Size-dependent zoogeographical distribution of gelatinous thaliaceans associated with current velocity and temperature.

Thaliaceans are globally distributed and play an important role in the world's biological carbon pump and marine ecosystems by forming dense swarms with high feeding rates and producing large amounts of fecal pellets and carcasses. The contribution of thaliacean swarms to the downward transport of carbon depends not only on their abundance but also on their body size. However, the key factors influencing the distribution of different-sized thaliaceans remain unstudied. To discriminate thaliacean assemblages and examine the key factors determining the zoogeographical distribution and abundance of different-sized thaliaceans during different monsoon periods, we conducted three cruises in the South China Sea from before the southwest monsoon to the peak of the northeast monsoon. Our results revealed that high thaliacean abundance corresponded to high chlorophyll a concentration, which were associated with hydrodynamic processes, such as upwelling and eddies. Hierarchical partitioning and niche difference analyses demonstrated that current velocity and temperature are key factors that shaped the zoogeographical distribution of different-sized thaliaceans. The global dataset indicated that small-sized thaliacean species tend to occur in coastal areas where the current velocity is generally high, while large-sized species tend to occur in open ocean areas where the current velocity is generally low. The results revealed that global warming-induced changes in surface current velocity and temperature may alter the zoogeographical distribution and abundance of thaliaceans with different sizes, thereby affecting the biological carbon pump and surrounding marine ecosystem. Overall, this study sheds light on the potential responses of pelagic tunicates to global climate change through changes in their hydrodynamic conditions.

Coordinating activation strategy enables 1,2-alkylamidation of alkynes.

The radical 1,2-difunctionalization reaction of alkynes has been evolved into a versatile approach for expeditiously increasing the complexity of the common feedstock alkyne. However, intermolecular 1,2-carboamidation with general alkyl groups is an unsolved problem. Herein, we show that a coordinating activation strategy could act as an efficient tool for enabling radical 1,2-alkylamidation of alkynes. With the employment of diacyl peroxides as both alkylating reagents and internal oxidants, a large library of ß-alkylated enamides is constructed in a three-component manner from readily accessible amides and alkynes. This protocol exhibits broad substrate scope with good functional group compatibility and is amenable for late-stage functionalization of natural molecules and biologically compounds.

Modular Synthesis of α-Aryl-α-Heteroaryl α-Amino Acid Derivatives via a Copper-Catalyzed Cross-Dehydrogenative-Coupling Reaction Using Air as the Sole Oxidant.

A novel copper-catalyzed cross-dehydrogenative-coupling (CDC) process of arylglycine derivatives with N-heteroarenes for the straightforward synthesis of α-aryl-α-heteroaryl α-amino acid scaffolds has been successfully developed. This protocol exhibits a broad substrate scope with good functional group compatibility by utilizing air as the sole oxidant. The use of the reaction is also displayed through the late-stage functionalization of arylglycines bearing natural compounds or drug motifs.

[Mechanism of Cyathulae Radix in treatment of knee osteoarthritis based on metabolomics].

Metabolomics based on ultra-high performance liquid chromatography-tandem quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF-MS) was employed to analyze the effect of Cyathulae Radix on serum and urine in rats with knee osteoarthritis, and to decipher the mechanism of Cyathulae Radix in the treatment of knee osteoarthritis. SD rats were randomized into a normal group, a model group, a positive drug group, and a Cyathulae Radix group. The knee osteoarthritis model was established by injecting 2% pa-pain and 0.03 mol·L~(-1) cysteine, and the serum levels of tumor necrosis factor-α(TNF-α) and matrix metalloproteinase-3(MMP-3) in the model group was measured to preliminarily evaluate the therapeutic effect of Cyathulae Radix on knee osteoarthritis. UHPLC-Q-TOF-MS was employed to establish the metabolic profile of endogenous small molecule metabolites in the four groups. Potential biomarkers were screened out by multivariate analysis methods such as partial least squares discriminant analysis(PLS-DA) and orthogonal partial least squares discriminant analysis(OPLS-DA) in combination with t-test, variable importance for projection(VIP), and fold-change. The related metabolic pathways were enriched with the help of MetaboAnalyst 5.0. The results showed that Cyathulae Radix alleviated the general signs of rats with knee osteoarthritis, and reduced the levels of TNF-α and MMP-3 in the rat serum. Twenty-eight differential metabolites that might be associated with the therapeutic effect of Cyathulae Radix were screened out from serum and urine. They were mainly involved in arginine biosynthesis, nicotinate and nicotinamide metabolism, tricarboxylic acid cycle, alanine, aspartate and glutamate metabolism, riboflavin metabolism, glyoxylate and dicarboxylate metabolism, and pyrimidine metabolism. Through metabonomics analysis, this study predicted the possible mechanism of Cyathulae Radix in the treatment of knee osteoarthritis, which laid a foundation for further research.

Role of jellyfish in mesozooplankton community stability in a subtropical bay under the long-term impacts of temperature changes.

To understand zooplankton community changes in the context of climate change and anthropogenic disturbances, we analyzed mesozooplankton samples from four seasons in the subtropical Daya Bay, which is susceptible to perceived disturbances in the South China Sea. The zooplankton community was found to be divided into two clusters, namely the Outer-bay Cluster (OC) comprising Noctiluca scintillans, Temora turbinata, and Paracalanus spp., and the Inner-bay Cluster (IC) which was dominated by Pseudevadne tergestina, Oikopleura rufescens, and Paracalanus spp. The OC was recorded in waters with low Chl a concentrations and high salinity, coinciding with open seawater intrusion. The IC occurred in waters with high Chl a concentrations, low salinity, with terrestrial inputs from the Dan'ao River. The dominant cladoceran species has changed in spring from Penilia avirostris to Pseudevadne tergestina owing to suitable temperature conditions and the low wind speed in this region. Most of the keystone species recorded during all seasons were found to be copepods based on co-occurrence network analysis. Numbers of keystone jellyfish (cnidaria) species, such as Geryonia proboscidalis, Chelophyes contorta, and Aeginura grimaldi were significantly higher in summer than in other seasons due to a low-temperature seawater intrusion, which can result in the highest stability of community structures and affect coastal food webs and fishery resources. Our results highlight that zooplankton community succession may occur with long-term temperature changes in the subtropical Daya Bay under global climate change conditions.

Effects of terrestrial inputs and seawater intrusion on zooplankton community structure in Daya Bay, South China Sea.

Daya Bay is a eutrophic coastal region with dynamic physico-chemical conditions influenced by terrestrial inputs and seawater intrusion. Zooplankton is a crucial trophic intermediary for energy transfer and fishery resources. In this study, we assessed the distribution and composition of zooplankton in Daya Bay during summer and winter of 2015. We found that zooplankton diversity was the lowest and dominated by small copepods (Acartia spp. and Paracalanus spp.) and gelatinous Oikopleura spp. under terrestrial inputs in the Dan'ao River estuary and Aotou barbour. The highest zooplankton diversity was observed at the bay mouth that influenced by salty intruded seawater, and the dominant oceanic species (such as Euchaeta concinna and Subeucalanus subcrassus invaded into the top of the bay in winter. The dominant species in the estuary shift from Penilia avirostris to Acartia spp. compared with historical researches, indicating the effect of human activities on the succession of dominant species.

Long-term changes in summer phytoplankton communities and their influencing factors in Daya Bay, China (1991-2017).

Spatial variations in summertime phytoplankton community structure from 1991 to 2017 in Daya Bay, China were investigated in this research. The abundance of total phytoplankton and diatoms significantly increased during the study period in all regions of the bay while an increase in dinoflagellates abundance was only significant in the inner and middle bay areas. Pseudo-nitzschia spp. were overwhelmingly dominant followed by Skeletonema costatum. Ceratium furca was the dominant dinoflagellate. Overall, species diversity and evenness indices showed downward trends during the study period. Moreover, the bloom frequency of Scrippsiella trochoidea (associated with red tides) has increased rapidly since the 2000s in the inner bay. These temporal dynamics are largely explained by enhanced dissolved inorganic nitrogen (DIN) concentrations, which increased by 64.58% during 2005-2017 relative to 1991-2004, induced by human activities, along with temperature reductions and salinity increases resulting from open oceanic seawater intrusion.

Cyclohexyl-Fused, Spirobiindane-Derived, Phosphine-Catalyzed Synthesis of Tricyclic γ-Lactams and Kinetic Resolution of γ-Substituted Allenoates.

A C2-symmetric chiral phosphine catalyst, NUSIOC-Phos, which can be easily derived from cyclohexyl-fused spirobiindane, was introduced. A highly enantioselective domino process involving pyrrolidine-2,3-diones and γ-substituted allenoates catalyzed by NUSIOC-Phos has been disclosed. Diastereospecific tricyclic γ-lactams containing five contiguous stereogenic centers were obtained in high yields and with nearly perfect enantioselectivities. A kinetic resolution process of racemic γ-substituted allenoates was developed for the generation of optically enriched chiral allenoates.

Loss of SDC1 Expression Is Associated with Poor Prognosis of Colorectal Cancer Patients in Northern China.

BACKGROUND: Syndecan-1 (SDC1/CD138) is a key cell surface adhesion molecule essential for maintaining cell morphology and the interactions with the surrounding microenvironment. SDC1 tumor immunoexpression may be increased or decreased in epithelial malignant neoplasms compared to that in adjacent non-neoplastic tissue, depending on the type of carcinoma, and it has been correlated with various clinicopathological parameters and patient prognosis. SDC1 expression is decreased in colorectal cancer (CRC) tissue, but the relationship between prognosis and SDC1 expression in CRC patients is controversial. METHODS: In this study, SDC1 expression was detected in 65 adjacent non-neoplastic colorectal tissues, 477 CRCs, and 79 metastatic lymph nodes using tissue microarray. RESULTS: The data show that SDC1 decreased in CRC tissues (p ≤ 0.001) and metastatic lymph node tissues (p ≤ 0.001) compared to that in adjacent non-neoplastic colorectal tissues. Loss of SDC1 protein expression is associated with poor overall (p < 0.0001) and disease-free survival (p < 0.0001), differentiation (p = 0.017), stage (p ≤ 0.001), and lymph node metastasis (p ≤ 0.001) in CRC patients. CONCLUSIONS: These data suggest that the loss of SDC1 plays an important role in CRC malignant progression. Loss of SDC1 expression indicates poor prognosis in patients from northern China with CRC.

Dearomatization of 3-Nitroindoles by a Phosphine-Catalyzed Enantioselective [3+2] Annulation Reaction.

The dearomatization of 3-nitroindoles through a chiral-phosphine-mediated [3+2] annulation reaction is described. This method makes use of readily available 3-nitroindoles as an aromatic feedstock and rapidly delivers a wide range of cyclopentaindoline alkaloid scaffolds in a highly enantioselective manner. Notably, phosphine-triggered cyclization has not been utilized previously in a dearomatization process.

CRMP4a suppresses cell motility by sequestering RhoA activity in prostate cancer cells.

Objectives: Distant metastasis is a critical factor for cancer-associated death. Our previous studies identified collapsin response mediator protein 4a (CRMP4a) as a metastasis suppressor in prostate cancers. Enhancing CRMP4 expression by promoter-targeted small activating RNAs reduced cell migration in vitro and abolished distal metastasis in mouse xenograft models. In this study, we investigated the mechanism for CRMP4a-mediated suppression of cell migration. Methods: PC-3 cells were stably infected with lentiviruses expressing CRMP4a cDNA or a shRNA sequence. Cytoskeletal organization was analyzed by measuring cellular focal adhesion area and number, percentage of cell area and lamellipodia numbers after phalloidin staining or anti-vinculin immunocytofluorescent staining. Cell migration was evaluated with TranswellTM chambers coated with MatriGel. RhoA activation was determined with a Rhotekin RBD agarose bead-based assay kit. Lentiviruses harboring RhoA-Q63L or RhoA-T19N mutant constructs were used to overexpress mutant RhoA proteins. Results: CRMP4a overexpression largely reduced while CRMP4a knockdown remarkably increased cytoskeletal organization in PC-3 cells. CRMP4a immunoprecipitation pulled down RhoA but not cdc42 or Rac1 proteins. Manipulating CRMP4a expression levels reversely altered active RhoA levels. Overexpression of RhoA active (Q63L) but not inactive (T19N) mutants reversed CRMP4a-mediated reduction of cancer cell migration while RhoA inhibitor Rhosin diminished CRMP4a shRNA-induced increase of cancer cell migration. CRMP4a overexpression also largely reduced cell spreading that was abolished by overexpressing RhoA active mutant. Conclusion: Our data demonstrated that CRMP4a interacts with RhoA and sequesters its activity, resulting in suppression of cytoskeletal organization, cell migration and spreading.

CD51 is an independent unfavorable prognostic factor in esophageal squamous cell carcinoma.

BACKGROUND: Esophageal squamous cell carcinoma (ESCC) is a common cancer in East Asia and some other parts of the world with a dismal prognosis. CD51 (integrin αv),a transmembrane glycoprotein responsible for cell-to-matrix binding has been found to enhance tumor progression. However, its expression and clinicopathological significance in ESCC tumors are not fully understood. The purpose of this study was to investigate the expression level of CD51 and to explore its clinicopathological significance in ESCC. METHODS: The expression of CD51 in 122 ESCC samples was examined by immunohistochemistry and its clinicopathological significance was evaluated. RESULTS: The expression of CD51 was observed in tumor cell membrane and/or cytoplasm, with a positive rate of 48.36% (59/122). High expression of CD51 was significantly associated with lymph node metastasis (P =  0.031), tumor size (P =  0.028) and invasive depth (P =  0.027). Kaplan-Meier analysis revealed that positive expression of CD51 was correlated with poor overall survival of ESCC patients (P =  0.015). Multivariate analysis suggested that CD51 was an independent prognositic factor for ESCC (hazard ration = 1.604; 95% CI, 1.086-2.368; P =  0.017). CONCLUSION: These data suggested CD51 was a predictor for the prognosis of ESCC patients.

Oldhamianoside II inhibits prostate cancer progression via regulation of EMT and the Wnt/ß-catenin signaling pathway.

Oldhamianoside II is a novel triterpenoidsaponin that can be isolated from the roots of Gypsophila oldhamiana. In vitro and in vivo experiments have revealed that it inhibits tumor growth and metastasis in various types of tumor; however, the exact mechanism remains to be fully elucidated. In the present study, oldhamianoside II treatment in prostate cancer cells exerted substantial anticancer activity, including decreased cell proliferation and invasion. Mechanistically, oldhamianoside II was found to reverse the epithelial-mesenchymal transition (EMT), as demonstrated by its induction of E-cadherin and suppression of vimentin and N-cadherin at the mRNA and protein levels. Furthermore, oldhamianoside II treatment upregulated Wnt antagonist expression and promoted the proteasome-mediated degradation of ß-catenin to inhibit the activity of ß-catenin signaling. In summary, the present study revealed that oldhamianoside II exerts its antitumor effects via the regulation of EMT and ß-catenin function, and further supports its potential for use in clinical treatment.

Manganese/cobalt-catalyzed oxidative C(sp3)-H/C(sp3)-H coupling: a route to α-tertiary ß-arylethylamines.

Reported herein is an oxidative coupling reaction of an α-C(sp3)-H bond of amine with a benzylic C(sp3)-H bond through Mn or Co catalysis to provide diverse collections of α-tertiary ß-arylethylamines. This protocol features an easily installed and removable coordinating activation group, a wide scope of substrates, low-cost metal catalysts, easily available starting materials and synthetic simplicity.

Cascade Oxidative Coupling/Cyclization: A Gateway to 3-Amino Polysubstituted Five-Membered Heterocycles.

Taking advantage of the coordinating activation strategy, we have developed the cascade oxidative coupling/cyclization of α-C(sp(3))-H bonds of amines with enamines or ß-keto esters for the synthesis of three types of five-membered heterocycles. α-Amino acids as the substrate lead to 3-amino 1,3-dihydro-2H-pyrrol-2-ones and furan-2(3H)-ones by using air or dioxygen as the sole clean oxidant, respectively. α-Amino ketones give a range of 3-amino 1H-pyrroles by using di-tert-butyl peroxide as the oxidant. A three-component, one-pot reaction from readily available amine, ß-keto ester, and α-amino ketone enhances the practicality of the modular construction of 1H-pyrrole scaffolds. This programmed protocol features simple reaction conditions, readily available starting materials, broad substrate scope, and high functional group tolerance.

Rhodium-catalyzed annulation of arenes with alkynes through weak chelation-assisted C-H activation.

The purpose of this article is to give a brief review of weak chelation-assistance as a powerful means for the rhodium-catalyzed annulation of arenes with alkynes. The use of commonly occurring functional groups (e.g., ketones, aldehydes, carboxylic acids and alcohols) as the directing groups enriches the versatility of auxiliary ligands and extends the scope of products. This short article offers an overview on emerging procedures, highlights their advantages and limitations, and covers the latest progress in the rapid synthesis of organic functional materials and natural products.

Coordinating activation strategy for C(sp(3))-H/C(sp(3))-H cross-coupling to access ß-aromatic α-amino acids.

The past decade has witnessed significant advances in C-H bond functionalizations with the discovery of new mechanisms. Non-precious transition-metal-catalysed radical oxidative coupling for C(sp(3))-H bond transformations is an appealing strategy for C-C bond formations. The radical oxidative C(sp(3))-H/C(sp(3))-H cross-coupling reactions of α-C(sp(3))-H bonds of amines with free radicals represent a conceptual and practical challenge. We herein develop the coordinating activation strategy to illustrate the nickel-catalysed radical oxidative cross-coupling between C(sp(3))-H bonds and (hetero)arylmethyl free radicals. The protocol can tolerate a rich variety of α-amino acids and (hetero)arylmethanes as well as arylmethylenes and arylmethines, affording a large library of α-tertiary and α-quaternary ß-aromatic α-amino acids. This process also features low-cost metal catalyst, readily handled and easily removable coordinating group, synthetic simplicity and gram-scale production, which would enable the potential for economical production at commercial scale in the future.

Bacterial growth efficiency in a partly eutrophicated bay of South China Sea: Implication for anthropogenic impacts and potential hypoxia events.

Bacterial metabolism plays a dual role [bacterial production (BP) and bacterial respiration (BR)] in the aquatic ecosystem and potentially leads to hypoxia in the coastal eutrophic area. Bacterial growth efficiency (BGE) is an important index showing the contribution of bacterial metabolism to marine biological production and carbon budget in the pelagic ecosystem. In this study, the spatial and seasonal variety as well as diurnal variation dynamics of BGE and associated ecological characteristics were investigated in a partly eutrophicated subtropical bay (the Daya Bay) located in the northern South China Sea. Furthermore, the relationship between bacterial metabolism and potential hypoxia event was analyzed. The average BGE was 0.14 and 0.22 in summer and winter, respectively, which was lower than the mean value ever reported in other coastal and estuarine waters. The diurnal variations of BGE and BP were widely fluctuated in the Daya Bay, with approximately 3-8 fold variation of BP and 2-3 fold variation of BR in different seasons, suggesting the importance of short-term ecological dynamics on evaluating the long-term ecological processes in the coastal waters. BR was the predominant contributor to the bacterial carbon demand; however, the variation of BGE was controlled by BP in both seasons. BGE was always high in the near-shore waters with higher eutrophic level and more active BP and BR. The bacterial metabolism could deplete dissolved oxygen (DO) in the Daya bay within about 9 days when the water body was enclosed and photosynthesis was prohibited. Therefore, low DO concentration and potential hypoxia was more likely to be found in the near-shore waters of the Daya Bay in summer, since the water was stratified and enclosed with poor water exchange capacity in this area. While in winter, hypoxia seldom occurred due to vertical mixing throughout the water column. Further biological-physical coupling research is recommended to find out the detailed formation mechanism of hypoxia in the bay, and to predict the potential hypoxia events and their environmental impacts in the future.

Nickel-catalyzed chelation-assisted direct arylation of unactivated C(sp3)-H bonds with aryl halides.

In this work, we have disclosed the nickel-catalyzed unactivated ß-C(sp(3))-H bond arylation of aliphatic acid derivatives with aryl iodides/bromides via bidentate chelation-assistance of an 8-aminoquinoline moiety. These preliminary results indicate the intrinsic catalytic potential of nickel metal for unactivated C(sp(3))-H bond arylation.

Iron-catalyzed oxidative C-H/C-H cross-coupling: an efficient route to α-quaternary α-amino acid derivatives.

Fully loaded: A coordinating activation strategy has been developed to furnish α-quaternary α-amino acids through the iron(III)-catalyzed oxidative functionalization of α-C(sp(3) )H bonds of α-tertiary α-amino acid esters. The reaction exhibits a broad substrate scope for both α-amino acids and nucleophiles (Nu) as well as good functional-group tolerance (see scheme, DTBP=di-tert-butyl peroxide, DCE=1,2-dichloroethane).