Assessing Spatial Representativeness of Global Flux Tower Eddy-Covariance Measurements Using Data from FLUXNET2015.

Large datasets of carbon dioxide, energy, and water fluxes were measured with the eddy-covariance (EC) technique, such as FLUXNET2015. These datasets are widely used to validate remote-sensing products and benchmark models. One of the major challenges in utilizing EC-flux data is determining the spatial extent to which measurements taken at individual EC towers reflect model-grid or remote sensing pixels. To minimize the potential biases caused by the footprint-to-target area mismatch, it is important to use flux datasets with awareness of the footprint. This study analyze the spatial representativeness of global EC measurements based on the open-source FLUXNET2015 data, using the published flux footprint model (SAFE-f). The calculated annual cumulative footprint climatology (ACFC) was overlaid on land cover and vegetation index maps to create a spatial representativeness dataset of global flux towers. The dataset includes the following components: (1) the ACFC contour (ACFCC) data and areas representing 50%, 60%, 70%, and 80% ACFCC of each site, (2) the proportion of each land cover type weighted by the 80% ACFC (ACFCW), (3) the semivariogram calculated using Normalized Difference Vegetation Index (NDVI) considering the 80% ACFCW, and (4) the sensor location bias (SLB) between the 80% ACFCW and designated areas (e.g. 80% ACFCC and window sizes) proxied by NDVI. Finally, we conducted a comprehensive evaluation of the representativeness of each site from three aspects: (1) the underlying surface cover, (2) the semivariogram, and (3) the SLB between 80% ACFCW and 80% ACFCC, and categorized them into 3 levels. The goal of creating this dataset is to provide data quality guidance for international researchers to effectively utilize the FLUXNET2015 dataset in the future.

Rapid Loss of Tidal Flats in the Yangtze River Delta since 1974.

As the home to national nature reserves and a Ramsar wetland, the tidal flats of the Yangtze River Delta are of great significance for ecological security, at both the local and global scales. However, a comprehensive understanding of the spatiotemporal conditions of the tidal flats in the Yangtze River Delta remains lacking. Here, we propose using remote sensing to obtain a detailed spatiotemporal profile of the tidal flats, using all available Landsat images from 1974 to 2018 with the help of the Google Earth Engine cloud platform. In addition, reclamation data were manually extracted from time series Landsat images for the same period. We found that approximately 40.0% (34.9-43.1%) of the tidal flats in the study area have been lost since 1980, the year in which the tidal flat area was maximal. The change in the tidal flat areas was consistent with the change in the riverine sediment supply. We also found that the cumulative reclamation areas totaled 816.6 km2 and 431.9 km2 in the Yangtze estuary zone and along the Jiangsu coast, respectively, between 1974 and 2018. Because of reclamation, some areas (e.g., the Hengsha eastern shoal and Pudong bank), which used to be quite rich, have lost most of their tidal flats. Currently, almost 70% of the remaining tidal flats are located in the shrinking branch (North Branch) and the two National Nature Reserves (Chongming Dongtan and Jiuduansha) in the Yangtze estuary zone. Consequently, the large-scale loss of tidal flats observed was primarily associated with reduced sediment supply and land reclamation at the time scale of the study. Because increasing demand for land and rising sea levels are expected in the future, immediate steps should be taken to prevent the further deterioration of this valuable ecosystem.

Asymmetric Synthesis of the Antiviral Diterpene Wickerol A.

Wickerol A (1) is an unusual diterpene with remarkable activity against the H1N1 influenza virus. Its tetracyclic skeleton contains three quaternary carbons and is marked by several syn-pentane interactions which force a six-membered ring into a twist-boat conformation. We present an asymmetric synthesis of wickerol A (1) that is based on a Jung Diels-Alder reaction, an intramolecular alkylation to complete the 6-5-6-6 ring system, and a conjugate addition, all of which overcome considerable steric strain. During the synthesis, we isolated an unexpected cyclopropane that presumably stems from a carbonium ion intermediate.

Optical control of AMPA receptors using a photoswitchable quinoxaline-2,3-dione antagonist.

AMPA receptors respond to the neurotransmitter glutamate and play a critical role in excitatory neurotransmission. They have been implicated in several psychiatric disorders and have rich pharmacology. Antagonists of AMPA receptors have been explored as drugs and one has even reached the clinic. We now introduce a freely diffusible photoswitchable antagonist that is selective for AMPA receptors and endows them with light-sensitivity. Our photoswitch, ShuBQX-3, is active in its dark-adapted trans-isoform but is significantly less active as its cis-isoform. ShuBQX-3 exhibits a remarkable red-shifting of its photoswitching properties through interactions with the AMPA receptor ligand binding site. Since it can be used to control action potential firing with light, it could emerge as a powerful tool for studying synaptic transmission with high spatial and temporal precision.

Pt(IV) complexes as prodrugs for cisplatin.

The antitumor effects of platinum(IV) complexes, considered prodrugs for cisplatin, are believed to be due to biological reduction of Pt(IV) to Pt(II), with the reduction products binding to DNA and other cellular targets. In this work we used pBR322 DNA to capture the products of reduction of oxoplatin, c,t,c-[PtCl(2)(OH)(2)(NH(3))(2)], 3, and a carboxylate-modified analog, c,t,c-[PtCl(2)(OH)(O(2)CCH(2)CH(2)CO(2)H)(NH(3))(2)], 4, by ascorbic acid (AsA) or glutathione (GSH). Since carbonate plays a significant role in the speciation of platinum complexes in solution, we also investigated the effects of carbonate on the reduction/DNA-binding process. In pH 7.4 buffer in the absence of carbonate, both 3 and 4 are reduced by AsA to cisplatin (confirmed using ((195))Pt NMR), which binds to and unwinds closed circular DNA in a manner consistent with the formation of the well-known 1, 2 intrastrand DNA crosslink. However, when GSH is used as the reducing agent for 3 and 4, ((195))Pt NMR shows that cisplatin is not produced in the reaction medium. Although the Pt(II) products bind to closed circular DNA, their effect on the mobility of Form I DNA is different from that produced by cisplatin. When physiological carbonate is present in the reduction medium, ((13))C NMR shows that Pt(II) carbonato complexes form which block or impede platinum binding to DNA. The results of the study vis-à-vis the ability of the Pt(IV) complexes to act as prodrugs for cisplatin are discussed.