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Protein misfolding products - amyloids - tend to form distinct fibrillar structures of the characteristic fold for a given neurodegenerative disease or pathology. Moreover, amyloids (also in the intermediate or distorted state) can act as secondary nuclei for

Noble metal nanoclusters allow for the atomically- precise control of their composition. However, to create nanoclusters with pre-defined optical properties, comprehensive description of their structure-property relation is required. Here, we report the gold atom doping impact on one-photon and two-photon absorption (TPA) and luminescence properties of ligated silver nanoclusters via combined experimental studies and time-dependent density functional theory simulations (TD-DFT). We synthesized a series of Ag25−xAux(DMBT)18 nanoclusters where x=0, 1 and 5–10. For Ag24Au1(DMBT)18 we demonstrate that the presence of the central Au dopant strongly influences linear and non-linear optical properties, increasing photoluminescence quantum yield and two-photon brightness, with respect to undoped silver nanoclusters. With improved TPA and luminescence, atomically-precise AuAg alloys presented in our work can serve as robust luminescent probes e.g. for bioimaging in the second biological window.

The antimicrobial properties of amylin, a polypeptide secreted by the pancreas, are far less known than its antidiabetic function. Among the studied amylin analogues, the coordination of zinc(II) enhances the antifungal properties of pramlintide, a non-fibrillating therapeutic analogue of amylin; binding at the N-terminal amino group and His18 imidazole, it induces a kink in the peptide structure, which, in turn, triggers a fibrillization process of the complex, resulting in an amyloid structure most likely responsible for the disruption of the fungal cell.

Chiral nanomaterials attract broad attention, as they offer new possibilities of modulation of optical properties and dissymmetry factors outperforming organic materials. Among various nanoparticles, plasmonic bipyramids present numerous advantages as building blocks of chiral nanomaterials (well-defined modulation of optical properties with the morphology of nanoparticles, narrow optical resonances, and high size and shape uniformity of synthesized particles). We study different possible orientations of gold bipyramids with respect to each other in dimers obtained by wet chemistry methods. For circularly polarized incident light we evaluate linear optical cross sections and plasmonic local field enhancement using COMSOL Multiphysics. We observe coupling of the nanoparticles' local fields and thus changes in extinction spectra, which modulate chiroptical properties of dimers. To assess the chirality of various arrangements, we note differences in cross sections for left- and right-handed polarized light which we further evaluate as the dissymmetry g-factor. Our results provide BPs configurations with dissymmetry factor as high as -0.3.

Amyloids are broadly investigated protein misfolding products with characteristic β-sheet assemblies that have an important role in neurodegenerative diseases (e.g., Alzheimer's disease). While they are usually visualized by staining with Thioflavin-T, Congo Red, or other fluorescent markers, it still arouses a controversy over possible staining molecule influence on the amyloid structure or aggregation process. In this work we present, for the first time, the polarization analysis of two-photon excited autofluorescence of amyloids and confirm that polarization dependence of the observed emission can be correlated with the orientation of fibrils. We show the potential of two-photon excited autofluorescence for resolution of molecular organization of fibrils within amyloid superstructures. This label-free method is compatible with two-photon imaging already applied in investigation of neurodegeneration model in mice.

The inner ear of the rainbow trout contains biominerals called otoliths that are composed of calcium carbonate crystals and a protein organic matrix. The organic matrix macromolecule – 64 (OMM-64) ...

The biological mediation of mineral formation (biomineralization) is realized through diverse organic macromolecules that guide this process in a spatial and temporal manner. Although the role of these molecules in biomineralization is being gradually revealed, the molecular basis of their regulatory function is still poorly understood. In this study, the incorporation and distribution of the model intrinsically disordered starmaker‐like (Stm‐l) protein, which is active in fish otoliths biomineralization, within calcium carbonate crystals, is revealed. Stm‐l promotes crystal nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of Stm‐l protein unexpectedly results in shrinkage (and not expansion, as commonly described in biomineral and bioinspired crystals) of the crystal lattice volume, which is described herein, for the first time, for bioinspired mineralization. A ring pattern was observed in crystals grown for 48 h; this was composed of a protein‐enriched region flanked by protein‐depleted regions. It can be explained as a result of the Ostwald‐like ripening process and intrinsic properties of Stm‐l, and bears some analogy to the daily growth layers of the otolith., Controlled growth: The starmaker‐like (Stm‐l) protein promotes calcium carbonate nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of protein results in shrinkage of the crystal lattice volume (see figure). The ring pattern, which is composed of a protein‐enriched region flanked by protein‐depleted regions, is a result of both the Ostwald‐like ripening process and intrinsic properties of Stm‐l.

The objective of this study is to investigate the bactericidal efficiency of atmospheric pressure non-thermal (cold) dielectric barrier discharge plasma on biofilms of Staphylococcus aureus and Escherichia coli. In general, cold plasma is a mixture of electrons, ions, neutral atoms and molecules. The different particles in cold plasmas exhibit different energies, i.e. electrons are much more energetic than other particles. This feature of cold plasmas allows to produce chemically reactive species at near room temperature that can be used in biological applications. Bacteria inactivation was performed using the air direct plasma (with reactive species, UV light, excited species and electric fields). Discharge power density during the experiment was equal to 70 mW/cm2 and plasma dose was regulated by the treatment time. Bacterial biofilms were treated with the non-thermal plasma for 10–300 s. The most effective reduction in the number of S. aureus cells was found after 300 s of treatment and was 2.77 log10 that is 99.83%. When the biofilm of E. coli was used in the experiment, killing of bacteria was independent of the exposure time and the mortality of cells did not exceed 0.48 that is 66.7% kill. The lethal effect on E. coli and S. aureus cells were observed after 300 and 120 s of plasma treatment, respectively but it was necessary to remove the layers of dead cells. The proposed process of removing dead cell layers was carried out due to the probable shielding effect, i.e. dead cells prevent further penetration of active plasma species into the deeper layers of the biofilm. It was shown that the effectiveness of cell destruction by the non-thermal plasma depends on the thickness of biofilm.

Many essential similarities between the behavior and arrangement of biological structures and liquid crystals can be found. Moreover, some of biomacromolecules, such as DNA, are shown to exhibit lyotropic liquid crystalline phases both in vitro and in vivo. In this study, we used natural DNA concentration condition to form DNA liquid crystal (LC) phases as a simplified in vitro model of DNA self-ordering in cells. Due to the increasing interest in the use of nanoparticles as optical markers, we investigated possible applications of silver-doped gold nanoclusters (AuAgNCs) for one- and two-photon imaging in condensed DNA samples. We studied the influence of NCs doping on the DNA LC properties and the distribution of NCs within the liquid crystalline matrix. Depending on the type of DNA liquid crystalline phase we observed different emission patterns of AuAgNCs correlated with the degree of DNA ordering.

Atomically-precise chiral gold nanoclusters hold promise for an accurate manipulation of chiro-optical properties, both in linear and nonlinear optics regimes. Here, we present the determination of two-photon linear-circular dichroism and two-photon circular dichroism (TPCD) of Au25[(Capt)18]- (where Capt is captopril). TPCD is found to be two orders of magnitude higher than one-photon circular dichroism.

Fluorescence imaging probes for specific G-quadruplex (G4) conformations are of considerable interest in biomedical research. Herein, we present the synthesis and the binding properties of a new water-soluble near-infrared (NIR) amphiphilic squaraine dye (CAS-C1) which is capable of selective detection of parallel over non-parallel and non G4 topologies. The striking changes in its linear optical response upon binding to parallel G4s give rise to high fluorescence quantum yields (Φf ≈ 0.7) and one-photon molecular brightness in the far-red-NIR region. The outstanding recognition process of CAS-C1 for parallel G4s via end-stacking provides binding constants in the nanomolar regime (Kb = 107 to 108 M−1) awarding it as one of the most potent parallel G4 binders currently available. Moreover, the CAS-C1-parallel G4 system exhibits large two-photon absorption (TPA) cross-sections and molecular brightness in the second NIR biological transparency window (λ ≈ 1275 nm), making it an ideal candidate for NIR-to-NIR ultrasensitive two-photon procedures.

We report on two-photon excitation properties of small silver-doped gold nanoclusters (AuAgNCs) and on their three-dimensional arrangement in a hybrid system composed of DNA liquid crystals (LCs) and AuAgNCs. UV-vis and fluorescence spectroscopy, transmission electron microscopy (TEM), and multiphoton excitation spectroscopy were used to characterize the nanoparticles. We show that AuAgNCs exhibit two-photon excited luminescence (2PL) emission and second-harmonic generation (SHG) and that these properties remain the same in liquid crystalline matrix. The results are described in detail and discussed in the context of possible imaging application of AuAgNC and specific AuAgNCs organization induced by liquid crystalline ordering of DNA molecules.

International audience; By attaching pyridine groups to a diaza[6]helicene, a helical, bis-ditopic, bis-N N-coordinating ligand can be accessed. Dinuclear rhenium complexes featuring this bridging ligand, of the form [{Re(CO) Cl} (N N-N N)], have been prepared and resolved to give enantiopure complexes. These complexes are phosphorescent in solution at room temperature under one- and two-photon excitation. Their experimental chiroptical properties (optical rotation, electronic circular dichroism and circularly polarized emission) have been measured. They show, for instance, emission dissymmetry factors of c.a. ±3x10 . Quantum-chemical calculations indicate the importance of stereochemistry on the optical activity, pointing towards further design improvements in such types of complexes.

This review provides a comprehensive description of nonlinear optical (NLO) properties of gold nanoparticles, which can be used in biological applications. The main focus is placed on two-photon absorption (2PA) and two-photon excited photoluminescence (2PEL) - the processes crucial for multiphoton microscopy, which allows deeper imaging of the material and causes less damage to the biological samples in comparison to conventional (one-photon) microscopy. We present the basics of 2PA measurement techniques and a summary of recent achievements in the understanding of multiphoton excitation and the resulting photoluminescence in gold nanoparticles, both plasmonic ones and small nanoclusters with molecule-like properties. The examples of 2PA applications in bioimaging are also presented, with a comment on future challenges and applications.

Nonlinear optical microscopy was employed to investigate the properties of microstructures of quinacridone, a hydrogen-bonded pigment, derivative of quinacridine. Recently, quinacridone hierarchical microstructures (μ-QNC) having different nature-inspired morphologies were reported, e.g. in the shape of hedgehogs formed by self-assembled nano-needles. We find that such microcrystals have structure-dependent linear optical properties and exhibit strong two-photon excited fluorescence when irradiated with a near-infrared femtosecond laser. μ-QNCs exhibit different nonlinear optical properties for different crystal structures, including the emergence of symmetry-forbidden second-harmonic generation.

Gold and silver nanoclusters aggregates have gained significant attention as their optical properties and chemical stability surpasses those of individual nanoclusters. Here, we present a systematic investigation of aggregation-induced changes of morphology and optical properties of glutathione-stabilized silver-doped gold nanoclusters (AuAg NCs). We show that the silver-doped clusters have the ability to spontaneously aggregate in solution, but in order to stabilize their structure and enhance the one-photon (1 P) and two-photon (2 P) properties we used poly(allylamine hydrochloride) (PAH) matrix. This resulted in obtaining NCs superstructures having narrow size distribution and efficient 1 P and 2 P excited photoluminescence.

Atomically-precise chiral gold nanoclusters hold promise for an accurate manipulation of chiro-optical properties, both in linear and nonlinear optics regimes. Here, we present the determination of two-photon linear-circular dichroism and two-photon circular dichroism (TPCD) of Au25[(Capt)18]- (where Capt is captopril). TPCD is found to be two orders of magnitude higher than one-photon circular dichroism.

The optical properties of atomically-precise gold nanoclusters differ significantly from those of plasmonic gold nanoparticles, in both linear and nonlinear regimes. Here, we present a systematic study on the third-order nonlinear optical (NLO) properties of thiol-protected gold clusters in a wide range of wavelengths. We applied the Z-scan technique to evaluate the wavelength dispersion of two-photon absorption (2PA) and nonlinear refraction of the nanoclusters in water. The results are discussed with reference to 2PA of plasmonic gold nanoparticles and literature data on NLO properties of gold nanoclusters.

VBK and ŽS appreciate funding from Center of Excellence (STIM) at the University of Split. This research was supported by STIM-REI, a project funded by European Union from European Structural and Investment Funds 2014–2020. Contract Number KK.01.1.1.01.0003. This work was supported by the National Science Centre under grants DEC-2013/10/A/ST4/00114 and DEC-2013/09/B/ST5/03417 and by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Science and Technology. We would like to acknowledge the financial support from the French-Croatian project “International Laboratory for Nano Clusters and Biological Aging, LIA NCBA”. IDWS acknowledges the support from a Royal Society Wolfson Research Merit Award. Thiolate-protected gold nanoclusters have recently attracted considerable attention due to their size-dependent luminescence characterized by a long lifetime and large Stokes shift. However, the optimization of nanocluster properties such as the luminescence quantum yield is still a challenge. We report here the transformation of Au25Capt18 (Capt labels captopril) nanoclusters occurring at low pH and yielding a product with a much increased luminescence quantum yield which we have identified as Au23Capt17. We applied a simple method of treatment with HCl to accomplish this transformation and we characterized the absorption and emission of the newly created ligated nanoclusters as well as their morphology. Based on DFT calculations we show which Au nanocluster size transformations can lead to highly luminescent species such as Au23Capt17. Postprint

We have studied the interaction of a polymeric water soluble anthracenyl derivative () with salmon testes DNA. The results from UV-Vis, fluorescence, Fourier transform infrared (FT-IR) and circular dichroism spectroscopies indicate that the groove binding process regulates the interaction between and DNA. The binding constants, calculated by absorption spectroscopy at 298, 304 and 310 K, were equal to 3.2 × 10(5) M(-1), 4.7 × 10(5) M(-1), and 6.6 × 10(5) M(-1) respectively, proving a relatively high affinity of for salmon testes DNA. Results of Hoechst 33258 displacement assays strongly support the groove binding mode of to DNA. The association stoichiometry of the :DNA adduct was found to be 1 for every 5 base pairs. FT-IR spectra, recorded at different /DNA molar ratios, indicate the involvement of the phosphate groups and adenine and thymine DNA bases in the association process. Thermodynamic results suggest that hydrophobic forces regulate the binding of with DNA without excluding some extent of involvement of van der Waals forces and hydrogen bonding arising due to surface binding between the hydrophilic polymeric arms of the ligand and the functional groups positioned on the edge of the groove. The resulting composite biomaterial could constitute a valuable candidate for future biological and/or photonic applications.

We report here the influence of the irradiation with femtosecond laser pulses on the gold nanoprisms synthesized using biological and chemical methods. For the bio-mediated growth, we used plant extract as a source of reducing, structure-directing, and stabilizing agents, while for the chemical method, we applied three-step protocol, involving chemicals commonly used in the synthesis of nanostructures. Exposition of the nanostructures to the laser beam causes morphological changes, which affect their extinction spectra. These modifications were followed using absorption spectroscopy and transmission electron microscopy. The observed effects depend on the applied laser power and excitation wavelength. Under resonance conditions, rounding of the tips of triangular nanoparticles and transformation towards more stable, spherical form were noticed. These changes were faster under higher laser power. Such shape modifications were weaker under off-resonance conditions. Moreover, chemically synthesized gold nanoprisms were less susceptible to the morphological changes than those obtained using plant extract; however, their colloidal stability was disrupted by long-time irradiation. Graphical abstractᅟ.

The anisotropic shape of DNA molecules allows them to form lyotropic liquid crystals (LCs) at high concentrations. This liquid crystalline arrangement is also found in vivo (e.g., in bacteriophage capsids, bacteria or human sperm nuclei). However, the role of DNA liquid crystalline organization in living organisms still remains an open question. Here we show that in vitro, the DNA spatial structure is significantly changed in mesophases compared to non-organized DNA molecules. DNA LCs were prepared from pBluescript SK (pBSK) plasmid DNA and investigated by photochemical analysis of structural transitions (PhAST). We reveal significant differences in the probability of UV-induced pyrimidine dimer photoproduct formation at multiple loci on the DNA indicative of changes in major groove architecture.

We report on synthesis and optical properties of new organic compounds based on substituted pyrazole ring. The investigated pyrazoline derivatives (PRDs) exhibit efficient broadband photoluminescence which covers nearly whole visible spectrum. The experimental results are compared to quantum chemical calculations. Amplified spontaneous emission and photodegradation measurements were performed for hybrid systems based on selected PRDs doped into poly(methyl methacrylate) matrix proving the potential utility of such systems in lasing applications. Two-photon absorption (TPA) properties were characterized by the femtosecond Z-scan technique.

International audience; We report the synthesis, spectroscopy, and the DNA binding properties of a biocompatible, water-soluble, polycationic two-photon absorbing anthracenyl derivative (Ant-PIm) specifically designed for biorelated applications. Detailed insights into the Ant-PIm–DNA binding interaction are provided by using several spectroscopic approaches, including UV–vis absorption, circular dichroism (CD), Fourier-transform infrared spectroscopy (FTIR), steady-state, and time-resolved fluorescence techniques. Absorption and fluorescence quantitative data analysis show a strong Ant-PIm-duplex interaction with binding constants of Kf = 4.7 ± 0.2 × 105 M–1, 7.1 ± 0.3 × 105 M–1, and 1.0 ± 0.1 × 106 M–1 at 298, 304, and 310 K, respectively. Spectral changes observed upon DNA binding provide evidence for a complex formation with off-on fluorescence pattern, which can be related to two consecutive binding equilibria. Results of DNA binders displacement and iodide quenching experimental assays unambiguously point to the groove binding mode of Ant-PIm to the DNA-helicate. Thermodynamic and chemical denaturation studies suggest that long-range interactions of hydrophobic nature regulate the association of Ant-PIm with the biopolymer. The ionic strength dependence of the binding constant shows that electrostatic component has an important contribution to the overall Gibbs free energy. FTIR and CD data provide evidence of partial modification of the B-DNA secondary structure, while the increase in the melting temperature clearly indicates the enhancement of the thermal stability of the duplex. Furthermore, the two-photon absorption cross section spectrum determined using the two-photon excited fluorescence (TPEF) technique shows a strong 2PA maximum at 820 nm with a σ2 > 800 GM, which emphasizes the advantageous combination of biological and optical properties possessed by this positively charged bioprobe.

International audience; A chromophore-engineering strategy that relies on the introduction of a ground-state distortion in a quadrupolar chromophore was used to obtain a quasi-quadrupolar chromophore with red emission and large two-photon absorption (2PA) cross-section in polar solvents. This molecule was functionalized with water-solubilizing polymer chains. It constitutes not only a remarkable contrast agent for intravital two-photon microscopy of the functional cerebral vasculature in a minimally invasive configuration but presents intriguing endothelial staining ability that makes it a valuable probe for premortem histological staining.

The photochromic properties of azobenzene, involving conformational changes occurring upon interaction with light, provide an excellent tool to establish new ways of selective regulation applied to biosystems. We report here on the binding of two water-soluble 4-(phenylazo)benzoic acid derivatives (Azo-2N and Azo-3N) with double stranded DNA and demonstrate that the photoisomerization of Azo-3N leads to changes in DNA structure. In particular, we show that stabilization and destabilization of the B-DNA secondary structure can be photochemically induced in situ by light. This photo-triggered process is fully reversible and could be an alternative pathway to control a broad range of biological processes. Moreover, we found that the bicationic Azo-3N exhibited a higher DNA-binding constant than the monocationic Azo-2N pointing out that the number of positive charges along the photosensitive polyamines chain plays a pivotal role in stabilizing the photochrome-DNA complex.

We report on the impact of doping with gold nanorods (NRs) on the formation and stability of DNA liquid crystals (LCs). Cetyl trimethylammonium (CTAB)-stabilized gold NRs were synthesized using the wet chemistry method. Different textures of cholesteric and columnar mesophases, as well as phase transitions, were observed using a polarized light microscope. It was found that liquid crystalline phases formed in the samples were qualitatively the same and the phase appearance sequence was preserved in the samples regardless of the doping. We show that depending on the concentration of gold NRs present in the phase, nanoparticle-doped cholesteric and columnar hexagonal phases existed in wider temperature ranges compared to pure DNA LCs. The potential applications of these liquid crystal–nanoparticle hybrid systems may include the fabrication of new optoelectronic devices and sensors.

We report the synthesis and characterization of new organometallic assemblies consisting of a central Zn(II) tetraphenylporphyrin (ZnTPP) core surrounded by four Ru(II) alkynyl complexes ( trans -Ru(dppe) 2 R) appended at the para phenyl positions and acting as peripheral donor groups. The synthesis of the tetra-chlorido derivative 2 (R=Cl) is reported first, followed by that of three extended homologues ( 3 –X) obtained from this building block by substitution of the chlorido ligands by functionalized arylacetylenes (R=C C(4-C 6 H 4 X); X=NO 2 , H, OMe). Measurement of the nonlinear absorption properties of the pentametallic derivatives 3 –X reveals that these extended π-networks incorporating polarizable organometallic units behave as good two-photon absorbers in the visible and near-IR range.

The synthesis, structure and optical properties of water-soluble fluoride nanophosphors co-doped with Eu 3+ and Tb 3+ are presented. Nanocrystals of NaYF 4 were synthesized via a hydrothermal microwave-assisted technique. XRD, TEM, AFM, FTIR as well as photoluminescence (PL) spectra were used to characterize the doped nanocrystals. The average size of nanocrystals, determined from XRD, AFM and TEM measurements, was ca. 28 nm. It was found that energy transfer occurs between Tb 3+ and Eu 3+ ions embedded in NaYF 4 matrix, both in nanocrystals dispersed in chloroform and those in aqueous solution. We demonstrate that this simple colloidal system possesses the essential features required for both energy transfer and potential application in biolabeling.

International audience; We report on the investigation of the structure of DNA liquid crystal (LC) phases by means of polarization sensitive two-photon microscopy (PSTPM). DNA was stained with fluorescent dyes, an intercalator propidium iodide or a groove binder Hoechst 3342 and the angular dependence of the intensity of two-photon excited fluorescence (TPEF) emitted by the dye was collected. The local orientation of DNA molecules in cholesteric and columnar liquid crystal phases was established on the basis of the relative angle between the transition dipole of the dye and the long axis of DNA helix. Three dimensional images of the cholesteric phase were obtained making use of the intrinsic 3D resolving ability of two-photon microscopy. We also discuss the influence of dyes on the parameters of DNA LC phases and comment on advantages and limitations of the PSTPM technique in comparison with other LC characterization techniques. © 2011 Wiley Periodicals, Inc. Biopolymers, 2011.

International audience; The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives (1-3 and 2') incorporating 2- or 2,7-fluorenyl and diphenylamino moieties are reported. The electroactivity of 1-3 and 2' was studied by cyclic voltammetry (CV), while the linear optical and (third order) nonlinear optical (NLO) properties were investigated by electronic spectroscopy and Z -scan studies, respectively. All experimental investigations were rationalized by DFT computations, providing an insight into the electronic structure of these derivatives and on their application potential. We show that these derivatives are nonluminescent in solution at ambient temperatures, but become fluorescent in solvent glasses. This finding constitutes an unprecedented observation for TCBD derivatives. Also, we show by Z-scan studies that these derivatives behave as two-photon absorbers in the near-IR range (800-1050 nm). These third-order NLO properties are discussed and compared with those of their alkynyl precursors (4-6), which have been investigated by two-photon excited fluorescence (TPEF).

We report here a “green” approach for the synthesis of gold nanoparticles (GNPs) in which the Mentha piperita extract was applied for the bioreduction of chloroauric acid and the stabilization of the formed nanostructures. The obtained GNPs were characterized by UV-Vis absorption spectroscopy and transmission electron microscopy (TEM). The reduction of gold ions with the plant extract leads to the production of nanoparticles with various shapes (spherical, triangular and hexagonal) and sizes (from 10 to 300 nm). The kinetics of the reaction was monitored and various conditions of the synthesis were investigated. As a result, we established protocols optimized towards the synthesis of nanospheres and nanoprisms of gold. The cytotoxic effect of the obtained gold nanoparticles was studied by performing MTT assay, which showed lower cytotoxicity of the biosynthesized GNPs compared to gold nanorods synthesized using the usual seed-mediated growth. The results suggest that the synthesis using plant extracts may be a useful method to produce gold nanostructures for various biological and medical applications.

A new type of dinuclear iridium complex, based on a quadrupolar Schiff base ligand, is synthesized and its structure fully characterized. Its linear and nonlinear spectroscopic properties are investigated, evidencing a strong contribution of the metal-to-ligand transitions not only to the linear absorption but also to the two- and three-photon absorption properties.

We report on the nonlinear optical properties measurements and quantum-chemical calculations of a well-known photochromic system consisting of spiropyran and the merocyanine photoproduct. The study of nonlinear absorption and refraction properties of the molecules dissolved in chloroform were performed with the Z-scan technique, using femtosecond pulses in a wide range of wavelengths. Maxima in the two-photon absorption spectrum at 700 and 1050 nm were found for the merocyanine form, and the corresponding two-photon absorption cross section is 80 GM and 20 GM, respectively. The latter feature does not vanish completely in the nonlinear spectrum of the spiropyran form, possibly because of the existence of some photoconversion caused by the laser beam during the measurements. A nonlinear absorption peak at 900 nm is found in the spiropyran form with an effective cross section of about 20 GM; it is likely due to three-photon absorption or to absorption by some intermediate species. The experimental data are supported by calculations performed with the use of a hybrid quantum mechanics-molecular mechanics approach. (Chemical Equation Presented).

A detailed comparison of third-order nonlinear optical properties of colloidal gold nanoshells (NSs) and gold nanorods (NRs) in water solutions has been carried out with the open- and closed-aperture Z-scan measurements, performed with femtosecond laser pulses over a broad range of wavelengths. Absorption saturation was found to be a dominant effect for all the studied nanoparticles, however two-photon absorption properties are also detected, especially at the shortest wavelengths studied. The value of the merit factor σ 2 /M (two-photon absorption cross section scaled by the molecular weight) for the NRs (10nm × 35 nm) at 530 nm is 7.5 (GM·mol/g), while for the NSs is 1.9 (GM·mol/g) at the same wavelength.

International audience; Third-order nonlinear optical properties of gold nanoshells of different thickness were investigated over a broad wavelength range (530-1200 nm) by the Z-scan technique using femtosecond laser pulses. Nonlinear absorption of the nanoshells is dominated by strong absorption saturation phenomena. Thereciprocals of the relevant saturation intensities are the highest at the maxima of one-photon absorption(1 PA) bands for all the studied nanoshells but the scaling with the one-photon extinction coefficientswithin the relevant absorption bands is rather approximate. The reciprocals of the saturation intensitiesscaled by the values of the extinction coefficients are also found to decrease with the increase of theshell thickness. This can be attributed mostly to the increase of the contribution of the scattering of NIRlight to the total extinction of the solutions. The two-photon absorption (2 PA) behavior is found to bedominant only within the shortest wavelength range studied for the gold nanoshells with the thinnestshells which exhibit high 2 PA cross-section values, withs2reaching 5.1 X 1010GM

International audience; The synthesis and photophysical properties of small gold nanoparticles (NPs, AuNP-[Ru-PFF]) surface functionalized by 5-substituted-1,10-phenanthroline-ligand based Ru(II) complexes are described. Luminescence of the grafted and confined Ru(II) complexes is totally quenched on the gold surface. Nonlinear optical properties were determined via Z-scan measurements in the range 600–1300 nm for both the free Ru(II) complex and the related NPs. In the short wavelength range (around 600 nm) the behaviour switches from that of two-photon absorption (2PA) for the complex to saturable absorption for the NPs. 2PA applications such as optical power limiting or two-photon dioxygen sensitization can be anticipated for these nanoplatforms.

There is considerable current interest in photodynamic inactivation (PDI) as potential antimicrobial therapy. This study reports successful implementation of PDI of Staphylococcus epidermidis using methylene blue (MB) in combination with biogenic gold nanoparticles (GNP). Monodispersed colloidal GNP were synthesized by reduction of Au+3 in the presence of cell-free filtrate of Trichoderma koningii and were characterized by a number of techniques including UV–Vis and fluorescence spectroscopy, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR) to be 12 ± 3 nm spherical gold particles coated with proteins. Studies on the role of the cell-free filtrate proteins in the synthesis of the GNP indicate that the process is nonenzymatic but involves interactions of various amino acids with gold ions. A Xe lamp (550–780 nm) or a He–Ne laser (632 nm) was used as light sources to study the effect of MB alone, the GNP alone, and the MB–GNP mixture on the viability of bacterial cells. Lethal photosensitization of S. epidermidis with the MB–GNP mixture was achieved after 5 and 10 min exposure to laser or Xe lamp, respectively. It has been found that the MB–GNP mixture exhibits a significant antibacterial activity already in the absence of any light source and gives an enhanced antimicrobial response when using either a laser or a Xe lamp source for photosensitization.

Single nanoparticle imaging is a powerful method to characterize nanoobjects and gain better understanding of their structural and optical properties. In our research we focus on plasmonic nanoparticles and particularly on anisotropic gold nanorods, which present interesting, polarization-dependent optical properties strictly correlated with their surface plasmon resonances. Here we discuss our results on two-photon excited luminescence imaging of a single gold nanorod. We analyze the dependence of the two-photon luminescence of a nanorod on the excitation wavelength, incident laser power and polarization, and contrast them with the data available in the literature.

We have been studying a number of nanosystems that either have potential applications in bioimaging and/or light-activated therapies, or are bioderived. The standard Z-scan technique was routinely used for most of the measurements which were carried out in a wide wavelength range, typically from ∼550 nm to 1.6 μm. The range of nanoparticles studied has included colloidal semiconductor nanoparticles (e.g. CdS, CdSe), plasmonic nanoparticles, metal clusters, lanthanide-doped fluoride and oxide nanocrystals as well as core-shell systems. Among the bioderived systems studied especially interesting one is that of protein amyloid fibers.Many of these materials exhibit nonlinear absorption features due not only to the typical two-photon absorption processes, but also due to multiple-photon absorption taking place, especially at longer wavelengths (e.g. three- four- and five-photon processes). On the other hand, absorption saturation processes may prevail or compete with multi-photon absorption in certain wavelength ranges in some of these materials, especially those characterized by broadband absorption due to surface plasmon excitation.

International audience; This work describes the interaction between femtosecond laser pulses (B130 fs, 800 nm) and gold nanorods (NRs) leading to reshaping of the NRs. We focus on the investigation of structural changes of the NRs and the parameters influencing the reshaping, like surface modification using sodium sulphide, laser power and the position of the longitudinal surface plasmon resonance band (l-SPR) with respect to the laser wavelength. A thermogravimetric analysis experiment is performed to examine changes in the composition of NRs upon heating. A new type of banana-shaped NPs is described and the conditions of their appearance are discussed.

We present the results of wide spectral range Z-scan measurements of the two-photon absorption (2PA) spectrum of the Hoechst 33342 dye. The strongest 2PA of the dye in aqueous solution is found at 575 nm, and the associated two-photon absorption cross section is 245 GM. A weak but clearly visible 2PA band at ∼850 nm is also observed, a feature that could not be anticipated from the one-photon absorption spectrum. On the basis of the results of hybrid quantum mechanics/molecular mechanics calculations, we put forward a notion that the long-wavelength feature observed in the two-photon absorption spectrum of Hoechst 33342 is due to the formation of dye aggregates.

The nonlinear optical effect of second harmonic generation can be very strong when originating from nanoplasmonic structures, due to enhancement of the surrounding material's intrinsic non-linear optical properties or due to its occurrence as a result of the plasmonic structure. However, manufacturing of large-scale three dimensional nanoplasmonic structures is still a challenge. Here, we demonstrate the two-photon luminescence and second-harmonic generation in a Bi2O3-Ag eutectic-based metamaterial exhibiting a hierarchic structure of nano- and micro-sized silver precipitates. The investigations employed a microscope system combined with polarimetric analysis. It appears that the second-harmonic-generation arises from the silver plasmonic structure rather than from the nonlinear effects of the bismuth oxide matrix. Both quadrupolar and dipolar modes of polarization are observed.