In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 1015 molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 1015 molec./cm2 (GOME-2) and (3.2 ± 3.2) × 1015 molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 1015 molec./cm2. Average ground measurements over “clean areas”, on 18 July 2011, give (2.5 ± 0.6) × 1015 molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 1015 molec./cm2.
Phytochrome photoreceptors in plants and microorganisms switch photochromically between two states, controlling numerous important biological processes. Although this phototransformation is generally considered to involve rotation of ring D of the tetrapyrrole chromophore, Ulijasz et al. (2010, Nature 463, 250-254) proposed that the A-ring rotates instead. Here, we apply MAS NMR to the two parent states of following studies of the 23-kDa GAF-domain fragment of phytochrome from Synechococcus OS-B'. Major changes occur at the A-ring covalent linkage to the protein as well as at the protein residue contact of ring D. Conserved contacts associated with the A-ring nitrogen rule out an A-ring photoflip, whereas loss of contact of the D-ring nitrogen to the protein implies movement of ring D. Although none of the methine bridges showed a chemical shift change comparable to those characteristic of the D-ring photoflip in canonical phytochromes, denaturation experiments showed conclusively that the same occurs in Synechococcus OS-B' phytochrome upon photoconversion. The results are consistent with the D-ring being strongly tilted in both states and the C15=C16 double bond undergoing a Z/E isomerization upon light absorption. More subtle changes are associated with the A-ring linkage to the protein. Our findings thus disprove A-ring rotation and are discussed in relation to the position of the D-ring, photoisomerization and photochromicity in the phytochrome family.
Shape plays an important role in defining the function of materials, particularly those found in nature. Several strategies exist to program materials to change from one shape to another; however, few can temporally and spatially control the shape. Programming the sequence of shape transformation with temporal control has been driven by the desire to generate complex shapes with high yield and to create multiple shapes from the same starting material. This paper demonstrates a markedly simple strategy for programmed self-folding of two-dimensional (2D) polymer sheets into 3D objects in a sequential manner using external light. Printed ink on the surface of the polymer sheets discriminately absorbs light on the basis of the wavelength of the light and the color of the ink that defines the hinge about which the sheet folds. The absorbed light gradually heats the underlying polymer across the thickness of the sheet, which causes relief of strain to induce folding. These color patterns can be designed to absorb only specific wavelengths of light (or to absorb differently at the same wavelength using color hues), thereby providing control of sheet folding with respect to time and space. This type of shape programming may have numerous applications, including reconfigurable electronics, actuators, sensors, implantable devices, smart packaging, and deployable structures.
The cleanup of accidental oil spills in water is an enormous challenge; conventional oil sorbents absorb large amounts of water in addition to oil and other cleanup methods can cause secondary pollution. In contrast, fresh leaves of the aquatic ferns Salvinia are superhydrophobic and superoleophilic, and can selectively absorb oil while repelling water. These selective wetting properties are optimal for natural oil absorbent applications and bioinspired oil sorbent materials. In this paper we quantify the oil absorption capacity of four Salvinia species with different surface structures, water lettuce (Pistia stratiotes) and Lotus leaves (Nelumbo nucifera), and compare their absorption capacity to artificial oil sorbents. Interestingly, the oil absorption capacities of Salvinia molesta and Pistia stratiotes leaves are comparable to artificial oil sorbents. Therefore, these pantropical invasive plants, often considered pests, qualify as environmentally friendly materials for oil spill cleanup. Furthermore, we investigated the influence of oil density and viscosity on the oil absorption, and examine how the presence and morphology of trichomes affect the amount of oil absorbed by their surfaces. Specifically, the influence of hair length and shape is analyzed by comparing different hair types ranging from single trichomes of Salvinia cucullata to complex eggbeater-shaped trichomes of Salvinia molesta to establish a basis for improving artificial bioinspired oil absorbents.
Semiconductor heterostructures provide a powerful platform to engineer the dynamics of excitons for fundamental and applied interests. However, the functionality of conventional semiconductor heterostructures is often limited by inefficient charge transfer across interfaces due to the interfacial imperfection caused by lattice mismatch. Here we demonstrate that MoS2/WS2 heterostructures consisting of monolayer MoS2 and WS2 stacked in the vertical direction can enable equally efficient interlayer exciton relaxation regardless the epitaxy and orientation of the stacking. This is manifested by a similar two orders of magnitude decrease of photoluminescence intensity in both epitaxial and non-epitaxial MoS2/WS2 heterostructures. Both heterostructures also show similarly improved absorption beyond the simple super-imposition of the absorptions of monolayer MoS2 and WS2. Our result indicates that 2D heterostructures bear significant implications for the development of photonic devices, in particular those requesting efficient exciton separation and strong light absorption, such as solar cells, photodetectors, modulators, and photocatalysts. It also suggests that the simple stacking of dissimilar 2D materials with random orientations is a viable strategy to fabricate complex functional 2D heterostructures, which would show similar optical functionality as the counterpart with perfect epitaxy.
Vertical arrays of ZnO nanowires can decouple light absorption from carrier collection in PbS quantum dot solar cells and increase power conversion efficiencies by 35%. The resulting ordered bulk heterojunction devices achieve short-circuit current densities in excess of 20 mA cm(-2) and efficiencies of up to 4.9%.
There is increasing interest in developing artificial systems that can mimic natural photosynthesis to directly harvest and convert solar energy into usable or storable energy resources. Photocatalysis, in which solar photons are used to drive redox reactions to produce chemical fuel, is the central process to achieve this goal. Despite significant efforts to date, a practically viable photocatalyst with sufficient efficiency, stability and low cost is yet to be demonstrated. It is often difficult to simultaneously achieve these different performance metrics with a single material component. The heterogeneous photocatalysts with multiple integrated functional components could combine the advantages of different components to overcome the drawbacks of single component photocatalysts. A wide range of heterostructures, including metal/semiconductor, semiconductor/semiconductor, molecule/semiconductor and multi-heteronanostructures, have been explored for improved photocatalysts by increasing the light absorption, promoting the charge separation and transportation, enhancing the redox catalytic activity and prolonging the functional life-time. The present review gives a concise overview of heterogeneous photocatalysts with a focus on the relationship between the structural architecture and the photocatalytic activity and stability.
We demonstrate series-integrated multijunction organic photovoltaics fabricated monolithically by vapor-deposition in a transposed subcell order with the near-infrared-absorbing subcell in front of the green-absorbing subcell. This transposed subcell order is enabled by the highly complementary absorption spectra of a near-infrared-absorbing visibly-transparent subcell and a visible-absorbing subcell and motivated by the non-spatially-uniform optical intensity in nanoscale photovoltaics. The subcell order and thicknesses are optimized via transfer-matrix formalism and short-circuit current simulations. An efficient charge recombination zone consisting of layers of BCP/Ag/MoOx leads to negligible voltage and series-resistance losses. Under 1-sun illumination the multijunction solar cells exhibit a power conversion efficiency of 5.5 ± 0.2% with an FF of 0.685 ± 0.002 and a V(OC) of 1.65 ± 0.02 V, corresponding to the sum of the V(OC) of the component subcells. These devices exhibit a broad spectral response (in the wavelength range of 350 nm to 850 nm) but are limited by subcell external quantum efficiencies between 20% and 30% over the photoactive spectrum.
A series of new bacteriochlorins was synthesized using 13(2)-oxo-bacteriopyropheophorbide a (derived from bacteriochlorophyll a) as a starting material, which on reacting with o-phenylenediamine and 1,10-diaminonaphthalene afforded highly conjugated annulated bacteriochlorins with fused quinoxaline, benzimidazole, and perimidine rings, respectively. The absorption spectra of these novel bacteriochlorins demonstrated remarkably red-shifted intense Q(y) absorption bands observed in the range of 816-850 nm with high molar extinction coefficients (89,900-136,800). Treatment of 13(2)-oxo-bacteriopyropheophorbide a methyl ester with diazomethane resulted in the formation of bacterioverdins containing a fused six-membered methoxy-substituted cyclohexenone (verdin) as an isomeric mixture. The pure isomers which exhibit long-wavelength absorptions in the near-IR region (865-890 nm) are highly stable at room temperature with high reactivity with O(2) at the triplet photoexcited state and favorable redox potential and could be potential candidates for use as photosensitizers in photodynamic therapy (PDT).
Anatase type nitrogen-fluorine (N-F) co-doped TiO2 nanobelts were successfully prepared by a solvothermal method, which amorphous titania microspheres were used as the precursors. The as-prepared TiO2 nanobelts are composed of thin narrow nanobelts, and it is noted that there are large amount of wormhole-like mesopores on these narrow nanobelts. Photocatalytic activity of the N-F co-doped TiO2 nanobelts was measured by the reaction of photocatalytic degradation of methyl orange. Results indicate that the photocatalytic activity of the N-F co-doped TiO2 nanobelts is higher than that of P25, which is mainly ascribed to wormhole-like mesopores like prison, larger surface area and enhanced absorption of light due to N-F co-doping. Interestingly, it is also found that the photocatalytic activity can be further enhanced when tested in a new testing method because more photons can be captured by the nanobelts to stimulate the formation of the hole-electron pair.