CO2-Promoted and Copper-Catalyzed Dehydroxylative Coupling of Benzylic Alcohols by the NaBH4/I2 System.

An efficient and CO2-promoted dehydroxylative coupling of benzylic alcohols catalyzed by ligand-free cuprous chloride has been achieved. The discovered catalytic reductive coupling reaction is a newly C-C bond-forming transformation of alcohols. Mechanistic insight is gained through control reactions.

Na2CO3-promoted synthesis of thiocarbamates from isocyanates and thiols under mild conditions.

Here, we developed an efficient method for the synthesis of s-alkyl or aryl thiocarbamates catalyzed by Na2CO3 under mild conditions using alkyl or aryl isocyanates and thiophenols or thiols. In situ reaction with deuterated tetrahydrofuran (d8-THF) was carried out to investigate the reaction mechanism. This method has the advantages of high yield, good functional group tolerance and high atom economy.

Oleate Promotes Triple-Negative Breast Cancer Cell Migration by Enhancing Filopodia Formation through a PLD/Cdc42-Dependent Pathway.

Breast cancer, particularly triple-negative breast cancer (TNBC), poses a global health challenge. Emerging evidence has established a positive association between elevated levels of stearoyl-CoA desaturase 1 (SCD1) and its product oleate (OA) with cancer development and metastasis. SCD1/OA leads to alterations in migration speed, direction, and cell morphology in TNBC cells, yet the underlying molecular mechanisms remain elusive. To address this gap, we aim to investigate the impact of OA on remodeling the actin structure in TNBC cell lines, and the underlying signaling. Using TNBC cell lines and bioinformatics tools, we show that OA stimulation induces rapid cell membrane ruffling and enhances filopodia formation. OA treatment triggers the subcellular translocation of Arp2/3 complex and Cdc42. Inhibiting Cdc42, not the Arp2/3 complex, effectively abolishes OA-induced filopodia formation and cell migration. Additionally, our findings suggest that phospholipase D is involved in Cdc42-dependent filopodia formation and cell migration. Lastly, the elevated expression of Cdc42 in breast tumor tissues is associated with a lower survival rate in TNBC patients. Our study outlines a new signaling pathway in the OA-induced migration of TNBC cells, via the promotion of Cdc42-dependent filopodia formation, providing a novel insight for therapeutic strategies in TNBC treatment.

The Phylogenetic Relationships of Major Lizard Families Using Mitochondrial Genomes and Selection Pressure Analyses in Anguimorpha.

Anguimorpha, within the order Squamata, represents a group with distinct morphological and behavioral characteristics in different ecological niches among lizards. Within Anguimorpha, there is a group characterized by limb loss, occupying lower ecological niches, concentrated within the subfamily Anguinae. Lizards with limbs and those without exhibit distinct locomotor abilities when adapting to their habitats, which in turn necessitate varying degrees of energy expenditure. Mitochondria, known as the metabolic powerhouses of cells, play a crucial role in providing approximately 95% of an organism's energy. Functionally, mitogenomes (mitochondrial genomes) can serve as a valuable tool for investigating potential adaptive evolutionary selection behind limb loss in reptiles. Due to the variation of mitogenome structures among each species, as well as its simple genetic structure, maternal inheritance, and high evolutionary rate, the mitogenome is increasingly utilized to reconstruct phylogenetic relationships of squamate animals. In this study, we sequenced the mitogenomes of two species within Anguimorpha as well as the mitogenomes of two species in Gekkota and four species in Scincoidea. We compared these data with the mitogenome content and evolutionary history of related species. Within Anguimorpha, between the mitogenomes of limbless and limbed lizards, a branch-site model analysis supported the presence of 10 positively selected sites: Cytb protein (at sites 183 and 187), ND2 protein (at sites 90, 155, and 198), ND3 protein (at site 21), ND5 protein (at sites 12 and 267), and ND6 protein (at sites 72 and 119). These findings suggested that positive selection of mitogenome in limbless lizards may be associated with the energy requirements for their locomotion. Additionally, we acquired data from 205 mitogenomes from the NCBI database. Bayesian inference (BI) and Maximum Likelihood (ML) trees were constructed using the 13 mitochondrial protein-coding genes (PCGs) and two rRNAs (12S rRNA and 16S rRNA) from 213 mitogenomes. Our phylogenetic tree and the divergence time estimates for Squamata based on mitogenome data are consistent with results from previous studies. Gekkota was placed at the root of Squamata in both BI and ML trees. However, within the Toxicofera clade, due to long-branch attraction, Anguimorpha and (Pleurodonta + (Serpentes + Acrodonta)) were closely related groupings, which might indicate errors and also demonstrate that mitogenome-based phylogenetic trees may not effectively resolve long-branch attraction issues. Additionally, we reviewed the origin and diversification of Squamata throughout the Mesozoic era, suggesting that Squamata originated in the Late Triassic (206.05 Mya), with the diversification of various superfamilies occurring during the Cretaceous period. Future improvements in constructing squamate phylogenetic relationships using mitogenomes will rely on identifying snake and acrodont species with slower evolutionary rates, ensuring comprehensive taxonomic coverage of squamate diversity, and increasing the number of genes analyzed.

Ecological health assessment using zooplankton index of biotic integrity (Z-IBI) in urban rivers in Hainan Island, China.

The Changwang, Meishe, and Wuyuan are urban rivers in Haikou City, Hainan Island. They are vital water sources, serving various purposes, from farmland irrigation to domestic and industrial use. Unfortunately, anthropogenic activities have influenced these "rivers," negatively impacting water quality and ecological functions; however, there is limited research on their ecological status. Thus, this study assessed the zooplankton community structure and developed the zooplankton index of biotic integrity (Z-IBI) to evaluate the ecological status. Samples were collected and analyzed seasonally in 2019. Generally, 159 zooplankton species belonging to 85 genera, 55 families, and 3 phyla were identified, dominated by Rotifer and Protozoa, followed by Arthropoda (groups of Copepod and Cladocera). The zooplankton density varied from 0.00 to 126.04 ind L-1, with averages of 19.49 ind L-1, 31.40 ind L-1, and 20.38 ind L-1 in Changwang, Meishe, and Wuyuan, respectively. The zooplankton density varied seasonally as summer > spring > winter > autumn. Analysis of similarity (ANOSIM) indicated a significant seasonal difference (R = 0.070, p < 0.001) in zooplankton community but not spatially (R = 0.004, p = 0.413). Thus, SIMPER revealed that Brachionus forficula, Didinium nasutum, Keratella valga, Nauplius, and Polyarthra vulgaris contributed to the seasonal differences. The redundancy analysis (RDA) revealed environmental factors, including total phosphorus (TP), total nitrogen (TN), ammonia nitrogen (NH3-N), chemical oxygen demand (CODMn), dissolved oxygen (DO), temperature, pH, Chl-a, and electrical conductivity (EC) influenced zooplankton species. The Z-IBI was established using Zooplankton abundance, Protozoa abundance, Copepod abundance, Cladoceran biomass %, and Shannon-Wiener diversity index. Based on Z-IBI evaluation, ecological status was "moderate" in Changwang and Wuyuan, while it was "low" in Meishe. Seasonally, the ecological status in autumn was better than in summer and spring. The Z-IBI showed that parameters, including pH, EC, CODMn, TN, TP, and Chl-a, decreased with improving water quality, while water transparency increased with improved water quality. Thus, the "rivers" ecological status could be adequately assessed using the Z-IBI to guide their water quality monitoring and management.

Spatio-temporal dynamics of phytoplankton community structure in the coastal waters of the Southern Beibu Gulf.

This study was conducted during October 2021 (autumn) and April 2022 (spring) to explore the phytoplankton community structure, their distribution characteristics, and the influence of environmental factors in the coastal waters of the Southern Beibu Gulf. The 15 sampling sites were grouped based on the difference in offshore distance to analyze the temporal and spatial differences in community structure and environmental driving in the investigated sea area of the coastal waters of the Southern Beibu Gulf. Permutational multivariate analysis of variance was conducted on the sample data in time and space, revealing that there is no significant difference in space (p > 0.05), but there is significant difference in time (p < 0.05). Notably, water pressure, pH, chemical oxygen demand, nitrite, and labile phosphate were higher in autumn, while total ammonia nitrogen, dissolved oxygen, and suspended solids were significantly higher in spring. Additionally, the study identified 87 phytoplankton species belonging to 6 phyla, dominating by Bacillariophyta, followed by Dinophyta and Cyanophyta. The phytoplankton density, Shannon Weiner's diversity index (H'), Pielou's evenness index (J), and Margalef's richness index (D) ranged from 84.88 to 4675.33 cells L-1, 0.56 to 2.58, 0.26 to 0.89, and 1.21 to 3.64, respectively. Permutational multivariate analysis of variance showed non-significant spatial differences in phytoplankton composition (p > 0.05) but seasonal differences (p < 0.05). Furthermore, canonical correspondence analysis (CCA) identified pH, dissolved oxygen, suspended solids, chemical oxygen demand, nitrite, and labile phosphate as key environmental factors influencing the phytoplankton community structure (p < 0.05). In this study, the dynamic changes of phytoplankton community structure and environmental factors in the southern coastal waters of Beibu Gulf were analyzed in detail from two aspects of time and space. The key environmental factors to protect the ecological environment in the southern coastal area of Beibu Gulf were found out. It provides a reference method and theoretical basis for the management and protection of Beibu Gulf and other tropical marine environment.

Right, but not left, posterior superior temporal gyrus is causally involved in vocal feedback control.

The posterior superior temporal gyrus (pSTG) has been implicated in the integration of auditory feedback and motor system for controlling vocal production. However, the question as to whether and how the pSTG is causally involved in vocal feedback control is currently unclear. To this end, the present study selectively stimulated the left or right pSTG with continuous theta burst stimulation (c-TBS) in healthy participants, then used event-related potentials to investigate neurobehavioral changes in response to altered auditory feedback during vocal pitch regulation. The results showed that, compared to control (vertex) stimulation, c-TBS over the right pSTG led to smaller vocal compensations for pitch perturbations accompanied by smaller cortical N1 and larger P2 responses. Enhanced P2 responses received contributions from the right-lateralized temporal and parietal regions as well as the insula, and were significantly correlated with suppressed vocal compensations. Surprisingly, these effects were not found when comparing c-TBS over the left pSTG with control stimulation. Our findings provide evidence, for the first time, that supports a causal relationship between right, but not left, pSTG and auditory-motor integration for vocal pitch regulation. This lends support to a right-lateralized contribution of the pSTG in not only the bottom-up detection of vocal feedback errors but also the involvement of driving motor commands for error correction in a top-down manner.

Cuproptosis-related LncRNA signatures as a prognostic model for head and neck squamous cell carcinoma.

Cuproptosis is a novel, distinct form of regulated cell death. However, little is known about the role of cuproptosis-related lncRNAs (CRlncRNAs) in head and neck squamous cell carcinoma (HNSCC). This study aimed to identify a CRlncRNAs signature, explore its prognostic value in HNSCC. RNA-seq data and relevant clinical data were downloaded from The Cancer Genome Atlas (TCGA) database, and cuproptosis-related genes were identified from a search of the relevant candidate-gene literature. Analysis of differentially expressed lncRNAs (DElncRNAs) was performed using the R package "edgeR". The intersection of the lncRNAs between DElncRNAs and CRlncRNAs was obtained using the R package "Venn Diagram". Univariate Cox regression was used to identify cuproptosis-related prognostic lncRNAs. LASSO-Cox method was used to narrow these cuproptosis-related prognostic lncRNAs and construct a prognostic model. Multiple statistical methods were used to evaluate the predictive ability of the model. Moreover, the relationships between the model and immune cell subpopulations, related functions and pathways and drug sensitivity were explored. Then, two risk groups were established according to the risk score calculated by the CRlncRNAs signature included three lncRNAs. In HNSCC patients, the risk score was a better predictor of survival than traditional clinicopathological features. In addition, significant differences in immune cells such as B cells, T cells and macrophages were observed between the two groups. Finally, the high-risk group had a lower IC50 for certain chemotherapeutic agents, such as cisplatin and cetuximab. This 3 CRlncRNAs signature is a powerful prognostic biomarker for predicting clinical outcomes and therapeutic responses in HNSCC patients.

Stemness-related lncRNAs signature as a biologic prognostic model for head and neck squamous cell carcinoma.

Cancer stem cells (CSCs) and long non-coding RNAs (lncRNAs) are particularly important for tumor cell growth and migration, and recurrence and drug resistance, including head and neck squamous cell carcinoma (HNSCC). The purpose of this study was to explore stemness-related lncRNAs (SRlncRNAs) that could be used for prognosis of patients with HNSCC. HNSCC RNA sequencing data and matched clinical data were obtained from TCGA database, and stem cell characteristic genes related to HNSCC mRNAsi were obtained from the online database by WGCNA analysis, respectively. Further, SRlncRNAs were obtained. Then, the prognostic model was constructed to forecast patient survival through univariate Cox regression and LASSO-Cox method based on SRlncRNAs. Kaplan-Meier, ROC and AUC were used to evaluate the predictive ability of the model. Moreover, we probed the underlying biological functions, signalling pathways and immune status hidden within differences in prognosis of patients. We explored whether the model could guide personalized treatments included immunotherapy and chemotherapy for HNSCC patients. At last, RT-qPCR was performed to analyze the expressions levels of SRlncRNAs in HNSCC cell lines. A SRlncRNAs signature was identified based on 5 SRlncRNAs (AC004943.2, AL022328.1, MIR9-3HG, AC015878.1 and FOXD2-AS1) in HNSCC. Also, risk scores were correlated with the abundance of tumor-infiltrating immune cells, whereas HNSCC-nominated chemotherapy drugs were considerably different from one another. The final finding was that these SRlncRNAs were abnormally expressed in HNSCCCS according to the results of RT-qPCR. These 5 SRlncRNAs signature, as a potential prognostic biomarker, can be utilized for personalized medicine in HNSCC patients.

The role of heavy metals in the development of colorectal cancer.

OBJECTIVE: To investigate the relationship among 18 heavy metals, microsatellite instability (MSI) status, ERCC1, XRCC1 (rs25487), BRAF V600E and 5 tumor markers and their role in the development of colorectal cancer (CRC). METHODS: A total of 101 CRC patients and 60 healthy controls were recruited in the present study. The levels of 18 heavy metals were measured by ICP-MS. MSI status and the genetic polymorphism were determined by PCR (FP205-02, Tiangen Biochemical Technology Co., Ltd., Beijing, China) and Sanger sequencing. Spearman's rank correlation was used to analyze the relationship among various factors. RESULTS: The level of selenium (Se) was lower in the CRC group compared with the control group (p < 0.01), while vanadium (V), arsenic (As), tin (Sn), barium (Ba) and lead (Pb) were higher (p < 0.05), chromium (Cr) and copper (Cu) were significantly higher (p < 0.0001) in the CRC group than those in the control group. Multivariate logistic regression analysis indicated that Cr, Cu, As and Ba were the risk factors for CRC. In addition, CRC was positively correlated with V, Cr, Cu, As, Sn, Ba and Pb, but negatively correlated with Se. MSI was positively correlated with BRAF V600E, but negatively correlated with ERCC1. BRAF V600E was positively correlated with antimony (Sb), thallium (Tl), CA19-9, NSE, AFP and CK19. XRCC1 (rs25487) was found to be positively correlated with Se but negatively correlated with Co. The levels of Sb and Tl were significantly higher in the BRAF V600E positive group compared to the negative group. The mRNA expression level of ERCC1 was significantly higher (P = 0.035) in MSS compared to MSI. And there was a significant correlation between XRCC1 (rs25487) polymorphism and MSI status (P<0.05). CONCLUSION: The results showed that low level of Se and high levels of V, As, Sn, Ba, Pb, Cr, and Cu increased the risk of CRC. Sb and Tl may cause BRAF V600E mutations, leading to MSI. XRCC1 (rs25487) was positively correlated with Se but negatively correlated with Co. The expression of ERCC1 may be related to MSS, while the XRCC1 (rs25487) polymorphism is related to MSI.