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2.
ACS Nano ; 15(12): 20105-20115, 2021 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-34870425

RESUMO

Solution co-deposition of two-dimensional (2D) nanosheets with chemical solutes yields nanosheet-molecular heterostructures. A feature of these macroscopic layered hybrids is their ability to release the intercalated molecular agent to express chemical functionality on their surfaces or in their near surroundings. Systematic design methods are needed to control this molecular release to match the demand for rate and lifetime in specific applications. We hypothesize that release kinetics are controlled by transport processes within the layered solids, which primarily involve confined molecular diffusion through nanochannels formed by intersheet van der Waals gaps. Here a variety of graphene oxide (GO)/molecular hybrids are fabricated and subject to transient experiments to characterize release kinetics, locations, and mechanisms. The measured release rate profiles can be successfully described by a numerical model of internal transport processes, and the results used to extract effective Z-directional diffusion coefficients for various film types. The diffusion coefficients are found to be 8 orders of magnitude lower than those in free solution due to nanochannel confinement and serpentine path effects, and this retardation underlies the ability of 2D materials to control and extend release over useful time scales. In-plane texturing of the heterostructured films by compressive wrinkling or crumpling is shown to be a useful design tool to control the release rate for a given film type and molecular intercalant. The potential of this approach is demonstrated through case studies on the controlled release of chemical virucidal agents.

3.
Nat Commun ; 12(1): 507, 2021 01 21.
Artigo em Inglês | MEDLINE | ID: mdl-33479231

RESUMO

There is great interest in exploiting van der Waals gaps in layered materials as nanofluidic channels. Graphene oxide (GO) nanosheets are known to spontaneously assemble into stacked planar membranes with transport properties that are highly selective to molecular structure. Use of conventional GO membranes in liquid-phase applications is often limited by low flux values, due to intersheet nanochannel alignment perpendicular to the desired Z-directional transport, which leads to circuitous fluid pathways that are orders of magnitude longer than the membrane thickness. Here we demonstrate an approach that uses compressive instability in Zr-doped GO thin films to create wrinkle patterns that rotate nanosheets to high angles. Capturing this structure in polymer matrices and thin sectioning produce fully dense membranes with arrays of near-vertically aligned nanochannels. These robust nanofluidic devices offer pronounced reduction in fluid path-length, while retaining the high selectivity for water over non-polar molecules characteristic of GO interlayer nanochannels.


Assuntos
Grafite/química , Membranas Artificiais , Técnicas Analíticas Microfluídicas/métodos , Nanoestruturas/química , Nanotecnologia/métodos , Técnicas Analíticas Microfluídicas/instrumentação , Nanotecnologia/instrumentação , Poliestirenos/química , Reprodutibilidade dos Testes , Temperatura , Água/química
4.
Nanoscale Adv ; 3(3): 800-804, 2021 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-36133841

RESUMO

There is widespread interest in new materials-based approaches for introducing flexibility to electromagnetic devices, such as displays, human-machine interfaces, smart textiles, and biomedical implants. From fabrication to application, incorporating ceramic components is particularly challenging due to their extreme stiffness. Here, we introduce a new approach for designing flexible ceramic films and demonstrate it by fabricating fully dense, pre-wrinkled magnetic cobalt ferrite films composed of tiled nanoplatelets. The method relies on the colloidal engineering of metalized graphene nanosheets, which are cast and compressed into wrinkled composite films with accurate control of composition and morphology. Removal of the graphene template by thermal oxidation yields free-standing cobalt ferrite films that can be stretched up to 200% and bent to radii of 2.5 mm while maintaining their magnetic properties. Magnetization retention of 73% is documented after 150% linear mechanical stretching over 100 cycles. The significant stretchability and flexibility in this hard magnetic material is achieved at near full metal oxide crystal density without addition of significant void space or a polymeric elastomer matrix.

5.
Environ Sci Nano ; 8(10): 2894-2907, 2021 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-35360702

RESUMO

Aquatic contamination by per- and polyfluorinated alkyl substances (PFAS) has attracted global attention due to their environmental and health concerns. Current health advisories and surface water regulatory limits require PFAS detection in the parts per trillion (ppt) range. One way to achieve those low detection limits is to use a reliable passive sampling-based monitoring tool for PFAS, as exists for numerous nonpolar persistent organic pollutants. Here we introduce a new graphene-based hydrogel monolith and describe its synthesis, chemical functionalization, property characterization, and testing as a PFAS equilibrium passive sampler. The graphene monoliths were self-assembled by hydrothermal treatment from graphene oxide (GO) aqueous dispersions to produce free standing cylinders of ~563 mm3 volume consisting of ~4 wt-% thin-walled porous graphene and ~96 wt-% water. The uptake of 23 PFAS was measured on the as-produced monoliths, and equilibrium partition coefficients (KSW), were derived for longer chain (C≥8) perfluoroalkyl acids (PFAA) and neutral precursors such as sulfonamides (log KSW range 1.9 - 3.6). To increase the KSW for shorter chain PFAA, the monoliths were chemically modified by a new diazonium-based grafting reaction that introduces positive surface charge without damage to the graphenic backbone. Introduction of benzylamine moieties through the diazonium intermediate switches zeta potential at pH 7 from -45mV (as-produced graphene) to + 5mV. This modification increased the sorption of short and middle chain PFAA by ten-fold (e.g. log KSW for PFBA increased from 1.3 to 2.2), thereby improving the functionality of the passive sampler device for a wider range of PFAS. Field deployments demonstrated that the graphene monoliths were capable of detecting key PFAS in the Delaware River.

6.
Carbon N Y ; 173: 410-418, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33223559

RESUMO

Liquid-phase deposition of exfoliated 2D nanosheets is the basis for emerging technologies that include writable electronic inks, molecular barriers, selective membranes, and protective coatings against fouling or corrosion. These nanosheet thin films have complex internal structures that are discontinuous assemblies of irregularly tiled micron-scale sheets held together by van der Waals (vdW) forces. On stiff substrates, nanosheet vdW films are stable to many common stresses, but can fail by internal delamination under shear stress associated with handling or abrasion. This "re-exfoliation" pathway is an intrinsic feature of stacked vdW films and can limit nanosheet-based technologies. Here we investigate the shear stability of graphene oxide and MoSe2 nanosheet vdW films through lap shear experiments on polymer-nanosheet-polymer laminates. These sandwich laminate structures fail in mixed cohesive and interfacial mode with critical shear forces from 40 - 140 kPa and fracture energies ranging from 0.2 - 6 J/m2. Surprisingly these energies are higher than delamination energies reported for smooth peeling of ordered stacks of continuous 2D sheets, which we propose is due to energy dissipation and chaotic crack motion during nanosheet film disassembly at the crack tip. Experiment results also show that film thickness plays a key role in determining critical shear force (maximum load before failure) and dissipated energy for different nanosheet vdW films. Using a mechanical model with an edge crack in the thin nanosheet film, we propose a shear-to-tensile failure mode transition to explain a maximum in critical shear force for graphene oxide films but not MoSe2 films. This transition reflects a weakening of the substrate confinement effect and increasing rotational deformation near the film edge as the film thickness increases. For graphene oxide, the critical shear force can be increased by electrostatic cross-linking achieved through interlayer incorporation of metal cations. These results have important implications for the stability of functional devices that employ 2D nanosheet coatings.

7.
Small ; 16(21): e2000303, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-32191401

RESUMO

Many layered crystal phases can be exfoliated or assembled into ultrathin 2D nanosheets with novel properties not achievable by particulate or fibrous nanoforms. Among these 2D materials are manganese dioxide (MnO2 ) nanosheets, which have applications in batteries, catalysts, and biomedical probes. A novel feature of MnO2 is its sensitivity to chemical reduction leading to dissolution and Mn2+ release. Biodissolution is critical for nanosafety assessment of 2D materials, but the timing and location of MnO2 biodissolution in environmental or occupational exposure scenarios are poorly understood. This work investigates the chemical and colloidal dynamics of MnO2 nanosheets in biological media for environmental and human health risk assessment. MnO2 nanosheets are insoluble in most aqueous phases, but react with strong and weak reducing agents in biological fluid environments. In vitro, reductive dissolution can be slow enough in cell culture media for MnO2 internalization by cells in the form of intact nanosheets, which localize in vacuoles, react to deplete intracellular glutathione, and induce cytotoxicity that is likely mediated by intracellular Mn2+ release. The results are used to classify MnO2 nanosheets within a new hazard screening framework for 2D materials, and the implications of MnO2 transformations for nanotoxicity testing and nanosafety assessment are discussed.


Assuntos
Compostos de Manganês , Nanoestruturas , Óxidos , Testes de Toxicidade , Animais , Linhagem Celular , Células/efeitos dos fármacos , Meios de Cultura/química , Exposição Ambiental , Brânquias/citologia , Glutationa/metabolismo , Humanos , Compostos de Manganês/química , Nanoestruturas/química , Nanoestruturas/toxicidade , Exposição Ocupacional , Oncorhynchus mykiss , Óxidos/química , Óxidos/toxicidade , Medição de Risco , Testes de Toxicidade/métodos , Testes de Toxicidade/normas
8.
J Environ Manage ; 259: 110044, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31929029

RESUMO

Graphene oxide (GO) is a single-atom-thick sheet of carbon with oxygen-containing functional groups decorating its basal plane and edge sites. Most of its high surface area can be lost due to restacking of individual layers during the synthesis and drying of GO-based bulk sorbents. There is great interest to increase the specific surface area of graphene-based sorbents by introducing organic molecules as "pillaring agents" between GO sheets to hinder the stacking process and create sorbents with elevated surface area. This work synthesizes pillared GO by introducing chitosan (CS), a linear polysaccharide with various molecular weights. A composite of low molecular weight CS at a CS/GO ratio of 0.1 is shown to have the highest specific surface area (up to 70.5 m2/g) in comparison to the medium and high CS molecular weight, pristine GO, and the CS/GO composite materials. The affinity of the optimized GO/CS composites towards benzene, toluene, and naphthalene was evaluated at 19.3 mg/L of organic matter content while altering pH. Sips and Langmuir adsorption isotherm models well described the adsorption behavior, and benzene adsorption performance was reduced at low pH. Related to the presence of dissolved organic matter (DOM) in solution, lower diffusivity constants (k1) in hydrocarbon systems were recorded. Our results demonstrate the feasibility of CS as a potential pillaring agent in CS/GO composites to increase specific surface area and enhance the capture of soluble hydrocarbons from aqueous solutions.


Assuntos
Grafite , Adsorção , Concentração de Íons de Hidrogênio , Óxidos , Água
9.
Colloids Surf A Physicochem Eng Asp ; 566: 188-195, 2019 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-31662597

RESUMO

The novel application of magnetite containing reduced graphene oxide nanosacks (MrGO-N) as electron shuttles to improve the reductive degradation of pharmaceutical pollutant, iopromide (IOP), was evaluated. The MrGO-N were synthesized by ultrasonicated nebulization process, and their physicochemical characterization was performed by potentiometric titrations, zeta potential, high resolution transmission electron microscopy (HR-TEM), X-ray diffraction, as well as by Raman and Fourier transform infrared spectroscopies. Results demonstrated the thermal reduction of precursor graphene oxide sheets, the removal of different oxygenated groups, and the successful assembly of magnetite nanoparticles (MNP) in the graphene sacks. Also, reduction experiments revealed 72 % of IOP removal efficiency and up to 2.5-fold faster degradation of this pollutant performed with MrGO-N as redox catalysts in batch assays and with sulfide as electron donor. Chemical transformation pathway of IOP provides evidence of complete dehalogenation and further transformation of aromatic ring substituents. Greater redox-mediating ability of MrGO-N was observed, which was reflected in the catalytic activity of these nanomaterials during the reductive degradation of IOP. Transformation byproducts with simpler chemical structure were identified, which could lead to complete degradation by conventional methodologies in a complementary treatment process. Redox-mediating activity of MrGO-N could potentially be applied in wastewater treatment systems in order to facilitate the biodegradation of priority contaminants.

10.
Proc Natl Acad Sci U S A ; 116(37): 18304-18309, 2019 09 10.
Artigo em Inglês | MEDLINE | ID: mdl-31451645

RESUMO

Graphene-based materials are being developed for a variety of wearable technologies to provide advanced functions that include sensing; temperature regulation; chemical, mechanical, or radiative protection; or energy storage. We hypothesized that graphene films may also offer an additional unanticipated function: mosquito bite protection for light, fiber-based fabrics. Here, we investigate the fundamental interactions between graphene-based films and the globally important mosquito species, Aedes aegypti, through a combination of live mosquito experiments, needle penetration force measurements, and mathematical modeling of mechanical puncture phenomena. The results show that graphene or graphene oxide nanosheet films in the dry state are highly effective at suppressing mosquito biting behavior on live human skin. Surprisingly, behavioral assays indicate that the primary mechanism is not mechanical puncture resistance, but rather interference with host chemosensing. This interference is proposed to be a molecular barrier effect that prevents Aedes from detecting skin-associated molecular attractants trapped beneath the graphene films and thus prevents the initiation of biting behavior. The molecular barrier effect can be circumvented by placing water or human sweat as molecular attractants on the top (external) film surface. In this scenario, pristine graphene films continue to protect through puncture resistance-a mechanical barrier effect-while graphene oxide films absorb the water and convert to mechanically soft hydrogels that become nonprotective.


Assuntos
Grafite/química , Mordeduras e Picadas de Insetos/prevenção & controle , Roupa de Proteção , Aedes , Animais , Feminino , Humanos , Hidrogéis , Nanoconchas , Nanotecnologia/métodos , Seda/química , Têxteis , Água , Dispositivos Eletrônicos Vestíveis
11.
Part Fibre Toxicol ; 16(1): 15, 2019 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-30943996

RESUMO

BACKGROUND: Multi-walled carbon nanotubes (MWCNT) have been shown to elicit the release of inflammatory and pro-fibrotic mediators, as well as histopathological changes in lungs of exposed animals. Current standards for testing MWCNTs and other nanoparticles (NPs) rely on low-throughput in vivo studies to assess acute and chronic toxicity and potential hazard to humans. Several alternative testing approaches utilizing two-dimensional (2D) in vitro assays to screen engineered NPs have reported conflicting results between in vitro and in vivo assays. Compared to conventional 2D in vitro or in vivo animal model systems, three-dimensional (3D) in vitro platforms have been shown to more closely recapitulate human physiology, providing a relevant, more efficient strategy for evaluating acute toxicity and chronic outcomes in a tiered nanomaterial toxicity testing paradigm. RESULTS: As inhalation is an important route of nanomaterial exposure, human lung fibroblasts and epithelial cells were co-cultured with macrophages to form scaffold-free 3D lung microtissues. Microtissues were exposed to multi-walled carbon nanotubes, M120 carbon black nanoparticles or crocidolite asbestos fibers for 4 or 7 days, then collected for characterization of microtissue viability, tissue morphology, and expression of genes and selected proteins associated with inflammation and extracellular matrix remodeling. Our data demonstrate the utility of 3D microtissues in predicting chronic pulmonary endpoints following exposure to MWCNTs or asbestos fibers. These test nanomaterials were incorporated into 3D human lung microtissues as visualized using light microscopy. Differential expression of genes involved in acute inflammation and extracellular matrix remodeling was detected using PCR arrays and confirmed using qRT-PCR analysis and Luminex assays of selected genes and proteins. CONCLUSION: 3D lung microtissues provide an alternative testing platform for assessing nanomaterial-induced cell-matrix alterations and delineation of toxicity pathways, moving towards a more predictive and physiologically relevant approach for in vitro NP toxicity testing.


Assuntos
Asbesto Crocidolita/toxicidade , Matriz Extracelular/efeitos dos fármacos , Pulmão/efeitos dos fármacos , Modelos Biológicos , Nanotubos de Carbono/toxicidade , Alternativas aos Testes com Animais , Sobrevivência Celular/efeitos dos fármacos , Técnicas de Cocultura , Células Epiteliais/citologia , Células Epiteliais/efeitos dos fármacos , Matriz Extracelular/ultraestrutura , Fibroblastos/citologia , Fibroblastos/efeitos dos fármacos , Humanos , Pulmão/ultraestrutura , Macrófagos/citologia , Macrófagos/efeitos dos fármacos , Testes de Toxicidade/métodos
12.
Toxicol Appl Pharmacol ; 361: 68-80, 2018 12 15.
Artigo em Inglês | MEDLINE | ID: mdl-29960000

RESUMO

Nanotechnology is an emerging industry based on commercialization of materials with one or more dimensions of 100 nm or less. Engineered nanomaterials are currently incorporated into thin films, porous materials, liquid suspensions, or filler/matrix nanocomposites with future applications predicted in energy and catalysis, microelectronics, environmental sensing and remediation, and nanomedicine. Carbon nanotubes are one-dimensional fibrous nanomaterials that physically resemble asbestos fibers. Toxicologic studies in rodents demonstrated that some types of carbon nanotubes can induce mesothelioma, and the World Health Organization evaluated long, rigid multiwall carbon nanotubes as possibly carcinogenic for humans in 2014. This review summarizes key physicochemical similarities and differences between asbestos fibers and carbon nanotubes. The "fiber pathogenicity paradigm" has been extended to include carbon nanotubes as well as other high-aspect-ratio fibrous nanomaterials including metallic nanowires. This paradigm identifies width, length, and biopersistence of high-aspect-ratio fibrous nanomaterials as critical determinants of lung disease, including mesothelioma, following inhalation. Based on recent theoretical modeling studies, a fourth factor, mechanical bending stiffness, will be considered as predictive of potential carcinogenicity. Novel three-dimensional lung tissue platforms provide an opportunity for in vitro screening of a wide range of high aspect ratio fibrous nanomaterials for potential lung toxicity prior to commercialization.


Assuntos
Amianto/toxicidade , Carcinógenos/toxicidade , Nanotubos de Carbono/toxicidade , Animais , Modelos Animais de Doenças , Humanos , Pneumopatias/induzido quimicamente , Nanoestruturas/toxicidade , Nanotecnologia , Exposição Ocupacional/efeitos adversos
13.
Appl Microbiol Biotechnol ; 102(20): 8951-8961, 2018 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-30058007

RESUMO

The redox-mediating capacity of magnetic reduced graphene oxide nanosacks (MNS) to promote the reductive biodegradation of the halogenated pollutant, iopromide (IOP), was tested. Experiments were performed using glucose as electron donor in an upflow anaerobic sludge blanket (UASB) reactor under methanogenic conditions. Higher removal efficiency of IOP in the UASB reactor supplied with MNS as redox mediator was observed as compared with the control reactor lacking MNS. Results showed 82% of IOP removal efficiency under steady state conditions in the UASB reactor enriched with MNS, while the reactor control showed IOP removal efficiency of 51%. The precise microbial transformation pathway of IOP was elucidated by high-performance liquid chromatography coupled to mass spectroscopy (HPLC-MS) analysis. Biotransformation by-products with lower molecular weight than IOP molecule were identified in the reactor supplied with MNS, which were not detected in the reactor control, indicating the contribution of these magnetic nano-carbon composites in the redox conversion of this halogenated pollutant. Reductive reactions of IOP favored by MNS led to complete dehalogenation of the benzene ring and partial rupture of side chains of this pollutant, which is the first step towards its complete biodegradation. Possible reductive mechanisms that took place in the biodegradation of IOP were stated. Finally, the novel and successful application of magnetic graphene composites in a continuous bioreactor to enhance the microbial transformation of IOP was demonstrated.


Assuntos
Bactérias/metabolismo , Meios de Contraste/metabolismo , Iohexol/análogos & derivados , Magnetismo/métodos , Nanocompostos/química , Anaerobiose , Biodegradação Ambiental , Reatores Biológicos/microbiologia , Biotransformação , Meios de Contraste/química , Iohexol/química , Iohexol/metabolismo , Magnetismo/instrumentação , Oxirredução , Esgotos/química , Esgotos/microbiologia
14.
Environ Sci Nano ; 5(11): 2545-2559, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-31548890

RESUMO

Two-dimensional (2D) materials are a broad class of synthetic ultra-thin sheet-like solids whose rapid pace of development motivates systematic study of their biological effects and safe design. A challenge for this effort is the large number of new materials and their chemical diversity. Recent work suggests that many 2D materials will be thermodynamically unstable and thus non-persistent in biological environments. Such information could inform and accelerate safety assessment, but experimental data to confirm the thermodynamic predictions is lacking. Here we propose a framework for early hazard screening of nanosheet materials based on biodissolution studies in reactive media, specially chosen for each material to match chemically feasible degradation pathways. Simple dissolution and in vitro tests allow grouping of nanosheet materials into four classes: A, potentially biopersistent; B: slowly degradable (>24-48 hours); C, biosoluble with potentially hazardous degradation products; and D, biosoluble with low-hazard degradation products. The proposed framework is demonstrated through an experimental case study on MoO3 nanoribbons, which have a dual 2D / 1D morphology and have been reported to be stable in aqueous stock solutions. The nanoribbons are shown to undergo rapid dissolution in biological simulant fluids and in cell culture, where they elicit no adverse responses up to 100µg ml-1 dose. These results place MoO3 nanoribbons in Class D, and assigns them a low priority for further nanotoxicology testing. We anticipate use of this framework could accelerate the risk assessment for the large set of new powdered 2D nanosheet materials, and promote their safe design and commercialization.

15.
Environ Sci Nano ; 5(9): 2144-2161, 2018 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-31565225

RESUMO

With increasing commercialization of high volume, two-dimensional carbon nanomaterials comes a greater likelihood of environmental release. In aquatic environments, black carbon binds contaminants like aromatic hydrocarbons, leading to changes in their uptake, bioavailability, and toxicity. Engineered carbon nanomaterials can also adsorb pollutants onto their carbon surfaces, and nanomaterial physicochemical properties can influence this contaminant interaction. We used 2D graphene nanoplatelets and isometric carbon black nanoparticles to evaluate the influence of particle morphology and surface properties on adsorption and bioavailability of benzo(a)pyrene, a model aromatic hydrocarbon, to brine shrimp (Artemia franciscana) and a fish liver cell line (PLHC-1). Acellular adsorption studies show that while high surface area carbon black (P90) was most effective at a given concentration, 2D graphene nanoplatelets (G550) adsorbed more benzo(a)pyrene than carbon black with comparable surface area (M120). In both biological models, co-exposure to nanomaterials lead to reduced bioavailability, with G550 graphene nanoplatelets cause a greater reduction in bioavailability or response than the M120 carbon black nanoparticles. However, on a mass basis the high surface area P90 carbon black was most effective. The trends in bioavailability and adsorption were consistent across all biological and acellular studies, demonstrating the biological relevance of these results in different models of aquatic organisms. While adsorption is limited by surface area, 2D graphene nanoplatelets adsorb more benzo(a)pyrene than carbon black nanoparticles of similar surface area and charge, demonstrating that both surface area and shape play important roles in the adsorption and bioavailability of benzo(a)pyrene to carbon nanomaterials.

16.
Adv Mater ; 30(4)2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29215171

RESUMO

There is great interest in exploiting van der Waals gaps in layered materials as confinement reaction vessels to template the synthesis of new nanosheet structures. The gallery spaces in multilayer graphene oxide, for example, can intercalate hydrated metal ions that assemble into metal oxide films during thermal oxidation of the sacrificial graphene template. This approach offers limited control of structure, however, and does not typically lead to 2D atomic-scale growth of anisotropic platelet crystals, but rather arrays of simple particles directionally sintered into porous sheets. Here, a new graphene-directed assembly route is demonstrated that yields fully dense, space-filling films of tiled metal oxide platelet crystals with tessellated structures. The method relies on colloidal engineering to produce a printable "metallized graphene ink" with accurate control of metal loading, grain size/porosity, composition, and micro/nanomorphologies, and is capable of achieving higher metal-carbon ratio than is possible by intercalation methods. These tiled structures are sufficiently robust to create free standing papers, complex microtextured films, 3D shapes, and metal oxide replicas of natural biotextures.

17.
ACS Nano ; 12(1): 234-244, 2018 01 23.
Artigo em Inglês | MEDLINE | ID: mdl-29165991

RESUMO

A wide range of technologies requires barrier films to impede molecular transport between the external environment and a desired internal microclimate. Adding stretchability to barrier films would enable the applications in packaging, textiles, and flexible devices, but classical barrier materials utilize dense, ordered molecular architectures that easily fracture under small tensile strain. Here, we show that textured graphene-based coatings can serve as ultrastretchable molecular barriers expandable to 1500% areal strain through programmed unfolding that mimics the elasticity of polymers. These coatings retain barrier function under large deformation and can be conformally applied to planar or curved surfaces, where they are washfast and mechanically robust to cycling. These graphene-polymer bilayer structures also function as sensors or actuators by transducing chemical stimuli into mechanical deformation and electrical resistance change through asymmetric polymer swelling. These results may enable multifunctional fabrics that integrate chemical protection, sensing, and actuation, with further applications as selective barriers, membranes, stretchable electronics, or soft robotics.


Assuntos
Elasticidade , Grafite/química , Membranas Artificiais , Polímeros/química , Difusão , Eletrônica/instrumentação , Humanos , Modelos Moleculares , Nanoestruturas/química , Roupa de Proteção , Robótica/instrumentação , Têxteis , Dispositivos Eletrônicos Vestíveis
18.
ACS Nano ; 11(6): 5670-5679, 2017 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-28582974

RESUMO

There is tremendous interest in graphene-based membranes as protective molecular barriers or molecular sieves for separation technologies. Graphene oxide (GO) films in the dry state are known to be effective barriers for molecular transport and to expand in the presence of moisture to create enlarged intersheet gallery spaces that allow rapid water permeation. Here we explore an application for GO membranes as water-breathable barrier layers for personal protective equipment, which are designed to allow outward perspiration while protecting the wearer from chemical toxicants or biochemical agents in the local environment. A device was developed to measure permeation rates of small-molecular toxicants in the presence of counter-current water flow simulating active perspiration. The technique was applied to trichloroethylene (TCE) and benzene, which are important environmental toxicants, and ethanol as a limiting case to model very small, highly water-soluble organic molecules. Submicron GO membranes are shown to be effective TCE barriers, both in the presence and absence of simulated perspiration flux, and to outperform current barrier technologies. A molecular transport model is developed, which suggests the limited toxicant back-permeation observed occurs not by diffusion against the convective perspiration flow in hydrophobic channels, but rather through oxidized domains where hydrogen-bonding produces a near-stagnant water phase. Benzene and ethanol permeation fluxes are higher than those for TCE, likely reflecting the effects of higher water solubility and smaller minimum molecular dimension. Overall, GO films have high water breathability relative to competing technologies and are known to exclude most classes of target toxicants, including particles, bacteria, viruses, and macromolecules. The present results show good barrier performance for some very small-molecule species, but not others, with permeation being favored by high water solubility and small minimum molecular dimension.


Assuntos
Poluentes Atmosféricos/isolamento & purificação , Benzeno/isolamento & purificação , Grafite/química , Membranas Artificiais , Roupa de Proteção , Tricloroetileno/isolamento & purificação , Difusão , Gases/isolamento & purificação , Humanos , Modelos Moleculares , Óxidos/química , Respiração , Têxteis , Volatilização , Água/química
19.
Nanoscale ; 9(17): 5398-5403, 2017 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-28426079

RESUMO

This letter demonstrates a simple method to achieve high-yields of 1H semiconducting MoS2 monolayers in concentrated, colloidally-stable aqueous suspension. The method is based on oxidation suppression during the hydrothermal processing step used for metal-to-semiconductor phase reversion. Accompanying DFT calculations on elementary steps in the MoS2 wet oxidation reaction suggest that a two-site corrosion mechanism is responsible for the observed high reactivity and low stability of 1T metallic MoS2.

20.
Adv Mater ; 29(23)2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28244157

RESUMO

The creation of three-dimensional (3D) structures from two-dimensional (2D) nanomaterial building blocks enables novel chemical, mechanical or physical functionalities that cannot be realized with planar thin films or in bulk materials. Here, we review the use of emerging 2D materials to create complex out-of-plane surface topographies and 3D material architectures. We focus on recent approaches that yield periodic textures or patterns, and present four techniques as case studies: (i) wrinkling and crumpling of planar sheets, (ii) encapsulation by crumpled nanosheet shells, (iii) origami folding and kirigami cutting to create programmed curvature, and (iv) 3D printing of 2D material suspensions. Work to date in this field has primarily used graphene and graphene oxide as the 2D building blocks, and we consider how these unconventional approaches may be extended to alternative 2D materials and their heterostructures. Taken together, these emerging patterning and texturing techniques represent an intriguing alternative to conventional materials synthesis and processing methods, and are expected to contribute to the development of new composites, stretchable electronics, energy storage devices, chemical barriers, and biomaterials.

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