Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids.

Alkylimidazolium chloride ionic liquids (ILs) have many uses in a variety of separation systems, including micro-confined separation systems. To understand the separation mechanism in these systems, the diffusion properties of analytes in ILs under relevant operating conditions, including micro-confinement dimension and temperature, should be known. For example, separation efficiencies for various IL-based microextraction techniques are dependent on the sample volume and temperature. Temperature-dependent (20-100 °C) fluorescence recovery after photobleaching (FRAP) was utilized to determine the diffusion properties of a zwitterionic, hydrophilic dye, ATTO 647, in alkylimidazolium chloride ILs in micro-confined geometries. These micro-confined geometries were generated by sandwiching the IL between glass substrates that were separated by ∼1 to 100 µm. From the measured temperature-dependent FRAP data, we note alkyl chain length-, thickness-, and temperature-dependent diffusion coefficients, with values ranging from 0.021 to 46 µm2/s. Deviations from Brownian diffusion are observed at lower temperatures and increasingly less so at elevated temperatures; the differences are attributed to alterations in intermolecular interactions that reduce temperature-dependent nanoscale structural heterogeneities. The temperature- and thickness-dependent data provide a useful foundation for efficient design of micro-confined IL separation systems.

Fast and non-destructive determination of water content in ionic liquids at varying temperatures by Raman spectroscopy and multivariate regression analysis.

Imidazolium acetate ionic liquids (ILs) have been utilized as promising solvents in many applications that involve varying water content and temperature. These experimental variables affect the anion-cation intermolecular interactions, which in turn influence the performance of the ILs in these applications. This paper shows Raman spectroscopy can be used as an operando method to measure water content in IL solvents when simultaneous temperature changes may occur. The Raman spectra of 1-alkyl-3-methylimidazolium acetate ILs (alkyl chain length n = 2, 4, 6, 8) with varying water content (from 0.028 to 0.899 water mole fraction) and temperature (from 78.1 K to 423.1 K) were measured. Increasing the water content or decreasing the temperature of the tested ILs weakens the anion-cation intermolecular interactions. The water content of these ILs can be quantified even in conditions when the temperature is changing using Raman spectroscopy combined with multivariate regression analysis, including principal component regression (PCR), partial-least-squares regression (PLSR), and artificial neural networks (ANNs). The ANN model combined with partial-least-squares (PLS) achieved the highest prediction accuracy of water content in ILs at varying temperatures (RMSECV = 0.017, R2CV = 99.1%, RMSEP = 0.019, R2P = 98.8%, RPD = 8.93). Raman spectroscopy provides a potential fast non-destructive operando method to monitor the water content of ILs even in applications when the temperature may be simultaneously altered; this information can lead to the optimized use of these ILs in many applications.

Localization of Nonblinking Point Sources Using Higher-Order-Mode Detection and Optical Heterodyning: Developing a Strategy for Extending the Scope of Molecular, Super-resolution Imaging.

While the stochastic, "blinking" nature of fluorescent systems has enabled the super-resolution of their localization by the fitting of their point-spread functions (PSFs), this strategy cannot be exploited for similar resolution of "nonblinking" systems, such as those that might be encountered in a coherent Raman experiment. An alternative method for subdiffraction-limited imaging lies in the exploitation of optical heterodyning. For example, if a Gaussian PSF (a TEM00 mode) of a point emitter is displaced with respect to the origin of the optical system, photons in the higher-order TEM modes carry information about that displacement. Information concerning the displacement can be extracted from photons in these higher-order modes. These photons can be collected by optical heterodyning, which exploits the large gain in a detector's response to an optical signal from an emitter coupled to a local oscillator, which is prepared in the TEM of interest, e.g., TEM10. We have generalized and developed the heterodyning technique to localize point emitters via the detection of higher-order spatial modes. We have developed a theoretical approach to find a practical estimation limit of the localization parameters using a realistic model that accounts for shot noise, background noise, and Gaussian noise. To demonstrate the applicability of the method, we designed experiments in which a laser is a surrogate for one and two point emitters. Using the Fisher information and its accompanying Cramér-Rao lower bound, we demonstrate super-resolution localization in these cases: we show that objects can be localized to roughly 2-3 orders of magnitude of their point-spread function's size for a given optical system. Finally and most importantly, it is suggested that the results will ultimately be generalizable to multiple emitters and, most importantly, to "nonblinking" molecular systems, which will be essential for broadening the scope of super-resolution measurements beyond the limits of fluorescence-based techniques.

The degradation of chlorophyll pigments in dairy silage: the timeline of anaerobic fermentation.

BACKGROUND: Detection of chlorophyll metabolites in milk has recently been suggested to be an indicator of a grass-fed diet fed for cattle. Such a means of detection, however, is complicated when the grazing season is over because cattle can be fed fermented silage ingredients, such as alfalfa and corn silage. During fermentation, chlorophyll compounds and other pigments undergo degradation due to the accumulation of lactic acid and the resultant decline in pH. RESULTS: We monitored degradation of chlorophyll compounds by measuring the fluorescence and absorption spectra of silage extracts. The spectroscopic evidence supports the hypothesis that chlorophylls are converted into fluorescent products, such as pheophytin, and further cleaved into pheophorbide. The degradation starts with dechelation and removal of the magnesium ion to produce pheophytin. Further removal of the phytol chain from pheophytin results in the production of pheophorbide. CONCLUSIONS: The fluorescence intensity of these degradation products is reduced compared to that of the parent molecule. These findings are important in understanding the fluorescent signal in milk when cows consume silage rather than fresh pasture grass. © 2020 Society of Chemical Industry.

Spectral Narrowing Accompanies Enhanced Spatial Resolution in Saturated Coherent Anti-Stokes Raman Scattering (CARS): Comparisons of Experiment and Theory.

We demonstrate theoretically and confirm experimentally the mechanism by which spectral narrowing accompanies enhanced spatial resolution in a saturated coherent anti-Stokes Raman scattering (CARS) signal that is demodulated at the third harmonic (3f) of the pump modulation frequency (f). Under these modulation conditions, theory predicts a narrowing of the full width at half-maximum (FWHM) of the CARS spectrum by a factor of 2.0 with respect to that of the spectrum obtained by demodulation at the fundamental frequency. Theory also predicts an improvement of spatial resolution by a factor of 1.7. Experimentally, narrowing of the FWHM of the CARS spectrum of 1,4-bis((E)-2-methylstyryl) benzene (MSB) crystals by a factor of 2.5 is observed upon saturation. Further experimental confirmation is provided from investigating diamond particles, for which spectral narrowing was enhanced by a factor of 2.8 and spatial resolution was enhanced by a factor of 2. Details of the mechanism and execution of the saturated CARS experiment are elucidated and limits to its applicability are suggested, one of which is the conclusion that the saturation approach is not suitable for extraction of harmonics beyond 3f. In this work, we have developed a more comprehensive understanding of the correlation between the observed experimental results and experimental factors than has been previously reported.

Fluorescence quenching of the SYBR Green I-dsDNA complex by in situ generated magnetic ionic liquids.

Magnetic ionic liquids (MILs) with metal-containing cations are promising extraction solvents that provide fast and high efficiency extraction of DNA. Hydrophobic MILs can be generated in situ in a methodology called in situ dispersive liquid-liquid microextraction. To consolidate the sample preparation workflow, it is desirable to directly use the DNA-enriched MIL microdroplet in the subsequent analytical detection technique. Fluorescence-based techniques employed for DNA detection often utilize SYBR Green I, a DNA binding dye that exhibits optimal fluorescence when bound to double-stranded DNA. However, the MIL may hinder the fluorescence signal of the SYBR Green I-dsDNA complex due to quenching. In this study, MILs with metal-containing cations were selected and their fluorescence quenching effects evaluated using FÓ§rster Resonance Energy Transfer and quantified using Stern-Volmer models. The MILs were based on N-substituted imidazole ligands (with butyl- and benzyl- groups as substituents) coordinated to Ni2+ or Co2+ metal centers as cations, and paired with chloride anions. The effects of NiCl2 and CoCl2 salts and of the 1-butyl-3-methylimidazolium chloride ionic liquid on the fluorophore complex were also studied to understand the components of the MIL structure that are responsible for quenching. The metal within the MIL chemical structure was found to be the main component contributing to fluorescence quenching. FÓ§rster critical distances between 11.9 and 18.8 Å were obtained for the MILs, indicating that quenching is likely not due to non-radiative energy transfer but rather to spin-orbit coupling or excited-state electron transfer. The MILs were able to be directly used in qPCR and fluorescence emission measurements using a microplate reader for detection, demonstrating their applicability in fluorescence-based detection methods. Graphical abstract.

Unveiling the Photo- and Thermal-Stability of Cesium Lead Halide Perovskite Nanocrystals.

Lead halide perovskites possess unique characteristics that are well-suited for optoelectronic and energy capture devices, however, concerns about their long-term stability remain. Limited stability is often linked to the methylammonium cation, and all-inorganic CsPbX3 (X=Cl, Br, I) perovskite nanocrystals have been reported with improved stability. In this work, the photostability and thermal stability properties of CsPbX3 (X=Cl, Br, I) nanocrystals were investigated by means of electron microscopy, X-ray diffraction, thermogravimetric analysis coupled with FTIR (TGA-FTIR), ensemble and single particle spectral characterization. CsPbBr3 was found to be stable under 1-sun illumination for 16 h in ambient conditions, although single crystal luminescence analysis after illumination using a solar simulator indicates that the luminescence states are changing over time. CsPbBr3 was also stable to heating to 250 °C. Large CsPbI3 crystals (34±5 nm) were shown to be the least stable composition under the same conditions as both XRD reflections and Raman bands diminish under irradiation; and with heating the γ (black) phase reverts to the non-luminescent δ phase. Smaller CsPbI3 nanocrystals (14±2 nm) purified by a different washing strategy exhibited improved photostability with no evidence of crystal growth but were still thermally unstable. Both CsPbCl3 and CsPbBr3 show crystal growth under irradiation or heat, likely with a preferential orientation based on XRD patterns. TGA-FTIR revealed nanocrystal mass loss was only from liberation and subsequent degradation of surface ligands. Encapsulation or other protective strategies should be employed for long-term stability of these materials under conditions of high irradiance or temperature.

Diffusional Dynamics of Tetraalkylphosphonium Ionic Liquid Films Measured by Fluorescence Correlation Spectroscopy.

Fluorescence correlation spectroscopy (FCS) is applied to investigate the diffusional dynamics of hydrophilic (Atto 590) and amphiphilic (DiD) fluorophores in a series of alkylphosphonium ionic liquid (IL) films ([P4448][Cl], [P6668][Cl], [P66614][Cl], and [P66614][NTf2]) in order to determine diffusional parameters and to elucidate nanoscale structural heterogeneities within the IL. From the measured correlation functions, the diffusion coefficients of the fluorescent molecules are estimated, rendering values that span from 0.39 to 1.2 and 0.146 to 5.2 µm2/s for Atto 590 and DiD, respectively. An increase in the diffusion coefficient values is correlated to the increase in the alkyl chain length, which in turn is correlated with a decrease in their viscosity. Interestingly, deviations from Brownian diffusion behavior of the fluorescent probes in the ILs are observed, showing a time-dependent diffusion coefficient in most of the cases. These deviations can be attributed to the presence of nanoscale structural heterogeneities in the tetraalkylphosphonium ILs. These results experimentally confirm the presence of nanosegregation in tetraalkylphosphonium ILs, which has been previously observed in molecular dynamics studies.

Characterization of the Photophysical Behavior of DFHBI Derivatives: Fluorogenic Molecules that Illuminate the Spinach RNA Aptamer.

( Z)-5-(3,5-Difluoro-4-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4 H-imidazol-4-one (DFHBI) and its analogues are fluorogenic molecules that bind the Spinach aptamer (a small RNA molecule), which was selected for imaging RNA. They are extremely weakly fluorescent in liquid solvents. It had been hypothesized that photoisomerization is a very efficient nonradiative process of deactivation. We show, consistent with the results of other studies, that if the isomerization is impeded, the fluorescence signal is enhanced significantly. In addition, we provide a thorough characterization of the photophysical behavior of DFHBI and its derivatives, notably that of ( Z)-5-(3,5-difluoro-4-hydroxybenzylidene)-2-methyl-3-((perfluorophenyl)methyl)-3,5-dihydro-4 H-imidazol-4-one (PFP-DFHBI) in various solvent environments. Solvent-dependent studies were performed with various mixtures of solvents. The results suggest that hydrogen bonding or strong interactions of the solvents with the phenolic-OH group change the absorption band near 420-460 nm and the nature of emission near 430 and 500 nm through various degrees of stabilization and the transformation between the neutral and the anionic species at both ground and excited states. These observations are confirmed by using a methoxy-substituted molecule (( Z)-5-(4-methoxybenzylidene)-2,3-dimethyl-3,5-dihydro-4 H-imidazol-4-one), where the 420-460 nm band is absent in the presence of methanol and the spectra are similar to those of PFP-DFHBI in noninteracting solvents, such as acetonitrile and dichloromethane. Thus, in addition to the major role of photoisomerization as a nonradiative process of deactivation of the excited state, the fluorescence of DFHBI-type molecules is very sensitively dependent upon the pH of the medium as well as upon solvent-specific interactions, such as hydrogen-bonding ability and polarity.

A Bayesian Approach for Extracting Fluorescence Lifetimes from Sparse Data Sets and Its Significance for Imaging Experiments.

The measurement of fluorescence lifetimes, especially in small sample volumes, presents the dual challenge of probing a small number of fluorophores and fitting the concomitant sparse data set to the appropriate excited-state decay function. A common method of analysis, such as the maximum likelihood (ML) technique, assumes a uniform probability distribution of the parameters describing the fluorescence decay function. An improvement is thus suggested by implementing a suitable nonuniform distribution, as is provided by a Bayesian framework, where the distribution of parameters is obtained from both their prior knowledge and the evidence-based likelihood of an event for a given set of parameters. We have also considered the Dirichlet prior distribution, whose mathematical form enables analytical solutions of the fitting parameters to be rapidly obtained. If Gaussian and exponential prior distributions are judiciously chosen, they reproduce the experimental target lifetime to within 20% with as few as 20 total photon counts for the data set, as does the Dirichlet prior distribution. But because of the analytical solutions afforded by the Dirichlet prior distribution, it is proposed to employ a Dirichlet prior to search parameter space rapidly to provide, if necessary, appropriate parameters for subsequent employment of a Gaussian or exponential prior distribution.

Exploiting Fluorescence Spectroscopy To Identify Magnetic Ionic Liquids Suitable for the Isolation of Oligonucleotides.

Magnetic ionic liquids (MILs), which incorporate paramagnetic ions, promise to minimize manual user intervention, decrease extraction times, and facilitate rapid recovery of the analyte-enriched extraction solvent. If, however, fluorescence is employed in the downstream analysis of an analyte tagged with a fluorophore, the paramagnetic ion may quench fluorescence by introducing new nonradiative processes. Thus, it is necessary to employ a paramagnetic ion that offers a compromise between possessing a high magnetic moment and not introducing new nonradiative channels. Mn(II), Fe(III), Co(II), and Ni(II) are considered in combination with phosphonium cations and anionic ligands based upon halides or hexafluoroacetylacetonate. Among the possibilities examined, MILs containing Mn(II) provide the best alternative for a model system involving DNA.

Using Fluorescence Spectroscopy To Identify Milk from Grass-Fed Dairy Cows and To Monitor Its Photodegradation.

Owing to its high ω-3 fatty acid content, milk from grass-fed dairy cows is becoming increasingly more attractive to consumers. Consequently, it is important to identify the origins of such products and to measure their content, at least relative to some standard. To date, chromatography has been the most extensively used technique. Sample preparation and cost, however, often reduce its widespread applicability. Here, we report the effectiveness of fluorescence spectroscopy for such quantification by measuring the amount of chlorophyll metabolites in the sample. Their content is significantly higher for milk from grass-fed cows compared to milk from grain/silage-fed cows. It is 0.11-0.13 µM in milk samples from grass-fed cows, whereas in milk from cows fed grain/silage rations, the concentration was 0.01-0.04 µM. In various organic milk samples, the chlorophyll metabolite concentration was in the range of 0.07-0.09 µM. In addition, we explored the mechanisms of photodegradation of milk. Riboflavin and chlorophyll metabolites act as photosensitizers in milk for type-I and type-II reactions, respectively. It was also observed that the presence of high levels of chlorophyll metabolites can synergistically degrade riboflavin, contributing to the degradation of milk quality.

Photoinduced Trans-to-cis Phase Transition of Polycrystalline Azobenzene at Low Irradiance Occurs in the Solid State.

The ability to produce large-scale, reversible structural changes in a variety of materials by photoexcitation of a wide variety of azobenzene derivatives has been recognized for almost two decades. Because photoexcitation of trans-azobenzene produces the cis-isomer in solution, it has generally been inferred that the macroscopic structural changes occurring in materials are also initiated by a similar large-amplitude trans-to-cis isomerization. This work provides the first demonstration that a trans-to-cis photoisomerization occurs in polycrystalline azobenzene, and is consistent with the previously hypothesized nature of the trigger in the photoactuated mechanisms of the materials in question. It is also demonstrated that under low irradiance, trans-to-cis isomerization occurs in the solid (not via a pre-melted phase); and the presence of the cis-isomer thus lowers the melting point of the sample, providing a liquid phase. A variety of experimental techniques were employed, including X-ray diffraction measurements of polycrystalline azobenzene during exposure to laser irradiation and fluorescence measurements of the solid sample. A practical consequence of this work is that it establishes trans-azobenzene as an easily obtainable and well-defined control for monitoring photoinduced structural changes in X-ray diffraction experiments, using easily accessible laser wavelengths.

Photon Counting Data Analysis: Application of the Maximum Likelihood and Related Methods for the Determination of Lifetimes in Mixtures of Rose Bengal and Rhodamine B.

It is often convenient to know the minimum amount of data needed to obtain a result of desired accuracy and precision. It is a necessity in the case of subdiffraction-limited microscopies, such as stimulated emission depletion (STED) microscopy, owing to the limited sample volumes and the extreme sensitivity of the samples to photobleaching and photodamage. We present a detailed comparison of probability-based techniques (the maximum likelihood method and methods based on the binomial and the Poisson distributions) with residual minimization-based techniques for retrieving the fluorescence decay parameters for various two-fluorophore mixtures, as a function of the total number of photon counts, in time-correlated, single-photon counting experiments. The probability-based techniques proved to be the most robust (insensitive to initial values) in retrieving the target parameters and, in fact, performed equivalently to 2-3 significant figures. This is to be expected, as we demonstrate that the three methods are fundamentally related. Furthermore, methods based on the Poisson and binomial distributions have the desirable feature of providing a bin-by-bin analysis of a single fluorescence decay trace, which thus permits statistics to be acquired using only the one trace not only for the mean and median values of the fluorescence decay parameters but also for the associated standard deviations. These probability-based methods lend themselves well to the analysis of the sparse data sets that are encountered in subdiffraction-limited microscopies.

Tailoring Nanoscale Morphology of Polymer:Fullerene Blends Using Electrostatic Field.

To tailor the nanomorphology in polymer/fullerene blends, we study the effect of electrostatic field (E-field) on the solidification of poly(3-hexylthiophene-2, 5-diyl) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) bulk heterojunction (BHJ). In addition to control; wet P3HT:PC60BM thin films were exposed to E-field of Van de Graaff (VDG) generator at three different directions-horizontal (H), tilted (T), and vertical (V)-relative to the plane of the substrate. Surface and bulk characterizations of the field-treated BHJs affirmed that fullerene molecules can easily penetrate the spaghetti-like P3HT and move up and down following the E-field. Using E-field treatment, we achieved favorable morphologies with efficient charge separation, transport, and collection. We improve; (1) the hole mobility values up to 19.4 × 10-4 ± 1.6 × 10-4 cm2 V-1 s-1 and (2) the power conversion efficiency (PCE) of conventional and inverted OPVs up to 2.58 ± 0.02% and 4.1 ± 0.40%, respectively. This E-field approach can serve as a new morphology-tuning technique, which is generally applicable to other polymer-fullerene systems.

PTOX Mediates Novel Pathways of Electron Transport in Etioplasts of Arabidopsis.

The immutans (im) variegation mutant of Arabidopsis defines the gene for PTOX (plastid terminal oxidase), a versatile plastoquinol oxidase in chloroplast membranes. In this report we used im to gain insight into the function of PTOX in etioplasts of dark-grown seedlings. We discovered that PTOX helps control the redox state of the plastoquinone (PQ) pool in these organelles, and that it plays an essential role in etioplast metabolism by participating in the desaturation reactions of carotenogenesis and in one or more redox pathways mediated by PGR5 (PROTON GRADIENT REGULATION 5) and NDH (NAD(P)H dehydrogenase), both of which are central players in cyclic electron transport. We propose that these elements couple PTOX with electron flow from NAD(P)H to oxygen, and by analogy to chlororespiration (in chloroplasts) and chromorespiration (in chromoplasts), we suggest that they define a respiratory process in etioplasts that we have termed "etiorespiration". We further show that the redox state of the PQ pool in etioplasts might control chlorophyll biosynthesis, perhaps by participating in mechanisms of retrograde (plastid-to-nucleus) signaling that coordinate biosynthetic and photoprotective activities required to poise the etioplast for light development. We conclude that PTOX is an important component of metabolism and redox sensing in etioplasts.

What Is the Best Method to Fit Time-Resolved Data? A Comparison of the Residual Minimization and the Maximum Likelihood Techniques As Applied to Experimental Time-Correlated, Single-Photon Counting Data.

The need for measuring fluorescence lifetimes of species in subdiffraction-limited volumes in, for example, stimulated emission depletion (STED) microscopy, entails the dual challenge of probing a small number of fluorophores and fitting the concomitant sparse data set to the appropriate excited-state decay function. This need has stimulated a further investigation into the relative merits of two fitting techniques commonly referred to as "residual minimization" (RM) and "maximum likelihood" (ML). Fluorescence decays of the well-characterized standard, rose bengal in methanol at room temperature (530 ± 10 ps), were acquired in a set of five experiments in which the total number of "photon counts" was approximately 20, 200, 1000, 3000, and 6000 and there were about 2-200 counts at the maxima of the respective decays. Each set of experiments was repeated 50 times to generate the appropriate statistics. Each of the 250 data sets was analyzed by ML and two different RM methods (differing in the weighting of residuals) using in-house routines and compared with a frequently used commercial RM routine. Convolution with a real instrument response function was always included in the fitting. While RM using Pearson's weighting of residuals can recover the correct mean result with a total number of counts of 1000 or more, ML distinguishes itself by yielding, in all cases, the same mean lifetime within 2% of the accepted value. For 200 total counts and greater, ML always provides a standard deviation of <10% of the mean lifetime, and even at 20 total counts there is only 20% error in the mean lifetime. The robustness of ML advocates its use for sparse data sets such as those acquired in some subdiffraction-limited microscopies, such as STED, and, more importantly, provides greater motivation for exploiting the time-resolved capacities of this technique to acquire and analyze fluorescence lifetime data.

Fluorescence Spectroscopy of the Retina for the Screening of Bovine Spongiform Encephalopathy.

Transmissible spongiform encephalopathies (TSE) are progressive, neurodegenerative disorders, of which bovine spongiform encephalopathy (BSE) is of special concern because it is infectious and debilitating to humans. The possibility of using fluorescence spectroscopy to screen for BSE in cattle was explored. Fluorescence spectra from the retinas of experimentally infected BSE-positive cattle with clinical disease were compared with those from both sham-inoculated and non-inoculated BSE-negative cattle. The distinct intensity difference of about 4-10-fold between the spectra of the BSE-positive and the BSE-negative (sham-inoculated and non-inoculated) eyes suggests the basis for a means of developing a rapid, noninvasive examination of BSE in particular and TSEs in general.

Shape evolution and single particle luminescence of organometal halide perovskite nanocrystals.

Organometallic halide perovskites CH3NH3PbX3 (X = I, Br, Cl) have quickly become one of the most promising semiconductors for solar cells, with photovoltaics made of these materials reaching power conversion efficiencies of near 20%. Improving our ability to harness the full potential of organometal halide perovskites will require more controllable syntheses that permit a detailed understanding of their fundamental chemistry and photophysics. In this manuscript, we systematically synthesize CH3NH3PbX3 (X = I, Br) nanocrystals with different morphologies (dots, rods, plates or sheets) by using different solvents and capping ligands. CH3NH3PbX3 nanowires and nanorods capped with octylammonium halides show relatively higher photoluminescence (PL) quantum yields and long PL lifetimes. CH3NH3PbI3 nanowires monitored at the single particle level show shape-correlated PL emission across whole particles, with little photobleaching observed and very few off periods. This work highlights the potential of low-dimensional organometal halide perovskite semiconductors in constructing new porous and nanostructured solar cell architectures, as well as in applying these materials to other fields such as light-emitting devices and single particle imaging and tracking.

Tryptophan and ATTO 590: mutual fluorescence quenching and exciplex formation.

Investigation of fluorescence quenching of probes, such as ATTO dyes, is becoming an increasingly important topic owing to the use of these dyes in super-resolution microscopies and in single-molecule studies. Photoinduced electron transfer is their most important nonradiative pathway. Because of the increasing frequency of the use of ATTO and related dyes to investigate biological systems, studies are presented for inter- and intramolecular quenching of ATTO 590 with tryptophan. In order to examine intramolecular quenching, an ATTO 590-tryptophan conjugate was synthesized. It was determined that tryptophan is efficiently quenching ATTO 590 fluorescence by excited-state charge transfer and two charge transfer complexes are forming. In addition, it was discovered that an exciplex (whose lifetime is 5.6 ns) can be formed between tryptophan and ATTO 590, and it is suggested that the possibility of such exciplex formation should be taken into account when protein fluorescence is monitored in a system tagged with ATTO dyes.