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1.
ACS Omega ; 7(7): 5908-5920, 2022 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-35224351

RESUMO

Advances in 3D bioprinting allows not only controlled deposition of cells or cell-laden hydrogels but also flexibility in creating constructs that match the anatomical features of the patient. This is especially the case for reconstructing the pinna (ear), which is a large feature of the face and made from elastic cartilage that primarily relies on diffusion for nutrient transfer. The selection of cell lines for reconstructing this cartilage becomes a crucial step in clinical translation. Chondrocytes and mesenchymal stem cells are both studied extensively in the area of cartilage regeneration as they are capable of producing cartilage in vitro. However, such monoculture systems involve unfavorable processes and produce cartilage with suboptimal characteristics. Co-cultures of these cell types are known to alleviate these limitations to produce synergically active chondrocytes and cartilage. The current study utilized a 3D bioprinted scaffold made from combined gelatine methacryloyl and methacrylated hyaluronic acid (GelMA/HAMA) to interrogate monocultures and co-cultures of human septal chondrocytes (primary chondrocytes, PCs) and human bone marrow-derived mesenchymal stem cells (BM-hMSCs). This study is also the first to examine co-cultures of healthy human chondrocytes with human BM-hMSCs encapsulated in GelMA/HAMA bioprinted scaffolds. Findings revealed that the combination of MSCs and PCs not only yielded cell proliferation that mimicked MSCs but also produced chondrogenic expressions that mimicked PCs. These findings suggested that co-cultures of BM-hMSCs and healthy septal PCs can be employed to replace monocultures in chondrogenic studies for cartilage regeneration in this model. The opportunity for MSCs used to replace PCs alleviates the requirement of large cartilage biopsies that would otherwise be needed for sufficient cell numbers and therefore can be employed for clinical applications.

2.
Acta Biomater ; 106: 156-169, 2020 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-32084598

RESUMO

Single Cell Force Spectroscopy was applied to measure the single cell de-adhesion between human neural stem cells (hNSC) and gelatin methacrylate (GelMA) hydrogel with varying modulus in the range equivalent to brain tissue. The cell de-adhesion force and energy were predominately generated via unbinding of complexes formed between RGD groups of the GelMA and cell surface integrin receptors and the de-adhesion force/energy were found to increase with decreasing modulus of the GelMA hydrogel. For the softer GelMA hydrogels (160 Pa and 450 Pa) it was proposed that a lower degree of cross-linking enables a greater number of polymer chains to bind and freely extend to increase the force and energy of the hNSC-GelMA de-adhesion. In this case, the multiple polymer chains are believed to act together in parallel like 'molecular tensors' to generate tensile forces on the bound receptors until the cell detaches. Counterintuitively for softer substrates, this type of interaction gave rise to higher force loading rates, including the appearance of high and low dynamic force regimes in de-adhesion rupture force versus loading rate analysis. For the stiffer GelMA hydrogel (900 Pa) it was observed that the extension and elastic restoring forces of the polymer chains contributed less to the cell de-adhesion. Due to the apparent lower extent of freely interacting chains on the stiffer GelMA hydrogel the intrinsic RGD groups are presumed to be "more fixed" to the substrate. Hence, the cell de-adhesion is suggested to be mainly governed by the discrete unbinding of integrin-RGD complexes as opposed to elastic restoring forces of polymer chains, leading to smaller piconewton rupture forces and only a single lower dynamic force regime. Intriguingly, when integrin antibodies were introduced for binding integrin α5ß1, ß1- and αv-subunits it was revealed that the cell modifies the de-adhesion force depending on the substrate stiffness. The antibody binding supressed the de-adhesion on the softer GelMA hydrogel while on the stiffer GelMA hydrogel caused an opposing reinforcement in the de-adhesion. STATEMENT OF SIGNIFICANCE: Conceptual models on cell mechanosensing have provided molecular-level insight to rationalize the effects of substrate stiffness. However most experimental studies evaluate the cell adhesion by analysing the bulk material properties. As such there is a discrepancy in the scale between the bulk properties versus the nano- and micro-scale cell interactions. Furthermore there is a paucity of experimental studies on directly measuring the molecular-level forces of cell-material interactions. Here we apply Single Cell Force Spectroscopy to directly measure the adhesion forces between human neural stem cells and gelatin-methacrylate hydrogel. We elucidate the mechanisms by which single cells bind and physically interact with hydrogels of varying stiffness. The study highlights the use of single cell analysis tools to probe molecular-level interactions at the cell-material interface which is of importance in designing material cues for regulating cell function.


Assuntos
Adesão Celular/efeitos dos fármacos , Gelatina/química , Hidrogéis/química , Metacrilatos/química , Células-Tronco Neurais/metabolismo , Animais , Linhagem Celular , Módulo de Elasticidade , Humanos , Camundongos
3.
ACS Appl Mater Interfaces ; 11(49): 46026-46033, 2019 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-31657900

RESUMO

A self-healing electrode is an electrical conductor that can repair internal damage by itself, similar to human skin. Since self-healing electrodes are based on polymers and hydrogels, these components are still limited by low electrical conductivity and mechanical strength. In this study, we designed an electrically conductive, mechanically strong, and printable self-healing electrode using liquid crystal graphene oxide (LCGO) and silver nanowires (AgNWs). The conductive ink was easily prepared by simply mixing LCGO and AgNWs solutions. The ultrathin (3 µm thick) electrode can be printed in various shapes, such as a butterfly, in a freestanding state. The maximum conductivity and strength of the LCGO/AgNW composite were 17 800 S/cm and 4.2 MPa, respectively; these values are 24 and 4 times higher, respectively, than those of a previously developed self-healing electrode. The LCGO/AgNW composite self-healed internal damage in ambient conditions with moisture and consequently recovered 96.8% electrical conductivity and 95% mechanical toughness compared with the undamaged state. The electrical properties of the composite exhibited metallic tendencies. Therefore, these results suggest that the composite can be used as an artificial electronic skin that detects environmental conditions, such as compression and temperature. This self-healing artificial electronic skin could be applied to human condition monitoring and robotic sensing systems.


Assuntos
Condutividade Elétrica , Fenômenos Mecânicos , Nanofios/química , Pele Artificial , Eletrodos , Grafite/química , Humanos , Hidrogéis/química , Cristais Líquidos/química , Prata/química
4.
ACS Appl Mater Interfaces ; 11(34): 31162-31168, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31356738

RESUMO

Spider silks represent stretchable and contractible fibers with high toughness. Those tough fibers with stretchability and contractibility are attractive as energy absorption materials, and they are needed for wearable applications, artificial muscles, and soft robotics. Although carbon-based materials and poly(vinyl alcohol) (PVA) composite fibers exhibit high toughness, they are still limited in low extensibility and an inability to operate in the wet-state condition. Herein, we report stretchable and contractible fiber with toughness that is inspired by the structure of spider silk. The bioinspired tough fiber provides 495 J/g of gravimetric toughness, which exceeds 165 J/g of spider silk. Besides, the tough fiber was reversibly stretched to ∼80% strain without damage. This toughness and stretchability are realized by hybridization of aligned graphene oxide/multiwalled carbon nanotubes in a polyurethane matrix as elastic amorphous regions and ß-sheet segments of spider silk. Interestingly, the bioinspired tough fiber contracted up to 60% in response to water and humidity similar to supercontraction of the spider silk. It exhibited 610 kJ/m3 of contractile energy density, which is higher than previously reported moisture driven actuators. Therefore, this stretchable and contractible tough fiber could be utilized as an artificial muscle in soft robotics and wearable devices.

5.
Biofabrication ; 11(3): 035003, 2019 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-30818298

RESUMO

Reliable and scalable sterilisation of hydrogels is critical to the clinical translation of many biofabrication approaches, such as extrusion-based 3D bioprinting of cell-laden bio-inks. However sterilisation methods can be destructive, and may have detrimental effects on the naturally-derived hydrogels that constitute much of the bio-ink palette. Determining effective sterilisation methods requires detailed analysis of the effects of sterilisation on relevant properties such as viscosity, printability and cytocompatibility. Yet there have been no studies specifically exploring the effects of sterilisation on bio-inks to date. In this work, we explored the effects of various sterilisation techniques on four of the most widely used bio-ink components: gelatin, gelatin methacryloyl, hyaluronic acid, and hyaluronic acid methacrylate. Autoclaving was the most destructive sterilisation method, producing large reductions in viscosity and in mechanical properties following crosslinking. Filter sterilisation caused some reduction in rheological properties of GelMA due to removal of higher molecular weight components, but did not affect photocrosslinking. Ethylene oxide (EtO) was the least destructive sterilisation method in terms of rheological properties for all materials, had no detrimental effect on the photocrosslinkable methacrylate/methacrylamide groups, and so was chosen for more detailed examination. In biological analyses, we found that EtO treatment successfully eradicated a bacterial challenge of E. coli, caused no decrease in viability of human mesenchyman stem cells (hMSCs), and had no effect on their rate of proliferation. Finally, we found that EtO-treated hydrogels supported encapsulated hMSCs to differentiate towards the chondrogenic lineage, and to produce new cartilage matrix. Our results bring to light various effects that sterilisation can have on bio-inks, as well as highlighting EtO sterilisation as a method which minimises degradation of properties, while still promoting biological function.


Assuntos
Gelatina/farmacologia , Ácido Hialurônico/farmacologia , Tinta , Metacrilatos/farmacologia , Esterilização/métodos , Tecido Adiposo/citologia , Animais , Cartilagem/efeitos dos fármacos , Sobrevivência Celular , Reagentes de Ligações Cruzadas/química , Óxido de Etileno/química , Humanos , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Células-Tronco Mesenquimais/citologia , Microtecnologia , Reologia , Suínos
6.
Soft Matter ; 14(35): 7228-7236, 2018 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-30132499

RESUMO

Using a customized ultrasound setup we investigate the feasibility of using a contactless approach to study the bulk mechanical properties of swollen hydrogels. The study involved two different hydrogels, gelatin methacrylate (GelMa) and green algae extract methacrylate (GAEM), which were prepared to provide materials with varying modulus and different swelling properties. Two approaches have been developed. In the first case, ultrasound was compared to Young's modulus measured by indentation. It was found that can be linearly related to indentation modulus values only when the hydrogel swelling ratio is taken into account. In the second approach, an exponential dependency between swelled thickness and indentation modulus was found. This is representative for each hydrogel and purification method in addition to being independent of the conditions used within the toughness range explored. The results of this study indicate that a simple thickness measurement via the proposed approach can provide a direct relationship to Young's modulus upon calibration.


Assuntos
Hidrogéis , Teste de Materiais/métodos , Fenômenos Mecânicos , Metacrilatos/química , Ondas Ultrassônicas
7.
ACS Appl Mater Interfaces ; 10(26): 22031-22041, 2018 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-29882651

RESUMO

The surfactant-assisted liquid-phase exfoliation of expanded graphite can produce graphene sheets in large quantities with minimal defects. However, it is difficult to completely remove the surfactant from the final product, thus affecting the electrochemical properties of the produced graphene. In this article, a novel approach to fabricate flexible graphene/polypyrrole film was developed: using surfactant cetyltrimethylammonium bromide as a template for growth of polypyrrole nanofibers (PPyNFs) instead of removal after the exfoliation process; followed by a simple filtration method. The introduction of PPyNF not only increases the electrochemical performance, but also ensures flexibility. This composite film electrode offers a capacitance up to 161 F g-1 along with a capacitance retention rate of over 80% after 5000 cycles.

8.
Soft Matter ; 14(11): 2142-2151, 2018 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-29488996

RESUMO

Photo-crosslinkable hydrogels, in particular gelatin methacryloyl (GelMa), are gaining increasing importance in biofabrication and tissue engineering. While GelMa is often described as mechanically 'tunable', clear relationships linking the photocrosslinking conditions to reaction rates, and the resulting mechanical properties, have not been described. Meanwhile the conditions employed in the literature are disparate, and difficult to compare. In this work, in situ rheological measurements were used to quantify the relative rate of reaction of GelMa hydrogels with respect to light intensity, exposure time and photo-initiator concentration. In addition the UV degradation of the photo-initiator Irgacure 2959 was measured by UV-vis spectroscopy, and used to estimate the rate of free radical production as a function of light exposure. Using these data an expression was derived which predicts the mechanical properties of GelMa hydrogels produced across a wide range of crosslinking conditions. The model was validated through fabrication of a GelMa gradient which matched predicted properties. Human mesenchymal stem cells encapsulated in crosslinked GelMa exhibited high (>90%) viability post encapsulation, however metabolic activity over one week was influenced by the intensity of light used during crosslinking. The expressions described may be used to aid rational choices of GelMa photocrosslinking conditions, especially in cell encapsulation experiments where minimising the cytotoxic elements in the reaction is a priority.

9.
RSC Adv ; 8(24): 13112-13120, 2018 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-35542516

RESUMO

Asymmetric supercapacitors are receiving much research interests due to their wide operating potential window and high energy density. In this study, we report the fabrication of asymmetrically configured yarn based supercapacitor by using liquid-state biscrolling technology. High loading amounts of reduced graphene oxide anode guest (90.1 wt%) and MnO2 cathode guest (70 wt%) materials were successfully embedded into carbon nanotube yarn host electrodes. The resulting asymmetric yarn supercapacitor coated by gel based organic electrolyte (PVDF-HFP-TEA·BF4) exhibited wider potential window (up to 3.5 V) and resulting high energy density (43 µW h cm-2). Moreover, the yarn electrodes were mechanically strong enough to be woven into commercial textiles. The textile supercapacitor exhibited stable electrochemical energy storage performances during dynamically applied deformations.

10.
Soft Matter ; 13(27): 4761-4772, 2017 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-28653073

RESUMO

Electrical stimulation of hydrogels has been performed to enable micro-actuation or controlled movement of ions and biomolecules such as in drug release applications. Hydrogels are also increasingly used as low modulus, biocompatible coatings on electrode devices and thus are exposed to the effects of electrical stimulation. As such, there is growing interest in the latter, especially on the dynamic and nanoscale physical properties of hydrogels. Here, we report on the electro-mechano properties of photocrosslinkable gelatin methacrylate (GelMA) hydrogel applied as coatings on conducting polymer polypyrrole-dodecylbenze sulfonate (PPy-DBSA) electrodes. In particular, Electrochemical-Atomic Force Microscopy (EC-AFM) was used to quantify the nanoscale actuation and dynamic changes in Young's modulus as the GelMA coating was electrically stimulated via the underlying PPy-DBSA electrode. Pulsed electrical stimulation was shown to induce dynamic expansion and contraction, or nanoscale actuation, of the GelMA hydrogel due to the reversible ingress of electrolyte ions and associated changes in osmotic pressure during oxidation and reduction of the PPy-DBSA film. In addition, dynamic changes in the Young's modulus of up to 50% were observed in the hydrogel and correlated with the actuation process and ion diffusion during oxidation and reduction of the underlying PPy-DBSA film. These dynamic properties were investigated for hydrogels with varying degrees of cross-linking, porosity and modulus, the latter ranging from ≈0.2-1 kPa. The study demonstrates an AFM-based approach to quantify the dynamic physical properties of hydrogels, which are shown to be modulated via electrical stimulation. This can enable a better understanding of the electro-mechano mechanisms that are important for the controlled release of drugs or controlling cell interactions at the hydrogel-cell interface.

11.
Nanoscale ; 9(5): 2038-2050, 2017 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-28112762

RESUMO

The development of conducting 3D structured biocompatible scaffolds for the growth of electroresponsive cells is critical in the field of tissue engineering. This work reports the synthesis and 3D processing of UV-crosslinkable conducting cytocompatible hydrogels that are prepared from methacrylated chitosan (ChiMA) containing graphenic nanosheets. The addition of chemically converted graphene resulted in mechanical and electrical properties of the composite that were significantly better than ChiMA itself, as well as improved adhesion, proliferation and spreading of L929 fibroblasts cells. The chemically converted graphene/ChiMA hydrogels were amenable to 3D printing and this was used to produce multilayer scaffolds with enhanced mechanical properties through UV-crosslinking.

12.
Biofabrication ; 8(1): 015019, 2016 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-27004561

RESUMO

We present a new approach which aims to translate freeform biofabrication into the surgical field, while staying true to the practical constraints of the operating theatre. Herein we describe the development of a handheld biofabrication tool, dubbed the 'biopen', which enables the deposition of living cells and biomaterials in a manual, direct-write fashion. A gelatin-methacrylamide/hyaluronic acid-methacrylate (GelMa/HAMa) hydrogel was printed and UV crosslinked during the deposition process to generate surgically sculpted 3D structures. Custom titanium nozzles were fabricated to allow printing of multiple ink formulations in a collinear (side-by-side) geometry. Independently applied extrusion pressure for both chambers allows for geometric control of the printed structure and for the creation of compositional gradients. In vitro experiments demonstrated that human adipose stem cells maintain high viability (>97%) one week after biopen printing in GelMa/HAMa hydrogels. The biopen described in this study paves the way for the use of 3D bioprinting during the surgical process. The ability to directly control the deposition of regenerative scaffolds with or without the presence of live cells during the surgical process presents an exciting advance not only in the fields of cartilage and bone regeneration but also in other fields where tissue regeneration and replacement are critical.


Assuntos
Hidrogéis/administração & dosagem , Injeções Intralesionais/instrumentação , Osteoartrite/terapia , Impressão Tridimensional/instrumentação , Transplante de Células-Tronco/instrumentação , Células-Tronco/citologia , Adipócitos/citologia , Adipócitos/transplante , Células Cultivadas , Desenho de Equipamento , Análise de Falha de Equipamento , Humanos , Osteoartrite/patologia , Projetos Piloto , Alicerces Teciduais , Resultado do Tratamento
13.
Adv Mater ; 25(45): 6513-8, 2013 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-23996616

RESUMO

Different nanocarbons, that is, single-wall carbon nanotubes, graphene, single-wall carbon nanohorns (SWCNHs), and their respective oxidized analogs have been used to fabricate novel doped TiO2 electrodes for DSSCs. Our results indicate that all of the nanocarbons significantly enhance the device characteristics when compared to standard TiO2 electrodes. Overall, our most outstanding finding is that SWCNH derivatives are also a plausible material for developing highly-efficient DSSCs.


Assuntos
Corantes/química , Nanotubos de Carbono/química , Energia Solar , Fontes de Energia Elétrica , Eletrodos , Porosidade , Titânio/química
14.
J Mater Chem B ; 1(16): 2162-2168, 2013 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-32260849

RESUMO

The ability to switch the physico-chemical properties of conducting polymers opens up new possibilities for a range of applications. Appropriately functionalised materials can provide routes to multi-modal switching, for example, in response to light and/or electrochemical stimuli. This capability is important in the field of bionics wherein remote and temporal control of the properties of materials is becoming attractive. The ability to actuate a film via photonic stimuli is particularly interesting as it facilitates the modulation of interactions between host binding sites and potential guest molecules. In this work, we studied two different poly-terthiophenes: one was functionalised with a spiropyran photoswitch (pTTh-SP) and the second with a non-photoswitchable methyl acetate moiety (pTTh-MA). These substrates were exposed to several cycles of illumination with light of different wavelengths and the resulting effect studied with UV-vis spectroscopy, contact angle and atomic force microscopy (AFM). The AFM tips were chemically activated with fibronectin (FN) and the adhesion force of the protein to the polymeric surface was measured. The pTTh-MA (no SP incorporated) showed a slightly higher average maximum adhesion (0.96 ± 0.14 nN) than the modified pTTh-SP surface (0.77 ± 0.08 nN), but after exposure of the pTTh-SP polymer to UV, the average maximum adhesion of the pTTh-MC (merocyanine form) was significantly smaller (0.49 ± 0.06 nN) than both the pTTh-MA and pTTh-SP. In addition, the tip-sample separation distances of the adhesive interactions are indicative of the FN interaction occurring over a distance more closely related to the average dimensions of its compact conformation. The results suggest that surface energy and hydrophobic forces are predominant in determining the protein adhesion to the films studied and that this effect can be photonically tuned. By extension, this further implies that it should be possible to obtain a degree of spatial and temporal control of the surface binding behaviour of certain proteins with these functionalised surfaces through photo-activation/deactivation, which, in principle, should facilitate patterned growth behaviour (e.g. using masks or directional illumination) or photocontrol of protein uptake and release.

15.
Phys Chem Chem Phys ; 14(25): 9112-20, 2012 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-22643958

RESUMO

The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-acetate (BSP-2) and 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E(a(MC-2)) = 75.05 kJ mol(-1), E(a(MC-3)) = 100.39 kJ mol(-1)) and entropies of activation (ΔS = 43.38 J K(-1) mol(-1), ΔS = 37.78 J K(-1) mol(-1)) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K(-1) mol(-1)) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.

16.
Nat Commun ; 3: 650, 2012 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-22337128

RESUMO

The extraordinary properties of graphene and carbon nanotubes motivate the development of methods for their use in producing continuous, strong, tough fibres. Previous work has shown that the toughness of the carbon nanotube-reinforced polymer fibres exceeds that of previously known materials. Here we show that further increased toughness results from combining carbon nanotubes and reduced graphene oxide flakes in solution-spun polymer fibres. The gravimetric toughness approaches 1,000 J g(-1), far exceeding spider dragline silk (165 J g(-1)) and Kevlar (78 J g(-1)). This toughness enhancement is consistent with the observed formation of an interconnected network of partially aligned reduced graphene oxide flakes and carbon nanotubes during solution spinning, which act to deflect cracks and allow energy-consuming polymer deformation. Toughness is sensitive to the volume ratio of the reduced graphene oxide flakes to the carbon nanotubes in the spinning solution and the degree of graphene oxidation. The hybrid fibres were sewable and weavable, and could be shaped into high-modulus helical springs.


Assuntos
Grafite/química , Nanotubos de Carbono/química , Óxidos/química , Polímeros/química , Carbono/química , Cristalização/métodos , Ácido Clorídrico/química , Ligação de Hidrogênio , Teste de Materiais , Microscopia Eletrônica de Varredura/métodos , Microscopia Eletrônica de Transmissão/métodos , Nanotecnologia/métodos , Análise Espectral Raman/métodos , Propriedades de Superfície , Resistência à Tração
17.
J Phys Chem Lett ; 3(17): 2425-30, 2012 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-26292127

RESUMO

Graphene oxide (GO) flakes dissolved in water can spontaneously form liquid crystals. Liquid crystallinity presents an opportunity to process graphene materials into macroscopic assemblies with long-range ordering, but most graphene electronic functionalities are lost in oxidation treatments. Reduction of GO allows recovering functionalities and makes reduced graphene oxide (RGO) of greater interest. Unfortunately, chemical reduction of GO generally results in the aggregation of the flakes, with no liquid crystallinity observed. We report in the present work liquid crystals made of RGO. The addition of surfactants in appropriate conditions is used to stabilize the RGO flakes against aggregation maintaining their ability to form water-based liquid crystals. Structural and thermodynamical studies allow the dimensions of the flakes to be deduced. It is found that the thickness and diameter of RGO flakes are close to that of neat GO flakes.

18.
J Am Chem Soc ; 133(14): 5453-62, 2011 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-21417306

RESUMO

An electroactive nitrospiropyran-substituted polyterthiophene, poly(2-(3,3''-dimethylindoline-6'-nitrobenzospiropyranyl)ethyl 4,4''-didecyloxy-2,2':5',2''-terthiophene-3'-acetate), has been synthesized for the first time. The spiropyran, incorporated into the polymer backbone by covalent attachment to the alkoxyterthiophene monomer units, leads to multiple colored states as a result of both photochemical and electrochemical isomerization of the spiropyran moiety to merocyanine forms as well as electrochemical oxidation of the polyterthiophene backbone and the merocyanine substituents. While electrochemical polymerization of the terthiophene monomer can take place without oxidation of the spiropyran, increasing the oxidation potential leads to complex electrochemistry that clearly involves this substituent. To understand this complex behavior, the first detailed electrochemical study of the oxidation of the precursor spiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, was undertaken, showing that, in solution, an irreversible electrochemical oxidation of the spiropyran occurs leading to reversible redox behavior of at least two merocyanine isomers. With these insights, an extensive electrochemical and spectroelectrochemical study of the nitrospiropyran-substituted polyterthiophene films reveals an initial irreversible electrochemical oxidative ring-opening of the spiropyran to oxidized merocyanine. Subsequent reduction and cyclic voltammetry of the resulting nitromerocyanine-substituted polyterthiophene film gives rise to the formation of both merocyanine π-dimers or oligomers and π-radical cation dimers, between polymer chains. Although merocyanine formation is not electrochemically reversible, the spiropyran can be photochemically regenerated, through irradiation with visible light. Subsequent electrochemical oxidation of the nitrospiropyran-substituted polymer reduces the efficiency of the spiropyran to merocyanine isomerization, providing electrochemical control over the polymer properties. SEM and AFM images support the conclusion that the bulky spiropyran substituent is electrochemically isomerized to the planar merocyanine moiety, affording a smoother polymer film. The conductivity of the freestanding polymer film was found to be 0.4 S cm(-1).

19.
J Chromatogr A ; 1217(48): 7593-7, 2010 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-20980009

RESUMO

The preparation of processable graphene oxide colloids called chemically converted graphene (CCG) involves the following steps: oxidation of graphite to form graphite oxide; exfoliation of graphite oxide to form graphene oxide (GO); and reduction of GO to form CCG. In this work, the exfoliation and reduction steps were monitored by capillary zone electrophoresis (CZE). CZE was performed in fused silica capillaries with UV absorbance at 230 nm (GO) and 270 nm (CCG) using 250 µM tetrapropylammonium hydroxide (pH 10.4). The results indicate that almost complete exfoliation of graphite oxide (0.05 wt%) and higher recovery of CCG were obtained by sonication at 50% power for more than 15 h. CZE is considered a valuable tool for the fractionation and analysis of GO nanoparticles and, hence, for the control of different steps in preparation of CCG.


Assuntos
Eletroforese Capilar/métodos , Grafite/química , Óxidos/química , Oxirredução
20.
J Am Chem Soc ; 132(28): 9543-5, 2010 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-20583832

RESUMO

Microsecond dye-regeneration kinetics was observed in efficient solid state dye-sensitized solar cells using photoelectrochemically deposited poly(3,4-ethylenedioxythiophene (PEDOT) hole conductors using transient absorption spectroscopy. The dye-regeneration rate is orders of magnitude slower than the case using the I(-)/I(3)(-) redox couple or commonly used small molecule hole conductor and is attributed to the low dye to PEDOT ratio within the films.

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