Electrochemical synthesis of phosphorylated azaspiro[4.5]di/trienones through dearomative spirocyclization.

Cp2Fe-mediated electrochemical synthesis of a diverse array of phosphorylated azaspiro[4.5]di/trienones has been developed, which demonstrated broad substrate scope and good diastereoselectivity. It represents the first example of electrochemical synthesis of phosphorylated azaspiro[4.5]di/trienones, circumventing the need for external oxidants and high temperatures. Moreover, a plausible mechanism including radical-initiated dearomative cyclization driven by ferrocenium cations has been provided, which was supported by the related mechanistic study.

Construction of a nomogram model to predict technical difficulty in performing laparoscopic sphincter-preserving radical resection for rectal cancer.

BACKGROUND: Colorectal surgeons are well aware that performing surgery for rectal cancer becomes more challenging in obese patients with narrow and deep pelvic cavities. Therefore, it is essential for colorectal surgeons to have a comprehensive understanding of pelvic structure prior to surgery and anticipate potential surgical difficulties. AIM: To evaluate predictive parameters for technical challenges encountered during laparoscopic radical sphincter-preserving surgery for rectal cancer. METHODS: We retrospectively gathered data from 162 consecutive patients who underwent laparoscopic radical sphincter-preserving surgery for rectal cancer. Three-dimensional reconstruction of pelvic bone and soft tissue parameters was conducted using computed tomography (CT) scans. Operative difficulty was categorized as either high or low, and multivariate logistic regression analysis was employed to identify predictors of operative difficulty, ultimately creating a nomogram. RESULTS: Out of 162 patients, 21 (13.0%) were classified in the high surgical difficulty group, while 141 (87.0%) were in the low surgical difficulty group. Multivariate logistic regression analysis showed that the surgical approach using laparoscopic intersphincteric dissection, intraoperative preventive ostomy, and the sacrococcygeal distance were independent risk factors for highly difficult laparoscopic radical sphincter-sparing surgery for rectal cancer (P < 0.05). Conversely, the anterior-posterior diameter of pelvic inlet/sacrococcygeal distance was identified as a protective factor (P < 0.05). A nomogram was subsequently constructed, demonstrating good predictive accuracy (C-index = 0.834). CONCLUSION: The surgical approach, intraoperative preventive ostomy, the sacrococcygeal distance, and the anterior-posterior diameter of pelvic inlet/sacrococcygeal distance could help to predict the difficulty of laparoscopic radical sphincter-preserving surgery.

Palladium-Catalyzed Esterification of Aryl Fluorosulfates with Aryl Formates.

An efficient palladium-catalyzed carbonylation of aryl fluorosulfates with aryl formates for the facile synthesis of esters was developed. The cross-coupling reactions proceeded effectively in the presence of a palladium catalyst, phosphine ligand, and triethylamine in DMF to produce the corresponding esters in moderate to good yields. Of note, functionalities or substituents, such as nitro, cyano, methoxycarbonyl, trifluoromethyl, methylsulfonyl, trifluoromethoxy, fluoro, chloro, bromo, methyl, methoxy, N,N-dimethyl, and [1,3]dioxolyl, were well-tolerated in the reactions, which could be kept for late-stage modification. The reactions employing readily available and relatively robust aryl fluorosulfates as coupling electrophiles could potentially serve as an attractive alternative to traditional cross-couplings with the use of aryl halides and pseudohalides as substrates.

Study on sex differences and potential clinical value of three-dimensional computerized tomography pelvimetry in rectal cancer patients.

BACKGROUND: Laparoscopic rectal cancer radical surgery is a complex procedure affected by various factors. However, the existing literature lacks standardized parameters for the pelvic region and soft tissues, which hampers the establishment of consistent conclusions. AIM: To comprehensively assess 16 pelvic and 7 soft tissue parameters through computerized tomography (CT)-based three-dimensional (3D) reconstruction, providing a strong theoretical basis to address challenges in laparoscopic rectal cancer radical surgery. METHODS: We analyzed data from 218 patients who underwent radical laparoscopic surgery for rectal cancer, and utilized CT data for 3D pelvic reconstruction. Specific anatomical points were carefully marked and measured using advanced 3D modeling software. To analyze the pelvic and soft tissue parameters, we employed statistical methods including paired sample t-tests, Wilcoxon rank-sum tests, and correlation analysis. RESULTS: The investigation highlighted significant sex disparities in 14 pelvic bone parameters and 3 soft tissue parameters. Males demonstrated larger measurements in pelvic depth and overall curvature, smaller measurements in pelvic width, a larger mesorectal fat area, and a larger anterior-posterior abdominal diameter. By contrast, females exhibited wider pelvises, shallower depth, smaller overall curvature, and an increased amount of subcutaneous fat tissue. However, there were no significant sex differences observed in certain parameters such as sacral curvature height, superior pubococcygeal diameter, rectal area, visceral fat area, waist circumference, and transverse abdominal diameter. CONCLUSION: The reconstruction of 3D CT data enabled accurate pelvic measurements, revealing significant sex differences in both pelvic and soft tissue parameters. This study design offer potential in predicting surgical difficulties and creating personalized surgical plans for male rectal cancer patients with a potentially "difficult pelvis", ultimately improving surgical outcomes. Further research and utilization of these parameters could lead to enhanced surgical methods and patient care in laparoscopic rectal cancer radical surgery.

Iron-Mediated Reductive Amidation of Triazine Esters with Nitroarenes.

A reductive amidation of triazine esters with nitroarenes by using cheap iron as a reducing metal in the presence of TMSCl in DMF was developed. The reactions proceeded efficiently under transition metal-free conditions to give the corresponding amides in moderate to good yields with good functional group compatibility. Preliminary mechanistic investigations indicated that nitrosobenzene, N-phenyl hydroxylamine, azoxybenzene, azobenzene, aniline, and N-arylformamide possibly served as the intermediates of the reaction.

Cp2Fe-Mediated Electrochemical Synthesis of Phosphorylated Oxindoles and Indolo[2,1-a]isoquinolin-6(5H)-ones.

An efficient and environmentally friendly electrochemical synthesis of phosphorylated oxindoles and indolo[2,1-a]isoquinolin-6(5H)-ones mediated by readily available Cp2Fe has been developed, which illustrated a broad substrate scope and diverse functional group compatibility. This protocol featured an external oxidant-free process and was at room temperature, which was proposed to be driven by the anodic oxidation of Cp2Fe.

Application of metal stent implantation with endoscope and X-ray fluoroscopy combined laparoscopic surgery in the treatment of acute left hemicolon cancer obstruction.

BACKGROUND: This study aimed to conduct a case-control study of endoscopic and fluoroscopic metal stent placement combined with laparoscopic surgery versus conventional open Hartmann's procedure in treating acute left-sided colon cancer obstruction. Additionally, the study aims to discuss the application value of endoscopic and X-ray-guided metal stent placement combined with laparoscopic surgery in the treatment of acute left-sided colon cancer obstruction. METHODS: From June 2011 to December 2019, 23 patients with acute left-sided colon cancer obstruction who underwent metal stent implantation combined with laparoscopic surgery under endoscopy and X-ray fluoroscopy in Wenzhou Central Hospital were collected, and 20 patients with acute left-sided colon cancer obstruction who underwent traditional emergency open Hartmann's surgery during the same period were selected as a control group. All patients were diagnosed with left colon obstruction by plain abdominal film and/or CT before the operation and colon adenocarcinoma by colonoscopic biopsy and/or postoperative pathology. The operation time, intraoperative blood loss, postoperative anal exhaust time, the success rate of one-stage anastomosis, postoperative hospital stay, and postoperative complications were compared between the two groups. RESULTS: This study showed a significant difference in the therapeutic effect between the two groups. Compared with the traditional Hartmann's operation group, the success rate of one-stage anastomosis in endoscopic and X-ray-guided metal stent placement combined with the laparoscopic operation group was significantly higher than that in the Hartmann's operation group (P < 0.05). The overall incidence of postoperative complications and hospital stay were significantly lower in the observation group than in the Hartmann's group (P < 0.05). Further subgroup analysis of the overall postoperative complication rate of the two groups showed that the traditional Hartmann's operation group was more likely to have an incomplete intestinal obstruction (P < 0.05). This study also showed no significant differences between the two groups in operation time, intraoperative blood loss, number of harvested lymph nodes, and postoperative anal exhaust time (all P > 0.05). This study also found no significant differences between the two groups in overall survival rates or recurrence-free survival rates (all P > 0.05). CONCLUSIONS: The comparison of the therapeutic effects of the two groups verified the feasibility of endoscopy combined with X-ray fluoroscopy metal stent placement in combination with laparoscopic surgery in the treatment of acute left-sided colon cancer obstruction. Compared with the traditional emergency open Hartmann's procedure, metal stent implantation under endoscopy and X-ray fluoroscopy combined with laparoscopic surgery is more minimally invasive, safe, and effective. It avoids the traditional second or even third surgical trauma to effectively improve the quality of life of patients, so that patients can recover quickly after surgery.

Nickel-Catalyzed Direct Cross-Coupling of Unactivated Aryl Fluorides with Aryl Bromides.

A nickel-catalyzed direct cross-coupling of unactivated aryl fluorides with aryl bromides is realized. The one-pot reaction, which avoids the use of preformed and sensitive organometallic reagents, proceeds effectively via C-F bond cleavage at room temperature in THF in the presence of the phosphine ligand and magnesium powder (with or without TMSCl) to produce the desired biaryls in modest to good yields.

Cp2Fe Mediated Electrochemical Synthesis of Phosphonylated Spirocyclic Indolines via Dearomatization of Indoles.

A general and robust strategy for the synthesis of phosphonylated spirocyclic indolines has been developed through Cp2Fe-catalyzed electrochemical dearomaztizaion of indoles, which has been proven challenging to achieve via chemical oxidants. A range of phosphonylated 3,3-spiroindolines were obtained in moderate to good yields with excellent diastereoselectivities. The synthetic application was further illustrated by its easy scalability and the antitumor activity of the product.

Analysis of surgical treatment of appendix neuroendocrine neoplasms-17 years of single-center experience.

BACKGROUND/AIM: This study investigated the clinicopathological characteristics and treatment of appendix neuroendocrine neoplasms in appendectomy specimens of our center. MATERIALS AND METHODS: The clinicopathological data, including age, sex, preoperative clinical manifestation, surgical method, and histopathological examination results of 11 patients with appendix neuroendocrine neoplasms confirmed by surgery and pathology between November 2005 and January 2023, were retrospectively analyzed. RESULTS: In the histopathological examination of 7277 appendectomy specimens, 11 cases (0.2%) had appendix neuroendocrine neoplasms. Among the 11 patients, 8(72.7%) were males, and 3(27.3%) were females, with an average age of 48.1 years. All patients underwent emergency surgery. A total of 9 patients underwent open appendectomy, including 1 patient who underwent second-stage simple right hemicolectomy after an appendectomy, and two who underwent laparoscopic appendectomy. All 11 patients were followed up for a period of 1 to 17 years. All patients survived without any indication of tumor recurrence. CONCLUSION: Appendiceal neuroendocrine neoplasms are low-grade malignant tumors originating from neuroendocrine cells. They are rarely seen in clinical practice and are often treated based on acute and chronic appendicitis symptoms. These tumors are challenging to diagnose before surgery due to the lack of specificity in clinical manifestations and auxiliary examinations. The diagnosis generally depends on postoperative pathology and immunohistochemistry. Despite the diagnostic challenges, these tumors have a favorable prognosis.

A meta-analysis of Legionella pneumophila contamination in hospital water systems.

BACKGROUND: Legionella pneumophila is a common cause of community-acquired pneumonia. We aimed to determine the pooled rates of L pneumophila contamination in the water environment of the hospital. METHODS: We searched PubMed, Embase, Web of Science, Chinese National Knowledge Infrastructure, WangFang and Science Direct, The Cochrane Library, and Science Finder, for relevant studies published until December 2022. Stata 16.0 software was used to determine pooled contamination rates, publication bias, and subgroup analysis. RESULTS: Forty-eight eligible articles with a total of 23,640 samples of water were evaluated, and the prevalence of L pneumophila was 41.6%. The results of the subgroup analysis showed that the pollution rate of L pneumophila in hot water (47.6%) was higher than that in other water bodies. The rates of L pneumophila contamination were higher in developed countries (45.2%), culture methods (42.3%), published between 1985 and 2015 (42.9%), and studies with a sample size of less than 100 (53.0%). CONCLUSIONS: L pneumophila contamination in medical institutions is still very serious and should be paid attention to, especially in developed countries and hot water tanks.

Nickel-Catalyzed Direct Cross-Coupling of Aryl Fluorosulfates with Aryl Bromides.

A one-pot, direct cross-coupling of aryl fluorosulfate with aryl bromide, which is step-economical and avoids the use of a preprepared/commercial organometallic reagent, could be accomplished by performing the reaction in THF at room temperature in the presence of nickel catalyst, magnesium turnings, and lithium chloride, giving rise to the corresponding biaryls in moderate to good yields with reasonable functional group compatibility.

Legionella pneumophila contamination in central air-conditioning systems of public places in China：a meta-analysis / 预防医学

Objective @#To systematically evaluate the detection of Legionella pneumophila in central air-conditioning systems of public places in China, so as to provide insights into the management of L. pneumophila contamination.@*Methods@#The publications pertaining to L. pneumophila contamination in central air-conditioning systems of public places in China were searched in international and national databases, including CNKI, Wanfang Data, CBM, PubMed and Web of Science from January 1, 2010 to December 31, 2022. The publication quality was evaluated using the Strengthening the Reporting of Observational Studies in Epidemiology. A meta-analysis was performed using the software Stata version 16.0. The pooled detection of L. pneumophila and its 95%CI were estimated. The publication bias was evaluated using Begg's test, and sensitivity analysis was performed with the leave-one-out evaluation for assessment of the robustness of the outcomes.@*Results@#A total of 742 publications were initially searched, and 29 publications were finally included, all of which were cross-sectional studies. The publications included 10 high-quality and 19 moderate-quality studies covering 6 160 samples, and the pooled detection of L. pneumophila was 17.20% (95%CI: 12.80%-21.90%). Subgroup analysis showed a higher detection rate of L. pneumophila in cooling water (21.80%) than in condensed water (5.50%) (P<0.01). According to the criteria defined in Hygienic Specification of Central Air-conditioning Ventilation System in Public Buildings (2006 version), the detection of L. pneumophila was 23.30%, which was higher than the detection (13.20%) according to the Hygienic Specification of Central Air-conditioning Ventilation System in Public Buildings (WS 394-2012) (P<0.05). The detection of L. pneumophila did not vary in place, region or sample (P>0.05). Begg's test showed no significant publication bias, and sensitivity analysis showed robustness of the results. @*Conclusions@#The detection of L. pneumophila ranges from 12.80% to 21.90% in central air-conditioning systems of public places in China. Health and environmental protection sectors need to improve the monitoring of L. pneumophila contamination in central air-conditioning systems of public places.

Mechanical overloading induces GPX4-regulated chondrocyte ferroptosis in osteoarthritis via Piezo1 channel facilitated calcium influx.

INTRODUCTIONS: Excessive mechanical stress is closely associated with cell death in various conditions. Exposure of chondrocytes to excessive mechanical loading leads to a catabolic response as well as exaggerated cell death. Ferroptosis is a recently identified form of cell death during cell aging and degeneration. However, it's potential association with mechanical stress remains to be illustrated. OBJECTIVES: To identify whether excessive mechanical stress can cause ferroptosis. To explore the role of mechanical overloading in chondrocyte ferroptosis. METHODS: Chondrocytes were collected from loading and unloading zones of cartilage in patients with osteoarthritis (OA), and the ferroptosis phenotype was analyzed through transmission electron microscope and microarray. Moreover, the relationship between ferroptosis and OA was analyzed by GPX4-conditional knockout (Col2a1-CreERT: GPX4flox/flox) mice OA model and chondrocytes cultured with high strain mechanical stress. Furthermore, the role of Piezo1 ion channel in chondrocyte ferroptosis and OA development was explored by using its inhibitor (GsMTx4) and agonist (Yoda1). Additionally, chondrocyte was cultured in calcium-free medium with mechanical stress, and ferroptosis phenotype was tested. RESULTS: Human cartilage and mouse chondrocyte experiments revealed that mechanical overloading can induce GPX4-associated ferroptosis. Conditional knockout of GPX4 in cartilage aggravated experimental OA process, while additional treatment with ferroptosis suppressor protein (FSP-1) and coenzyme Q10 (CoQ10) abated OA development in GPX4-CKO mice. In mouse OA model and chondrocyte experiments, inhibition of Piezo1 channel activity increased GPX4 expression, attenuated ferroptosis phenotype and reduced the severity of osteoarthritis. Additionally, high strain mechanical stress induced ferroptosis damage in chondrocyte was largely abolished by blocking calcium influx through calcium-free medium. CONCLUSIONS: Our findings show that mechanical overloading induces ferroptosis through Piezo1 activation and subsequent calcium influx in chondrocytes, which might provide a potential target for OA treatment.

Manganese-Mediated Electrochemical Dearomatization of Indoles To Access 2-Azido Spirocyclic Indolines.

An efficient and environmentally friendly electrochemical protocol for dearomatization of indoles was developed, delivering a series of azido-containing spirocyclic indolines with good functional group tolerance. This dearomatization process is proposed to result from the oxidation of MnII-N3 species, supported by cyclic voltammetry experiments. Moreover, synthetic transformations can provide an alternative approach to a range of functionalized indolines.

Nickel-Catalyzed Direct Cross-Coupling of Diaryl Sulfoxide with Aryl Bromide.

The direct cross-couplings of diaryl sulfoxides with aryl bromides via C-S bond cleavage could be readily accomplished using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF, leading to the corresponding biaryls in moderate to good yields. The reaction exhibited a broad substrate scope and could be applied to a gram-scale synthesis. The "one-pot" reaction, which avoids the utility of presynthesized and moisture-labile organometallic compounds, is operationally simple and step-economic.

Electrochemical Dearomatization of Indoles: Access to Diversified Fluorine-Containing Spirocyclic Indolines.

A robust and green electrochemical dearomatization of indoles was developed by merging a fluorine-containing group to an indole nucleus under oxidant-free conditions, delivering a diverse array of tri- and difluoromethylated 3,3-spiroindolines with good functional group tolerance.

Radical-induced denitration of N-(p-nitrophenyl)propiolamides coupled with dearomatization: access to phosphonylated/trifluoromethylated azaspiro[4.5]-trienones.

A robust dearomative denitration of nitroarene derivatives induced by a radical ipso-cyclization process has been developed, delivering valuable phosphonated or trifluoromethylated azaspiro[4.5]trienones with good functional group tolerance. This represents a convenient and powerful approach to activate nitroarenes in a radical manner.

Titanium(IV)-Mediated Ring-Opening/Dehydroxylative Cross-Coupling of Diaryl-Substituted Methanols with Cyclopropanol Derivatives.

A titanium(IV)-mediated ring-opening/dehydroxylative cross-coupling of diaryl-substituted methanols with a cyclopropanol derivative was developed. The reactions proceeded efficiently to provide synthetically useful γ,γ-diaryl esters in moderate to good yields, which could be applied to the functionalization of complex molecules derived from bioactive fenofibrate and isoxepac and the synthesis of a precursor of Zoloft.