Rapid photodegradation of terrestrial soil dissolved organic matter (DOM) with abundant humic-like substances under simulated ultraviolet radiation.

Solar ultraviolet (UV) radiation exhibits a significant degradation for dissolved organic matter (DOM) in natural water ecosystems. However, research on photodegradation process of terrestrial components (e.g., humic-like substances) of DOM are limited due to drastic water dilution and rapid degradation. Here, photochemical degradation of terrestrial soil DOM with abundant humic-like substances from different land use were investigated by utilizing spectral technologies. Simulated UV radiation caused obvious losses on concentration, component structures, and fluorescence characteristic of soil DOM samples. The correlations between absorption specific parameters (a280, SUVA254, and SR) and dissolved organic carbon (DOC) were especially pronounced (p < 0.05), which could be used as valid indicators to determine changes in DOM composition and molecular size during photobleaching process. The decreases of DOM fluorescence intensity were corresponded to first-order kinetic and half-life reactions. The greatest reduction on fluorescence intensity (31.56-81.97%) belonged to peak C (i.e., humic-like substances). Overall, DOM from forest and grass soil ecosystems was more easily photochemical degraded than anthropogenic soil DOM. Enhancive contribution of fresh DOM formed by photodegradation increased autochthonous characteristic and bioavailable nutrition by increasing biological index (BIX) values and ammonia nitrogen (NH4+-N) concentration. The slight microbial decomposition effects on DOM happened in unsterilized dark condition. Our findings provided insights for understanding the rapid photodegradation processes of composition and structure of terrestrial DOM. Graphical abstract.

Efficient and Long-Lived Room-Temperature Organic Phosphorescence: Theoretical Descriptors for Molecular Designs.

Room-temperature phosphorescence (RTP) with long afterglow from pure organic materials has attracted great attention for its potential applications in biological imaging, digital encryption, optoelectronic devices, and so on. Organic materials have been long considered to be nonphosphorescent owing to their weak molecular spin-orbit coupling and high sensitivity to temperature. However, recently, some purely organic compounds have demonstrated highly efficient RTP with long afterglow upon aggregation, while others fail. Namely, it remains a challenge to expound on the underlying mechanisms. In this study, we present the molecular descriptors to characterize the phosphorescence efficiency and lifetime. For a prototypical RTP system consisting of a carbonyl group and π-conjugated segments, the excited states can be regarded as an admixture of n → π* (with portion α) and π → π* (portion ß). Starting from the phosphorescent process and El-Sayed rule, we deduced that (i) the intersystem crossing (ISC) rate of S1 → T n is mostly governed by the modification of the product of α and ß and (ii) the ISC rate of T1 → S0 is determined by the ß value of T1. Thus, the descriptors (γ = α × ß, ß) can be employed to describe the RTP character of organic molecules. From hybrid quantum mechanics and molecular mechanics (QM/MM) calculations, we illustrated the relationships among the descriptors (γ, ß), phosphorescence efficiency and lifetime, and spin-orbit coupling constants. We stressed that the large γ and ß values are favorable for the strong and long-lived RTP in organic materials. Experiments have reported confirmations of these molecular design rules.

Gated Materials for On-Command Release of Guest Molecules.

Multidisciplinary research at the forefront of the field of hybrid materials has paved the way to the development of endless examples of smart devices. One appealing concept in this fertile field is related to the design of gated materials. These are constructed for finely tuning the delivery of chemical or biochemical species from voids of porous supports to a solution in response to predefined stimuli. Such gated materials are composed mainly of two subunits: (i) a porous inorganic support in which a cargo is loaded and (ii) certain molecular or supramolecular entities, generally grafted onto the external surface, which can control mass transport from pores. On the basis of this concept, a large number of imaginative examples have been developed. This review intends to be a comprehensive analysis of papers published until 2014 on hybrid mesoporous gated materials. The molecules used as gates, the opening mechanisms, and controlled release behavior are detailed. We hope this review will not only help researchers who work in this field but also may open the minds of related ones to develop new advances in this fertile research area.

Modulation of the Singlet Oxygen Generation from the Double Strand DNA-SYBR Green I Complex Mediated by T-Melamine-T Mismatch for Visual Detection of Melamine.

Singlet oxygen (1O2), generated via photosensitization, has been proved to oxidize chromogenic substrates with neither H2O2 oxidation nor enzyme (horseradish peroxidase, HRP) catalysis. Of the various methods for modulation of the 1O2 generation, DNA-controlled photosensitization received great attention. Therefore, integration of the formation/deformation DNA structures with DNA-controlled photosensitization will be extremely appealing in visual biosensor developments. Here, the stable melamine-thymine complex was explored in combination with DNA-controlled photosensitization for visual detection of melamine. A T-rich single stand DNA was utilized as the recognition unit. Upon the formation of the T-M-T complex, double stand DNA was formed, which was ready for the binding of SYBR Green I and activated the photosensitization. Subsequent oxidation of TMB allowed visual detection of melamine in dairy products, with spike-recoveries ranging from 94% to 106%.

Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

Time Resolved Spectroscopic Studies on a Novel Synthesized Photo-Switchable Organic Dyad and Its Nanocomposite Form in Order to Develop Light Energy Conversion Devices.

UV-vis absorption, steady state and time resolved spectroscopic investigations in pico and nanosecond time domain were made in the different environments on a novel synthesized dyad, 3-(2-methoxynaphthalen-1-yl)-1-(4-methoxyphenyl)prop-2-en-1-one (MNTMA) in its pristine form and when combined with gold (Au) nanoparticles i.e., in its nanocomposite structure. Both steady state and time resolved measurements coupled with the DFT calculations performed by using Gaussian 03 suit of software operated in the linux operating system show that though the dyad exhibits mainly the folded conformation in the ground state but on photoexcitation the nanocomposite form of dyad prefers to be in elongated structure in the excited state indicating its photoswitchable nature. Due to the predominancy of elongated isomeric form of the dyad in the excited state in presence of Au Nps, it appears that the dyad MNTMA may behave as a good light energy converter specially in its nanocomposite form. As larger charge separation rate (kcs ~ 4 x 10(8) s-1) is found relative to the rate associated with the energy wasting charge recombination processes (kcR ~ 3 x 10(5) s-1) in the nanocomposite form of the dyad, it demonstrates the suitability of constructing the efficient light energy conversion devices with Au-dyad hybrid nanomaterials.

Photochemical and microbial alterations of DOM spectroscopic properties in the estuarine system Ria de Aveiro.

The influence of photochemical transformations of chromophoric dissolved organic matter (CDOM) on microbial communities was evaluated in the estuarine system Ria de Aveiro. Two sites, representative of the marine and brackish water zones of the estuary, were surveyed regularly in order to determine seasonal and vertical profiles of variation of CDOM properties. Optical parameters of CDOM indicative of aromaticity and molecular weight were used to establish CDOM sources, and microbial abundance and activity was characterized. Additionally, microcosm experiments were performed in order to simulate photochemical reactions of CDOM and to evaluate microbial responses to light-induced changes in CDOM composition. The CDOM of the two estuarine zones showed different spectral characteristics, with significantly higher values of the specific ultra-violet absorbance at 254 nm (SUVA254) (5.5 times) and of the absorption coefficient at 350 nm (a350) (12 times) and lower SR (S275-295/S350-400) ratio at brackish water compared with the marine zone, reflecting the different amounts and prevailing sources of organic matter, as well as distinct riverine and oceanic influences. At the marine zone, the abundance of bacteria and the activity of Leu-AMPase correlated with a350 and a254, suggesting a microbial contribution to the HMW CDOM pool. The irradiation of DOM resulted in a decrease of the values of a254 and a350 and an increase of the slope S275-295 and of the ratios E2 : E3 (a250/a365) and SR, which in turn increase its bioavailability. However, the extent of photoinduced transformations and microbial responses was dependent on the initial optical characteristics of CDOM. In Ria de Aveiro both photochemical and microbial processes yielded optical changes in CDOM and the overall results of these combined processes determine the fate of CDOM in the estuarine system and have an influence on local productivity and in adjacent coastal areas.

Impact of UV/H2O2 pre-oxidation on the formation of haloacetamides and other nitrogenous disinfection byproducts during chlorination.

Haloacetamides (HAcAms), an emerging class of nitrogen-based disinfection byproducts (N-DBPs) of health concern in drinking water, have been found in drinking waters at µg/L levels. However, there is a limited understanding about the formation, speciation, and control of halogenated HAcAms. Higher ultraviolet (UV) doses and UV advanced oxidation (UV/H2O2) processes (AOPs) are under consideration for the treatment of trace organic pollutants. The objective of this study was to examine the potential of pretreatment with UV irradiation, H2O2 oxidation, and a UV/H2O2 AOP for minimizing the formation of HAcAms, as well as other emerging N-DBPs, during postchlorination. We investigated changes in HAcAm formation and speciation attributed to UV, H2O2 or UV/H2O2 followed by the application of free chlorine to quench any excess hydrogen peroxide and to provide residual disinfection. The results showed that low-pressure UV irradiation alone (19.5-585 mJ/cm(2)) and H2O2 preoxidation alone (2-20 mg/L) did not significantly change total HAcAm formation during subsequent chlorination. However, H2O2 preoxidation alone resulted in diiodoacetamide formation in two iodide-containing waters and increased bromine utilization. Alternatively, UV/H2O2 preoxidation using UV (585 mJ/cm(2)) and H2O2 (10 mg/L) doses typically employed for trace contaminant removal controlled the formation of HAcAms and several other N-DBPs in drinking water.

Surface plasmonic effects on organic solar cells.

Most high-performance organic photovoltaic (OPV) devices reported in the literature have been fabricated using the bulk heterojunction (BHJ) concept. Typically, the optimum thickness of the active layer for an OPV device is around 100 nm, or possibly less; such a thin layer can lead to low absorption of light. A thicker layer, however, inevitably increases the device resistance, due to the low carrier mobilities and short exciton diffusion lengths in organic materials. This situation imposes a trade-off between light absorption and charge transport efficiencies in OPV devices, motivating the development of a variety of light-trapping techniques. Metallic nanoparticles (NPs) such as Ag, Au, etc. and other metallic nanostructures are potential candidates for improving the light absorption due to the localized surface plasmon resonance (LSPR). LSPR contributes to the significant enhancement of local electromagnetic fields and improves the optical properties of the nanostructure devices. The excitation of LSPR is achieved when the frequency of the incident light matches its resonance peak, resulting in unique optical properties; selective light extinction as well as local enhancement of electromagnetic fields near the surface of metallic NPs. The resonance peak of LSPR depends strongly on the size, shape, and the dielectric environment of the metallic NPs. In this review article, progress on plasmonic enhanced OPV device performance is examined. The concepts of surface plasmonics for OPV devices, suitable plasmonic materials, location, optimum size and concentration of NP materials within the device are explored.

Fullerene derivatives as electron acceptors for organic photovoltaic cells.

Energy is currently one of the most important problems humankind faces. Depletion of traditional energy sources such as coal and oil results in the need to develop new ways to create, transport, and store electricity. In this regard, the sun, which can be considered as a giant nuclear fusion reactor, represents the most powerful source of energy available in our solar system. For photovoltaic cells to gain widespread acceptance as a source of clean and renewable energy, the cost per watt of solar energy must be decreased. Organic photovoltaic cells, developed in the past two decades, have potential as alternatives to traditional inorganic semiconductor photovoltaic cells, which suffer from high environmental pollution and energy consumption during production. Organic photovoltaic cells are composed of a blended film of a conjugated-polymer donor and a soluble fullerene-derivative acceptor sandwiched between a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)-coated indium tin oxide positive electrode and a low-work-function metal negative electrode. Considerable research efforts aim at designing and synthesizing novel fullerene derivatives as electron acceptors with up-raised lowest unoccupied molecular orbital energy, better light-harvesting properties, higher electron mobility, and better miscibility with the polymer donor for improving the power conversion efficiency of the organic photovoltaic cells. In this paper, we systematically review novel fullerene acceptors synthesized through chemical modification for enhancing the photovoltaic performance by increasing open-circuit voltage, short-circuit current, and fill factor, which determine the performance of organic photovoltaic cells.

Photodegradation of organic matter in fresh garbage leachate using immobilized nano-sized TiO2 as catalysts.

Two immobilized nano-sized TiO2 catalysts, TiO2/activated carbon (TiO2/AC) and TiO2/silica gel (SG) (TiO2/SG), were prepared by the sol-gel method, and their use in the photocatalytic degradation of organic matter in fresh garbage leachate under UV irradiation was investigated. The influences of the catalyst dosage, the initial solution pH, H2O2 addition and the reuse of the catalysts were evaluated. The degradation of organic matter was assessed based on the decrease of the chemical oxygen demand (COD) in the leachate. The results indicated that the degradation of the COD obeyed first-order kinetics in the presence of both photocatalysts. The degradation rate of COD was found to increase with increasing catalyst dosage up to 9 g/L for TiO2/AC and 6 g/L for TiO2/SG, above which the degradation began to attenuate. Furthermore, the degradation rate first increased and then decreased as the solution pH increased from 2 to 14, and the degradation rate increased as the amount of H2O2 increased to 2.93 mM, after which it remained constant. No obvious decrease in the rate of COD degradation was observed during the first four repeated uses of the photocatalysts, indicating that the catalysts could be recovered and reused. Compared with TiO2/AC, TiO2/SG exhibited higher efficiency in photocatalyzing the degradation of COD in garbage leachate.

Optoelectrical and low-frequency noise characteristics of flexible ZnO-SiO2 photodetectors with organosilicon buffer layer.

The present study demonstrates the optoelectrical and low-frequency noise characteristics of ZnO-SiO(2) nanocomposite solar-blind metal-semiconductor-metal photodetectors (MSM PDs) on flexible polyethersulfone (PES) substrate with and without an organosilicon [SiO(x)(CH(3))] buffer layer. For a given bandwidth of 100 Hz and a -5 V applied bias, the noise equivalent powers of the ZnO-SiO(2) nanocomposite MSM PD on PES with and without the SiO(x)(CH(3)) buffer layer were 1.39 × 10(-14) and 5.72 × 10(-14) W at 240nm, respectively, corresponding to the normalized detectivities of 5.04 × 10(14) and 1.22 × 10(14) Hz(0.5) W(-1), respectively. These findings indicate that a lower noise level and a higher detectivity can be achieved for ZnO-SiO(2) nanocomposite MSM PDs on PES by introducing a SiO(x)(CH(3)) buffer layer.

Effect of structure and interlayer diffusion in organic position sensitive photodetectors based on complementary wedge donor/acceptor layers.

We have developed organic photodetectors based on two complementary wedge layers made of CuPc and C60 and observed a strong spatial dependence of the spectral response on the position of the incident light spot. Photocurrent measurements are correlated with atomic force microscopy (AFM), micro-Raman and ellipsometry maps in order to provide insights into the local donor/acceptor concentration, layer thickness and nature of the donor-acceptor interface along the direction of the thickness gradient. Deviations in spatial dependence between experimental photocurrent values and those predicted with a model assuming a sharp and well defined organic-organic interface are discussed in terms of inter-diffusion layers.

Organic photovoltaic solar cells with cathode modified by ZnO.

Solution processed cathode organic photovoltaic cells (OPVs) utilizing thin layer of ZnO with 27% increase in power conversion efficiency (PCE) to control devices have been demonstrated. Devices without the presence of ZnO layer have much lower PCE than the ones with ZnO layer. Cathode modification layer can be used to reduce photogenerated excitions and finally improve the performance of the OPVs. The successful demonstrations of OPVs with an introduction of ZnO cathode layer give promise of further device progresses.

Two-dimensional simulation of organic bulk heterojunction solar cell: influence of the morphology.

Recent developments in organic solar cells show interesting power conversion efficiencies. However, with the use of organic semiconductors and bulk heterojunction cells, many new concepts have to be introduced to understand their characteristics. Only few models investigate these new concepts, and most of them are one-dimensional only. In this work, we present a two-dimensional model based on solving the drift-diffusion equations. The model describes the generation of excitons in the donor phase of the active layer and their diffusion towards an interface between the two separate acceptor and donor domains. Then, when the exciton reaches the interface, it forms a charge transfer state which can split into free charges due to the internal potential. Finally, these free charges are transported toward the electrodes within their respective domains (electrons in acceptor domain, holes in donor domain) before being extracted. In this model, we can follow the distribution of each species and link it to the physical processes taken into account. Using the finite element method to solve the equations of the model, we simulate the effect of the bulk heterojunction morphology on photocurrent curves. We concentrate on the morphology parameters such as the mean acceptor/donor domain sizes and the roughness of,the interface between the donor and acceptor domains. Results are discussed in relation with experimental observations.

Colour-coded photoluminescence and chemiluminescence of fluorene polymer-based organic nanowires in random and organised arrangements.

Organic nanowires based on a fluorene homopolymer and a copolymer, i.e., poly(9,9-dioctylfluorene), F8, and poly(9,9-dioctylfluorene-co-benzothiadiazole), F8BT, respectively, were synthesised by solution assisted wetting of porous anodic alumina templates. Nanowires ranged between 3 microm and 50 microm in length, and were ca. 200 nm in diameter. Absorption and photoluminescence studies of F8BT nanowires yielded spectra characteristic of the parent material. By contrast, the well resolved spectra obtained for F8 nanowires indicated that, during synthesis, a fraction of the molecules within the wires underwent intra-chain re-orientation from the more random molecular conformations of the glassy phase to the more planar extended molecular conformation of the beta-phase. Importantly, both F8 and F8BT nanowires exhibited a distinct emission anisotropy, consistent with internal alignment of the emissive polymer chains along the long axes of the wires. This property was exploited by forming nanowire crossbar structures in which, by selecting either luminescence wavelength or polarisation state, spatial confinement and colour tuning of polarised light emission could be readily achieved. Finally, nanowire chemiluminescence was demonstrated. Characteristic blue and green-yellow luminescence was observed for F8 and F8BT wires, respectively, confirming that these novel nanostructures may act as nanoscale chemiluminescent light sources.

Inkjet printed solar cell active layers based on a novel, amorphous polymer.

Organic solar cells are a favorable alternative to their inorganic counterparts because the functional layers of these devices can be processed with printing or coating on a large scale. In this study, a novel polymer was synthesized, blended with fullerene and deposited with inkjet printing for solar cell applications. Devices with printed layers were compared to those with spin coated films in order to evaluate inkjet printing as a thin film deposition method. Efficiency values of 3.7% were found for devices with inkjet printed or spin coated layers. Inkjet printing can be used to successfully process the active layers of organic solar cells consisting of novel polymers without sacrificing device performance.

Comparison of graphene oxide with reduced graphene oxide as hole extraction layer in organic photovoltaic cells.

A comparison was performed between the use of graphene oxide (GO) and reduced graphene oxide (rGO) as a hole extraction layer (HEL) in organic photovoltaic (OPV) cells with poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester. Hydrazine hydrate (HYD) and the thermal method (Thermal) were adopted to change the GO to rGO. The GO HEL was deposited on an indium tin oxide electrode by spin coating, followed by the reduction process to form the rGO HELs. The success of the reduction processes was confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoemission spectroscopy, transmittance, and 2-point probe method. The OPV cell with the GO (-3 nm) HEL exhibits an increased power conversion efficiency (PCE) as high as 2.5% under 100 mW/cm2 illumination under air mass conditions, which is higher than that of the OPV cell without HEL, viz. 1.78%. However, the PCE of the OPV cell with rGO HEL is not high as the values of 1.8% for the HYD-rGO and 1.9% for the Thermal-rGO. The ultraviolet photoemission spectroscopy results showed that the work function of GO was 4.7 eV, but those of HYD-rGO and Thermal-rGO were 4.2 eV and 4.5 eV, respectively. Therefore, it is considered that GO is adequate to extract the holes from the active layer, but HYD-rGO and Thermal-rGO are not appropriate to use as HELs in OPV cells from the viewpoint of the energy alignment.

Organic solar cells using a ZnO/Cu/ZnO anode deposited by ion beam sputtering at room temperature for flexible devices.

The development of indium-free transparent conductive oxides (TCOs) on polymer substrates for flexible devices requires deposition at low temperatures and a limited thermal treatment. In this paper, we investigated the optical and electrical properties of ZnO/Cu/ZnO multi-layer electrodes obtained by ion beam sputtering at room temperature for flexible optoelectronic devices. This multilayer structure has the advantage of adjusting the layer thickness to favor antireflection and surface plasmon resonance of the metallic layer. We found that the optimal electrode is made up of a 10 nm-thick Cu layer between two 40 nm-thick ZnO layers, which results in a sheet resistance of 12 omega/(see symbol), a high transmittance of 85% in the visible range, and the highest figure of merit of 5.4 x 10(-3) (see symbol)/omega. A P3HT:PCBM-based solar cell showed a power conversion efficiency (PCE) of 2.26% using the optimized ZnO (40 nm)/Cu (10 nm)/ZnO (40 nm) anode.

Preparation of graphene-ZrO2 nanocomposites by heat treatment and photocatalytic degradation of organic dyes.

ZrO2 nanoparticles were synthesized by combining a solution containing zinconyl chloride in distilled water with a NH4OH solution under microwave irradiation. Graphene and ZrO2 nanocomposites were synthesized in an electric furnace at 700 degrees C for 2 hours. The heated graphene-ZrO2 nanocomposites were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. In addition, UV-vis spectrophotometry was used to evaluate the heated graphene-ZrO2 nanocomposites as a catalyst in the photocatalytic degradation of organic dyes. The photocatalytic effect of the heated graphene-ZrO2 nanocomposites was compared with that of unheated graphene nanoparticles, heated graphene nanoparticles, and unheated graphene-ZrO2 nanocomposites in organic dyes (methylene blue, methyl orange, and rhodamine B) under ultraviolet light at 254 nm.