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1.
J Med Food ; 2024 Apr 29.
Article in English | MEDLINE | ID: mdl-38682284

ABSTRACT

Tao-Hong-Si-Wu-Tang (THSWT), a traditional Chinese herbal remedy, is commonly utilized for the treatment of female perimenopausal depression through regulating menstruation, but the mechanism remains unknown. In this study, ICR mice were randomly divided into six groups: low, medium, and high dose of THSWT (0.5, 1.5, and 4.5 g/kg), soy isoflavone (250 mg/kg), ovariectomy group, and control group. All mice, except the control group, had ovaries removed and were exposed to hypoxic stimulation for 28 days to establish a perimenopausal depression mice model. The mice, having unrestricted access to food and water, were administered THSWT treatment for a duration of 14 days. The Western blotting and Enzyme linked immunosorbent assay kits were used to determine protein and hormone levels, respectively. Experimental results showed that THSWT reduced the immobility time of mice from 150.8 s to 104.9 s in the tail suspension test, and it decreased the immobility time of mice from 165.7 s to 119.0 s in the forced swimming test, outperforming the results obtained with soy isoflavones. In addition, THSWT upregulated the protein expression of follicle-stimulating hormone receptor and downregulated the protein expression of corticotropin-releasing hormone-receptor 1 in the hippocampus. Compared with the oophorectomized group, treatment with THSWT decreased the levels of corticosterone and adrenocorticotropic hormone in serum by 173.7 and 23.4 ng/mL, respectively. These findings showed that THSWT could stimulate the perimenopausal nerve tissue and regulate the level of serum hormones in mice. THSWT exhibited promising potential as a viable alternative drug for hormone treatment of perimenopause in clinical use.

2.
Mar Environ Res ; 197: 106474, 2024 May.
Article in English | MEDLINE | ID: mdl-38547594

ABSTRACT

Climate change influences the distribution of many marine species. To project the biogeographical changes of benthic mollusks in response to climate change in the Yellow Sea and East China Sea, ensemble species distribution models (SDMs) were applied. Ensemble SDMs performed well for ten of the thirteen selected benthic mollusks with environmental variables including temperature, salinity, current velocity, and depth. Six cold water mollusks, including bivalves Acila mirabilis, Ennucula niponica, Ennucula tenuis, Nuculana yokoyamai, Pendaloma otohimeae and Megayoldia japonica, were projected to contract their habitats and move northward in 2050s and 2100s under all of the RCP2.6, 4.5, 6.0 and 8.5 climate scenarios, with temperature being the most important environmental variable. Two warm water mollusks (bivalves Nucula tokyoensis and Leptomya minuta) were projected to lose their suitable habitats under future climate scenarios (all RCP scenarios), while two (the gastropod Cylichna biplicata and the bivalve Moerella hilaris) were projected to expand their habitats to the deeper water area. The most important environmental variable varied among warm water species between temperature, salinity and depth. This study will contribute to better understanding the marine species biogeographical changes under climate change, and thus we can better protect their biodiversity.


Subject(s)
Bivalvia , Gastropoda , Animals , Ecosystem , Biodiversity , Climate Change , Water , China
3.
Angew Chem Int Ed Engl ; 63(21): e202402843, 2024 May 21.
Article in English | MEDLINE | ID: mdl-38512004

ABSTRACT

The construction of two distal stereocenters through a single catalytic process is of great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation of 1,3- or 1,4-stereocenters, the more challenged 1,5-nonadjacent stereocenters have never been achieved in a stereodivergent fashion. Herein we describe a synergistic palladium/copper catalysis for 1,4-difunctionalization reactions of 1,3-dienes, providing access to 1,5-nonadjacent quaternary stereocenters. Because each of the two catalysts separately controlled one of the newly formed stereocenters, stereodivergent synthesis of all four diastereomers of the products could readily be achieved simply by choosing an appropriate combination of chiral catalysts. Experimental and computational studies supported a mechanism involving a Heck/Tsuji-Trost cascade reaction, and the origins of the stereoselectivity were elucidated.

4.
Acc Chem Res ; 2024 Jan 31.
Article in English | MEDLINE | ID: mdl-38295513

ABSTRACT

ConspectusTransition-metal-catalyzed coupling reactions of dienes (such as 1,3-dienes, alkoxyallenes, and aminoallenes) with carbon nucleophiles have proven to be a highly effective method for creating Csp3-Csp3 bonds. These reactions have perfect atom economy and typically occur under mild reaction conditions. By using chiral metal complexes as catalysts, it is possible to create enantioenriched molecules bearing allylic stereocenters with high enantioselectivities. However, challenges arise when Csp3-Csp3 bonds bearing two vicinal stereocenters are constructed through this type of coupling reaction. Due to the inherent diastereoselectivities, only the kinetically favored diastereoisomers (either the syn- or anti-product) are usually obtained through the transition-metal catalyst system. Achieving complementary stereoisomers with high selectivity, which require complete control of both absolute and relative configurations of multiple chiral centers in a single chemical transformation, is usually impossible.Over the past decade, significant advancements have been made in stereodivergent synthesis. Notably, iridium-related synergistic catalysis has been rapidly developed for stereodivergent allylic alkylation reactions. However, these systems were limited to using allylic alcohol derivatives as electrophilic partners. Finding ways to extend the use of synergistic catalysis to other types of stereodivergent reactions is a crucial issue that needs to be addressed.In 2019, we reported the first palladium-mediated synergistic system for the stereodivergent Csp3-Csp3 coupling between 1,3-dienes and aldimine esters. Lately, this strategy has proven successful in accessing stereodivergent coupling with diverse substrate patterns. In this Account, we will summarize our laboratory's efforts in developing a range of palladium-involved synergistic catalysis systems for the stereodivergent Csp3-Csp3 coupling reactions of dienes. We discovered several synergistic catalysis systems, including Pd/Cu(Ag), Pd/amine, Pd/Lewis base, and Pd/PTC. Additionally, we developed diverse dienes, such as 1,3-dienes, alkoxyallenes, and aminoallenes, to serve as suitable coupling partners for stereodivergent coupling. These processes provide an efficient method for constructing a range of chiral scaffolds bearing vicinal stereocenters. Density functional theory (DFT) calculations have been performed to elucidate the reaction mechanism and to rationalize the origins of the stereochemistry for some of the synergistic catalyst systems. Finally, the synthetic application of these methods has been demonstrated in the concise total synthesis of a number of natural products and bioactive molecules. It is anticipated that an increasing number of chemists will join in the research on stereodivergent Csp3-Csp3 coupling reactions and contribute to more elegant examples in this area. We believe future development will further push the boundary of asymmetric catalysis and find more innovative applications soon for synthesizing complex chiral molecules.

5.
IEEE Trans Image Process ; 33: 825-839, 2024.
Article in English | MEDLINE | ID: mdl-38231817

ABSTRACT

Scene text spotting is a challenging task, especially for inverse-like scene text, which has complex layouts, e.g., mirrored, symmetrical, or retro-flexed. In this paper, we propose a unified end-to-end trainable inverse-like antagonistic text spotting framework dubbed IATS, which can effectively spot inverse-like scene texts without sacrificing general ones. Specifically, we propose an innovative reading-order estimation module (REM) that extracts reading-order information from the initial text boundary generated by an initial boundary module (IBM). To optimize and train REM, we propose a joint reading-order estimation loss ( LRE ) consisting of a classification loss, an orthogonality loss, and a distribution loss. With the help of IBM, we can divide the initial text boundary into two symmetric control points and iteratively refine the new text boundary using a lightweight boundary refinement module (BRM) for adapting to various shapes and scales. To alleviate the incompatibility between text detection and recognition, we propose a dynamic sampling module (DSM) with a thin-plate spline that can dynamically sample appropriate features for recognition in the detected text region. Without extra supervision, the DSM can proactively learn to sample appropriate features for text recognition through the gradient returned by the recognition module. Extensive experiments on both challenging scene text and inverse-like scene text datasets demonstrate that our method achieves superior performance both on irregular and inverse-like text spotting.

6.
J Mater Chem B ; 11(44): 10678-10691, 2023 11 15.
Article in English | MEDLINE | ID: mdl-37909648

ABSTRACT

With the rapid development of social industrialization, environmental problems seriously threaten people's health, especially water pollution. Therefore, there is an urgent need to construct a multifunctional nanoplatform for different scenarios. Two-dimensional MXene@AgAu@PDA nanosheets loaded with AgAu bimetallic nanocages have been prepared by a one-step method. First, the in situ generated MXene@Ag is used as an auxiliary template, and then HAuCl4 and dopamine are added for in situ redox-oxidizing polymerization reactions to obtain AgAu catalytic nanocages and the protective polydopamine (PDA) layer which can improve the stability and biocompatibility. MXene and PDA have excellent photothermal conversion ability while hollow AgAu nanocages have strong absorption in the near-infrared region and a local surface plasmonic resonance effect. In comparison to the catalytic reaction rates under dark and room temperature conditions, the catalytic kinetic rate of MXene@AgAu@PDA nanosheets under near-infrared irradiation increases from 0.13 to 0.69 min-1 mg-1. Density functional theory (DFT) is used to study the electron transfer behavior between AgAu nanocages and MXene nanosheets, and the mechanism of the enhanced catalytic reaction rate is analyzed. Besides, due to its Ag ions and photothermal coupling antibacterial properties, 40 µg mL-1 MXene@AgAu@PDA nanosheets inactivates nearly all E. coli and S. aureus after irradiation with near-infrared light for 6 min.


Subject(s)
Escherichia coli , Staphylococcus aureus , Humans , Anti-Bacterial Agents/pharmacology
7.
J Environ Manage ; 344: 118846, 2023 Oct 15.
Article in English | MEDLINE | ID: mdl-37666079

ABSTRACT

Different sub-regions of Zhengzhou city have various levels of sensitivity to flood due to the impact of urbanization. Thus, an accurate flood sensitivities assessment is a key tool for flood prevention and urban planning and development. To successfully link the urban flood sensitivity assessment with the real flood situation, a method combining clustering algorithm with comprehensive evaluation is presented. The proposed method is not affected by the classification standard of sensitivities levels and has a small and undemanding demand for flood data. First, Maximal Information Coefficient between conditional factors and flood is employed to determine the weight. Then, the different results are obtained by three clustering algorithms. Finally, a four-layer evaluation structure weighted by analytic hierarchy process is established to select the best flood susceptibility map. A case study in the Zhengzhou city, China shows that the positive scale amplification strategy is relatively best and the flood sensitivity of sub-regions in Zhengzhou city should be divided into four levels obtained by K-Means clustering. Hence, it supplies the valuable insights for the urban planning and flood mitigation.


Subject(s)
Algorithms , Floods , China , City Planning , Cluster Analysis
8.
Mar Pollut Bull ; 194(Pt B): 115246, 2023 Sep.
Article in English | MEDLINE | ID: mdl-37453168

ABSTRACT

To detect potential impacts of climate change on the distribution of common echinoderm species in the Yellow Sea (YS) and East China Sea (ECS), species distribution models (SDMs) were applied. Ensemble SDMs were constructed and were in good model performance for six of the eight selected common echinoderm species. Under future climate scenarios, the brittle stars Ophiopholis mirabilis, Amphioplus depressus and the sea cucumber Protankyra bidentata were projected to expand in the southwestern areas of the YS, the ECS, and the coastal areas of the YS and ECS, respectively; the brittle stars Stegophiura sladeni, Amphiura digitula and Amphiura vadicola will likely contract their ranges in the south distribution areas and expand in the north, showing a northward movement trend. Temperature was the most important environmental variable influencing the distribution of the latter three echinoderms. Our findings will improve our understanding of the impacts of climate change on marine species distributions.


Subject(s)
Climate Change , Sea Cucumbers , Animals , Echinodermata , China , Temperature
9.
J Cell Biochem ; 124(9): 1249-1258, 2023 09.
Article in English | MEDLINE | ID: mdl-37450693

ABSTRACT

This study aims to investigate the effect of placenta-derived mesenchymal stem cells (PMSCs) administration on tissue repair following acute lung injury (ALI). PMSCs were transplanted intravenously to a mouse model of lipopolysaccharide-induced ALI. The therapeutic effects were determined by evaluating several indicators, including pathology; the wet/dry ratio of the lungs; blood gas analysis; the total protein content, cell numbers, and the activity of myeloperoxidase (MPO) in bronchial alveolar lavage fluid (BALF); and the levels of anti-inflammatory and proinflammatory cytokines in serum and BALF. To investigate the underlying mechanism, PMSC-derived exosomes were used for ALI treatment. Administration of PMSCs improved the degree of lung injury, reduced inflammation, increased the expression levels of anti-inflammatory cytokines, and protected lung function. As expected, the effects of PMSC-derived exosomes in the ALI model were similar to those of PMSCs, both in terms of improved lung function and reduced inflammation. These findings suggest that PMSCs have ameliorating effects on ALI that are potentially mediated via their secreted exosomes.


Subject(s)
Acute Lung Injury , Mesenchymal Stem Cells , Mice , Animals , Humans , Mesenchymal Stem Cells/metabolism , Acute Lung Injury/chemically induced , Acute Lung Injury/therapy , Acute Lung Injury/metabolism , Lung/metabolism , Cytokines/metabolism , Lipopolysaccharides/adverse effects , Immunologic Factors , Inflammation/metabolism
10.
Front Biosci (Landmark Ed) ; 28(4): 72, 2023 04 06.
Article in English | MEDLINE | ID: mdl-37114535

ABSTRACT

BACKGROUND: Adipose tissue-derived stem cells (ADSCs), a type of mesenchymal stem cell, have been used extensively in clinical trials for the treatment of multiple conditions, including sepsis. However, increasing evidence indicates that ADSCs vanish from tissues within days of administration. Consequently, it would be desirable to establish the mechanisms underlying the fate of ADSCs following transplantation. METHODS: In this study, sepsis serum from mouse models was used to mimic microenvironmental effects. Healthy donor-derived human ADSCs were cultured in vitro in the presence of mouse serum from normal or lipopolysaccharide (LPS)-induced sepsis models for the purposes of discriminant analysis. The effects of sepsis serum on ADSC surface markers and cell differentiation were analyzed by flow cytometry, and the proliferation of ADSCs was assessed using a Cell Counting Kit-8 (CCK-8) assay. Quantitative real-time PCR (qRT-PCR) was applied to assess the degree of ADSC differentiation. The effects of sepsis serum on the cytokine release and migration of ADSCs were determined based on ELISA and Transwell assays, respectively, and ADSC senescence was assessed by ß-galactosidase staining and western blotting. Furthermore, we performed metabolic profiling to determine the rates of extracellular acidification and oxidative phosphorylation and the production of adenosine triphosphate and reactive oxygen species. RESULTS: We found that sepsis serum enhanced the cytokine and growth factor secretion and migratory capacities of ADSCs. Moreover, the metabolic pattern of these cells was reprogrammed to a more activated oxidative phosphorylation stage, leading to an increase in osteoblastic differentiation capacity and reductions in adipogenesis and chondrogenesis. CONCLUSIONS: Our findings in this study reveal that a septic microenvironment can regulate the fate of ADSCs.


Subject(s)
Adipose Tissue , Sepsis , Humans , Mice , Animals , Cell Proliferation , Stem Cells , Cell Differentiation/physiology , Cytokines , Cells, Cultured
11.
Front Cardiovasc Med ; 9: 1049600, 2022.
Article in English | MEDLINE | ID: mdl-36505383

ABSTRACT

The past decade has witnessed unprecedented medical progress, which has translated into cardiac surgery being increasingly common and safe. However, complications such as postoperative delirium remain a major concern. Although the pathophysiological changes of delirium after cardiac surgery remain poorly understood, it is widely thought that inflammation and oxidative stress may be potential triggers of delirium. The development of delirium following cardiac surgery is associated with perioperative risk factors. Multiple interventions are being explored to prevent and treat delirium. Therefore, research on the potential role of biomarkers in delirium as well as identification of perioperative risk factors and pharmacological interventions are necessary to mitigate the development of delirium.

12.
RSC Adv ; 12(41): 26994-27001, 2022 Sep 16.
Article in English | MEDLINE | ID: mdl-36320841

ABSTRACT

The experimental fabrication of novel two-dimensional ZnSb inspires us to explore the tunability of its fundamental physical properties. In this work, we present the density functional theory simulations on the mechanical, electronic and transport properties of the two-dimensional ZnSb monolayers functionalized with halogen atoms. It is found that the halogen atoms prefer to form ionic bonds with Sb atoms and these ZnSbX (X = Cl, Br and I) monolayers are very flexible with Young's moduli ranging from 24.02 N m-1 to 30.16 N m-1 along the armchair and zigzag directions. The pristine ZnSb monolayer sheet exhibits metallic phase while the functionalization can lead to a metal-to-semiconductor transition with band gaps as large as 0.55 eV. The transport study reveals a large tunability with the hole mobility reaching 43.44 × 103 cm2 V-1 s-1 along the armchair direction and the electron mobility as high as 36.99 × 103 cm2 V-1 s-1 along the zigzag direction. In contrast, the electron mobility along the armchair direction and the hole mobility along the zigzag direction are of relatively small magnitude. The ultrahigh carrier mobility together with the directional anisotropy can boost the separation of photo-excited electron-hole pairs. The finite band gaps and exceptional transport property of ZnSbX monolayers render them new materials with promising applications in flexible optoelectronic and nanoelectronic devices.

13.
Oxid Med Cell Longev ; 2022: 5815843, 2022.
Article in English | MEDLINE | ID: mdl-36132228

ABSTRACT

Stroke is a neurological disease that causes significant disability and death worldwide. Ischemic stroke accounts for 75% of all strokes. The pathophysiological processes underlying ischemic stroke include oxidative stress, the toxicity of excitatory amino acids, ion disorder, enhanced apoptosis, and inflammation. Noncoding RNAs (ncRNAs) may have a vital role in regulating the pathophysiological processes of ischemic stroke, as confirmed by the altered expression of ncRNAs in blood samples from acute ischemic stroke patients, animal models, and oxygen-glucose-deprived (OGD) cell models. Due to specific changes in expression, ncRNAs can potentially be biomarkers for the diagnosis, treatment, and prognosis of ischemic stroke. As an important brain cell component, glial cells mediate the occurrence and progression of oxidative stress after ischemic stroke, and ncRNAs are an irreplaceable part of this mechanism. This review highlights the impact of ncRNAs in the oxidative stress process of ischemic stroke. It focuses on specific ncRNAs that underlie the pathophysiology of ischemic stroke and have potential as diagnostic biomarkers and therapeutic targets.


Subject(s)
Brain Ischemia , Ischemic Stroke , Stroke , Animals , Biomarkers/metabolism , Brain Ischemia/genetics , Brain Ischemia/metabolism , Glucose , Ischemic Stroke/genetics , Oxidative Stress/genetics , Oxygen , RNA, Untranslated/genetics , RNA, Untranslated/metabolism , Stroke/metabolism
14.
J Oncol ; 2022: 4516537, 2022.
Article in English | MEDLINE | ID: mdl-35720226

ABSTRACT

Objective: To observe the effects of propofol and sevoflurane anesthesia on patients undergoing glioma surgery. Methods: 192 patients with gliomas treated in our hospital from January 2016 to January 2021 were selected. All patients were randomly divided into observation group and control group. The observation group was given sevoflurane and the control group was given propofol. The clinical effects of the two groups were observed. Results: Comparison of clinical indexes related to intraoperative conditions between the two groups revealed that the time of anesthesia and extubation after operation in the observation group were shorter than those in the control group, and the difference was statistically significant (P < 0.05). The amount of intraoperative bleeding in the observation group was less than that in the control group, and the difference was statistically significant (P < 0.05). There was no significant difference in intracranial operation time, operation time, fluid volume, and urine volume between the two groups (P < 05). Comparing the recovery time of anesthesia between the two groups, the recovery time of orientation and the time of eye-opening in the observation group were significantly shorter than those in the control group (P < 0.05). Comparing the consciousness and cognitive function of the two groups, the OAAS score of the observation group after extubation, before leaving the operating room and 1 hour after extubation, was significantly higher than that of the control group (P < 0.05), and the MMSE score l h after extubation was significantly higher than that of the control group (P < 0.05). Comparing the incidence of postoperative complications between the two groups, the number of cases of restlessness, urinary infection, deep vein thrombosis, and hypertension in the observation group was lower than that in the control group, with statistical significance (P < 0.05). Conclusion: The anesthesia time and extubation time of the sevoflurane anesthesia group were shorter than that of the propofol anesthesia group, and the orientation recovery time and eye-opening time were shortened. The OAAS score of the sevoflurane anesthesia group was higher than that of the propofol anesthesia group after extubation, before extubation, and 1 hour after extubation. The probability of postoperative complications in the sevoflurane anesthesia group was lower than that in the propofol anesthesia group. Sevoflurane anesthesia may be more suitable for surgical induction of glioma patients than propofol anesthesia.

15.
Front Cell Neurosci ; 16: 864426, 2022.
Article in English | MEDLINE | ID: mdl-35602556

ABSTRACT

Ischemic stroke is an acute cerebrovascular disease characterized by sudden interruption of blood flow in a certain part of the brain, leading to serious disability and death. At present, treatment methods for ischemic stroke are limited to thrombolysis or thrombus removal, but the treatment window is very narrow. However, recovery of cerebral blood circulation further causes cerebral ischemia/reperfusion injury (CIRI). The endoplasmic reticulum (ER) plays an important role in protein secretion, membrane protein folding, transportation, and maintenance of intracellular calcium homeostasis. Endoplasmic reticulum stress (ERS) plays a crucial role in cerebral ischemia pathophysiology. Mild ERS helps improve cell tolerance and restore cell homeostasis; however, excessive or long-term ERS causes apoptotic pathway activation. Specifically, the protein kinase R-like endoplasmic reticulum kinase (PERK), activating transcription factor 6 (ATF6), and inositol-requiring enzyme 1 (IRE1) pathways are significantly activated following initiation of the unfolded protein response (UPR). CIRI-induced apoptosis leads to nerve cell death, which ultimately aggravates neurological deficits in patients. Therefore, it is necessary and important to comprehensively explore the mechanism of ERS in CIRI to identify methods for preserving brain cells and neuronal function after ischemia.

16.
RSC Adv ; 12(5): 2693-2700, 2022 Jan 18.
Article in English | MEDLINE | ID: mdl-35425290

ABSTRACT

Using first-principles density-functional theory simulations, we explore the effects of hydrogenation and strain on the mechanical, electronic and transport properties of two-dimensional ZnSb monolayers. We find that the fully hydrogenated ZnSb monolayer exhibits large mechanical anisotropy between armchair and zigzag directions and the biaxial tensile strain reduces the anisotropy. In addition, we find that the hydrogenation can induce a metal-to-semiconductor transition with a direct band gap of 1.12 (1.92) eV using the PBE (HSE) functional. With biaxial strains, the band gaps decrease monotonically and remain direct for strains smaller than 5%. Moreover, large transport anisotropy is demonstrated by computing the effective masses of charge carriers along the asymmetric armchair and zigzag directions. We further reveal that strain can significantly tune the effective masses and a 3% strain can even switch the effective transport direction for holes. Our simulations suggest that the hydrogenated ZnSb monolayer is a promising candidate for electronic and opto-electronic applications with controllable modification via strain engineering.

17.
Mar Pollut Bull ; 174: 113238, 2022 Jan.
Article in English | MEDLINE | ID: mdl-34920240

ABSTRACT

Species distribution models (SDMs) are used to detect potential effects of climate change on the habitat suitability of macrobenthos in the Yellow Sea and East China Sea. We obtained the presence/absence data of five dominant and characteristic macrobenthos from 268 sites investigated during 2000-2016 and 13 environmental variables from online datasets. The ensemble SDMs were constructed and were in good model performance for all five species. Model projections showed that the five species displayed different reactions to future climate scenarios: two species (the ophiuroid Ophiura sarsii vadicola and the bivalve Thyasira tokunagai) will likely contract their ranges, two (the crab Xenophthalmus pinnotheroides and the polychaete Sternaspis chinensis) will likely expand their ranges, and one (the ophiuroid Amphioplus japonicus) will likely move northward. Those differences were mainly due to their difference in thermal tolerance. Our findings provide important scientific basis for understanding the influence of climate change on marine benthic ecosystems.


Subject(s)
Bivalvia , Polychaeta , Animals , China , Climate Change , Ecosystem
18.
J Am Chem Soc ; 143(29): 10948-10962, 2021 07 28.
Article in English | MEDLINE | ID: mdl-34264662

ABSTRACT

Metal-hydride-catalyzed hydroalkylation of 1,3-dienes with enolizable carbonyl compounds is an atom- and step-economical method for preparing chiral molecules with allylic stereocenters. Although high diastereo- and enantioselectivities have been achieved for many coupling partners, aldehydes have not yet been used for this purpose because they are less stable than other carbonyl compounds under basic conditions and they have the potential to rapidly epimerize at the α-position. Moreover, stereodivergent hydroalkylation reactions of 1,3-dienes to access complementary diastereomers with vicinal stereocenters is challenging. Herein, we describe a synergistic palladium/amine catalyst system that allowed us to achieve the first stereodivergent hydroalkylation reactions of 1,3-dienes with aldehydes. By choosing an appropriate combination of chiral palladium and amine catalysts, we could obtain either syn or anti coupling products, and this method therefore provides highly diastereo- and enantioselective access to complementary diastereomers of chiral aldehydes with α,ß-vicinal stereocenters. Density functional theory calculations revealed a mechanism involving PdH formation and migratory insertion into the alkene, followed by C-C bond formation. The origin of the stereoselectivities was investigated by means of distortion/interaction analysis.

19.
Org Lett ; 23(7): 2676-2681, 2021 Apr 02.
Article in English | MEDLINE | ID: mdl-33720734

ABSTRACT

A dual gold-catalyzed hexadehydro-Diels-Alder/carboalkoxylation cascade reaction is reported. In this transformation, the gold catalyst participated in the hexadehydro-Diels-Alder step, switching the mechanism from a radical type to a cationic one, and then the catalyst activated the resulting aryne to form an ortho-Au phenyl cation species, which underwent a carboalkoxylation rearrangement rather than the expected aryne-ene reaction.

20.
Sci Total Environ ; 739: 139760, 2020 Oct 15.
Article in English | MEDLINE | ID: mdl-32544674

ABSTRACT

To examine the temporal variation of macrobenthic community zonation over nearly 60 years and the effects of latitude and depth in the southern Yellow Sea and East China Sea, a total of 1386 box-corer samples from four large spatial scale studies during 1958-1959, 2000-2004, 2011-2013 and 2014-2016 period, respectively, were compiled. A total of 26, 14, 13 and 18 communities were identified, respectively during the four periods with the same analytical method. The Yellow Sea Cold Water Mass (YSCWM) community, restricted to the 34°N latitude in the south and 50 m isobaths in the west, varied little in its spatial pattern over nearly 60 years, while other communities did not. The representative species in the YSCWM community changed from the polychaetes to the brittle stars during 1958-2016. However, in other large spatial scale communities except the YSCWM community, the representative species changed from the echinoderms, nemerteans or crustaceans to the polychaetes. For the revisited locations across studies, significant temporal and spatial variations in community structure at both species and family levels were detected. Macrobenthic species with high consecutive contributions to the community similarity were significantly influenced by latitude, depth, temperature and salinity, among which latitude and depth were the first two most significant environmental variables. Species diversity increased from 32 to 37°N during 1958-1959, but decreased during 2014-2016. It seems that the latitude of 32°N is an ecological barrier for macrobenthic community and diversity, but its effects weakened from 1958 to 2016. Species diversity roughly showed a first increasing then decreasing trend with the increase of the water depth in the southern Yellow Sea and East China Sea.


Subject(s)
Crustacea , Seawater , Animals , China , Ecosystem , Oceans and Seas , Salinity
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