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Reduced-oxidation-state phosphorus (reduced P, hereafter) compounds were likely available on the early Earth via meteorites or through various geologic processes. Due to their reactivity and high solubility, these compounds could have played a significant role in the origin of various organophosphorus compounds of biochemical significance. In the present work, we study the reactions between reduced P compounds and their oxidation products, with the three nucleosides (uridine, adenosine, and cytidine), with organic alcohols (glycerol and ethanolamine), and with the tertiary ammonium organic compound, choline chloride. These reactions were studied in the non-aqueous solvent formamide and in a semi-aqueous solvent comprised of urea: ammonium formate: water (UAFW, hereafter) at temperatures of 55–68 °C. The inorganic P compounds generated through Fenton chemistry readily dissolve in the non-aqueous and semi-aqueous solvents and react with organics to form organophosphites and organophosphates, including those which are identified as phosphate diesters. This dual approach (1) use of non-aqueous and semi-aqueous solvents and (2) use of a reactive inorganic P source to promote phosphorylation and phosphonylation reactions of organics readily promoted anhydrous chemistry and condensation reactions, without requiring any additive, catalyst, or other promoting agent under mild heating conditions. We also present a comparative study of the release of P from various prebiotically relevant phosphate minerals and phosphite salts (e.g., vivianite, apatite, and phosphites of iron and calcium) into formamide and UAFW. These results have direct implications for the origin of biological P compounds from non-aqueous solvents of prebiotic provenance. [ABSTRACT FROM AUTHOR]

A good understanding of the processes of land surface temperature (LST) change is important for assessing regional climate change. In the present study, we obtained the MODIS MOD11A2 LST products over the Yangtze River Delta (YRD) from 2001 to 2020. In order to comprehensively assess the spatial and temporal variability of LST in the YRD region over the past two decades, the Theil–Sen Median trend analysis and Mann–Kendall test, BFAST01 trend decomposition, and landscape pattern analysis were used in this study. We show that the rate of linear change in LST in the YRD ranges from −0.019 °C/month to 0.046 °C/month. The BFAST01 trend decomposition identifies more details of LST change and monotonic increases, reversal increase, and interruption increase are the main warming trends. The distribution of the different trend types shows strong aggregation with high spatial heterogeneity. The LST breakpoints are mainly located in the northern and southern YRD, which frequently occurred during 2010–2013. Of the various land types, breakpoints occur most frequently in cropland and high NDVI (0.5–0.7) areas, and the intensity of most of them is within 2 °C. In addition, much stronger warming occurs in urban areas than in other land types. Our study provides a better understanding of the dynamics of LST in the YRD region over the past 20 years and highlights that breakpoints cannot be circumvented in regional temperature assessment. [ABSTRACT FROM AUTHOR]

The in-fall of meteorites and interstellar dust particles during the Hadean–Archean heavy bombardment may have provided the early Earth with various reduced oxidation state phosphorus compounds and minerals, including phosphite (HPO32−)([Pi(III)]). The ion phosphite ([Pi(III)])has been postulated to be ubiquitous on the early Earth and consequently could have played a role in the emergence of organophosphorus compounds and other prebiotically relevant P species such as condensed P compounds, e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)]). In the present study, we show that phosphite ([Pi(III)]) oxidizes under mild heating conditions (e.g., wet–dry cycles and a prebiotic scenario mimicking a mildly hot-evaporating/drying pool on the early Earth at 78–83 °C) in the presence of urea and other additives, resulting in changes to orthophosphate ([Pi(V)]) alongside the formation of reactive condensed P compounds (e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)])) through a one-pot mechanism. Additionally, we also show that phosphite ([Pi(III)]) and the condensed P compounds readily react with organics (nucleosides and organic alcohol) to form organophosphorus compounds. [ABSTRACT FROM AUTHOR]

Simple Summary: Phosphorus (P) is essential to life in the form of various phosphate esters that make up DNA, RNA and other cellular structures. It mainly exists in the form of phosphate. However, other reduced-oxidation-state P compounds have also been found in natural waters, in living organisms, and in natural glasses formed by lightning called fulgurites. Iron meteorites often bear a P mineral, schreibersite, which corrodes in water to produce various P species including reduced-oxidation-state compounds such as phosphite. This form of natural P is reactive and unstable as ultimately the phosphides and phosphites convert into phosphate, the most stable form of P on an oxidizing world. Previous analyses of 3.5 billion rocks identified various P species including phosphite revealing that phosphite was present on the early Earth and, despite its reactivity, it was stable under geologic timescales. In the present communication, we present the analyses of a meteoritic sample, the pallasite Seymchan, which is rich in the mineral schreibersite and was allowed to corrode for eight years in water. At room temperature, the schreibersite corroded in water to give P species including phosphate and phosphite. These results indicate that phosphite is not an ephemeral species and it is stable enough to be detected in multiple environments. In-fall of extraterrestrial material including meteorites and interstellar dust particles during the late heavy bombardment are known to have brought substantial amounts of reduced oxidation-state phosphorus to the early Earth in the form of siderophilic minerals, e.g., schreibersite ((FeNi)3P). In this report, we present results on the reaction of meteoritic phosphide minerals in the Seymchan meteorite in ultrapure water for 8 years. The ions produced during schreibersite corrosion (phosphite, hypophosphate, pyrophosphate, and phosphate) are stable and persistent in aqueous solution over this timescale. These results were also compared with the short-term corrosion reactions of the meteoritic mineral schreibersite's synthetic analog Fe3P in aqueous and non-aqueous solutions (ultrapure water and formamide). This finding suggests that the reduced-oxidation-state phosphorus (P) compounds including phosphite could be ubiquitous and stable on the early Earth over a long span of time and such compounds could be readily available on the early Earth. [ABSTRACT FROM AUTHOR]

Background: Patients with rectal cancer can prospectively be favored for neoadjuvant concurrent chemoradiotherapy (CCRT) to downstage before a radical proctectomy, but the risk stratification and clinical outcomes remain disappointing. Methods: From a published rectal cancer transcriptome dataset (GSE35452), we highlighted extracellular matrix (ECM)-linked genes and identified the serine protease inhibitor Kazal-type 4 (SPINK4) gene as the most relevant among the top 10 differentially expressed genes associated with CCRT resistance. We accumulated the cases of 172 rectal cancer patients who received neoadjuvant CCRT followed by surgery and collected tumor specimens for the evaluation of the expression of SPINK4 using immunohistochemistry. Results: The results revealed that high SPINK4 immunoexpression was significantly related to advanced pre-CCRT and post-CCRT tumor status (both p < 0.001), post-CCRT lymph node metastasis (p = 0.001), more vascular and perineurial invasion (p = 0.015 and p = 0.023), and a lower degree of tumor regression (p = 0.001). In univariate analyses, high SPINK4 immunoexpression was remarkably correlated with worse disease-specific survival (DSS) (p < 0.0001), local recurrence-free survival (LRFS) (p = 0.0017), and metastasis-free survival (MeFS) (p < 0.0001). Furthermore, in multivariate analyses, high SPINK4 immunoexpression remained independently prognostic of inferior DSS and MeFS (p = 0.004 and p = 0.002). Conclusion: These results imply that high SPINK4 expression is associated with advanced clinicopathological features and a poor therapeutic response among rectal cancer patients undergoing CCRT, thus validating the prospective prognostic value of SPINK4 for those patients. [ABSTRACT FROM AUTHOR]

Objectives: Mesenchymal stem cells (MSCs) are potential effective therapy for tissue repair and bone regeneration. In present study, the effects of CXC chemokine ligand-13 (CXCL13) were evaluated on tendon-bone healing of rats. Methods: Tendon bone healing of the rat model was established and biomechanical testing was performed at 2, 4, 8 weeks after surgery. Murine mesenchymal cell line (C3HIOT1/2 cells) was cultured. The expression of miRNA-23a was detected by real-time PCR. The protein expression of ERK1/2, JNK and p38 was detected by western blotting. MiR-23a mimic and inhibitor were used to overexpress or silence the expression of miR-23a. Results: MSCs significantly elevated the levels of ultimate load to failure, stiffness and stress in specimens of rats, the effects of which were enhanced by CXCL13. The expression of miR-23a was down-regulated and the protein of ERK1/2 level was up-regulated by CXCL13 treatment in both in vivo and in vitro experiments. ERK1/2 expression was elevated by overexpression of miR-23a and reduced by miR-23a inhibitor. Conclusions: These findings revealed that CXCL13 promoted the tendon-bone healing in rats with MSCs treatment, and implied that the activation of ERK1/2 via miR-23a was involved in the process of MSCs treated bone regeneration. [ABSTRACT FROM AUTHOR]

miR-155 plays a crucial role in proinflammatory activation. This study was carried out to assess the association of abnormal expression of miR-155 in peripheral blood of patients with Rheumatoid arthritis with the expression of TNF-ɑ and IL-1β. Release of TNF-ɑ and IL-1β, and expression of miR-155 were determined in RA peripheral blood or peripheral blood macrophages, followed by correlation analysis of the cytokines release and miR-155 expression. Furthermore, in vitro studies indicate that miR-155 inhibited the expression of SOCS1. Our results suggest that there is a correlation between the high-level expression of miR-155 and the enhanced expression of TNF-ɑ and IL-1β. miR-155 targets and suppresses the expression of SOCS1, and the decrease of SOCS1 may lead to the upregulation of TNF-ɑ and IL-1β. [ABSTRACT FROM AUTHOR]

The increasingly intensive and extensive coal mining activities on the Loess Plateau pose a threat to the fragile local ecosystems. Quantifying the effects of coal mining activities on environmental conditions is of great interest for restoring and managing the local ecosystems and resources. This paper generates dense NDVI (Normalized Difference Vegetation Index) time series between 2000 and 2011 at a spatial resolution of 30 m by blending Landsat and MODIS (Moderate Resolution Imaging Spectroradiometer) data using the Spatial and Temporal Adaptive Reflectance Fusion Model (STARFM) and further evaluates its capability for mapping vegetation trends around a typical coalfield on the Loss Plateau. Synthetic NDVI images were generated using (1) STARFM-generated NIR (near infrared) and red band reflectance data (scheme 1) and (2) Landsat and MODIS NDVI images directly as inputs for STARFM (scheme 2). By comparing the synthetic NDVI images with the corresponding Landsat NDVI, we found that scheme 2 consistently generated better results (0.70 < R² < 0.76) than scheme 1 (0.56 < R² < 0.70) in this study area. Trend analysis was then performed with the synthetic dense NDVI time series and the annual maximum NDVI (NDVImax) time series. The accuracy of these trends was evaluated by comparing to those from the corresponding MODIS time series, and it was concluded that both the trends from synthetic/MODIS NDVI dense time series and synthetic/MODIS NDVImax time series (2000-2011) were highly consistent. Compared to trends from MODIS time series, trends from synthetic time series are better able to capture fine scale vegetation changes. STARFM-generated synthetic NDVI time series could be used to quantify the effects of mining activities on vegetation, but the test areas should be selected with caution, as the trends derived from synthetic and MODIS time series may be significantly different in some areas. [ABSTRACT FROM AUTHOR]

Iron silicide minerals (Fe-Si group) are found in terrestrial and solar system samples. These minerals tend to be more common in extraterrestrial rocks such as meteorites, and their existence in terrestrial rocks is limited due to a requirement of extremely reducing conditions to promote their formation. Such extremely reducing conditions can be found in fulgurites, which are glasses formed as cloud-to-ground lightning heats and fuses sand, soil, or rock. The objective of this paper is to review reports of iron silicides in fulgurites, note any similarities between separate fulgurite observations, and to explain the core connection between geological environments wherein these minerals are found. In addition, we also compare iron silicides in fulgurites to those in extraterrestrial samples. [ABSTRACT FROM AUTHOR]

Background: Concerning the judgments bias and cue utilization in basketball athletes, previous shot anticipation tasks were hard to examine in regards to whether the experts' judgement bias relies more on the cue of the player's body or the ball trajectory. Methods: Four types of body–ball cues shots were employed: IN–IN, IN–OUT, OUT–IN, and OUT–OUT. Four temporal stages (i.e., shooting, rising, high point, and falling) were divided during a shot. Forty-two participants predicted the fate of the ball after watching the shot videos. Results: The results suggested that for the shooting, rising, and high point phase, compared to the non-athletes, the experts provided superior predictions for IN–IN condition and OUT–IN condition but fewer accurate predictions for IN–OUT condition and OUT–OUT condition. Moreover, a higher bias toward predicting the shots as "in" for the athletes than the non-athletes under early temporal conditions was confirmed. Conclusions: These findings strengthen the idea that the IN cues from both body information and ball trajectory could elicit the experts' judgement bias for made shots and then influence their response, thus rendered two distinct (e.g., impeding and facilitating) effects for the incongruent body–ball cues, respectively. [ABSTRACT FROM AUTHOR]

The formose reaction is a plausible prebiotic chemistry, famed for its production of sugars. In this work, we demonstrate that the Cannizzaro process is the dominant process in the formose reaction under many different conditions, thus necessitating a catalyst for the formose reaction under various environmental circumstances. The investigated formose reactions produce primarily organic acids associated with metabolism, a protometabolic system, and yield very little sugar left over. This is due to many of the acids forming from the degradation and Cannizaro reactions of many of the sugars produced during the formose reaction. We also show the heterogeneous Lewis-acid-based catalysis of the formose reaction by mineral systems associated with serpentinization. The minerals that showed catalytic activity include olivine, serpentinite, and calcium, and magnesium minerals including dolomite, calcite, and our Ca/Mg-chemical gardens. In addition, computational studies were performed for the first step of the formose reaction to investigate the reaction of formaldehyde, to either form methanol and formic acid under a Cannizzaro reaction or to react to form glycolaldehyde. Here, we postulate that serpentinization is therefore the startup process necessary to kick off a simple proto metabolic system—the formose protometabolic system. [ABSTRACT FROM AUTHOR]

Life is a complex, open chemical system that must be supported with energy inputs. If one fathoms how simple early life must have been, the complexity of modern-day life is staggering by comparison. A minimally complex system that could plausibly provide pyrophosphates for early life could be the oxidation of reduced phosphorus sources such as hypophosphite and phosphite. Like all plausible prebiotic chemistries, this system would have been altered by minerals and rocks in close contact with the evolving solutions. This study addresses the different types of perturbations that minerals might have on this chemical system. This study finds that minerals may inhibit the total production of oxidized phosphorus from reduced phosphorus species, they may facilitate the production of phosphate, or they may facilitate the production of pyrophosphate. This study concludes with the idea that mineral perturbations from the environment increase the chemical complexity of this system. [ABSTRACT FROM AUTHOR]

The availability of nucleotides on the early Earth is of great significance for the origin of a self-replicating system capable of undergoing evolution. We hereby report the successful phosphorylation reactions of the nucleoside uridine under heating in the "drying pool" prebiotic model at temperatures ranging from 60–75 °C, and by using pyrophosphate as a phosphorylation agent. Uridine monophosphates (UMP) such as uridine-5′-monophosphate (5′-UMP), 2′-UMP, and 3′-UMP, as well as cyclic 2′-3′-UMP, were identified by 31P-NMR. In addition to the above-mentioned products, a dimer of uridine-phosphate-uridine (U-P-U) was also observed. The reactions were promoted by white quartz sand, Mg2+, and by using urea as a condensation agent. The reactions also proceeded without this mixture; however, the yields increased remarkably with the presence of the above-mentioned materials. The results suggest that a hot/evaporating-drying pool of water containing organics, salts, and reactive phosphorus could be sufficient to form significant phosphate esters. [ABSTRACT FROM AUTHOR]

Central Asia comprises a large fraction of the world's drylands, known to be vulnerable to climate change. We analyzed the inter-annual trends and the impact of climate variability in the vegetation greenness for Central Asia from 1982 to 2011 using GIMMS3g normalized difference vegetation index (NDVI) data. In our study, most areas showed an increasing trend during 1982-1991, but experienced a significantly decreasing trend for 1992-2011. Vegetation changes were closely coupled to climate variables (precipitation and temperature) during 1982-1991 and 1992-2011, but the response trajectories differed between these two periods. The warming trend in Central Asia initially enhanced the vegetation greenness before 1991, but the continued warming trend subsequently became a suppressant of further gains in greenness afterwards. Precipitation expanded its influence on larger vegetated areas in 1992-2011 when compared to 1982-1991. Moreover, the time-lag response of plants to rainfall tended to increase after 1992 compared to the pre-1992 period, indicating that plants might have experienced functional transformations to adapt the climate change during the study period. The impact of climate on vegetation was significantly different for the different sub-regions before and after 1992, coinciding with the collapse of the Union of Soviet Socialist Republics (USSR). It was suggested that these spatio-temporal patterns in greenness change and their relationship with climate change for some regions could be explained by the changes in the socio-economic structure resulted from the USSR collapse in late 1991. Our results clearly illustrate the combined influence of climatic/anthropogenic contributions on vegetation growth in Central Asian drylands. Due to the USSR collapse, this region represents a unique case study of the vegetation response to climate changes under different climatic and socio-economic conditions. [ABSTRACT FROM AUTHOR]