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.

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.

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.

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.

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.

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.

Clinical utility of serum cystatin C for prediction of multi-vessel disease by coronary angiography in type 2 diabetes mellitus patients with normal renal function.

BACKGROUND: The aim of this study was to evaluate whether serum cystatin C could serve as a predictor of multivessel coronary artery disease identified by coronary angiography in type 2 diabetes patients with normal renal function and to suggest the cutoff point of serum cystatin C for predicting multivessel disease. METHODS: Serum cystatin C concentrations were measured by using particle-enhanced immunonephelometric assays before coronary angiography in 135 consecutive type 2 diabetes patients and 179 nondiabetic patients with normal renal function. Routine anthropometric and serologic data were collected. The severity of multivessel disease was assessed with the Gensini score after coronary angiography. The associations of serum cystatin C with the Gensini score were investigated, and the independent risk factors associated with multivessel disease were assessed. RESULTS: Serum cystatin C and the Gensini score were significantly elevated in diabetes patients. Cystatin C had a positive correlation with Gensini score. A multiple logistic regression analysis demonstrated that cystatin C was independently associated with the presence of multivessel disease (the OR score is 2.21, P = 0.003). Based on the ROC curve, a cystatin C level of 0.865 mg/L showed 67.7% sensitivity and 76.3% specificity with an AUC of 0.748 in diabetes patients for detecting multivessel disease. CONCLUSION: Serum cystatin C is significantly correlated with the presence of multivessel disease, suggesting that cystatin C might be utilized as a screening tool for predicting multivessel disease in type 2 diabetes mellitus patients with normal renal function.

Highly Chemically Stable MOFs with Trifluoromethyl Groups: Effect of Position of Trifluoromethyl Groups on Chemical Stability.

Metal-organic frameworks (MOFs) are a class of advanced porous crystalline materials. However, numerous MOFs have poor chemical stability, significantly restricting their industrial application. The introduction of trifluoromethyl groups around clusters of MOFs results in a shielding effect caused by their hydrophobicity and bulkiness, thus preventing guest molecules from attacking the coordination bonds. To prove such a shielding effect, the position of the trifluoromethyl groups is rationally adjusted, with trifluoromethyl groups at the ortho positions of carboxyl groups significantly improving the chemical stability of UiO-67. The prepared UiO-67- o-2CF3 remains intact after treatment with boiling water, 8 M HCl, 10 mM NaOH, and 50 ppm of NaF aqueous solutions. As the control experiment, trifluoromethyl groups at the meta positions of carboxyl groups have no shielding effect; hence, UiO-67- m-2CF3 has a stability that is lower than that of UiO-67- o-2CF3. In addition, the shielding effect is also applied to other MOFs, including DUT-5- o-2CF3 and Al-TPDC- o-2CF3, confirming the universality of this strategy.

Four-component acyloxy-trifluoromethylation of arylalkenes mediated by a photoredox catalyst.

A four-component intermolecular trifluoromethylation-acyloxylation of arylalkenes induced by visible light has been developed in the presence of the photoredox catalyst Ru(bpy)3(PF6)2 under mild reaction conditions. A new Umemoto's reagent was used as a trifluoromethyl radical source, and this redox neutral reaction demonstrated good functional group tolerance for aryl alkenes with high yields up to 91%. The detailed reaction process was investigated based on control, deuterium and O18-labeling experiments to support that N,N-dimethylformamide (DMF)/H2O acted as an acyloxyl source.

Powerful, Thermally Stable, One-Pot-Preparable, and Recyclable Electrophilic Trifluoromethylating Agents: 2,8-Difluoro- and 2,3,7,8-Tetrafluoro-S-(trifluoromethyl)dibenzothiophenium Salts.

Although many electrophilic trifluoromethylating agents have been reported to date, practically useful reagents have yet to be developed. S-(Trifluoromethyl)dibenzothiophenium salts, known as Umemoto's reagents, have two significant drawbacks that have hampered their practical application: (1) synthesis involving many steps and (2) the formation of large amounts of dibenzothiophene as waste after trifluoromethylation. Our idea to substitute fluorine at specific positions on the dibenzothiophenium rings has resulted in massive improvements in the synthesis, properties, reactivity, and applications of these compounds. On the basis of this idea, 2,8-difluoro- and 2,3,7,8-tetrafluoro-S-(trifluoromethyl)dibenzothiophenium triflates and other salts were developed as powerful, thermally stable, one-pot-preparable, and recyclable reagents for the trifluoromethylation of various types of nucleophilic substrates, such as carbanions, (hetero)aromatics, alkenes, alkynes, thiols, sulfinates, and phosphines. This one-pot and recycled production tremendously decreases the chemical and environmental costs of this process. Because of their higher reactivity and thermal stability, these new reagents may have wider applications than Umemoto's reagents. Therefore, these new versions of Umemoto's reagents could be widely used as the first practically useful electrophilic trifluoromethylating agents for the production of many types of trifluoromethyl-containing compounds in academic and industrial applications.

Inhibition of epidermal growth factor receptor signaling prohibits metastasis of gastric cancer via downregulation of MMP7 and MMP13.

The molecular pathway regulating gastric carcinoma (GC) invasiveness and metastasis remains elusive. Here, we detected significant increase in the phosphorylated epidermal growth factor receptor (pEGFR), MMP7, and MMP13 in the resected GC, compared with the adjacent normal tissue, in patients. Moreover, strong positive correlation was detected between pEGFR and MMP7, and between pEGFR and MMP13 in GC. To examine whether a causal link exists, we used two human GC lines, SNU-5 and AGS, to study the cross talk between EGFR signaling activation, and expression of MMP7 and MMP13. We found that EGF-induced EGFR phosphorylation activated both MMP7 and MMP13, and consequently cancer invasiveness. EGF-induced activation of MMP7 and MMP13 can be both inhibited by use of an inhibitor for EGFR. EGF-induced activation of MMP7 can be also significantly inhibited by use of an inhibitor for Akt, but not an inhibitor for ERK1/2, while EGF-induced activation of MMP13 can be significantly inhibited by use of an inhibitor for ERK1/2, but not by an inhibitor for Akt. These data suggest that EGF-induced activation of MMP7 and MMP13 in GC is through phosphatidylinositol 3-kinase (PI3K) and extracellular-related kinase/mitogen-activated protein kinase (ERK/MAPK) signaling pathway, respectively. Our study thus highlights EGFR signaling regulated MMP7 and MMP13 activation as molecular basis for metastasis of GC, and further demonstrate that different signaling pathway cascades are involved in the downstream signaling transduction.

Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

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.

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.

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.

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.

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.

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.

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.