Soil system budgets of N,Si and P in an agricultural irrigated watershed: surplus,differential export and underlying mechanisms

Ongoing socio-economic and climatic changes can differentially affect the biogeochemistry of the key nutrients nitrogen (N), silica (Si), and phosphorus (P) by altering their soil budgets, their transfer to aquatic environments and their ecological stoichiometry. This may lead to cascade consequences for aquatic communities and biogeochemical processes. Soil budgets, river export, and N, Si, and P ecological stoichiometry were assessed in a heavy impacted basin (Mincio River, Italy) in two decades (1991–2000; 2001–2010). The main aim was to analyse element-specific mechanisms of terrestrial-aquatic transport and retention within aquatic habitats. Budget results suggest a net accumulation (inputs exceeding outputs) of all nutrients in agricultural lands, mainly due to livestock manure, with a reduction for N (196 kg N ha^?1 year^?1 in 2000, and 132 kg N ha^?1 year^?1 in 2010), and constant values for Si (up to 3 kg Si ha^?1 year^?1) and P (43 kg P ha^?1 year^?1) along the study period. River export of N and P accounted for 3–27% and?~?2% of N and P soil net accumulation, respectively, while Si export was significantly greater (25 kg Si ha^?1 year^?1) than Si net accumulation on farmlands. The stoichiometry of net nutrient accumulation in soils was not reflected by the stoichiometry of nutrient riverine export, due to element-specific mechanisms. We speculate that N and Si vertical and horizontal mobilization is increased by the irrigation loop, while P retention is favored by limited erosion due to limited slopes in the Mincio River basin. The simultaneous analysis of N, Si and P allows us to better understand the different paths, transformation and retention mechanisms at the watershed scale.     

A computational investigation on the antioxidant potential of myricetin 3,4′-di-<Emphasis Type="Italic">O</Emphasis>-<Emphasis Type="Italic">α</Emphasis>-<Emphasis Type="Italic">L</Emphasis>-rhamnopyranoside

In this work, we present a computational study on the antioxidant potential of myricetin 3,4\(^{\prime }\)-di-O-α-L-rhamnopyranoside (Compound M). A density functional theory (DFT) approach with the B3LYP and LC-ωPBE functionals and with both the 6-311G(d,p) and 6-311+G(d,p) basis sets was used. The focus of the investigation was on the structural and energetic parameters including both bond dissociation enthalpies (BDEs) and ionization potentials (IPs), which provide information on the potential antioxidant activity. The properties computed were compared with BDEs and IPs available in the literature for myricetin, a compound well known for presenting antioxidant activity (and the parent molecule of the compound of interest in the present work). Myricetin 3,4\(^{\prime }\)-di-O-α-L-rhamnopyranoside presented the lowest BDE to be 79.13 kcal/mol (as determined using B3LYP/6-311G(d,p) in water) while myricetin has a quite similar value (within 3.4 kcal/mol). IPs computed in the gas phase [B3LYP/6-311G(d,p)] are 157.18 and 161.4 kcal/mol for myricetin 3,4\(^{\prime }\)-di-O-α-L-rhamnopyranoside and myricetin, respectively. As the values of BDEs are considerably lower than the ones probed for IPs (in the gas phase or in any given solvent environment), the hydrogen atom transfer mechanism is preferred over the single electron transfer mechanism. The BDEs obtained suggest that myricetin 3,4\(^{\prime }\)-di-O-α-L-rhamnopyranoside can present antioxidant potential as good as the parent molecule myricetin (a well-known antioxidant). Therefore, experimental tests on the antioxidant activity of Compound M are encouraged.     

Mapping Nonfullerene Acceptors with a Novel Wide Bandgap Polymer for High Performance Polymer Solar Cells

A new weak electron‐deficient building block, bis(2‐ethylhexyl) 2,5‐bis(5‐bromothiophen‐2‐yl) thieno[3,2‐b]thiophene‐3,6‐dicarboxylate ( TT‐Th ), is incorporated to construct a wide‐bandgap (1.88 eV) polymer PBDT‐TT for nonfullerene polymer solar cells (NF‐PSCs). PBDT‐TT possesses suitable energy levels and complementary absorption when blended with both ITIC analogues ( ITIC and IT‐M ) and a near‐infrared (NIR) acceptor ( 6TIC ). Moreover, PBDT‐TT exhibits good conjugated planarity and preferable face‐on orientation in the blended thin film, which are beneficial for charge transfer and carrier transport. The PSCs based on PBDT‐TT : IT‐M and PBDT‐TT : 6TIC blend films yield high power conversion efficiencies of 11.38% and 11.03%, respectively. To the best of the authors' knowledge, the PCE of 11.03% for PBDT‐TT : 6TIC‐ based device is one of the highest values reported for NIR NF‐PSCs. This work demonstrates that TT‐Th is a useful new electron‐accepting building block for making p‐type wide bandgap polymers for efficient NIR NF‐PSCs.     

Inorganic CsPb1−xSnxIBr2 for Efficient Wide‐Bandgap Perovskite Solar Cells

Recently, the stability of organic–inorganic perovskite thin films under thermal, photo, and moisture stresses has become a major concern for further commercialization due to the high volatility of the organic cations in the prototype perovskite composition (CH₃NH₃PbI₃). All inorganic cesium (Cs) based perovskite is an alternative to avoid the release or decomposition of organic cations. Moreover, substituting Pb with Sn in the organic–inorganic lead halide perovskites has been demonstrated to narrow the bandgap to 1.2–1.4 eV for high‐performance perovskite solar cells. In this work, a series of CsPb_1?xSn_xIBr₂ perovskite alloys via one‐step antisolvent method is demonstrated. These perovskite films present tunable bandgaps from 2.04 to 1.64 eV. Consequently, the CsPb_0.75Sn_0.25IBr₂ with homogeneous and densely crystallized morphology shows a remarkable power conversion efficiency of 11.53% and a high V_oc of 1.21 V with a much improved phase stability and illumination stability. This work provides a possibility for designing and synthesizing novel inorganic halide perovskites as the next generation of photovoltaic materials.     

Terthieno[3,2‐b]Thiophene (6T) Based Low Bandgap Fused‐Ring Electron Acceptor for Highly Efficient Solar Cells with a High Short‐Circuit Current Density and Low Open‐Circuit Voltage Loss

A terthieno[3,2‐b]thiophene ( 6T ) based fused‐ring low bandgap electron acceptor, 6TIC , is designed and synthesized for highly efficient nonfullerene solar cells. The chemical, optical, and physical properties, device characteristics, and film morphology of 6TIC are intensively studied. 6TIC shows a narrow bandgap with band edge reaching 905 nm due to the electron‐rich π‐conjugated 6T core and reduced resonance stabilization energy. The rigid, π‐conjugated 6T also offers lower reorganization energy to facilitate very low V_OC loss in the 6TIC system. The analysis of film morphology shows that PTB7‐Th and 6TIC can form crystalline domains and a bicontinuous network. These domains are enlarged when thermal annealing is applied. Consequently, the device based on PTB7‐Th : 6TIC exhibits a high power conversion efficiency (PCE) of 11.07% with a high J_SC > 20 mA cm^?2 and a high V_OC of 0.83 V with a relatively low V_OC loss (≈0.55 V). Moreover, a semitransparent solar cell based on PTB7‐Th : 6TIC exhibits a relatively high PCE (7.62%). The device can have combined high PCE and high J_SC is quite rare for organic solar cells.     

Friends without benefits: When we react negatively to helpful and generous friends

Being able to identify reliable friends and allies is key to surviving and thriving in the social world. Many cooperative accounts of friendship argue that people select friends based on how helpful and generous they are. While people certainly like helpful and generous others, here we explore a context in which people might respond negatively to a friend being prosocial: When one's friend is more helpful or generous toward another friend. We argue that such preferential prosociality prompts negative reactions, even when the alternative is a friend being less prosocial overall, because giving preferentially to another friend may be viewed as a threat of potential displacement of one's own friendship. In four studies (N?=?702), we predict and find that people respond negatively to a friend who was more helpful (Studies 1–2) and generous (Studies 3–4), preferring instead that a friend be less helpful and generous overall. Importantly, this preferential prosociality was viewed as particularly negative when the recipient was another friend and was seen as much less negative when the recipient was a relative (Study 1 and 4) or a romantic partner (Study 2). We discuss the implications of these results for cooperation and alliance-based accounts of friendship.     

Ten years of forest restoration in the Upwey Corridor,Dandenong Ranges,Victoria

The Upwey Corridor Biodiversity Project has seen substantial investment by agencies and in‐kind voluntary work by the community over a ten year period. Comparison of Habitat Hectare scores prior to the project and after ten years showed that significant improvement in ecological condition of weed‐degraded areas is possible given adequate investment, appropriate re‐treatment and continuous management.