Enhancing the adhesion of graphene to polymer substrates by controlled defect formation.

The mechanical integrity of composite materials depends primarily on the interface strength and the defect density of the reinforcement which is the provider of enhanced strength and stiffness. In the case of graphene/polymer nanocomposites which are characterized by an extremely large interface region, any defects in the inclusion (such as folds, cracks, holes, etc) will have a detrimental effect to the internal strain distribution and the resulting mechanical performance. This conventional wisdom, however, can be challenged if the defect size is reduced beyond the critical size for crack formation to the level of atomic vacancies. In that case, there should be no practical effect on crack propagation and depending on the nature of the vacancies the interface strength may in fact increase. In this work we employed argon ion (Ar+) bombardment and subsequent exposure to hydrogen (H2) to induce (as revealed by x-ray and ultraviolet photoelectron spectroscopy and Raman spectroscopy) passivated atomic single vacancies to CVD graphene. The modified graphene was subsequently transferred to PMMA bars and the morphology, wettability and the interface adhesion of the CVD graphene/PMMA system were investigated with atomic force microscopy technique and Raman analysis. The results obtained showed clearly an overall improved mechanical behavior of graphene/polymer interface, since an increase as well as a more uniform shift distribution with strain is observed. This paves the way for interface engineering in graphene/polymer systems which, in pristine condition, suffer from premature graphene slippage and subsequent failure.

Benzothiazoles with tunable electron-withdrawing strength and reverse polarity: a route to triphenylamine-based chromophores with enhanced two-photon absorption.

A series of dipolar and octupolar triphenylamine-derived dyes containing a benzothiazole positioned in the matched or mismatched fashion have been designed and synthesized via palladium-catalyzed Sonogashira cross-coupling reactions. Linear and nonlinear optical properties of the designed molecules were tuned by an additional electron-withdrawing group (EWG) and by changing the relative positions of the donor and acceptor substituents on the heterocyclic ring. This allowed us to examine the effect of positional isomerism and extend the structure-property relationships useful in the engineering of novel heteroaromatic-based systems with enhanced two-photon absorption (TPA). The TPA cross-sections (δ(TPA)) in the target compounds dramatically increased with the branching of the triphenylamine core and with the strength of the auxiliary acceptor. In addition, a change from the commonly used polarity in push-pull benzothiazoles to a reverse one has been revealed as a particularly useful strategy (regioisomeric control) for enhancing TPA cross-sections and shifting the absorption and emission maxima to longer wavelengths. The maximum TPA cross-sections of the star-shaped three-branched triphenylamines are ∼500-2300 GM in the near-infrared region (740-810 nm); thereby the molecular weight normalized δ(TPA)/MW values of the best performing dyes within the series (2.0-2.4 GM·g(-1)·mol) are comparable to those of the most efficient TPA chromophores reported to date. The large TPA cross-sections combined with high emission quantum yields and large Stokes shifts make these compounds excellent candidates for various TPA applications, including two-photon fluorescence microscopy.

Direct Iodination of Electron-Deficient Benzothiazoles: Rapid Access to Two-Photon Absorbing Fluorophores with Quadrupolar D-π-A-π-D Architecture and Tunable Heteroaromatic Core.

Direct iodination of benzothiazoles under strong oxidative/acidic conditions leads to a mixture of iodinated heteroarenes with 1-2 major components, which are easily separable and which structures depend on the I2 equivalents used. Among the unexpected but dominant products were identified 4,7-diiodobenzothiazoles with a rare substitution pattern for SEAr reactions of this scaffold. These were employed in the synthesis of 4,7-bis(triarylamine-ethynyl)benzothiazoles - a new class of highly efficient quasi-quadrupolar fluorophores displaying large two-photon absorption cross sections (540-1374 GM) in the near-infrared region.

Oxidative C-H Homocoupling of Push-Pull Benzothiazoles: An Atom-Economical Route to Highly Emissive Quadrupolar Arylamine-Functionalized 2,2'-Bibenzothiazoles with Enhanced Two-Photon Absorption.

Copper(II)-catalyzed C-H/C-H coupling of dipolar 2-H-benzothiazoles end-capped with triphenylamine moieties affords highly fluorescent 2,2'-bibenzothiazoles with quadrupolar (D-π-A-π-D) architecture displaying large two-photon absorption (TPA) cross sections (543-1252 GM) in the near-infrared region. The notably higher TPA performance as compared to quadrupolar π-systems with a widely used 2,2'-bipyridine core, along with the ease of the synthesis and chelating N^N ability, makes the title biheteroaryl platform an attractive building block for a large scope of functional dyes exploiting nonlinear optical phenomena.

Two- and three-photon absorption of organic ionic pyrylium based materials.

Pyrylium dyes having the same basic chemical structure, differing only to a specific substituent, have been used as novel materials for multiphoton three-dimensional data storage. Electronic absorption spectra, two-photon and three-photon absorption properties of this class of pyrylium dyes, have been studied theoretically and compared to experimental results. The effects of the counteranion, the surrounding solvent, and electron releasing and electron withdrawing groups in specific positions of the basic structure have been explored in detail. It is argued that on grounds of the quality of experimental spectroscopic agreement, the computed two- and three-photon data may be used in pulse propagation simulations of three-dimensional recording in optical memories.

3-Arm star pyrene-functional PMMAs for efficient exfoliation of graphite in chloroform: fabrication of graphene-reinforced fibrous veils.

3-Arm PMMAs end-functionalized by pyrene were designed as dispersing/stabilizing agents for the liquid-phase exfoliation of graphite in low-boiling point solvents like chloroform. The synthetic procedure comprised ARGET ATRP controlled polymerization, click chemistry and the quaternization reaction of triazole, ensuring tailor-made, well-defined pyrene-functional star PMMAs. Among a series of different pyrene-functional macromolecular topologies, the (PMMA-py2)3 proved the most efficient exfoliation agent giving relatively high graphene concentration (0.36 mg ml-1) at exceptionally low polymer/graphite mass ratio (mP/mGF = 0.003) and short sonication time (3 h). A 5-cycle iterative procedure relying on the redispersion of the sediment was developed yielding CG = 1.29 mg ml-1 with 14.8% exfoliation yield, under the favorable conditions of 10.5 h total shear mixing/tip sonication time and overall mP/mGF ratio as low as 0.15. In parallel, all-atom molecular dynamics simulations were conducted which helped understand the mechanism by which pyrene-functional macromolecular topologies act as efficient dispersing agents of graphene. Finally the G@(PMMA-Py)3 hybrids were well dispersed into the PMMA matrix by electrospinning to fabricate graphene-based nanocomposite fibrous veils. These graphene/polymer nanocomposites exhibited enhanced stiffness and strength by a factor of 4.4 with 1.5 wt% graphene hybrids as nanofillers.

Strong two photon absorption and photophysical properties of symmetrical chromophores with electron accepting edge substituents.

Two photon absorption (TPA) and photophysical properties of three new symmetrical chromophores with electron accepting phthalimide edge substituents have been studied. The three chromophores contain fluorene, alcoxy-substituted divinyl benzene, and carbazole moieties as central cores, respectively. The femtosecond time-resolved fluorescence upconversion spectroscopy and two photon excited fluorescence technique have been carried out. The effect of solvent polarity on TPA and on photophysics has also been determined. Ultrafast fluorescence dynamics, with decay times ranging from 1 to 13 ps, are revealed in polar solvents. This is attributed to the relaxation of the chromophores to the intramolecular charge transfer state. The chromophore bearing fluorene central core, being of the type A-pi-A, is the most efficient concerning TPA. Strong TPA, with a cross section value as high as 2100 GM at an excitation wavelength of 770 nm is found in acetophenone which is a solvent of intermediate polarity. The TPA spectra were also reproduced using a sum over states three-state model. A study of the TPA induced photobleaching of the fluorene molecule, doped in a solid poly(methyl-methacrylate) film, has shown that this material is very promising for efficient TPA optical data storage.

Strain Engineering in Highly Wrinkled CVD Graphene/Epoxy Systems.

Chemical vapor deposition (CVD) is regarded as a promising fabrication method for the automated, large-scale, production of graphene and other two-dimensional materials. However, its full commercial exploitation is limited by the presence of structural imperfections such as folds, wrinkles, and even cracks that downgrade its physical and mechanical properties. For example, as shown here by means of Raman spectroscopy, the stress transfer from an epoxy matrix to CVD graphene is on average 30% of that of exfoliated monolayer graphene of over 10 µm in dimensions. However, in terms of electrical response, the situation is reversed; the resistance has been found here to decrease by the imposition of mechanical deformation possibly due to the opening up of the structure and the associated increase of electron mobility. This finding paves the way for employing CVD graphene/epoxy composites or coatings as conductive "networks" or bridges in cases for which the conductivity needs to be increased or at least retained when the system is under deformation. The tuning/control of such systems and their operative limitations are discussed here.

Substituent effect on the photobleaching of pyrylium salts under ultrashort pulsed illumination.

The current article presents the photobleaching properties of a group of pyrylium salts under ultrashort pulsed illumination. These pyrylium salts have the same basic chemical structure and differ only by a specific substituent. It is proven experimentally that two different mechanisms are simultaneously present to the photobleaching of all molecules studied (independently of their specific chemical structure). However, the particular parameters of each mechanism are influenced significantly by the substituent change. The experimental investigation of these parameters showed the presence of multiphoton interactions in the photobleaching of pyrylium salts depending essentially on the specific substituent.

Molecular Modeling Combined with Advanced Chemistry for the Rational Design of Efficient Graphene Dispersing Agents.

Pyrene-functional PMMAs were prepared via ATRP-controlled polymerization and click reaction, as efficient dispersing agents for the exfoliation of few-layered graphene sheets (GS) in easily processable low boiling point chloroform. In parallel, detailed atomistic simulations showed fine dispersion of the GS/polymer hybrids in good agreement with the experiment. Moreover, the molecular dynamics simulations revealed interesting conformations (bridges, loops, dangling ends, free chains) of GS/polymer hybrids and allowed us to monitor their time evolution both in solution and in the polymer nanocomposite where the solvent molecules were replaced with PMMA chains. Microscopic information about these structures is very important for optimizing mechanical performance. It seems that the combination of atomistic simulation with advanced chemistry constitutes a powerful tool for the design of effective graphene dispersing agents that could be used for the production of graphene-based nanocomposites with tailor-made mechanical properties.

Study of the isotropic and anisotropic fluorescence of two oligothiophenes by femtosecond time-resolved spectroscopy.

The excited-state dynamics of two oligothiophenes, 5,5'-dicarboxyhaldehyde 2,2',5',2' '-terthiophene and 5-carboxyhaldehyde 2,2',5',2' '-terthiophene, were studied by time-resolved fluorescence spectroscopy, in the femtosecond regime. The isotropic and anisotropic parameters of their fluorescence were calculated. The angle (alpha) between the absorption and emission molecular dipoles was estimated from the initial fluorescence anisotropy. The effect of the chemical substituents, at the ends of the main chain of the molecule, on the temporal behavior of the fluorescence was investigated. Particularly, the nonsymmetric oligothiophene molecule (containing one aldehyde group) exhibits shorter excited-state isotropic decay time than the symmetric one (containing two aldehyde groups). This is due to the higher value of the emission dipole moment of the nonsymmetric oligothiophene in comparison with that of the symmetric one. Additionally, the two materials have almost the same anisotropic fluorescence parameters, and this is attributed to the same rotational motions in the excited state due to their similar molecular structures.

Stress transfer mechanisms at the submicron level for graphene/polymer systems.

The stress transfer mechanism from a polymer substrate to a nanoinclusion, such as a graphene flake, is of extreme interest for the production of effective nanocomposites. Previous work conducted mainly at the micron scale has shown that the intrinsic mechanism of stress transfer is shear at the interface. However, since the interfacial shear takes its maximum value at the very edge of the nanoinclusion it is of extreme interest to assess the effect of edge integrity upon axial stress transfer at the submicron scale. Here, we conduct a detailed Raman line mapping near the edges of a monolayer graphene flake that is simply supported onto an epoxy-based photoresist (SU8)/poly(methyl methacrylate) matrix at steps as small as 100 nm. We show for the first time that the distribution of axial strain (stress) along the flake deviates somewhat from the classical shear-lag prediction for a region of ∼ 2 µm from the edge. This behavior is mainly attributed to the presence of residual stresses, unintentional doping, and/or edge effects (deviation from the equilibrium values of bond lengths and angles, as well as different edge chiralities). By considering a simple balance of shear-to-normal stresses at the interface we are able to directly convert the strain (stress) gradient to values of interfacial shear stress for all the applied tensile levels without assuming classical shear-lag behavior. For large flakes a maximum value of interfacial shear stress of 0.4 MPa is obtained prior to flake slipping.

Suspended monolayer graphene under true uniaxial deformation.

2D crystals, such as graphene, exhibit the higher strength and stiffness of any other known man-made or natural material. So far, this assertion has been primarily based on modelling predictions and on bending experiments in combination with pertinent modelling. True uniaxial loading of suspended graphene is not easy to accomplish; however such an experiment is of paramount importance in order to assess the intrinsic properties of graphene without the influence of an underlying substrate. In this work we report on uniaxial tension of graphene up to moderate strains of ∼0.8%. This has been made possible by sandwiching the graphene flake between two polymethylmethacrylate (PMMA) layers and by suspending its central part by the removal of a section of PMMA with e-beam lithography. True uniaxial deformation is confirmed by the measured large phonon shifts with strain by Raman spectroscopy and the indication of lateral buckling (similar to what is observed for thin macroscopic membranes under tension). Finally, we also report on how the stress is transferred to the suspended specimen through the adhesive grips and determine the value of interfacial shear stress that is required for efficient axial loading in such a system.

Quadrupolar benzobisthiazole-cored arylamines as highly efficient two-photon absorbing fluorophores.

A computer-aided design of novel D-π-A-π-D styrylamines containing five isomeric benzobisthiazole moieties as the electron-accepting core has revealed the linear centrosymmetric benzo[1,2-d:4,5-d']bisthiazole as the most promising building block for engineering chromophores displaying high two-photon absorption (TPA) in the near-IR region, as also confirmed experimentally. The ease of synthesis of quadrupolar derivatives thereof, combined with extraordinarly high TPA action cross sections (δTPAΦf > 1500 GM), makes these heteroaromatic systems particularly attractive as diagnostic agents in 3D fluorescence imaging.