Single-Molecule Fluorescence Probes Interactions between Photoactive Protein-Silver Nanowire Conjugate and Monolayer Graphene.

In this work, we apply single-molecule fluorescence microscopy and spectroscopy to probe plasmon-enhanced fluorescence and Förster resonance energy transfer in a nanoscale assemblies. The structure where the interplay between these two processes was present consists of photoactive proteins conjugated with silver nanowires and deposited on a monolayer graphene. By comparing the results of continuous-wave and time-resolved fluorescence microscopy acquired for this structure with those obtained for the reference samples, where proteins were coupled with either a graphene monolayer or silver nanowires, we find clear indications of the interplay between plasmonic enhancement and the energy transfer to graphene. Namely, fluorescence intensities calculated for the structure, where proteins were coupled to graphene only, are less than for the structure playing the central role in this study, containing both silver nanowires and graphene. Conversely, decay times extracted for the latter are shorter compared to a protein-silver nanowire conjugate, pointing towards emergence of the energy transfer. Overall, the results show that monitoring the optical properties of single emitters in a precisely designed hybrid nanostructure provides an elegant way to probe even complex combination of interactions at the nanoscale.

Impact of the Anthryl Linking Mode on the Photophysics and Excited-State Dynamics of Re(I) Complexes [ReCl(CO)3(4'-An-terpy-κ2N)].

Rhenium(I) complexes with 2,2':6',2″-terpyridines (terpy) substituted with 9-anthryl (1) and 2-anthryl (2) were synthesized, and the impact of the anthryl linking mode on the ground- and excited-state properties of resulting complexes [ReCl(CO)3(4'-An-terpy-κ2N)] (An─anthryl) was investigated using a combination of steady-state and time-resolved optical techniques accompanied by theoretical calculations. Different attachment positions of anthracene modify the overlap between the molecular orbitals and thus the electronic coupling of the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores. Following the femtosecond transient absorption, the lowest triplet excited state of both complexes was found to be localized on the anthracene chromophore. The striking difference between 1 and 2 concerns the triplet-state formation dynamics. A more planar geometry of 2-anthryl-terpy (2), and thus better electronic communication between the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores, facilitates the formation of the 3An triplet state. In steady-state photoluminescence spectra, the population ratio of 3MLCT and 3An was found to be dependent not only on the anthryl linking mode but also on solvent polarity and excitation wavelengths. In dimethyl sulfoxide (DMSO), compounds 1 and 2 excited with λexc > 410 nm show both 3MLCT and 3An emissions, which are rarely observed. Additionally, the abilities of the designed complexes for 1O2 generation and light emission under the external voltage were preliminary examined.

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.

Controlling of Photophysical Behavior of Rhenium(I) Complexes with 2,6-Di(thiazol-2-yl)pyridine-Based Ligands by Pendant π-Conjugated Aryl Groups.

The structure-property correlations and control of electronic excited states in transition metal complexes (TMCs) are of high significance for TMC-based functional material development. Within these studies, a series of Re(I) carbonyl complexes with aryl-substituted 2,6-di(thiazol-2-yl)pyridines (Arn-dtpy) was synthesized, and their ground- and excited-state properties were investigated. A number of condensed aromatic rings, which function as the linking mode of the aryl substituent, play a fundamental role in controlling photophysics of the resulting [ReCl(CO)3(Arn-dtpy-κ2N)]. Photoexcitation of [ReCl(CO)3(Arn-dtpy-κ2N)] with 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl leads to the population of 3MLCT. The lowest triplet state of Re(I) chromophores bearing 9-anthryl, 2-anthryl, 1-pyrenyl groups is ligand localized. The rhenium(I) complex with appended 1-pyrenyl group features long-lived room temperature emission attributed to the equilibrium between 3MLCT and 3IL/3ILCT. The excited-state dynamics in complexes [ReCl(CO)3(9-anthryl-dtpy-κ2N)] and [ReCl(CO)3(2-anthryl-dtpy-κ2N)] is strongly dependent on the electronic coupling between anthracene and {ReCl(CO)3(dtpy-κ2N)}. Less steric hindrance between the chromophores in [ReCl(CO)3(2-anthryl-dtpy-κ2N)] is responsible for the faster formation of 3IL/3ILCT and larger contribution of 3ILCTanthracene→dtpy in relation to the isomeric complex [ReCl(CO)3(9-anthryl-dtpy-κ2N)]. In agreement with stronger electronic communication between the aryl and Re(I) coordination centre, [ReCl(CO)3(2-anthryl-dtpy-κ2N)] displays room-temperature emission contributed to by 3MLCT and 3ILanthracene/3ILCTanthracene→dtpy phosphorescence. The latter presents rarely observed phenomena in luminescent metal complexes.

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.

Controlling plasmon propagation and enhancement via reducing agent in wet chemistry synthesized silver nanowires.

Silver nanowires with varying diameters and submillimeter lengths were obtained by changing a reducing agent used during hydrothermal synthesis. The control over the nanowire diameter turns out to play a critical role in determining their plasmonic properties, including fluorescence enhancement and surface plasmon polariton propagation. Advanced fluorescence imaging of hybrid nanostructures assembled of silver nanowires and photoactive proteins indicates longer propagation lengths for nanowires featuring larger diameters. At the same time, with increasing diameter of the nanowires, we measure a substantial reduction of fluorescence enhancement. The results point at possible ways to control the influence of plasmon excitations in silver nanowires by tuning their morphology.

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.

Immunosensor Based on Long-Period Fiber Gratings for Detection of Viruses Causing Gastroenteritis.

Since the norovirus is the main cause of acute gastroenteritis all over the world, its fast detection is crucial in medical diagnostics. In this work, a rapid, sensitive, and selective optical fiber biosensor for the detection of norovirus virus-like particles (VLPs) is reported. The sensor is based on highly sensitive long-period fiber gratings (LPFGs) coated with antibodies against the main coat protein of the norovirus. Several modification methods were verified to obtain reliable immobilization of protein receptors on the LPFG surface. We were able to detect 1 ng/mL norovirus VLPs in a 40-min assay in a label-free manner. Thanks to the application of an optical fiber as the sensor, there is a possibility to increase the user's safety by separating the measurement point from the signal processing setup. Moreover, our sensor is small and light, and the proposed assay is straightforward. The designed LPFG-based biosensor could be applied in both fast norovirus detection and in vaccine testing.

Giant Fine Structure Splitting of the Bright Exciton in a Bulk MAPbBr3 Single Crystal.

Exciton fine structure splitting in semiconductors reflects the underlying symmetry of the crystal and quantum confinement. Because the latter factor strongly enhances the exchange interaction, most work has focused on nanostructures. Here, we report on the first observation of the bright exciton fine structure splitting in a bulk semiconductor crystal, where the impact of quantum confinement can be specifically excluded, giving access to the intrinsic properties of the material. Detailed investigation of the exciton photoluminescence and reflection spectra of a bulk methylammonium lead tribromide single crystal reveals a zero magnetic field splitting as large as ∼200 µeV. This result provides an important starting point for the discussion of the origin of the large bright exciton fine structure splitting observed in perovskite nanocrystals.

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.

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.

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.

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.

NCN-Coordinating Ligands based on Pyrene Structure with Potential Application in Organic Electronics.

Five novel derivatives of pyrene, substituted at positions 1,3,6,8 with 4-(2,2-dimethylpropyloxy)pyridine (P1), 4-decyloxypyridine (P2), 4-pentylpyridine (P3), 1-decyl-1,2,3-triazole (P4), and 1-benzyl-1,2,3-triazole (P5), are obtained through a Suzuki-Miyaura cross-coupling reaction or CuI -catalyzed 1,3-dipolar cycloaddition reaction, respectively, and characterized thoroughly. TGA measurements reveal the high thermal stability of the compounds. Pyrene derivatives P1-P5 all show photoluminescence (PL) quantum yields (Φ) of approximately 75 % in solution. Solid-state photo- and electroluminescence characteristics of selected compounds as organic light-emitting diodes are tested. In the guest-host configuration, two matrixes, that is, poly(N-vinylcarbazole) (PVK) and a binary matrix consisting of PVK and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) (50:50 wt %), are applied. The diodes show red, green, or blue electroluminescence, depending on both the compound chemical structure and the actual device architecture. In addition, theoretical studies (DFT and TD-DFT) provide a deeper understanding of the experimental results.

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.

Aqueous Growth of Gold Clusters with Tunable Fluorescence Using Photochemically Modified Lipoic Acid-Based Ligands.

We report a one-phase aqueous growth of fluorescent gold nanoclusters (AuNCs) with tunable emission in the visible spectrum, using a ligand scaffold that is made of poly(ethylene glycol) segment appended with a metal coordinating lipoic acid at one end and a functional group at the other end. This synthetic scheme exploits the ability of the UV-induced photochemical transformation of LA-based ligands to provide DHLA and other thiol byproducts that exhibit great affinity to metal nanoparticles, obviating the need for chemical reduction of the dithiolane ring using classical reducing agents. The influence of various experimental conditions, including the photoirradiation time, gold precursor-to-ligand molar ratios, time of reaction, temperature, and the medium pH, on the growth of AuNCs has been systematically investigated. The photophysical properties, size, and structural characterization were carried out using UV-vis absorption and fluorescence spectroscopy, TEM, DOSY-NMR, and X-ray photoelectron spectroscopy. The hydrodynamic size (RH) obtained by DOSY-NMR indicates that the size of these clusters follows the trend anticipated from the absorption and PL data, with RH(red) > RH(yellow) > RH(blue). The tunable emission and size of these gold nanoclusters combined with their high biocompatibility would make them greatly promising for potential use in imaging and sensing applications.

Spectroscopic Studies of Dual Fluorescence in 2-((4-Fluorophenyl)amino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole.

The paper presents results of fluorescence analysis of ionic and nonionic 2-((4-fluorophenyl)amino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole (FABT) in monocrystals and solutions. We found a single fluorescence band in the case of FABT crystals grown in methanol and dual fluorescence for FABT crystals grown in an aqueous environment. The effect of dual fluorescence was preserved for FABT dissolved in aqueous solutions with pH ranging from 7.5 to 1. In contrast, FABT dissolved in methanol exhibited a single fluorescence band. The dual fluorescence effect is associated with conformational changes in the FABT molecule, which can be induced by aggregation effects. On the basis of crystallographic data, two types of FABT crystal molecule conformations were distinguished. In methanol, FABT molecules are in conformation "S" (the -OH group from the resorcyl ring oriented toward the sulfur atom from the 1,3,4-thiadiazole ring), which a gives single fluorescence band. In water, FABT in conformation "N" (the -OH group from the resorcyl ring oriented toward the nitrogen atom from the 1,3,4-thiadiazole ring due to 180° rotation) has two fluorescence bands. This significant finding implies the possibility of performing a rapid analysis of conformational changes in FABT molecules using fluorescence spectroscopy both in solutions and in biological samples.

Lesion simulating disease1, enhanced disease susceptibility1, and phytoalexin deficient4 conditionally regulate cellular signaling homeostasis, photosynthesis, water use efficiency, and seed yield in Arabidopsis.

There is growing evidence that for a comprehensive insight into the function of plant genes, it is crucial to assess their functionalities under a wide range of conditions. In this study, we examined the role of lesion simulating disease1 (LSD1), enhanced disease susceptibility1 (EDS1), and phytoalexin deficient4 (PAD4) in the regulation of photosynthesis, water use efficiency, reactive oxygen species/hormonal homeostasis, and seed yield in Arabidopsis (Arabidopsis thaliana) grown in the laboratory and in the field. We demonstrate that the LSD1 null mutant (lsd1), which is known to exhibit a runaway cell death in nonpermissive conditions, proves to be more tolerant to combined drought and high-light stress than the wild type. Moreover, depending on growing conditions, it shows variations in water use efficiency, salicylic acid and hydrogen peroxide concentrations, photosystem II maximum efficiency, and transcription profiles. However, despite these changes, lsd1 demonstrates similar seed yield under all tested conditions. All of these traits depend on EDS1 and PAD4. The differences in the pathways prevailing in the lsd1 in various growing environments are manifested by the significantly smaller number of transcripts deregulated in the field compared with the laboratory, with only 43 commonly regulated genes. Our data indicate that LSD1, EDS1, and PAD4 participate in the regulation of various molecular and physiological processes that influence Arabidopsis fitness. On the basis of these results, we emphasize that the function of such important regulators as LSD1, EDS1, and PAD4 should be studied not only under stable laboratory conditions, but also in the environment abounding in multiple stresses.

Strong angular and spectral narrowing of electroluminescence in an integrated Tamm-plasmon-driven halide perovskite LED.

Next-generation light-emitting applications such as displays and optical communications require judicious control over emitted light, including intensity and angular dispersion. To date, this remains a challenge as conventional methods require cumbersome optics. Here, we report highly directional and enhanced electroluminescence from a solution-processed quasi-2-dimensional halide perovskite light-emitting diode by building a device architecture to exploit hybrid plasmonic-photonic Tamm plasmon modes. By exploiting the processing and bandgap tunability of the halide perovskite device layers, we construct the device stack to optimise both optical and charge-injection properties, leading to narrow forward electroluminescence with an angular full-width half-maximum of 36.6° compared with the conventional isotropic control device of 143.9°, and narrow electroluminescence spectral full-width half-maximum of 12.1 nm. The device design is versatile and tunable to work with emission lines covering the visible spectrum with desired directionality, thus providing a promising route to modular, inexpensive, and directional operating light-emitting devices.

Comparative studies of structural, thermal, optical, and electrochemical properties of azines with different end groups with their azomethine analogues toward application in (opto)electronics.

Two series of azines and their azomethine analogues were prepared via condensation reaction of benzaldehyde, 2-hydroxybenzaldehyde, 4-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde, and 4-(diphenylamino)benzaldehyde with hydrazine monohydrate and 1,4-phenylenediamine, respectively. The structures of given compounds were characterized by FTIR, (1)H NMR, and (13)C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of all compounds were investigated by means of differential scanning calorimetry (DSC), UV-vis spectroscopy, stationary and time-resolved photoluminescence spectroscopy, and cycling voltammetry (CV). Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). Influence of chemical structure of the compounds on their properties was analyzed.