Nitrite (NO 2 − ) and its conjugate acid, nitrous acid (HNO 2 ), have long been recognized as a ubiquitous atmospheric pollutant as well as an important photochemical source of hydroxyl radicals (•OH) and reactive nitrogen species (•NO, • NO 2 , •N 2 O 3 , etc.) in both the gas phase and aqueous phase. Although NO 2 − /HNO 2 plays an important role in atmospheric chemistry, our understanding on its role in the chemical evolution of organic components in atmospheric waters is rather incomplete and is still in dispute. In this study, the nitrite-mediated photooxidation of vanillin (VL), a phenolic compound abundant in biomass burning emissions, was investigated under pH conditions relevant for atmospheric waters. The influence of solution pH, dissolved oxygen, and •OH scavengers on the nitrite-mediated photooxidation of VL was discussed in detail. Our study reveals that the molecular composition of the products is dependent on the molar ratio of NO 2 − /VL in the solution and that nitrophenols are the major reaction products. We also found that the light absorbance of the oxidative products increases with increasing pH in the visible region, which can be attributed to the deprotonation of the nitrophenols formed. These results contribute to a better understanding of methoxyphenol photooxidation mediated by nitrite as a source of toxic nitrophenols and climatically important brown carbon in atmospheric waters.

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Intervertebral disc (IVD) degeneration and trauma is a major socio-economic burden and the focus of cell-based regenerative medicine approaches. Despite numerous ongoing clinical trials attempting to replace ailing IVD cells with mesenchymal stem cells, a solid understanding of the identity and nature of cells in a healthy mature IVD is still in need of refinement. Although anatomically simple, the IVD is comprised of heterogeneous cell populations. Therefore, methods involving cell pooling for RNA profiling could be misleading. Here, by using RNA in situ hybridization and z proportion test, we have identified potential novel biomarkers through single cell assessment. We quantified the proportion of RNA transcribing cells for 50 genetic loci in the outer annulus fibrosus (AF) and nucleus pulposus (NP) in coccygeal bovine discs isolated from tails of four skeletally mature animals. Our data reconfirm existing data and suggest 10 novel markers such as Lam1 and Thy1 in the outer AF and Gli1, Gli3, Noto, Scx, Ptprc, Sox2, Zscan10 and LOC101904175 in the NP, including pluripotency markers, that indicate stemness potential of IVD cells. These markers could be added to existing biomarker panels for cell type characterization. Furthermore, our data once more demonstrate heterogeneity in cells of the AF and NP, indicating the need for single cell assessment by methods such as RNA in situ hybridization. Our work refines the molecular identity of outer AF and NP cells, which can benefit future regenerative medicine and tissue engineering strategies in humans.

Fe(III)−oxalate complexes are likely abundant in clouds, fogs and aerosol water. They are photoreactive and can act as an important source of reactive oxygen species ( • OH, H 2 O 2 and HO 2 •) in tropospheric aqueous phases. Although the mechanisms involved in ferrioxalate photolysis have been investigated extensively, few kinetic and mechanistic information is available on the aging of dissolved organic compounds by this photochemical system. In this work, the Fe(III)−oxalate mediated photooxidation of guaiacol (GUA), a model for phenolic compounds emitted from biomass burning, was investigated under typical pH conditions of the atmospheric water. The effect of Fe(III) concentration, oxalate concentration and pH on the photooxidation of GUA was studied in detail. Our results revealed that oxalate can inhibit the oxidation of GUA by Fe(III) under the dark condition. However, the iron-catalyzed photooxidation of GUA can be strongly promoted in the presence of oxalate due to the formation of photoactive Fe(III)−oxalate complexes. GUA was rapidly oxidized to form a number of polymeric, functionalized and open-ring products with low volatility. Detailed reaction pathways for the photooxidation of GUA by Fe(III)−oxalate complexes were proposed based on the results of high-resolution mass spectrometry. This work suggests that ferrioxalate photochemistry can play an important role in the transformation of dissolved organics in atmospheric aqueous phases.

Anthocyanins are important components in skins of red table grapes and contribute to the berries appearance, a key quality characteristic for customers. In recent years, exogenous foliage fertilizers has been applied to grapevines to improve the pigmentation of the fruit. The present study examines the effect on a biostimulant (SUNRED) pre- véraison application in the accumulation of anthocyanins in ‘Red Globe’ grapes, and investigates the related changes in expression of key genes and their enzyme activities in the flavonoid pathways. Additionally, abscisic acid (S-ABA) was also applied to grapevines to evaluate the comparative effect of SUNRED. Our analyses showed that total anthocyanin contents increased in both SUNRED and S-ABA treated grapes; for S-ABA, a 1% dilution (A100) of the commercially available stock solution treatments represented the greatest effect on pigmentation; for SUNRED, a 0.1% dilution (S1000) was most effective. The anthocyanin contents increased by 1.16-fold and 1.4-fold after A100 and S1000 treatments, respectively. The gene expression analyses showed that almost all genes involved in the anthocyanin biosynthesis pathway up-regulated after A100 and S1000 treatments, suggesting that the increment in total anthocyanin content was attributed to the increased expression level of related genes. Moreover, the activities of phenylalanine ammonia-lyase (PAL), chalcone isomerase (CHI), UDP glucose: flavonoid 3-o-glucosyl transferase (UFGT) and dihydroflavonol 4-reductase (DFR), key enzymes for biosynthesis of anthocyanin, were increased by the exogenous treatments. Overall, our findings clearly demonstrate that application of exogenous biostimulant have a positive effect on the pigment characteristics of grape crop.

The performances of satellite-to-ground downlink optical communications over Gamma-Gamma distributed atmospheric turbulence are studied for a coherent detection receiving system with spatial diversity. Maximum ratio combining (MRC) and selection combining (SC) techniques are considered as practical schemes to mitigate the atmospheric turbulence. Bit-error rate (BER) performances for binary phase-shift keying modulated coherent detection and outage probabilities are analyzed and compared for SC diversity using analytical results and for MRC diversity through an approximation method with different numbers of receiving aperture each with the same aperture area. To show the net diversity gain of a multiple aperture receiver system, BER performances and outage probabilities of MRC and SC multiple aperture receiver systems are compared with a single monolithic aperture with the same total aperture area (same total average incident optical power) for satellite-to-ground downlink optical communications. All the numerical results are verified by Monte-Carlo simulations.

A novel palladium‐catalyzed approach to direct C‐3‐arylation of 1H‐indoles with arylhydrazines using air as the oxidant via CN bond cleavage has been developed. Various substituents are tolerated in this system in moderate to good yields. This reaction could also be compatible with a larger scale. Thus, this strategy using arylhydrazines as arylating reagents provides a powerful method for constructing substituted 3‐aryl‐1H‐indoles.

Despite the importance of high-resolution population distribution in urban planning, disaster prevention and response, region economic development, and improvement of urban habitant environment, traditional urban investigations mainly focused on large-scale population spatialization by using coarse-resolution nighttime light (NTL) while few efforts were made to fine-resolution population mapping. To address problems of generating small-scale population distribution, this paper proposed a method based on the Random Forest Regression model to spatialize a 25 m population from the International Space Station (ISS) photography and urban function zones generated from social sensing data—point-of-interest (POI). There were three main steps, namely HSL (hue saturation lightness) transformation and saturation calibration of ISS, generating functional-zone maps based on point-of-interest, and spatializing population based on the Random Forest model. After accuracy assessments by comparing with WorldPop, the proposed method was validated as a qualified method to generate fine-resolution population spatial maps. In the discussion, this paper suggested that without help of auxiliary data, NTL cannot be directly employed as a population indicator at small scale. The Variable Importance Measure of the RF model confirmed the correlation between features and population and further demonstrated that urban functions performed better than LULC (Land Use and Land Cover) in small-scale population mapping. Urban height was also shown to improve the performance of population disaggregation due to its compensation of building volume. To sum up, this proposed method showed great potential to disaggregate fine-resolution population and other urban socio-economic attributes.