3D-Printed Eosin Y-Based Heterogeneous Photocatalyst for Organic Reactions.

Heterogenization of Eosin Y by 3D-printing and its application in photocatalysis are reported. The approach allows a fine tuning of the photocatalyst morphology and its rapid preparation. Photocatalytic activity was evaluated through model organic reactions involving oxidation, reduction, and photosensitization pathways. The efficiency, recyclability and stability of 3D printed EY is remarkable paving the way to new generation of heterogeneous photocatalysts with a perfect control of their shape and adaptable to any photoreactors.

Very High-Aspect-Ratio Polymeric Micropillars Made by Two-Photon Polymerization.

Polymeric micropillars with a high-aspect-ratio (HAR) are of interest for a wide range of applications, including drug delivery and the micro-electro-mechanical field. While molding is the most common method for fabricating HAR microstructures, it is affected by challenges related to demolding the final structure. In this study, we present very HAR micropillars using two-photon polymerization (TPP), an established technique for creating complex 3D microstructures. Polymeric micropillars with HARs fabricated by TPP often shrink and collapse during the development process. This is due to the lack of mechanical stability of micropillars against capillary forces primarily acting during the fabrication process when the solvent evaporates. Here, we report different parameters that have been optimized to overcome the capillary force. These include surface modification of the substrate, fabrication parameters such as laser power, exposure time, the pitch distance between the pillars, and the length of the pillars. On account of adopting these techniques, we were able to fabricate micropillars with a very HAR up to 80.

Smart Nematic Liquid Crystal Polymers for Micromachining Advances.

The miniaturization of tools is an important step in human evolution to create faster devices as well as precise micromachines. Studies around this topic have allowed the creation of small-scale objects capable of a wide range of deformation to achieve complex tasks. Molecular arrangements have been investigated through liquid crystal polymer (LCP) to program such a movement. Smart polymers and hereby liquid crystal matrices are materials of interest for their easy structuration properties and their response to external stimuli. However, up until very recently, their employment at the microscale was mainly limited to 2D structuration. Among the numerous issues, one concerns the ability to 3D structure the material while controlling the molecular orientation during the polymerization process. This review aims to report recent efforts focused on the microstructuration of LCP, in particular those dealing with 3D microfabrication via two-photon polymerization (TPP). Indeed, the latter has revolutionized the production of 3D complex micro-objects and is nowadays recognized as the gold standard for 3D micro-printing. After a short introduction highlighting the interest in micromachines, some basic principles of liquid crystals are recalled from the molecular aspect to their implementation. Finally, the possibilities offered by TPP as well as the way to monitor the motion into the fabricated microrobots are highlighted.

Shape influence on the ultrafast plasmonic properties of gold nanoparticles.

The aim of shape-controlled colloidal synthesis of gold (Au) is to produce Au nanoparticles (NPs) with fine control of shapes, sizes, and dispersities. We show how transient absorption spectroscopy (TAS) can be used to rapidly and accurately quantify the vast ensemble of shapes of Au NPs in solution within minutes, including the synthesized nanorods, decahedra, and nanospheres. Colloidal solutions containing Au NPs were measured in TAS and their localized surface plasmon resonance (LSPR) modes were classified according to the shape, wavelength and number of peaks. Then their excited-state relaxation dynamics were used to ascertain their electron-phonon (e-ph) coupling time constant and frequency of optomechanical modes. TAS can quickly show that an Au nanosphere sample contains a tiny fraction of Au nanorods, whereas steady-state absorbance is totally blind to the presence of nanorods. Additionally, the TAS experiments indicate that the characteristic e-ph coupling time constants in Au nanorods depend on the NPs dimensions at high excitation intensity (> 6 µJ/cm2) which can help identify if there are any elongated Au NPs in Au spheres samples. Finally, optomechanical oscillations formed by NPs breathing modes were observed, providing information related to the average size and monodispersity of Au nanospheres and nanorods.

Two-Photon Initiating Efficiency of a Ditopic Alkoxynitrostilbene Reacting through a Self-Regenerative Mechanism.

The photophysical properties and the photoinitiating reactivity of a ditopic alkoxynitrostilbene were compared to those of its single branch chromophore used as a reference. Whereas a trivial additive effect is observed when considering the one- and two-photon absorption properties, a clear and very significant amplification has been highlighted for the photoreactivity of this free radical photoinitiator which was used as a hydrogen abstractor in presence of an aliphatic amine co-reactant. We indeed demonstrate that the proximity of two nitroaromatics moieties within the same molecular architecture gives rise to an original cycling mechanism based on a stepwise photo triggering of each photoredox center followed by a subsequent regenerative process. The combination of a high two-photon absorption cross-section (δ780nm ≈330 GM) with a strong enhancement in photoreactivity makes this nitrostilbene bichromophore a very suitable candidate for two-photon polymerization applications.

Laser Direct Writing of Arbitrary Complex Polymer Microstructures by Nitroxide-Mediated Photopolymerization.

In this paper, we demonstrate the possibility of generating arbitrary polymer microstructures covalently linked to a first polymer layer by laser direct writing. At the molecular scale, the process relies on nitroxide-mediated photopolymerization triggered by a light-sensitive alkoxyamine. In addition to the proof of concept and examples of achievable structures, including multichemistry patterns and 3D structures, this paper aims at investigating the physicochemical phenomena involved under such conditions. In particular, the parameters influencing the repolymerization process are considered, and special attention is paid to the study of the impact of oxygen on the spatial control of the polymerization. Such a work opens many possibilities toward the fabrication of on-demand high-resolution (multi)functional polymer micro and nanostructures.

Branching effect on the linear and nonlinear optical properties of styrylpyrimidines.

This contribution aims at investigating the branching effect on the steady state, time resolved fluorescence and two-photon absorption (2PA) properties of dimethylamino and diphenylamino substituted styrylpyrimidine derivatives, by means of a combined experimental and theoretical study. In contrast to classical branched molecules with a triphenylamine central core and electron accepting groups at the periphery, here, branched molecules with reverse topology and different symmetries are examined, namely a styrylpyrimidine group is used as the electron withdrawing core and dimethylamino or diphenylamino donors are incorporated at the periphery. Besides, compared to the great majority of existing branched systems, the herein studied molecules do not have C3 symmetry. For this reason, the region of the linear and non-linear optical spectra of the two and three branched chromophores is actually similar. Interestingly, while the one-photon absorption spectra of one-branched systems versus two- or three-branched ones are spectrally shifted, there is almost no spectral shift in the main 2PA spectral region. Meanwhile, there is still an enhancement of both linear and nonlinear optical responses. Overall, here we developed a strategy that enhances the 2PA response while maintaining the spectral position. Specifically, 2PA cross section values as high as 500 GM have been obtained for the diphenylamino A-(π-D)3 molecule in dichloromethane.

Highly Virulent Bactericidal Effects of Curcumin-Based µ-Cages Fabricated by Two-Photon Polymerization.

A new antibacterial strategy is reported based on two-photon fabrication of three-dimensional curcumin-embedded µ-cages. Such devices were designed to entrap and kill Staphylococcus aureus bacteria upon visible light irradiation. The proposed concept mainly relies on the pivotal role of curcumin, which is sequentially used as a two-photon active free radical initiator and as a photogenerator of reactive oxygen species within the cage µ-volumes. We show that these µ-cages exhibit extremely high antimicrobial properties, leading to 95% bacteria mortality after only 10 min visible irradiation. A preconcentration mechanism of photogenerated oxygen species is proposed to account for this highly performing bactericidal effect whose virulence can be strikingly switched on by increasing the light exposure time from 5 to 10 min.

A two-photon active chevron-shaped type I photoinitiator designed for 3D stereolithography.

We present herein the properties of a highly reactive type I photoinitiator with significant 2PA cross-sections (δ720nm ∼ 90 GM). We demonstrate that this new type of photocleavable system exhibits very efficient two-photon polymerization abilities with performances amplified by more than two orders of magnitude with regards to those of a commercially available type I photoinitiator (Lucirin TPO-L) which is extensively employed for multiphoton 3D stereolithography.

Direct Laser Writing of Crystallized TiO2 and TiO2 /Carbon Microstructures with Tunable Conductive Properties.

Metal oxides are an important class of materials for optoelectronic applications. In this context, developing simple and versatile processes for integrating these materials at the microscale and nanoscale has become increasingly important. One of the major remaining challenges is to control the microstructuration and electro-optical properties in a single step. It is shown here that near-infrared femtosecond laser irradiation can be successfully used to prepare amorphous or crystallized TiO2 microstructures in a single step using a direct laser writing (DLW) approach from a TiO2 precursor thin film doped with a suitable dye. When laser writing is conducted under a nitrogen atmosphere, simultaneous to the crosslinking of the Ti-oxide precursor, the graphitization of the organic species embedded in the initial film is observed. In this case, a carbon network is generated within the TiO2 matrix, which significantly increases the conductivity. Moreover, the TiO2 /C nanocomposite exhibits piezoresistive behavior that is used in a pressure sensor device. Using this route, it is possible to use DLW to fabricate microsized pressure sensors.

Curvotaxis directs cell migration through cell-scale curvature landscapes.

Cells have evolved multiple mechanisms to apprehend and adapt finely to their environment. Here we report a new cellular ability, which we term "curvotaxis" that enables the cells to respond to cell-scale curvature variations, a ubiquitous trait of cellular biotopes. We develop ultra-smooth sinusoidal surfaces presenting modulations of curvature in all directions, and monitor cell behavior on these topographic landscapes. We show that adherent cells avoid convex regions during their migration and position themselves in concave valleys. Live imaging combined with functional analysis shows that curvotaxis relies on a dynamic interplay between the nucleus and the cytoskeleton-the nucleus acting as a mechanical sensor that leads the migrating cell toward concave curvatures. Further analyses show that substratum curvature affects focal adhesions organization and dynamics, nuclear shape, and gene expression. Altogether, this work identifies curvotaxis as a new cellular guiding mechanism and promotes cell-scale curvature as an essential physical cue.

Light-Sensitive Alkoxyamines as Versatile Spatially- and Temporally- Controlled Precursors of Alkyl Radicals and Nitroxides.

The use of UV/visible light irradiation as a means to initiate organic syntheses is increasingly attractive due to the high spatial and temporal control conferred by photochemical processes. The aim of this work is thus to demonstrate that alkoxyamines bearing a chromophore on the alkyl moiety can provide a photoprotecting group for the sensitive nitroxide functionality, that is known to degrade through redox processes. The dissociation of various photosensitive alkoxyamines was studied from 223 to 298 K under UV/visible irradiation, depending on the nature of the chromophore. In each case a rapid (typically in less than 1 h) and near-quantitative dissociation was observed. As an illustration of the interest of this approach, a pyrene-based alkoxyamine was employed for the spatially controlled coupling of polymer chains onto Si wafers to produce micropatterned surfaces.

Rapid Prototyping of Polymeric Nanopillars by 3D Direct Laser Writing for Controlling Cell Behavior.

Mammalian cells have been widely shown to respond to nano- and microtopography that mimics the extracellular matrix. Synthetic nano- and micron-sized structures are therefore of great interest in the field of tissue engineering, where polymers are particularly attractive due to excellent biocompatibility and versatile fabrication methods. Ordered arrays of polymeric pillars provide a controlled topographical environment to study and manipulate cells, but processing methods are typically either optimized for the nano- or microscale. Here, we demonstrate polymeric nanopillar (NP) fabrication using 3D direct laser writing (3D DLW), which offers a rapid prototyping across both size regimes. The NPs are interfaced with NIH3T3 cells and the effect of tuning geometrical parameters of the NP array is investigated. Cells are found to adhere on a wide range of geometries, but the interface depends on NP density and length. The Cell Interface with Nanostructure Arrays (CINA) model is successfully extended to predict the type of interface formed on different NP geometries, which is found to correlate with the efficiency of cell alignment along the NPs. The combination of the CINA model with the highly versatile 3D DLW fabrication thus holds the promise of improved design of polymeric NP arrays for controlling cell growth.

Rapid Prototyping of Chemical Microsensors Based on Molecularly Imprinted Polymers Synthesized by Two-Photon Stereolithography.

Two-photon stereolithography is used for rapid prototyping of submicrometre molecularly imprinted polymer-based 3D structures. The structures are evaluated as chemical sensing elements and their specific recognition properties for target molecules are confirmed. The 3D design capability is exploited and highlighted through the fabrication of an all-organic molecularly imprinted polymeric microelectromechanical sensor.

One- and two-photon absorption and emission properties of an oligo(phenylenethienylene)s series.

The photophysical and nonlinear absorption properties of an oligo(phenylenethienylene)s series (nTBT) are investigated in this article. The length of the chromophore is gradually increased from one to four phenylenethienylene repeating units in order to evaluate the effects of the electronic delocalization on the two-photon absorption cross sections (δ). According to the excitation anisotropy measurements and quantum chemical calculations, two electronic transitions with distinctive symmetries, 1Ag → 1Bu and 1Ag → 2Ag, are present in the low energy region of the linear absorption spectrum. The lowest-energy transition 1Ag → 1Bu is one-photon allowed but two-photon forbidden and implies an electronic charge delocalization all along the oligomer segment whereas the weakly-allowed 1Ag → 2Ag transition exhibits a transition moment perpendicular to the average plane of the chromophore. The latter transition mainly contributes to the two-photon absorption ability of the oligomers. All derivatives are poorly solvatochromic and the breakdown of the mirror symmetry rule observed between absorption and fluorescence spectra at room temperature has been attributed to a photoinduced geometrical relaxation leading to a very efficient planarization process of the oligomer irrespective of its size. Increasing the oligomer length results in a slight shift of the two-photon absorption band (∼1300 cm(-1)) and in a drastic increase of δ from 2 ± 1 GM up to 802 ± 160 GM for 1TBT and 4TBT respectively. Based on a three-level model, it was found that main contributions to the strong increase of δ stem from the transition moments Mge and Mee' which are multiplied by a factor of 2.8 and 5 when going from 1TBT to 4TBT.

Synthesis, photophysics and nonlinear optical properties of stilbenoid pyrimidine-based dyes bearing methylenepyran donor groups.

The nonlinear properties and the photophysical behavior of two π-conjugated chromophores that incorporate an electron-deficient pyrimidine core (A) and γ-methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes' scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end-groups. This latter structural parameter also has a strong influence on the excited-state dynamics, which leads to a very efficient fluorescence quenching.

Photoswitchable interactions between photochromic organic diarylethene and surface plasmon resonance of gold nanoparticles in hybrid thin films.

Hybrid materials combining gold nanoparticles (GNP) of variable diameter and an organic thin layer of photochromic diarylethenes were achieved. Solid-state photoswitching based on ring-closure/ring-opening reaction was carried out under alternate UV and visible irradiations. In addition to the spectral changes due to the photochromism itself, the surface plasmon resonance related to the GNP is significantly modified, influenced by a photoinduced change in the refractive index of its environment. These two contributions were sorted out, showing the possibility of probing a photochromic switch by following the plasmon band. The shape change of the plasmon band was consistently compared to calculations based on the Mie theory. Additionally, with one given diarylethene compound, both UV-visible spectroscopy and surface enhanced Raman scattering (SERS) spectroscopy showed an acceleration of the ring-opening photochromic reaction in the presence of GNP.

Direct nanopatterning of 100 nm metal oxide periodic structures by Deep-UV immersion lithography.

Deep-UV lithography using high-efficiency phase mask has been developed to print 100 nm period grating on sol-gel based thin layer. High efficiency phase mask has been designed to produce a high-contrast interferogram (periodic fringes) under water immersion conditions for 244 nm laser. The demonstration has been applied to a new developed immersion-compatible sol-gel layer. A sol-gel photoresist prepared from zirconium alkoxides caped with methacrylic acids was developed to achieve 50 nm resolution in a single step exposure. The nanostructures can be thermally annealed into ZrO(2). Such route considerably simplifies the process for elaborating nanopatterned surfaces of transition metal oxides, and opens new routes for integrating materials of interest for applications in the field of photocatalysis, photovoltaic, optics, photonics or microelectronics.

Orienting the demixion of a diblock copolymer using 193 nm interferometric lithography for the controlled deposition of nanoparticles.

DUV interferometric lithography and diblock copolymer self-organization have successfully been combined to provide a simple and highly collective nanopatterning technique enabling the organization of nanoparticles over several orders of magnitude, from nanometre to millimetre. The nanostructural changes at the surface of the polymer film after thermal annealing have been monitored by AFM and the process parameters optimized for obtaining a long-range organization of the lamellar domains. In particular, the impact of the annealing conditions and geometric parameters of the substrate patterns have been investigated. The nanopatterns resulting from the lamellar demixion of (PS-b-MMA) were used for a controlled deposition of nanoparticles. The affinity of the hydrophobic particles for the PS block was demonstrated, opening new doors towards the preparation of high-density arrays of nanoparticles with potential applications in data storage.

Probing photochromic properties by correlation of UV-visible and infra-red absorption spectroscopy: a case study with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene.

Quantification of the relative composition of the isomers in a photochromic system at any irradiation time interval is a critical issue in determining absolute quantum yields. For this purpose, we have developed a simple and convenient protocol involving combination of UV-visible and infra-red absorption spectroscopy. Photochromic cyclization reaction of cis-l,2-dicyano-l,2-bis(2,4,5-trimethyl-3-thieny1)ethene (CMTE) is analyzed to demonstrate the efficiency of the proposed methodology. This approach is based on the fact that the two isomers show distinctive infra-red bands. Detailed investigations of the UV-visible and infra-red spectra of the mixture obtained at different irradiation times in CCl(4) supported by quantum chemical computations lead to the unambiguous estimation of molar absorption coefficients of the closed isomer (epsilon(CF) = 4650 L mol(-1) cm(-1) at 512 nm). It facilitates the first determination of absolute quantum yields of this reversible photochromic reaction in CCl(4) by fitting the UV-visible spectral data (Phi(OF-->CF) = 0.41 +/- 0.05 and Phi(CF-->OF) = 0.12 +/- 0.02 at 405 nm and 546 nm, respectively).