Polyhedral Oligomeric Silsesquioxane Nanocages Research Articles

POSS-graphene oxide nanocomposite membranes for ethanol permselective pervaporation

Pervaporation has shown great promise in recovering alcohol from fermentation broth. However, the separation performance determined by membrane material and structure should be further improved. In this study, polyhedral oligomeric silsesquioxane (POSS) nanocage was used as nanofillers to provide preferential pathways for ethanol molecules in polydimethylsiloxane (PDMS) membrane. To improve dispersion of POSS nanocages in PDMS matrix, the POSS were anchored on the graphene oxide (GO) nanosheets. At the meantime, the aggregation of GO nanosheets could also be prevented as the GO surface turned to be hydrophobic by the modification of POSS, and the nanoporous POSS cage could reduce interface defects between GO nanosheets and PDMS matrix. The obtained POSS-GO/PDMS nanocomposite membranes exhibited excellent separation performance for ethanol permselectivity. The flux could reach 1346.9 g m −2 h −1 with a separation factor of 11.2 when recovery of ethanol from 5 wt% ethanol/water mixture. In addition, the separation performance of the POSS-GO/PDMS membrane could maintain stability in 120 h. Therefore, the POSS modified GO nanosheets shown great potential in the fabrication of ethanol permselective pervaporation membranes. • POSS-GO nanocomposites were fabricated and incorporated into the PDMS matrix for preparation of pervaporation membranes. • The nanoplates can be well dispersed in PDMS as the hydrophobic POSS has been uniformed anchored to the GO nanosheets. • The obtained POSS-GO/PDMS membranes exhibited excellent pervaporation performance for ethanol permselectivity.

Silver nanoparticles decorated polyhedral oligomeric silsesquioxane nanocages as an effective nanoadditive for improved structural and biological properties of poly(vinylidene fluoride-co-hexafluoropropylene) nanofiltration membrane

Incorporation of a well-defined functionalized polyhedral oligomeric silsesquioxane (POSS) into a polymer matrix represents a new chemical advancement for applied membrane technology. Herein, POSS nanocages densely decorated with silver (Ag) nanoparticles (NPs) were used as effective hydrophilic and antibacterial additive. In this work, first, a facile and simple chemical reduction strategy is employed to prepare the organic–inorganic hybrid nanocages of Ag@POSS by in situ reduction of the Ag NPs with octa-ammonium molecules of POSS. These Ag@POSS nanocages were added as nanofiller for the fabrication of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanohybrid membrane. Ag@POSS nanocages added PVDF-HFP membrane exhibited formation of homogeneous and stable films compared to the unmodified polymeric membranes due to van der Waals and hydrogen bonding interactions of Ag@POSS with –CH2 groups and F atoms of polymer matrix. Pure water flux measurement of nanohybrid membrane showed that Ag@POSS PVDF membrane displays dramatic increase in the permeability (1,554.6 L/m2/h) and hydrophilicity (67°) properties. Furthermore, antibacterial activity and protein adsorption capacity of Ag@POSS PVDF membrane were evaluated by quantitative analysis of living bacterial cells and protein mass adsorption using Escherichia coli and bovine serum albumin (BSA) protein, respectively. The E. coli colonies (108 CFU/mL) on the Ag@POSS PVDF membrane samples tended to decline with 0.5 × 106 CFU/mL compared to neat PVDF-HFP membrane sample (1.3 × 108 CFU/mL). The improvement in biological properties of Ag@POSS PVDF membrane is due to the formation of Ag-octamine on the surface of POSS which lead to the formation of a boundary protection film. The surface–modified POSS with Ag NPs can be used as a nanofiller in polymeric membrane for developing high-performance permeable nanofiltration and antibacterial/antifouling polymeric membranes.

Polyhedral oligomeric silsesquioxane cage integrated soluble and fluorescent poly(3,4-propylenedioxythiophene) dye

A new analog of poly (3,4-propylenedioxythiophene) conjugated polymers called PProDOT-POSS, where polyhedral oligomeric silsesquioxane (POSS) nanocage with alkyl substitutions was integrated on the bridge of 3,4-propylenedioxythiophene unit and its structure was confirmed by spectroscopic techniques, was reported. The polymers were synthesized via both chemical and electrochemical polymerization techniques. While chemical polymerization was carried out in the presence of anhydrous FeCl3 as an oxidant, a solution of 0.1 M tetrabutylammonium hexafluoride electrolyte dissolved in a mixture of dichloromethane and acetonitrile (1/3: v/v) was used as an electrolyte solution for electrochemical polymerization. Electro-optical properties of the corresponding polymers were characterized by using electroanalytical techniques such as cyclic voltammetry and square wave potentiometry, and spectrophotometric methods like ultraviolet–visible and fluorescent spectrophotometry. Corresponding polymers obtained both electrochemically and chemically are soluble completely in common organic solvents such as chloroform, toluene, dichloromethane, tetrahydrofuran, etc. Polymer samples both in film and solution forms can be doped/dedoped reversibly by using a chemical oxidant or an external potential. The optical bandgap of the neutral polymer film with a maximum absorption band at 555 nm was calculated as 1.95 eV. Polymers have fluorescent property and excited polymers represented a red/orange light with an emission band centered at 605 nm in toluene. Also, PProDOT-POSS polymers have electrochromic properties under external potentials and they have an optical contrast of 55% at 555 nm between their neutral and oxidized states. Upon oxidation, they showed high transparency and they can switch between redox states in a short time (switching time = ~1.0 s) as well as high coloration efficiency (502 cm2/C for 95% switching). It can be concluded that POSS based PProDOT polymers can be good candidates for optoelectronic and bioelectronics applications.Short Abstract for Paper Submission: A new analog of poly (3,4-propylenedioxythiophene) conjugated polymers called PProDOT-POSS, was reported with the integrated of alkyl-substituted polyhedral oligomeric silsesquioxane nanocage structure. The polymers were synthesized via both chemical and electrochemical polymerization techniques. Corresponding polymers obtained both electrochemically and chemically are soluble completely in common organic solvents such as chloroform, toluene, dichloromethane, tetrahydrofuran, etc. Polymer samples both in film and solution forms can be doped/dedoped reversibly by using a chemical oxidant or an external potential. The optical bandgap of the neutral polymer film with a maximum absorption band at 555 nm was calculated as 1.95 eV. Polymers have fluorescent property and excited polymers represented a red/orange light with an emission band centered at 605 nm in toluene.

Crosslinked poly(ethylene oxide)-based membrane electrolyte consisting of polyhedral oligomeric silsesquioxane nanocages for all-solid-state lithium ion batteries

Development of suitable solid membrane electrolyte for all-solid-state lithium ion battery is of great importance to address the safety issue arisen from the current lithium ion battery technology. Herein, we report the synthesis and properties of a poly(ethylene oxide)-based, crosslinked solid membrane electrolyte with nanocages of polyhedral oligomeric silsesquioxane through UV-induced crosslinking technique. Benefiting from the crosslinked structure, the synthesized membrane electrolyte exhibits an improved mechanical strength and electrochemical stability compared to the sample without crosslinked structure. The optimized membrane electrolyte has the ionic conductivity of 3.83 × 10−4 Scm−1 at 60 °C with an electrochemical window of 5.3 V. The thus-assembled battery using lithium plate as anode and lithium iron phosphate as cathode delivers an initial discharge capacity of 150 mAhg−1 at 60 °C, higher than that of battery assembled from membrane electrolyte without crosslinked structure. Although the battery is more stable than that assembled from membrane electrolyte without crosslinked structure, the initial discharge capacity decreases to 139 mAhg−1 after 42 charging-discharging cycles. Nevertheless, the results presented here demonstrate that the UV-induced crosslinking strategy can be an effective approach for the practical synthesis of solid-state membrane electrolyte.

Amphiphilic tadpole-shaped POSS-poly(glycerol methacrylate) hybrid polymers: synthesis and self-assembly

A new series of well-defined amphiphilic hybrid polymers of tadpole-shaped architecture with polyhedral oligomeric silsesquioxane (POSS) nanocage as the hydrophobic head and poly(glycerol methacrylate) (PGMA) as the hydrophilic tail (POSS-PGMA) has been synthesized via atom transfer radical polymerization (ATRP). The aminopropylIsobutyl POSS, a monofunctional POSS nanocage, was transformed into ATRP initiator by treating with 2-bromoisobutyrylbromide. The POSS-PGMA was achieved in two steps. First, solketal methacrylate (SMA) (the precursor monomer for GMA), synthesized by reacting solketal with methacryloyl chloride, was polymerized under typical ATRP conditions with THF as the solvent at 40 °C, employing the synthesized POSS based initiator, and CuCl/N,N,N,N,N-pentamethyldiethylenetriamine as the catalyst system. The size exclusion chromatography (SEC) chromatograms reveal monomodal molecular weight distributions and narrow polydispersity indices; suggesting that well-defined tadpole-shaped hybrid polymers have been achieved. This further confirms that the monofunctional POSS initiator is able to affectively polymerize SMA in a controlled fashion under ATRP conditions. In the second step, the obtained POSS-PSMA was transformed into amphiphilic POSS-PGMA by acid hydrolysis. The successful transformation could be verified by 1H NMR and FTIR spectroscopy. Finally, because of the amphiphilic nature, the obtained POSS-PGMA could self-assemble when dispersed in water as confirmed by measuring the critical aggregation concentration (CAC) by fluorescence spectroscopy, using pyrene as the fluorescence probe. The CAC was found to increase with increasing the PGMA chain length. The large hydrodynamic size of the self-assembled structures, as determined by the laser light scattering data, however, suggests that the aggregates are not of typical core-shell type micelles.

Light‐Driven Reversible Transformation between Self‐Organized Simple Cubic Lattice and Helical Superstructure Enabled by a Molecular Switch Functionalized Nanocage

Self-organized stimuli-responsive smart materials with adjustable attributes are highly desirable for a plethora of device applications. Simple cubic lattice is quite uncommon in soft condensed matter due to its lower packing factor. Achieving a stable simple cubic soft lattice and endowing such a lattice with dynamic reconstruction capability solely by a facile light irradiation are of paramount significance for both fundamental studies and engineering explorations. Herein, an elegant stable self-organized simple cubic soft lattice, i.e., blue phase II, in a chiral liquid crystal (LC) system is disclosed, which is stable down to room temperature and exhibits both reversible lattice deformation and transformation to a helical superstructure, i.e., cholesteric LC, by light stimulation. Such an amazing trait is attained by doping a judiciously designed achiral photoresponsive molecular switch functionalized polyhedral oligomeric silsesquioxane nanocage into a chiral LC host. An unprecedented reversible collapse and reconstruction of such a high symmetric simple cubic blue phase II driven by light has been achieved. Furthermore, a well-defined conglomerate micropattern composed of simple cubic soft lattice and helical superstructure, which is challenging to fabricate in organic and inorganic crystalline materials, is produced using photomasking technology. Moreover, the promising photonic application based on such a micropattern is demonstrated.

A Biodesigned Nanocomposite Biomaterial for Auricular Cartilage Reconstruction.

Current biomaterials for auricular replacement are associated with high rates of infection and extrusion. The development of new auricular biomaterials that mimic the mechanical properties of native tissue and promote desirable cellular interactions may prevent implant failure. A porous 3D nanocomposite scaffold (NS) based on POSS-PCU (polyhedral oligomeric silsesquioxane nanocage into polycarbonate based urea-urethane) is developed with an elastic modulus similar to native ear. In vitro biological interactions on this NS reveal greater protein adsorption, increased fibroblast adhesion, proliferation, and collagen production compared with Medpor (the current synthetic auricular implant). In vivo, the POSS-PCU with larger pores (NS2; 150-250 μm) have greater tissue ingrowth (≈5.8× and ≈1.4 × increase) than the POSS-PCU with smaller pores (NS1; 100-50 μm) and when compared to Medpor (>100 μm). The NS2 with the larger pores demonstrates a reduced fibrotic encapsulation compared with NS1 and Medpor (≈4.1× and ≈1.6×, respectively; P < 0.05). Porosity also influences the amount of neovascularization within the implants, with no blood vessel observed in NS1 (12 weeks postimplantation). The lack of chronic inflammatory response for all materials may indicate that the elastic modulus and pore size of the implant scaffold could be important design considerations for influencing fibrotic responses to auricular and other soft tissue implants.

Injectable polymeric biomaterials: a brief review

This review summarizes some recent work done by the corresponding author and his co-workers on photo-crosslinkable and injectable polymeric systems developed for biomedical applications. First, we discuss the synthesis, chemical structures, and physical properties of different injectable polymeric systems, including poly(propylene fumarate)-based, poly(ε-caprolactone)-based, and poly(ethylene glycol)-based homo-polymers, their copolymers and blends, and their nanocomposites containing hydroxyapatite (HA) nanoparticles or polyhedral oligomeric silsesquioxane nanocages. Then we present different fabrication methods of two-dimensional (2D) surface features, for example, honey-comb pores and microgrooves, and three-dimensional (3D) porous scaffolds and nerve conduits using these injectable polymeric systems. At last, we elaborate on the applications of these injectable polymeric systems, including regulation of in vitro cellular behavior on 2D substrates and 3D structures, and in vivo animal implantation of porous scaffolds and nerve conduits aiming for assisting bone regeneration and peripheral nerve regeneration, respectively.

Curing and thermo-mechanical studies of a modified thermosetting clearcoat containing OH-functional POSS nanocages

Abstract This paper attempts to study the chemical, thermo-mechanical and rheological properties of an acrylic/melamine clearcoat modified with a polyhedral oligomeric silsesquioxane (POSS) macromolecule. OH-functional groups of the linear acrylic resin were stoichiometrically substituted with those of the POSS. This modification resulted in a drop in viscosity compared with the pristine sample, mainly because of the globular compact structure of the modifier. This lowered the chain entanglements and provided more mobile functional groups during curing. FTIR spectroscopy, dynamic mechanical thermal analysis (DMTA) and transmission electron microscopy (TEM) techniques were utilized to study the resultant clearcoats. It was illustrated that reduced viscosity facilitated curing reactions and lead to a more efficient and more extensive curing degree, leading to an enhanced cross-linking density in presence of the POSS nanostructure. It was also illustrated that compatibility of POSS and acrylic/melamine lead to a molecular-scale dispersion of POSS nanostructures within the matrix.

Enhanced bone cell functions on poly(ε-caprolactone) triacrylate networks grafted with polyhedral oligomeric silsesquioxane nanocages

Poly(ε-caprolactone) triacrylate (PCLTA) developed in our laboratory is a photo-crosslinkable, injectable, and biodegradable polymeric biomaterial for diverse tissue engineering applications. To engineer its physical properties for bone regeneration, we incorporated PCLTA networks with a photo-reactive methacryl isobutyl polyhedral oligomeric silsesquioxane (POSS), which is a silicon-based monomer with a nano-sized cage. Homogeneous nanohybrid networks were prepared by photo-crosslinking POSS with two PCLTAs having molecular weights of ∼7000 and ∼20,000 g/mol at the POSS weight compositions (ϕPOSS) of 0–20%. The lower-molecular-weight PCLTA resulted in amorphous networks while the higher one resulted in semi-crystalline networks. POSS nanocages tethered in the PCLTA networks greatly enhanced the mechanical and rheological properties, but did not significantly alter the surface wettability and the capability of adsorbing serum proteins from cell culture media. Better mouse pre-osteoblastic MC3T3-E1 cell attachment, spreading, and proliferation were found on the stiffer PCLTA20k networks than on the PCLTA7k ones, and on the networks with ϕPOSS of 10–20% than the networks containing no POSS. Mineralization of MC3T3-E1 cell cultured for two weeks showed a significantly higher alkaline phosphatase activity and more mineralized nodules on the PCLTA20k networks with ϕPOSS of 10–20%, in correlation with their enhanced mechanical properties. The present results indicated that this series of nanohybrid PCLTA/POSS networks with improved mechanical properties and osteoconductivity has great potential as scaffolding materials for bone repair and regeneration.

Supercritical carbon dioxide-soluble polyhedral oligomeric silsesquioxane (POSS) nanocages and polymer surface modification

In this work, a functionalized polyhedral oligomeric silsesquioxane (POSS) has been investigated for its solubility in supercritical carbon dioxide for the first time in literature. POSS nanocages, which can be functionalized with a wide variety of organic substituents, are most commonly studied as nanofillers in polymer nanocomposites and coatings. Solubility of trifluoropropyl POSS in supercritical carbon dioxide has been determined by cloud-point measurements performed in a high-pressure view cell. At temperature and pressure ranges of 308–323K and 8.3–14.8MPa, these fluorinated organic–inorganic hybrid nanocage structures exhibit solubility up to 4.4% by weight, which is promising for green material processing applications using the environmentally benign solvent. Solubility of CO2-philic POSS decreases with increasing temperature, while the solubility isotherms at two different temperatures converge. Choosing the processing conditions from the performed solubility studies, trifluoropropyl POSS–supercritical carbon dioxide system has been applied in high-pressure surface modification of a high-molecular weight, rigid poly(methyl methacrylate) (PMMA). Scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analysis of the processed PMMA sheet show that the functionalized nanoparticles were deposited on the PMMA surface, forming a uniform coating of POSS aggregates. This work proves that functionalized POSS with CO2-philic groups can be solubilized in supercritical CO2, which might allow them to be applied in a plethora of materials modification processes using supercritical carbon dioxide.

Reactivity, viscoelastic behaviour and mechanical performances of hybrid systems based on epoxy resins and reactive polyhedral oligosilsesquioxanes

An epoxy formulation was modified by adding various amounts of an epoxy functionalized polyhedral oligomeric silsesquioxane (POSS). The obtained networks were characterized in terms of reactivity, viscoelastic behaviour and mechanical properties. Spectroscopy measurements by FT-NIR demonstrated that the epoxy groups of POSS were almost as reactive as those of the DGEBA in the curing stage, while in the post-curing a lower reactivity of the latter was found, possibly due to steric hindrance effects. The dynamic-mechanical analysis showed an increase in the storage modulus in both glassy and rubbery regions. On the other hand, Tg and Tβ decreased with POSS content. The viscoelastic analysis showed that the addition of POSS enhanced the free volume and the tendency of the network to undergo thermal expansion. In particular, the β transition was made increasingly localized by increasing the POSS content. With respect to mechanical performances, the yield process was facilitated by incorporation of the POSS nanocages within the network, possibly due to an enhancement of the chain mobility. Fracture measurements showed an improvement of the parameters Kc and Gc up to 5wt% of POSS, after which a decrease of toughness was observed. These results were supported by a fractographic analysis.

A new biodegradable nanocomposite based on polyhedral oligomeric silsesquioxane nanocages: cytocompatibility and investigation into electrohydrodynamic jet fabrication techniques for tissue‐engineered scaffolds

Our group has developed a non-biodegradable nanocomposite based on POSS (polyhedral oligomeric silsesquioxane) nanocages with PCU [poly(carbonate urethane)] and previous studies have shown good cell-compatibility and antithrombogenic properties. The latest biodegradable formulation is a POSS-modified poly(hexanolactone/carbonate)urethane/urea containing 80% hexanolactone (caprolactone) with the tradename UCL-NanoBio. The direct effect of the polymer on cells was investigated by seeding stem cells on to circular discs of the polymer in 24-well plates; these discs were prepared mainly by electrohydrodynamic jetting. To assess the indirect effect of the polymer, various concentrations of the polymer powder were added to CCM (cell culture medium) and left on a shaker for 10 days. The precipitate was then removed and the CCM was used for culturing the cells seeded on to 24-well plates. Cell viability and growth at 48 and 96 h were assessed using Alamar Blue and lactate dehydrogenase, and morphology was studied by scanning electron microscopy. Cells were shown to adhere well to the polymer, with cell metabolism being comparable with that found on TCP (tissue-culture plastic). Indirect assessment demonstrated some decrease in cell viability with high concentrations of polymer, but showed no difference in cell death between polymer concentrations. The viability of cells seeded on to the polymer was comparable with that of those seeded on to TCP. Cell viability was comparable on both electrosprayed and electrospun scaffolds, but infiltration into the scaffold was much more evident on the electrospun scaffolds. It can be concluded that this new nanocomposite can support the growth and viability of stem cells and that scaffolds of this polymer nanocomposite fabricated by electrohydrodynamic jetting routes have potential use for tissue engineering in the future.

Degradation studies on biodegradable nanocomposite based on polycaprolactone/polycarbonate (80:20%) polyhedral oligomeric silsesquioxane

The development of biocompatible polymers has greatly advanced the field of tissue engineering. Some tissues can be propagated on a nondegradable scaffold. Tissue such as cartilage, however, is a complex tissue in which the chondrocytes require their own synthesized extracellular matrix (ECM) to function. Suitable scaffolds for tissue engineering cartilage should provide mechanical strength and degrade at a similar rate to that of cell growth and ECM production. We have developed a biodegradable nanocomposite based on polycaprolactone and polycarbonate polyurethane (PCU) with an incorporated polyhedral oligomeric silsesquioxane (POSS) (POSS modified Poly(caprolactone/carbonate) urethane/urea). Previous work on POSS incorporated into PCU (POSS-PCU) has been shown to possess good mechanical strength, elasticity and resistance to degradation. This series of experiments involved exposing this polymer to a selection of accelerated degradative solutions for up to 8 weeks. The samples were analyzed by infra-red spectroscopy, scanning electron microscopy, X-ray microanalysis, contact angle analysis, and stress-strain mechanical analysis. Degradation of hard and soft segments of the nanocomposite was evident by infra-red spectroscopy in all conditioned samples. POSS nanocage degradation was evident in some oxidative/peroxidative systems accompanied by gross changes in surface topography and significant changes in mechanical properties. The hydrophobic polymer became more hydrophilic in all conditions. This biodegradable nanocomposite demonstrated steady degradation with protection of mechanical properties when exposed to hydrolytic enzymes and plasma protein fractions and exhibited more dramatic degradation by oxidation.This pattern may be potentially employed in tissue engineering scaffolds where controlled degradation and retained structural stability of the scaffold is required.

Enhancement of Electrochromic Contrast by Tethering Conjugated Polymer Chains onto Polyhedral Oligomeric Silsesquioxane Nanocages

AbstractCopolymerization of aniline with octa(aminophenyl) silsesquioxane (OAPS) was performed, which resulted in polyaniline‐tethered, polyhedral oligomeric silsesquioxane (POSS‐PANI), with star‐like molecular geometry. The spectro‐electrochemical studies show that the electrochromic contrast of POSS‐PANI is much higher than that of polyaniline (PANI). The great improvement can be attributed to the more accessible doping sites and the facile ion movement during the redox switching, brought by the loose packing of the PANI chains. This was evidenced by a drastic increase in ionic conductivity, a decrease in the electrical conductivity, and a decrease in the crystallinity and crystal size, with the increase of the OAPS concentration in the POSS‐PANI.magnified image

Thermorheological properties near the glass transition of oligomeric poly(methyl methacrylate) blended with acrylic polyhedral oligomeric silsesquioxane nanocages

Two distinct oligomeric species of similar mass and chemical functionality (M w≈2,000 g/mol), one a linear methyl methacrylate oligomer (radius of gyration R g≈1.1 nm) and the other a hybrid organic–inorganic polyhedral silsesquioxane nanocage (methacryl-POSS, r≈1.0 nm), were subjected to thermal and rheological tests to compare the behaviors of these geometrically dissimilar molecules over the entire composition range. The glass transition temperatures of the blends varied monotonically between the glass transition temperatures of the pure oligomer (T g=−47.3°C) and the pure POSS (T g=−61.0°C). Blends containing high POSS contents (with volume fraction φ POSS≥0.90) exhibited enhanced enthalpy relaxation in differential scanning calorimetry (DSC) measurements, and the degree of enthalpy relaxation was used to calculate the kinetic fragility indices m of the oligomeric MMA (m=59) and the POSS (m=74). The temperature dependences of the viscosities were fitted by the free-volume based Williams–Landel–Ferry (WLF) and Vogel–Fulcher–Tammann (VFT) framework and a dynamic scaling relation. The calculated values of the fragility from the WLF–VFT fits were similar for the POSS (m=82) and for the oligomer (m=76), and the dynamic scaling exponent was similar for the oligomeric MMA and the POSS. Within the range of known fragilities for glass-forming liquids, the temperature dependence of the viscosity was found to be similarly fragile for the two species. The difference in shape of the nanocages and oligomer chains is unimportant in controlling the glass-forming properties of the blends at low volume fractions (φ POSS<0.20). However, at higher volume fractions, adjacent POSS cages begin to crowd each other, leading to an increase in the fractional free volume at the glass transition temperature and the observed enhanced enthalpy relaxation in DSC.

The Antithrombogenic Potential of a Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposite

We have developed a nanocomposite using a silica nanocomposite polyhedral oligomeric silsesquioxane (POSS) and poly(carbonate-urea)urethane (PCU) for potential use in cardiovascular bypass grafts and the microvascular component of artificial capillary beds. In this study, we sought to compare its antithrombogenicity to that of conventional polymers used in vascular bypass grafts so as to improve upon current patency rates, particularly in the microvascular setting. Using atomic force microscopy (AFM) and transmission electron microscopy (TEM), surface topography and composition were studied, respectively. The ability of the nanocomposite surface to repel both proteins and platelets in vitro was assessed using thromboelastography (TEG), fibrinogen ELISA assays, antifactor Xa assays, scanning electron microscopy (SEM), and platelet adsorption tests. TEG analysis showed a significant decrease in clot strength (one-way ANOVA, p < 0.001) and increase in clot lysis (one-way ANOVA, p < 0.0001) on the nanocomposite when compared to both poly(tetrafluoroethylene) (PTFE) and PCU. ELISA assays indicate lower adsorption of fibrinogen to the nanocomposite compared to PTFE (one-way ANOVA, p < 0.01). Interestingly, increasing the concentration of POSS nanocages within these polymers was shown to proportionately inhibit factor X activity. Platelet adsorption at 120 min was also lower compared to PTFE and PCU (two-way ANOVA, p < 0.05). SEM images showed a "speckled" morphologic pattern with Cooper grades I platelet adsorption morphology on the nanocomposite compared to PTFE with grade IV morphology. On the basis of these results, we concluded that POSS nanocomposites possess greater thromboresistance than PTFE and PCU, making it an ideal material for the construction of both bypass grafts and microvessels.