Palladium- and Brønsted acid-catalyzed enantio-, site- and E/Z-selective addition of alkylidenecyclopropanes with imines.

Transition-metal catalyzed functionalization of ACPs has been widely investigated in cycloaddition and 1,3-difunctionalization reactions. However, the transition metal catalyzed nucleophilic reactions of ACPs have rarely been reported. In this article, an enantio-, site- and E/Z-selective addition of ACPs with imines for the synthesis of dienyl substituted amines has been developed via palladium- and Brønsted acid co-catalysis. A range of synthetically valuable dienyl substituted amines were effectively prepared with good to excellent yields and excellent enantio- and E/Z-selectivities.

Lethal and sublethal effects of broflanilide on four tephritid pests (Diptera: Tephritidae).

BACKGROUND: Fruit flies are internationally important quarantine or invasive pests of many fruits and vegetables and can cause serious economic losses. Long-term reliance on insecticides for controlling these pests has led to increasing resistance to multiple insecticides; hence, a new agent is needed. In this study, the acute toxicity and sublethal effects of the novel insecticide broflanilide on four adult fruit fly species, Bactrocera dorsalis, Bactrocera cucurbitae, Bactrocera tau, and Bactrocera correcta, were evaluated. RESULTS: Broflanilide was effective against B. dorsalis and B. correcta, with lethal concentration values (amount required to kill 50% of animals; LC50 ) of 0.390 and 1.716 mg/L. However, for B. cucurbitae (19.673 mg/L) and B. tau (24.373 mg/L), the LC50 was 50-60 times higher than that of B. dorsalis. The survival rates of B. correcta and B. cucurbitae were significantly lower under LC50 treatment than those of the control (corrected for mortality rate). Sublethal concentrations of broflanilide stimulated fecundity in all species except B. tau. The hatching rate at LC50 was significantly lower for B. correcta and B. tau compared with the control and even more so for B. correcta, which was zero. CONCLUSION: Broflanilide is potentially an effective insecticide for controlling B. dorsalis and B. correcta. However, the variation in toxicity of broflanilide to the four fruit flies suggests that species variation needs to be carefully considered. Our results highlight the importance of clarifying the sublethal effects of insecticides on target insects to ensure the comprehensive evaluation and rational use of insecticides. © 2023 Society of Chemical Industry.

Rational Synthesis of Core-Shell-Structured Nickel Sulfide-Based Nanostructures for Efficient Seawater Electrolysis.

Versatile electrocatalysis at higher current densities for natural seawater splitting to produce hydrogen demands active and robust catalysts to overcome the severe chloride corrosion, competing chlorine evolution, and catalyst poisoning. Hereto, the core-shell-structured heterostructures composed of amorphous NiFe hydroxide layer capped Ni3 S2 nanopyramids which are directly grown on nickel foam skeleton (NiS@LDH/NF) are rationally prepared to regulate cooperatively electronic structure and mass transport for boosting oxygen evolution reaction (OER) performance at larger current densities. The prepared NiS@LDH/NF delivers the anodic current density of 1000 mA cm-2 at the overpotential of 341 mV in 1.0 m KOH seawater. The feasible surface reconstruction of Ni3 S2 -FeNi LDH interfaces improves the chemical stability and corrosion resistance, ensuring the robust electrocatalytic activity in seawater electrolytes for continuous and stable oxygen evolution without any hypochlorite production. Meanwhile, the designed Ni3 S2 nanopyramids coated with FeNi2 P layer (NiS@FeNiP/NF) still exhibit the improved hydrogen evolution reaction (HER) activity in 1.0 m KOH seawater. Furthermore, the NiS@FeNiP/NF||NiS@LDH/NF pair requires cell voltage of 1.636 V to attain 100 mA cm-2 with a 100% Faradaic efficiency, exhibiting tremendous potential for hydrogen production from seawater.

[Clinical Features and Prognosis of Patients with Castleman's Disease].

OBJECTIVE: To analyze the clinical features and prognosis of patients with Castleman's disease (CD) and improve the diagnosis and treatment of CD. METHODS: Clinical data of patients diagnosed with CD by pathological biopsy in Gansu Provincial Hospital from January 2009 to November 2020 were retrospectively analyzed. According to clinical classification, the patients were divided into two groups: UCD (unicentric CD) group (n=20) and MCD (multicentric CD) group (n=9). The clinical manifestations, laboratory examination, treatment regimens, pathological examination and follow-up data were statistically analyzed. RESULTS: There were no significant differences in average age and gender ratio between UCD group and MCD group. In UCD patients, 80.0% were hyaline vascular type, and 20.0% were plasma cell type. In MCD patients, 33.3% were hyaline vascular type, 55.6% were plasma cell type, and 11.1% were mixed type. There was significant difference in pathological classification between the two groups (P=0.039). The UCD patients usually presented asymptomatic single lymph node enlargement with mild clinical symptoms, while the MCD patients were characterized by multiple superficial and deep lymph node enlargement throughout the body. The incidences of asthenia, splenomegaly, serous effusion in MCD group were higher than those in UCD group (P<0.05). Meanwhile, the incidences of anemia, hypoproteinemia, increased ESR, elevated serum globulin and elevated ß2-microglobulin were significantly higher than those in UCD group too (P<0.05). There was no significant difference in the incidences of abnormal WBC, PLT and elevated LDH between the two groups (P>0.05). Among 20 patients with UCD, 13 cases reached complete remission (CR), 1 case achieved partial remission (PR). Among 9 patients with MCD, 3 cases received CR and 4 cases received PR. CONCLUSION: Patients with CD requires pathological examination for diagnosis. Patients with UCD show mild clinical symptoms, good surgical treatment effect and good prognosis. Patients with MCD have diversified clinical manifestations and relatively poor prognosis, and these patients require comprehensive treatment.

Solving the inverse problem in electrocardiography imaging for atrial fibrillation using various time-frequency decomposition techniques based on empirical mode decomposition: A comparative study.

Electrocardiographic imaging (ECGI) can aid in identifying the driving sources that cause and sustain atrial fibrillation (AF). Traditional regularization strategies for addressing the ECGI inverse problem are not currently concerned about the multi-scale analysis of the inverse problem, and these techniques are not clinically reliable. We have previously investigated the solution based on uniform phase mode decomposition (UPEMD-based) to the ECGI inverse problem. Numerous other methods for the time-frequency analysis derived from empirical mode decomposition (EMD-based) have not been applied to the inverse problem in ECGI. By applying many EMD-based solutions to the ECGI inverse problem and evaluating the performance of these solutions, we hope to find a more efficient EMD-based solution to the ECGI inverse problem. In this study, five AF simulation datasets and two real datasets from AF patients derived from a clinical ablation procedure are employed to evaluate the operating efficiency of several EMD-based solutions. The Pearson's correlation coefficient (CC), the relative difference measurement star (RDMS) of the computed epicardial dominant frequency (DF) map and driver probability (DP) map, and the distance (Dis) between the estimated and referenced most probable driving sources are used to evaluate the application of various EMD-based solutions in ECGI. The results show that for DF maps on all simulation datasets, the CC of UPEMD-based and improved UPEMD (IUPEMD)-based techniques are both greater than 0.95 and the CC of the empirical wavelet transform (EWT)-based solution is greater than 0.889, and the RDMS of UPEMD-based and IUPEMD-based approaches is less than 0.3 overall and the RDMS of EWT-based method is less than 0.48, performing better than other EMD-based solutions; for DP maps, the CC of UPEMD-based and IUPEMD-based techniques are close to 0.5, the CC of EWT-based is 0.449, and the CC of the remaining EMD-based techniques on the SAF and CAF is all below 0.1; the RDMS of UPEMD-based and IUPEMD-based are 0.06∼0.9 less than that of other EMD-based methods for all the simulation datasets overall. On two authentic AF datasets, the Dis between the first 10 real and estimated maximum DF positions of UPEMD-based and EWT-based methods are 212∼1440 less than that of others, demonstrating these two EMD-based solutions are superior and are suggested for clinical application in solving the ECGI inverse problem. On all datasets, EWT-based algorithms deconstruct the signal in the shortest time (no more than 0.12s), followed by UPEMD-based solutions (less than 0.81s), showing that these two schemes are more efficient than others.

Interface Metal Oxides Regulating Electronic State around Nickel Species for Efficient Alkaline Hydrogen Electrocatalysis.

Heterogeneous electrocatalysis typically depends on the surface electronic states of active sites. Modulating the surface charge state of an electrocatalysts can be employed to improve performance. Among all the investigated materials, nickel (Ni)-based catalysts are the only non-noble-metal-based alternatives for both hydrogen oxidation and evolution reactions (HOR and HER) in alkaline electrolyte, while their activities should be further improved because of the unfavorable hydrogen adsorption behavior. Hereto, Ni with exceptional HOR electrocatalytic performance by changing the d-band center by metal oxides interface coupling formed in situ is endowed. The resultant MoO2 coupled Ni heterostructures exhibit an apparent HOR activity, even approaching to that of commercial 20% Pt/C benchmark, but with better long-term stability in alkaline electrolyte. An exceptional HER performance is also achieved by the Ni-MoO2 heterostructures. The experiment results are rationalized by the theoretical calculations, which indicate that coupling MoO2 with Ni results in the downshift of d-band center of Ni, and thus weakens hydrogen adsorption and benefits for hydroxyl adsorption. This concept is further proved by other metal oxides (e.g., CeO2 , V2 O3 , WO3 , Cr2 O3 )-formed Ni-based heterostructures to engineer efficient hydrogen electrocatalysts.

Palladium-Catalyzed Nucleophilic Reaction of Alkylidenecyclopropanes with ß,γ-Unsaturated α-Ketoesters: Ligand-Controlled Divergent Synthesis.

A palladium-catalyzed ligand-controlled selective 1,4-addition and cycloaddition reaction of ß,γ-unsaturated α-ketoesters with alkylidenecyclopropanes (ACPs) has been developed. Using ACPs and ß,γ-unsaturated α-ketoesters as starting materials, γ-dienyl-α-ketoesters and dihydro-2H-pyrans could be prepared selectively by modulating the ligand. A range of multisubstituted α-ketoesters and dihydro-2H-pyrans were obtained in moderate to excellent yields with excellent regioselectivities.

Cervical sympathetic trunk transection alleviates acute lung injury caused by intestinal obstruction via inhibition of phospholipase A2 in rats.

BACKGROUND: Intestinal obstruction can result in inflammatory injury to distant organs, especially the lungs. Stellate ganglion block (SGB) provides sympathetic nervous homeostasis and inhibits the systemic inflammatory response. This study aimed to investigate whether SGB can alleviate acute lung injury by inhibiting phospholipase A2 expression in rats. METHODS: Thirty healthy male Sprague-Dawley rats were divided into three groups: C group (sham-operated); CLP group (cecal ligation and puncture with intestinal obstruction), and cervical sympathetic trunk transection (CSTT) group (transection of the cervical sympathetic trunk following CLP).Arterial blood samples were obtained to determine the ratio of partial arterial pressure of oxygen (PaO2) to fraction of oxygen in inspired air (FiO2). Venous blood samples were used to evaluate the serum concentrations of chemokines, tumor necrosis factor (TNF)-α, interleukin (IL)-6, and IL-10 using enzyme-linked immunosorbent assays. Following euthanasia, the lungs were isolated to estimate the wet/dry lung weight (W/D) ratio, evaluate the pathological damage to lung tissues on microscopy, and determine secretory-type phospholipase A2 (sPLA2) expression using western blotting. RESULTS: Rats in the CLP group showed increased fatigue, decreased activity levels, and coarse, gray hair. The levels of chemokines, TNF-α, and IL-6 in the CLP and CSTT groups were higher than those in the C group. However, the levels were lower in the CSTT group than those in the CLP group. IL-10 levels in the CLP group were higher and lower than those in the C and CSTT groups, respectively. W/D ratios and PaO2/FiO2 in the CLP and CSTT groups were higher than those in the C group, whereas these ratios in the CSTT group were lower than those in the CLP group. No lung injury was noted in group C, and the lung injury scores were lower in the CSTT group than those in the CLP group. sPLA2 expression levels in the CLP group were higher than those in the C group, whereas these levels in the CSTT group were lower than those in the CLP group. CONCLUSIONS: sPLA2 overexpression in the lungs may be a pathogenic factor in acute lung injury. CSTT alleviated acute lung injury by inhibiting sPLA2 expression.

Copper catalyzed borocarbonylation of benzylidenecyclopropanes through selective proximal C-C bond cleavage: synthesis of γ-boryl-γ,δ-unsaturated carbonyl compounds.

A copper catalyzed borocarbonylation of BCPs via proximal C-C bond cleavage for the synthesis of γ-boryl-γ,δ-unsaturated carbonyl compounds has been developed. Using substituted benzylidenecyclopropanes (BCPs) and chloroformates as starting material, a broad range of γ-boryl-γ,δ-unsaturated esters were prepared in moderate to excellent yields with excellent regio- and stereoselectivity. Besides, when aliphatic acid chlorides were used in this reaction, γ-boryl-γ,δ-unsaturated ketones could be produced in excellent yields. When substituted BCPs were used as substrates, the borocarbonylation occurred predominantly at the proximal C-C bond trans to the phenyl group in a regio- and stereoselective manner, which leads to the Z-isomers as the products. This efficient methodology involves the cleavage of a C-C bond and the formation of a C-C bond as well as a C-B bond, and provides a new method for the proximal C-C bond difunctionalization of BCPs.

Palladium Catalyzed Dicarbonylation of α-Iodo-Substituted Alkylidenecyclopropanes: Synthesis of Carbamoyl Substituted Indenones.

A palladium catalyzed dicarbonylation of α-iodo-substituted ACPs for the synthesis of carbamoyl substituted indenones has been developed. Two carbonyl groups were incorporated into the product with the cleavage of the proximal C-C bond of the ACPs. A broad range of carbamoyl substituted indenones were efficiently prepared in good to excellent yields.

Copper-catalyzed 1,2-Borylacylation of 1,3-Enynes: synthesis of ß-Alkynyl ketones.

A copper catalyzed 1,2-borylacylation of 1,3-enynes with B2pin2 and acid chlorides has been developed. Using readily available 1,3-enynes, B2pin2 and acid chlorides as substrates, a range of highly functionalized α,α-disubstituted ß-alkynyl ketones were readily prepared under mild conditions in moderate to good yields. The borylacylated products can be easily derivatized to give several valuable structures. Notably, treatment of the products with NaBO3·4H2O provided 1,2-allenyl ketones, which is proposed to proceed via a retro-aldol process of the corresponding homopropargyl alcohols.

New Bioactive Polyacetylenes from the Marine Sponge Petrosia sp.

Three new polyacetylenes, pellynols P (1), Q (2), and R (3) were isolated from the marine sponge Petrosia sp., along with the known compound pellynol H (4). Their structures were determined by analyses of extensive NMR, HR-MS, and ESI-MS/MS data. All compounds displayed potent cytotoxicities against human hepatocellular carcinoma HepG2, human melanoma A375, and human colorectal carcinoma HT29 cell lines with IC50 values at the range of 1.4-4.4 µM.

Two cardenolide glycosides from the seed fairs of Asclepias curassavica and their cytotoxic activities.

Two cardenolide glycosides, corotoxigenin 3-O-[ß-D-glucopyranosyl-(1→4)-6-deoxy-ß-D-glucopyranoside] (1) and coroglaucigenin 3-O-[ß-D-glucopyranosyl-(1→4)-6-deoxy-ß-D-glucopyranoside] (2), were isolated from the seed fairs of Asclepias curassavica. The structures of 1-2 were determined based on the combination of the analysis of their MS, NMR spectroscopic data and acid hydrolysis. The inhibitory effects of compounds 1 and 2 on human colorectal carcinoma cells (HCT116), non-small cell lung carcinoma cells (A549) and hepatic cancer cells (SMMC-7721) were evaluated. The results showed that both compounds 1 and 2 significantly inhibited the viability, proliferation, and migration of A549, HCT116 and SMMC-7721 cells, suggesting that compounds 1 and 2 can be applied in the treatment of lung, colon and liver cancers in clinical practice. This study may not only provide a scientific basis for clarifying the active ingredients in A. curassavica, but also help to understand its antitumor activity, which can promote the application of A. curassavica in clinical treatment of various cancers.

Palladium-Catalyzed Carbonylative Sonogashira/Annulation Reaction: Synthesis of Indolo[1,2-b]isoquinolines.

A palladium-catalyzed carbonylative Sonogashira/annulation reaction for the synthesis of indolo[1,2-b]isoquinolines has been developed. Tetracyclic 6/5/6/6 indoline skeletons were synthesized in moderate to good yields from easily available 2-bromo-N-(2-iodophenyl)benzamides and terminal alkynes. Notably, this efficient methodology established three C-C bonds and a C-N bond through a one-step transformation and provided a new method for the synthesis of indolo[1,2-b]isoquinoline derivatives.

The teaching practice and exploration of the course of New Technology of Radiotherapy and Oncology / 中华放射肿瘤学杂志

Objective:To evaluate and summarize the teaching effect of" New Technology of Radiotherapy and Oncology" in the form of questionnaire, understand the degree of demand for the course of all kinds of medical students and improve the teaching contents and methods.Methods:The course of" New Technology of Radiotherapy and Oncology" was a specialized elective course in Peking Union Medical College. After two rounds of teaching practices, we evaluated the students participating in the course or non-course participants by anonymous questionnaire. The questionnaire items include the course content, setting, teachers and improvement suggestions.Results:A total of 73 questionnaires were sent out, and the recovery rate was 100%. Among them, 52(71%) were from students who chose the courses. 83% of the students" strongly agree" that the teaching content of this course is the latest development, the latest achievement or the problem to be solved, 94% were" satisfied" or" very satisfied" with their learning effect, and 92% and 83% were satisfied with the teachers and teaching plan, respectively. After taking the course, students rated" broadening of mind" (96%) as the biggest gain, followed by" facilitating interdisciplinary collaboration" (79%). 86% of the non-course participants felt the need to supplement the existing curriculum with new techniques in oncology radiotherapy, hoping that the curriculum would" broaden the mind" (76%), improve clinical application (81%) and facilitate interdisciplinary collaboration (71%).Conclusion:The questionnaire results show that the teaching practice of this course covers the different needs of all kinds of students, which is worthy of implementation and further improvement.

Two cardenolide glycosides from the seed fairs of Asclepias curassavica and their cytotoxic activities / 中国天然药物

Two cardenolide glycosides, corotoxigenin 3-O-[β-D-glucopyranosyl-(1→4)-6-deoxy-β-D-glucopyranoside] (1) and coroglaucigenin 3-O-[β-D-glucopyranosyl-(1→4)-6-deoxy-β-D-glucopyranoside] (2), were isolated from the seed fairs of Asclepias curassavica. The structures of 1-2 were determined based on the combination of the analysis of their MS, NMR spectroscopic data and acid hydrolysis. The inhibitory effects of compounds 1 and 2 on human colorectal carcinoma cells (HCT116), non-small cell lung carcinoma cells (A549) and hepatic cancer cells (SMMC-7721) were evaluated. The results showed that both compounds 1 and 2 significantly inhibited the viability, proliferation, and migration of A549, HCT116 and SMMC-7721 cells, suggesting that compounds 1 and 2 can be applied in the treatment of lung, colon and liver cancers in clinical practice. This study may not only provide a scientific basis for clarifying the active ingredients in A. curassavica, but also help to understand its antitumor activity, which can promote the application of A. curassavica in clinical treatment of various cancers.

T helper 2-driven immune dysfunction in chronic arsenic-exposed individuals and its link to the features of allergic asthma.

Limited information is available regarding the effects of arsenic exposure on immune function. We have recently reported that chronic exposure to As was associated asthma, as determined by spirometry and respiratory symptoms. Because T helper 2 (Th2)-driven immune responses are implicated in the pathogenesis of allergic diseases, including asthma, we studied the associations of serum Th1 and Th2 mediators with the As exposure markers and the features of asthma among individuals exposed to As. A total of 553 blood samples were selected from the same study subjects recruited in our previous asthma study. Serum levels of Th1 and Th2 cytokines were analyzed by immunoassay. Subjects' arsenic exposure levels (drinking water, hair and nail arsenic concentrations) were determined by inductively coupled plasma mass spectroscopy. Arsenic exposure levels of the subjects showed significant positive associations with serum Th2-mediators- interleukin (IL)-4, IL-5, IL-13, and eotaxin without any significant changes in Th1 mediators- interferon-γ and tumor necrosis factor-α. The ratios of Th2 to Th1 mediators were significantly increased with increasing exposure to As. Notably, most of the Th2 mediators were positively associated with serum levels of total immunoglobulin E and eotaxin. The serum levels of Th2 mediators were significantly higher in the subjects with asthma than those without asthma. The results of our study suggest that the exacerbated Th2-driven immune responses are involved in the increased susceptibility to allergic asthma among individuals chronically exposed to As.

Unprecedented Multicomponent Reaction of Indoles, CS2 and Nitroarenes: Stereoselective Synthesis of (Z)-3-((Arylamino)methylene)indoline-2-thiones.

An efficient method for the stereoselective synthesis of (Z)-3-((arylamino)methylene)indoline-2-thiones have been developed via a novel multicomponent reaction of indoles, CS2 and nitroarenes. A range of functionalized indoline-2-thiones were prepared in moderate to good yields from easily available starting materials. The indoline-2-thione products can be easily derivatized to give biologically active thieno[2,3-b]indole and thiopyrano[2,3-b]indole skeletons in high yields.

Analysis of middle/long-term clinical efficacy of expanded criteria donor kidney transplantation / 中华器官移植杂志

Objective:To compare the medium/long-term prognosis of kidney transplant recipients with expanded criteria donor(ECD)versus standard criteria donor(SCD).Methods:From August 2011 to May 2017, a total of 506 cases underwent renal transplantation.Based upon baseline clinical data, they were divided into two groups of ECD(67 cases)and SCD(230 cases). And 1: 4 propensity score matching was employed for maximizing the elimination of selection bias influence on the results by rank-sum test.Results:There was no statistical difference existed between ECD and SCD donor kidney in acute rejection, delayed graft function and all-cause infection(all P>0.05). The value of eGFR of ECD donor kidney recipients was slightly lower than that of SCD group at Week 1 and Year 4 postoperatively( P<0.05). And there was no inter-group statistical significance in the fifth year( P=0.273). No significant inter-group difference existed in human/renal survival rate( P=0.143, P=0.076). Conclusions:Appropriate selection criteria and recipient selection criteria can make the application of ECD donor kidney safer and more scientific so as to benefit more patients.

The clinical effect of living kidney transplantation between spouses / 中华器官移植杂志

Objective:To investigate the clinical effect of spousal kidney transplantation , and to explore the significance in today's society.Methods:We retrospectively collected the relevant clinical data from the transplantation department of the first hospital of jilin university, from October 2009 to December 2018. Receptors who accepted spousal, parental and compatriot donor kidney is respectively obtained.Then the postoperative efficacy of the three groups were compared.Results:The graft survival rates of spousal kidney transplantation were 94.1% at 3 years and 83.7% at 5 years, which were not significantly different from other types of living kidney transplantation ( P=0.260). There was no significant difference in creatinine at each time point within 3 years after operation between three groups. At 3 years and 5 years after operation, there was no significant difference in creatinine between spouse group and sibling group.But the creatinine of spouse group was lower compared with parent group ( P=0.014, 0.038). The incidence of rejection within 1 years after spousal renal transplantation was 25%, which was significantly higher than parent group and sibling group ( P=0.029). Age of donor, gender of recipient, D/R BMI and incidence of AR or not in recipient were independent predictors for 1-year creatinine in living kidney transplantation (correlation coefficient: 0.048、-26.03、-15.95、10.23; P=0.003、<0.001、0.021、0.013). Conclusions:Spousal kidney transplantation has same clinical efficacy compared with other types of living kidney transplantation, which can greatly improve the donor kidney resource.So it worth being further promotion, but compared with other types of living kidney transplantation, we should be more alert to the incidence of rejection reaction, so as to obtain better curative effect.