Understanding Yb3+-sensitized photon avalanche in Pr3+ co-doped nanocrystals: modelling and optimization.

Among different upconversion processes where the emitted photon has higher energy than the one absorbed, photon avalanche (PA) is unique, because the luminescence intensity increases by 2-3 orders of magnitude in response to a tiny increase in excitation intensity. Since its discovery in 1979, PA has been observed in bulk materials but until recently, obtaining it at the nanoscale has been a significant challenge. In the present work, the PA phenomenon in ß-NaYF4 colloidal nanocrystals co-doped with Pr3+ and Yb3+ ions was successfully observed at 482 nm (3P0 → 3H4) and 607 nm (3P0 → 3H6) under excitation at 852 nm. The impact of Pr3+ ion concentration and pump power dependence on PA behavior was investigated, i.e. PA non-linearity slopes of luminescence intensity curves as a function of pump power density as well as PA thresholds. The highest slopes, namely 8.6 and 9.0, and the smallest thresholds equal to 286 kW cm-2 and 281 kW cm-2, observed for emission bands at 607 nm and 482 nm, respectively, were obtained for NaYF4:0.5%Pr3+,15%Yb3+@NaYF4 colloidal nanocrystals. Besides experimental research, simulations of PA behavior in Pr3+, Yb3+ co-doped materials were performed based on differential rate equations describing the phenomena that contribute to the existence of PA. The influence of different processes leading to PA, e.g. the rates of nonradiative and radiative transitions as well as energy transfers, on PA performance was simulated aiming to understand their roles in this complex sensitized system.

Effect of N-phenyl substituent on thermal, optical, electrochemical and luminescence properties of 3-aminophthalimide derivatives.

The seven N-phthalimide derivatives substituted with the amine group at the 3-C position in the phenylene ring were synthesized. The effect of N-substituent chemical structure was investigated. The thermal, electrochemical and optical studies were performed and supported by the density functional theory calculations (DFT). The electrochemical investigations of the synthesized low-molecular phthalimides revealed the one oxidation and reduction process with the HOMO energy level under - 5.81 eV and energy-band gap below 3 eV. The N-phthalimide derivatives were emitted light in a blue spectral region in solutions (in polar and non-polar) with the quantum yield between 2 and 68%, dependent on the substituent at the nitrogen atom, solvent and concentration. The N-phthalimide derivatives were emissive also in a solid state as a thin film and powder. They were tested as a component of the active layer with PVK:PBD matrix and as an independent active layer in the organic light-emitting diodes. The registered electroluminescence spectra exhibited the maximum emission band in the 469-505 nm range, confirming the possibility of using N-phthalimides with PVK:PBD matrix as the blue emitters.

All-Optical Data Processing with Photon-Avalanching Nanocrystalline Photonic Synapse.

Data processing and storage in electronic devices are typically performed as a sequence of elementary binary operations. Alternative approaches, such as neuromorphic or reservoir computing, are rapidly gaining interest where data processing is relatively slow, but can be performed in a more comprehensive way or massively in parallel, like in neuronal circuits. Here, time-domain all-optical information processing capabilities of photon-avalanching (PA) nanoparticles at room temperature are discovered. Demonstrated functionality resembles properties found in neuronal synapses, such as: paired-pulse facilitation and short-term internal memory, in situ plasticity, multiple inputs processing, and all-or-nothing threshold response. The PA-memory-like behavior shows capability of machine-learning-algorithm-free feature extraction and further recognition of 2D patterns with simple 2 input artificial neural network. Additionally, high nonlinearity of luminescence intensity in response to photoexcitation mimics and enhances spike-timing-dependent plasticity that is coherent in nature with the way a sound source is localized in animal neuronal circuits. Not only are yet unexplored fundamental properties of photon-avalanche luminescence kinetics studied, but this approach, combined with recent achievements in photonics, light confinement and guiding, promises all-optical data processing, control, adaptive responsivity, and storage on photonic chips.

On the role of Gd3+ions in enhancement of UV emission from Yb3+-Tm3+up-converting LiYF4nanocrystals.

Materials capable of emitting ultraviolet (UV) radiation are sought for applications ranging from theranostics or photodynamic therapy to specific photocatalysis. The nanometer size of these materials, as well as excitation with near-infrared (NIR) light, is essential for many applications. Tetragonal tetrafluoride LiY(Gd)F4nanocrystalline host for up-converting Tm3+-Yb3+activator-sensitizer pair is a promising candidate to achieve UV-vis up-converted radiation under NIR excitation, important for numerous photo-chemical and bio-medical applications. Here, we provide insights into the structure, morphology, size and optical properties of up-converting LiYF4:25%Yb3+0.5%Tm3+colloidal nanocrystals, where 1, 5, 10, 20, 30 and 40% of Y3+ions were substituted with Gd3+ions. Low gadolinium dopant concentrations modify the size and up-conversion luminescence, while the Gd3+doping that is exceeding the structure resistance limit of the tetragonal LiYF4results in appearance of foreign phase and significant decrease of luminescence intensity. The intensity and kinetic behavior of Gd3+up-converted UV emission are also analyzed for various gadolinium ions concentrations. The obtained results form a background for further optimized materials and applications based on LiYF4nanocrystals.

Spectral Dependence of the Energy Transfer from Photosynthetic Complexes to Monolayer Graphene.

Fluorescence excitation spectroscopy at cryogenic temperatures carried out on hybrid assemblies composed of photosynthetic complexes deposited on a monolayer graphene revealed that the efficiency of energy transfer to graphene strongly depended on the excitation wavelength. The efficiency of this energy transfer was greatly enhanced in the blue-green spectral region. We observed clear resonance-like behavior for both a simple light-harvesting antenna containing only two chlorophyll molecules (PCP) and a large photochemically active reaction center associated with the light-harvesting antenna (PSI-LHCI), which pointed towards the general character of this effect.

Improving Photostability of Photosystem I-Based Nanodevice by Plasmonic Interactions with Planar Silver Nanostructures.

One of the crucial challenges for science is the development of alternative pollution-free and renewable energy sources. One of the most promising inexhaustible sources of energy is solar energy, and in this field, solar fuel cells employing naturally evolved solar energy converting biocomplexes-photosynthetic reaction centers, such as photosystem I-are of growing interest due to their highly efficient photo-powered operation, resulting in the production of chemical potential, enabling synthesis of simple fuels. However, application of the biomolecules in such a context is strongly limited by the progressing photobleaching thereof during illumination. In the current work, we investigated the excitation wavelength dependence of the photosystem I photodamage dynamics. Moreover, we aimed to correlate the PSI-LHCI photostability dependence on the excitation wavelength with significant (ca. 50-fold) plasmonic enhancement of fluorescence due to the utilization of planar metallic nanostructure as a substrate. Finally, we present a rational approach for the significant improvement in the photostability of PSI in anoxic conditions. We find that photobleaching rates for 5 min long blue excitation are reduced from nearly 100% to 20% and 70% for substrates of bare glass and plasmonically active substrate, respectively. Our results pave promising ways for optimization of the biomimetic solar fuel cells due to synergy of the plasmon-induced absorption enhancement together with improved photostability of the molecular machinery of the solar-to-fuel conversion.

In-Depth Studies of Ground- and Excited-State Properties of Re(I) Carbonyl Complexes Bearing 2,2':6',2″-Terpyridine and 2,6-Bis(pyrazin-2-yl)pyridine Coupled with π-Conjugated Aryl Chromophores.

In the current work, comprehensive photophysical and electrochemical studies were performed for eight rhenium(I) complexes incorporating 2,2':6',2″-terpyridine (terpy) and 2,6-bis(pyrazin-2-yl)pyridine (dppy) with appended 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl, and 1-pyrenyl groups. Naphthyl and phenanthrenyl substituents marginally affected the energy of the MLCT absorption and emission bands, signaling a weak electronic coupling of the appended aryl group with the Re(I) center. The triplet MLCT state in these complexes is so low lying relative to the triplet 3ILaryl that the thermal population of the triplet excited state delocalized on the organic chromophore is ineffective. The attachment of the electron-rich pyrenyl group resulted in a noticeable red shift and a significant increase in molar absorption coefficients of the lowest energy absorption of the resulting Re(I) complexes due to the contribution of intraligand charge-transfer (ILCT) transitions occurring from the pyrenyl substituent to the terpy/dppy core. At 77 K, the excited states of [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-functionalized ligands were found to have predominant 3ILpyrene/3ILCTpyrene→terpy character. The 3IL/3ILCT nature of the lowest energy excited state of [ReCl(CO)3(4'-(1-pyrenyl)-terpy-κ2N)] was also evidenced by nanosecond transient absorption and time-resolved emission spectroscopy. Enhanced room-temperature emission lifetimes of the complexes [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-substituted ligands are indicative of the thermal activation between 3MLCT and 3IL/3ILCT excited states. Deactivation pathways occurring upon light excitation in [ReCl(CO)3(4'-(1-naphthyl)-terpy-κ2N)] and [ReCl(CO)3(4'-(1-pyrenyl)-terpy-κ2N)] were determined by femtosecond transient absorption studies.

Silver Island Film for Enhancing Light Harvesting in Natural Photosynthetic Proteins.

The effects of combining naturally evolved photosynthetic pigment-protein complexes with inorganic functional materials, especially plasmonically active metallic nanostructures, have been a widely studied topic in the last few decades. Besides other applications, it seems to be reasonable using such hybrid systems for designing future biomimetic solar cells. In this paper, we describe selected results that point out to various aspects of the interactions between photosynthetic complexes and plasmonic excitations in Silver Island Films (SIFs). In addition to simple light-harvesting complexes, like peridinin-chlorophyll-protein (PCP) or the Fenna-Matthews-Olson (FMO) complex, we also discuss the properties of large, photosynthetic reaction centers (RCs) and Photosystem I (PSI)-both prokaryotic PSI core complexes and eukaryotic PSI supercomplexes with attached antenna clusters (PSI-LHCI)-deposited on SIF substrates.

Photochemical Printing of Plasmonically Active Silver Nanostructures.

In this paper, we demonstrate plasmonic substrates prepared on demand, using a straightforward technique, based on laser-induced photochemical reduction of silver compounds on a glass substrate. Importantly, the presented technique does not impose any restrictions regarding the shape and length of the metallic pattern. Plasmonic interactions have been probed using both Stokes and anti-Stokes types of emitters that served as photoluminescence probes. For both cases, we observed a pronounced increase of the photoluminescence intensity for emitters deposited on silver patterns. By studying the absorption and emission dynamics, we identified the mechanisms responsible for emission enhancement and the position of the plasmonic resonance.

Towards better understanding of photophysical properties of rhenium(I) tricarbonyl complexes with terpy-like ligands.

Series of Re(I) carbonyls complexes were designed and synthesized to explore the impact of the triimine skeleton and number of methoxy groups attached to aryl substituents on their optoelectronic and thermal properties. The chemical structures of the prepared complexes were confirmed by 1H and 13C NMR spectroscopy, HR-MS, elemental anlsysis, and X-ray measurements. DSC measuremtns showed that they melted in the range of 198-325 °C. Some of them form stable molecular glasses with high glass transition temperatures (158-173 °C). Experimentally obtained optical properties were supported by DFT calculations. The UV-Vis spectra display a series of overlapping absorption bands in the range 200-350 nm, and much weaker broad band in the visible spectral region, due to intraligand and charge transfer transitions, respectively. All synthesized complexes were emissive in solution and in solid state as powder. Moreover, when applied in diodes, some of them exhibited ability for emission of light under external voltage with maximum of electroluminescence band located at 591-630 nm.

Wide-Field Fluorescence Microscopy of Real-Time Bioconjugation Sensing.

We apply wide-field fluorescence microscopy to measure real-time attachment of photosynthetic proteins to plasmonically active silver nanowires. The observation of this effect is enabled, on the one hand, by sensitive detection of fluorescence and, on the other hand, by plasmonic enhancement of protein fluorescence. We examined two sample configurations with substrates being a bare glass coverslip and a coverslip functionalized with a monolayer of streptavidin. The different preparation of the substrate changes the observed behavior as far as attachment of the protein is concerned as well as its subsequent photobleaching. For the latter substrate the conjugation process is measurably slower. The described method can be universally applied in studying protein-nanostructure interactions for real-time fluorescence-based sensing.

Spectrally selective fluorescence imaging of Chlorobaculum tepidum reaction centers conjugated to chelator-modified silver nanowires.

A polyhistidine tag (His-tag) present on Chlorobaculum tepidum reaction centers (RCs) was used to immobilize photosynthetic complexes on a silver nanowire (AgNW) modified with nickel-chelating nitrilo-triacetic acid (Ni-NTA). The optical properties of conjugated nanostructures were studied using wide-field and confocal fluorescence microscopy. Plasmonic enhancement of RCs conjugated to AgNWs was observed as their fluorescence intensity dependence on the excitation wavelength does not follow the excitation spectrum of RC complexes in solution. The strongest effect of plasmonic interactions on the emission intensity of RCs coincides with the absorption spectrum of AgNWs and is observed for excitation into the carotenoid absorption. From the absence of fluorescence decay shortening, we attribute the emission enhancement to increase of absorption in RC complexes.

Plasmon-induced absorption of blind chlorophylls in photosynthetic proteins assembled on silver nanowires.

We demonstrate that controlled assembly of eukaryotic photosystem I with its associated light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c553 (cyt c553) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) molecules that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c553 as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.

Origin of bimodal fluorescence enhancement factors of Chlorobaculum tepidum reaction centers on silver island films.

We focus on the spectral dependence of plasmon-induced enhancement of fluorescence of Chlorobaculum tepidum reaction centers. When deposited on silver island film, they exhibit up to a 60-fold increase in fluorescence. The dependence of enhancement factors on the excitation wavelength is not correlated with the absorption spectrum of the plasmonic structure. In particular, the presence of one (or multiple) trimers of the Fenna-Matthews-Olson (FMO) protein reveals itself in bimodal distribution of enhancement factors for the excitation at 589 nm, the wavelength corresponding to bacteriochlorophyll absorption of FMO and the core of the RC. We conclude that the structure of multichromophoric complexes can substantially affect the impact of plasmonic excitations, which is important in the context of assembling functional biohybrid systems.

Silver island film substrates for ultrasensitive fluorescence detection of (bio)molecules.

A silver island film (SIF) substrate was used to demonstrate that Metal-Enhanced Fluorescence (MEF) is a powerful tool to enable detection of emission from (bio)molecules at very low concentrations. The experiments were carried out with the Fenna-Matthews-Olson (FMO) pigment-protein complex from the photosynthetic green sulfur bacterium Chlorobaculum tepidum. FMO was diluted to a level, at which no emission was detectable on a glass substrate. In contrast, the fluorescence of FMO was readily observed on the SIF substrate, even though the emission wavelength of FMO is displaced by over 300 nm from the maximum of the plasmon resonance of the SIF layer. Estimated enhancements of the fluorescence intensity of FMO on SIF are about 40-fold. The enhancement factor correlates with the improvement of the signal-to-noise ratio for FMO emission on SIF substrates.