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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)3Cl}2(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. ±3x10−3. Quantum‐chemical calculations indicate the importance of stereochemistry on the optical activity, pointing towards further design improvements in such types of complexes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 (thirdorder) 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). [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We have studied the interaction of a polymeric water soluble anthracenyl derivative (Ant-PHEA) 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 Ant-PHEA and DNA. The binding constants, calculated by absorption spectroscopy at 298, 304 and 310 K, were equal to 3.2 × 105 M−1, 4.7 × 105 M−1, and 6.6 × 105 M−1 respectively, proving a relatively high affinity of Ant-PHEA for salmon testes DNA. Results of Hoechst 33258 displacement assays strongly support the groove binding mode of Ant-PHEA to DNA. The association stoichiometry of the Ant-PHEA:DNA adduct was found to be 1 for every 5 base pairs. FT-IR spectra, recorded at different Ant-PHEA/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 Ant-PHEA 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A subject index for the September 21, 2014 issue of "Journal of Materials Chemistry" is presented.

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. The reciprocals 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 coefficients within the relevant absorption bands is rather approximate. The reciprocals of the saturation intensities scaled by the values of the extinction coefficients are also found to decrease with the increase of the shell thickness. This can be attributed mostly to the increase of the contribution of the scattering of NIR light to the total extinction of the solutions. The two-photon absorption (2 PA) behavior is found to be dominant only within the shortest wavelength range studied for the gold nanoshells with the thinnest shells which exhibit high 2 PA cross-section values, with σ2 reaching 5.1 × 1010 GM. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A quiz concerning the optical microscope image which reveals the assembly of colloidal photonic crystals and a DNA liquid-crystal phase is presented.

This work describes the interaction between femtosecond laser pulses (∼130 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. [ABSTRACT FROM AUTHOR]

Plasmonic-enhanced luminescence of single molecules enables imaging and detection of low quantities of fluorophores, down to individual molecules. In this work, we present two-photon excited luminescence of single gold nanoclusters, Au18(SG)14, in close proximity to bare gold nanorods (AuNRs). We observed 25-times enhanced emission of gold nanoclusters (AuNCs) in near infrared region, which was mainly attributed to the resonant excitation of localized surface plasmon resonance (LSPR) of AuNRs and spectral overlap of LSPR band with photoluminescence of AuNCs. This work is an initial step in application of combined nanoparticles: gold nanorods and ultrasmall nanoclusters in a wide range of multiphoton imaging and biosensing applications. [ABSTRACT FROM AUTHOR]

Gold nanoparticles hold a great promise for both clinical and preclinical applications. The major factors impeding such applications are toxicity of new nanomaterials including e.g., pro-apoptotic activities or inflammatory effects, but also their potential to accumulate in the body or inadequate absorption, distribution, metabolism and excretion (ADME) profiles. Since such adverse effects depend on the size, form and coating of nanomaterials, the search for new, less toxic nanomaterials with low tendency to accumulate is highly active domain of research. Here, we describe optical and biological properties of Au18 gold nanoclusters (NCs), small gold nanoparticles composed of 18 atoms of gold and stabilized with glutathione ligands. These nanoclusters may be suitable for in vivo applications owing to their low toxicity and biodistribution profile. Specifically, using lactate dehydrogenase (LDH) test in P19 cell line we found that Au18 NCs display low toxicity in vitro. Importantly, using primary microglial cells we showed that at low concentrations Au18 NCs display anti-inflammatory signaling on evidence of reduced interleukin 1-β (IL1-β) levels and unchanged levels of tumor necrosis factor (TNF-α) or Ym1/2. Such effect was dose dependent as higher concentrations of Au18 NCs induced expression of pro-inflammatory cytokines and suppression of anti-inflammatory cytokine Ym1/2, pointing, thus, to global inflammatory activity. Finally, we also showed that within 3 days Au18 NCs can be completely eliminated from the liver reported as the major target organ for accumulation of gold nanoparticles. These data point to a potential of gold nanoparticles for further biomedical studies. [ABSTRACT FROM AUTHOR]