Light-driven dissipative self-assembly of a peptide hydrogel.

Light energy provides an attractive fuel source for energy dissipating systems because of the lack of waste production, wavelength tunability and the potential for spatial and temporal resolution. In this work, we describe a peptide-spiropyran conjugate that assembled into a transient nanofiber hydrogel in the presence of visible light, and dissociated when the light source was removed.

Shortwave infrared polymethine fluorophores matched to excitation lasers enable non-invasive, multicolour in vivo imaging in real time.

High-resolution, multiplexed experiments are a staple in cellular imaging. Analogous experiments in animals are challenging, however, due to substantial scattering and autofluorescence in tissue at visible (350-700 nm) and near-infrared (700-1,000 nm) wavelengths. Here, we enable real-time, non-invasive multicolour imaging experiments in animals through the design of optical contrast agents for the shortwave infrared (SWIR, 1,000-2,000 nm) region and complementary advances in imaging technologies. We developed tunable, SWIR-emissive flavylium polymethine dyes and established relationships between structure and photophysical properties for this class of bright SWIR contrast agents. In parallel, we designed an imaging system with variable near-infrared/SWIR excitation and single-channel detection, facilitating video-rate multicolour SWIR imaging for optically guided surgery and imaging of awake and moving mice with multiplexed detection. Optimized dyes matched to 980 nm and 1,064 nm lasers, combined with the clinically approved indocyanine green, enabled real-time, three-colour imaging with high temporal and spatial resolutions.

Self-Propelled Supracolloidal Fibers from Multifunctional Polymer Surfactants and Droplets.

Advanced synthetic materials are needed to produce nano- and mesoscale structures that function autonomously, catalyze reactions, and convert chemical energy into motion. This paper describes supracolloidal fiber-like structures that are composed of self-adhering, or "sticky," oil-in-water emulsion droplets. Polymer zwitterion surfactants serve as the key interfacial components of these materials, enabling multiple functions simultaneously, including acting as droplet-stabilizing surfactants, interdroplet adhesives, and building blocks of the fibers. This fiber motion, a surprising additional feature of these supracolloidal structures, is observed at the air-water interface and hinged on the chemistry of the polymer surfactant. The origin of this motion is hypothesized to involve transport of polymer from the oil-water interface to the air-water interface, which generates a Marangoni (interfacial) stress. Harnessing this fiber motion with functional polymer surfactants, and selection of the oil phase, produced worm-like objects capable of rotation, oscillation, and/or response to external fields. Overall, these supracolloidal fibers fill a design gap between self-propelled nano/microscale particles and macroscale motors, and have the potential to serve as new components of soft, responsive materials structures.

Light-activated "cycle-reversible intramolecular charge transfer" fluorescent probe: monitoring of pHi trace change induced by UV light in programmed cell death.

Under the synergistic effects of protonation and deprotonation, a light-activated fluorescent probe (UV-SP) exhibited "cycle-reversible intramolecular charge transfer (ICT)" for different pH after activation by UV light, resulting in emission of multiple ratio fluorescent signals (FI563/FI595 and FI664/FI595). Based on these kinds of response signals, UV-SP can specifically monitor the cycle-reversible trace change of intracellular pH caused by UV radiation. More importantly, according to the stable and invariant multiple ratio fluorescent signals, UV-SP can sort cells entering programmed death.

Ratiometric Fluorescent Probe for Lysosomal pH Measurement and Imaging in Living Cells Using Single-Wavelength Excitation.

A novel lysosome-targeting ratiometric fluorescent probe (CQ-Lyso) based on the chromenoquinoline chromorphore has been developed for the selective and sensitive detection of intracellular pH in living cells. In acidic media, the protonation of the quinoline ring of CQ-Lyso induces an enhanced intramolecular charge transfer (ICT) process, which results in large red-shifts in both the absorption (104 nm) and emission (53 nm) spectra which forms the basis of a new ratiometric fluorescence pH sensor. This probe efficiently stains lysosomes with high Pearson's colocalization coefficients using LysoTrackerDeep Red (0.97) and LysoTrackerBlue DND-22 (0.95) as references. Importantly, we show that CQ-Lyso quantitatively measures and images lysosomal pH values in a ratiometric manner using single-wavelength excitation.

Insights into photolytic mechanism of sulfapyridine induced by triplet-excited dissolved organic matter.

The ubiquity of sulfonamide antibiotics (SAs) in natural waters urges insights into their fate for ecological risk assessment in the aqueous euphotic zone. In this study, we investigated the effect of dissolved organic matter (DOM) on the photolysis of SAs with sulfapyridine as a reprentative. Results show that excited triplet state DOM ((3)DOM(∗)) is largely responsible for the photodegradation of sulfapyridine. The reaction of (3)DOM(∗) with a substructure model compound of SAs confirmed that sulfapyridine has one reaction site (aniline-N). Density functional theory (DFT) calculation was performed, which indicates that the anionic sulfapyridine has higher (3)DOM(∗) reactivity than that of the neutral form, which was also confirmed by steady state photolytic experiments. In the reaction, electrons of the aniline-N transfer to the carbonyl oxygen atom of (3)DOM(∗) moiety, followed by proton transfer, and leading to the formation of sulfapyridine radicals. The photolytic mechansim of sulfapyridine initiated by (3)DOM(∗) is helpful in understanding the photochemical fate and assessing the ecological risks of SAs in the aquatic environment.

Photooxidation-induced changes in optical, electrochemical, and photochemical properties of humic substances.

Two aquatic fulvic acids and one soil humic acid were irradiated to examine the resulting changes in the redox and photochemical properties of the humic substances (HS), the relationship between these changes, and their relationship to changes in the optical properties. For all HS, irradiation caused photooxidation, as shown by decreasing electron donating capacities. Photooxidation was accompanied by decreases in specific UV absorbance and increases in the E2/E3 ratio (254 nm absorbance divided by that at 365 nm). In contrast, photooxidation had little effect on the samples' electron accepting capacities. The coupled changes in optical and redox properties for the different HS suggest that phenols are an important determinant of aquatic HS optical properties and that quinones may play a more important role in soil HS. Apparent quantum yields of H2O2, ·OH, and triplet HS decreased with photooxidation, thus demonstrating selective destruction of HS photosensitizing chromophores. In contrast, singlet oxygen ((1)O2) quantum yields increased, which is ascribed to either decreased (1)O2 quenching within the HS microenvironment or the presence of a pool of photostable sensitizers. The photochemical properties show clear trends with SUVA and E2/E3, but the trends differ substantially between aquatic and soil HS. Importantly, photooxidation produces a relationship between the (1)O2 quantum yield and E2/E3 that differs distinctly from that observed with untreated HS. This finding suggests that there may be watershed-specific correlations between HS chemical and optical properties that reflect the dominant processes controlling the HS character.

Visible light photodegradation of phenanthrene catalyzed by Fe(III)-smectite: role of soil organic matter.

In the present study, phenanthrene is employed as a model to explore the roles played by three soil organic matter (SOM) fractions, i.e., dissolved organic matter (DOM), humic acid (HA), and fulvic acid (FA), in its photodegradation with assistance of Fe(III)-smectite under visible-light. Slight decrease in phenanthrene photodegradation rate was observed in the presence of DOM, which is explained in terms of oxidative-radical competition between DOM and target phenanthrene molecules due to the high electron-donor capacity of phenolic moieties in DOM. On the other hand, a critic content is observed with FA (0.70mg/g) and HA (0.65mg/g). Before reaching the critic content, the removal of phenanthrene is accelerated; while after that, the photodegradation rate is suppressed. The acceleration of phenanthrene degradation can be attributed to the photosensitization of FA and HA. Due to the strong interaction between phenanthrene and the phenyl rings, however, the retention of phenanthrene on SOM-Fe(III)-smectite in the presence of high content of HA or FA is enhanced, thus slowing down its photodegradation. Those observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and open a window for using clay-humic substances complexes for remediation of contaminated soil.

Investigating the mechanism of hydrogen peroxide photoproduction by humic substances.

The mechanism(s) by which hydrogen peroxide (H(2)O(2)) is photoproduced by humic substances and chromophoric dissolved organic matter was probed by examining the dependence of the initial H(2)O(2) photoproduction rate (R(H(2)O(2))) and apparent H(2)O(2) quantum yields on dioxygen concentration for both untreated and borohydride-reduced samples. Although borohydride reduction substantially reduced light absorption, the R(H(2)O(2)) values were largely unaffected. Apparent monochromatic and polychromatic quantum yields thus increased following reduction. The results indicate that light absorption by charge-transfer states or by (aromatic) ketone/aldehydes does not lead to significant H(2)O(2) photoproduction. High concentrations of triplet quenchers relative to that of dioxygen produced only small decreases (sorbic acid) or small increases (Cl(-) and Br(-)) in R(H(2)O(2)), indicating that neither (1)O(2) nor excited triplet states of quinones contribute significantly to H(2)O(2) photoproduction. The dependence of R(H(2)O(2)) on O(2) concentration provides evidence that the intermediate(s) reacting with O(2) to produce superoxide are relatively long-lived (approximately tens of microseconds or more). Evidence of the photochemical formation of O(2)-reducing intermediates under anaerobic conditions was also obtained; these reducing intermediates appeared to be relatively stable in the absence of O(2). Our data suggest that these O(2)-reducing intermediates are generated by intramolecular electron transfer from short-lived excited states of electron donors to ground-state acceptors.

Selenophene-thiophene block copolymer solar cells with thermostable nanostructures.

The nanostructure morphology and electron donor performance of a poly(3-hexylselenophene)-block-poly(3-hexylthiophene) (P3HS-b-P3HT) copolymer was studied in a photovoltaic device with a [6,6]-phenyl C61 butyric acid methyl ester (PCBM) acceptor. P3HS-b-P3HT forms fiberlike nanostructures spontaneously, which leads to an initial optimal device performance. Furthermore the nanostructure morphology is not greatly affected by annealing, which leads to a device stability that outperforms P3HT, P3HS, or a P3HS/P3HT mixture under identical conditions. External quantum efficiency, hole mobility, and current-voltage measurements show that the block copolymer also outperforms a ternary blend that consists of a physical mixture of P3HS, P3HT, and PCBM with the same overall composition. Overall, the observation of optimal device performance and morphology without annealing as well as enhanced thermal stability demonstrates the advantage of fully conjugated diblock copolymers in nanostructured devices.

Effect of water composition on TiO2 photocatalytic removal of endocrine disrupting compounds (EDCs) and estrogenic activity from secondary effluent.

The effect of inorganic ions and dissolved organic matter (DOM) on the TiO(2) photocatalytic removal of estrogenic activity from secondary effluents of municipal wastewater treatment plants was investigated. The presence of HPO(4)(2-), NH(4)(+), and HCO(3)(-) resulted in a significantly negative impact on the photocatalytic removal of estrogenic activity from synthetic water due to their strong adsorption on the surface of TiO(2). However, only a weak impact was noted during photocatalytic removal of estrogenic activity from secondary effluent with these ions added, since the presence of DOM in real wastewater played a more important role in inhibiting photocatalytic removal of estrogenic activity than inorganic ions. By investigating the effect of different DOM fractions on photocatalytic removal of estrogenic activity, polar compounds (PC) were found to cause a temporary increase in estrogenic activity during TiO(2) photocatalysis. Fluorescence spectroscopy and molecular weight (MW) analysis on secondary effluent spiked with PC during TiO(2) photocatalysis suggest that large MW organic matter (>4.5kDa) in secondary effluent, such as humic/fulvic acid, not only could play an important role in inhibiting photocatalytic removal of estrogenic activity but also is responsible for the temporary increase in estrogenic activity during the same process.

Characterization of spectral responses of humic substances upon UV irradiation using two-dimensional correlation spectroscopy.

The spectral responses of a leaf litter derived humic substance (LLHS) and Suwannee River fulvic acid (SRFA) upon ultraviolet (UV) A irradiation were characterized using two-dimensional correlation spectroscopy (2D-COS) based on the absorption and the synchronous fluorescence spectra at different irradiation times. A 12 day irradiation on the humic substances (HS) resulted in higher reduction of the absorbance relative to the dissolved organic carbon concentration, suggesting that aromatic chromophores were preferentially oxidized and/or non UV-absorbing compounds were generated by the photobleaching. Synchronous fluorescence spectra revealed the preferential removal of fulvic-like and humic-like fluorophores and delayed response of protein-like fluorescence upon the irradiation. The spectral features at long wavelengths (>430 nm) appear to be affected by intra-molecular interactions of the individual chromophores associated with shorter wavelengths. Absorption-based 2D-COS demonstrated that there are three types of absorption bands for the two HS, which changed sequentially in the order of 290-400 nm → 200-250 nm → 250-290 nm. In addition, two or three distinctive fluorescence bands in response to the irradiation were identified from 2D-COS. The sequential orders and the associated wavelength bands were possibly explained by the irradiation wavelengths and the differences between direct and indirect photochemical reactions. The interpretation of the 2D-COS results was very consistent with the kinetic rate constants individually calculated at several discrete wavelengths. Our study demonstrated that 2D-COS could be used as a powerful tool in identifying distinctive bands of HS that have dissimilar behavior and the associated sequential orders by visualizing the spectral changes at continuous wavelengths.

Transient Brewster angle reflectometry of spiropyran monolayers.

Brewster angle reflectometry has been developed as a tool for determining the absorbance and refractive index changes in molecular monolayers containing spiropyran. The method is sensitive to changes in both the real and imaginary parts of the refractive index in the monolayers. It was used to monitor the conversion of spiropyran to merocyanine and the reversal of this reaction when the molecules were immobilised on quartz using silane coupling. An analytical solution of Fresnel formula allowed the transient reflectometry data to be converted into transient absorption information. Absorbances of transients as low as approximately 10(-6) were possible using the current apparatus with a single laser pulse transient measurement. It was found that spiropyran photoconverted to merocyanine with an efficiency of approximately 0.1. The photochemical reversion of converted merocyanine to spiropyran occurred with efficiencies of 0.03-0.2 and this was probably site dependent. It was found that the thermal conversion from merocyanine to spiropyran was slow and even after 10 min there was no significant thermal reversion. This measurement was possible because the real part of the refractive index of the monolayer could be monitored with time using an off-resonance probe at a wavelength where the merocyanine did not absorb light meaning that the probe did not photobleach the sample. Thus our method also provides a non-intrusive method for probing changes in molecules in thin films.

Spiropyrans as molecular optical switches.

Optical microscopes use visible light and an arrangement of lenses to provide us with magnified images of small samples. Combined with efficient fluorescent probes and highly sensitive fluorescence detection techniques they allow the non-invasive 3D study of subcellular structures even in living cells or tissue. However, optical microscopes are subject to diffraction of light which limits optical resolution to approximately 200 nm in the imaging plane. In the recent past, powerful methods emerged that enable fluorescence microscopy with subdiffraction optical resolution. Since most of these methods are based on the temporal control of fluorescence emission of fluorophores, photochromic molecules that can be switched reversibly between a fluorescent on- and a non-fluorescent off-state are the key for super-resolution imaging methods. Here, we present our approach to use spiropyran-fluorophore conjugates as efficient molecular optical switches (photoswitches). In these photochromic conjugates fluorescence emission of the fluorophore is controlled by the state of the spiropyran, which can be switched reversibly between a colorless spiropyran and a colored merocyanine form upon irradiation with light. Thus, the efficiency of energy transfer from the fluorophore to the spiropyran can be modulated by the irradiation conditions. We present ensemble data of the switching process of various spiropyrans and spiropyran-fluorophore conjugates and demonstrate photoswitching at the single-molecule level. Our data suggest that spiropyrans have to be immobilized in polymers to stabilize the merocyanine form in order to be useful for super-resolution fluorescence imaging based on precise localization of individual emitters. Special emphasis is put on photobleaching of donor fluorophores due to UV irradiation, i.e. photoswitching of the photochromic acceptor. Furthermore, we present a water soluble switchable spiropyran derivative and demonstrate the first intermolecular single-molecule photoswitching experiments in polymers.

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation.

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV-Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.

Photoswitched DNA-binding of a photochromic spiropyran.

The dramatically different DNA-binding properties of the two isomeric forms of a photochromic spiropyran have been demonstrated, enabling photoswitched DNA binding. The closed, UV-absorbing form shows no signs of interaction with DNA. Upon UV exposure the spiropyran is isomerized to the open form that binds to DNA by intercalation. The process is fully reversible as the corresponding dissociation process is induced by visible light.

Ultraviolet absorbance titration for determining stability constants of humic substances with Cu(II) and Hg(II).

We describe an ultraviolet (UV) absorbance titration method that can be used to determine complexing capacities (C(L)) and conditional stability constants (logK) of humic substances (HSs) with metal ions such as Cu(II) and Hg(II). Two fulvic acids (FA) and one humic acid (HA) were used for this study. UV absorbance of HSs gradually increased with the addition of Cu(II) or Hg(II) after blank correction, and these increases followed the theoretical 1:1 (ligand:metal ion) binding model. The results from the absorbance titration calculation for HSs with Cu(II) and Hg(II) compared well with those from fluorescence quenching titration. The titration of the model compound l-tyrosine with Cu(II) proved the validity of this method, and the K and C(L) were within 2.3% and 7.4% of the fluorescence quenching titration. The results suggest that the UV absorbance titration can be used to study the binding capacities of HSs and/or dissolved organic matter (DOM) with trace metals. The advantages and disadvantages of the absorbance titration method were also discussed.

Optimising photoelectrocatalytic oxidation of fulvic acid using response surface methodology.

In this paper, statistics-based experimental design with response surface methodology (RSM) was employed to investigate the effect of operation conditions on photoelectrocatalytic oxidation of fulvic acid (FA) using a Ti/TiO(2) electrode in a photoreactor. Initially, the Box-Behnken design was employed including the three key variables (initial pH, potassium peroxodisulphate (K(2)S(2)O(8)) and bias potential). Thereafter, the mutual interaction and effects between these parameters and optimum conditions were obtained in greater detail by means of SAS and Matlab software. The results of this investigation reveal that: (1) the regression analysis with R(2) value of 0.9754 shows a close fit between the experimental results and the model predictions; (2) three-dimension response surface plot can provide a good manner for visualizing the parameter interactions; (3) the optimum pH, K(2)S(2)O(8) and bias potential is found to be 3.8, 88.40 mg/L, 0.88 V, respectively, and the highest FA removal efficiency of 57.06% can be achieved.

Nature and abundance of organic radicals in natural organic matter: effect of pH and irradiation.

Dissolved natural organic matter (NOM) plays an essential role in freshwater geochemical and biochemical processes. A major property, its redox behavior, can be attributed to the chinone building blocks, which can form stable radicals. However, electron paramagnetic resonance (EPR) data indicating free radicals on solid NOM are sparse. Here we present EPR spectra of 23 NOM from European surface waters isolated by reverse osmosis. The organic radical concentrations of NOM ranged from 5 x 10(15) to 1.84 x 10(17) spins g(-1), and g values ranged from 2.0031 to 2.0045. Number and type of organic radicals in solid NOM are significantly influenced by the pH of raw water. EPR experiments indicate the presence of semiquinone-type radicals in coexistence with carbon-centered "aromatic" radicals, with the semiquinone-type radicals dominating at alkaline pH. Basically these processes are reversible. Organic radical concentrations in NOM adjusted to pH 6.5 before freeze-drying correlate with iron and aluminum contents. UV- and VIS-irradiation of solid NOM can lead to more than a 10-fold increase of the concentration of organic radicals. These radicals were long-lived and had the same g value as the original radical. Similar effects were not observed with isolated humic and fulvic acids, demonstrating the limited reflection of environmental properties of organic carbon by the classical isolation procedure.

Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances.

The photodegradation of endocrine disrupter bisphenol A (BPA) in the presence of natural humic substances (HS) under simulated solar irradiation was studied. BPA underwent slow direct photolysis in neutral pure water, but rapid photosensitized degradation in four kinds of HS, following pseudo-first-order reaction. Reactive oxygen species (ROS) formed from HS were determined, including OH, (1)O(2) and H(2)O(2). The enhancement of BPA degradation by adding Fe(III) was primarily attributed to the oxidation of OH produced from photo-Fenton-like reaction. And the joint effects of HS and nitrate ions coexisting on BPA degradation appeared to depend on respective concentration levels. The effects of dissolved oxygen suggested that the energy transfer between excited state of SRFA and NOFA likely occurred, while the abstraction of phenolic hydrogen atom to reactive triplet state of NOHA possibly took place. Based on the structural analyses of main intermediates and degradation products of BPA detected by GC-MS, the possible photodegradation pathways were proposed, involving the alky cleavage, alkyl oxidation and OH addition. This study gave a better understanding for the photochemical transformation of BPA induced by ROS generated from natural water composition under sunlight irradiation.