Dissolved polycyclic aromatic hydrocarbons (PAHs-d) in response to hydrology variation and anthropogenic activities in the Yangtze River, China.

Owing to their bioavailability and toxicity, the dissolved polycyclic aromatic hydrocarbons (PAHs-d) loaded in rivers are harmful to both inland and marine ecosystems. Thus, exploring the changes in PAHs-d levels and sources is important for controlling PAHs pollution. In this study, the concentration of PAHs-d in the mainstream of the Yangtze River during dry and wet seasons was investigated and the source was analyzed using the positive matrix factorization (PMF) model to assess the response of PAHs-d to hydrological and anthropogenic activities changes. The concentration of PAHs-d in the wet season (166.2 ± 52.51 ng/L) was significantly higher than that in the dry season (89.05 ± 20.89 ng/L) (ANOVA, P < 0.001), and the sampling sites with high pollution were mainly distributed in the downstream urban agglomeration. Herein, 2-3 rings were identified to play a dominant role in the composition of PAHs-d. Compared with the dry season, the proportion of the low molecular weight (LMW) PAHs-d were relatively depleted and the high molecular weight (HMW) PAHs-d were accumulated in the wet season. Coal and coke combustion were identified as the main sources of PAHs-d (65.9% in the dry season and 59.2% in the wet season), followed by vehicle emissions, petroleum sources, and biomass combustion. Owing to the change in energy consumption structure and climate characteristics, the sources of PAHs-d displayed seasonal variation and spatial heterogeneity. Further, flow was identified as the most important factor affecting PAHs-d in the hydrological parameters. Increases of flow, pH, and SPM decreased the proportion of LMW PAHs-d, and increased that of HMW PAHs-d. The increase in anthropogenic activities intensified the residual levels of 2-3rings and 5-6 rings in water, but had no significant impact on the levels of 4 rings.

Nonhomologous Black Carbon Decoupled Char and Soot Sequestration Based on Stable Carbon Isotopes in Tibetan Plateau Lake Sediment.

Combustion-derived black carbon (BC) is an important component of sedimentary carbon pool. Due to different physicochemical properties, determining the source of char and soot is crucial for BC cycling, especially for nonhomologous char and soot in the Tibetan Plateau (TP). This study analyzed the sequestration and source of BC, char, and soot in the Dagze Co (inner TP) sediment core via the content and δ13C, revealing the biomass and fossil fuel driving on nonsynchronous char and soot and their response to local anthropogenic activities and atmospheric transmission. The results showed that BC concentration increased from 1.19 ± 0.35 mg g-1 (pre-1956) to 2.03 ± 1.05 mg g-1 (after 1956). The variation of char was similar to BC, while nonhomologous growth was detected in char and soot (r = 0.29 and p > 0.05). The source apportionment showed that biomass burning for 71.52 ± 10.23% of char and promoted char sequestration. The contribution of fossil fuel combustion to soot (46.67 ± 14.07%) is much higher than char (28.48 ± 10.23%). Redundancy analysis confirmed that local anthropogenic activities significantly influenced BC burial and atmospheric transport from outside TP-regulated BC burial. The contribution of biomass and fossil fuels to nonsynchronous char and soot is conducive to understanding the anthropogenic effect on BC burial in the TP.

Polycyclic aromatic hydrocarbons in remote lakes from the Tibetan Plateau: Concentrations, source, ecological risk, and influencing factors.

Polycyclic aromatic hydrocarbons (PAHs) have received worldwide attention due to their potential teratogenic, persistent, and carcinogenic characteristics. In this study, the PAHs concentrations in two dated sediment cores taken from central Tibetan Plateau (TP) were analyzed to study the deposition history, potential sources, ecological risks, and influencing factors. Total concentration of PAHs (∑PAHs) ranged from 50.0 to 195 ng g-1 and 51.9-133 ng g-1 in sediments of Pung Co (PC) and Dagze Co (DZC), respectively. 2-3-ring PAHs were dominant in the two lake sediments, accounting for an average of 77.5% and 80.1%, respectively. The historical trends of ∑PAHs in the two lakes allowed to distinguish three periods, namely, relative stability before the 1950s, a gradual increase between the 1950s and the 1990s, and then a decline to the present-day. In addition, the trend in the concentration level of each PAH composition was consistent with ∑PAHs before the 1990s, while they exhibited different trends since the 1990s, which may be the result of a combination of anthropogenic activities and climate change in recent years, whereas before the 1990s the PAH profile was mainly influenced by atmospheric deposition. The results of source apportionment examined according to diagnostic ratios and positive matrix factorization were consistent and revealed that PAHs were primarily derived from biomass and coal combustion. Significant correlations between PAHs and organic carbon (OC) indicate that OC might be a key factor influencing the concentration of PAHs in sediments. The ecological risk assessment demonstrated that PAHs in TP sediments occurred at a low risk level. Results of this study could be helpful to develop a deeper insight into the deposition history of PAHs in remote lakes of the TP region and explore the response of these variations to climate change and human activities.

Source apportionment of polycyclic aromatic hydrocarbons (PAHs) in a sediment core from Lake Dagze Co, Tibetan Plateau, China: Comparison of three receptor models.

Receptor models are a useful tool for identifying sources of polycyclic aromatic hydrocarbons (PAHs) in multiple environmental media. In this study, three different receptor models (including the principal component analysis-multiple linear regression (PCA-MLR), positive matrix factorization (PMF), and Unmix models) were used to apportion the sources of 16 priority PAHs in a sediment core of Lake Dagze Co. The ∑PAHs (sum of all 16 measured PAHs) concentrations ranged from 51.89 to 132.82 ng/g with an average of 80.39 ng/g. The ∑PAHs were dominated by 2-3 ring PAHs, accounting for 80.12% on average, thereby indicating that they mainly originated from biomass and coal combustion and/or from long-range atmospheric transportation. The three models produced consistent source apportionment results. The greatest contributor to ∑PAHs was biomass combustion, followed by coal combustion, vehicle emissions, and petrogenic sources. Moreover, the temporal variation of the common sources was well-correlated among models. The multi-method comparison and evaluation results showed that all three models were useful tools for source apportionment of PAHs, with the PMF model providing better results than the PCA-MLR and Unmix models. The temporal trends of factor contributions were verified by PAHs with different ring numbers. Significant correlations were found between the simulated concentrations of each source factor and the PAHs with different ring numbers (P<0.01), except for the petrogenic source identified by the Unmix model (P>0.05). This study can provide useful information for further investigation of source apportionment of PAHs in the sediment cores.

Stable carbon isotopes trace the effect of fossil fuels on fractions of particulate black carbon in a large urban lake in China.

Black carbon (BC), the highly recalcitrant aromatic carbonaceous from the incomplete combustion of fossil fuel and biomass, is an important carbon sink in carbon cycle. Char and soot, the main components of BC, have significantly different origin and physicochemical characteristics (particle sizes and resultant transportability). The limited understanding of char and soot sources leads to poor insight into the effect of BC on carbon cycle. Sources of char and soot were investigated in this study using stable carbon isotopes to study the effect of BC on the organic carbon pool in a lake, thereby improving the knowledge of lacustrine carbon cycling. The concentration of BC in Taihu Lake ranged from 0.0 to 0.7 mg·L-1and accounted for 10.9 ± 4.7% of the particulate organic carbon. The spatial-mean δ13C values of BC, char, and soot were -23.2 ± 2.0‰, -23.5 ± 2.2‰, and -22.9 ± 1.6‰, respectively. The BC in water was primarily derived from fossil fuels (66.0 ± 9.3%), with liquid fossil fuel accounting for 48.2 ± 13.2% of the BC. The contribution of liquid fossil fuel to soot (49.3%) was much higher than that to char (36.1%); correspondingly, the contributions of biomass and coal to soot (29.2% and 21.5%) were lower than those to char (38.1% and 25.8%). The contribution of liquid fossil fuel combustion to organic carbon (OC), char, and soot gradually increased from 31.9% to 49.3%. Biomass and coal combustion primarily contributed to char (38.1% and 25.8%) and OC (37.5% and 30.6%). The source apportionment of BC, char, and soot revealed the influence of anthropogenically driven BC, char, and soot on the lake and, by extension, to the global carbon cycle.

Spatial variation of particulate black carbon, and its sources in a large eutrophic urban lake in China.

Black carbon (BC), characterized by high aromaticity and stability, has been recognized as a substantial fraction of the carbon pool in soil and sediment. The effect of BC on the particulate organic carbon (POC) pool in lake water, which is an important medium of carbon transmission and transformation, has not been thoroughly studied. The investigations of BC composition and distribution, POC, polycyclic aromatic hydrocarbons (PAHs), and stable carbon and nitrogen isotopes were conducted in a eutrophic urban lake, Taihu Lake, which is the third largest freshwater lake in China. The results indicate that the BC is composed of 55 ± 12% char and 45 ± 12% soot and accounted for 12 ± 6% of POC (the maximum value is 31%). The comparatively high levels of BC and char are distributed in the northern Taihu Lake, especially in Meiliang Bay (0.72 ± 0.38 mg L-1 and 0.45 ± 0.24 mg L-1). The distribution of soot presents a declining trend from the lakeshore to the central lake, particularly in the northern, western, and southern lakes. Source apportionment results from positive matrix factorization of PAHs suggest that consumption of fossil fuel (79 ± 20%) is the dominant source of BC, which agrees with the low ratio of char/soot (1.41 ± 0.71) and relatively depleted δ13C. The covariation of BC and PAHs and terrestrial dissolved organic carbon indicate that the effect of terrestrial input significantly regulates the distribution of BC in Taihu Lake, which is reflected in the high BC value along the lakeshore.

[Spatial Variation Characteristics and Remote Sensing Retrieval of Total Suspended Matter in Surface Water of the Yangtze River].

Total suspended matter(TSM) is an important parameter that describes optical characteristics and water pollution level. Remote sensing was used to obtain suspended matter concentrations in the planar water body, which can monitor and analyze the reliability of turbidity and pollution levels. In this study, a semi-empirical model of suspended matter along the Yangtze River mainstream(from Chongqing to Shanghai) was constructed based on the field measured hyperspectral data and suspended matter concentration and its components, with reference to MODIS(1-4 band), Landsat 8(1-5 band), Sentinel 2(2-6 band), HJ-B1(1-4 band), and other commonly used band ranges. The results show that:① Turbidity and TSM of the Yangtze River mainstream increased from Chongqing to Shanghai during the dry season, whereas the proportion of OSM to TSM(OSM/TSM) decreased from Chongqing to Shanghai. ② The spectral properties of chlorophyll-a were not obvious; however, it showed a bimodal spectral characteristic of suspended matter concentration. Due to the low concentration of suspended matter in the water(<114.68 mg·L-1), the first peak value was significantly higher than the second peak. However, peak reflection and position had an obvious "red shift" phenomenon in the direction of the wavelength. ③ The reflectance values of the Yangtze River mainstream were most sensitive to the concentration of suspended matter in the 600-710 nm and 475-550 nm bands. Most of these fall in the green and red band of MODI, Landsat 8, Sentinel 2, and HJ-1B satellites. Therefore, the commonly used satellites have a band setting to detect the inversion of turbidity degree index of the Yangtze River main stream water body. The Sentinel 2 satellite band is most suitable for the inversion of suspended matter concentration in the Yangtze River mainstream. The mean absolute percentage error(MAPE) and root mean square error(RMSE) of the optimal exponential model were 10.23 mg·L-1 and 23%, respectively.

Anthropogenic-Driven Alterations in Black Carbon Sequestration and the Structure in a Deep Plateau Lake.

The continuous flux of organic carbon (OC) from terrestrial ecosystems into inland water is an important component of the global carbon cycle. The buried OC pool in inland water sediments is considerable, and black carbon (BC) is a significant contributor to this OC pool because of the continuous growth in BC emissions. Therefore, determining the effect of BC on total OC burial and variations in the structure of BC during the burial process will contribute significantly to our understanding of lacustrine carbon cycling. This study investigated BC burial and its structural variations in response to anthropogenic drivers using four dated sedimentary cores from a deep plateau lake in China. The BC burial rate rose from 0.96 ± 0.64 g·m-2·y-1 (mean of sedimentary cores pre-1960s) to 4.83 ± 1.25 g·m-2·y-1 (after 2000), which is a 5.48 ± 2.12-fold rise. The increase of char was similar to those of BC. The growth rate of soot was 7.20 ± 4.30 times, which is higher than that of BC and char, increasing from 0.12 ± 0.08 to 0.64 ± 0.23 g·m-2·y-1. There was a decreasing trend in the ratio of char and soot at a mean rate of 62.8 ± 6.46% (excluding core 3) in relation to increased fossil fuel consumption. The contribution of BC to OC burial showed a significant increasing trend from the past to the present, particularly in cores 3 and 4, and the mean contribution of the four cores was 11.78 ± 2.84%. Source tracer results from positive matrix factorization confirmed that the substantial use of fossil fuels has promoted BC burial and altered the BC structure. This has resulted in BC with a higher aromatic content in the lake sediment, which exhibits reduced reactivity and increased stability. The strong correlation between BC and allochthonous total OC indicates that the input pathways of the buried BC in this plateau lake sediment were terrestrial surface processes and not atmospheric deposition.

MC37, a new mono-carbonyl curcumin analog, induces G2/M cell cycle arrest and mitochondria-mediated apoptosis in human colorectal cancer cells.

(E)-1-(3'-fluoro-[1,1'-biphenyl-3-yl)-3-(3-hydroxy-4-methoxyphenyl)prop-2-en-1-one) (MC37), a novel mono-carbonyl curcumin analog, was previously synthesized in our laboratory as a nuclear factor kappa B (NF-κB) inhibitor with excellent cytotoxicity against several cancer cell lines. In this study, our further investigations showed that the potent growth inhibitory activity of MC37 in human colorectal cancer cells was associated with the arrest of cell cycle progression and the induction of apoptosis. As a multi-targeted agent, MC37 inhibited the intracellular microtubule assembly, altered the expression of cyclin-dependent kinase 1 (CDK1), and ultimately induced G2/M cell cycle arrest. Moreover, MC37 collapsed the mitochondrial membrane potential (MMP), increased the Bax/Bcl-2 ratio, activated the caspase-9/3 cascade, and finally led to cancer cells apoptosis, suggesting that the mitochondrial-mediated apoptotic pathway was involved in MC37-induced apoptosis. In conclusion, these observations demonstrated that mono-carbonyl curcumin analogs would serve as multi-targeted lead for promising anti-colorectal cancer agent development.

Discovery of potent cytotoxic ortho-aryl chalcones as new scaffold targeting tubulin and mitosis with affinity-based fluorescence.

A series of new ortho-aryl chalcones have been designed and synthesized. Many of these compounds were found to exhibit significant antiproliferation activity toward a panel of cancer cell lines. Selected compounds show potent cytotoxicity against several drug resistant cell lines including paclitaxel (Taxol) resistant human ovarian carcinoma cells, vincristine resistant human ileocecum carcinoma cells, and doxorubicin resistant human breast carcinoma cells. Further investigation revealed that active analogues could inhibit the microtubule polymerization by binding to colchicine site and thus induce multipolar mitosis, G2/M phase arrest, and apoptosis of cancer cells. Furthermore, affinity-based fluorescence enhancement was observed during the binding of active compounds with tubulin, which greatly facilitated the determination of tubulin binding site of the compounds. Finally, selected compound 26 was found to exhibit obvious in vivo antitumor activity in A549 tumor xenografts model. Our systematic studies implied a new scaffold targeting tubulin and mitosis for novel antitumor drug discovery.

Discovery of 3-(4-hydroxybenzyl)-1-(thiophen-2-yl)chromeno[2,3-c]pyrrol-9(2H)-one as a phosphodiesterase-5 inhibitor and its complex crystal structure.

Phosphodiesterase-5 (PDE5) inhibitors have been approved for the treatment of erectile dysfunction and pulmonary hypertension, but enthusiasm on discovery of PDE5 inhibitors continues for their potential new applications. Reported here is discovery of a series of new PDE5 inhibitors by structure-based design, molecular docking, chemical synthesis, and enzymatic characterization. The best compound, 3-(4-hydroxybenzyl)-1-(thiophen-2-yl)chromeno[2,3-c]pyrrol-9(2H)-one (57), has an IC50 of 17 nM against the PDE5 catalytic domain and good selectivity over other PDE families. The crystal structure of the PDE5 catalytic domain in complex with 57 was determined at 2Å resolution and showed that 57 occupies the same pocket as other PDE5 inhibitors, but has a different binding pattern in detail. On the basis of the binding pattern of 57, a novel scaffold can be proposed as a candidate of PDE inhibitors.

Synthesis and identification of new flavonoids targeting liver X receptor ß involved pathway as potential facilitators of Aß clearance with reduced lipid accumulation.

Alzheimer's disease (AD) is associated with impaired Aß degradation in the brain. Enhancing the process of Aß clearance is an attractive potential AD therapy. Treatment with LXR agonists may reduce Aß levels in vivo. However, the clinical potential of many LXR agonists is limited because of their nonselective actions on LXRα/ß, which lead to undesired hepatic lipogenesis via LXRα-dependent pathways. In this study, ABCA1 up-regulators were identified from a series of flavonoids and were found to preferentially activate LXRß and up-regulate expression of ABCA1 and apoE in different cell lines. Further investigations confirmed that these compounds facilitate intracellular Aß clearance in Aß-loaded BV2 cells. Administration of compound 19 reduced total brain Aß and plaque burden in APP/PS1 double transgenic mice, associated with elevated ABCA1 and apoE expression. Compared with the nonselective LXR agonists, the active compounds reported here induced less accumulation of undesired lipids and triglycerides in HepG2 cells.