Estimation of multiexponential fluorescence decay parameters using compressive sensing.

Fluorescence lifetime imaging microscopy (FLIM) is a microscopic imaging technique to present an image of fluorophore lifetimes. It circumvents the problems of typical imaging methods such as intensity attenuation from depth since a lifetime is independent of the excitation intensity or fluorophore concentration. The lifetime is estimated from the time sequence of photon counts observed with signal-dependent noise, which has a Poisson distribution. Conventional methods usually estimate single or biexponential decay parameters. However, a lifetime component has a distribution or width, because the lifetime depends on macromolecular conformation or inhomogeneity. We present a novel algorithm based on a sparse representation which can estimate the distribution of lifetime. We verify the enhanced performance through simulations and experiments.

Revolutionizing the FRET-based light emission in core-shell nanostructures via comprehensive activity of surface plasmons.

We demonstrate the surface-plasmon-induced enhancement of Förster resonance energy transfer (FRET)using a model multilayer core-shell nanostructure consisting of an Au core and surrounding FRET pairs, i.e., CdSe quantum dot donors and S101 dye acceptors. The multilayer configuration was demonstrated to exhibit synergistic effects of surface plasmon energy transfer from the metal to the CdSe and plasmon-enhanced FRET from the quantum dots to the dye. With precise control over the distance between the components in the nanostructure, significant improvement in the emission of CdSe was achieved by combined resonance energy transfer and near-field enhancement by the metal, as well as subsequent improvement in the emission of dye induced by the enhanced emission of CdSe. Consequently, the Förster radius was increased to 7.92 nm and the FRET efficiency was improved to 86.57% in the tailored plasmonic FRET nanostructure compared to the conventional FRET system (22.46%) without plasmonic metals.

Excited-state dynamics of bis(9-fluorenyl)methane and its derivative 9-(9-ethylfluorenyl)-9'-fluorenylmethane: steric effect on energetics and dynamics of ground- and excited-state conformations.

Intramolecular excimer formation of bis(9-fluorenyl)methane (BFM) and 9-(9'-ethylfluorenyl)-9-fluorenylmethane (EFFM), in which an ethyl group is substituted to a 9-H atom in BFM, was studied by means of steady-state and time-resolved fluorescence. Ab initio and DFT calculations enabled the prediction of three conformers as stable species of orthogonal, trans-gauche, and gauche-gauche. The theoretical and experimental results reveal that the substitution effect is also found to appreciably influence the energies, spectroscopy, and kinetics associated with the interconversion of various conformers of the diaryl compounds. We have not observed the rising components in the excimer fluorescence decay of BFM and EFFM in PMMA as observed in the liquid solutions probably because of the existence of the sandwich conformer responsible for the excimer fluorescence prior to the laser irradiation.

Characterization of early-stage amyloid aggregates by incorporating extrinsic fluorescence and atomic force microscopy.

Amyloid-ß (Aß) oligomers are nanosized bio-assemblies that cause Alzheimer's disease. Characterizing early-stage Aß aggregates becomes an important issue because it is a prerequisite in exploring small molecule inhibitors that bind to Aß oligomers. Of special interest are efficient screening systems that characterize the Aß oligomer size with respect to the aging time. In this work, highly sensitive fluorescence techniques and atomic force microscopy (AFM) were employed to investigate the size determination of Aß and screening of small molecule inhibitors. A solvatochromic dye, 1-anilinonaphthalene-8-sulfonic acid (ANS), was used as an extrinsic fluorophore to monitor the growth mechanism of the Aß aggregates. Then, the time-resolved fluorescence anisotropy method was employed to estimate the hydrodynamic size of Aß oligomers. Finally, AFM was used to characterize the Aß oligomer size in the absence and presence of potential inhibitors. We present that the combination of such three experimental techniques is an excellent way to detect the early stage of Aß aggregation and to screen small molecule inhibitors.

Laser-induced graphitization of colloidal nanodiamonds for excellent oxygen reduction reaction.

Graphitized nanodiamonds were conveniently prepared by the laser irradiation of colloidal solution using various solvents. The nanodiamonds were converted into a fully graphitized onion-like structure, which became a cage-like mesoporous structure by the degradation of graphitic layers. Alcohols, acetone, and acetonitrile are more efficient solvents for the graphitization compared to water and hydrocarbons. Therefore the number and morphology of the graphitic layers can be simply controlled by the solvent and laser-irradiation duration. We suggest a graphitization model, in which the photocatalytic oxidation of the solvent accelerates the graphitization of nanodiamonds. The graphitized nanodiamonds were easily doped with the nitrogen and sulfur atoms in a controlled manner. In particular, the spherical graphitic layers were preferentially doped with the pyrrolic nitrogen that enhances remarkably electrocatalytic activity for the oxygen reduction reaction.

Volume increment effect on the photoisomerization of hemicyanine dyes in oligo(ethylene glycol)s.

We studied the excited-state dynamics of three hemicyanine dyes that undergo internal twisting from the localized excited state to the twisted intramolecular charge-transfer state. The dyes differ in the length of the alkyl chain in the aniline moiety and, thus, the volume of the motional moiety increases without having much of an effect on the excited-state potential surface. By employing oligo(ethylene glycol)s as a new homologous series of solvents that covers a high viscosity region, we showed that the excited-state lifetime of the hemicyanines gradually increases at any given viscosity when the size of the substituent increases. We describe our results for the solution-phase photoisomerization processes in terms of the breakdown of Stokes' law, multidimensionality, and the Hubbard relation.

Penalized maximum likelihood estimation of lifetime and amplitude images from multi-exponentially decaying fluorescence signals.

We investigated the penalized maximum likelihood estimation of lifetime and amplitude images for fluorescence lifetime imaging microscopy. The proposed method penalizes large variations in the lifetimes and amplitudes in the spatial domain to reduces noise in the images, which is a serious problem in the conventional maximum likelihood estimation method. For an effective optimization of the objective function, we applied an optimization transfer method that is based on a separable surrogate function. Simulations show that the proposed method outperforms the conventional MLE method in terms of the estimation accuracy, and the proposed method yielded less noisy images in real experiments.

Highly efficient electrochemical responses on single crystalline ruthenium-vanadium mixed metal oxide nanowires.

Highly efficient single crystalline ruthenium-vanadium mixed metal oxide (Ru1-xVxO2, 0≤x≤1) nanowires were prepared on a SiO2 substrate and a commercial Au microelectrode for the first time through a vapor-phase transport process by adjusting the mixing ratios of RuO2 and VO2 precursors. Single crystalline Ru1-xVxO2 nanowires show homogeneous solid-solution characteristics as well as the distinct feature of having remarkably narrow dimensional distributions. The electrochemical observations of a Ru1-xVxO2 (x=0.28 and 0.66)-decorated Au microelectrode using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) demonstrate favorable charge-transfer kinetics of [Fe(CN)6]3-/4- and Ru(NH3)6(3+/2+) couples compared to that of a bare Au microelectrode. The catalytic activity of Ru1-xVxO2 for oxygen and H2O2 reduction at neutral pH increases as the fraction of vanadium increases within our experimental conditions, which might be useful in the area of biofuel cells and biosensors.

Estimation of particle size distribution using photon autocorrelation function from dynamic light scattering considering unknown baseline.

Conventional methods for estimating particle size distribution (PSD) based on the computed field autocorrelation function (ACF) of dynamic light scattering data are prone to baseline error and random measurement errors. To reduce the effects of the errors efficiently and automatically, we propose a penalized nonlinear nonnegative least squares (NNLS) method based on the measured photon ACF that simultaneously determines the PSD and the unknown baseline. In simulations and experiments, the proposed method was able to estimate the PSD more accurately than the existing NNLS method using the computed field ACF.

Hydrogen and carbon monoxide generation from laser-induced graphitized nanodiamonds in water.

Nanodiamonds (ND) were found to generate hydrogen (H2) and carbon monoxide (CO) from water at a remarkable rate under pulsed laser (532 nm) irradiation. The transformation of diamond structure into graphitic layers takes place to form an onion-like carbon structure. The CO generation suggests the oxidative degradation reaction of graphitic layers, C + H2O → CO + 2H(+) + 2e(-), which produced a unique laser-induced reaction: C + H2O → CO + H2. Au, Pt, Pd, Ag, and Cu nanoparticles on the ND enhance both gas evolution rates (~2 times for Au) and graphitization and, specifically, Au was found to be the most efficient amongst other nanoparticles. The enhancement effect was ascribed to effective charge separation between the metal nanoparticles and ND. The Au-ND hybrid on the reduced graphene oxide produced consistently a greater photocurrent than the ND upon visible light irradiation.

Effect of conjugated linoleic acid, µ-calpain inhibitor, on pathogenesis of Alzheimer's disease.

µ-Calpain is a calcium-dependent cysteine protease, which is activated by µM concentration of calcium in vitro. Disrupted intracellular calcium homeostasis leads to hyper-activation of µ-calpain. Hyper-activated µ-calpain enhances the accumulation of ß-amyloid peptide by increasing the expression level of ß-secretase (BACE1) and induces hyper-phosphorylation of tau along with the formation of neurofibrillary tangle by mediating p35 cleavage into p25, both of which are the major mechanisms of neurodegeneration in Alzheimer's disease (AD). Hence, inhibition of µ-calpain activity is very important in the treatment and prevention of AD. In this study, conjugated linoleic acid (CLA), an eighteen-carbon unsaturated fatty acid, was discovered as a µ-calpain-specific inhibitor. CLA showed neuroprotective effects against neurotoxins such as H2O2 and Aß1-42 in SH-SY5Y cells, and inhibited Aß oligomerization/fibrillation and Aß-induced Zona Occludens-1 degradation. In addition, CLA decreased the levels of proapoptotic proteins, p35 conversion to p25 and tau phosphorylation. These findings implicate CLA as a new core structure for selective µ-calpain inhibitors with neuroprotective effects. CLA should be further evaluated for its potential use as an AD therapeutic agent.

Excluded volume effect in the fluorescence energy transfer of single donor-multiple acceptors in polymer.

Fluorescence resonance energy transfer (FRET) from a donor to multiple acceptors is an interesting subject. Numerous studies using theoretical models and simulations have focused on the excluded volume effect, which was not considered in Förster's first derivation. In this work, we first present the experimental results on the excluded volume effect by employing time-resolved FRET. Coumarin 334 (C334) was used as the energy donor whereas hemin and cytochrome c (cyt c) were used as the energy acceptors. The fluorescence intensity decays were measured for C334 surrounded by a number of acceptors in poly(acrylic acid). We have observed that the excluded volume effect is markedly pronounced with cyt c compared with hemin when the acceptor concentration is high (>5 mM). The results, which may be explicitly described by the relative molecular sizes of two acceptors, showed that the excluded volume effect should be considered in the interpretation of FRET data, especially when bulk chromophores are used.

Communication: Time-resolved fluorescence of highly single crystalline molecular wires of azobenzene.

We report the enhanced fluorescence with the remarkably long lifetime (1.17 ns) in the first excited state (S(1)) of highly crystalline molecular wires of azobenzene at the excitation wavelength of 467 nm for the first time. This observation suggests that trans-cis photoisomerization through the rotation or inversion mechanism may not be a favorable pathway after excitation to the S(1) state in highly single crystalline molecular wires of azobenzene due to the hindered motion within densely packed crystal structure. We also measured the fluorescence lifetime image of a single crystalline molecular wire of azobenzene, indicating that the lifetime was remarkably uniform and that there was only a very minor variation within the crystal.

Nanodiamonds as photocatalysts for reduction of water and graphene oxide.

Detonated nanodiamonds (NDs) exhibit remarkable photocatalytic activity towards the hydrogen gas generation upon 532 nm laser pulse irradiation. Hydrogenation dramatically increases the quantum yield, suggesting that hydrogen-terminated sites work as electron reservoirs. NDs can also be used as effective photocatalysts to reduce graphene oxide. The resulting composites exhibit high and stable photocurrent generation upon visible light irradiation.

Photomechanical effects in a dye-doped polymer nanocomposite.

Nile Red (NR) has been widely used as a microenvironmental probe since its luminescence characteristics depend strongly on medium polarity, viscosity, and hydrophobicity. The driving source for the internal motion of NR in rigid media is an absorbed photon that induces the molecule to rotate internally, causing the matrix deformed. Reversible (elastic) deformation and irreversible (plastic) deformation will influence the twisting dynamics in a different manner. In this work, we have investigated its excited state motion in a polymer nanocomposite, wherein polyvinyl alcohol (PVA) and nanodiamonds (NDs) were used as a matrix and a filler, respectively. PVA is a hydrophilic polymer having good chemical resistance, processability, and gel formation ability. Nanodiamond is a good candidate as a nanofiller for polymer composites. The elastic modulus of the polymer nanocomposite was measured by atomic force microscopy (AFM) nanoindentation and the emission lifetime of NR embedded in the polymer nanocomposite by time-resolved emission spectroscopy. Our results show that the fluorescence lifetime of NR is correlated well to the elastic modulus of polymer nanocomposite.

Light-induced isomerization dynamics of a cyanine dye in the modulus-controlled regime.

The trans-cis isomerization of an excited molecule converts light energy into mechanical motion, which interacts cooperatively with its surroundings. To understand such a photodynamic process in solids, we investigated the internal twisting motion of 1,1'-diethyl-2,2'-cyanine iodide (DCI) in a series of poly(alkyl methacrylate) (PAMA) polymers by measuring the Young's moduli of the polymers with atomic force microscopy nanoindentation and the fluorescence lifetimes of the dye with time-correlated single photon counting. We found that the isomerization rate constant obtained from the average lifetime correlated well with the mechanical property of the matrix. Our results show that the light-induced molecular motion lies in the modulus-controlled regime in which the polymer matrix not only provides a rigid environment for the dynamics of the molecules but also participates actively in the motion. The concept of elastic modulus may be applicable to molecular rotor dynamics in any synthetic polymer and, in principle, can be extended to biopolymers such as proteins or DNA.

Mechanical properties of polycarbonate and poly(methyl methacrylate) films reinforced with surface-functionalized nanodiamonds.

Polymer nanocomposites (PNCs) possess highly versatile characteristics, depending on the nanofiller properties such as its chemical composition, particle size, dimension, polydispersity, concentration, or surface functional groups. In comparison with micron-sized materials, the nanofiller having a large surface area facilitates stronger interaction with the matrix. In this work, various surface-functionalized nanodiamonds (sf-NDs) having hydroxyl, carboxyl, amino, and amide group were prepared, and dispersed into polycarbonate (PC) and poly(methyl methacrylate) (PMMA) polymers. The polymer nanocomposites (PNCs) which contain the ND content of 5 wt% were subjected to the measurements of mechanical properties such as hardness and Young's modulus by atomic force microscopy (AFM) nanoindentation. It was observed that the hardness and Young's modulus of the polymer nanocomposites depend on strongly the nature of functional groups. The amine or amide functionalization gives the high mechanical properties for both polymers. The interfacial interaction between sf-NDs and polymer matrices is an important factor determining the mechanical properties of the PNCs.

Unilamellar nanosheet of layered manganese cobalt nickel oxide and its heterolayered film with polycations.

The exfoliation of layered Li[Mn(1/3)Co(1/3)Ni(1/3)]O(2) into individual monolayers could be achieved through the intercalation of quaternary tetramethylammonium (TMA(+)) ions into protonated metal oxide. An effective exfoliation occurred when the TMA(+)/H(+) ratio was 0.5-50. Reactions outside this range produced no colloidal suspension, but all the manganese cobalt nickel oxides precipitated. Atomic force microscopy and transmission electron microscopy clearly demonstrated that exfoliated manganese cobalt nickel oxide nanosheets have a nanometer-level thickness, underscoring the formation of unilamellar nanosheets. The maintenance of the hexagonal atomic arrangement of the manganese cobalt nickel oxide layer upon the exfoliation was confirmed by selected area electron diffraction analysis. According to diffuse reflectance ultraviolet--visible spectroscopy, the exfoliated manganese cobalt nickel oxides displayed distinct absorption peaks at approximately 354 and approximately 480 nm corresponding to the d-d transitions of octahedral metal ions, which contrasted with the featureless spectrum of the pristine metal oxide. In the light of zeta potential data showing the negative surface charge of manganese cobalt nickel oxide nanosheets, a heterolayered film of manganese cobalt nickel oxide and conductive polymers could be prepared through the successive coating process with colloidal suspension and polycations. The UV--vis and X-ray diffraction studies verified the layer-by-layer ordered structure of the obtained heterolayered film, respectively.

Internal motion of an electronically excited molecule in viscoelastic media.

The twisting motion of trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (4-DASPI) in the excited state was investigated in solutions and various polymers in order to understand dependence of molecular rotor dynamics on viscoelasticity. It was observed that the internal motion of electronically excited 4-DASPI correlates strongly with dynamic viscosity and elastic modulus. Our results also showed that condensed phase dynamics of 4-DASPI are governed by the explicit mode coupling between the rotamerizing coordinate and mechanical properties of viscoelastic media.