Robust silicon-on-insulator adiabatic splitter optimized by metamodeling.

A robust integrated power splitter based on a silicon-on-insulator adiabatic coupler configuration is demonstrated. The power separation is achieved by a slow and simultaneous change of phase and coupling constants. The geometrical parameters of the device are determined thanks to a metamodel-based iterative optimization strategy. Solving the multiple parameter problem together with a realistic bandwidth constraint provides a clear improvement of the power splitting stability. The robustness is confirmed experimentally on a single device and at the wafer scale.

trans- and cis-(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6): promising candidates for NO release in the NIR region.

cis- and trans-(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6) complexes show efficient NO photodelivery upon two-photon excitation in the NIR region. Moreover, cytotoxicity and phototoxicity studies provide evidence that these complexes are promising candidates as photoactivatable molecular tools for resection of malignancies.

Cooperative Veratryle and Nitroindoline Cages for Two-Photon Uncaging in the NIR.

Tandem uncaging systems in which a two-photon absorbing module and a cage moiety, linked via a phosphorous clip, that act together by Förster resonance energy transfer (FRET) have been developed. A library of these compounds, using different linkers and cages (7-nitroindolinyl or nitroveratryl) has been synthesized. The investigation of their uncaging and two-photon absorption properties demonstrates the scope and versatility of the engineering strategy towards efficient two-photon cages and reveals surprising cooperative and topological effects. The interactions between the 2PA module and the caging moiety are found to promote cooperative effects on the 2PA response while additional processes that enhance the uncaging efficiency are operative in well-oriented nitroindoline-derived dyads. These synergic effects combine to lead to record two-photon uncaging cross-section values (i.e., up to 20 GM) for uncaging of carboxylic acids.

Solvatofluorochromic, non-centrosymmetric π-expanded diketopyrrolopyrrole.

A novel non-centrosymmetric π-expanded diketopyrrolopyrrole was designed and synthesized. Strategic placement of tert-butyl groups at the periphery of a diketopyrrolopyrrole allowed us to selectively fuse one moiety via tandem Friedel-Crafts-dehydration reactions, resulting in a non-centrosymmetric dye. The structure of the dye was confirmed by X-ray crystallography, revealing that it contains a nearly flat arrangement of four fused rings. Extensive photophysical studies of this new functional dye revealed that the intensity of its emission strongly depends on solvent polarity, which is typical for dipolar chromophores. In non-polar solvents, the fluorescence quantum yield is high whereas in polar solvents such as MeOH, it is 12%. However, upon two-photon excitation the compound behaves like a centrosymmetric dye, showing a two-photon absorption maximum at significantly shorter wavelengths than twice the wavelength of the one-photon absorption maximum.

A cyclometallated fluorenyl Ir(iii) complex as a potential sensitiser for two-photon excited photodynamic therapy (2PE-PDT).

A new Ir(iii) cyclometallated complex bearing a fluorenyl 5-substituted-1,10-phenanthroline ligand ([Ir(ppy)2()][PF6], ppy = 2-phenylpyridine) is presented which exhibits enhanced triplet oxygen sensing properties. The efficacy of this complex to act as a photosensitiser for altering the morphology of C6 Glioma cells that represent malignant nervous tumours has been evaluated. The increased heavy metal effect and related spin-orbit coupling parameters on the photophysical properties of this complex are evidenced by comparison with Ru(ii) analogues. The complex [Ir(ppy)2()][PF6] is shown to exhibit relatively high two-photon absorption efficiencies for the lowest energy MLCT electronic transitions with two-photon absorption cross sections that range from 50 to 80 Goeppert-Mayer units between 750 to 800 nm. Quantum yields for the complex were measured up to 23% and the Stern-Volmer quenching constant, KSV was determined to be 40 bar(-1) in acetonitrile solution, confirming the high efficiency of the complex as a triplet oxygen sensitiser. Preliminary in vitro experiments with C6 Glioma cells treated with [Ir(ppy)2()][PF6], show that the complex is an efficient sensitizer for triplet oxygen, producing cytotoxic singlet oxygen ((1)O2) by two-photon excitation at 740 nm resulting in photodynamic effects that lead to localised cell damage and death.

Polar diketopyrrolopyrrole-imidazolium salts as selective probes for staining mitochondria in two-photon fluorescence microscopy.

Three rationally designed polar derivatives of diketopyrrolopyrrole consisting of 1,3-dimethylimidazolium cationic units and benzene, thiophene, or furan rings as π spacers were synthesized and thoroughly studied. The obtained salts are soluble in polar organic solvents and show satisfactory solubility in water, which makes them suitable for the applications in bioimaging. Photophysical measurements revealed that the obtained derivatives are characterized by strong absorption and good fluorescence quantum yields. The corresponding two-photon properties were also examined and showed that the synthesized salts exhibit large two-photon absorption cross-sections reaching 4000 GM (GM=Goeppert-Mayer unit, 1 GM=10(-50)  cm(4) s photon(-1) ) and very high two-photon brightness values exceeding 2000 GM. It was demonstrated that these salts can be safely applied in two-photon fluorescence microscopy for selective staining of mitochondria in living cells.

Enhanced two-photon fluorescence imaging and therapy of cancer cells via Gold@bridged silsesquioxane nanoparticles.

A two-photon photosensitizer with four triethoxysilyl groups is synthesized through the click reaction. This photosensitizer allows the design of bridged silsesquioxane (BS) nanoparticles through a sol-gel process; moreover, gold core BS shells or BS nanoparticles decorated with gold nanospheres are synthesized. An enhancement of the two-photon properties is noted with gold and the nanoparticles are efficient for two-photon imaging and two-photon photodynamic therapy of cancer cells.

Cooperative dyads for two-photon uncaging.

A series of dyads that combine a photolabile protecting group (PPG) 4,5-dimethoxy-2-nitrobenzyl and different bis-donor or bis-acceptor dissymmetric chromophores acting as two-photon (2P) absorbers were synthesized. Even for low energy transfer efficiency from the 2PA subunit to the uncaging one, improvement of the 2P uncaging sensitivity in the NIR is achieved as compared to isolated PPG. Moreover enhancement of the 2PA response is achieved by tuning the electronic dissymmetry of the 2PA subunit and the arrangement of the complementary subunits in the dyads.

Disulfide-gated mesoporous silica nanoparticles designed for two-photon-triggered drug release and imaging.

We report a two-photon-actuated cancer cell killing system that kills the cancer cells via drug delivery through multifunctional mesoporous silica nanogates. Two-photon-sensitive mesoporous organosilica (M2PS) nanocarriers were synthesized via the co-condensation of a silica precursor and a two-photon electron donor. The nanogates were constructed using a fast one-pot process at room temperature on the drug-loaded M2PS nanoparticles (NPs) with the bis(3-triethoxysilylpropyl)disulfide precursor. One and two-photon-actuated cargo releases from the M2PS nanogates were successfully monitored in aqueous solutions. Furthermore, the cellular uptake in MCF-7 cells was demonstrated via two-photon fluorescence imaging of the NPs, which were then applied successfully for drug delivery in cells.

Influence of the synthetic method on the properties of two-photon-sensitive mesoporous silica nanoparticles.

Herein we report the modulation of the properties of mesoporous silica nanoparticles (NPs) via various synthetic approaches. Three types of elaborations were compared, one in aqueous media at 25 °C, and the other two at 80 °C in water or in a water-ethanol mixture. For all these methods, an alkoxysilylated two-photon photosensitizer (2PS) was co-condensed with tetraethylorthosilicate (TEOS) in the presence of cetyltrimethylammonium bromide (CTAB), leading to five two-photon-sensitive mesoporous silica (M2PS) NPs. The M2PS NP porous structure could be tuned from radial to worm-like and MCM-41 types of organization. Besides, the 2PS precursor spatial dispersion was found to be highly dependent on both the 2PS initial concentration and the elaboration process. As a result, two-photon properties were modulated by the choice of the synthesis, the best results being found in aqueous media at 25 or 80 °C. Finally, the M2PS NPs were used for in vitro two-photon imaging of cancer cells.

Two-photon excitation of porphyrin-functionalized porous silicon nanoparticles for photodynamic therapy.

Porous silicon nanoparticles (pSiNPs) act as a sensitizer for the 2-photon excitation of a pendant porphyrin using NIR laser light, for imaging and photodynamic therapy. Mannose-functionalized pSiNPs can be vectorized to MCF-7 human breast cancer cells through a mannose receptor-mediated endocytosis mechanism to provide a 3-fold enhancement of the 2-photon PDT effect.

Two-photon-induced fluorescence in new π-expanded diketopyrrolopyrroles.

Structurally unique π-expanded diketopyrrolopyrroles (EDPP) were designed and synthesized. Strategic placement of a fluorene scaffold at the periphery of a diketopyrrolopyrrole through tandem Friedel-Crafts-dehydration reactions resulted in dyes with supreme solubility. The structure of the dyes was confirmed by X-ray crystallography verifying a nearly flattened arrangement of the ten fused rings. Despite the extended ring system, the dye still preserved good solubility and was further functionalized by using Pd-catalyzed coupling reactions, such as the Buchwald-Hartwig amination. Photophysical studies of these new functional dyes revealed that they possess enhanced properties when compared with expanded DPPs in terms of two-photon absorption cross-section. It is further demonstrated that in addition to the initial diacetals, the final electrophilic cyclization step can also be applied to diketones. By placing two amine groups at peripheral positions of the resulting dyes, values of two-photon absorption cross-section on the level of 2000 GM around 1000 nm were achieved, which in combination with high fluorescence quantum yield (Φfl ), generated a two-photon brightness of approximately 1600 GM. These characteristics in combination with strong red emission (665 nm) make these new π-expanded diketopyrrolopyrroles of major promise as two-photon dyes for bioimaging applications. Finally, the corresponding N-alkylated DPPs displayed a solid-state fluorescence.

Bright, fluorescent dyes based on imidazo[1,2-a]pyridines that are capable of two-photon absorption.

A library of imidazo[1,2-a]pyridines was synthesized by using the Gevorgyan method and their linear and non-linear optical properties were studied. Derivatives that contained both electron-donating and electron-withdrawing groups at the 2 position were comprehensively investigated. Their emission quantum yield ranged between 0.2-0.7 and it was shown to depend on the substitution pattern, most notably that on the phenyl ring. Electron-donating substituents improved the luminescence performance of these compounds, whereas electron-withdrawing substituents led to a more erratic behavior. Substitution on the six-membered ring had less effect on the fluorescence properties. Extension of the delocalization increased the luminescence quantum yield. A new quadrupolar system was designed that contained two imidazo[1,2-a]pyridine units on its periphery and a 1,4-dicyanobenzene unit at its center. This system exhibited a large Stokes-shifted luminescence that was affected by the polarity and rigidity of the solvent, which was ascribed to emission from an excited state with strong charge-transfer character. This quadrupolar feature also led to an acceptable two-photon absorption response in the NIR region.

Fluorescence and two-photon absorption of push-pull aryl(bi)thiophenes: structure-property relationships.

Photophysical and TPA properties of series of push-pull aryl(bi)thiophene chromophores bearing electron-donating (D) and electron-withdrawing (A) end-groups of increasing strength are presented. All compounds show an intense intramolecular charge transfer (ICT) absorption band in the visible region. Increasing the D and/or A strength as well as the length of the conjugated path induces bathochromic and hyperchromic shifts of the absorption band as reported for analogous push-pull polyenes. Yet, in contrast with corresponding push-pull polyenes, a significant increase in fluorescence is observed. In particular, chromophores built from a phenyl-bithienyl conjugated path and bearing strong D and A end-groups were found to combine very large one and two-photon brightness as well as strong emission in the red/NIR region. These molecules hold promise as biphotonic fluorescent probes for bioimaging.

Synthesis of quinoline dicarboxylic esters as biocompatible fluorescent tags.

A series of dicarboxylic quinoline derivatives bearing electron-releasing or -withdrawing substituents have been synthesized using mono- or/and biphasic methodologies. By controlling the regioselectivity of addition into our electrophilic intermediate, we also characterized by which mechanism the Doebner-Miller cyclization step occurred. As anticipated, electron-releasing substituents induce a red shift of the low-energy absorption allowing excitation in the visible region. In addition, by playing on the strength and position of the electron-releasing substituents, chromophore having interesting fluorescent properties such as large Stoke shifts, good fluorescent quantum yields, emission in the visible green-yellow region and reasonable two-photon absorption in the NIR region have been obtained. These small-size fluorophores, which can be made water-soluble and have been shown to be non-toxic, can be hetero- and/or polyfunctionalized and thus represent promising key units for fluorescence-based physiological experiments with low background interactions.

Benzo[1,2-d:4,5-d']bisimidazoles as a convenient platform towards dyes that are capable of excited-state intramolecular proton transfer and of two-photon absorption.

New, strongly fluorescent benzo[1,2-d:4,5-d']bisimidazoles have been prepared by the reaction of Bandrowski's base with various aldehydes. Their structures were carefully designed to achieve efficient excited-state intramolecular proton transfer and good two-photon-absorption (2PA) cross-sections. Functional dyes that possessed both high fluorescence quantum yields and large Stokes shifts were prepared. A π-expanded D-A-D derivative that possessed Φ(fl)=50 % and σ(2)=230 GM in the spectroscopic area of interest for biological imaging is an excellent candidate as a fluorescent probe. Thanks to the presence of two reactive amino groups, such compounds can be easily transformed into probes for bioconjugation. All of these benzo[1,2-d:4,5-d']bisimidazoles were also strongly fluorescent in the solid state.

Triaryl-1,3,5-triazinane-2,4,6-triones (isocyanurates) peripherally functionalized by donor groups: synthesis and study of their linear and nonlinear optical properties.

The linear optical (LO) and nonlinear optical (NLO) properties of a series of isocyanurates functionalized by donor arms at the periphery are reported herein. These octupolar derivatives were obtained in a straightforward way from commercial isocyanate derivatives and were fully characterized. Although several of these compounds are known, those that exhibited the largest NLO activities are all new compounds. In terms of second-order activity, several of these derivatives exhibit remarkable activity/transparency tradeoffs. In terms of third-order activity, the longer derivatives with the stronger donor groups (X = NH(2), NMe(2), or NPh(2)) were shown to possess significant two-photon absorption cross sections. These strongly luminescent derivatives exhibit two-photon absorption cross sections up to 410 GM. DFT computations were also conducted to unravel their electronic structures and to rationalize their NLO properties. To our knowledge, the present study is the first concerned with the nonlinear optical properties of these original cyclotrimers.

Octupolar merocyanine dyes: a new class of nonlinear optical chromophores.

A set of new octupolar merocyanine chromophores was designed and synthesized. These compounds were prepared from the reaction of 1,3,5-triformyl-2,4,6-trihydroxybenzene with heterocyclic nucleophiles. Octupolar dyes were formed exclusively in their open-dye form. The one- and two-photon-absorption spectra of the dyes consist of two bands: The long-wavelength band in the two-photon absorption spectrum (a few hundreds GM above 1000 nm) matches well with the intense, long-wavelength-absorption band that is located in the visible region in the linear spectrum. Interestingly, an additional, much-more-intense TPA band in the NIR region is observed at higher energy, which corresponds to a weakly allowed one-photon electronic transition. Changing the peripheral heterocyclic moieties allows tuning of the optical properties to approach the cyanine limit (i.e., polymethine state), thus resulting in a red-shift of the low-energy one-photon-absorption band as well as to the rise of an intense two-photon-absorption band in the NIR region. To the best of our knowledge, this is the first synthesis and TPA characterization of octupolar merocyanine chromophores with typical low-bond-length alternation.