, FT-IR, GC, 1D and 2D NMR combined with Smith degradation and methylation analysis. The LRP had a (1→3)-β-d-Glcp backbone with every three residues bearing a (1→6)-linked and hyperbranched side chain that contained three (1→6)-β-d-Glcp residues as secondary main chain and two terminal β-d-Glcp residues linked at O3. The degree of branching was 0.76 from GC-MS analysis, implying a highly branched structure for LRP. The Mw, z(1/2), Rh and [η] values of LRP in 0.25M LiCl/DMSO were measured by SEC-MALLS-Vis-RI combination technology to be 2.88×10(5)g/mol, 30.36nm, 22.34nm and 131.50ml/g, respectively. Furthermore, the exponent α of [η]-Mw, β of z(1/2)-Mw, the fractal dimension df and molecular parameter ρ were determined to be 0.20, 0.33, 2.50 and 1.36, demonstrating that the LRP was a hyperbranched polysaccharide and adopted a compact coil conformation in LiCl/DMSO.

  3. Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers

    NASA Astrophysics Data System (ADS)

    Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

    Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

  4. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    DOE PAGES

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; ...

    2016-01-05

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.« less

  5. Fabrication of poly(glycerol sebacate) fibrous membranes by coaxial electrospinning: Influence of shell and core solutions.

    PubMed

    You, Zhi-Rong; Hu, Ming-Hsien; Tuan-Mu, Ho-Yi; Hu, Jin-Jia

    2016-10-01

    Although poly(glycerol sebacate) (PGS) has enjoyed great success in soft tissue engineering, it remains challenging to fabricate PGS fibers. In this study, coaxial electrospinning, in which polylactide (PLA) was used to confine and draw PGS prepolymer, was used to fabricate PGS fibrous membranes. Specifically, effects of adding poly(ethylene oxide) (PEO), which was removed prior to curing, in the shell were investigated. Transmission and scanning electron microscopy were used to confirm core-shell structure and morphology of fibers, respectively. Both the removal of PEO or PLA in the shell and the efficacy of PGS curing were verified by Fourier transform infrared spectroscopy and differential scanning calorimetry. Mechanical properties of the membranes with different shell and core contents were examined. We found that the addition of PEO to the shell reduced Young׳s modulus of the resulting cured membrane and increased its elongation at break significantly, the latter indicating better PGS curing. Moreover, with the addition of PEO, increasing PGS prepolymer concentration further increased the elongation at break and appeared to enhance the structural integrity of fibers; PGS fibrous membranes (with no PLA shell) were thus successfully fabricated after the removal of PLA. The Young׳s modulus of the PGS fibrous membrane was ~0.47MPa, which is similar to that of PGS solid sheets and some soft tissues. Finally, the cytocompatibility of the electrospun membranes was validated by Alamar blue and LDH assays.

  6. Characterisation of a soft elastomer poly(glycerol sebacate) designed to match the mechanical properties of myocardial tissue.

    PubMed

    Chen, Qi-Zhi; Bismarck, Alexander; Hansen, Ulrich; Junaid, Sarah; Tran, Michael Q; Harding, Siân E; Ali, Nadire N; Boccaccini, Aldo R

    2008-01-01

    The myocardial tissue lacks significant intrinsic regenerative capability to replace the lost cells. Therefore, the heart is a major target of research within the field of tissue engineering, which aims to replace infarcted myocardium and enhance cardiac function. The primary objective of this work was to develop a biocompatible, degradable and superelastic heart patch from poly(glycerol sebacate) (PGS). PGS was synthesised at 110, 120 and 130 degrees C by polycondensation of glycerol and sebacic acid with a mole ratio of 1:1. The investigation was focused on the mechanical and biodegrading behaviours of the developed PGS. PGS materials synthesised at 110, 120 and 130 degrees C have Young's moduli of 0.056, 0.22 and 1.2 MPa, respectively, which satisfy the mechanical requirements on the materials applied for the heart patch and 3D myocardial tissue engineering construction. Degradation assessment in phosphate buffered saline and Knockout DMEM culture medium has demonstrated that the PGS has a wide range of degradability, from being degradable in a couple of weeks to being nearly inert. The matching of physical characteristics to those of the heart, the ability to fine tune degradation rates in biologically relevant media and initial data showing biocompatibility indicate that this material has promise for cardiac tissue engineering applications.

  7. A comparative study on poly(xylitol sebacate) and poly(glycerol sebacate): mechanical properties, biodegradation and cytocompatibility.

    PubMed

    Li, Yuan; Huang, Wenchao; Cook, Wayne D; Chen, Qizhi

    2013-06-01

    In order to develop degradable elastomers with a satisfactory combination of flexibility and enzyme-mediated degradation rate, the mechanical properties, enzymatic degradation kinetics and biocompatibility of poly(xylitol sebcate) (PXS) has been systematically investigated in comparison with poly(glycerol sebacate) (PGS). Under the same level of crosslinked density, the PXS elastomer networks have approximately twice the stretchability (elongation at break) of their PGS counterparts. This observation is attributable to the relatively longer and more orientable xylitol monomers, compared with glycerol molecules. Although xylitol monomers have two more hydroxyl groups, we, surprisingly, found that the hydrophilic side chains did not accelerate the water attack on the ester bonds of the PXS network, compared with their PGS counterpart. This observation was attributed to a steric hindrance effect, i.e. the large-sized hydroxyl groups can shield ester bonds from the attack of water molecules. In conclusion, the use of polyols of more than three -OH groups is an effective approach enhancing flexibility, whilst maintaining the degradation rate of polyester elastomers. Further development could be seen in the copolymerization of PPS with appropriate thermoplastic polyesters, such as poly(lactic acid) and polyhydroxyalkanoate.

  8. Bioactive electrospun fibers of poly(glycerol sebacate) and poly(ε-caprolactone) for cardiac patch application.

    PubMed

    Rai, Ranjana; Tallawi, Marwa; Frati, Caterina; Falco, Angela; Gervasi, Andrea; Quaini, Federico; Roether, Judith A; Hochburger, Tobias; Schubert, Dirk W; Seik, Lothar; Barbani, Niccoletta; Lazzeri, Luigi; Rosellini, Elisabetta; Boccaccini, Aldo R

    2015-09-16

    Scaffolds for cardiac patch application must meet stringent requirements such as biocompatibility, biodegradability, and facilitate vascularization in the engineered tissue. Here, a bioactive, biocompatible, and biodegradable electrospun scaffold of poly(glycerol sebacate)-poly(ε-caprolactone) (PGS-PCL) is proposed as a potential scaffold for cardiac patch application. The fibers are smooth bead free with average diameter = 0.8 ± 0.3 μm, mean pore size = 2.2 ± 1.2 μm, porosity = 62 ± 4%, and permeability higher than that of control biological tissue. For the first time, bioactive PGS-PCL fibers functionalized with vascular endothelial growth factor (VEGF) are developed, the approach used being chemical modification of the PGS-PCL fibers followed by subsequent binding of VEGF via amide bonding. The approach results in uniform immobilization of VEGF on the fibers; the concentrations are 1.0 μg cm(-2) for the PGS-PCL (H) and 0.60 μg cm(-2) for the PGS-PCL (L) samples. The bioactive scaffold supports the attachment and growth of seeded myogenic and vasculogenic cell lines. In fact, rat aortic endothelial cells also display angiogenic features indicating potential for the formation of vascular tree in the scaffold. These results therefore demonstrate the prospects of VEGF-functionalized PGS-PCL fibrous scaffold as promising matrix for cardiac patch application.

  9. Mechanical characterization and non-linear elastic modeling of poly(glycerol sebacate) for soft tissue engineering.

    PubMed

    Mitsak, Anna G; Dunn, Andrew M; Hollister, Scott J

    2012-07-01

    Scaffold tissue engineering strategies for repairing and replacing soft tissue aim to improve reconstructive and corrective surgical techniques whose limitations include suboptimal mechanical properties, fibrous capsule formation and volume loss due to graft resorption. An effective tissue engineering strategy requires a scaffolding material with low elastic modulus that behaves similarly to soft tissue, which has been characterized as a nonlinear elastic material. The material must also have the ability to be manufactured into specifically designed architectures. Poly(glycerol sebacate) (PGS) is a thermoset elastomer that meets these criteria. We hypothesize that the mechanical properties of PGS can be modulated through curing condition and architecture to produce materials with a range of stiffnesses. To evaluate this hypothesis, we manufactured PGS constructs cured under various conditions and having one of two architectures (solid or porous). Specimens were then tensile tested according to ASTM standards and the data were modeled using a nonlinear elastic Neo-Hookean model. Architecture and testing conditions, including elongation rate and wet versus dry conditions, affected the mechanical properties. Increasing curing time and temperature led to increased tangent modulus and decreased maximum strain for solid constructs. Porous constructs had lower nonlinear elastic properties, as did constructs of both architectures tested under simulated physiological conditions (wetted at 37 °C). Both solid and porous PGS specimens could be modeled well with the Neo-Hookean model. Future studies include comparing PGS properties to other biological tissue types and designing and characterizing PGS scaffolds for regenerating these tissues.

  10. Biodistribution, cellular localization, and in vivo tolerability of 35S-labeled antiinflammatory dendritic polyglycerol sulfate amine

    NASA Astrophysics Data System (ADS)

    Holzhausen, Cornelia; Gröger, Dominic; Mundhenk, Lars; Donat, Cornelius K.; Schnorr, Jörg; Haag, Rainer; Gruber, Achim D.

    2015-03-01

    Antiinflammatory dendritic polyglycerol sulfate (dPGS) holds great potential in the treatment and imaging of inflammatory processes. Here, we studied its biokinetic behavior, biodistribution, target cells, and in vivo toxicology. Following intravenous or subcutaneous application of 35sulfur-labeled dPGS amine with a molecular weight of 10.05 kDa and a hydrodynamic diameter of 5.7 ± 1.5 nm to mice, tissues were collected at specific time points (2, 15 min; 1, 24 h; 5, 21 days) and analyzed by liquid scintillation counting, autoradiography, radioluminography, and light microscopic autoradiography. The blood half-life of dPGS amine was 12 days. The major route of elimination was via the bile and feces. Elimination via the kidney and urine was only initially observed after i.v., but not after s.c. injection. Regardless of the administration mode, liver and spleen were late target organs where dPGS amine accumulated in phagocytic cells. Despite bioaccumulation, toxicological histopathology failed to identify any adverse effects at any time and in any tissues examined suggesting a high in vivo biocompatibility and encouraging future investigation for biomedical applications.

  11. An orthogonal click-chemistry approach to design poly(glycerol monomethacrylate)-based nanomaterials for controlled immunostimulation.

    PubMed

    Ragupathy, Lakshminarayanan; Millar, Douglas G; Tirelli, Nicola; Cellesi, Francesco

    2014-11-01

    A versatile approach is proposed for the synthesis of novel immunoactive nanomaterials based on biocompatible poly(glycerol monomethacrylate) (PGMMA). Propargyl-terminated PGMMA is synthesized via atom transfer radical polymerization and then modified through the introduction of dangling acrylate groups, at controlled degree of functionalisation. Acrylates are then able to react quantitatively with thiols, such as immunoactive thiomannose, through Michael-type addition under mild conditions and at a physiologically acceptable pH. The terminal propargyl group can be modified independently with azide end-capping groups and it is utilized to graft the macromolecules to a fluorescent dye. The resulting mannose-linked PGMMAs confirm a safe cytotoxic profile and are able to stimulate cytokine production (TNFα), membrane protein expression (CD40), and cellular uptake in bone marrow derived dendritic cells. Cell stimulation is dependent on the mannose content and enhanced by serum proteins, suggesting a role for mannose-binding receptors and/or complement receptors in the cell membrane.

  12. Effect of polyglycerol esters additive on palm oil crystallization using focused beam reflectance measurement and differential scanning calorimetry.

    PubMed

    Saw, M H; Hishamuddin, E; Chong, C L; Yeoh, C B; Lim, W H

    2017-01-01

    The effect of 0.1-0.7% (w/w) of polyglycerol esters (PGEmix-8) on palm oil crystallization was studied using focused beam reflectance measurement (FBRM) to analyze the in-line changes of crystal size distribution during the crystallization. FBRM results show that 0.1-0.5% (w/w) of PGEmix-8 did not significantly affect nucleation but slightly retarded crystal growth. The use of 0.7% (w/w) additive showed greater heterogeneous nucleation compared to those with lower dosages of additive. Crystal growth was also greatly reduced when using 0.7% (w/w) dosage. The morphological study indicated that the palm oil crystals were smaller and more even in size than when more additive was added. Isothermal crystallization studies using differential scanning calorimetry (DSC) showed increased inhibitory effects on palm oil crystal growth with increasing concentration of PGEmix-8. These results imply that PGEmix-8 is a nucleation enhancing and crystal growth retarding additive in palm oil crystallization at 0.7% (w/w) dosage.

  13. Phase diagram for assembly of biologically-active peptide amphiphiles.

    PubMed

    Tsonchev, Stefan; Niece, Krista L; Schatz, George C; Ratner, Mark A; Stupp, Samuel I

    2008-01-17

    We construct a phase diagram for self-assembling biologically active peptide amphiphiles. The structure and stability of the assemblies are studied as a function of pH and salinity of the solution. The general features of the phase diagram are predicted based on theoretical modeling of the self-assembly process, as well as experimental data, and further experiments are performed to verify and ascertain the boundary locations of the diagram. Depending on solution conditions, the amphiphiles can form cylindrical or spherical micelles, intermediate structures between these, or may not assemble at all. We also demonstrate that changing conditions may result in phase transitions among these structures. This type of phase diagram could be useful in the design of certain supramolecular nanostructures by providing information on the necessary conditions to form them.

  14. Prebiotic Lipidic Amphiphiles and Condensing Agents on the Early Earth

    PubMed Central

    Fiore, Michele; Strazewski, Peter

    2016-01-01

    It is still uncertain how the first minimal cellular systems evolved to the complexity required for life to begin, but it is obvious that the role of amphiphilic compounds in the origin of life is one of huge relevance. Over the last four decades a number of studies have demonstrated how amphiphilic molecules can be synthesized under plausibly prebiotic conditions. The majority of these experiments also gave evidence for the ability of so formed amphiphiles to assemble in closed membranes of vesicles that, in principle, could have compartmented first biological processes on early Earth, including the emergence of self-replicating systems. For a competitive selection of the best performing molecular replicators to become operative, some kind of bounded units capable of harboring them are indispensable. Without the competition between dynamic populations of different compartments, life itself could not be distinguished from an otherwise disparate array or network of molecular interactions. In this review, we describe experiments that demonstrate how different prebiotically-available building blocks can become precursors of phospholipids that form vesicles. We discuss the experimental conditions that resemble plausibly those of the early Earth (or elsewhere) and consider the analytical methods that were used to characterize synthetic products. Two brief sections focus on phosphorylating agents, catalysts and coupling agents with particular attention given to their geochemical context. In Section 5, we describe how condensing agents such as cyanamide and urea can promote the abiotic synthesis of phospholipids. We conclude the review by reflecting on future studies of phospholipid compartments, particularly, on evolvable chemical systems that include giant vesicles composed of different lipidic amphiphiles. PMID:27043635

  15. Proteomic analysis of amphiphilic proteins of hexaploid wheat kernels.

    PubMed

    Amiour, Nardjis; Merlino, Marielle; Leroy, Philippe; Branlard, Gérard

    2002-06-01

    Wheat proteins and specially gluten proteins have been well studied and are closely associated with baking products. Amphiphilic proteins (proteins that are soluble using nonionic detergent Triton X-114 ) also play an important role in wheat quality. Some of them, like puroindolines, are lipid binding proteins, and are strongly linked to dough foaming properties and to fine crumb texture. However many amphiphilic proteins are still unknown and both their physiological and technological functions remain to be analysed. In order to explore these proteins, proteomic analysis was carried out using 81 F9 lines, progeny obtained from an interspecific cross "W7984"x"Opata", and already used to built a map of more than 2000 molecular markers (International Triticeae Mapping Initiative, ITMImap). Two-dimensional electrophoresis (immobilized pH gradient (pH 6-11)x sodium dodecyl sulfate-polyacrylamide gel electrophoresis) was performed on amphiphilic proteins with three to five replicates for each line. Silver stained gels were analysed using Melanie 3 software. Genetic determinism was carried out on 170 spots segregating between the two parental hexaploïd wheats. Many of these spots were mapped on different chromosomes of the ITMImap. Spots of interest were identified using matrix-assisted laser desorption/ionization-time of flight and some of them were partly sequenced using electrospray ionization-tandem mass spectrometry. This proteomic approach provided some very useful information about some proteic components linked to bread wheat quality and particularly to kernel hardness.

  16. Incorporation of amphiphilic cyclodextrins into liposomes as artificial receptor units.

    PubMed

    Kauscher, Ulrike; Stuart, Marc C A; Drücker, Patrick; Galla, Hans-Joachim; Ravoo, Bart Jan

    2013-06-18

    In this article, we describe the introduction of amphiphilic β-cyclodextrins into liposomes to act as artificial receptor units. Using dynamic light scattering, dye encapsulation, and cryogenic transmission electron microscopy, we show that amphiphilic β-cyclodextrins can be mixed in any proportion with a typical mixture of phospholipids and cholesterol to provide stable, spherical, and unilamellar mixed vesicles. It is also possible to form giant unilamellar vesicles with mixtures of lipids and cyclodextrin. The permeability of the mixed vesicles increases with the percentage of cyclodextrin. The cyclodextrins can act as host molecules for hydrophobic guest molecules, even when they are dispersed at a low percentage in the vesicle membrane. It is shown that mixed vesicles can be decorated with carbohydrate-functionalized guest molecules, with photoresponsive guest molecules, and with dye-functionalized guest molecules. Taken together, it is demonstrated that the host-guest chemistry of amphiphilic cyclodextrins is fully compatible with a liposomal bilayer membrane and the advantages of each can be combined to give superior nanocontainers.

  17. Amphiphilic dendritic peptides: Synthesis and behavior as an organogelator and liquid crystal

    PubMed Central

    Li, Hongxia; Xia, Defang; Sun, Sufang; Ba, Xinwu

    2011-01-01

    Summary New amphiphilic dendritic peptides on dendritic polyaspartic acid were designed and synthesized. The organogel and liquid crystal properties of these amphiphilic dendritic peptides were fully studied by field-emission SEM, temperature dependent FT-IR, differential scanning calorimetry, polarization optical microscopy and X-ray diffraction experiments. Amphiphilic dendritic peptides G3 show good organogel properties with a minimum gelation concentration as low as 1 wt %. Furthermore, amphiphilic dendritic peptides G3 can form a hexagonal columnar liquid crystal assembly over a wide temperature range. PMID:21448258

  18. Gemini amphiphiles regulated photopolymerization of diacetylene acid in organized molecular films.

    PubMed

    Zhong, Ling; Jiao, Tifeng; Liu, Minghua

    2009-07-02

    In this paper, we have investigated the photopolymerization of an amphiphilic diacetylene, 10,12-pentacosadiynoic acid (PCDA), in organized molecular films in the presence of a series of gemini amphiphiles with different spacer lengths. It has been found that, when gemini amphiphiles were mixed with the diacetylene, the film-forming properties were greatly improved and the photopolymerization could be regulated by the gemini amphiphiles. Miscibility and Fourier transform infrared spectroscopy (FT-IR) investigations revealed that the polymerization of PCDA in a mixed film was regulated by the mixing ratio and spacer length of the gemini amphiphiles. Although a slight amount of gemini amphiphile did not make the PCDA polymerize into blue films, the increment of the gemini amphiphile with the short spacer length in the mixed film caused the formation of a red film, and the intensity of red phase to blue phase can be modulated by changing the mixing ratios. When gemini amphiphiles with longer spacer lengths were mixed, blue films were predominantly obtained in all mixing ratios. A mechanism including the interaction between the headgroup of the gemini amphiphiles and the diacetylene and the regulation of the spacer was proposed.

  19. Cationic amphiphiles with fatty acyl chain asymmetry of coconut oil deliver genes selectively to mouse lung.

    PubMed

    Chandrashekhar, Voshavar; Srujan, Marepally; Prabhakar, Rairala; Reddy, Rakesh C; Sreedhar, Bojja; Rentam, Kiran K R; Kanjilal, Sanjit; Chaudhuri, Arabinda

    2011-03-16

    Recent structure-activity studies have revealed a dramatic influence of hydrophobic chain asymmetry in enhancing gene delivery efficacies of synthetic cationic amphiphiles (Nantz, M. H. et al. Mol. Pharmaceutics2010, 7, 786-794; Koynova, R. et al. Mol. Pharmaceutics2009, 6, 951-958). The present findings demonstrate for the first time that such a transfection enhancing influence of asymmetric hydrocarbon chains observed in pure synthetic cationic amphiphiles also works for cationic amphiphiles designed with natural, asymmetric fatty acyl chains of a food-grade oil. Herein, we demonstrate that cationic amphiphiles designed with the natural fatty acyl chain asymmetry of food-grade coconut oil are less cytotoxic and deliver genes selectively to mouse lung. Despite lauroyl chains being the major fatty acyl chains of coconut oil, both the in vitro and In vivo gene transfer efficiencies of such cationic amphiphiles were found to be remarkably superior (>4-fold) to those of their pure dilauroyl analogue. Mechanistic studies involving the technique of fluorescence resonance energy transfer (FRET) revealed higher biomembrane fusibility of the cationic liposomes of the coconut amphiphiles than that of the symmetric dilauroyl analogue. AFM study revealed pronounced fusogenic nonlamellar structures of the liposomes of coconut amphiphiles. Findings in the FRET and cellular uptake study, taken together, support the notion that the higher cellular uptake resulting from the more fusogenic nature of the liposomes of coconut amphiphiles 1 are likely to play a dominant role in making the coconut amphiphiles transfection competent.

  20. Edge-modified amphiphilic Laponite nano-discs for stabilizing Pickering emulsions.

    PubMed

    Yang, Ying; Liu, Zhi; Wu, Dayong; Wu, Man; Tian, Ye; Niu, Zhongwei; Huang, Yong

    2013-11-15

    We investigated the effect of amphiphilic Laponite nano-discs, which were edge-modified by hydrophobic chains, on the properties of Pickering emulsions and Pickering emulsions polymerization. Comparing to unmodified Laponites, these amphiphilic nano-discs can greatly reduce the surface tension, resulting in very stable Pickering emulsions. These particles uniquely combine the Pickering effect with amphiphilic properties similar to the surfactant. Taking advantage of these amphiphilic Pickering emulsifiers, miniemulsion polymerization of styrene was performed. Homogeneous polystyrene nanoparticles with size around 150 nm could thus be prepared.

  1. Hyperbranched-dendrimer architectural copolymer gene delivery using hyperbranched PEI conjugated to poly(propyleneimine) dendrimers: synthesis, characterization, and evaluation of transfection efficiency

    NASA Astrophysics Data System (ADS)

    Alavi, Seyyed Jamal; Gholami, Leila; Askarian, Saeedeh; Darroudi, Majid; Massoudi, Abdolhossein; Rezaee, Mehdi; Kazemi Oskuee, Reza

    2017-02-01

    The applications of dendrimer-based vectors seem to be promising in non-viral gene delivery because of their potential for addressing the problems with viral vectors. In this study, generation 3 poly(propyleneimine) (G3-PPI) dendrimers with 1, 4-diaminobutane as a core initiator was synthesized using a divergent growth approach. To increase the hydrophobicity and reduce toxicity, 10% of primary amines of G3-PPI dendrimers were replaced with bromoalkylcarboxylates with different chain lengths (6-bromohexanoic and 10-bromodecanoic). Then, to retain the overall buffering capacity and enhance transfection, the alkylcarboxylate-PPIs were conjugated to 10 kDa branched polyethylenimine (PEI). The results showed that the modified PPI was able to form complexes with the diameter of less than 60 nm with net-positive surface charge around 20 mV. No significant toxicity was observed in modified PPIs; however, the hexanoate conjugated PPI-PEI (PPI-HEX-10% PEI) and the decanoate conjugated PPI-PEI (PPI-DEC-10%-PEI) showed the best transfection efficiency in murine neuroblastoma (Neuro-2a) cell line, even PPI-HEX-10%-PEI showed transfection efficiency equal to standard PEI 25 kDa with reduced toxicity. This study suggested a new series of hyperbranched (PEI)-dendrimer (PPI) architectural copolymers as non-viral gene delivery vectors with high transfection efficiency and low toxicity.

  2. Hyperbranched quasi-1D TiO2 nanostructure for hybrid organic-inorganic solar cells.

    PubMed

    Ghadirzadeh, Ali; Passoni, Luca; Grancini, Giulia; Terraneo, Giancarlo; Li Bassi, Andrea; Petrozza, Annamaria; Di Fonzo, Fabio

    2015-04-15

    The performance of hybrid solar cells is strongly affected by the device morphology. In this work, we demonstrate a poly(3-hexylthiophene-2,5-diyl)/TiO2 hybrid solar cell where the TiO2 photoanode comprises an array of tree-like hyperbranched quasi-1D nanostructures self-assembled from the gas phase. This advanced architecture enables us to increase the power conversion efficiency to over 1%, doubling the efficiency with respect to state of the art devices employing standard mesoporous titania photoanodes. This improvement is attributed to several peculiar features of this array of nanostructures: high interfacial area; increased optical density thanks to the enhanced light scattering; and enhanced crystallization of poly(3-hexylthiophene-2,5-diyl) inside the quasi-1D nanostructure.

  3. Non-enzymatic glucose biosensor based on hyperbranched pine-like gold nanostructure.

    PubMed

    Heli, H; Amirizadeh, O

    2016-06-01

    Hyperbranched pine-like gold nanostructure was electrodeposited on the polycrystalline gold surface at 0 mV (vs. AgCl) with the assistance of histidine as a soft template. The nanostructure was then applied as a highly sensitive nonenzymatic sensor for glucose. The catalytic activity and sensitivity of the gold nanostructure toward the electrooxidation of glucose was excellent without surface fouling and deterioration effects. The current related to the oxidation of glucose rapidly and linearly depended on its concentration with a sensitivity of 776.8 μA cm(-2)mmol(-1)dm(3), a detection limit of 3.39 μmol dm(-3) with a relative standard deviation of 2.32%.

  4. Hybrid Solar Cells with Prescribed Nanoscale Morphologies Based onHyperbranched Semiconductor Nanocrystals

    SciTech Connect

    Gur, Ilan; Fromer, Neil A.; Chen, Chih-Ping; Kanaras, AntoniosG.; Alivisatos, A. Paul

    2006-09-09

    In recent years, the search to develop large-area solar cells at low cost has led to research on photovoltaic (PV) systems based on nanocomposites containing conjugated polymers. These composite films can be synthesized and processed at lower costs and with greater versatility than the solid state inorganic semiconductors that comprise today's solar cells. However, the best nanocomposite solar cells are based on a complex architecture, consisting of a fine blend of interpenetrating and percolating donor and acceptor materials. Cell performance is strongly dependent on blend morphology, and solution-based fabrication techniques often result in uncontrolled and irreproducible blends, whose composite morphologies are difficult to characterize accurately. Here we incorporate 3-dimensional hyper-branched colloidal semiconductor nanocrystals in solution-processed hybrid organic-inorganic solar cells, yielding reproducible and controlled nanoscale morphology.

  5. Functionalization of MWNTs with hyperbranched PEI for highly selective isolation of BSA.

    PubMed

    Chen, Mei-Ling; Chen, Ming-Li; Chen, Xu-Wei; Wang, Jian-Hua

    2010-08-11

    Cationic hyperbranched BPEI was immobilized on the surface of MWNTs via electrostatic interactions between the positively charged protonated amines within the polymer and the carboxyl groups on the chemically oxidized MWNT surface. The functionalized BPEI-MWNTs were characterized by FT-IR, TGA, TEM and surface charge analysis, and it was used as a bio-sorbent for the adsorption of proteins. CD spectra showed no conformational change of BSA during the adsorption/desorption process. A dynamic adsorption capacity of 167 mg · g⁻¹ for BSA was achieved. With a sample volume of 2.0 mL, an enrichment factor of 10 was obtained along with an adsorption efficiency of 100%, a recovery of 100%, a sampling frequency of 10 h⁻¹ and a RSD of 2.6% at 25 µg · mL⁻¹ BSA.

  6. Hyperbranched poly(epsilon-caprolactone) as a nonmigrating alternative plasticizer for phthalates in flexible PVC.

    PubMed

    Choi, Jeongsoo; Kwak, Seung-Yeop

    2007-05-15

    Hyperbranched (dendritic) poly(epsilon-caprolactone)s (HPCLs) were synthesized to have architectural variations, which are the different lengths of linear segments and different numbers of branches, and were used as plasticizers for flexible poly(vinyl chloride) (PVC). The plasticization efficiency estimated by the lowering of glass transition temperature and the enhancement in ultimate elongation indicated that the HPCLs with the shorter linear segments and the larger number of branches imparted as high flexibility as di(ethylhexyl) phthalate (DEHP) and much higher flexibility than their linear analogue, linear poly(epsilon-caprolactone), which is one of currently used polymer plasticizers. Volatility, extractability, and exudation tests for PVC/HPCL samples showed that there was no plasticizer migration even at very harsh condition, while ca. 7-78% of additives in PVC/DEHP was migrated out of samples, indicating that the HPCL can be used as an alternative plasticizer to remove the potential health risk from migrating phthalates during end use.

  7. Pressure-Volume-Temperature Behavior of Hyperbranched Polyols: Experiment and Modelling

    NASA Astrophysics Data System (ADS)

    Kaushik, Mukul; Nazarenko, Sergei; Olson, Brian

    2011-03-01

    The pressure volume temperature behavior of two generations of hyperbranched polyesters Boltorn TM H40 and H20 was studied by PVT measurements using high pressure dilatometer. Volumetric expansivity, and free volume parameters were determined for both generations in the melt state. The PVT data were fitted to Simha-Somcynsky (SS) equation of state (EOS) and Sanchez--Lacombe (SL) equation of state (EOS) to calculate occupied volume and fractional free volume. The values of occupied volume and fractional free volumes obtained through both the equations of states were similar. Simulated atmospheric pressure V-T data were generated by using Discover module of Accelrys. Quality of equilibrium was confirmed by energy stabilization and closeness of experimental and simulation densities. WAXD and temperature-volume curves obtained by molecular dynamics simulations were comparable to the experimental data. Well relaxed amorphous cell was further utilized to study hydrogen bond network and determination of O-O pair correlation function of terminal hydroxyl groups.

  8. The Time Evolution of the Surface Segregation of Hyperbranched Molecules from a Linear Matrix

    NASA Astrophysics Data System (ADS)

    Swader, Onome; Dadmun, Mark; Hutchings, Lian; Thompson, Richard

    2010-03-01

    Modification of a surface by the selective surface segregation of an additive in a mixture is a process with many commercial applications including biocompatibility, wettability, and anti-fouling in coatings. In a blend of branched and linear polymers, there exists an entropic driving force for the selective surface segregation of the branched polymer. Unfortunately, a systematic study of the impact of the branched copolymer structure on the dynamics and thermodynamics of this surface segregation is not currently available. Neutron reflectivity experiments that seek to fill this void have been completed and will be discussed. High molecular weight poly(styrene) (PS) hyperbranched molecules, hypermacs (HM) and dendrimacs (DM), with 10 % HM or DM and 90 % deuterated PS are the model systems studied. Reflectivity profiles for all blends were obtained as a function of annealing time from 30 minutes up to 48 hours.

  9. Role of branching architecture on the glass transition of hyperbranched polyethers.

    PubMed

    Zhu, Qi; Wu, Jieli; Tu, Chunlai; Shi, Yunfeng; He, Lin; Wang, Ruibin; Zhu, Xinyuan; Yan, Deyue

    2009-04-30

    The influence of branching architecture on the glass transition of hyperbranched polyethers has been investigated. For amorphous samples, the glass transition temperature (T(g)) first increases with the degree of branching (DB), passes through a maximum, and then decreases sharply. An attempt is made to explain this by the competition between the junction density and the free volume of terminal units. For the crystalline samples, the crystallization of polymer chains makes the relationship of DB and T(g) more complicated. By the introduction of branching architecture, the crystallization ability of the branched polymer is weakened gradually. When the samples are isothermally crystallized for a long time, the T(g) of polyethers decreases monotonically with DB.

  10. A lattice model Monte Carlo study of coil-to-globule and other conformational transitions of polymer, amphiphile, and solvent

    NASA Astrophysics Data System (ADS)

    Jennings, Deirdre E.; Kuznetsov, Yuri A.; Timoshenko, Edward G.; Dawson, Kenneth A.

    2000-05-01

    A model of polymer-amphiphile-solvent systems on a cubic lattice is used to investigate the phase diagram of such systems. The polymer is treated within the canonical ensemble (T,V,N) and the amphiphile and solvent are treated within the grand canonical ensemble (T,V,μ). Using a range of Monte Carlo moves the phase diagram of polymer-amphiphile-solvent mixtures, as a function of solvent quality (parametrized by χ) and relative chemical potential, μ, is studied for the dilute polymer limit. The effect of increasing the polymer chain length, N, on the critical aggregation concentration (CAC), and the type of polymer-amphiphile complex formed above the CAC are also examined. For some parameters, it is found that the polymer and amphiphile form a polymer-micelle complex at low amphiphile concentrations, and that the polymer coil-to-globule transition point increases with increasing amphiphile concentration. The resulting collapsed globule has a solvent core and is surrounded by a layer of amphiphile. These results are in good qualitative agreement with experimental results for the poly(N-isopropylacrylamide) (PNIPAM)/sodium dodecyl sulfate (SDS) system. At higher amphiphile concentrations, the polymer and amphiphile form several layered structures depending on the strength of the three-body amphiphilic interactions, l. Finally, the effect of the polymer chain length, N, and the strength of the three-body amphiphilic interactions, l, on the stability of the polymer-amphiphile structures is investigated.

  11. A hyperbranched dopamine-containing PEG-based polymer for the inhibition of α-synuclein fibrillation

    PubMed Central

    Breydo, Leonid; Newland, Ben; Zhang, Hong; Rosser, Anne; Werner, Carsten; Uversky, Vladimir N.; Wang, Wenxin

    2016-01-01

    Aggregation of α-synuclein is believed to play an important role in Parkinson's disease and in other neurodegenerative maladies. Small molecule inhibitors of this process are among the most promising drug candidates for neurodegenerative diseases. Dendrimers have also been studied for anti-fibrillation applications but they can be difficult and expensive to synthetize. Here we show that RAFT polymerization can be used to produce a hyperbranched polyethylene glycol structure via a one-pot reaction. This polymer included a dopamine moiety, a known inhibitor of α-synuclein fibril formation. Dopamine within the polymer structure was capable of aggregation inhibition, although not to the same degree as free dopamine. This result opens up new avenues for the use of controlled radical polymerizations as a means of preparing hyperbranched polymers for anti-fibrillation activity, but shows that the incorporation of functional groups from known small molecules within polymers may alter their biological activity. PMID:26707645

  12. Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates

    PubMed Central

    Tsiourvas, D.; Arkas, M.; Diplas, S.; Mastrogianni, E.

    2010-01-01

    This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid. PMID:21069559

  13. Selenium/Tellurium-Containing Hyperbranched Polymers: Effect of Molecular Weight and Degree of Branching on Glutathione Peroxidase-Like Activity.

    PubMed

    Thomas, Joice; Dong, Zeyuan; Dehaen, Wim; Smet, Mario

    2012-12-21

    A series of novel hyperbranched polyselenides and polytellurides with multiple catalytic sites at the branching units has been synthesized via the polycondensation of A2 + B3 monomers. The GPx-like activities of these polymer mimics were assessed and it was found that the polytellurides showed higher GPx-like activities than the corresponding polyselenides. Interestingly, the polymers with higher molecular weights and degree of branching (DB) showed higher GPx-like activities than the analogous lower molecular weight polymer. The enhancement in the catalytical activity of the hyperbranched polymers with increasing molecular weight affirmed the importance of the incorporation of multiple catalytic groups in the macromolecule which increases the local concentration of catalytic sites.

  14. A hyperbranched dopamine-containing PEG-based polymer for the inhibition of α-synuclein fibrillation.

    PubMed

    Breydo, Leonid; Newland, Ben; Zhang, Hong; Rosser, Anne; Werner, Carsten; Uversky, Vladimir N; Wang, Wenxin

    2016-01-22

    Aggregation of α-synuclein is believed to play an important role in Parkinson's disease and in other neurodegenerative maladies. Small molecule inhibitors of this process are among the most promising drug candidates for neurodegenerative diseases. Dendrimers have also been studied for anti-fibrillation applications but they can be difficult and expensive to synthetize. Here we show that RAFT polymerization can be used to produce a hyperbranched polyethylene glycol structure via a one-pot reaction. This polymer included a dopamine moiety, a known inhibitor of α-synuclein fibril formation. Dopamine within the polymer structure was capable of aggregation inhibition, although not to the same degree as free dopamine. This result opens up new avenues for the use of controlled radical polymerizations as a means of preparing hyperbranched polymers for anti-fibrillation activity, but shows that the incorporation of functional groups from known small molecules within polymers may alter their biological activity.

  15. Controlled Synthesis of Uniform Cobalt Phosphide Hyperbranched Nanocrystals Using Tri-n-octylphosphine Oxide as a Phosphorus Source

    SciTech Connect

    Zhang, Haitao; Ha, Don-Hyung; Hovden, Robert; Fitting Kourkoutis, Lena; Robinson, Richard D.

    2011-01-12

    A new method to produce hyperbranched Co{sub 2}P nanocrystals that are uniform in size, shape, and symmetry was developed. In this reaction tri-n-octylphosphine oxide (TOPO) was used as both a solvent and a phosphorus source. The reaction exhibits a novel monomer-saturation-dependent tunability between Co metal nanoparticle (NP) and Co{sub 2}P NP products. The morphology of Co{sub 2}P can be controlled from sheaflike structures to hexagonal symmetric structures by varying the concentration of the surfactant. This unique product differs significantly from other reported hyperbranched nanocrystals in that the highly anisotropic shapes can be stabilized as the majority shape (>84%). This is the first known use of TOPO as a reagent as well as a coordinating background solvent in NP synthesis.

  16. Controlled synthesis of uniform cobalt phosphide hyperbranched nanocrystals using tri-n-octylphosphine oxide as a phosphorus source.

    PubMed

    Zhang, Haitao; Ha, Don-Hyung; Hovden, Robert; Kourkoutis, Lena Fitting; Robinson, Richard D

    2011-01-12

    A new method to produce hyperbranched Co(2)P nanocrystals that are uniform in size, shape, and symmetry was developed. In this reaction tri-n-octylphosphine oxide (TOPO) was used as both a solvent and a phosphorus source. The reaction exhibits a novel monomer-saturation-dependent tunability between Co metal nanoparticle (NP) and Co(2)P NP products. The morphology of Co(2)P can be controlled from sheaflike structures to hexagonal symmetric structures by varying the concentration of the surfactant. This unique product differs significantly from other reported hyperbranched nanocrystals in that the highly anisotropic shapes can be stabilized as the majority shape (>84%). This is the first known use of TOPO as a reagent as well as a coordinating background solvent in NP synthesis.

  17. Identification of Dormancy-Associated MicroRNAs for the Design of Osteosarcoma-Targeted Dendritic Polyglycerol Nanopolyplexes.

    PubMed

    Tiram, Galia; Segal, Ehud; Krivitsky, Adva; Shreberk-Hassidim, Rony; Ferber, Shiran; Ofek, Paula; Udagawa, Taturo; Edry, Liat; Shomron, Noam; Roniger, Maayan; Kerem, Batsheva; Shaked, Yuval; Aviel-Ronen, Sarit; Barshack, Iris; Calderón, Marcelo; Haag, Rainer; Satchi-Fainaro, Ronit

    2016-02-23

    The presence of dormant, microscopic cancerous lesions poses a major obstacle for the treatment of metastatic and recurrent cancers. While it is well-established that microRNAs play a major role in tumorigenesis, their involvement in tumor dormancy has yet to be fully elucidated. We established and comprehensively characterized pairs of dormant and fast-growing human osteosarcoma models. Using these pairs of mouse tumor models, we identified three novel regulators of osteosarcoma dormancy: miR-34a, miR-93, and miR-200c. This report shows that loss of these microRNAs occurs during the switch from dormant avascular into fast-growing angiogenic phenotype. We validated their downregulation in patients' tumor samples compared to normal bone, making them attractive candidates for osteosarcoma therapy. Successful delivery of miRNAs is a challenge; hence, we synthesized an aminated polyglycerol dendritic nanocarrier, dPG-NH2, and designed dPG-NH2-microRNA polyplexes to target cancer. Reconstitution of these microRNAs using dPG-NH2 polyplexes into Saos-2 and MG-63 cells, which generate fast-growing osteosarcomas, reduced the levels of their target genes, MET proto-oncogene, hypoxia-inducible factor 1α, and moesin, critical to cancer angiogenesis and cancer cells' migration. We further demonstrate that these microRNAs attenuate the angiogenic capabilities of fast-growing osteosarcomas in vitro and in vivo. Treatment with each of these microRNAs using dPG-NH2 significantly prolonged the dormancy period of fast-growing osteosarcomas in vivo. Taken together, these findings suggest that nanocarrier-mediated delivery of microRNAs involved in osteosarcoma tumor-host interactions can induce a dormant-like state.

  18. An elastomeric patch derived from poly(glycerol sebacate) for delivery of embryonic stem cells to the heart.

    PubMed

    Chen, Qi-Zhi; Ishii, Hikaru; Thouas, George A; Lyon, Alexander R; Wright, Jamie S; Blaker, Jonny J; Chrzanowski, Wojciech; Boccaccini, Aldo R; Ali, Nadire N; Knowles, Jonathan C; Harding, Siân E

    2010-05-01

    We hypothesize that a combinatorial approach of ventricle constraint and stem cell therapy would offer a greater benefit for the treatment of heart failure than either strategy alone. A heart patch would serve two therapeutic purposes: biomechanical support and cell delivery. In this study, we describe a hybrid heart patch engineered from a synthetic elastomer, poly(glycerol sebacate) (PGS), supplemented with cardiomyocytes differentiated from human embryonic stem cells (hESCs). In line with two therapeutically relevant considerations, i.e. biocompatibility and cell delivery efficiency, the PGS was (a) pre-conditioned in culture medium for 6 days, and (b) prepared without gelatin coatings to facilitate detachment and delivery of cardiomyocytes following patch implantation. Following pre-conditioning under physiological conditions, the PGS patch material without gelatin coating was found to satisfactorily support cardiomyocyte viability and attachment, with active cell beating for periods of longer than 3 months until interrupted. Dynamic culture studies revealed that cells detached more efficiently from the uncoated surface of PGS than from gelatin-coated PGS. No significant differences were detected between the beating rates of human embryonic stem cell-derived cardiomyocytes on tissue culture plate and the pre-conditioned and gelatin-uncoated PGS. PGS patches sutured over the left ventricle of rats in vivo remained intact over a 2 week period without any deleterious effects on ventricular function. We conclude that PGS is a suitable biomaterial for stem cell-based regeneration strategies to restore cardiomyocyte function, and the hybrid heart patch engineered under optimal conditions would be a promising support device for the cardiac repair.

  19. Poly(glycerol sebacate)/poly(butylene succinate-butylene dilinoleate) fibrous scaffolds for cardiac tissue engineering.

    PubMed

    Tallawi, Marwa; Zebrowski, David C; Rai, Ranjana; Roether, Judith A; Schubert, Dirk W; El Fray, Miroslawa; Engel, Felix B; Aifantis, Katerina E; Boccaccini, Aldo R

    2015-06-01

    The present article investigates the use of a novel electrospun fibrous blend of poly(glycerol sebacate) (PGS) and poly(butylene succinate-butylene dilinoleate) (PBS-DLA) as a candidate for cardiac tissue engineering. Random electrospun fibers with various PGS/PBS-DLA compositions (70/30, 60/40, 50/50, and 0/100) were fabricated. To examine the suitability of these fiber blends for heart patches, their morphology, as well as their physical, chemical, and mechanical properties were measured before examining their biocompatibility through cell adhesion. The fabricated fibers were bead-free and exhibited a relatively narrow diameter distribution. The addition of PBS-DLA to PGS resulted in an increase of the average fiber diameter, whereas increasing the amount of PBS-DLA decreased the hydrophilicity and the water uptake of the nanofibrous scaffolds to values that approached those of neat PBS-DLA nanofibers. Moreover, the addition of PBS-DLA significantly increased the elastic modulus. Initial toxicity studies with C2C12 myoblast cells up to 72 h confirmed nontoxic behavior of the blends. Immunofluorescence analyses and scanning electron microscopy analyses confirmed that C2C12 cells showed better cell attachment and proliferation on electrospun mats with higher PBS-DLA content. However, immunofluorescence analyses of the 3-day-old rat cardiomyocytes cultured for 2 and 5 days demonstrated better attachment on the 70/30 fibers containing well-aligned sarcomeres and expressing high amounts of connexin 43 in cellular junctions indicating efficient cell-to-cell communication. It can be concluded, therefore, that fibrous PGS/PBS-DLA scaffolds exhibit promising characteristics as a biomaterial for cardiac patch applications.

  20. Enantiopure chiral poly(glycerol methacrylate) self-assembled monolayers knock down protein adsorption and cell adhesion.

    PubMed

    Li, Zheng; Köwitsch, Alexander; Zhou, Guoying; Groth, Thomas; Fuhrmann, Bodo; Niepel, Marcus; Amado, Elkin; Kressler, Jörg

    2013-10-01

    Chirality plays a fundamental role not only in biological systems, but also in synthetic materials intended for bio-applications. Self-assembled monolayers (SAMs) are prepared on gold surfaces through a "grafting to" method from racemic or enantiopure chiral poly(glycerol methacrylate)s (PGMA(rac), PGMA(R), and PGMA(S)), having a thiol endgroup. Such SAMs constitute a chemically and structurally well-defined model substrate for studying protein adsorption and cell adhesion as a function of the polymer chirality. Surface plasmon resonance measurements reveal that PGMA SAMs greatly reduce the adsorption of bovine serum albumin (BSA) compared to bare gold surfaces. Interestingly, enantiopure SAMs based on PGMA(R) or PGMA(S) show a significantly larger reduction in BSA adsorption than PGMA(rac)-covered surfaces. Studies with the monocytic cell line THP-1 show a similar relationship between enantiopurity of PGMA SAMs and the extent of cell adhesion. Ellipsometry and Raman spectroscopy measurements indicate that SAMs formed by PGMA(rac) have a higher grafting density compared to SAMs of PGMA(R) and PGMA(S). This seems to be due to the ability of PGMA(rac) to form more intermolecular hydrogen bonds among polymer chains compared to the enantiopure PGMAs. Circular dichroism spectroscopy provide evidence that enantiopure polymers adopt a chiral ordered conformation, most likely helical, in aqueous solutions. It is concluded that a higher water content of SAMs formed by enantiopure PGMA(S) and PGMA(R) SAMs arises from the macromolecular chiral conformation adopted by their enantiopure PGMA chains, and it is the decisive reason for the reduced BSA adsorption and cell adhesion as compared to PGMA(rac) SAMs.

  1. Stimuli-Responsive Biodegradable Hyperbranched Polymer-Gadolinium Conjugates as Efficient and Biocompatible Nanoscale Magnetic Resonance Imaging Contrast Agents.

    PubMed

    Sun, Ling; Li, Xue; Wei, Xiaoli; Luo, Qiang; Guan, Pujun; Wu, Min; Zhu, Hongyan; Luo, Kui; Gong, Qiyong

    2016-04-27

    The efficacy and biocompatibility of nanoscale magnetic resonance imaging (MRI) contrast agents depend on optimal molecular structures and compositions. Gadolinium [Gd(III)] based dendritic macromolecules with well-defined and tunable nanoscale sizes are excellent candidates as multivalent MRI contrast agents. Here, we propose a novel alternate preparation of biodegradable hyperbranched polymer-gadolinium conjugates via a simple strategy and report potentially efficient and biocompatible nanoscale MRI contrast agents for cancer diagnosis. The enzyme-responsive hyperbranched poly(oligo-(ethylene glycol) methacrylate)-gadolinium conjugate (HB-POEGMA-Gd) was prepared via one-step reversible addition-fragmentation chain transfer (RAFT) polymerization and Gd(III) chelating, and the cRGDyK functionalized polymer (HB-POEGMA-cRGD-Gd) was obtained via click chemistry. By using an enzyme similar to lysosomal cathepsin B, hyperbranched conjugates of high molecular weights (MW) (180 and 210 kDa) and nanoscale sizes (38 and 42 nm) were degraded into low MW (25 and 30 kDa) and smaller products (4.8 and 5.2 nm) below the renal threshold. Conjugate-based nanoscale systems had three-fold more T1 relaxivity compared to clinical agent diethylenediaminepentaacetic acid (DTPA)-Gd. Animal studies with the nanoscale system offered greater tumor accumulation and enhanced signal intensity (SI) in mouse U87 tumors of which the greatest activity was conferred by the cRGDyK moiety functionalized hyperbranched conjugate. In vitro cytotoxicity, hemocompatibility and in vivo toxicity studies confirmed no adverse events. This design strategy for multifunctional Gd(III)-labeled biodegradable dendritic macromolecules may have significant potential as future efficient, biocompatible polymeric nanoscale MRI diagnostic contrast agents for cancer.

  2. Experimental and theoretical studies of scaling of sizes and intrinsic viscosity of hyperbranched chains in good solvents

    NASA Astrophysics Data System (ADS)

    Li, Lianwei; Lu, Yuyuan; An, Lijia; Wu, Chi

    2013-03-01

    Using a set of hyperbranched polystyrenes with different overall molar masses but a uniform subchain length or a similar overall molar mass but different subchain lengths, we studied their sizes and hydrodynamic behaviors in toluene (a good solvent) at T = 25 °C by combining experimental (laser light scattering (LLS) and viscometry) and theoretical methods based on a partially permeable sphere model. Our results show that both the average radii of gyration (⟨Rg⟩) and hydrodynamic radius (⟨Rh⟩) are scaled to the weight-average molar mass (Mw) as ⟨Rg⟩ ˜ ⟨Rh⟩ ˜ MwγMw,sφ, with γ = 0.47 ± 0.01 and φ = 0.10 ± 0.01; and their intrinsic viscosity ([η]) quantitatively follow the Mark-Houwink-Sakurada (MHS) equation as [η] = KηMwνMw,sμ with Kη = 2.26 × 10-5, ν = 0.39 ± 0.01, and μ = 0.31 ± 0.01, revealing that these model chains with long subchains are indeed fractal objects. Further, our theoretical and experimental results broadly agree with each other besides a slight deviation from the MHS equation for short subchains, similar to dendrimers, presumably due to the multi-body hydrodynamic interaction. Moreover, we also find that the average viscometric radius (⟨Rη⟩) determined from intrinsic viscosity is slightly smaller than ⟨Rh⟩ measured in dynamic LLS and their ratio (⟨Rη⟩/⟨Rh⟩) roughly remains 0.95 ± 0.05, reflecting that linear polymer chains are more draining with a smaller ⟨Rh⟩ than their hyperbranched counterparts for a given intrinsic viscosity. Our current study of the "defect-free" hyperbranched polymer chains offers a standard model for further theoretical investigation of hydrodynamic behaviors of hyperbranched polymers and other complicated architectures, in a remaining unexploited research field of polymer science.

  3. Hyperbranched-polyol-tethered poly (amic acid) electrospun nanofiber membrane with ultrahigh adsorption capacity for boron removal

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Wu, Zhongyu; Zhang, Yufeng; Meng, Jianqiang

    2017-04-01

    The development of efficient adsorbents with high sorption capacity remains as a challenge for the removal of micropollutants occurred globally in water resources. In this work, poly (amic acid) (PAA) electrospun nanofiber membranes grafted with hyperbranched polyols were synthesized and used for boron removal. The PAA nanofiber was reacted with hyperbranched polyethylenimine (HPEI) and further with glycidol to introduce the vicinal hydroxyl groups. The chemical composition and surface characteristics of the obtained PAA-g-PG membranes were evaluated by FESEM, FTIR, XPS and water contact angles (WCA) measurements. The boron adsorption thermodynamics and kinetics were investigated systematically. The results showed that the PAA nanofiber spun from concentration of 15% had uniform morphology and narrow diameter distribution. The PAA-g-PG nanofiber membrane had a maximum boron uptake of 5.68 mmol/g and could adsorb 0.82 mmol/g boron from a 5 mg/L solution in 15 min. Both the high surface area of nanofibers and the hyperbranched structure should contribute to the high boron uptake and high adsorption rate. The nanofiber membrane obeyed the Langmuir adsorption model and the pseudo-first-order kinetic model. The regeneration efficiency of the nanofiber membrane remained 93.9% after 10 cycled uses, indicating good regenerability of the membrane.

  4. Composition and method for self-assembly and mineralization of peptide amphiphiles

    DOEpatents

    Stupp, Samuel I.; Beniash, Elia; Hartgerink, Jeffrey D.

    2009-06-30

    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  5. Composition and method for self-assembly and mineralization of peptide-amphiphiles

    DOEpatents

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Pearland, TX

    2012-02-28

    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  6. Self-assembly of peptide-amphiphile nanofibers under physiological conditions

    DOEpatents

    Stupp, Samuel I [Chicago, IL; Hartgerink, Jeffrey D [Pearland, TX; Beniash, Elia [Auburndale, MA

    2011-11-22

    The present invention provides a method of promoting neuron growth and development by contacting cells with a peptide amphiphile molecule in an aqueous solution in the presence of a metal ion. According to the method, the peptide amphiphile forms a cylindrical micellar nanofiber composed of beta-sheets, which promote neuron growth and development.

  7. Facile synthesis of nucleic acid-polymer amphiphiles and their self-assembly.

    PubMed

    Jia, Fei; Lu, Xueguang; Tan, Xuyu; Zhang, Ke

    2015-05-07

    A solid-phase synthesis for nucleic acid-polymer amphiphiles is developed. Using this strategy, several DNA-b-polymer amphiphiles are synthesized, and their self-assembly in aqueous solution is investigated. This general method can in principle be extended to nearly all polymers synthesized by atom transfer radical polymerization to produce a variety of nucleic acid-polymer conjugates.

  8. Interaction of amphiphiles with integral membrane proteins. II. A simple, minimal model for the nonspecific interaction of amphiphiles with the anion exchanger of the erythrocyte membrane.

    PubMed

    Gruber, H J

    1988-10-20

    In a previous paper we have reported on the structural perturbation of the erythrocyte membrane anion exchanger by a regular series of model amphiphiles, as shown by differential scanning calorimetry (Gruber, H.J. and Low, P.S., Biochim. Biophys. Acta, preceding article). Now the data are interpreted by a model in which the effects of amphiphile structure upon buffer-membrane partitioning are well separated from the dependence of the intrinsic potencies of membrane-bound amphiphiles upon amphiphile structure. The buffer-membrane partitioning situation was demonstrated to regularly change between extremes within a series of homologous amphiphiles, i.e. from a negligible to a predominant fraction of total amphiphile in the sample residing in the membrane. Based upon this demonstration a large number of reports on the chain length dependence of apparent potency could be reinterpreted in terms of chain length profiles of intrinsic potency, allowing for a comparison of the responses of various membrane proteins to homologous series of amphiphiles. The response patterns for chain length variation could be divided into three distinct classes: the intrinsic potency (i) can be independent of chain length over a very wide range of length, (ii) it can be rather independent up to a critical length where a sudden cut-off in potency occurs, or (iii) it can drop monotonically over a wide range of chain length. The intrinsic potency values of saturated fatty acids in destabilizing the anion exchanger were interpreted by very simple assumptions: only direct interactions between amphiphiles and target proteins and a simple amphiphile partition equilibrium between a pool of equivalent low affinity sites on the protein and the bulk lipid matrix. The observed monotonic decay of the intrinsic potency of saturated fatty acids with increasing chain length from C8 to C20 was translated into a constant increment of free energy by which each additional CH2 favors the transfer away from sites

  9. Impact of structural differences in hyperbranched polyglycerol–polyethylene glycol nanoparticles on dermal drug delivery and biocompatibility.

    PubMed

    Kumar, Sumit; Alnasif, Nesrin; Fleige, Emanuel; Kurniasih, Indah; Kral, Vivian; Haase, Andrea; Luch, Andreas; Weindl, Günther; Haag, Rainer; Schäfer-Korting, Monika; Hedtrich, Sarah

    2014-11-01

    Polyglycerol scaffolds and nanoparticles emerged as prominent material for various biomedical applications including topical drug delivery. The impact of slight structural modifications on the nanoparticles' properties, drug delivery potential, and biocompatibility, however, is still not fully understood.Hence, we explored the influence of structural modifications of five structurally related polyglycerol-based nanoparticles (PG-PEG, SK1-SK5) on dermal drug delivery efficiency and biocompatibility. The PG-PEG particles were synthesized via randomly and controlled alkylated chemo-enzymatic approaches resulting in significantly varying particle sizes and interactions with guest molecules. Furthermore, weobserved considerably improved dermal drug delivery with the smallest particles SK4 and SK5 (11 nm and 14 nm) which also correlated with well-defined surface properties achieved by the controlled alkylated synthesis approach. The consistently good biocompatibility for all PG-PEG particles was mainly attributed to the neutral surface charge. No irritation potential, major cytotoxicity or genotoxicity was observed. Nevertheless, slightly better biocompatibility was again seen for the particles characterized by alkyl chain substitution in the core and not on the particle surface.Despite the high structural similarity of the PG-PEG particles, the synthesis and the functionalization significantly influenced particle properties, biocompatibility, and most significantly the drug delivery efficiency.

  10. Single-crystalline hyperbranched nanostructure of iron hydroxyl phosphate Fe5(PO4)4(OH)3·2H2O for highly selective capture of phosphopeptides.

    PubMed

    Chen, Qun; Wei, Chengzhen; Zhang, Yizhou; Pang, Huan; Lu, Qingyi; Gao, Feng

    2014-01-17

    Single-crystalline hyperbranched nanostructures of iron hydroxyl phosphate Fe5(PO4)4(OH)3·2H2O (giniite) with orthorhombic phase were synthesized through a simple route. They have a well-defined dendrite fractal structure with a pronounced trunk and highly ordered branches. The toxicity test shows that the hyperbranched nanostructures have good biocompatibility and low toxicity level, which makes them have application potentials in life science. The study herein demonstrated that the obtained hyperbranched giniite nanostructures show highly selective capture of phosphopeptides and could be used as a kind of promising nanomaterial for the specific capture of phosphopeptides from complex tryptic digests with the detection of MALDI-TOF mass spectrometry.

  11. Single-Crystalline Hyperbranched Nanostructure of Iron Hydroxyl Phosphate Fe5(PO4)4(OH)3·2H2O for Highly Selective Capture of Phosphopeptides

    PubMed Central

    Chen, Qun; Wei, Chengzhen; Zhang, Yizhou; Pang, Huan; Lu, Qingyi; Gao, Feng

    2014-01-01

    Single-crystalline hyperbranched nanostructures of iron hydroxyl phosphate Fe5(PO4)4(OH)3·2H2O (giniite) with orthorhombic phase were synthesized through a simple route. They have a well-defined dendrite fractal structure with a pronounced trunk and highly ordered branches. The toxicity test shows that the hyperbranched nanostructures have good biocompatibility and low toxicity level, which makes them have application potentials in life science. The study herein demonstrated that the obtained hyperbranched giniite nanostructures show highly selective capture of phosphopeptides and could be used as a kind of promising nanomaterial for the specific capture of phosphopeptides from complex tryptic digests with the detection of MALDI-TOF mass spectrometry. PMID:24435094

  12. Tunable Hydrophilic or Amphiphilic Coatings: A "Reactive Layer Stack" Approach.

    PubMed

    Frenzel, Ralf; Höhne, Susanne; Hanzelmann, Christian; Schmidt, Thomas; Winkler, René; Drechsler, Astrid; Bittrich, Eva; Eichhorn, Klaus-Jochen; Uhlmann, Petra

    2015-06-17

    Thin films with tunable properties are very interesting for potential applications as functional coatings with, for example, anti-icing or improved easy-to-clean properties. A novel "reactive layer stack" approach was developed to create covalently grafted mono- and multilayers of poly(glycidyl methacrylate)/poly(tert-butyl acrylate) diblock copolymers. Because these copolymers contain poly(glycidyl methacrylate) blocks they behave as self-cross-linking materials after creation of acrylic acid functionalities by splitting off the tert-butyl units. The ellipsometrically determined coating thickness of the resulting hydrophilic multilayers depended linearly on the number of applied layers. Amphiphilic films with tunable wettability were prepared using triblock terpolymers with an additional poly(methyl methacrylate) block. The mechanism of the formation of the (multi)layers was investigated in detail by studying the acidolysis of the surface-linked tert-butyl acrylate blocks by infrared reflection absorbance spectroscopy, accompanied by surface analysis using atomic force microscopy and contact angle measurements. In the case of the amphiphilic and switchable terpolymer layers this reaction was very sensitive to the used acidic reagent.

  13. Nanoassemblies from amphiphilic cytarabine prodrug for leukemia targeted therapy.

    PubMed

    Liu, Jing; Zhao, Dujuan; He, Wenxiu; Zhang, Huiyuan; Li, Zhonghao; Luan, Yuxia

    2017-02-01

    The anti-leukemia effect of cytarabine (Ara-C) is severely restricted by its high hydrophilic properties and rapid plasma degradation. Herein, a novel amphiphilic small molecular prodrug of Ara-C was developed by coupling a short aliphatic chain, hexanoic acid (HA) to 4-NH2 of the parent drug. Based on the amphiphilic nature, the resulting bioconjugate (HA-Ara) could spontaneously self-assemble into stable spherical nanoassemblies (NAs) with an extremely high drug loading (∼71wt%). Moreover, folate receptor (FR)-targeting NAs with high grafting efficient folic acid - bovine serum albumin (FA-BSA) conjugate immobilized on the surface (NAs/FA-BSA) was prepared. The results of MTT assays on FR-positive K562 cells and FR-negative A549 cells demonstrated higher cytotoxicity of HA-Ara NAs than the native drug. Especially, the IC50 values revealed that NAs/FA-BSA was 3 and 2-fold effective than non-targeted NAs after 24 and 48h treatment with K562 cells, respectively indicating FR-mediated enhanced anti-tumor efficacy. In vitro cellular uptake, larger accumulation of HA-Ara NAs were observed in comparative with the free FITC and the results further confirmed the selective uptake of NAs/FA-BSA in folate receptor enriched cancer cells. Above all, self-assembled HA-Ara NAs exhibited potential superiority for Ara-C delivery and FA-modified NAs would be an excellent candidate for targeting leukemia therapy.

  14. Organogels from Double-Chained Vitamin C Amphiphilic Derivatives.

    PubMed

    Tempestini, Elia; Bucci, Martina; Mastromartino, Vincenzo; Gori, Marianna; Tanini, Damiano; Ambrosi, Moira; Fratini, Emiliano; Capperucci, Antonella; Lo Nostro, Pierandrea

    2017-03-20

    The syntheses and physicochemical characterization of double-chained amphiphilic compounds obtained from vitamin C are reported: dialkanoyl-5,6-O-ascorbic acid esters (Di-ASCn, n=8, 10, and 12). The acetyl-5-dodecanoyl-6-ascorbic acid ester is synthesized and investigated for comparison. These products are quite insoluble in water and in polar solvents, although they form homogeneous dispersions in cyclohexane. Upon cooling, these dispersions turn into a gel-like phase. Differential scanning calorimetry, FTIR spectroscopy, and small- and wide-angle X-ray scattering experiments are performed to investigate the properties of pure solids and their liquid dispersions. Di-ASCn retain the same redox properties of the parent molecule and represent a valid candidate for the production of nanosized protective carriers for valuable guests that are sensitive to oxidative radical attack. Moreover, the contribution of the vitamin C hydroxyl group in position 5 to the overall hydration properties of single- and double-chained amphiphilic derivatives is discussed.

  15. Immobilization of Amphiphilic Polycations by Catechol Functionality for Antimicrobial Coatings

    PubMed Central

    Han, Hua; Wu, Jianfeng; Avery, Christopher W.; Mizutani, Masato; Jiang, Xiaoming; Kamigaito, Masami; Chen, Zhan; Xi, Chuanwu; Kuroda, Kenichi

    2011-01-01

    A new strategy to prepare antimicrobial surfaces by a simple dip-coating procedure is reported. Amphiphilic polycations with different mole ratios of monomers containing dodecyl quaternary ammonium, methoxyethyl, and catechol groups were synthesized by free-radical polymerization. The polymer coatings were prepared by immersing glass slides into a polymer solution and subsequent drying and heating. The quaternary ammonium side chains endow the coatings with potent antibacterial activity, while the methoxyetyhyl side chains enable tuning the hydrophobic/hydrophilic balance and the catachol groups promote immobilization of the polymers into films. The polymer coated surfaces displayed bactericidal activity against Escherichia coli and Staphylococcus aureus in a dynamic contact assay and prevented accumulation of viable E. coli, S. aureus, and Acinetobacter baumannii for up to 96 hours. Atomic force microscopy (AFM) images of coating surfaces indicated that the surfaces exhibit virtually the same smoothness for all polymers except the most hydrophobic. The hydrophobic polymer without methoxyethyl side chains showed clear structuring into polymer domains, causing high surface roughness. Sum-frequency generation (SFG) vibrational spectroscopy characterization of the surface structures demonstrated that the dodecyl chains are predominantly localized at the surface-air interface of the coatings. SFG also showed that the phenyl groups of the catechols are oriented on the substrate surface. These results support our hypothesis that the adhesive or cross-linking functionality of catechol groups discourages leaching of polymers, allowing tuning of the amphiphilic balance by incorporating hydrophilic components into the polymer chains to gain potent biocidal activity. PMID:21391641

  16. Detachment of surface membrane invagination systems by cationic amphiphilic drugs

    PubMed Central

    Osman, Sangar; Taylor, Kirk A.; Allcock, Natalie; Rainbow, Richard D.; Mahaut-Smith, Martyn P.

    2016-01-01

    Several cell types develop extensive plasma membrane invaginations to serve a specific physiological function. For example, the megakaryocyte demarcation membrane system (DMS) provides a membrane reserve for platelet production and muscle transverse (T) tubules facilitate excitation:contraction coupling. Using impermeant fluorescent indicators, capacitance measurements and electron microscopy, we show that multiple cationic amphiphilic drugs (CADs) cause complete separation of the DMS from the surface membrane in rat megakaryocytes. This includes the calmodulin inhibitor W-7, the phospholipase-C inhibitor U73122, and anti-psychotic phenothiazines. CADs also caused loss of T tubules in rat cardiac ventricular myocytes and the open canalicular system of human platelets. Anionic amphiphiles, U73343 (a less electrophilic U73122 analogue) and a range of kinase inhibitors were without effect on the DMS. CADs are known to accumulate in the inner leaflet of the cell membrane where they bind to anionic lipids, especially PI(4,5)P2. We therefore propose that surface detachment of membrane invaginations results from an ability of CADs to interfere with PI(4,5)P2 interactions with cytoskeletal or BAR domain proteins. This establishes a detubulating action of a large class of pharmaceutical compounds. PMID:26725955

  17. Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Xu, Binbin; Yao, Wenqiang; Li, Yongjun; Zhang, Sen; Huang, Xiaoyu

    2016-12-01

    A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

  18. Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer

    PubMed Central

    Xu, Binbin; Yao, Wenqiang; Li, Yongjun; Zhang, Sen; Huang, Xiaoyu

    2016-01-01

    A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents. PMID:28000757

  19. Changes in two-phase emulsion morphology in temperature-amphiphile concentration or fish diagram for ternary amphiphile/oil/water systems.

    PubMed

    Lee, Jong-Moon; Lim, Kyung-Hee

    2005-10-01

    We examined the morphologies of two-phase emulsions in the ternary 2-butoxyethanol/n-decane/water system at various temperatures and water-to-oil ratios (WORs). The two-phase emulsion morphologies depended on temperature, WOR, and amphiphile concentration, and the results are presented in a temperature-amphiphile concentration coordinate system or a "fish" diagram. The observations made in this work contradict the predictions by the phase-inversion-temperature (PIT) concept. At WOR<1, a vertical inversion line was observed at TT(uc) (upper critical endpoint temperature) and at low amphiphile concentrations, only B/T emulsions appeared, irrespective of temperature. At WOR>1, the situation was reversed; T/B emulsions at TT(uc), and T/B emulsions at low amphiphile concentrations, irrespective of temperature. At WOR=1, two horizontal inversion lines, one each at TT(uc), were observed. The morphologies of the two-phase emulsions were B/T or T/B emulsions at low amphiphile concentrations, and at higher amphiphile concentrations T/B at TT(uc). All these findings along with three-phase emulsion data result in complete emulsion morphology diagrams in the temperature-amphiphile concentration space or fish diagram.

  20. Mussel-inspired hyperbranched poly(amino ester) polymer as strong wet tissue adhesive.

    PubMed

    Zhang, Hong; Bré, Lígia P; Zhao, Tianyu; Zheng, Yu; Newland, Ben; Wang, Wenxin

    2014-01-01

    Current medical adhesives based on cyanoacrylates typically exhibit cellular toxicity. In contrast, fibrin adhesives are non-toxic but have poor adhesive properties. To overcome these drawbacks we designed a simple and scalable adhesive precursor inspired by marine mussel adhesion that functioned with strong adhesion in wet conditions and with low cytotoxicity. Dopamine, an-amine derivative of an amino acid abundantly present in mussel adhesive proteins, was co-polymerised with a tri-functional vinyl monomer, to form a hyperbranched poly(β-amino ester) polymer termed poly(dopamine-co-acrylate) (PDA). A variety of molecular weights and crosslinking methods were analysed using an ex vivo porcine skin model and an almost 4 fold increase in wet adhesion strength was observed compared to TISSEEL(®) fibrin sealant. With a fast curing time, degradable properties and low cytotoxicity, PDA is highly attractive for medical purposes and could have a broad impact on surgeries where surgical tissue adhesives, sealants, and haemostatic agents are used.

  1. Hydrolytically degradable hyperbranched PEG-polyester adhesive with low swelling and robust mechanical properties.

    PubMed

    Zhang, Hong; Zhao, Tianyu; Duffy, Patrick; Dong, Yixiao; Annaidh, Aisling Ní; O'Cearbhaill, Eoin; Wang, Wenxin

    2015-10-28

    Photocrosslinkable and water soluble hyperbranched PEG-polyester polymers (HPEGDA) have been developed as robust degradable adhesives. The HPEGDA polymers have been synthesized from controlled homopolymerization of poly(ethylene glycol) diacrylate (PEGDA700 ) via in situ deactivation enhanced atom transfer radical polymerization (DE-ATRP). By introducing a high initiator-to-monomer ratio, the obtained HPEGDA polymer is composed of extremely short carbon-carbon backbones interconnected together by the long PEG chains as well as pendent photocrosslinkable acrylate moieties. Due to the extremely short C-C backbone, the long PEG chains can therefore be seen as the main chain, thus, HPEGDA polymers behave more like polyester which is a category of polymers that contain the ester functional group in their main chain. Photo-cured HPEGDA can be readily adhered to tissue forming a patch with robust mechanical and adhesive strengths. The degradation profile by hydrolysis of polyester blocks as well as a significantly low swelling ratio of HPEGDA gels in an aqueous environment allow them to have great potential for sealing and repair of internal tissue. Furthermore, HPEGDA gels appear to have minor significant cytotoxicity in vitro. These unique properties indicate that the reported HPEGDA polymers are well poised for the development of adhesive tissue engineering matrixes, wound dressings, and sealants.

  2. Bio-functionalized MWCNT/hyperbranched polyurethane bionanocomposite for bone regeneration.

    PubMed

    Das, Beauty; Chattopadhyay, Pronobesh; Maji, Somnath; Upadhyay, Aadesh; Das Purkayastha, Manashi; Mohanta, Charu Lata; Maity, Tapas Kumar; Karak, Niranjan

    2015-04-17

    The proper fabrication of biomaterials, particularly for purposes like bone regeneration, is of the utmost importance for the clinical success of materials that fulfill the design criteria at bio-interfacial milieu. Building on this aspect, a polyurethane nanocomposite (PNC) was fabricated by the combination of rapeseed protein functionalized multi-walled carbon nanotubes (MWCNTs) and vegetable-oil-based hyperbranched polyurethane. Biofunctionalized MWCNTs showed incredible biocompatibility compared to pristine MWCNTs as ascertained via in vitro and in vivo studies. PNC showed enhanced MG63 cell differentiation ability compared to the control and carboxyl functionalized MWCNT-based nanocomposite, as postulated by alkaline phosphatase activity together with better cellular adhesion, spreading and proliferation. Consequently, a critical-sized fracture gap (6 mm) bridged by the sticky PNC scaffold illustrated rapid bone neoformation within 30-45 d, with 90-93% of the defect area filling up. Histopathological studies demonstrated the reorganization of the normal tibial architecture and biodegradation of the implant. The subsequent toxicological study through cytokine expression, biochemical analysis and hematological studies suggested non-immunogenic and non-toxic effects of PNCs and their degraded/leached products. Their excellent bio-physiological features with high load-bearing ability (49-55.5 Mpa), ductility (675-790%) and biodegradability promote them as the best alternative biomaterials for bone regeneration in a comprehensive manner.

  3. Isolation and characterization of a hyperbranched proteoglycan from Ganoderma lucidum for anti-diabetes.

    PubMed

    Pan, Deng; Wang, Linqiang; Chen, Congheng; Hu, Bingwen; Zhou, Ping

    2015-03-06

    Presently, an efficient protein tyrosine phosphatase 1B (PTP1B) inhibitor, named FYGL-n, was isolated from Ganoderma Lucidum and characterized for its structure and bioactivity. Structure and chain conformation of FYGL-n based on both chemical and spectroscopic analysis showed that FYGL-n was a hyperbranched heteropolysaccharide bonded with protein via both serine and threonine residues by O-type glycoside, and showed a sphere observed by AFM. Specifically, monosaccharide composition indicated that FYGL-n consisted of D-arabinose, D-galactose, L-rhamnose and D-glucose in a mole ratio of 0.08:0.21:0.24:0.47, with a molecular mass of 72.9 kDa. The analysis of amino acids in FYGL-n indicated that there were 16 common amino acids, among which aspartic acid, glycine, serine, alanine, glutamic acid and threonine were the dominant components. Also it was demonstrated that FYGL-n could inhibit the PTP1B activity on a competitive mechanism in vitro.

  4. Glycodendritic structures based on Boltorn hyperbranched polymers and their interactions with Lens culinaris lectin.

    PubMed

    Arce, Eva; Nieto, Pedro M; Díaz, Vicente; Castro, Rossana García; Bernad, Antonio; Rojo, Javier

    2003-01-01

    Multivalent scaffolds bearing carbohydrates have been prepared to mediate biological processes where carbohydrates are involved. These systems consist of dendritic structures based on Boltorn H20 and H30 hyperbranched polymers to which carbohydrates are linked through a convenient spacer. Mannose has been chosen as a sugar unit to test the viability of this strategy. These glycodendritic compounds have been prepared in a few steps with good yields, showing a high solubility in physiological media and low toxicity. The binding of these dendritic polymers to the mannose-binding lectin Lens culinaris (LCA) was studied using STD-NMR experiments and quantitative precipitation assays. The results demonstrate the existence of a clear interaction between the mannose derivative systems and the Lens lectin where the dendritic scaffold does not have an important role in mannose binding but supplies the necessary multivalence for lectin cluster formation. These glycodendritic structures are able to interact with a receptor, and therefore they can be considered as promising tools for biological studies.

  5. Hydrophobic acrylic hard coating by surface segregation of hyper-branched polymers

    NASA Astrophysics Data System (ADS)

    Haraguchi, Masayuki; Hirai, Tomoyasu; Ozawa, Masaaki; Miyaji, Katsuaki; Tanaka, Keiji

    2013-02-01

    The ability of hyperbranched polymers (HBPs) to preferentially segregate to the surface of its matrix owing to its unique structure makes it a good candidate as a surface modifier. One particular challenge in its application as an efficient surface modifier, however, is its possible elimination from the surface due to the lack of attachments between a HBP (modifier) and its host material (polymer matrix). Here, we present a novel approach to efficiently prevent the removal of HBPs from the surface of its host material by directly reacting a HBP containing fluoroalkyl segments (F-HBP) to a multi-functional acrylate monomer prior to curing. We also have characterized surface structure and wettability of the acrylic hard coating material by X-ray photoelectron spectroscopic and contact angle measurements, respectively. The results show that since F-HBP was segregated at the surface, the surface became hydrophobic and more stable. Thus, we claim that our approach results in the formation of a water-repellent acrylic hard coating material.

  6. Efficient gene delivery with osmotically active and hyperbranched poly(ester amine)s.

    PubMed

    Arote, Rohidas B; Lee, Eun-Sun; Jiang, Hu-Lin; Kim, You-Kyoung; Choi, Yun-Jaie; Cho, Myung-Haing; Cho, Chong-Su

    2009-12-01

    Degradable and hyperbranched poly (ester amine)s (PEAs) were successfully synthesized by Michael addition reaction between hydrophilic glycerol triacrylate (GTA) and low-molecular-weight polyethylenimine (LMW-PEI) and evaluated as nonviral gene carriers. PEAs effectively condensed DNA with particle sizes below 200 nm and suitable surface charges (15-45 mV), suitable for intracellular delivery. PEAs degraded in a controlled fashion showing half-lives of more than 12 days and were essentially nontoxic in three different cell lines. Elevated transfection levels by luciferase assay revealed the superiority of PEAs over PEI 25K and Lipofectamine. PEAs synthesized using 1:4 mol ratio of GTA to PEI [GTA/PEI-1.2(1:4)] showed highest transfection efficiency in HepG2 cells. PEAs showed significant gene expression in vitro as well as in vivo through aerosol administration. Reduction in packed cell volume (PCV) of cells when treated with polyplexes supported the hyperosmotic effect of PEAs. Effect of bafilomycin A1 on transfection efficiency of PEAs on 293T cells indicated its endosomal buffering capacity. High transfection efficiency was attributed to the synergism from hyperosmotic glycerol backbone in the PEAs and endosomal buffering capacity of PEI amine groups. Therefore, this convergence of osmotically active biodegradable PEAs suggests their potential as a safe and efficient gene delivery vector.

  7. Adsorption of Pb(II) from aqueous solution by silica-gel supported hyperbranched polyamidoamine dendrimers.

    PubMed

    Niu, Yuzhong; Qu, Rongjun; Sun, Changmei; Wang, Chunhua; Chen, Hou; Ji, Chunnuan; Zhang, Ying; Shao, Xia; Bu, Fanling

    2013-01-15

    The adsorption properties of silica-gel supported hyperbranched polyamidoamine dendrimers (SiO(2)-G0-SiO(2)-G4.0) have been investigated by batch method. The effect of pH of the solution, contact time, initial Pb(II) ion concentration, temperature and coexisting metal ions have been demonstrated. The results indicated that the optimum pH value was 5. Adsorption kinetics was found to follow the pseudo-second-order model and controlled by film diffusion. The adsorption isotherms were fitted by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Langmuir isotherm model was found to be more suitable to describe the equilibrium data, suggesting the uptake of Pb(II) ions by monolayer adsorption. From D-R isotherm model, the calculated mean free energy E demonstrated the adsorption processes occurred by chemical ion-exchange mechanism. FTIR analysis revealed that amine groups were mainly responsible for the adsorption of Pb(II) by amino-terminated adsorbents, while CO of ester groups also participated in the adsorption process of ester-terminated ones. The adsorbents can selectively adsorb Pb(II) from binary ion systems in the presence of Mn(II), Cu(II), Co(II), and Ni(II). Based on the results, it is concluded that SiO(2)-G0-SiO(2)-G4.0 had great potential for the removal of Pb(II) from aqueous solution.

  8. Dynamics of Hyperbranched Polymers in the Bulk and under Confinement: Effect of Dendritic Generation

    NASA Astrophysics Data System (ADS)

    Chrissopoulou, Kiriaki; Androulaki, Krystalenia; Anastasiadis, Spiros H.; Prevosto, Daniele; Labardi, Massimiliano

    2014-03-01

    The structure and dynamics of three generations of a hyperbranched polyester polyol (Boltorn) and their nanocomposites with natural montmorillonite (Na+-MMT) are investigated to offer a detailed picture of the behavior in bulk and under confinement. The structure was studied with X-ray diffraction (XRD) and differential scanning calorimetry (DSC), while the dynamics using dielectric spectroscopy (DS). XRD reveals that the polymer chains reside within the galleries of the Na+-MMT producing an intercalated nanocomposite. The glass transition temperature, Tg, of the bulk polymers shows a dependence on the generation whereas the transition is completely suppressed when all chains are intercalated. The dynamics of the polymers and nanocomposites with ~50wt% polymer, where all chains are confined, were investigated for temperatures both below and above the polymer Tg. A sub-Tg process was found, showing similar features for the three polymers whereas the segmental relaxation was observed around Tg. For the nanocomposites, the dynamics that are observed show similarities and differences with the respective of the pure polymers depending on the specific process. Partially sponsored by EU (COST Action MP0902) and by the Greek GSRT (Research Funding Program: THALES (MIS 377278))

  9. Adsorption behaviors of Hg(II) on chitosan functionalized by amino-terminated hyperbranched polyamidoamine polymers.

    PubMed

    Ma, Fang; Qu, Rongjun; Sun, Changmei; Wang, Chunhua; Ji, Chunnuan; Zhang, Ying; Yin, Ping

    2009-12-30

    The adsorption behaviors of Hg(II) on adsorbents, chitosan functionalized by generation 1.0-3.0 of amino-terminated hyperbranched polyamidoamine polymers (denoted as CTS-1.0, CTS-2.0 and CTS-3.0, respectively), were studied. The optimum pH corresponding to the maximum adsorption capacities was found to be 5.0 for the three adsorbents. The experimental equilibrium data of Hg(II) on the three adsorbents were fitted to the Freundlich and the Langmuir models, and it is found that the Langmuir isotherm was the best fitting model to describe the equilibrium adsorption. The kinetics data indicated that the adsorption process of Hg(II) ions on CTS-1.0, CTS-2.0 and CTS-3.0 were governed by the film diffusion and followed pseudo-second-order rate model. Thermodynamic analysis and FTIR analysis revealed that the adsorption behaviors of Hg(II) ions on the three adsorbents could be considered as spontaneous, endothermic and chemical sorption process, resulting in their higher adsorption capacities at higher temperature.

  10. Development of novel electrically conductive scaffold based on hyperbranched polyester and polythiophene for tissue engineering applications.

    PubMed

    Jaymand, Mehdi; Sarvari, Raana; Abbaszadeh, Parisa; Massoumi, Bakhshali; Eskandani, Morteza; Beygi-Khosrowshahi, Younes

    2016-11-01

    A novel electrically conductive scaffold containing hyperbranched aliphatic polyester (HAP), polythiophene (PTh), and poly(ε-caprolactone) (PCL) for regenerative medicine application was succesfully fabricated via electrospinning technique. For this purpose, the HAP (G4; fourth generation) was synthesized via melt polycondensation reaction from tris(methylol)propane and 2,2-bis(methylol)propionic acid (bis-MPA). Afterward, the synthesized HAP was functionalized with 2-thiopheneacetic acid in the presence of N,N-dicyclohexyl carbodiimide, and N-hydroxysuccinimide as coupling agent and catalyst, respectively, to afford a thiophene-functionalized G4 macromonomer. This macromonomer was subsequently used in chemical oxidation copolymerization with thiophene monomer to produce a star-shaped PTh with G4 core (G4-PTh). The solution of the G4-PTh, and PCL was electrospun to produce uniform, conductive, and biocompatible nanofibers. The conductivity, hydrophilicity, and mechanical properties of these nanofibers were investigated. The biocompatibility of the electrospun nanofibers were evaluated by assessing the adhesion and proliferation of mouse osteoblast MC3T3-E1 cell line and in vitro degradability to demonstrate their potential uses as a tissue engineering scaffold. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2673-2684, 2016.

  11. Composite Electrolyte Membranes from Partially Fluorinated Polymer and Hyperbranched, Sulfonated Polysulfone

    PubMed Central

    Subianto, Surya; Roy Choudhury, Namita; Dutta, Naba

    2013-01-01

    Macromolecular modification of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) was done with various proportions of sulfonic acid terminated, hyperbranched polysulfone (HPSU) with a view to prepare ion conducting membranes. The PVDF-co-HFP was first chemically modified by dehydrofluorination and chlorosulfonation in order to make the membrane more hydrophilic as well as to introduce unsaturation, which would allow crosslinking of the PVDF-co-HFP matrix to improve the stability of the membrane. The modified samples were characterized for ion exchange capacity, morphology, and performance. The HPSU modified S-PVDF membrane shows good stability and ionic conductivity of 5.1 mS cm−1 at 80 °C and 100% RH for blends containing 20% HPSU, which is higher than the literature values for equivalent blend membranes using Nafion. SEM analysis of the blend membranes containing 15% or more HPSU shows the presence of spherical domains with a size range of 300–800 nm within the membranes, which are believed to be the HPSU-rich area.

  12. Hyperbranched polyamine assisted synthesis of dual-luminescent gold composite with pH responsive character

    NASA Astrophysics Data System (ADS)

    Yuan, Zhiqin; Du, Yi; He, Yan

    2017-03-01

    We present a facile one-pot, two-step strategy to prepare water-soluble dual-luminescent gold nanodots (AuNDs) and few-atom gold nanocluster composites simultaneously by using high molecular weight and hyperbranched polyethyleneimine (hPEI) as the protection ligand and stabilization agent. It was found that in the presence of hPEI, Au(III) ion can be reduced to a metastable Au(I) charge state in aqueous solution. Subsequently, adding 11-mercaptoundonioic acid induces parallel pathways of restricted Au(I) assembly, leading to the formation of both red-emitting hPEI stabilized AuNDs and blue-emitting hPEI-protected Au8 nanoclusters. The intensity ratio between the blue and red species shows a sensitive and reversible response to the solution pH in the range 2–11 and the dual-luminescent gold composites can act as an effective and reversible pH indicator.

  13. Capillary electrophoresis using core-based hyperbranched polyethyleneimine (CHPEI) static-coated capillaries.

    PubMed

    Boonyakong, Cheerapa; Tucker, Sheryl A

    2009-10-01

    With unique 3-D architecture, the application of core-based hyperbranched polyethyleneimine (CHPEI), as a capillary coating in capillary electrophoresis, is demonstrated by manipulation of the electroosmotic mobility (EOF). CHPEI coatings (CHPEI5, M(w) approximately 5000 and CHPEI25, M(w) approximately 25,000) were physically adsorbed onto the inner surface of bare fused-silica capillary (BFS) via electrostatic interaction of the oppositely charged molecules by rinsing the capillaries with different CHPEI aqueous solutions. The EOF values of the coated capillaries were measured over the pH range of 4.0-9.0. At higher pH (pH >6) the coated capillary surface possesses excess negative charges, which causes the reversal of the EOF. The magnitudes of the EOF obtained from the coated capillaries were three-fold lower than that of BFS capillary. Desirable reproducibility of the EOF with % RSD (n = 5) < or = 2 was obtained. Effect of ionic strength, stability of the coating (% RSD = 0.3) and the dependence of the EOF on pH (% RSD = 0.5) were also investigated. The CHPEI-coated capillaries were successfully utilized to separate phenolic compounds, B vitamins, as well as basic drugs and related compounds with reasonable analysis time (< 20 min) and acceptable migration-time repeatability (< 0.7% RSD for intra-capillary and < 2% RSD for inter-capillary).

  14. Long-term active antimicrobial coatings for surgical sutures based on silver nanoparticles and hyperbranched polylysine.

    PubMed

    Ho, Chau Hon; Odermatt, Erich K; Berndt, Ingo; Tiller, Joerg C

    2013-01-01

    The goal of this study was to develop a long-term active antimicrobial coating for surgical sutures. To this end, two water-insoluble polymeric nanocontainers based on hyperbranched polylysine (HPL), hydrophobically modified by either using glycidyl hexadecyl ether, or a mixture of stearoyl/palmitoyl chloride, were synthesized. Highly stabilized silver nanoparticles (AgNPs, 2-5 nm in size) were generated by dissolving silver nitrate in the modified HPL solutions in toluene followed by reduction with L-ascorbic acid. Poly(glycolic acid)-based surgical sutures were dip-coated with the two different polymeric silver nanocomposites. The coated sutures showed high efficacies of more than 99.5% reduction of adhesion of living Staphylococcus aureus cells onto the surface compared to the uncoated specimen. Silver release experiments were performed on the HPL-AgNP modified sutures by washing them in phosphate buffered saline for a period of 30 days. These coatings showed a constant release of silver ions over more than 30 days. After this period of washing, the sutures retained their high efficacies against bacterial adhesion. Cytotoxicity tests using L929 mouse fibroblast cells showed that the materials are basically non-cytotoxic.

  15. Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

    PubMed

    Lin, Cuiling; Xu, Luonan; Huang, Libo; Chen, Jia; Liu, Yuanyuan; Ma, Yifan; Ye, Feixiang; Qiu, Huayu; He, Tian; Yin, Shouchun

    2016-09-01

    Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials.

  16. New core-shell hyperbranched chitosan-based nanoparticles as optical sensor for ammonia detection.

    PubMed

    El-Sherbiny, Ibrahim M; Hefnawy, Amr; Salih, Ehab

    2016-05-01

    In this paper, preparation of new core-shell amino-terminated hyperbranched chitosan nanoparticles (HBCs-NH2) NPs is described. The synthesized nanoparticles were characterized using ninhydrin assay, FTIR, TGA, and FESEM. The newly prepared (HBCs-NH2) NPs were then used as a platform for facile and controlled synthesis of silver nanoparticles (AgNPs) which was confirmed using FTIR, UV-vis spectrometry, X-ray diffraction, SEM and HRTEM. Formation of the AgNPs was also noted upon changing the color of (HBCs-NH2) NPs suspension from colorless into yellow as well as through the appearance of surface plasmon resonance (SPR) peak at 400 nm. HRTEM showed a uniform and spherical morphology of the resulting HBCs-NH2 NPs with average size 400 nm, and the AgNPs were formed mainly on their surface with average size of 20-50 nm. The newly developed (HBCs-NH2) NPs-AgNPs showed a great potential as optical sensor for efficient detection of the ammonia concentration in solutions based on the change in the SPR.

  17. Hyperbranched polyglycidol assisted green synthetic protocols for the preparation of multifunctional metal nanoparticles.

    PubMed

    Li, Haiqing; Jo, Jung Kyu; Zhang, Li Dong; Ha, Chang-Sik; Suh, Hongsuk; Kim, Il

    2010-12-07

    Biocompatible hyperbranched polyglycidol (HBP) has been demonstrated to be an effective reducing and stabilizing agent for the synthesis of highly water-soluble monometallic (Au, Ag, Pt, Pd, and Ru) and bimetallic (Au/Pt, Au/Pd, and Au/Ru) nanoparticles (NPs), which provides a general and green protocol to fabricate metal NPs. The HBP-assisted reduction of metal ions follows an analogous polyol process. The reduction reaction rate increases sharply by increasing the temperature and the molecular weight of HBP. The size of NPs is controllable simply by changing the concentration of the metal precursor. High molecular weight HBP is favorable for the formation of NPs with uniform size and improved stability. By utilizing hydroxyl groups in the HBP-passivation layer of Au NPs, TiO(2)/Au, GeO(2)/Au, and SiO(2)/Au nanohybrids are also fabricated via sol-gel processes, which sets a typical example for the creation of versatile metal NPs/inorganic oxide hybrids based on the as-prepared multifunctional NPs.

  18. Hyperbranched Polyester Hydrogels with Controlled Drug Release and Cell Adhesion Properties

    PubMed Central

    Zhang, Hongbin; Patel, Alpesh; Gaharwar, Akhilesh K.; Mihaila, Silvia M.; Iviglia, Giorgio; Mukundan, Shilpaa; Bae, Hojae; Yang, Huai; Khademhosseini, Ali

    2013-01-01

    Hyperbranched polyesters (HPE) have a high efficiency to encapsulate bioactive agents, including drugs, genes and proteins, due to their globe-like nanostructure. However, the use of these highly branched polymeric systems for tissue engineering applications has not been broadly investigated. Here, we report synthesis and characterization of photocrosslinkable HPE hydrogels with sustained drug release characteristics for cellular therapies. These HPE can encapsulate hydrophobic drug molecules within the HPE cavities, due to the presence of hydrophobic inner structure that is otherwise difficult to achieve in conventional hydrogels. The functionalization of HPE with photocrosslinkable acrylate moieties renders the formation of hydrogels with highly porous interconnected structure, and mechanically tough network. The compressive modulus of HPE hydrogels was tunable by changing the crosslinking density. The feasibility of using these HPE networks for cellular therapies was investigated by evaluating cell adhesion, spreading and proliferation on hydrogel surface. Highly crosslinked and mechanically stiff HPE hydrogels have higher cell adhesion, spreading, proliferation compared to soft and complaint HPE hydrogels. Overall, we showed that hydrogels made from HPE could be used for biomedical applications that require control cell adhesion and control release of hydrophobic clues. PMID:23394067

  19. Influence of rice bran stearin on stability, properties and encapsulation efficiency of polyglycerol polyricinoleate (PGPR)-stabilized water-in-rice bran oil emulsions.

    PubMed

    Prichapan, Nattapong; McClements, David Julian; Klinkesorn, Utai

    2017-03-01

    In the present study, rice bran stearin was used to improve the physical stability and encapsulation efficiency of water-in-oil (W/O) emulsions fabricated from rice bran oil and polyglycerol polyricinoleate ester (PGPR). In the absence of rice bran stearin, the emulsions were highly unstable to phase separation with an oil layer forming on their surfaces. Phase separation was delayed by increasing the PGPR concentration because this reduced the water droplet size. Phase separation could be completely inhibited by replacement of 30 to 45wt% of rice bran oil with rice bran stearin due to the formation of a semi-solid fat crystal network that prevented droplet movement. Moreover, addition of rice bran stearin delayed the release of ferrous sulfate from the W/O emulsions. These results demonstrate that rice bran stearin can be used to improve the stability and encapsulation efficiency of W/O emulsions and reduce the level of PGPR required to stabilize them.

  20. RGD based peptide amphiphiles as drug carriers for cancer targeting

    NASA Astrophysics Data System (ADS)

    Saraf, Poonam S.

    Specific interactions of ligands with receptors is one of the approaches for active targeting of anticancer drugs to cancer cells. Over expression of integrin receptors is a physiological manifestation in several cancers and is associated with cancer progression and metastasis, which makes it an attractive target for cancer chemotherapy. The peptide sequence for this integrin recognition is the Arg-Gly-Asp (RGD). Self-assembly offers a unique way of presenting ligands to target receptors for recognition and binding. This study focuses on development of integrin specific peptide amphiphile self-assemblies as carriers for targeted delivery of paclitaxel to αvbeta 3 integrin overexpressing cancers. Amphiphiles composed of conjugates of different analogs of RGD (linear, cyclic or glycosylated) and aliphatic fatty acid with or without 8-amino-3,6-dioxaoctanoic acid (ADA) as linker were synthesized and characterized. The amphiphiles exhibited Critical Micellar Concentration in the range of 7-30 μM. Transmission electron microscopy images revealed the formation of spherical micelles in the size range of 10-40 nm. Forster Resonance Energy Transfer studies revealed entrapment of hydrophobic dyes within a tight micellar core and provided information regarding the cargo exchange within micelles. The RGD micelles exhibited competitive binding with 55% displacement of a bound fluorescent probe by the cyclic RGD micelles. The internalization of fluorescein isothiocynate (FITC) loaded RGD micelles was significantly higher in A2058 melanoma cells compared to free FITC within 20 minutes of incubation at 37°C. The same micelles showed significantly lower internalization at 4°C and on pretreatment with 0.45M sucrose confirming endocytotic uptake of the RGD micellar carriers. The IC50 of paclitaxel in A2058 melanoma cells was lower when treated within RGD micelles as compared to treatment of free drug. On the other hand, IC50 values increased by 2 to 9 fold for micellar treatment

  1. Peroxidase-like activity of gold nanoparticles stabilized by hyperbranched polyglycidol derivatives over a wide pH range

    NASA Astrophysics Data System (ADS)

    Drozd, Marcin; Pietrzak, Mariusz; Parzuchowski, Paweł; Mazurkiewicz-Pawlicka, Marta; Malinowska, Elżbieta

    2015-12-01

    The aim of this work was to carry out comparative studies on the peroxidase-like activity of gold nanoparticles (AuNPs) stabilized with low molecular weight hyperbranched polyglycidol (HBPG-OH) and its derivative modified with maleic acid residues (HBPG-COOH). The influence of the stabilizer to gold precursor ratio on the size and morphology of nanoparticles obtained was checked, and prepared nanoparticles were characterized by means of transmission electron microscopy and UV-Vis spectroscopy. The results indicated the divergent effect of increasing the concentration of stabilizers (HBPG-OH or HBPG-COOH) on the size of the nanostructures obtained. The gold nanoparticles obtained were characterized as having intrinsic peroxidase-like activity and the mechanism of catalysis in acidic and alkaline mediums was consistent with the standard Michaelis-Menten kinetics, revealing a strong affinity of AuNPs with 2, 2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 3, 3‧, 5, 5‧-tetramethylbenzidine (TMB), and significantly lower affinity towards phenol. By comparing the kinetic parameters, a negligible effect of polymeric ligand charge on activity against various types of substrates (anionic or cationic) was indicated. The superiority of steric stabilization via the application of tested low-weight hyperbranched polymers over typical stabilizers in preventing salt-induced aggregation and maintaining high catalytic activity in time was proved. The applied hyperbranched stabilizers provide a good tool for manufacturing gold-based nanozymes, which are highly stable and active over a wide pH range.

  2. A new approach for the synthesis of hyperbranched N-glycan core structures from locust bean gum.

    PubMed

    Ravi Kumar, H V; Naruchi, Kentaro; Miyoshi, Risho; Hinou, Hiroshi; Nishimura, Shin-Ichiro

    2013-12-20

    A novel protocol for the synthesis of general N-glycan core structures was established by means of Manβ(1→4)Man peracetate derived from a naturally abundant locust bean gum as a key starting material. Phenyl (2-O-benzyl-4,6-O-benzylidine-β-D-mannopyranosyl)-(1→4)-3,6-di-O-benzyl-2-azido-2-deoxy-1-thio-β-D-glucopyranoside facilitated the synthesis of key intermediates leading to hyperbranched N-glycan core structures.

  3. Antibacterial activities of aminoglycoside antibiotics-derived cationic amphiphiles. Polyol-modified neomycin B-, kanamycin A-, amikacin-, and neamine-based amphiphiles with potent broad spectrum antibacterial activity.

    PubMed

    Bera, Smritilekha; Zhanel, George G; Schweizer, Frank

    2010-05-13

    Cationic amphiphiles containing multiple positively charged amino functions define a structurally diverse class of antibacterials with broad-spectrum activity and different modes of action. Oligocationic amphiphiles have been used as antibiotics to treat infections and as antiseptics and disinfectants for decades with little or no occurrence of resistance. We have prepared a novel class of cationic amphiphiles termed aminoglycoside antibiotics-derived amphiphiles in which the polyol scaffold of the aminoglycosides neomycin B, kanamycin A, amikacin, and neamine has been uniformly decorated with hydrophobic residues in the form of polycarbamates and polyethers. Our results show that the nature of the polyol modification as well as the nature of the aminoglycoside antibiotics has a strong effect on the antibacterial potency. The most potent antibacterials are polyol-modified neomycin B-based amphiphiles containing unsubstituted aromatic rings. These analogues exhibit up to 256-fold enhanced antibacterial activity against resistant strains when compared to neomycin B while retaining most of their activity against neomycin B-susceptible strains.

  4. Optimal conditions for opening of membrane pore by amphiphilic peptides

    NASA Astrophysics Data System (ADS)

    Kabelka, Ivo; Vácha, Robert

    2015-12-01

    Amphiphilic peptides can interact with biological membranes and severely affect their barrier and signaling functions. These peptides, including antimicrobial peptides, can self-assemble into transmembrane pores that cause cell death. Despite their medical importance, the conditions required for pore formation remain elusive. Monte Carlo simulations with coarse-grained models enabled us to calculate the free energies of pore opening under various conditions. In agreement with oriented circular dichroism experiments, a high peptide-to-lipid ratio was found to be necessary for spontaneous pore assembly. The peptide length has a non-monotonic impact on pore formation, and the optimal length matches with the membrane thickness. Furthermore, the hydrophobicity of the peptide ends and the mutual positions of peptides on the membrane play a role.

  5. Interaction of amphiphilic drugs with human and bovine serum albumins

    NASA Astrophysics Data System (ADS)

    Khan, Abbul Bashar; Khan, Javed Masood; Ali, Mohd. Sajid; Khan, Rizwan Hasan; Kabir-ud-Din

    2012-11-01

    To know the interaction of amphiphilic drugs nortriptyline hydrochloride (NOT) and promazine hydrochloride (PMZ) with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)), techniques of UV-visible, fluorescence, and circular dichroism (CD) spectroscopies are used. The binding affinity is more in case of PMZ with both the serum albumins. The quenching rate constant (kq) values suggest a static quenching process for all the drug-serum albumin interactions. The UV-visible results show that the change in protein conformation of PMZ-serum albumin interactions are more prominent as compared to NOT-serum albumin interactions. The CD results also explain the conformational changes in the serum albumins on binding with the drugs. The increment in %α-helical structure is slightly more for drug-BSA complexes as compared to drug-HSA complexes.

  6. Interaction of amphiphilic drugs with human and bovine serum albumins.

    PubMed

    Khan, Abbul Bashar; Khan, Javed Masood; Ali, Mohd Sajid; Khan, Rizwan Hasan; Kabir-Ud-Din

    2012-11-01

    To know the interaction of amphiphilic drugs nortriptyline hydrochloride (NOT) and promazine hydrochloride (PMZ) with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)), techniques of UV-visible, fluorescence, and circular dichroism (CD) spectroscopies are used. The binding affinity is more in case of PMZ with both the serum albumins. The quenching rate constant (k(q)) values suggest a static quenching process for all the drug-serum albumin interactions. The UV-visible results show that the change in protein conformation of PMZ-serum albumin interactions are more prominent as compared to NOT-serum albumin interactions. The CD results also explain the conformational changes in the serum albumins on binding with the drugs. The increment in %α-helical structure is slightly more for drug-BSA complexes as compared to drug-HSA complexes.

  7. Bulk modification of PDMS microchips by an amphiphilic copolymer.

    PubMed

    Xiao, Yan; Yu, Xiao-Dong; Xu, Jing-Juan; Chen, Hong-Yuan

    2007-09-01

    A simple and rapid bulk-modification method based on adding an amphiphilic copolymer during the fabrication process was employed to modify PDMS microchips. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was used as the additive substance. Compared to the native PDMS microchips, both the contact angle and the EOF of the bulk-modified PDMS microchips decreased. The effects of the additive loading and the pH on the EOF were investigated in detail. The bulk-modified PDMS microchips exhibited reproducible and stable EOF behavior. The application of the bulk-modified PDMS microchips was also studied and the results indicated that they could be successfully used to separate amino acids and to suppress protein adsorption.

  8. Amphiphilic block copolymer membrane for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

    2013-11-01

    An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

  9. Probing the interaction of amphiphilic triblockcopolymers with a biomimetic membrane.

    SciTech Connect

    Firestone, M. A.; Seifert, S.

    2002-02-04

    In the last several years, there has been growing interest in the use of synthetic surfactants to augment cellular repair. Amphiphilic triblock copolymers such as PEO-PPO-PEO have been demonstrated to aid in the repair of a variety of cells. In spite of the reported success of these compounds in clinical trials, the mechanism of their interaction with cell membranes remains poorly understood. In this work, they describe their efforts to examine the effect of the mode of incorporation of triblock polyalkyleneoxide copolymers on membrane structure and stability. For this work, they have employed a model biomembrane whose structure and physical properties have been previously determined. Several modes of polymer incorporation are examined: introduction via a membrane spanning triblock copolymer, grafting onto a phospholipid headgroup, or introduction via a partially inserted triblock copolymer. The polymer-membrane interactions are probed by small angle X-ray scattering and thermal analysis.

  10. Surfactant Behavior of Amphiphilic Polymer-Tethered Nanoparticles.

    PubMed

    Zhang, Yue; Zhao, Hanying

    2016-04-19

    In recent years, an emerging research area has been the surfactant behavior of polymer-tethered nanoparticles. In this feature article, we have provided a general introduction to the synthesis, self-assembly, and interfacial activity of polymer-tethered inorganic nanoparticles, polymer-tethered organic nanoparticles, and polymer-tethered natural nanoparticles. In addition, applications of the polymer-tethered nanoparticles in colloidal and materials science are briefly reviewed. All research demonstrates that amphiphilic polymer-tethered nanoparticles exhibit surfactant behavior and can be used as elemental building blocks for the fabrication of advanced structures by the self-assembly approach. The polymer-tethered nanoparticles provide new opportunities to engineer materials and biomaterials possessing specific functionality and physical properties.

  11. Electrostatically Tuned Self-Assembly of Branched Amphiphilic Peptides

    DOE PAGES

    Ting, Christina L.; Frischknecht, Amalie L.; Stevens, Mark J.; ...

    2014-06-19

    Electrostatics plays an important role in the self-assembly of amphiphilic peptides. To develop a molecular understanding of the role of the electrostatic interactions, we develop a coarse-grained model peptide and apply self-consistent field theory to investigate the peptide assembly into a variety of aggregate nanostructures. We find that the presence and distribution of charged groups on the hydrophilic branches of the peptide can modify the molecular configuration from extended to collapsed. This change in molecular configuration influences the packing into spherical micelles, cylindrical micelles (nanofibers), or planar bilayers. The effects of charge distribution therefore has important implications for the designmore » and utility of functional materials based on peptides.« less

  12. Rational Design of Pathogen-Mimicking Amphiphilic Materials as Nanoadjuvants

    NASA Astrophysics Data System (ADS)

    Ulery, Bret D.; Petersen, Latrisha K.; Phanse, Yashdeep; Kong, Chang Sun; Broderick, Scott R.; Kumar, Devender; Ramer-Tait, Amanda E.; Carrillo-Conde, Brenda; Rajan, Krishna; Wannemuehler, Michael J.; Bellaire, Bryan H.; Metzger, Dennis W.; Narasimhan, Balaji

    2011-12-01

    An opportunity exists today for cross-cutting research utilizing advances in materials science, immunology, microbial pathogenesis, and computational analysis to effectively design the next generation of adjuvants and vaccines. This study integrates these advances into a bottom-up approach for the molecular design of nanoadjuvants capable of mimicking the immune response induced by a natural infection but without the toxic side effects. Biodegradable amphiphilic polyanhydrides possess the unique ability to mimic pathogens and pathogen associated molecular patterns with respect to persisting within and activating immune cells, respectively. The molecular properties responsible for the pathogen-mimicking abilities of these materials have been identified. The value of using polyanhydride nanovaccines was demonstrated by the induction of long-lived protection against a lethal challenge of Yersinia pestis following a single administration ten months earlier. This approach has the tantalizing potential to catalyze the development of next generation vaccines against diseases caused by emerging and re-emerging pathogens.

  13. Amphiphilic properties of poly(oxyalkylene)amine-intercalated smectite aluminosilicates.

    PubMed

    Lin, Jiang-Jen; Chen, Yu-Min

    2004-05-11

    Layered aluminosilicates, including synthetic fluorine mica and natural montmorillonite (MMT), were intercalated with poly(oxypropylene)-polyamine quaternary salts with a 230-5000 molecular weight range. The X-ray basal spacing of these silicates had been expanded from 13.5 to 83.7 A for the synthetic mica and to 92.0 A for MMT. The relative silicate dimensions (300-1000 nm for synthetic mica and 80-100 nm for MMT) were ascertained by direct TEM observations in the case of the co-intercalated synthetic mica and MMT mixtures with Mw = 2000 quaternary ammonium salts. The tailored organic incorporation of synthetic mica and MMT clays could alter these hydrophilic clays, making them amphiphilic, and enable the lowering of toluene/water interfacial tension to 2.0 mN/m at the critical concentration of 0.1 wt %.

  14. [Study of novel artificial lung surfactants incorporating partially fluorinated amphiphiles].

    PubMed

    Nakahara, Hiromichi

    2012-01-01

    Lung surfactants (LS), a complex of ∼90 wt% lipids (mainly dipalmitoylphosphatidylcholine or DPPC) and ∼10 wt% surfactant proteins (SP-A, -B, -C, and -D), adsorb to an air-alveolar fluid interface and then lower its surface tension down to near zero during expiration. Intratracheal instillation of exogenous LS preparations can effectively compensate for surfactant deficiency in premature infants with respiratory distress syndrome (RDS). Surfacten® (Mitsubishi Tanabe Pharma Corporation, Osaka, Japan), a modified bovine lung extract and an effective surfactant replacement in treatment for RDS patients, is supplemented with DPPC, palmitic acid, and tripalmitin. For the premature infants suffering from RDS, instillation of Surfacten® leads to a dramatic improvement in lung function and compliance. Herein, the author reviews potential use of newly designed preparations containing a mimicking peptide of SP-B and also introduces the current research on the preparations incorporated with partially fluorinated amphiphiles to improve their efficacy.

  15. Electrostatically Tuned Self-Assembly of Branched Amphiphilic Peptides

    SciTech Connect

    Ting, Christina L.; Frischknecht, Amalie L.; Stevens, Mark J.; Spoerke, Erik D.

    2014-06-19

    Electrostatics plays an important role in the self-assembly of amphiphilic peptides. To develop a molecular understanding of the role of the electrostatic interactions, we develop a coarse-grained model peptide and apply self-consistent field theory to investigate the peptide assembly into a variety of aggregate nanostructures. We find that the presence and distribution of charged groups on the hydrophilic branches of the peptide can modify the molecular configuration from extended to collapsed. This change in molecular configuration influences the packing into spherical micelles, cylindrical micelles (nanofibers), or planar bilayers. The effects of charge distribution therefore has important implications for the design and utility of functional materials based on peptides.

  16. Antitumor Activity of Peptide Amphiphile Nanofiber-Encapsulated Camptothecin

    SciTech Connect

    Soukasene, Stephen; Toft, Daniel J.; Moyer, Tyson J.; Lu, Hsuming; Lee, Hyung-Kun; Standley, Stephany M.; Cryns, Vincent L.; Stupp, Samuel I.

    2012-04-02

    Self-assembling peptide amphiphile (PA) nanofibers were used to encapsulate camptothecin (CPT), a naturally occurring hydrophobic chemotherapy agent, using a solvent evaporation technique. Encapsulation by PA nanofibers was found to improve the aqueous solubility of the CPT molecule by more than 50-fold. PAs self-assembled into nanofibers in the presence of CPT as demonstrated by transmission electron microscopy. Small-angle X-ray scattering results suggest a slight increase in diameter of the nanofiber to accommodate the hydrophobic cargo. In vitro studies using human breast cancer cells show an enhancement in antitumor activity of the CPT when encapsulated by the PA nanofibers. In addition, using a mouse orthotopic model of human breast cancer, treatment with PA nanofiber-encapsulated CPT inhibited tumor growth. These results highlight the potential of this model PA system to be adapted for delivery of hydrophobic therapies to treat a variety of diseases including cancer.

  17. Fundamental behavior of a model biomolecular amphiphile system

    NASA Astrophysics Data System (ADS)

    Haverstick, Kraig Leonard

    An interest in the fundamental interactions between protein components, in the form of either single amino acids or peptides, unifies the work represented in this thesis. These fundamental interactions drive protein folding, enzyme-substrate binding, and cell adhesion to extracellular ligands. The technology of lipidation was used to isolate these protein interactions. Lipidation of a water-soluble amino acid or peptide sequence confined the protein component to the air-water interface or to a self-assembled structure in water. Compression of the molecules at the air-water interface ordered them into a solid-like monolayer, and Langmuir-Blodgett deposition produced a surface modification with protein component presented in a controlled, orderly manner. These molecules have potential applications as biomaterials coatings or drug delivery devices. A method for determination of specific hydrogen bonding interactions through cocrystallization of two complementary peptide sequences is also described. In order to understand the effect of lipidation and lipid structure on peptide behavior, a comprehensive study of tail designs was first undertaken. Tail length, linkage group, linker, spacer length, and headgroup chirality, orientation, and terminal group were systematically varied in simple amino acid amphiphiles. Monolayer assembly, thermal stability, and structure were studied with Langmuir isotherms and Fourier transform infrared spectroscopy. Each part of the tail structure was found to affect monolayer behavior. With lipid effects better understood, peptide amphiphiles were designed, synthesized, and studied using peptide sequences of importance for cell adhesion. The sequences [IV-H1] from type IV collagen and Arg-Gly-Asp (RGD) were lipidated and characterized in monolayers by Langmuir isotherms and Fourier transform infrared spectroscopy. Biological functionality was determined by melanoma cell spreading assays. Peptide presentation was found to be critical for

  18. Amphiphilic Tobramycin Analogues as Antibacterial and Antifungal Agents

    PubMed Central

    Shrestha, Sanjib K.; Fosso, Marina Y.; Green, Keith D.

    2015-01-01

    In this study, we investigated the in vitro antifungal activities, cytotoxicities, and membrane-disruptive actions of amphiphilic tobramycin (TOB) analogues. The antifungal activities were established by determination of MIC values and in time-kill studies. Cytotoxicity was evaluated in mammalian cell lines. The fungal membrane-disruptive action of these analogues was studied by using the membrane-impermeable dye propidium iodide. TOB analogues bearing a linear alkyl chain at their 6″-position in a thioether linkage exhibited chain length-dependent antifungal activities. Analogues with C12 and C14 chains showed promising antifungal activities against tested fungal strains, with MIC values ranging from 1.95 to 62.5 mg/liter and 1.95 to 7.8 mg/liter, respectively. However, C4, C6, and C8 TOB analogues and TOB itself exhibited little to no antifungal activity. Fifty percent inhibitory concentrations (IC50s) for the most potent TOB analogues (C12 and C14) against A549 and Beas 2B cells were 4- to 64-fold and 32- to 64-fold higher, respectively, than their antifungal MIC values against various fungi. Unlike conventional aminoglycoside antibiotics, TOB analogues with alkyl chain lengths of C12 and C14 appear to inhibit fungi by inducing apoptosis and disrupting the fungal membrane as a novel mechanism of action. Amphiphilic TOB analogues showed broad-spectrum antifungal activities with minimal mammalian cell cytotoxicity. This study provides novel lead compounds for the development of antifungal drugs. PMID:26033722

  19. Tailoring peptide amphiphiles and their assemblies for biomedical applications

    NASA Astrophysics Data System (ADS)

    Lin, Brian

    Peptide amphiphiles (PAs) are molecules composed of a peptide conjugated to a hydrophobic moiety, commonly a fatty acid. They closely resemble the structure of naturally occurring lipopeptides, produced by microbes as signaling and antimicrobial agents. The amphiphilic nature of PAs in concert with the large number of discovered functional peptides inspired scientists to exploit this molecular architecture for producing synthetic self-assembled bioactive materials. PA assemblies are sought after for a wide breadth of applications including disease therapy, regenerative medicine, and catalysis. However, with PAs, the peptide chemistry is a double-edged sword. The peptide component contributes significantly to both the activity and self-assembly. The physiochemical properties of different PAs lead to unique aggregation stability and morphological characteristics which are unpredictable, a priori. Therefore it is challenging to design bioactive PAs and control their self-assembly, simultaneously. This limitation slows the development of PAs for medical use. In this dissertation, methods to control the self-assembly of PAs and the effects of acylating a functional peptide will be discussed. In one part, efforts to direct the self-assembly of PAs into small spherical aggregates, a morphology infrequently observed, will be described. In another section, a strategy to control the stability of PA assemblies will be discussed. In the last section, a pH-responsive membrane perturbing peptide was modified with fatty acid tails and the properties of the resulting PAs will be presented. This dissertation provides some fundamental insight for the use and design of PA self-assemblies.

  20. Aminoglycoside-derived amphiphilic nanoparticles for molecular delivery.

    PubMed

    Miryala, Bhavani; Godeshala, Sudhakar; Grandhi, Taraka Sai Pavan; Christensen, Matthew D; Tian, Yanqing; Rege, Kaushal

    2016-10-01

    The development of effective drug carriers can lead to improved outcomes in a variety of disease conditions. Aminoglycosides have been used as antibacterial therapeutics, and are attractive as monomers for the development of polymeric materials in various applications. Here, we describe the development of novel aminoglycoside-derived amphiphilic nanoparticles for drug delivery, with an eye towards ablation of cancer cells. The aminoglycoside paromomycin was first cross-linked with resorcinol diglycidyl ether leading to the formation of a poly (amino ether), PAE. PAE molecules were further derivatized with methoxy-terminated poly(ethylene glycol) or mPEG resulting in the formation of mPEG-PAE polymer, which self-assembled to form nanoparticles. Formation of the mPEG-PAE amphiphile was characterized using (1)H NMR, (13)C NMR, gel permeation chromatography (GPC) and FTIR spectroscopy. Self-assembly of the polymer into nanoparticles was characterized using dynamic light scattering, zeta potential analyses, atomic force microscopy (AFM) and the pyrene fluorescence assay. mPEG-PAE nanoparticles were able to carry significant amounts of doxorubicin (DOX), presumably by means of hydrophobic interactions between the drug and the core. Cell-based studies indicated that mPEG-PAE nanoparticles, loaded with doxorubicin, were able to induce significant loss in viabilities of PC3 human prostate cancer, MDA-MB-231 human breast cancer, and MB49 murine bladder cancer cells; empty nanoparticles resulted in negligible losses of cell viability under the conditions investigated. Taken together, our results indicate that the mPEG-PAE nanoparticle platform is attractive for drug delivery in different applications, including cancer.

  1. Self-assembling peptide amphiphiles and related methods for growth factor delivery

    DOEpatents

    Stupp, Samuel I.; Donners, Jack J. J. M.; Silva, Gabriel A.; Behanna, Heather A.; Anthony, Shawn G.

    2009-06-09

    Amphiphilic peptide compounds comprising one or more epitope sequences for binding interaction with one or more corresponding growth factors, micellar assemblies of such compounds and related methods of use.

  2. Self-assembling peptide amphiphiles and related methods for growth factor delivery

    DOEpatents

    Stupp, Samuel I [Chicago, IL; Donners, Jack J. J. M.; Silva, Gabriel A [Chicago, IL; Behanna, Heather A [Chicago, IL; Anthony, Shawn G [New Stanton, PA

    2012-03-20

    Amphiphilic peptide compounds comprising one or more epitope sequences for binding interaction with one or more corresponding growth factors, micellar assemblies of such compounds and related methods of use.

  3. Self-Assembly and Headgroup Effect in Nanostructured Organogels via Cationic Amphiphile-Graphene Oxide Composites

    PubMed Central

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Yan, Xuehai; Zhao, Xiaoqing; Zhou, Jingxin; Gao, Faming

    2014-01-01

    Self-assembly of hierarchical graphene oxide (GO)-based nanomaterials with novel functions has received a great deal of attentions. In this study, nanostructured organogels based on cationic amphiphile-GO composites were prepared. The gelation behaviors of amphiphile-GO composites in organic solvents can be regulated by changing the headgroups of amphiphiles. Ammonium substituted headgroup in molecular structures in present self-assembled composites is more favorable for the gelation in comparison to pyridinium headgroup. A possible mechanism for headgroup effects on self-assembly and as-prepared nanostructures is proposed. It is believed that the present amphiphile-GO self-assembled system will provide an alternative platform for the design of new GO nanomaterials and soft matters. PMID:24983466

  4. Grafting amphiphilic brushes onto halloysite nanotubes via a living RAFT polymerization and their Pickering emulsification behavior.

    PubMed

    Hou, Yifan; Jiang, Junqing; Li, Kai; Zhang, Yanwu; Liu, Jindun

    2014-02-20

    Amphiphilic brushes of poly(4-vinylpyridine)-block-polystyrene (P4VP-b-PS) and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) are grafted onto halloysite nanotubes (HNTs) via a surface reversible addition-fragmentation chain transfer (RAFT) living polymerization through anchoring R group in RAFT agent S-1-dodecyl-S'-(R,R'-dimethyl-R″-acetic acid) trithiocarbonates (DDMAT). The characterization of TGA, TEM, and GPC show that amphiphilic brushes are successfully grafted onto HNTs in a living manner. To verify the amphiphilicity of HNTs grafted with block copolymers, their Pickering emulsification behavior in water/soybean oil diphase mixture is studied. The results show that modified HNTs can emulsify water/soybean oil diphase mixture and the emulsification performance is dependent on microstructure of amphiphilic brushes such as hydrophilic/hydrophobic segment size and sequence.

  5. Self-assembling peptide amphiphiles and related methods for growth factor delivery

    DOEpatents

    Stupp, Samuel I; Donners, Jack J.J.M.; Silva, Gabriel A; Behanna, Heather A; Anthony, Shawn G

    2013-11-12

    Amphiphilic peptide compounds comprising one or more epitope sequences for binding interaction with one or more corresponding growth factors, micellar assemblies of such compounds and related methods of use.

  6. Superior SWNT dispersion by amino acid based amphiphiles: designing biocompatible cationic nanohybrids.

    PubMed

    Brahmachari, Sayanti; Das, Dibyendu; Das, Prasanta Kumar

    2010-11-28

    Stable aqueous SWNT dispersion up to 92% was achieved using amino acid based amphiphiles through a structure-property investigation. The nanohybrids showed remarkable serum stability and biocompatibility to mammalian cells.

  7. Branched peptide amphiphiles, related epitope compounds and self assembled structures thereof

    DOEpatents

    Stupp, Samuel I.; Guler, Mustafa O.

    2008-11-18

    Branched peptide amphiphilic compounds incorporating one or residues providing a pendant amino group for coupling one or more epitope sequences thereto, such compounds and related compositions for enhanced epitope presentation.

  8. The use of 4-substituted pyridines to afford amphiphilic, pegylated cadmium selenide nanoparticles.

    PubMed

    Skaff, Habib; Emrick, Todd

    2003-01-07

    Amphiphilic cadmium selenide (CdSe) nanoparticles were prepared by surface functionalization with novel ligands 1 and 2, composed of pyridine moieties substituted in the 4-position with polyethylene glycol (PEG) chains.

  9. Tunable catalysts for solvent-free biphasic systems: pickering interfacial catalysts over amphiphilic silica nanoparticles.

    PubMed

    Zhou, Wen-Juan; Fang, Lin; Fan, Zhaoyu; Albela, Belén; Bonneviot, Laurent; De Campo, Floryan; Pera-Titus, Marc; Clacens, Jean-Marc

    2014-04-02

    Stabilization of oil/oil Pickering emulsions using robust and recyclable catalytic amphiphilic silica nanoparticles bearing alkyl and propylsulfonic acid groups allows fast and efficient solvent-free acetalization of immiscible long-chain fatty aldehydes with ethylene glycol.

  10. Self-Assembly of Peptide Amphiphiles: From Molecules to Nanostructures to Biomaterials

    PubMed Central

    Cui, Honggang; Webber, Matthew J.

    2010-01-01

    Peptide amphiphiles are a class of molecules that combine the structural features of amphiphilic surfactants with the functions of bioactive peptides and are known to assemble into a variety of nanostructures. A specific type of peptide amphiphiles are known to self-assemble into one-dimensional (1D) nanostructures under physiological conditions, predominantly nanofibers with a cylindrical geometry. The resultant nanostructures could be highly bioactive and are of great interest in many biomedical applications, including tissue engineering, regenerative medicine and drug delivery. In this context, we highlight our strategies for using molecular self-assembly as a toolbox to produce peptide amphiphile nanostructures and materials and efforts to translate this technology into applications as therapeutics. We also review our recent progress in using these materials for treating spinal cord injury, inducing angiogenesis, and for hard tissue regeneration and replacement. PMID:20091874

  11. Ru(II) Tris(3,8-Dibromo-1,10-Phenanthro1ine): A New Versatile Core for the Divergent Synthesis of Hyperbranched Systems

    NASA Technical Reports Server (NTRS)

    Sotiriou-Leventis, Chariklia; Yang, Jinhua; Duan, Penggao; Leventis, Nicholas

    2004-01-01

    We report the first synthesis of Ru(II) tris(3,8-dibromo-1,lO-phenanthroline) bishexafluorophosphate, and we demonstrate its utility as a building core for the divergent synthesis of hyperbranched systems by coupling with phenylacetylene in the preparation of Rum tris(3,8-diphenylethynyl- 1,lO-phenanthroline) dihexafluorophosphate.

  12. Self-Controlled Synthesis of Hyperbranched Poly(etherketone)s from A2 + B3 Approach in Poly(phosphoric acid)

    DTIC Science & Technology

    2009-01-01

    polymerization condition was indeed strong enough to effi- ciently facilitate polycondensation via ‘‘direct’’ Friedel - Crafts reaction without gelation...Keywords: Friedel - Crafts acylation; high performance polymer; hyperbranched polymer; poly(ether-ketone)s; poly(phosphoric acid) INTRODUCTION Dendritic...Hence, the applied polymerization condition was indeed strong enough to efficiently facilitate polycondensation via ??direct?? Friedel - Crafts reaction

  13. Amphiphilic organoplatinum(II) complexes: Self-assembly in solution and at interfaces

    NASA Astrophysics Data System (ADS)

    Maran, Umamageswaran

    Organoplatinum(II) gemini amphiphiles with three different chain lengths and a predefined angle of 60° are synthesized. Self-organization at the air-water interface is investigated as a function of chain length and reduction in surface area, by using Langmuir-trough techniques. The atomic force microscopy (AFM) images of the transferred Langmuir-Schaefer (LS) films reveals wormlike aggregates for the organoplatinum(II) gemini amphiphiles, possessing hexyloxy- and dodecyloxy-chains. A neutral crown ether functionalized [1+1] facial amphiphile was self-assembled from a flexible 32-membered dibenzo crown ether and a diplatinum acceptor clip. A homologous series of charged triangle-shaped amphiphilic metallomacrocyles was self-assembled from stoichiometric amounts of organoplatinum(II) gemini amphiphiles and bipyridyl donor molecules in quantitative yields. The amphiphilic triangular scaffolds were characterized by multinuclear NMR and ESI-MS. A new amphiphilic organoplatinum(II) precursor with a predefined angle of 90° was synthesized. The precursor was mixed in stoichiometric ratios with two different 3-substituted pyridines and a rigid bipyridyl ligand to construct three charged amphiphilic metallomacrocyles. The computational calculations on the assemblies constructed from flexible 3-substituted pyridines indicate that the assemblies exist largely as chair isomers. The self-organization of the hexacationic triangular amphiphiles at liquid-liquid, air-water and solid-air interfaces was studied using confocal microscopy, in situ Raman spectroscopy, Langmuir-trough techniques, fluorescence spectroscopy and AFM. The amphiphilic triangle with octadecyloxy-chains was found to form a bicontinuous coacervate with pores in a chloroform/water solvent mixture. The pressure-area isotherms revealed formation of surface aggregates at the air-water interface. Fluid AFM studies on the transferred LS layers reveal ridge-like patterns with a flat top. Models were constructed to

  14. Temperature and concentration dependence of SANS spectra of aqueous solutions of short-chain amphiphiles

    NASA Astrophysics Data System (ADS)

    D'Arrigo, G.; Giordano, R.; Teixeira, J.

    2009-05-01

    The small-angle neutron scattering (SANS) of some aqueous solutions of short-chain amphiphiles (glycols, diglycols, diols) has been measured as a function of concentration and temperature. The analysis of the spectra in terms of the Teubner-Strey phenomelogical formula indicates that, on increasing the concentration of the amphiphile, the structure of all these systems evolves in a similar way, i.e. a transition from disordered structures toward correlated aggregates (microstructures). The transition is depressed by increasing the temperature.

  15. Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes

    PubMed Central

    Song, Jibin; Huang, Peng; Chen, Xiaoyuan

    2016-01-01

    Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a ‘grafting to’ method or mixed hydrophilic and hydrophobic polymer brushes using tandem ‘grafting to’ and ‘grafting from’ methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ~3 d. PMID:27763624

  16. Solvent-free, molecular-level modeling of self-assembling amphiphiles in water

    NASA Astrophysics Data System (ADS)

    Dey, Somajit; Saha, Jayashree

    2017-02-01

    Aggregation mesophases of self-assembling amphiphiles in water are highly important in the context of biology (biomembranes), therapy (liposomes), industry (polymer surfactants), and condensed-matter physics (lyotropic liquid crystals). Besides helping to increase fundamental understanding of collective molecular behavior, simulations of these lyotropic phases are pivotal to technological and medical developments such as smart drug carriers for gene therapy. Implicit-solvent, coarse-grained, low resolution modeling with a simple pair potential is the key to realizing the larger length and time scales associated with such mesoscopic phenomena during a computer simulation. Modeling amphiphiles by directed, soft, ellipsoidal cores interacting via a computationally simple yet tunable anisotropic pair potential, we have come to such a single-site model amphiphile that can rapidly self-assemble to give diverse lyotropic phases (such as fluid bilayers, micelles, etc.) without requiring the explicit incorporation of solvent particles. The model directly represents a tunable packing parameter that manifests in the spontaneous curvature of the amphiphile aggregates. Besides the all-important hydrophobic interaction, the hydration force is also treated implicitly. Thanks to the efficient solvent-free molecular-level coarse graining, this model is suitable for generic mesoscale studies of phenomena such as self-assembly, amphiphile mixing, domain formation, fusion, elasticity, etc., in amphiphile aggregates.

  17. Antimicrobial hyperbranched poly(ester amide)/polyaniline nanofiber modified montmorillonite nanocomposites.

    PubMed

    Pramanik, Sujata; Bharali, Pranjal; Konwar, B K; Karak, Niranjan

    2014-02-01

    There has been growing interest in the use of nanomaterials featuring potent of antimicrobial activity in the biomedical domain. It still remains a challenge for the researchers to develop an efficient nanocomposite possessing antimicrobial efficacy against broad spectrum microbes including bacteria, fungi as well as algal consortium, posing serious challenges for the human survival. In addressing the above problem, we report the fabrication of bio-based hyperbranched poly(ester amide) (HBPEA)/polyaniline nanofiber modified montmorillonite (MMT) nanocomposites by an ex-situ polymerization technique at varied weight percentages (1, 2.5, 5 wt.%) of the modified MMT (nanohybrid). The Fourier transform infrared spectroscopy confirmed the structural changes upon interaction of the nanohybrid with HBPEA. A probable mechanism is proposed for the formation of nanocomposites with partially exfoliated nanoplatelet structure, which was further confirmed from the high resolution transmission electron microscopic analyses. The prepared nanocomposites exhibited potent efficacy against gram positive bacteria like Bacillus subtilis and Staphylococcus aureus as compared to the gram negative ones like Pseudomonas aeruginosa and Escherichia coli. The nanocomposites showed significant antifungal activity against Aspergillus niger, Fusarium oxysporum and Coleotricum capcii and antialgal activity against algal consortium comprising of Chlorella, Hormidium and Cladophorella species. The formation of thermosetting nanocomposites resulted in the acceptable improvement of desired physico-chemical and mechanical properties including thermostability. Thus pronounced antimicrobial activity of the nanocomposites against a spectrum of bacterial and fungal strains as well as a consortium of algal species along with other desired performance vouched them as potent antimicrobial materials in the realm of health and biomedical industry.

  18. Self-adapting peripherally heterofunctionalized hyperbranched polymers: formation of Janus and tripodal structures.

    PubMed

    Samuel, Ashok Zachariah; Ramakrishnan, S

    2013-01-29

    A peripherally clickable hyperbranched polyester carrying numerous propargyl terminal groups was prepared by a simple melt transesterification polycondensation of a suitably designed AB(2) monomer; this clickable hyperscaffold was then transformed into a variety of different derivatives by using the Cu-catalyzed azide-yne click reaction. Functionalization of the periphery with equimolar quantities of mutually immiscible segments, such as hydrocarbon, fluorocarbon, and PEG, yielded frustrated molecular systems that readapt and form structures wherein the immiscible segments appear to self-segregate to generate either Janus structures (when two immiscible segments are present) or tripodal structures (when three immiscible segments are present). Evidence for such self-segregation was obtained from a variety of studies, such as differential scanning calorimetry, Langmuir isotherms, AFM imaging, and small-angle X-ray scattering measurements. Crystallization of one or more of the peripheral segments reinforced this self-segregation; the weight-fraction-normalized enthalpies of melting associated with the different domains revealed a competition between the segments to optimize their crystalline organization. When one or more of the segments are amorphous, the remaining segments crystallize more effectively and consequently exhibit a higher melting enthalpy. AFM images of monolayers, transferred from the Langmuir trough, revealed that the thickness matches the expected values; furthermore, contact angle measurements clearly demonstrated that the monolayer films are fairly hydrophobic, and in the case of the tripodal hybramers, the presence of domains of hydrocarbon and fluorocarbon appears to impart nanoscale chemical heterogeneity that is reflected in the strong hysteresis in the advancing and receding contact angles.

  19. Novel Low-Density Ablators Containing Hyperbranched Poly(azomethine)s

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean

    2011-01-01

    An ablative composite is low-density (0.25 to 0.40 g/cu cm), easy to fabricate, and superior to the current state-of-the-art ablator (phenolic impregnated carbon ablator, PICA) in terms of decomposition temperature, char yield, and mechanical strength. Initial ablative testing with a CO2 laser under high-heat-flux (1,100 W/sq cm) conditions showed these new ablators are over twice as effective as PICA in terms of weight loss, as well as transfer of heat through the specimen. The carbon fiber/poly(azomethine) composites have the same density as PICA, but are 8 to 11 times stronger to irreversible breaking by tensile compression. In addition, polyazomethine char yields by thermogravimetric analysis are 70 to 80 percent at 1,000 C. This char yield is 10 to 20 percent higher than phenolic resins, as well as one of the highest char yields known for any polymer. A high char yield holds the composite together better toward shearing forces on reentry, as well as reradiates high heat fluxes. This innovative composite is stronger than PICA, so multiple pieces can be sealed together without fracture. Researchers have also studied polyazomethines before as linear polymers. Due to poor solubility, these polymers precipitate from the polymerization solvent as a low-molecular-weight (2 to 4 repeat units) powder. The only way found to date to keep linear polyazomethines in solution is by adding solubilizing side groups. However, these groups sacrifice certain polymer properties. These hyperbranched polyazomethines are high molecular weight and fully aromatic.

  20. Grafting the surface of carbon nanotubes and carbon black with the chemical properties of hyperbranched polyamines

    PubMed Central

    Morales-Lara, Francisco; Domingo-García, María; López-Garzón, Rafael; Luz Godino-Salido, María; Peñas-Sanjuán, Antonio; López-Garzón, F. Javier; Pérez-Mendoza, Manuel; Melguizo, Manuel

    2016-01-01

    Abstract Controlling the chemistry on the surface of new carbon materials is a key factor to widen the range of their applicability. In this paper we show a grafting methodology of polyalkylamines to the surface of carbon nanomaterials, in particular, carbon nanotubes and a carbon black. The aim of this work is to reach large degrees of covalent functionalization with hyperbranched polyethyleneimines (HBPEIs) and to efficiently preserve the strong chelating properties of the HBPEIs when they are fixed to the surface of these carbon materials. This functionalization opens new possibilities of using these carbon nanotubes-based hybrids. The results show that the HBPEIs are covalently attached to the carbon materials, forming hybrids. These hybrids emerge from the reaction of amine functions of the HBPEIs with carbonyls and carboxylic anhydrides of the carbon surface which become imine and imide bonds. Thus, due to the nature of these bonds, the pre-oxidized samples with relevant number of C=O groups showed an increase in the degree of functionalization with the HBPEIs. Furthermore, both the acid-base properties and the coordination capacity for metal ions of the hybrids are equivalent to that of the free HBPEIs in solution. This means that the chemical characteristics of the HBPEIs have been efficiently transferred to the hybrids. To reach this conclusion we have developed a novel procedure to assess the acid-base and the coordination properties of the hybrids (solids) by means of potentiometric titration. The good agreement of the values obtained for the hybrids and for the free HBPEIs in aqueous solution supports the reliability of the procedure. Moreover, the high capacity of the hybrids to capture Ni2+ by complexation opens new possibilities of using these hybrids to capture high-value metal ions such as Pd2+ and Pt2+. PMID:27877902

  1. Nano-Bio Engineered Carbon Dot-Peptide Functionalized Water Dispersible Hyperbranched Polyurethane for Bone Tissue Regeneration.

    PubMed

    Gogoi, Satyabrat; Maji, Somnath; Mishra, Debasish; Devi, K Sanjana P; Maiti, Tapas Kumar; Karak, Niranjan

    2017-03-01

    The present study delves into a combined bio-nano-macromolecular approach for bone tissue engineering. This approach relies on the properties of an ideal scaffold material imbued with all the chemical premises required for fostering cellular growth and differentiation. A tannic acid based water dispersible hyperbranched polyurethane is fabricated with bio-nanohybrids of carbon dot and four different peptides (viz. SVVYGLR, PRGDSGYRGDS, IPP, and CGGKVGKACCVPTKLSPISVLYK) to impart target specific in vivo bone healing ability. This polymeric bio-nanocomposite is blended with 10 wt% of gelatin and examined as a non-invasive delivery vehicle. In vitro assessment of the developed polymeric system reveals good osteoblast adhesion, proliferation, and differentiation. Aided by this panel of peptides, the polymeric bio-nanocomposite exhibits in vivo ectopic bone formation ability. The study on in vivo mineralization and vascularization reveals the occurrence of calcification and blood vessel formation. Thus, the study demonstrates carbon dot/peptide functionalized hyperbranched polyurethane gel for bone tissue engineering application.

  2. Self-assembly of amphiphilic molecules in organic liquids

    NASA Astrophysics Data System (ADS)

    Tung, Shih-Huang

    2007-12-01

    Amphiphilic molecules are well-known for their ability to self-assemble in water to form structures such as micelles and vesicles. In comparison, much less is known about amphiphilic self-assembly in nonpolar organic liquids. Such "reverse" self assembly can produce many of the counterparts to structures found in water. In this dissertation, we focus on the formation and dynamics of such reverse structures. We seek to obtain fundamental insight into the driving forces for reverse self-assembly processes. Three specific types of reverse structures are studied: (a) reverse wormlike micelles, i.e., long, flexible micellar chains; (b) reverse vesicles, i.e., hollow containers enclosed by reverse bilayers; and (c) organogel networks. While our focus is on the fundamentals, we note that reverse structures can be useful in a variety of applications ranging from drug delivery, controlled release, hosts for enzymatic reactions, and templates for nanomaterials synthesis. In the first part of this study, we describe a new route for forming reverse wormlike micelles in nonpolar organic liquids. This route involves the addition of trace amounts of a bile salt to solutions of the phospholipid, lecithin. We show that bile salts, due to their unique "facially amphiphilic" structure, can promote the aggregation of lecithin molecules into these reverse micellar chains. The resulting samples are viscoelastic and show interesting rheological properties. Unusual trends are seen in the temperature dependence of their rheology, which indicates the importance of hydrogen-bonding interactions in the formation of these micelles. Another remarkable feature of their rheology is the presence of strain-stiffening, where the material becomes stiffer at high deformations. Strain-stiffening has been seen before for elastic gels of biopolymers; here, we demonstrate the same properties for viscoelastic micellar solutions. The second reverse aggregate we deal with is the reverse vesicle. We present a

  3. Membrane deformation controlled by monolayer composition of embedded amphiphilic nanoparticles

    NASA Astrophysics Data System (ADS)

    van Lehn, Reid; Alexander-Katz, Alfredo

    2014-03-01

    In recent work, we have shown that charged, amphiphilic nanoparticles (NPs) can spontaneously insert into lipid bilayers, embedding the NP in a conformation resembling a transmembrane protein. Many embedded membrane proteins exert an influence on surrounding lipids that lead to deformation and membrane-mediated interactions that may be essential for function. Similarly, embedded NPs will also induce membrane deformations related to the same physicochemical forces. Unlike many transmembrane proteins, however, the highly charged NPs may exert preferential interactions on surrounding lipid head groups. In this work, we use atomistic molecular dynamics simulations to show that the membrane around embedded particles may experience local thinning, head group reorientation, and an increase in lipid density depending on the size and surface composition of the NP. We quantify the extent of these deformations and illustrate the complex interplay between lipid tail group and head group interactions that go beyond pure thickness deformations that may be expected from coarse-grained or continuum models. This work thus suggests guidelines for the design of particles that spontaneously partition into lipid bilayers and influence local membrane mechanical properties in a targeted manner.

  4. Electrophoretic coating of amphiphilic chitosan colloids on regulating cellular behaviour

    PubMed Central

    Wang, Yen-Jen; Lo, Teng-Yuan; Wu, Chieh-Hsi; Liu, Dean-Mo

    2013-01-01

    In this communication, we report a facile nanotopographical control over a stainless steel surface via an electrophoretic deposition of colloidal amphiphilic chitosan for preferential growth, proliferation or migration of vascular smooth muscle cells (VSMCs) and human umbilical vein endothelial cells (HUVECs). Atomic force microscopy revealed that the colloidal surface exhibited a deposition time-dependent nanotopographical evolution, wherein two different nanotopographic textures indexed by ‘kurtosis’ (Rkur) value were easily designed, which were termed as ‘sharp’ (i.e. high peak-to-valley texture) surface and ‘flat’ (i.e. low peak-to-valley texture) surface. Cellular behaviour of VSMCs and HUVECs on both surfaces demonstrated topographically dependent morphogenesis, adherent responses and biochemical properties in comparison with bare stainless steel. The formation of a biofunctionalized surface upon a facile colloidal chitosan deposition envisions the potential application towards numerous biomedical devices, and this is especially promising for cardiovascular stents wherein a new surface with optimized texture can be designed and is expected to create an advantageous environment to stimulate HUVEC growth for improved healing performance. PMID:23804439

  5. Extending the Hydrophobic Mismatch Concept to Amphiphilic Membranolytic Peptides.

    PubMed

    Grau-Campistany, Ariadna; Strandberg, Erik; Wadhwani, Parvesh; Rabanal, Francesc; Ulrich, Anne S

    2016-04-07

    A series of nine amphiphilic, pore-forming α-helical KIA peptides (KIAGKIA repeats) with lengths between 14 and 28 residues were studied by solid-state (15)N NMR to determine their alignment in oriented lipid bilayers. In a 2:1 mixture of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) with its corresponding 1-myristoyl-2-hydroxy-sn-glycero-3-phosphocholine (lyso-MPC), which has a highly positive spontaneous curvature, the helix tilt angle was found to vary steadily with peptide length. The shortest peptide was aligned transmembrane and upright, while the longer ones successively became tilted away from the membrane normal. This behavior is in agreement with the hydrophobic matching concept, conceived so far only for hydrophobic helices. In 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine, with a negative spontaneous curvature, all KIA peptides remained flat on the bilayer surface, while the cylindrical DMPC lipids permitted a slight tilt. Peptide insertion thus depends critically on the intrinsic lipid curvature, and helix orientation is then fine-tuned by membrane thickness. A refined toroidal pore model is proposed.

  6. Self-assembly of model amphiphilic Janus particles.

    PubMed

    Rosenthal, Gerald; Gubbins, Keith E; Klapp, Sabine H L

    2012-05-07

    We apply molecular dynamics simulations to investigate the structure formation of amphiphilic Janus particles in the bulk phase. The Janus particles are modeled as (soft) spheres composed of a hydrophilic and hydrophobic part. Their orientation is described by a vector representing an internal degree of freedom. Investigating energy fluctuations and cluster size distributions, we determine the aggregation line in a temperature-density-diagram, where the reduced temperature is an inverse measure for the anisotropic coupling. Below this aggregation line clusters of various sizes depending on density and reduced temperature are found. For low densities in the range ρ∗ ≤ 0.3, the cluster size distribution has a broad maximum, indicating simultaneous existence of various cluster sizes between 5 and 10. We find no hint of a condensation transition of these clustered systems. In the case of higher densities (ρ∗ = 0.5 and 0.6), the cluster size distribution shows an extremely narrow peak at clusters of size 13. In these icosahedrons, the particles are arranged in a closed-packed manner, thereby maximizing the number of bonds. Analyzing the translational mean-square displacement we also observe indications of hindered diffusion due to aggregation.

  7. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles

    PubMed Central

    Kim, Dae-Yoon; Lee, Sang-A; Jung, Daseal; Jeong, Kwang-Un

    2016-01-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials. PMID:27339163

  8. Cationic Amphiphilic Drugs Are Potent Inhibitors of Yeast Sporulation

    PubMed Central

    Schlecht, Ulrich; St. Onge, Robert P.; Walther, Thomas; François, Jean-Marie; Davis, Ronald W.

    2012-01-01

    Meiosis is a highly regulated developmental process that occurs in all eukaryotes that engage in sexual reproduction. Previous epidemiological work shows that male and female infertility is rising and environmental factors, including pollutants such as organic solvents, are thought to play a role in this phenomenon. To better understand how organic compounds interfere with meiotic development, the model organism Saccharomyces cerevisiae was exposed to 446 bioactive molecules while undergoing meiotic development, and sporulation efficiency was quantified employing two different high-throughput assays. 12 chemicals were identified that strongly inhibited spore formation but did not interfere with vegetative growth. Many of these chemicals are known to bind to monoamine-receptors in higher eukaryotes and are cationic amphiphilic drugs. A detailed analysis of one of these drugs, tripelennamine, revealed that it induces sporulation-specific cytotoxicity and a strong inhibition of meiotic M phase. The drug, however, only mildly interfered with pre-meiotic DNA synthesis and the early meiotic transcriptional program. Chemical-genomic screening identified genes involved in autophagy as hypersensitive to tripelennamine. In addition, we found that growing and sporulating yeast cells heterozygous for the aminophospholipid translocase, NEO1, are haploinsufficient in the presence of the drug. PMID:22905177

  9. Amphiphilic Zwitterionic Coatings for Marine Anti-Biofouling Applications

    NASA Astrophysics Data System (ADS)

    Walker, Edwin, Jr.; Pandiyarajan, C. K.; Efimenko, Kirill; Genzer, Jan

    Marine biofouling is a problem plaguing the surfaces of cargo ships, military ships and submarines. Previous approaches have relied primarily on the use of Cu-based coatings, which have deleterious effects on aquatic life. Recently, the vast majority of research efforts have focused on the use of polymer brushes synthesized by controlled radical polymerization to create either, the commonly used PEG/PEO materials, amphiphilic alternatives or promising zwitterionic-based moieties. Our approach is based on copolymerizing N, N -2-dimethylaminoethyl methacrylate (DMAEMA) and propargyl methacrylate (PgMA) in different molar ratios (typically, 1:1 and 3:1) using AIBN-based free radical initiator. The copolymers are then betainized with 1, 3- propane sultone to obtain zwitterionic macromolecules. We create substrate-anchored hydrogels by casting the copolymers as films onto polystyrene-based substrates and crosslink them using a photo-active reagent benzophenone. We investigate the cross-linking reaction with IR, the thickness and swelling as a function of ionic strength and electrolyte using spectroscopic ellipsometry and the wettability using water contact angle. We study the resistance of the coatings towards non-specific protein adsorption using fibrinogen and BSA.

  10. Amphiphilic organic ion pairs in solution: a theoretical study.

    PubMed

    Pradines, Vincent; Poteau, Romuald; Pimienta, Veronique

    2007-07-16

    The macroscopic manifestation of hydrophobic interactions for amphiphilic organic ion pairs (tetraalkylammonium-anion) has been shown experimentally by measuring their association constants and their affinity with the organic phase. Beyond a certain size, there is a direct relation between association constants and chain lengths in tetraalkylammonium ions. We propose to cast a bridge between these results and geometrical properties considered at the level of a single ion pair by means of quantum chemistry calculations performed on model systems: trimethylalkylammonium-pentyl sulfate instead of tetraalkylammonium-dodecyl sulfate. Two limiting cases are considered: head-to-head configurations, which yield an optimal electrostatic interaction between polar heads, and parallel configurations with a balance between electrostatic and hydrophobic interactions. All properties (geometries, complexation energies, and atomic charges) were obtained at the MP2 level of calculation, with water described by a continuum model (CPCM). Dispersion forces link hydrocarbon chains of tetraalkylammonium ions and pentyl sulfate, thus yielding (for the largest ion pairs) parallel configurations favored with respect to head-to-head geometries by solute-solvent electrostatic interactions. Given the small experimental association energies, we probe the accuracy limit of the MP2 and CPCM methods. However, clear trends are obtained as a function of chain length, which agree with the experimental observations. The calculated monotonic stabilization of ion pairs when the hydrocarbon chain increases in length is discussed in terms of electrostatic interactions (between ions and between ion pairs and water), dispersion forces, and cavitation energies.

  11. Synthesis and Bioactivities of Kanamycin B-Derived Cationic Amphiphiles.

    PubMed

    Fosso, Marina Y; Shrestha, Sanjib K; Green, Keith D; Garneau-Tsodikova, Sylvie

    2015-12-10

    Cationic amphiphiles derived from aminoglycosides (AGs) have been shown to exhibit enhanced antimicrobial activity. Through the attachment of hydrophobic residues such as linear alkyl chains on the AG backbone, interesting antibacterial and antifungal agents with a novel mechanism of action have been developed. Herein, we report the design and synthesis of seven kanamycin B (KANB) derivatives. Their antibacterial and antifungal activities, along with resistance/enzymatic, hemolytic, and cytotoxicity assays were also studied. Two of these compounds, with a C12 and C14 aliphatic chain attached at the 6″-position of KANB through a thioether linkage, exhibited good antibacterial and antifungal activity, were poorer substrates than KANB for several AG-modifying enzymes, and could delay the development of resistance in bacteria and fungi. Also, they were both relatively less hemolytic than the known membrane targeting antibiotic gramicidin and the known antifungal agent amphotericin B and were not toxic at their antifungal MIC values. Their oxidation to sulfones was also demonstrated to have no effect on their activities. Moreover, they both acted synergistically with posaconazole, an azole currently used in the treatment of human fungal infections.

  12. Effect of Amphiphiles on the Rheology of Triglyceride Networks

    NASA Astrophysics Data System (ADS)

    Seth, Jyoti

    2014-11-01

    Networks of aggregated crystallites form the structural backbone of many products from the food, cosmetic and pharmaceutical industries. Such materials are generally formulated by cooling a saturated solution to yield the desired solid fraction. Crystal nucleation and growth followed by aggregation leads to formation of a space percolating fractal-network. It is understood that microstructural hierarchy and particle-particle interactions determine material behavior during processing, storage and use. In this talk, rheology of suspensions of triglycerides (TAG, like tristearin) will be explored. TAGs exhibit a rich assortment of polymorphs and form suspensions that are evidently sensitive to surface modifying additives like surfactants and polymers. Here, a theoretical framework will be presented for suspensions containing TAG crystals interacting via pairwise potentials. The work builds on existing models of fractal aggregates to understand microstructure and its correlation with material rheology. Effect of amphiphilic additives is derived through variation of particle-particle interactions. Theoretical predictions for storage modulus will be compared against experimental observations and data from the literature and micro structural predictions against microscopy. Such a theory may serve as a step towards predicting short and long-term behavior of aggregated suspensions formulated via crystallization.

  13. Amphiphilically modified chitosan cationic nanoparticles for drug delivery

    NASA Astrophysics Data System (ADS)

    You, Jie; Li, Wenfeng; Yu, Chang; Zhao, Chengguang; Jin, Langping; Zhou, Yili; Xu, Xuzhong; Dong, Siyang; Lu, Xincheng; Wang, Ouchen

    2013-12-01

    A series of amphiphilic N-(2-hydroxy)propyl-3-trimethylammonium-chitosan-cholic acid (HPTA-CHI-CA) polymers were synthesized by grafting cholic acid (CA) and glycidyltrimethylammonium chloride onto chitosan. The self-assembly behavior of HPTA-CHI-CA was studied by fluorescence technique. The polymers were able to self-assemble into NPs in phosphate buffered saline with a critical aggregation concentration (CAC) in the range of 66-26 mg/L and the CAC decreased with the increasing of the degree of substitution (DS) of CA. The size of cationic HPTA-CHI-CA NPs ranges from 170 to 220 nm (PDI < 0.2). It was found that doxorubicin (DOX) could be encapsulated into HPTA-CHI-CA NPs based on self-assembly. The drug loading content and efficiency varies depending on the DS of CA and feeding ratio of DOX to polymer. In vitro release studies suggested that DOX released slowly from HPTA-CHI-CA NPs without any burst initial release. Besides, the confocal microscopic measurements indicated that DOX-HPTA-CHI-CA NPs could easily be uptaken by breast cancer (MCF-7) cells and release DOX in cytoplasm. Anti-tumor efficacy results showed that DOX-HPTA-CHI-CA NPs have a significant activity of inhibition MCF-7 cells growth. These results suggest cationic HPTA-CHI-CA may have great potential for anticancer drug delivery.

  14. Dynamic in vivo biocompatibility of angiogenic peptide amphiphile nanofibers.

    PubMed

    Ghanaati, Shahram; Webber, Matthew J; Unger, Ronald E; Orth, Carina; Hulvat, James F; Kiehna, Sarah E; Barbeck, Mike; Rasic, Angela; Stupp, Samuel I; Kirkpatrick, C James

    2009-10-01

    Biomaterials that promote angiogenesis have great potential in regenerative medicine for rapid revascularization of damaged tissue, survival of transplanted cells, and healing of chronic wounds. Supramolecular nanofibers formed by self-assembly of a heparin-binding peptide amphiphile and heparan sulfate-like glycosaminoglycans were evaluated here using a dorsal skinfold chamber model to dynamically monitor the interaction between the nanofiber gel and the microcirculation, representing a novel application of this model. We paired this model with a conventional subcutaneous implantation model for static histological assessment of the interactions between the gel and host tissue. In the static analysis, the heparan sulfate-containing nanofiber gels were found to persist in the tissue for up to 30 days and revealed excellent biocompatibility. Strikingly, as the nanofiber gel biodegraded, we observed the formation of a de novo vascularized connective tissue. In the dynamic experiments using the dorsal skinfold chamber, the material again demonstrated good biocompatibility, with minimal dilation of the microcirculation and only a few adherent leukocytes, monitored through intravital fluorescence microscopy. The new application of the dorsal skinfold model corroborated our findings from the traditional static histology, demonstrating the potential use of this technique to dynamically evaluate the biocompatibility of materials. The observed biocompatibility and development of new vascularized tissue using both techniques demonstrates the potential of these angiogenesis-promoting materials for a host of regenerative strategies.

  15. Growth of bimolecular films of three-tailed amphiphiles

    SciTech Connect

    Kundu, S.; Datta, A.; Sanyal, M. K.; Daillant, J.; Luzet, D.; Blot, C.; Struth, B.

    2006-06-15

    The three-tailed amphiphile ferric stearate molecule, which forms a bimolecular layer on water surface with molecules in the lower and upper layers in different conformations, has been studied to understand transfer and growth of bimolecular films on the surface of hydrophilic silicon substrates. This bimolecular film forms a two-dimensional lattice on water with a slightly distorted hexagonal lattice where both the in-plane and out-of-plane domain sizes are small. The film also showed larger microscopic rigidity compared to its macroscopic mechanical response. This asymmetric bimolecular layer was found to be preserved when the film is transferred on the substrates at different values of surface pressures ranging from 1 mN/m to near-collapse (55 mN/m). Both the upper and lower layers become denser and interfaces between these layers become sharper with increase in deposition pressure but the growths have different natures. The lower layer of transferred film is dense from 1 mN/m and, except for a steplike increase between 20 and 30 mN/m, changes slowly in density. The density of the upper molecular layer grows continuously with surface pressure.

  16. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles

    NASA Astrophysics Data System (ADS)

    Kim, Dae-Yoon; Lee, Sang-A.; Jung, Daseal; Jeong, Kwang-Un

    2016-06-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials.

  17. Anti-biofouling properties of amphiphilic phosphorylcholine polymer films.

    PubMed

    Li, Yan; Liu, Cheng-Mei; Yang, Jin-Ying; Gao, Ya-Hui; Li, Xue-Song; Que, Guo-He; Lu, J R

    2011-07-01

    Surfaces of amphiphilic phosphorylcholine polymer (PC1036) prepared by spin-coating were characterized by spectroscopic ellipsometry, water contact angle and atomic force microscopy. The antifouling properties of the PC1036 films to marine benthic diatom Nitzschia closterium MMDL533 were also investigated. The results showed that the dry PC1036 film promoted the adhesion of N. closterium MMDL533 because the hydrophobic lauryl groups were present in the film surface. The 2 h-swelled PC1036 films had excellent anti-fouling properties with extremely low attachment densities and retention densities no matter what the annealing temperature was. The thickness of the coated films lower than 147 Å had a profound effect on the film anti-fouling properties. Otherwise, when the film thickness was higher than that value, there was no more improvement of diatom cell reduction observed. The annealing temperature had only a little effect on the film resistant to diatom adhesion, which might be attributed to two factors including the PC group packing densities in the outer PC layer and the equilibrated water volume fraction in the 2 h-swelled PC1036 films.

  18. Nanoparticle-directed self-assembly of amphiphilic block copolymers.

    PubMed

    Kamps, Amanda C; Sanchez-Gaytan, Brenda L; Hickey, Robert J; Clarke, Nigel; Fryd, Michael; Park, So-Jung

    2010-09-07

    Nanoparticles can form unique cavity-like structures in core-shell type assemblies of block copolymers through the cooperative self-assembly of nanoparticles and block copolymers. We show that the self-assembly behavior is general for common as-synthesized alkyl-terminated nanoparticles for a range of nanoparticle sizes. We examined various self-assembly conditions such as solvent compositions, nanoparticle coordinating ligands, volume fraction of nanoparticles, and nanoparticle sizes in order to elucidate the mechanism of the radial assembly formation. These experiments along with strong segregation theory calculations indicated that both the enthalpic interaction and the polymer stretching energy are important factors in the coassembly formation. The slightly unfavorable interaction between the hydrophobic segment of polymers and alkyl-terminated nanoparticles causes the accumulation of nanoparticles at the interface between the polymer core and the shell, forming the unique cavity-like structure. The coassemblies were stabilized for a limited range of nanoparticle volume fractions within which the inclusion of nanoparticle layers reduces the polymer stretching. The volume fraction range yielding the well-defined radial coassembly structure was mapped out with varying nanoparticle sizes. The experimental and theoretical phase map provides the guideline for the coassembly formation of as-synthesized alkyl-terminated nanoparticles and amphiphilic block copolymers.

  19. Self-assembly of ssDNA-amphiphiles into micelles, nanotapes and nanotubes

    NASA Astrophysics Data System (ADS)

    Pearce, Timothy R.

    The field of DNA nanotechnology utilizes DNA as a construction material to create functional supramolecular and multi-dimensional structures like two-dimensional periodic lattices and three-dimensional polyhedrons with order on the nanometer scale for many nanotechnology applications including molecular templating, nanosensors, and drug delivery. Single-stranded DNA (ssDNA) is often used to create these nanostructures as the DNA bases provide an intrinsic molecular code that can be exploited to allow for the programmed assembly of structures based upon Watson-Crick base-pairing. However, engineering these complex structures from biopolymers alone requires careful design to ensure that the intrinsic forces responsible for organizing the materials can produce the desired structures. Additional control over supramolecular assembly can be achieved by chemically modifying the ssDNA with hydrophobic moieties to create amphiphilic molecules, which adds the hydrophobic interaction to the list of contributing forces that drive the self-assembly process. We first explored the self-assembly behavior of a set of ssDNA aptamer-amphiphiles composed of the same hydrophobic tail and hydrophilic ssDNA aptamer headgroup but with different spacer molecules linking these groups together. Through the use of cryo-transmission electron microscopy (cryo-TEM), small angle x-ray scattering (SAXS), and circular dichroism (CD) we show that the aptamer-amphiphiles can assemble into a variety of structures depending on the spacer used. We demonstrated, for the first time, the creation of self-assembled aptamer-amphiphile nanotape structures and show that the choice of the spacer used in the design of aptamer-amphiphiles can influence their supramolecular self-assembly as well as the secondary structure of the aptamer headgroup. We next explored the role of the ssDNA headgroup on the amphiphile self-assembly behavior by designing amphiphiles with headgroups of multiple lengths and nucleotides

  20. Composite Polymer Electrolytes Based on Hyperbranched Polymer and Application to Lithium Polymer Batteries

    NASA Astrophysics Data System (ADS)

    Itoh, Takahito; Ichikawa, Yosiaki; Miyamura, Yuko; Uno, Takahiro; Kubo, Masataka; Takeda, Yasuo; Li, Qi; Yamamoto, Osamu

    2002-12-01

    Composite polymer electrolytes based on poly(ethylene oxide) (PEO), hyperbranched polymer (HBP), poly[bis(triethylene glycol)benzoate] capped with an acetyl group, a ceramic filler BaTiO3, and a lithium salt such as LiN(CF3SO2)2, LiN(CF3CF2SO2)2, or LiN(CF3SO2)2/LiPF6 were investigated as the electrolyte for all solid-state lithium polymer batteries. The ionic conductivities of the optimized [(PEO-20wt%HBP)12(LiN(CF3SO2)2)]-10wt% BaTiO3, [(PEO-20wt%HBP)12(LiN(CF3CF2SO2)2)]-10wt%BaTiO3, and [(PEO-10wt%HBP)10(LiN(CF3SO2)2-10wt%LiPF6)]-10wt%BaTiO3 electrolytes were found to be 2.6 × 10-4 S/cm at 30 °C and 5.2 × 10-3 S/cm at 80 °C, 1.3 × 10-4 S/cm at 30 °C and 1.6 × 10-3 S/cm at 80 °C, and 1.6 × 10-4 S/cm at 25 °C and 1.5 × 10-3 S/cm at 60 °C, respectively. The lithium polymer batteries composed of the [(PEO-10wt%HBP)10(LiN(CF3SO2)2-10wt%LiPF6)]-10wt%BaTiO3 electrolyte and 4 V class cathode, LiNi0.8Co0.2O2, showed excellent charge-discharge cycling performance. The initial cathode discharge capacity of 154 mAh/g declined only 0.1 %/cycle during first 30 cycles at 60 °C.

  1. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    SciTech Connect

    Purdy Drew, Kirstin R.; Sanders, Lori K.; Culumber, Zachary W.; Zribi, Olena; Wong, Gerard C.L.

    2009-06-17

    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  2. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    SciTech Connect

    Drew, K.R.Purdy; Sanders, L.K.; Culumber, Z.W.; Zribi, O.; Wong, G.C.L.

    2009-05-21

    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  3. DNA nanotubes and helical nanotapes via self-assembly of ssDNA-amphiphiles.

    PubMed

    Pearce, Timothy R; Kokkoli, Efrosini

    2015-01-07

    DNA nanotubes were created using molecular self-assembly of single-stranded DNA (ssDNA)-amphiphiles composed of a hydrophobic dialkyl tail and polycarbon spacer and a hydrophilic ssDNA headgroup. The nanotube structures were formed by bilayers of amphiphiles, with the hydrophobic components forming an inner layer that was shielded from the aqueous solvent by an outer layer of ssDNA. The nanotubes appeared to form via an assembly process that included transitions from twisted nanotapes to helical nanotapes to nanotubes. Amphiphiles that contained different ssDNA headgroups were created to explore the effect of the length and secondary structure of the ssDNA headgroup on the self-assembly behavior of the amphiphiles in the presence and absence of the polycarbon spacer. It was found that nanotubes could be formed using a variety of headgroup lengths and sequences. The ability to create nanotubes via ssDNA-amphiphile self-assembly offers an alternative to the other purely DNA-based approaches like DNA origami and DNA tile assembly for constructing these structures and may be useful for applications in drug delivery, biosensing, and electronics.

  4. Unusual, promoted release of guests from amphiphilic cross-linked polymer networks.

    PubMed

    Brown, Gerald O; Bergquist, Catherine; Ferm, Paul; Wooley, Karen L

    2005-08-17

    Hyperbranched fluoropolymer-poly(ethylene glycol) (HBFP-PEG) cross-linked networks have been found to exhibit capabilities for the encapsulation of high levels of geraniol guest molecules coupled with unusually rapid release of the volatile compound. The promotion of the release of the volatile fragrance geraniol, observed as decreasing volatilization temperatures and increasing volatilization rates by thermogravimetric analyses, was found to be dependent upon the HBFP-PEG network composition, with increasing effects from decreasing wt % PEG and a maximum effect occurring at 5 wt % PEG.

  5. Bio-based hyperbranched thermosetting polyurethane/triethanolamine functionalized multi-walled carbon nanotube nanocomposites as shape memory materials.

    PubMed

    Kalita, Hemjyoti; Karak, Niranjan

    2014-07-01

    Here, bio-based shape memory polymers have generated immense interest in recent times. Here, Bio-based hyperbranched polyurethane/triethanolamine functionalized multi-walled carbon nanotube (TEA-f-MWCNT) nanocomposites were prepared by in-situ pre-polymerization technique. The Fourier transform infrared spectroscopy and the transmission electron microscopic studies showed the strong interfacial adhesion and the homogeneous distribution of TEA-f-MWCNT in the polyurethane matrix. The prepared epoxy cured thermosetting nanocomposites exhibited enhanced tensile strength (6.5-34.5 MPa), scratch hardness (3.0-7.5 kg) and thermal stability (241-288 degrees C). The nanocomposites showed excellent shape fixity and shape recovery. The shape recovery time decreases (24-10 s) with the increase of TEA-f-MWCNT content in the nanocomposites. Thus the studied nanocomposites have potential to be used as advanced shape memory materials.

  6. Fabrication and photoluminescence of hyperbranched silicon nanowire networks on silicon substrates by laser-induced forward transfer.

    PubMed

    Rigout, Muriel LA; Niu, Haijun; Qin, Chuanli; Zhang, Li; Li, Chenming; Bai, Xuduo; Fan, Naiying

    2008-06-18

    The structure and photoluminescent properties of films obtained by modified laser-induced forward transfer of silicon are presented. Strong variations in structure with ambient gas composition are observed: in Ar, porous films of mutually agglomerated silicon nanoparticles are observed, while in air the films consist of a network of hyperbranched nanowires (SiHBNWs) whose diameter varies periodically along their length, and which are composed of crystalline silicon nanoparticles surrounded and interconnected by amorphous silicon oxide of varying stoichiometry. The mechanisms of formation of the structures are dwelt upon and explained in term of dynamics within the plume. For the SiHBNWs, the pioneering use of fluorescence imaging was employed to obtain evidence for the photoluminescence originating from the crystalline nanoparticles themselves, and origins of the emission bands are thus attributed to radiative recombination of excitons at the Si/SiO(2) interface accordingly.

  7. Hyperbranched poly(NIPAM) polymers modified with antibiotics for the reduction of bacterial burden in infected human tissue engineered skin.

    PubMed

    Shepherd, Joanna; Sarker, Prodip; Rimmer, Stephen; Swanson, Linda; MacNeil, Sheila; Douglas, Ian

    2011-01-01

    The escalating global incidence of bacterial infection, particularly in chronic wounds, is a problem that requires significant improvements to existing therapies. We have developed hyperbranched poly(NIPAM) polymers functionalized with the antibiotics Vancomycin and Polymyxin-B that are sensitive to the presence of bacteria in solution. Binding of bacteria to the polymers causes a conformational change, resulting in collapse of the polymers and the formation of insoluble polymer/bacteria complexes. We have applied these novel polymers to our tissue engineered human skin model of a burn wound infected with Pseudomonas aeruginosa and Staphylococcus aureus. When the polymers were removed from the infected skin, either in a polymer gel solution or in the form of hydrogel membranes, they removed bound bacteria, thus reducing the bacterial load in the infected skin model. These bacteria-binding polymers have many potential uses, including coatings for wound dressings.

  8. In situ preparation of fluorescent CdTe quantum dots with small thiols and hyperbranched polymers as co-stabilizers

    PubMed Central

    2014-01-01

    A new strategy for in situ preparation of highly fluorescent CdTe quantum dots (QDs) with 3-mercaptopropionic acid (MPA) and hyperbranched poly(amidoamine)s (HPAMAM) as co-stabilizers was proposed in this paper. MPA and HPAMAM were added in turn to coordinate Cd2+. After adding NaHTe and further microwave irradiation, fluorescent CdTe QDs stabilized by MPA and HPAMAM were obtained. Such a strategy avoids the aftertreatment of thiol-stabilized QDs in their bioapplication and provides an opportunity for direct biomedical use of QDs due to the existence of biocompatible HPAMAM. The resulting CdTe QDs combine the mechanical, biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs together. PMID:24636234

  9. Performance of an in situ formed bioactive hydrogel dressing from a PEG-based hyperbranched multifunctional copolymer.

    PubMed

    Dong, Yixiao; Hassan, Waqar U; Kennedy, Robert; Greiser, Udo; Pandit, Abhay; Garcia, Yolanda; Wang, Wenxin

    2014-05-01

    Hydrogel dressings have been widely used for wound management due to their ability to maintain a hydrated wound environment, restore the skin's physical barrier and facilitate regular dressing replacement. However, the therapeutic functions of standard hydrogel dressings are restricted. In this study, an injectable hybrid hydrogel dressing system was prepared from a polyethylene glycol (PEG)-based thermoresponsive hyperbranched multiacrylate functional copolymer and thiol-modified hyaluronic acid in combination with adipose-derived stem cells (ADSCs). The cell viability, proliferation and metabolic activity of the encapsulated ADSCs were studied in vitro, and a rat dorsal full-thickness wound model was used to evaluate this bioactive hydrogel dressing in vivo. It was found that long-term cell viability could be achieved for both in vitro (21days) and in vivo (14days) studies. With ADSCs, this hydrogel system prevented wound contraction and enhanced angiogenesis, showing the potential of this system as a bioactive hydrogel dressing for wound healing.

  10. Quantum dots-hyperbranched polyether hybrid nanospheres towards delivery and real-time detection of nitric oxide.

    PubMed

    Liu, Shuiping; Gu, Tianxun; Fu, Jiajia; Li, Xiaoqiang; Chronakis, Ioannis S; Ge, Mingqiao

    2014-12-01

    In this work, novel hybrid nanosphere vehicles were synthesized for nitric oxide (NO) donating and real-time detection. The hybrid nanosphere vehicles consist of cadmium selenide quantum dots (CdSe QDs) as NO fluorescent probes, and the modified hyperbranched polyether (mHP)-based diazeniumdiolates as NO donors, respectively. The nanospheres have spherical outline with dimension of ~127 nm. The data of systematic characterization demonstrated that the mHP-based hybrid nanosphere vehicles (QDs-mHP-NO) can release and real-time detect NO with the low limit of 25 nM, based on fluorescence quenching mechanism. The low cell-toxicity of QDs-mHP-NO nanospheres was verified by means of MTT assay on L929 cells viability. The QDs-mHP-NO nanospheres provide perspectives for designing a new class of biocompatible NO donating and imaging systems.

  11. Water- and organo-dispersible gold nanoparticles supported by using ammonium salts of hyperbranched polystyrene: preparation and catalysis.

    PubMed

    Gao, Lei; Nishikata, Takashi; Kojima, Keisuke; Chikama, Katsumi; Nagashima, Hideo

    2013-12-01

    Gold nanoparticles (1 nm in size) stabilized by ammonium salts of hyperbranched polystyrene are prepared. Selection of the R groups provides access to both water- and organo-dispersible gold nanoparticles. The resulting gold nanoparticles are subjected to studies on catalysis in solution, which include reduction of 4-nitrophenol with sodium borohydride, aerobic oxidation of alcohols, and homocoupling of phenylboronic acid. In the reduction of 4-nitrophenol, the catalytic activity is clearly dependent on the size of the gold nanoparticles. For the aerobic oxidation of alcohols, two types of biphasic oxidation are achieved: one is the catalyst dispersing in the aqueous phase, whereas the other is in the organic phase. The catalysts are reusable more than four times without loss of the catalytic activity. Selective synthesis of biphenyl is achieved by the homocoupling of phenylboronic acid catalyzed by organo-dispersible gold nanoparticles.

  12. Influences of fatty acid moiety and esterification of polyglycerol fatty acid esters on the crystallization of palm mid fraction in oil-in-water emulsion.

    PubMed

    Sakamoto, Mitsuhiro; Ohba, Azusa; Kuriyama, Juhei; Maruo, Kouichi; Ueno, Satoru; Sato, Kiyotaka

    2004-08-15

    We examined the crystallization of palm mid fraction (PMF) in oil-in-water (O/W) emulsion, after adding polyglycerol fatty acid esters (PGFEs). We employed ultrasonic velocity measurements and DSC techniques, with special emphases on the influences of fatty acid moiety and esterification of PGFE. Twelve types of PGFEs were examined as additives. PGFEs have a large hydrophilic moiety composed of 10 glycerol molecules to which palmitic, stearic and behenic acids were esterified as the fatty acid moiety with different degrees of esterification. Crystallization temperature (T(c)) of PMF remarkably increased with increasing concentrations of the PGFEs as the chain length of the fatty acid moiety increased, and the PGFE became more hydrophobic in accordance with increasing degree of esterification. We observed that the heterogeneous nucleation of PMF in the O/W emulsion was activated at the oil-water interface, where the template effect of very hydrophobic long saturated fatty acid chains of the PGFE might play the main role of heterogeneous nucleation.

  13. Layer-by-layer supramolecular assemblies based on linear and star-shaped poly(glycerol methacrylate)s for doxorubicin delivery.

    PubMed

    Sun, Yanfang; Gao, Hui; Yang, Ying-Wei; Wang, Anning; Wu, Guolin; Wang, Yinong; Fan, Yunge; Ma, Jianbiao

    2013-08-01

    Hollow microcapsules, composed of pH responsive polyelectrolytes via a layer-by-layer (LBL) adsorption technique, were prepared. Linear or star-shaped poly(glycerol metha crylate)s (PGOHMAs) modified with 1,4-butanediamine and 1,2-ethanediamine (EDA) were synthesized and used as polycations. Poly(acrylic acid) was employed as polyanion and SiO2 (about 170 nm) as template. After LBL absorption, SiO2 cores were removed by HF treatment. The particle size and zeta potential were measured by dynamic light scattering, showing that the diameter of star-shaped amino-PGOHMA was larger than linear counterpart. The LBL assembly and core-etching process were evidenced by scanning electron microscope, transmission electron microscope, and energy dispersive spectrometer. The cytotoxicity experiments on human umbilical vein endothelial cells were carried out to evaluate the toxicity of LBL assembly. The star-shaped and EDA-modified PGOHMA exhibited better cell viability. The microcapsules were then used to load an anticancer drug, doxorubicin hydrochloride. High loading capacity (about 42%) and entrapment efficiency (84%) were obtained for star-shaped polymer-based microcapsules. The cumulative release rate was evaluated in vitro, showing faster release at an acidic condition compared to neutral pH. Confocal laser scanning microscopy evidenced the successful cellular uptake of DOX-loaded microparticles.

  14. Deciphering the role of charge, hydration, and hydrophobicity for cytotoxic activities and membrane interactions of bile acid based facial amphiphiles.

    PubMed

    Singh, Manish; Singh, Ashima; Kundu, Somanath; Bansal, Sandhya; Bajaj, Avinash

    2013-08-01

    We synthesized four cationic bile acid based facial amphiphiles featuring trimethyl ammonium head groups. We evaluated the role of these amphiphiles for cytotoxic activities against colon cancer cells and their membrane interactions by varying charge, hydration and hydrophobicity. The singly charged cationic Lithocholic acid based amphiphile (LCA-TMA1) is most cytotoxic, whereas the triply charged cationic Cholic acid based amphiphile (CA-TMA3) is least cytotoxic. Light microscopy and Annexin-FITC assay revealed that these facial amphiphiles caused late apoptosis. In addition, we studied the interactions of these amphiphiles with model membrane systems by Prodan-based hydration, DPH-based anisotropy, and differential scanning calorimetry. LCA-TMA1 is most hydrophobic with a hard charge causing efficient dehydration and maximum perturbations of membranes thereby facilitating translocation and high cytotoxicity against colon cancer cells. In contrast, the highly hydrated and multiple charged CA-TMA3 caused least membrane perturbations leading to low translocation and less cytotoxicity. As expected, Chenodeoxycholic acid and Deoxycholic acid based amphiphiles (CDCA-TMA2, DCA-TMA2) featuring two charged head groups showed intermediate behavior. Thus, we deciphered that charge, hydration, and hydrophobicity of these amphiphiles govern membrane interactions, translocation, and resulting cytoxicity against colon cancer cells.

  15. Amphiphilic, ultralight, and multifunctional graphene/nanofibrillated cellulose aerogel achieved by cation-induced gelation and chemical reduction.

    PubMed

    Yao, Xuelin; Yu, Wenjin; Xu, Xin; Chen, Feng; Fu, Qiang

    2015-03-07

    Nanofibrillated cellulose (NFC) was incorporated to reduced graphene oxide (rGO) for fabrication of multifunctional amphiphilic aerogels. The as-prepared amphiphilic aerogel showed excellent recoverability, superior absorption capacity for both organic solvents and water, and an electrical conductivity sensitive to compressive strain making it highly potential to be used as a pressure-responsive sensor.

  16. Sugar-based amphiphilic nanoparticles arrest atherosclerosis in vivo

    PubMed Central

    Lewis, Daniel R.; Petersen, Latrisha K.; York, Adam W.; Zablocki, Kyle R.; Joseph, Laurie B.; Kholodovych, Vladyslav; Prud’homme, Robert K.; Uhrich, Kathryn E.; Moghe, Prabhas V.

    2015-01-01

    Atherosclerosis, the build-up of occlusive, lipid-rich plaques in arterial walls, is a focal trigger of chronic coronary, intracranial, and peripheral arterial diseases, which together account for the leading causes of death worldwide. Although the directed treatment of atherosclerotic plaques remains elusive, macrophages are a natural target for new interventions because they are recruited to lipid-rich lesions, actively internalize modified lipids, and convert to foam cells with diseased phenotypes. In this work, we present a nanomedicine platform to counteract plaque development based on two building blocks: first, at the single macrophage level, sugar-based amphiphilic macromolecules (AMs) were designed to competitively block oxidized lipid uptake via scavenger receptors on macrophages; second, for sustained lesion-level intervention, AMs were fabricated into serum-stable core/shell nanoparticles (NPs) to rapidly associate with plaques and inhibit disease progression in vivo. An AM library was designed and fabricated into NP compositions that showed high binding and down-regulation of both MSR1 and CD36 scavenger receptors, yielding minimal accumulation of oxidized lipids. When intravenously administered to a mouse model of cardiovascular disease, these AM NPs showed a pronounced increase in lesion association compared with the control nanoparticles, causing a significant reduction in neointimal hyperplasia, lipid burden, cholesterol clefts, and overall plaque occlusion. Thus, synthetic macromolecules configured as NPs are not only effectively mobilized to lipid-rich lesions but can also be deployed to counteract atheroinflammatory vascular diseases, highlighting the promise of nanomedicines for hyperlipidemic and metabolic syndromes. PMID:25691739

  17. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles

    SciTech Connect

    Chang, Hung-Yu; Sheng, Yu-Jane E-mail: hktsao@cc.ncu.edu.tw; Tu, Sheng-Hung; Tsao, Heng-Kwong E-mail: hktsao@cc.ncu.edu.tw

    2014-08-07

    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n{sup ′}) motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n{sup ′}-part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings.

  18. Amphiphilic phase-transforming catalysts for transesterification of triglycerides

    NASA Astrophysics Data System (ADS)

    Nawaratna, Gayan Ivantha

    Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

  19. High Selective Performance of Designed Antibacterial and Anticancer Peptide Amphiphiles.

    PubMed

    Chen, Cuixia; Chen, Yucan; Yang, Cheng; Zeng, Ping; Xu, Hai; Pan, Fang; Lu, Jian Ren

    2015-08-12

    Short designed peptide amphiphiles are attractive at killing bacteria and inhibiting cancer cell growth, and the flexibility in their structural design offers a great potential for improving their potency and biocompatibility to mammalian host cells. Amino acid sequences such as G(IIKK)nI-NH2 (n≥3) have been shown to be membrane lytic, but terminal amino acid modifications could impose a huge influence on their performance. We report in this work how terminal amino acid modifications to G(IIKK)3I-NH2 influence its α-helical structure, membrane penetrating ability, and selective actions against different cell types. Deletion of an N-terminal Gly or a C-terminal Ile did not affect their antibacterial activity much, an observation consistent with their binding behavior to negatively charged membrane lipid monolayers. However, the cytotoxicity against mammalian cells was much worsened by the N-terminal Gly deletion, consistent with an increase in its helical content. Despite little impact on the antibacterial activity of G(IIKK)3I-NH2, deletion of both terminal amino acids greatly reduced its antitumor activity. Cholesterol present in tumor cell membrane-mimic was thought to constrain (IIKK)3-NH2 from penetrating into the cancerous membranes, evident from its lowest surface physical activity at penetrating model lipid membranes. On the other hand, its low toxicity to normal mammalian cells and high antibacterial activity in vitro and in vivo made it an attractive antibacterial agent. Thus, terminal modifications can help rebalance the different interactions involved and are highly effective at manipulating their selective membrane responses.

  20. Synthetic cationic amphiphilic α-helical peptides as antimicrobial agents.

    PubMed

    Wiradharma, Nikken; Khoe, Ulung; Hauser, Charlotte A E; Seow, See Voon; Zhang, Shuguang; Yang, Yi-Yan

    2011-03-01

    Antimicrobial peptides (AMPs) secreted by the innate immune system are prevalent as the effective first-line of defense to overcome recurring microbial invasions. They have been widely accepted as the blueprints for the development of new antimicrobial agents for the treatment of drug resistant infections. However, there is also a growing concern that AMPs with a sequence that is too close to the host organism's AMP may inevitably compromise its own natural defense. In this study, we design a series of synthetic (non-natural) short α-helical AMPs to expand the arsenal of the AMP families and to gain further insights on their antimicrobial activities. These cationic and amphiphilic peptides have a general sequence of (XXYY)(n) (X: hydrophobic residue, Y: cationic residue, and n: the number of repeat units), and are designed to mimic the folding behavior of the naturally-occurring α-helical AMPs. The synthetic α-helical AMPs with 3 repeat units, (FFRR)(3), (LLRR)(3), and (LLKK)(3), are found to be more selective towards microbial cells than rat red blood cells, with minimum inhibitory concentration (MIC) values that are more than 10 times lower than their 50% hemolytic concentrations (HC(50)). They are effective against Gram-positive B. subtilis and yeast C. albicans; and the studies using scanning electron microscopy (SEM) have elucidated that these peptides possess membrane-lytic activities against microbial cells. Furthermore, non-specific immune stimulation assays of a typical peptide shows negligible IFN-α, IFN-γ, and TNF-α inductions in human peripheral blood mononuclear cells, which implies additional safety aspects of the peptide for both systemic and topical use. Therefore, the peptides designed in this study can be promising antimicrobial agents against the frequently-encountered Gram-positive bacteria- or yeast-induced infections.

  1. A bioengineered peripheral nerve construct using aligned peptide amphiphile nanofibers

    PubMed Central

    Yalom, Anisa; Berns, Eric J.; Stephanopoulos, Nicholas; McClendon, Mark T.; Segovia, Luis A.; Spigelman, Igor; Stupp, Samuel I.; Jarrahy, Reza

    2014-01-01

    Peripheral nerve injuries can result in lifelong disability. Primary coaptation is the treatment of choice when the gap between transected nerve ends is short. Long nerve gaps seen in more complex injuries often require autologous nerve grafts or nerve conduits implemented into the repair. Nerve grafts, however, cause morbidity and functional loss at donor sites, which are limited in number. Nerve conduits, in turn, lack an internal scaffold to support and guide axonal regeneration, resulting in decreased efficacy over longer nerve gap lengths. By comparison, peptide amphiphiles (PAs) are molecules that can self-assemble into nanofibers, which can be aligned to mimic the native architecture of peripheral nerve. As such, they represent a potential substrate for use in a bioengineered nerve graft substitute. To examine this, we cultured Schwann cells with bioactive PAs (RGDS-PA, IKVAV-PA) to determine their ability to attach to and proliferate within the biomaterial. Next, we devised a PA construct for use in a peripheral nerve critical sized defect model. Rat sciatic nerve defects were created and reconstructed with autologous nerve, PLGA conduits filled with various forms of aligned PAs, or left unrepaired. Motor and sensory recovery were determined and compared among groups. Our results demonstrate that Schwann cells are able to adhere to and proliferate in aligned PA gels, with greater efficacy in bioactive PAs compared to the backbone-PA alone. In vivo testing revealed recovery of motor and sensory function in animals treated with conduit/PA constructs comparable to animals treated with autologous nerve grafts. Functional recovery in conduit/PA and autologous graft groups was significantly faster than in animals treated with empty PLGA conduits. Histological examinations also demonstrated increased axonal and Schwann cell regeneration within the reconstructed nerve gap in animals treated with conduit/PA constructs. These results indicate that PA nanofibers may

  2. Protein Conjugation with Amphiphilic Block Copolymers for Enhanced Cellular Delivery

    PubMed Central

    Yi, Xiang; Batrakova, Elena; Banks, William A.; Vinogradov, Serguei; Kabanov, Alexander V.

    2008-01-01

    Modification of a model protein, horseradish peroxidase (HRP), with amphiphilic block copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (Pluronic), was previously shown to enhance the transport of this protein across the blood—brain barrier in vivo and brain microvessel endothelial cells in vitro. This work develops procedures for synthesis and characterization of HRP with Pluronic copolymers, having different lengths of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) blocks. Four monoamine Pluronic derivatives (L81, P85, L121, P123) were synthesized and successfully conjugated to a model protein, HRP, via biodegradable or nondegradable linkers (dithiobis(succinimidyl propionate) (DSP), dimethyl 3,3′-dithiobispropionimidate (DTBP), and disuccinimidyl propionate (DSS)). The conjugation was confirmed by HRP amino group titration, matrix-assisted laser desorption/ionization-time of flight spectroscopy, and cation-exchange chromatography. HRP conjugates containing an average of one to two Pluronic moieties and retaining in most cases over 70% of the activity were synthesized. Increased cellular uptake of these conjugates was demonstrated using the Mardin-Derby canine kidney cell line and primary bovine brain microvessel endothelial cells. The optimal modifications included Pluronic L81 and P85. These copolymers have shorter PPO chains compared to Pluronic P123 and L121, which were less efficient. There was little if any dependence of the uptake on the length of the hydrophilic PEO block for the optimal modifications. The proposed modifications may be used to increase cellular uptake of other proteins. PMID:18447367

  3. Mesoscale inhomogeneities in aqueous solutions of small amphiphilic molecules.

    PubMed

    Subramanian, Deepa; Boughter, Christopher T; Klauda, Jeffery B; Hammouda, Boualem; Anisimov, Mikhail A

    2013-01-01

    Small amphiphilic molecules, also known as hydrotropes, are too small to form micelles in aqueous solutions. However, aqueous solutions of nonionic hydrotropes show the presence of a dynamic, loose, non-covalent clustering in the water-rich region, This clustering can be viewed as "micelle-like structural fluctuations". Although these fluctuations are short ranged (approximately 1 nm) and short lived (10 ps-50 ps), they may lead to thermodynamic anomalies. In addition, many experiments on aqueous solutions of hydrotropes show the occasional presence of mesoscale (approximately 100 nm) inhomogeneities. We have combined results obtained from molecular dynamics simulations, small-angle neutron scattering, and dynamic light-scattering experiments carried out on tertiary butyl alcohol (hydrotrope)-water solutions and on tertiary butyl alcohol-water-cyclohexane (hydrophobe) solutions to elucidate the nature and structure of these inhomogeneities. We have shown that stable mesoscale inhomogeneities occur in aqueous solutions of nonionic hydrotropes only when the solution contains a third, more hydrophobic, component. Moreover, these inhomogeneities exist in ternary systems only in the concentration range where structural fluctuations and thermodynamic anomalies are observed in the binary water-hydrotrope solutions. Addition of a hydrophobe seems to stabilize the water-hydrotrope structural fluctuations, and leads to the formation of larger (mesoscopic) droplets. The structure of these mesoscopic droplets is such that they have a hydrophobe-rich core, surrounded by a hydrogen-bonded shell of water and hydrotrope molecules. These droplets can be extremely long-lived, being stable for over a year. We refer to the phenomenon of formation of mesoscopic droplets in aqueous solutions of nonionic hydrotropes containing hydrophobes, as mesoscale solubilization. This phenomenon may represent a ubiquitous feature of nonionic hydrotropes that exhibit clustering in water, and may have

  4. Probing peptide amphiphile self-assembly in blood serum.

    PubMed

    Ghosh, Arijit; Buettner, Christian J; Manos, Aaron A; Wallace, Ashley J; Tweedle, Michael F; Goldberger, Joshua E

    2014-12-08

    There has been recent interest in designing smart diagnostic or therapeutic self-assembling peptide or polymeric materials that can selectively undergo morphological transitions to accumulate at a disease site in response to specific stimuli. Developing approaches to probe these self-assembly transitions in environments that accurately amalgamate the diverse plethora of proteins, biomolecules, and salts of blood is essential for creating systems that function in vivo. Here, we have developed a fluorescence anisotropy approach to probe the pH-dependent self-assembly transition of peptide amphiphile (PA) molecules that transform from spherical micelles at pH 7.4 to nanofibers under more acidic pH's in blood serum. By mixing small concentrations of a Ru(bipy)3(2+)-tagged PA with a Gd(DO3A)-tagged PA having the same lipid-peptide sequence, we showed that the pH dependence of self-assembly is minimally affected and can be monitored in mouse blood serum. These PA vehicles can be designed to transition from spherical micelles to nanofibers in the pH range 7.0-7.4 in pure serum. In contrast to the typical notion of serum albumin absorbing isolated surfactant molecules and disrupting self-assembly, our experiments showed that albumin does not bind these anionic PAs and instead promotes nanofibers due to a molecular crowding effect. Finally, we created a medium that replicates the transition pH in serum to within 0.08 pH units and allows probing self-assembly behavior using conventional spectroscopic techniques without conflicting protein signals, thus simplifying the development pathway from test tube to in vivo experimentation for stimuli-responsive materials.

  5. Pore-free matrix with cooperative chelating of hyperbranched ligands for high-performance separation of uranium.

    PubMed

    Li, Yang; Wang, Lei; Li, Bo; Zhang, Meicheng; Wen, Rui; Guo, Xinghua; Li, Xing; Zhang, Ji; Li, Shoujian; Ma, Lijian

    2016-10-04

    A new strategy combining pore-free matrix and cooperative-chelating was proposed in the present paper in order to effectively avoid undesired non-selective physical adsorption and intra-particle diffusion caused by pores and voids in porous sorbents, and to greatly enhance uranium-chelating capability based on hyperbranched amidoxime ligands on the surface of nanodiamond particles. Thus a pore-free, amidoxime-terminated hyperbranched nanodiamond (ND-AO) was designed and synthesized. The experimental results demonstrate that the strategy endows the as-synthesized ND-AO with following expected features: (1) distinctively high uranium selectivity (SU = qe-U /qe-tol ×100 %) from over 80% to nearly 100 % over the whole weak acidity range (pH < 4.5), especially, the SU can reach up to unprecedented > 91 % at pH 4.5, more than 20 percent of selectivity increment over any analogous sorbent materials reported so far, with a uranium sorption capacity of 121mg/g in simulated nuclear industry effluent samples containing 12 coexistent nuclide ions, (2) super-fast equilibrium sorption time of < 30s, (3) one of the highest distribution coefficient ( Kd ) of ~ 3×106 ml/g for U(VI) as well as fairly high sorption capacity of 212 mg/g at pH 4.5 in pure-uranium solution. The strategy could also provide an optional approach for the design and fabrication of other new high-performance sorbing materials with prospective applications in selective separation of other interested metal ions.

  6. Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles

    PubMed Central

    Honda, Satoshi; Yamamoto, Takuya; Tezuka, Yasuyuki

    2013-01-01

    Cyclic molecules provide better stability for their aggregates. Typically in nature, the unique cyclic cell membrane lipids allow thermophilic archaea to inhabit extreme conditions. By mimicking the biological design, the robustness of self-assembled synthetic nanostructures is expected to be improved. Here we report topology effects by cyclized polymeric amphiphiles against their linear counterparts, demonstrating a drastic enhancement in the thermal, as well as salt stability of self-assembled micelles. Furthermore, through coassembly of the linear and cyclic amphiphiles, the stability was successfully tuned for a wide range of temperatures and salt concentrations. The enhanced thermal/salt stability was exploited in a halogen exchange reaction to stimulate the catalytic activity. The mechanism for the enhancement was also investigated. These topology effects by the cyclic amphiphiles offer unprecedented opportunities in polymer materials design unattainable by traditional means. PMID:23481382

  7. Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures.

    PubMed

    Purceno, Aluir D; Machado, Bruno F; Teixeira, Ana Paula C; Medeiros, Tayline V; Benyounes, Anas; Beausoleil, Julien; Menezes, Helvecio C; Cardeal, Zenilda L; Lago, Rochel M; Serp, Philippe

    2015-01-07

    In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.

  8. Effect of Topological Structures on the Self-Assembly Behavior of Supramolecular Amphiphiles.

    PubMed

    Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

    2015-12-29

    Three types of azobenzene-based telechelic guest polymers, PEG-azo, azo-PEG-azo, and PEG-azo4, were synthesized by a facile method. Subsequently, a series supramolecular amphiphiles with three distinct topological structures (hemitelechelic, ditelechelic, and quadritelechelic) were constructed through coupling with host polymer β-cyclodextrin-poly(l-lactide) (β-CD-PLLA) by combined host-guest complexation. Research on the self-assembly behavior of these amphiphiles demonstrated that the variation in self-assembly was tuned by the synergistic interaction of hydrophilicity and the curvature of the polymer chains, and very importantly, the topological structure of amphiphiles demonstrated effective control of the self-assembly behavior.

  9. Biomimetic Self-Templated Hierarchical Structures of Collagen-Like Peptide Amphiphiles.

    PubMed

    Jin, Hyo-Eon; Jang, Jaein; Chung, Jinhyo; Lee, Hee Jung; Wang, Eddie; Lee, Seung-Wuk; Chung, Woo-Jae

    2015-10-14

    Developing hierarchically structured biomaterials with tunable chemical and physical properties like those found in nature is critically important to regenerative medicine and studies on tissue morphogenesis. Despite advances in materials synthesis and assembly processes, our ability to control hierarchical assembly using fibrillar biomolecules remains limited. Here, we developed a bioinspired approach to create collagen-like materials through directed evolutionary screening and directed self-assembly. We first synthesized peptide amphiphiles by coupling phage display-identified collagen-like peptides to long-chain fatty acids. We then assembled the amphiphiles into diverse, hierarchically organized, nanofibrous structures using directed self-assembly based on liquid crystal flow and its controlled deposition. The resulting structures sustained and directed the growth of bone cells and hydroxyapatite biominerals. We believe these self-assembling collagen-like amphiphiles could prove useful in the structural design of tissue regenerating materials.

  10. Mixtures of ions and amphiphilic molecules in slit-like pores: A density functional approach

    SciTech Connect

    Pizio, O.; Rżysko, W. Sokołowski, S.; Sokołowska, Z.

    2015-04-28

    We investigate microscopic structure and thermodynamic properties of a mixture that contains amphiphilic molecules and charged hard spheres confined in slit-like pores with uncharged hard walls. The model and the density functional approach are the same as described in details in our previous work [Pizio et al., J. Chem. Phys. 140, 174706 (2014)]. Our principal focus is in exploring the effects brought by the presence of ions on the structure of confined amphiphilic particles. We have found that for some cases of anisotropic interactions, the change of the structure of confined fluids occurs via the first-order transitions. Moreover, if anions and cations are attracted by different hemispheres of amphiphiles, a charge at the walls appears at the zero value of the wall electrostatic potential. For a given thermodynamic state, this charge is an oscillating function of the pore width.

  11. Preparation of gemini-type amphiphiles bearing cyclitol head groups and their application as high-performance modifiers for lipases.

    PubMed

    Mine, Yurie; Fukunaga, Kimitoshi; Samejima, Ken-ichi; Yoshimoto, Makoto; Nakao, Katsumi; Sugimura, Yoshiaki

    2004-02-25

    Five gemini-type amphiphiles bearing cyclitol head groups, which have abundance of axial hydroxy groups, are newly synthesized. The syntheses are based on a common mixed anhydride method utilizing N,N'-[iminobis(trimethylene)]bisquinamide, prepared from iminobispropylamine and quino-1,5-lactone, and dialkyl N-(3-carboxypropanoyl)-L-glutamates as polar and hydrophobic components, respectively. Candida rugosa lipase (CRL) and Pseudomonas cepacia lipase (PCL) are co-lyophilized with these synthesized gemini-type amphiphiles, and their transesterification activities in organic solvents are evaluated. The modified PCL and CRL prepared by using each amphiphile showed highly enhanced and moderately enhanced enzyme activity, respectively. These results are discussed in terms of the increased preferential exclusion of the hydrophilic heads of the amphiphile and of the topological view of the amphiphile.

  12. Self-assembly mechanisms of nanofibers from peptide amphiphiles in solution and on substrate surfaces

    NASA Astrophysics Data System (ADS)

    Liao, Hsien-Shun; Lin, Jing; Liu, Yang; Huang, Peng; Jin, Albert; Chen, Xiaoyuan

    2016-08-01

    We report the investigation of the self-assembly mechanism of nanofibers, using a small peptide amphiphile (NapFFKYp) as a model. Combining experimental and simulation methods, we identify the self-assembly pathways in the solution and on the substrates, respectively. In the solution, peptide amphiphiles undergo the nucleation process to grow into nanofibers. The nanofibers can further twist into high-ordered nanofibers with aging. On the substrates, peptide amphiphiles form nanofibers and nanosheet structures simultaneously. This surface-induced nanosheet consists of rod-like structures, and its thickness is substrate-dependent. Most intriguingly, water can transform the nanosheet into the nanofiber. Molecular dynamic simulation suggests that hydrophobic and ion-ion interactions are dominant forces during the self-assembly process.We report the investigation of the self-assembly mechanism of nanofibers, using a small peptide amphiphile (NapFFKYp) as a model. Combining experimental and simulation methods, we identify the self-assembly pathways in the solution and on the substrates, respectively. In the solution, peptide amphiphiles undergo the nucleation process to grow into nanofibers. The nanofibers can further twist into high-ordered nanofibers with aging. On the substrates, peptide amphiphiles form nanofibers and nanosheet structures simultaneously. This surface-induced nanosheet consists of rod-like structures, and its thickness is substrate-dependent. Most intriguingly, water can transform the nanosheet into the nanofiber. Molecular dynamic simulation suggests that hydrophobic and ion-ion interactions are dominant forces during the self-assembly process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr04672j

  13. Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures

    NASA Astrophysics Data System (ADS)

    Purceno, Aluir D.; Machado, Bruno F.; Teixeira, Ana Paula C.; Medeiros, Tayline V.; Benyounes, Anas; Beausoleil, Julien; Menezes, Helvecio C.; Cardeal, Zenilda L.; Lago, Rochel M.; Serp, Philippe

    2014-11-01

    In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and

  14. Sacrificial amphiphiles: Eco-friendly chemical herders as oil spill mitigation chemicals.

    PubMed

    Gupta, Deeksha; Sarker, Bivas; Thadikaran, Keith; John, Vijay; Maldarelli, Charles; John, George

    2015-06-01

    Crude oil spills are a major threat to marine biota and the environment. When light crude oil spills on water, it forms a thin layer that is difficult to clean by any methods of oil spill response. Under these circumstances, a special type of amphiphile termed as "chemical herder" is sprayed onto the water surrounding the spilled oil. The amphiphile forms a monomolecular layer on the water surface, reducing the air-sea surface tension and causing the oil slick to retract into a thick mass that can be burnt in situ. The current best-known chemical herders are chemically stable and nonbiodegradable, and hence remain in the marine ecosystem for years. We architect an eco-friendly, sacrificial, and effective green herder derived from the plant-based small-molecule phytol, which is abundant in the marine environment, as an alternative to the current chemical herders. Phytol consists of a regularly branched chain of isoprene units that form the hydrophobe of the amphiphile; the chain is esterified to cationic groups to form the polar group. The ester linkage is proximal to an allyl bond in phytol, which facilitates the hydrolysis of the amphiphile after adsorption to the sea surface into the phytol hydrophobic tail, which along with the unhydrolyzed herder, remains on the surface to maintain herding action, and the cationic group, which dissolves into the water column. Eventual degradation of the phytol tail and dilution of the cation make these sacrificial amphiphiles eco-friendly. The herding behavior of phytol-based amphiphiles is evaluated as a function of time, temperature, and water salinity to examine their versatility under different conditions, ranging from ice-cold water to hot water. The green chemical herder retracted oil slicks by up to ~500, 700, and 2500% at 5°, 20°, and 35°C, respectively, during the first 10 min of the experiment, which is on a par with the current best chemical herders in practice.

  15. Sacrificial amphiphiles: Eco-friendly chemical herders as oil spill mitigation chemicals

    PubMed Central

    Gupta, Deeksha; Sarker, Bivas; Thadikaran, Keith; John, Vijay; Maldarelli, Charles; John, George

    2015-01-01

    Crude oil spills are a major threat to marine biota and the environment. When light crude oil spills on water, it forms a thin layer that is difficult to clean by any methods of oil spill response. Under these circumstances, a special type of amphiphile termed as “chemical herder” is sprayed onto the water surrounding the spilled oil. The amphiphile forms a monomolecular layer on the water surface, reducing the air–sea surface tension and causing the oil slick to retract into a thick mass that can be burnt in situ. The current best-known chemical herders are chemically stable and nonbiodegradable, and hence remain in the marine ecosystem for years. We architect an eco-friendly, sacrificial, and effective green herder derived from the plant-based small-molecule phytol, which is abundant in the marine environment, as an alternative to the current chemical herders. Phytol consists of a regularly branched chain of isoprene units that form the hydrophobe of the amphiphile; the chain is esterified to cationic groups to form the polar group. The ester linkage is proximal to an allyl bond in phytol, which facilitates the hydrolysis of the amphiphile after adsorption to the sea surface into the phytol hydrophobic tail, which along with the unhydrolyzed herder, remains on the surface to maintain herding action, and the cationic group, which dissolves into the water column. Eventual degradation of the phytol tail and dilution of the cation make these sacrificial amphiphiles eco-friendly. The herding behavior of phytol-based amphiphiles is evaluated as a function of time, temperature, and water salinity to examine their versatility under different conditions, ranging from ice-cold water to hot water. The green chemical herder retracted oil slicks by up to ~500, 700, and 2500% at 5°, 20°, and 35°C, respectively, during the first 10 min of the experiment, which is on a par with the current best chemical herders in practice. PMID:26601197

  16. Synthesis of amphiphilic aminated inulin via 'click chemistry' and evaluation for its antibacterial activity.

    PubMed

    Dong, Fang; Zhang, Jun; Yu, Chunwei; Li, Qing; Ren, Jianming; Wang, Gang; Gu, Guodong; Guo, Zhanyong

    2014-09-15

    Inulins are a group of abundant, water-soluble, renewable polysaccharides, which exhibit attractive bioactivities and natural properties. Improvement such as chemical modification of inulin is often performed prior to further utilization. We hereby presented a method to modify inulin at its primary hydroxyls to synthesize amphiphilic aminated inulin via 'click chemistry' to facilitate its chemical manipulation. Additionally, its antibacterial property against Staphylococcus aureus (S. aureus) was also evaluated and the best inhibitory index against S. aureus was 58% at 1mg/mL. As the amphiphilic aminated inulin is easy to prepare and exhibits improved bioactivity, this material may represent as an attractive new platform for chemical modifications of inulin.

  17. Precisely Controlled 2D Free-Floating Nanosheets of Amphiphilic Molecules through Frame-Guided Assembly.

    PubMed

    Zhou, Chao; Zhang, Yiyang; Dong, Yuanchen; Wu, Fen; Wang, Dianming; Xin, Ling; Liu, Dongsheng

    2016-11-01

    2D assembly of amphiphilic molecules in aqueous solution is a challenging and intriguing topic as it is normally thermodynamically unfavorable. However, through frame-guided assembly strategy and using DNA origami as the frame, monodispersed and shape-defined nanosheets are prepared. As leading hydrophobic groups (LHGs) are anchored on the frames, amphiphilic molecules in aqueous solution are guided to assemble in the hydrophobic region. By adjusting the distribution of the LHGs, the size and shape of the assemblies can be controlled precisely.

  18. Dynamics of water in the amphiphilic pore of amyloid β fibrils

    NASA Astrophysics Data System (ADS)

    GhattyVenkataKrishna, Pavan K.; Mostofian, Barmak

    2013-09-01

    Alzheimers disease related amyloid peptide, Aβ, forms a fibrillar structure through aggregation. The aggregate is stabilized by a salt bridge that is responsible for the formation of an amphiphilic pore that can accommodate water molecules. None of the reported structures of Aβ, however, contain water. We present results from molecular dynamics simulations on dimeric Aβ fibrils solvated in water. Water penetrates and fills the amphiphilic pore increasing its volume. We observe a thick wire of water that is translationally and rotationally stiff in comparison to bulk water and may be essential for the stabilization of the amyloid Aβ protein.

  19. Metastable tetragonal Cu2Se hyperbranched structures: large-scale preparation and tunable electrical and optical response regulated by phase conversion.

    PubMed

    Zhu, Jinbao; Li, Qiuyang; Bai, Liangfei; Sun, Yongfu; Zhou, Min; Xie, Yi

    2012-10-08

    Despite the promising applications of copper selenide nanoparticles, an in-depth elucidation of the inherent properties of tetragonal Cu(2)Se (β-Cu(2)Se) has not been performed because of the lack of a facile synthesis on the nanoscale and an energy-intensive strategy is usually employed. In this work, a facile wet-chemical strategy, employing HCOOH as reducing agent, has been developed to access single-crystalline metastable β-Cu(2)Se hyperbranched architectures for the first time. The process avoids hazardous chemistry and high temperatures, and thus opens up a facile approach to the large-scale low-cost preparation of metastable β-Cu(2)Se hyperbranched architectures. A possible growth mechanism to explain the formation of the β-Cu(2)Se dendritic morphology has been proposed based on time-dependent shape evolution. Further investigations revealed that the metastable β-Cu(2)Se can convert into the thermodynamically more stable cubic α-Cu(2-x)Se maintaining the dendritic morphology. An increase in electrical conductivity and a tunable optical response were observed under ambient conditions. This behavior can be explained by the oxidation of the surface of the β-Cu(2)Se hyperbranched structures, ultimately leading to solid-state phase conversion from β-Cu(2)Se into superionic conductor α-Cu(1.8)Se, which has potential applications in energy-related devices and sensors.

  20. Chain-growth click polymerization of AB2 monomers for the formation of hyperbranched polymers with low polydispersities in a one-pot process.

    PubMed

    Shi, Yi; Graff, Robert W; Cao, Xiaosong; Wang, Xiaofeng; Gao, Haifeng

    2015-06-22

    Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one-pot one-batch synthesis of polytriazole-based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB2 monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a "living" chain-growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed Cu(I) , which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83.

  1. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

    PubMed

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

    2015-08-05

    In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs.

  2. Amphiphilic semi-interpenetrating polymer networks using pulverized rubber

    NASA Astrophysics Data System (ADS)

    Shahidi, Nima

    Scrap rubber materials provide a significant challenge to either reuse or safe disposal. Every year, millions of tires are discarded to landfills in the United States, consuming a staggering amount of land space, creating a high risk for large fires, breeding mosquitoes that spread diseases, and wasting the planet's natural resources. This situation cannot be sustained. The challenge of reusing scrap rubber materials is mainly due to the crosslinked structure of vulcanized rubber that prevent them from melting and further processing for reuse. The most feasible recycling approach is believed to be a process in which the vulcanized rubber is first pulverized into a fine powder and then incorporated into new products. The production of fine rubber particles is generally accomplished through the use of a cryogenic process that is costly. Therefore, development of a cost effective technology that utilizes a large quantity of the scrap rubber materials to produce high value added materials is an essential element in maintaining a sustainable solution to rubber recycling. In this research, a cost effective pulverization process, solid state shear extrusion (SSSE), was modified and used for continuous pulverization of the rubber into fine particles. In the modified SSSE process, pulverization takes place at high compressive shear forces and a controlled temperature. Furthermore, an innovative particle modification process was developed to enhance the chemical structure and surface properties of the rubber particles for manufacturing of high value added products. Modification of rubber particles was accomplished through the polymerization of a hydrophilic monomer mixture within the intermolecular structure of the hydrophobic rubber particles. The resulting composite particles are considered as amphiphilic particulate phase semi-interpenetrating polymer networks (PPSIPNs). The modified rubber particles are water dispersible and suitable for use in a variety of aqueous media

  3. Self-assembling peptide amphiphile nanostructures for cancer therapy

    NASA Astrophysics Data System (ADS)

    Soukasene, Stephen

    The application of nanotechnology to cancer therapy shows great promise for reducing the burden of the disease. By virtue of their size, nanoscale objects preferentially accumulate in tumor tissue through an enhanced permeability and retention (EPR) effect. However, to fully overcome the issues that limit current cancer treatments, viable nanostructures must also impart multifunctionality and be fully compatible with their biological surrounds. The self-assembling peptide amphiphile (PA) materials studied extensively in the Stupp Research Group form very biocompatible high aspect ratio nanostructures that meet these criteria. This thesis investigates the development of PA nanostructures designed to treat cancer. We first look to use the PA as a drug delivery vehicle by entrapping a small hydrophobic anti-cancer drug, camptothecin, in the core of the nanostructures. Using a solvent evaporation technique to load the drug into the PA nanofibers, we are able to improve the aqueous solubility of the molecule by nearly 30-fold. TEM and AFM studies show that entrapment of drug molecules does not disrupt the self-assembled morphology of the nanofiber. In vitro and in vivo studies are also conducted to demonstrate the bioactivity of the drug after its entrapment. As a potential platform for novel therapeutics, we next develop techniques for using light irradiation to trigger self-assembly inside the confined space of liposomes. We encapsulate PA monomers that assemble under acidic conditions along with a photoacid generator inside liposomes. Upon exposure to 254 nm light, the PA monomers self assemble inside the liposome to form nanostructures, which we observe through a quick freeze/deep etch technique that allows us to look inside the liposomes by SEM and TEM. Last of all, the development and discovery of epitopes for targeting PA nanostructures to tumors are explored. Using phage display technology we generate two groups of peptide sequences, one of which can potentially

  4. Self-Assembling Peptide Amphiphiles for Targeted Drug Delivery

    NASA Astrophysics Data System (ADS)

    Moyer, Tyson

    The systemic delivery of therapeutics is currently limited by off-target side effects and poor drug uptake into the cells that need to be treated. One way to circumvent these issues is to target the delivery and release of therapeutics to the desired location while limiting systemic toxicity. Using self-assembling peptide amphiphiles (PAs), this work has investigated supramolecular nanostructures for the development of targeted therapies. Specifically, the research has focused on the interrelationships between presentation of targeting moeities and the control of nanostructure morphology in the context of systemic delivery for targeting cancer and vascular injuries. The self-assembly region of the PA was systematically altered to achieve control of nanostructure widths, from 100 nm to 10 nm, by the addition of valine-glutamic acid dimers into the chemical structure, subsequently increasing the degree of nanostructure twist. For the targeting of tumors, a homing PA was synthesized to include a dimeric, cyclic peptide sequence known to target the cancer-specific, death receptor 5 (DR5) and initiate apoptosis through the oligomerization of DR5. This PA presented a multivalent display of DR5-binding peptides, resulting in improved binding affinity measured by surface plasmon resonance. The DR5-targeting PA also showed enhanced efficacy in both in vitro and in vivo tumor models relative to non-targeted controls. Alternative modifications to the PA-based antitumor therapies included the use of a cytotoxic, membrane-lytic PA coassembled with a pegylated PA, which showed enhanced biodistribution and in vivo activity after coassembly. The functionalization of the hydrophobic core was also accomplished through the encapsulation of the chemotherapy camptothecin, which was shown to be an effective treatment in vivo. Additionally, a targeted PA nanostructure was designed to bind to the site of vascular intervention by targeting collagen IV. Following balloon angioplasty

  5. Kinetics of amphiphile association with two-phase lipid bilayer vesicles.

    PubMed Central

    Pokorny, A; Almeida, P F; Melo, E C; Vaz, W L

    2000-01-01

    We examined the consequences of membrane heterogeneity for the association of a simple amphiphilic molecule with phospholipid vesicles with solid-liquid and liquid-liquid phase coexistence. To address this problem we studied the association of a single-chain, fluorescent amphiphile with dimyristoylphosphatidylcholine (DMPC) vesicles containing varying amounts of cholesterol. DMPC bilayers containing 15 mol% cholesterol show a region of solid-liquid-ordered (s-l(o)) coexistence below the T(m) of pure DMPC (23.9 degrees C) and a region of liquid-disordered-liquid-ordered coexistence (l(d)-l(o)) above the T(m). We first examined equilibrium binding and kinetics of amphiphile insertion into single-phase vesicles (s, l(d), and l(o) phase). The data obtained were then used to predict the behavior of the equivalent process in a two-phase system, taking into account the fractions of phases present. Next, the predicted kinetics were compared to experimental kinetics obtained from a two-phase system. We found that association of the amphiphile with lipid vesicles is not influenced by the existence of l(d)-l(o) phase boundaries but occurs much more slowly in the s-l(o) phase coexistence region than expected on the basis of phase composition. PMID:10620291

  6. The encapsulation of an amphiphile into polystyrene microspheres of narrow size distribution.

    PubMed

    Pellach, Michal; Margel, Shlomo

    2011-12-06

    Encapsulation of compounds into nano- or microsized organic particles of narrow size distribution is of increasing importance in fields of advanced imaging and diagnostic techniques and drug delivery systems. The main technology currently used for encapsulation of molecules within uniform template particles while retaining their size distribution is based on particle swelling methodology, involving penetration of emulsion droplets into the particles. The swelling method, however, is efficient for encapsulation only of hydrophobic compounds within hydrophobic template particles. In order to be encapsulated, the molecules must favor the hydrophobic phase of an organic/aqueous biphasic system, which is not easily achieved for molecules of amphiphilic character.The following work overcomes this difficulty by presenting a new method for encapsulation of amphiphilic molecules within uniform hydrophobic particles. We use hydrogen bonding of acid and base, combined with a pseudo salting out effect, for the entrapment of the amphiphile in the organic phase of a biphasic system. Following the entrapment in the organic phase, we demonstrated, using fluorescein and (antibiotic) tetracycline as model molecules, that the swelling method usually used only for hydrophobes can be expanded and applied to amphiphilic molecules.

  7. From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces

    DOE PAGES

    Rother, Gernot; Müter, Dirk; Bock, Henry; ...

    2017-03-27

    Adsorption of a short-chain nonionic amphiphile (C6E3) at the surface of mesoporous silica glass (CPG-10) was studied by a combination of adsorption measurements and mesoscale simulations. Adsorption measurements covering a wide composition range of the C6E3 + water system show that no adsorption occurs up to the critical micelle concentration (cmc), at which a sharp increase of adsorption is observed that is attributed to ad-micelle formation at the pore walls. Intriguingly, as the concentration is increased further, the surface excess of the amphiphile begins to decrease and eventually becomes negative, which corresponds to preferential adsorption of water rather than amphiphilemore » at high amphiphile concentrations. The existence of such a surface-azeotropic point has not previously been reported in the surfactant adsorption field. Dissipative particle dynamics (DPD) simulations were performed to reveal the structural origin of this transition from aggregative adsorption to surface depletion. Finally, the simulations indicate that this transition can be attributed to the repulsive interaction between head groups, causing amphiphilic depletion in the region around the corona of the surface micelles.« less

  8. Hydrophilic modification of PVDF microfiltration membranes by adsorption of facial amphiphile cholic acid.

    PubMed

    Hu, Meng-Xin; Li, Ji-Nian; Zhang, Shi-Lin; Li, Liang; Xu, Zhi-Kang

    2014-11-01

    Amphiphilic molecules have been widely used in surface modification of polymeric materials. Bile acids are natural biological compounds and possess special facial amphiphilic structure with a unusual distribution of hydrophobic and hydrophilic regions. Based on the facial amphiphilicity, cholic acid (CA), one of the bile acids, was utilized for the hydrophilic modification of poly(vinylidene fluoride) (PVDF) microfiltration membranes via the hydrophobic interactions between the hydrophobic face of CA and the membrane surfaces. Ethanol, methanol, and water were respectively used as solvent during CA adsorption procedure. Their polarity affects the CA adsorption amount, as similar to CA concentration and adsorption time. There are no changes on the membrane surface morphology after CA adsorption. The hydrophilicity of PVDF membranes is greatly enhanced and the water drops permeates into the CA modified membranes quickly after modification. All these factors benefit to the permeation flux of membrane for water. When CA concentration is higher than 0.088 M, the water permeation flux is doubled as compared with the nascent PVDF membrane and shows a good stability during filtration procedure. These results reveal the promising potential of facial amphiphilic bile acids for the surface modification of polymeric materials.

  9. Aqueous Self-Assembly of Y-Shaped Amphiphilic Block Copolymers into Giant Vesicles.

    PubMed

    Li, Hanping; Jin, Yong; Fan, Baozhu; Lai, Shuangquan; Sun, Xiaopeng; Qi, Rui

    2017-02-06

    The preparation and aqueous self-assembly of newly Y-shaped amphiphilic block polyurethane (PUG) copolymers are reported here. These amphiphilic copolymers, designed to have two hydrophilic poly(ethylene oxide) (PEO) tails and one hydrophobic alkyl tail via a two-step coupling reaction, can self-assemble into giant unilamellar vesicles (GUVs) (diameter ≥ 1000 nm) with a direct dissolution method in aqueous solution, depending on their Y-shaped structures and initial concentrations. More interesting, the copolymers can self-assemble into various distinct nano-/microstructures, such as spherical micelles, small vesicles, and GUVs, with the increase of their concentrations. The traditional preparation methods of GUVs generally need conventional amphiphilic molecules and additional complicated conditions, such as alternating electrical field, buffer solution, or organic solvent. Therefore, the self-assembly of Y-shaped PUGs with a direct dissolution method in aqueous solution demonstrated in this study supplies a new clue to fabricate GUVs based on the geometric design of amphiphilic polymers.

  10. Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive

    NASA Astrophysics Data System (ADS)

    Li, Jian-Hua; Li, Mi-Zi; Miao, Jing; Wang, Jia-Bin; Shao, Xi-Sheng; Zhang, Qi-Qing

    2012-06-01

    An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.

  11. A poly(glycerol sebacate)-coated mesoporous bioactive glass scaffold with adjustable mechanical strength, degradation rate, controlled-release and cell behavior for bone tissue engineering.

    PubMed

    Lin, Dan; Yang, Kai; Tang, Wei; Liu, Yutong; Yuan, Yuan; Liu, Changsheng

    2015-07-01

    Various requirements in the field of tissue engineering have motivated the development of three-dimensional scaffold with adjustable physicochemical properties and biological functions. A series of multiparameter-adjustable mesoporous bioactive glass (MBG) scaffolds with uncrosslinked poly(glycerol sebacate) (PGS) coating was prepared in this article. MBG scaffold was prepared by a modified F127/PU co-templating process and then PGS was coated by a simple adsorption and lyophilization process. Through controlling macropore parameters and PGS coating amount, the mechanical strength, degradation rate, controlled-release and cell behavior of the composite scaffold could be modulated in a wide range. PGS coating successfully endowed MBG scaffold with improved toughness and adjustable mechanical strength covering the bearing range of trabecular bone (2-12MPa). Multilevel degradation rate of the scaffold and controlled-release rate of protein from mesopore could be achieved, with little impact on the protein activity owing to an "ultralow-solvent" coating and "nano-cavity entrapment" immobilization method. In vitro studies indicated that PGS coating promoted cell attachment and proliferation in a dose-dependent manner, without affecting the osteogenic induction capacity of MBG substrate. These results first provide strong evidence that uncrosslinked PGS might also yield extraordinary achievements in traditional MBG scaffold. With the multiparameter adjustability, the composite MBG/PGS scaffolds would have a hopeful prospect in bone tissue engineering. The design considerations and coating method of this study can also be extended to other ceramic-based artificial scaffolds and are expected to provide new thoughts on development of future tissue engineering materials.

  12. O/W nano-emulsion formation using an isothermal low-energy emulsification method in a mixture of polyglycerol polyricinoleate and hexaglycerol monolaurate with glycerol system.

    PubMed

    Wakisaka, Satoshi; Nishimura, Takahisa; Gohtani, Shoichi

    2015-01-01

    We investigated how phase behavior changes by replacing water with glycerol in water/mixture of polyglycerol polyricinoleate (PGPR) and hexaglycerol monolaurate (HGML) /vegetable oil system, and studied the effect of glycerol on o/w nano-emulsion formation using an isothermal low-energy method. In the phase behavior study, the liquid crystalline phase (Lc) + the sponge phase (L3) expanded toward lower surfactant concentration when water was replaced with glycerol in a system containing surfactant HLP (a mixture of PGPR and HGML). O/W nano-emulsions were formed by emulsification of samples in a region of Lc + L3. In the glycerol/surfactant HLP/vegetable oil system, replacing water with glycerol was responsible for the expansion of a region containing Lc + L3 toward lower surfactant concentration, and as a result, in the glycerol/surfactant HLP/vegetable oil system, the region where o/w nano-emulsions or o/w emulsions could be prepared using an isothermal low-energy emulsification method was wide, and the droplet diameter of the prepared o/w emulsions was also smaller than that in the water/surfactant HLP/vegetable oil system. Therefore, glycerol was confirmed to facilitate the preparation of nano-emulsions from a system of surfactant HLP. Moreover, in this study, we could prepare o/w nano-emulsions with a simple one-step addition of water at room temperature without using a stirrer. Thus, the present technique is highly valuable for applications in several industries.

  13. Biocompatibility and characterization of polyglycerol-based thermoresponsive nanogels designed as novel drug-delivery systems and their intracellular localization in keratinocytes.

    PubMed

    Gerecke, Christian; Edlich, Alexander; Giulbudagian, Michael; Schumacher, Fabian; Zhang, Nan; Said, Andre; Yealland, Guy; Lohan, Silke B; Neumann, Falko; Meinke, Martina C; Ma, Nan; Calderón, Marcelo; Hedtrich, Sarah; Schäfer-Korting, Monika; Kleuser, Burkhard

    2017-03-01

    Novel nanogels that possess the capacity to change their physico-chemical properties in response to external stimuli are promising drug-delivery candidates for the treatment of severe skin diseases. As thermoresponsive nanogels (tNGs) are capable of enhancing penetration through biological barriers such as the stratum corneum and are taken up by keratinocytes of human skin, potential adverse consequences of their exposure must be elucidated. In this study, tNGs were synthesized from dendritic polyglycerol (dPG) and two thermoresponsive polymers. tNG_dPG_tPG are the combination of dPG with poly(glycidyl methyl ether-co-ethyl glycidyl ether) (p(GME-co-EGE)) and tNG_dPG_pNIPAM the one with poly(N-isopropylacrylamide) (pNIPAM). Both thermoresponsive nanogels are able to incorporate high amounts of dexamethasone and tacrolimus, drugs used in the treatment of severe skin diseases. Cellular uptake, intracellular localization and the toxicological properties of the tNGs were comprehensively characterized in primary normal human keratinocytes (NHK) and in spontaneously transformed aneuploid immortal keratinocyte cell line from adult human skin (HaCaT). Laser scanning confocal microscopy revealed fluorescently labeled tNGs entered into the cells and localized predominantly within lysosomal compartments. MTT assay, comet assay and carboxy-H2DCFDA assay, demonstrated neither cytotoxic or genotoxic effects, nor any induction of reactive oxygen species of the tNGs in keratinocytes. In addition, both tNGs were devoid of eye irritation potential as shown by bovine corneal opacity and permeability (BCOP) test and red blood cell (RBC) hemolysis assay. Therefore, our study provides evidence that tNGs are locally well tolerated and underlines their potential for cutaneous drug delivery.

  14. Dendritic polyglycerol and N-isopropylacrylamide based thermoresponsive nanogels as smart carriers for controlled delivery of drugs through the hair follicle.

    PubMed

    Sahle, Fitsum Feleke; Giulbudagian, Michael; Bergueiro, Julian; Lademann, Jürgen; Calderón, Marcelo

    2017-01-07

    Nanoparticles with a size of several hundred nanometers can effectively penetrate into the hair follicles and may serve as depots for controlled drug delivery. However, they can neither overcome the hair follicle barrier to reach the viable cells nor release the loaded drug adequately. On the other hand, small drug molecules cannot penetrate deep into the hair follicles. Thus, the most efficient way for drug delivery through the follicular route is to employ nanoparticles that can release the drug close to the target structure upon exposure to some external or internal stimuli. Accordingly, 100-700 nm sized thermoresponsive nanogels with a phase transition temperature of 32-37 °C were synthesized by the precipitation polymerization technique using N-isopropylacrylamide as a monomer, acrylated dendritic polyglycerol as a crosslinker, VA-044 as an initiator, and sodium dodecyl sulphate as a stabilizer. The follicular penetration of the indodicarbocyanine (IDCC) labeled nanogels into the hair follicles and the release of coumarin 6, which was loaded as a model drug, in the hair follicles were assessed ex vivo using porcine ear skin. Confocal laser scanning microscopy (CLSM) enabled independent tracking of the nanogels and the loaded dye, although it is not as precise and accurate as standard analytical methods. The results showed that, unlike smaller nanogels (<100 nm), medium and larger sized nanogels (300-500 nm) penetrated effectively into the hair follicles with penetration depths proportional to the nanogel size. The release of the loaded dye in the hair follicles increased significantly when the investigation on penetration was carried out above the cloud point temperature of the nanogels. The follicular penetration of the nanogels from the colloidal dispersion and a 2.5% hydroxyethyl cellulose gel was not significantly different.

  15. 3D Cell Entrapment as a Function of the Weight Percent of Peptide-Amphiphile Hydrogels

    PubMed Central

    Scott, Carolyn M.; Forster, Colleen L.; Kokkoli, Efrosini

    2015-01-01

    The design of scaffolds which mimic the stiffness, nanofiber structure, and biochemistry of the native extra-cellular matrix (ECM) has been a major objective for the tissue engineering field. Furthermore, mimicking the innate three dimensional (3D) environment of the ECM has been shown to significantly alter cellular response compared to traditional two dimensional (2D) culture. We report the development of a self-assembling, fibronectin-mimetic, peptide-amphiphile nanofiber scaffold for 3D cell culture. To form such a scaffold, 5 mol% of a bioactive PR_g fibronectin-mimetic peptide-amphiphile was mixed with 95 mol% of a diluent peptide-amphiphile (E2) whose purpose was to neutralize electrostatic interactions, increase the gelation kinetics and promote cell survival. Atomic force microscopy verified the fibrilar structure of the gels and the mechanical properties were characterized for various weight percent (wt%) formulations of the 5 mol% PR_g - 95 mol% E2 peptide-amphiphile mixture. The 0.5 wt% formulations had an elastic modulus of 429.0 ± 21.3 Pa while the 1.0 wt% peptide-amphiphile hydrogels had an elastic modulus of 808.6 ± 38.1 Pa. The presence of entrapped cells in the gels decreased the elastic modulus and the decrease was a function of the cell loading. While both formulations supported cell proliferation, the 0.5 wt% gels supported significantly greater NIH3T3/GFP fibroblast cell proliferation throughout the gels than the 1.0 wt% gels. However, compared to the 0.5 wt% formulations, the 1.0 wt% hydrogels promoted greater increase in mRNA expression and production of fibronectin and type IV collagen ECM proteins. This study suggests that this fibronectin-mimetic scaffold holds great promise in the advance of 3D culture applications and cell therapies. PMID:25970351

  16. Structure and reactions in some amphiphilic association systems

    NASA Astrophysics Data System (ADS)

    Guo, Rong

    1999-06-01

    surfactant CTAB system with various co-surfactants: n-pentanol, n-octanol, n-valeric acid, and n-caproic acid, but not in SDS or Triton X-100 systems. Presence of VC stabilizes both W/O and O/W microemulsions but destabilizes the lamellar liquid crystalline phase. Hence, the "phase transition" from the lamellar liquid crystalline phase to the isotropic phase of O/W, W/O and bicontinuous structure phase occurs with the addition of VC. The hydrotropic action of VC has been used in sunscreens to increase the solubility of sunscreen E 557. The UV absorption spectra of E557 in various media surprisingly had a dependence on the colloid structure. A new method, the preparation of water-soluble nanoparticles, has been found by employing the effect of the penetration of solvent from water layer to amphiphilic layer in lamellar liquid crystals on the solubility of inorganic salts. Water-insoluble nanoparticles have been synthesized by the reaction of two water-soluble inorganic salts in the lamellar liquid crystal. The particle size is less than 10nm and can be controlled by the thickness of the solvent layer in the lamellar liquid crystal. The lamellar liquid crystalline phase of the Triton X-100/decanol/water system has been chosen as a medium because of its large lamellar liquid crystal region and its stability when inorganic salts are added.

  17. Conjugation of cytochrome c with ferrocene-terminated hyperbranched polymer and its influence on protein structure, conformation and function

    NASA Astrophysics Data System (ADS)

    Xiao, Fengjuan; Yue, Lin; Li, Song; Li, Xinxin

    2016-06-01

    Interaction mechanism of a new hyperbranched polyurethane-based ferrocene (HPU-Fc) with cytochrome c (cyt c) and cyt c structure and conformation change induced by HPU-Fc were investigated using cyclic voltammogram(CV), differential pulse voltammetry (DPV), circular dichroism (CD), fluorescence, synchronous fluorescence and absorbance spectroscopy technique. The peroxidase activity of cyt c in the presence of HPU-Fc was also studied. The structure and conformation of protein are relatively stable at moderate concentration of HPU-Fc without obvious perturbation of the heme pocket and significant changes in protein secondary structure. Conjugation of cyt c with excessive HPU-Fc (over about 3 times of cyt c) slightly changed the α-helix structure in protein, disturbed the microenvironment around heme as well as away from the heme crevice, which caused the changes of the electrochemical behavior and the absorption spectra. Reasonable amount of HPU-Fc has no significant influence on the protein enzymatic activity, while excess HPU-Fc may cause a conformation not suitable for H2O2 activation and guaiacol oxidation. The interaction of HPU-Fc with cyt c and the conservation of protein function at suitable HPU-Fc amount make prepared complex promising for the synergistic anticancer therapy. CV curves of 10 μM HPU-Fc, 10 μM cyt c and HPU-Fc/cyt c complex (n HPU-Fc: n cyt c = 3.5:1) in 0.5 M KCl (versus SCE) at a sweep rate of 100 mV ṡ s- 1 (b). Interaction mechanism of a new hyperbranched polyurethane-based ferrocene (HPU-Fc) with cytochrome c (cyt c) and cyt c structure and conformation change induced by HPU-Fc were investigated. The structure and conformation of protein are relatively stable at moderate concentration of HPU-Fc. Conjugation of cyt c with excessive HPU-Fc (over about 3 times of cyt c) slightly changed the α-helix structure in protein, disturbed the microenvironment around heme as well as away from the heme crevice, which caused the changes of the

  18. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: the study of hydrophilic and hydrophobic microdomain.

    PubMed

    Zhou, Xiangyu; Wei, Junfu; Zhang, Huan; Liu, Kai; Wang, Han

    2014-05-30

    A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application.

  19. Two-dimensional self-assembly of amphiphilic peptides; adsorption-induced secondary structural transition on hydrophilic substrate.

    PubMed

    Tanaka, Masayoshi; Abiko, Souhei; Himeiwa, Takahiro; Kinoshita, Takatoshi

    2015-03-15

    Adsorption of sequential amphiphilic peptides on solid substrates triggered the spontaneous construction of nanoscaled architecture. An amphiphilic peptide designed with a cationic amino acid as a hydrophilic residue turned an anionic mica substrate into a water-repellent surface, simply by adsorbing it on the substrate surface. In contrast, an amphiphilic peptide designed with an anionic amino-acid residue formed a precisely controlled fiber array comprising a β-sheet fiber monolayer at the anionic substrate/water interface. This phenomenon was based on the secondary structural transition from random-coil to β-sheet, which occurred specifically when amphiphilic peptide adsorbed on the substrate surface. Such surface-specific nonorder/order transition was implemented by exploiting the strength of adsorption between the peptide and the substrate. A strategic design exploiting weak bonding such as hydrophobic interactions is essential for constructing precisely controlled nano-architectures in two dimensions.

  20. Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition.

    PubMed

    Keleş, Elif; Hazer, Baki; Cömert, Füsun B

    2013-04-01

    A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene-block-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS-b-PI-b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, (1)H NMR, (13)C NMR, GPC and FTIR.

  1. Molecular aggregation of naphthalimide organic semiconductors assisted by amphiphilic and lipophilic interactions: a joint theoretical and experimental study.

    PubMed

    Arrechea-Marcos, I; de Echegaray, P; Mancheño, M J; Ruiz Delgado, M C; Ramos, M M; Quintana, J A; Villalvilla, J M; Díaz-García, M A; López Navarrete, J T; Ponce Ortiz, R; Segura, J L

    2017-02-22

    Amphiphilic and lipophilic donor-acceptor naphthalimide-oligothiophene assemblies exhibiting almost identical intramolecular properties, but differing in their intermolecular interactions, have been synthesized. Here we analyze the effect of replacing the normally used lipophilic alkyl chains with hydrophilic ones in directing molecular aggregation from an antiparallel to a parallel stacking. This different molecular packing of the amphiphilic, NIP-3TAmphi, and lipophilic, NIP-3TLipo, systems is assessed by electronic spectroscopies, scanning electronic microscopy and DFT quantum-chemical calculations. Theoretical calculations indicate that the presence of amphiphilic interactions promotes a face-to-face parallel arrangement of neighbor molecules, which induces improved electronic coupling and therefore enhances the charge transport ability and photoconducting properties of this type of materials. Time of flight and photoconducting measurements are used to determine the impact of the amphiphilic and lipophilic interactions on their possible performance in optoelectronic devices.

  2. Amphiphilic, ultralight, and multifunctional graphene/nanofibrillated cellulose aerogel achieved by cation-induced gelation and chemical reduction

    NASA Astrophysics Data System (ADS)

    Yao, Xuelin; Yu, Wenjin; Xu, Xin; Chen, Feng; Fu, Qiang

    2015-02-01

    Nanofibrillated cellulose (NFC) was incorporated to reduced graphene oxide (rGO) for fabrication of multifunctional amphiphilic aerogels. The as-prepared amphiphilic aerogel showed excellent recoverability, superior absorption capacity for both organic solvents and water, and an electrical conductivity sensitive to compressive strain making it highly potential to be used as a pressure-responsive sensor.Nanofibrillated cellulose (NFC) was incorporated to reduced graphene oxide (rGO) for fabrication of multifunctional amphiphilic aerogels. The as-prepared amphiphilic aerogel showed excellent recoverability, superior absorption capacity for both organic solvents and water, and an electrical conductivity sensitive to compressive strain making it highly potential to be used as a pressure-responsive sensor. Electronic supplementary information (ESI) available: Details of experimental procedures and supporting figures and tables. See DOI: 10.1039/c4nr07402e

  3. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 2. Study of the asphaltene-amphiphile interactions and structures using Fourier transform infrared spectroscopy and small-angle X-ray scattering techniques

    SciTech Connect

    Chang, C.L.; Fogler, H.S. )

    1994-06-01

    In the preceding paper in this issue, the influence of the chemical structure of a series of alkylbenzene-derived amphiphiles on the stabilization of asphaltenes was described. In this paper, we present the results of using Fourier transform infrared (FTIR) spectroscopy and small-angle X-ray scattering (SAXS) techniques to study the interaction between asphaltenes and two alkylbenzene-derived amphiphiles, p-alkylphenol and p-alkylbenzenesulfonic acid. FTIR spectroscopy was used to characterize and quantify the acid-base interactions between asphaltenes and amphiphiles. It was found that asphaltenes could hydrogen-bond to p-dodecylphenol amphiphiles. The hydrogen-bonding capacity of asphaltenes was estimated to be 1.6-2.0 mmol/g of asphaltene. On the other hand, the FTIR spectroscopic study indicated that asphaltenes had a complicated acid-base interaction with p-dodecylbenzenesulfonic acid (DBSA) amphiphiles with a stoichiometry of about 1.8 mmol of DBSA/g of asphaltene. The UV/vis spectroscopic study suggested that asphaltenes and DBSA could associate into large electronic conjugated complexes. Physical evidence of the association between asphaltenes and amphiphiles was obtained by SAXS measurements. 27 refs., 10 figs.

  4. From bola-amphiphiles to supra-amphiphiles: the transformation from two-dimensional nanosheets into one-dimensional nanofibers with tunable-packing fashion of n-type chromophores.

    PubMed

    Liu, Kai; Yao, Yuxing; Wang, Chao; Liu, Yu; Li, Zhibo; Zhang, Xi

    2012-07-09

    With a rational design of the supra-amphiphiles, we have successfully demonstrated that not only the dimension of the self-assembled nanostructures, but also the packing fashion of the functional naphthalene diimide (a typical n-type chromophore), can be tuned in a noncovalent way in aqueous solution. Naphthalene diimide is incorporated into a bola-amphiphile as the rigid core, whereas viologen derivatives are used as the hydrophilic head. The bola-amphiphile self-assembles into two-dimensional nanosheets, in which naphthalene diimide adopts a "J-type" aggregation. Water-soluble supramolecular complexation between viologen derivatives and the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is used as a driving force for the formation of the supra-amphiphiles. Upon formation of the supra-amphiphiles, the nanosheets transform into ultralong nanofibers with a close packing of naphthalene diimide. Notably, just by mixing the two building blocks of the supra-amphiphiles in aqueous solution, a dimension-controlled evolution of the nanostructures is formed that leads to a different packing fashion of the n-type functional chromophores, which is facile and environmental friendly.

  5. Nanostructured films of amphiphilic fluorinated block copolymers for fouling release application.

    PubMed

    Martinelli, Elisa; Agostini, Serena; Galli, Giancarlo; Chiellini, Emo; Glisenti, Antonella; Pettitt, Michala E; Callow, Maureen E; Callow, James A; Graf, Katja; Bartels, Frank W

    2008-11-18

    New amphiphilic block copolymers S nSz m consisting of blocks with varied degrees of polymerization, n and m, of polystyrene, S, and polystyrene carrying an amphiphilic polyoxyethylene-polytetrafluoroethylene chain side-group, Sz, were prepared by controlled atom transfer radical polymerization (ATRP). The block copolymers, either alone or in a blend with commercial SEBS (10 wt% SEBS), were spin-coated in thinner films (200-400 nm) on glass and spray-coated in thicker films ( approximately 500 nm) on a SEBS underlayer (150-200 microm). Angle-resolved X-ray photoelectron spectroscopy (XPS) measurements proved that at any photoemission angle, varphi, the atomic ratio F/C was larger than that expected from the known stoichiometry. Consistent with the enrichment of the outer film surface (3-10 nm) in F content, the measured contact angles, theta, with water (theta w > or = 107 degrees ) and n-hexadecane (theta h > or = 64 degrees ) pointed to the simultaneous hydrophobic and lipophobic character of the films. The film surface tension gamma S calculated from the theta values was in the range 13-15 mN/m. However, the XPS measurements on the "wet" films after immersion in water demonstrated that the film surface underwent reconstruction owing to its amphiphilic nature, thereby giving rise to a more chemically heterogeneous structure. The atomic force microscopy (AFM) images (tapping mode/AC mode) revealed well-defined morphological features of the nanostructured films. Depending on the chemical composition of the block copolymers, spherical (ca. 20 nm diameter) and lying cylindrical (24-29 nm periodicity) nanodomains of the S discrete phase were segregated from the Sz continuous matrix (root-mean-square, rms, roughness approximately 1 nm). After immersion in water, the underwater AFM patterns evidenced a transformation to a mixed surface structure, in which the nanoscale heterogeneity and topography (rms = 1-6 nm) were increased. The coatings were subjected to laboratory

  6. Photophysical and photochemical studies of a novel amphiphilic zinc phthalocyanine and its interaction with calf thymus DNA

    NASA Astrophysics Data System (ADS)

    Yuan, Linxin; Gui, Li; Wang, Yue; Zhang, Quanquan; Zhou, Lin; Wei, Shaohua

    2016-04-01

    β-tetra (aminophenoxy) sulfonic substituted zinc phthalocyanines (SNZnPc), a novel amphiphilic zinc phthalocyanine (Pc), was synthesized. The photophysical, photochemical, and photobiology properties were studied. Results indicated that the synthesized SNZnPc has good amphiphilic property and high reactive oxygen species (ROSs) generation ability. Furthermore, SNZnPc has strong affinity to calf thymus DNA (CT-DNA) through intercalation ways and can effectively cleavage CT-DNA after irradiation by light with appropriate wavelength.

  7. A label-free and high sensitive aptamer biosensor based on hyperbranched polyester microspheres for thrombin detection.

    PubMed

    Sun, Chong; Han, Qiaorong; Wang, Daoying; Xu, Weimin; Wang, Weijuan; Zhao, Wenbo; Zhou, Min

    2014-11-19

    In this paper, we have synthesized hyperbranched polyester microspheres with carboxylic acid functional groups (HBPE-CA) and developed a label-free electrochemical aptamer biosensor using thrombin-binding aptamer (TBA) as receptor for the measurement of thrombin in whole blood. The indium tin oxide (ITO) electrode surface modified with HBPE-CA microspheres was grafted with TBA, which has excellent binding affinity and selectivity for thrombin. Binding of the thrombin at the modified ITO electrode surface greatly restrained access of electrons for a redox probe of [Fe(CN)6](3-/4-). Moreover, the aptamer biosensor could be used for detection of thrombin in whole blood, a wide detection range (10fM-100nM) and a detection limit on the order of 0.90fM were demonstrated. Control experiments were also carried out by using bull serum albumin (BSA) and lysozyme in the absence of thrombin. The good stability and repeatability of this aptamer biosensor were also proved. We expect that this demonstration will lead to the development of highly sensitive label-free sensors based on aptamer with lower cost than current technology. The integration of the technologies, which include anticoagulant, sensor and nanoscience, will bring significant input to high-performance biosensors relevant to diagnostics and therapy of interest for human health.

  8. Electrochemiluminescence biosensor for ultrasensitive determination of ochratoxin A in corn samples based on aptamer and hyperbranched rolling circle amplification.

    PubMed

    Yang, Linlin; Zhang, Ying; Li, Ruibao; Lin, Cuiying; Guo, Longhua; Qiu, Bin; Lin, Zhenyu; Chen, Guonan

    2015-08-15

    Determination of ochratoxin A (OTA) is highly important for food safety control. In this study, a signal-on electrochemiluminescence (ECL) biosensor which combined the characteristics of high efficiency of hyperbranched rolling circle amplification (HRCA) and high selectivity of aptamer was developed for OTA determination. The capture probe DNA (CDNA) was firstly immobilized on the gold electrode surface through Au-S interaction, then the OTA aptamer was modified on the electrode surface through hybridization with CDNA. Since OTA can competitively bind with the aptamer due to their high affinity, which would induce the releasing of aptamer from the electrode surface. Subsequently, the free CDNA on the electrode surface can hybridize with the padlock probe and induce HRCA reaction subsequently. Thus, the HRCA products which contained large amount of double-stranded DNA (dsDNA) fragments can be accumulated on the electrode surface. Since Ru(phen)3(2+) can intercalate into the groove of dsDNA and acts as ECL indicator, high ECL intensity can be detected from the electrode surface. The enhanced ECL intensity has a linear relationship with OTA in the range of 0.05-500 pg/mL with a correlation coefficient of 0.9957, and the limit of detection (LOD) was 0.02 pg/mL. The developed biosensor has been applied to determine OTA concentration in the corn samples with satisfied results.

  9. Fabrication of magnetic water-soluble hyperbranched polyol functionalized graphene oxide for high-efficiency water remediation

    NASA Astrophysics Data System (ADS)

    Hu, Lihua; Li, Yan; Zhang, Xuefei; Wang, Yaoguang; Cui, Limei; Wei, Qin; Ma, Hongmin; Yan, Liangguo; Du, Bin

    2016-06-01

    Magnetic water-soluble hyperbranched polyol functionalized graphene oxide nanocomposite (MWHPO-GO) was successfully prepared and applied to water remediation in this paper. MWHPO-GO was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), magnetization curve, zeta potential, scanning electron microscope (SEM) and transmission electron microscope (TEM) analyses. MWHPO-GO exhibited excellent adsorption performance for the removal of synthetic dyes (methylene blue (MB) and methyl violet (MV)) and heavy metal (Pb(II)). Moreover, MWHPO-GO could be simply recovered from water with magnetic separation. The pseudo-second order equation and the Langmuir model exhibited good correlation with the adsorption kinetic and isotherm data, respectively, for these three pollutants. The thermodynamic results (ΔG < 0, ΔH < 0, ΔS < 0) implied that the adsorption process of MB, MV and Pb(II) was feasible, exothermic and spontaneous in nature. A possible adsorption mechanism has been proposed where π-π stacking interactions, H-bonding interaction and electrostatic attraction dominated the adsorption of MB/MV and chelation and electrostatic attraction dominated the adsorption of Pb(II). In addition, the excellent reproducibility endowed MWHPO-GO with the potential for application in water remediation.

  10. Fabrication of magnetic water-soluble hyperbranched polyol functionalized graphene oxide for high-efficiency water remediation

    PubMed Central

    Hu, Lihua; Li, Yan; Zhang, Xuefei; Wang, Yaoguang; Cui, Limei; Wei, Qin; Ma, Hongmin; Yan, Liangguo; Du, Bin

    2016-01-01

    Magnetic water-soluble hyperbranched polyol functionalized graphene oxide nanocomposite (MWHPO-GO) was successfully prepared and applied to water remediation in this paper. MWHPO-GO was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), magnetization curve, zeta potential, scanning electron microscope (SEM) and transmission electron microscope (TEM) analyses. MWHPO-GO exhibited excellent adsorption performance for the removal of synthetic dyes (methylene blue (MB) and methyl violet (MV)) and heavy metal (Pb(II)). Moreover, MWHPO-GO could be simply recovered from water with magnetic separation. The pseudo-second order equation and the Langmuir model exhibited good correlation with the adsorption kinetic and isotherm data, respectively, for these three pollutants. The thermodynamic results (ΔG < 0, ΔH < 0, ΔS < 0) implied that the adsorption process of MB, MV and Pb(II) was feasible, exothermic and spontaneous in nature. A possible adsorption mechanism has been proposed where π-π stacking interactions, H-bonding interaction and electrostatic attraction dominated the adsorption of MB/MV and chelation and electrostatic attraction dominated the adsorption of Pb(II). In addition, the excellent reproducibility endowed MWHPO-GO with the potential for application in water remediation. PMID:27354318

  11. Hyper-branched polymer grafting graphene oxide as an effective flame retardant and smoke suppressant for polystyrene.

    PubMed

    Hu, Weizhao; Yu, Bin; Jiang, Shu-Dong; Song, Lei; Hu, Yuan; Wang, Bibo

    2015-12-30

    A well-defined functionalized graphene oxide (FGO) grafted by hyper-branched flame retardant based on N-aminoethyl piperazine and phosphonate derivative was synthesized to reduce flammability and toxicity of polystyrene (PS). The chemical structure, morphological and thermal properties were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis, respectively. Micro combustion calorimeter and steady state tube furnace were employed to evaluate the heat and non-heat fire hazards of PS nanocomposites. The incorporation of FGO into PS matrix effectively improved the flame retardancy and restrained the toxicity of the volatiles escaped, which is attributed to that the homogeneous dispersion of FGO in the PS matrix enhanced barrier effect that reduced peak heat release rate, total heat release and toxic gas release during combustion. Furthermore, PS-FGO nanocompsites obviously decreased the amount of flammable and toxic volatiles evolved, such as the aromatic compounds, carbonyl compounds, carbon monoxide, indicating suppressed fire hazards of the PS composites.

  12. An amperometric urea biosensor based on covalently immobilized urease on an electrode made of hyperbranched polyester functionalized gold nanoparticles.

    PubMed

    Tiwari, Ashutosh; Aryal, Santosh; Pilla, Srikanth; Gong, Shaoqin

    2009-06-15

    An amperometric biosensor was fabricated for the quantitative determination of urea in aqueous medium using hematein, a pH-sensitive natural dye. The urease (Urs) was covalently immobilized onto an electrode made of gold nanoparticles functionalized with hyperbranched polyester-Boltron H40 (H40-Au) coated onto an indium-tin oxide (ITO) covered glass substrate. The covalent linkage between the Urs enzyme and H40-Au nanoparticles provided the resulting enzyme electrode (Urs/H40-Au/ITO) with a high level of enzyme immobilization and excellent lifetime stability. The response studies were carried out as a function of urea concentration with amperometric and photometric measurements. The biosensor based on Urs/H40-Au/ITO as the working electrode showed a linear current response to the urea concentration ranging from 0.01 to 35 mM. The urea biosensor exhibited a sensitivity of 7.48 nA/mM with a response time of 3s. The Michaelis-Menten constant for the Urs/H40-Au/ITO biosensor was calculated to be 0.96 mM, indicating the Urs enzyme immobilized on the electrode surface had a high affinity to urea.

  13. Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer

    NASA Astrophysics Data System (ADS)

    Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-aki

    2015-04-01

    Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp 2 carbon network of the HB-FePc catalysts may occur up to 900°C.

  14. Characterization of oligosaccharide-functionalized hyperbranched poly(ethylene imine) and their complexes with retinol in aqueous solution.

    PubMed

    Bekhradnia, Sara; Naz, Iram; Lund, Reidar; Effenberg, Christiane; Appelhans, Dietmar; Sande, Sverre Arne; Nyström, Bo

    2015-11-15

    Structure, internal density distribution, and size of hyperbranched poly(ethylene imine) (PEI) functionalized with various amounts of maltose (PEI-Mal) in phosphate buffer were studied by small angle X-ray scattering (SAXS) and dynamic light scattering (DLS). The value of pH was varied in the range from 3 to 9. Virtually no effect of pH on the nanostructure was found in this interval. The SAXS results revealed a broad segmental radial density distribution, i.e. a "fluffy" globular structure rather than a distinct core-shell structure with a high-density compact core and a low-density corona. This suggests that the maltose units are rather evenly distributed both in the interior and on the surface of the species with a PEI-core of molar mass of 25,000g/mol. The DLS measurements showed that the overall size of the PEI-Mal derivatives increased as the number of maltose units in the PEI-Mal structures rises. The interaction of the hydrophobic model drug retinol with PEI or PEI-Mal derivatives was also investigated. The UV-visible spectroscopy results disclosed that the solubility of retinol in the phosphate buffer is very poor and it takes a very long time to solubilize retinol. Moreover, retinol induces aggregation of dendritic glycopolymers where the growth of aggregates occurs continuously over several days and then remains virtually constant.

  15. A sensitive and specific hyperbranched rolling circle amplification assay and test strip for white spot syndrome virus.

    PubMed

    Zhao, Yu-Ran; Yin, Wei-Li; Yue, Zhi-Qin; Li, Ba-Fang

    2014-01-01

    White spot syndrome virus (WSSV) is a global threat to the prawn industry, and there is no simple method for field-based testing of this virus. We designed a padlock probe and primers to the capsid protein gene VP28 of WSSV, and established a hyperbranched rolling circle amplification (HRCA) assay and a corresponding strip-based test. The assay and the test strip both had similar high accuracy and specificity, and their sensitivity was about 10 copies/μL, which is 100 times higher than conventional PCR. In this study, 68 batches of prawns were tested for WSSV with the HRCA assay and test strip, and the results were compared with the PCR assay. The results indicated that both the assay and test strip had accuracy similar to each other and to the PCR results. However, the assay and strip were more sensitive and user-friendly than PCR. Establishment of this method will provide a rapid detection of WSSV and also a basis for field-based detection of animal disease.

  16. Bio-based hyperbranched polyurethane/Fe3O4 nanocomposites: smart antibacterial biomaterials for biomedical devices and implants.

    PubMed

    Das, Beauty; Mandal, Manabendra; Upadhyay, Aadesh; Chattopadhyay, Pronobesh; Karak, Niranjan

    2013-06-01

    The fabrication of a smart magnetically controllable bio-based polymeric nanocomposite (NC) has immense potential in the biomedical domain. In this context, magneto-thermoresponsive sunflower oil modified hyperbranched polyurethane (HBPU)/Fe3O4 NCs with different wt.% of magnetic nanoparticles (Fe3O4) were prepared by an in situ polymerization technique. Fourier-transform infrared, x-ray diffraction, vibrating sample magnetometer, scanning electron microscope, transmission electron microscope, thermal analysis and differential scanning calorimetric were used to analyze various physico-chemical structural attributes of the prepared NC. The results showed good interfacial interactions between HBPU and well-dispersed superparamagnetic Fe3O4, with an average diameter of 7.65 nm. The incorporation of Fe3O4 in HBPU significantly improved the thermo-mechanical properties along with the shape-memory behavior, antibacterial activity, biocompatibility as well as biodegradability in comparison to the pristine system. The cytocompatibility of the degraded products of the NC was also verified by in vitro hemolytic activity and MTT assay. In addition, the in vivo biocompatibility and non-immunological behavior, as tested in Wistar rats after subcutaneous implantation, show promising signs for the NC to be used as antibacterial biomaterial for biomedical device and implant applications.

  17. Preparation of complementary glycosylated hyperbranched polymer/poly(ethylene glycol) brushes and their selective interactions with hepatocytes.

    PubMed

    Liang, Su; Yu, Shan; Gao, Changyou

    2016-09-01

    Selective cell adhesion and migration, which mimics the natural biological events in vivo, is very important for the right repair of damaged tissues. In this study, glycosylated hyperbranched polymers (LA-HPMA) were synthesized, and were grafted on glass slide through dopamine deposition with different densities adjusted by co-grafting of poly(ethylene glycol) (PEG). The LA-HPMA and PEG molecular brushes were characterized by X-ray photoelectron spectroscopy (XPS), quartz crystal microbalance with dissipation (QCM-d) and ellipsometry. The adhesion of human hepatoma (HepG2) cells was promoted on the surface of a higher LA-HPMA density, and the migration rate was accelerated from 6.4μm/h on PEG surface to 12.7μm/h on 75% LA-HPMA surface. By contrast, the density and spreading area of mouse embryonic fibroblast (NIH3T3) cells were not significantly influenced by the LA-HPMA density, and the migration rate did not change significantly on all types of surfaces either. Therefore, the specific interactions of carbohydrate-protein can be used to modulate cell behaviors in vitro, for example the selective adhesion and migration of HepG2 cells.

  18. Liquid-Gel-Liquid Transition and Shear-Thickening in Mixed Suspensions of Silica Colloid and Hyperbranched Polyethyleneimine

    NASA Astrophysics Data System (ADS)

    Yuan, Guangcui; Zhang, Huan; Han, Charles C.

    2014-03-01

    The rheological property of mixed suspensions of silica colloid and hyperbranched polylethyleneimine was studied as functions of particle volume fraction, ratio of polymer to particle, and pH value. A mechanism of liquid-gel-liquid transition for this mixed system was proposed based on the amount and the conformation of polyelectrolyte bridges which were able to self-arrange with solution environments. The equilibrium adsorbed amount (Cp*) for a given volume fraction of particles is an important concentration ratio of polymer to particle denoting the transition of irreversible and reversible bridging. For mixed suspensions at equilibrium adsorbed state (Cp ~Cp *), the adsorption-desorption of polymer bridges on the particles can reversibly take place, and shear thickening is observed under a steady shear flow as a result of rapid extension of bridges when the relaxation time scale of extension is shorter than that of desorption. This work is supported by the National Basic Research Program of China (973 Program, 2012CB821503).

  19. Facile synthesis of titania/hyperbranched polyglycidol nanohybrids with controllable morphologies: from solid spheres, capsules to tubes

    NASA Astrophysics Data System (ADS)

    Li, Haiqing; Zhang, Lin; Jo, Jung Kyu; Ha, Chang-Sik; Shchipunov, Yury A.; Kim, Il

    2011-05-01

    Titania/Hyperbranched polyglycidol (HBP) nanohybrids with tunable morphologies have been synthesized via a sol-gel process at ambient temperature. One-shot addition of varied amounts of titanium precursor tetraisopropoxide (TTIP) yields spherical titania/HBP solid particles with tunable size, while a controlled addition of TTIP results in spherical titania/HBP capsules. The average outer and inner diameters of the resultant capsules are also controllable according to the amount of TTIP via an Oswald ripening process. In addition, the modality of additional water supplied in the reaction systems can tune the morphologies of the resulting titania/HBP particles from nanocapsules to nanotubes owing to the accelerated hydrolysis rate of TTIP. The tunability in morphologies of the titania/HBP nanostructures ranging from solid spheres, capsules to tubes could be attributed to the self-assembly of a large amount of titania/HBP aggregates in a rapid, controlled and anisotropic manner, respectively. Surprisingly, by means of HBP contained in the resulting titania/HBP nanostructures, the gold nanoparticles are in situ generated and encapsulated into titania/HBP matrix in the absence of additional reducing agent. The as-prepared gold nanoparticles functionalized titania/HBP hybrids exhibit excellent catalytic function toward the reduction of 4-nitrophenol. This strategy demonstrates a typical example for functionalizing the titania/HBP hybrids targeted to specific applications.

  20. Solution-Processable Hyperbranched Conjugated Polymer Nanoparticles Based on C3h -Symmetric Benzotrithiophene for Polymer Solar Cells.

    PubMed

    Wu, Xiaofu; Zhang, Zijian; Hang, Hao; Chen, Yonghong; Xu, Yuxiang; Tong, Hui; Wang, Lixiang

    2017-02-21

    The development of photovoltaic polymers based on C3h -symmetric benzotrithiophene (C3h -BTT), an analogue of the well-known benzodithiophene (BDT) donor unit, has been severely limited due to difficult processability. Here the authors report the preparation of solution-processable C3h -BTT-based hyperbranched conjugated polymer nanoparticles (BTT-HCPNs) with tunable particle sizes via Stille miniemulsion polymerization. Compared with the corresponding star-shaped small molecule (C3h -BTT core with three diketopyrrolopyrrole arms, BTT-3DPP) with a wide bandgap (1.83 eV), both BTT-HCPNs show strong aggregation even in dilute solutions, leading to much-extended absorption (up to ≈1000 nm) and lower bandgaps (1.38 eV). The larger BTT-HCPN particle exhibits stronger aggregation and more extended absorption than the smaller one. As a result, solar cells fabricated from BTT-HCPNs/PC71 BM solutions show a power conversion efficiency up to 1.51% after DIO additive treatment, much higher than that of BTT-3DPP (0.31%).