Electroreductive Remote Benzylic C(sp3)-H Arylation of Aliphatic Ethers Using Cyanoarenes for the Synthesis of α-(Hetero)aryl Ethers.

An iodoarene-driven electroreductive remote C(sp3)-H arylation of unsymmetrical 1-(o-iodoaryl)alkyl ethers with cyanoarenes for the site selective synthesis of α-(hetero)aryl ethers is developed. With the introduction of cyanoarenes as both aryl sources and electron transfer mediators, this method includes an iodoarene-driven strategy to enable the regiocontrollable formation of two new bonds, one C(sp2)-H bond, and one C(sp2)-C(sp3) bond, in a single reaction step through the sequence of halogen atom transfer (XAT), hydrogen atom transfer (HAT), radical-radical coupling, and decyanation.

Adsorption Behavior and Kinetics of 1,4-Dioxane by Carbon Aerogel.

1,4-dioxane is a potential carcinogen in water and is difficult to deal with due to its robust cycloether bond and complete miscibility with water. To remove 1,4-dioxane in an economically viable and environmentally friendly way, a series of carbon aerogels were synthesized as adsorbents for 1,4-dioxane. The experiment results showed that adsorption performances were closely related to the preparation conditions of carbon aerogels, such as the molar ratio, heating rate, pyrolysis temperature and residence time, which were carefully controlled. Scanning electron microscope analysis revealed the presence of a three-dimensional porous network structure in carbon aerogels. Brunauer-Emmett-Teller analysis results demonstrated an increase in specific surface area (673.89 m2/g) and total pore volume after carbonization, with an increase in mesoporous porosity and a decrease in microporosity. When considering each variable individually, the highest specific surface area of prepared carbon aerogels was achieved at a pyrolysis temperature of 800 °C, a holding time of 1 h, and a heating rate of 2 °C/min. Under optimal experimental conditions, the adsorption removal of 1,4-dioxane by carbon aerogels exceeded 95%, following quasi-second-order kinetics and Langmuir isothermal adsorption isotherms, indicating that monolayer adsorption on the surface of carbon aerogels occurred. The maximum adsorption capacity obtained was 67.28 mg/g at a temperature of 318 K, which was attributed to the presence of a large proportion of mesopores and abundant micropores simultaneously in carbon aerogels. Furthermore, with the interference of chlorinated solvents such as trichloroethylene (TCE), the removal efficiency of 1,4-dioxane had no obvious inhibition effect. Regeneration experiments showed that after five continuous cycles, the carbon aerogels still kept a comparable adsorption capacity, which illustrates its potential application in 1,4-dioxane-polluted water purification.

Visible-Light-Induced Photoredox 1,2-Dialkylation of Styrenes with α-Carbonyl Alkyl Bromides and Pyridin-1-ium Salts.

A visible-light-driven photoredox dialkylation of styrenes with α-carbonyl alkyl bromides and pyridin-1-ium salts for the synthesis of polysubstituted 1,4-dihydropyridines is reported. This reaction enables the formation of two new C(sp3)-C(sp3) bonds in a single reaction step and provides a strategy that employs pyridin-1-ium salts as the functionalized alkylating reagents via dearomatization to directly trap the resulting alkyl radicals from radical addition of alkenes and then terminate the alkene dialkylation.

Palladium-Catalyzed ß-C(sp3)-H Arylation of Silyl Prop-1-en-1-ol Ethers with Aryl Halides: Entry to α,ß-Unsaturated Ketones.

A palladium(0)-catalyzed ß-C(sp3)-H arylation of silyl prop-1-en-1-ol ethers with aryl halides for the synthesis of α,ß-unsaturated ketones is presented. In contrast to the reported ß-C(sp3)-H arylation of ketones, the chemoselectivity of this current method relies on the Pd(0) catalytic systems and reaction temperatures: While using the Pd(dba)2/DavePhos/KF system at 80 °C resulted in ß-C(sp3)-H monoarylation to produce ß-monoarylated α,ß-unsaturated ketones, harnessing the Pd(OAc)2/t-Bu XPhos/K2HPO4 system at 110 °C induced ß-C(sp3)-H diarylation to afford ß,ß-diarylated α,ß-unsaturated ketones. The method provides a versatile route that uses readily available ketone-derivatized α-nonsubstituted silyl prop-1-en-1-ol ethers as the alkene sources and is characterized by a good functional group compatibility, a broad substrate scope, and an excellent selectivity.

Nickel Photocatalyzed Reductive 1,4-Dicarbofunctionalization of 1,3-Enynes with N-Methylamines and Organohalides Enabled by Site-Selective C(sp3)-H Functionalization.

A cooperative nickel and photoredox reductive catalysis for 1,4-dicarbofunctionalization of 1,3-enynes with tertiary N-methylamines and organohalides to produce tetrasubstituted allenes is presented. This method enables the generation of the aminoalkyl C(sp3)-centered radicals by site selective cleavage of the N-methyl C(sp3)-H bonds in tertiary N-methylamines and is extended to alkyl bromides as the electrophilic terminating regents. Mechanistic studies indicate that the reaction involves a radical process and a Ni0/NiI/NiIII catalytic cycle.

MiR-7-5p/KLF4 signaling inhibits stemness and radioresistance in colorectal cancer.

Resistance to radiotherapy remains a major unmet clinical obstacle in the treatment of locally advanced rectal cancer. Cancer stem cells (CSCs) are considered to mediate tumor development and radioresistance. However, the role of CSCs in regulating resistance to radiotherapy in colorectal cancer (CRC) remains largely unknown. We established two radioresistant CRC cell lines, HCT116-R and RKO-R, using fractionated irradiation. Analysis using miRNA sequencing and quantitative real-time PCR confirmed lower levels of miR-7-5p in both of the radioresistant cells compared to their parental cells. Subsequently, we validated that miR-7-5p expression was decreased in cancerous tissues from radiotherapy-resistant rectal cancer patients. The Cancer Genome Atlas (TCGA) database analyses revealed that low miR-7-5p expression was significantly correlated with poor prognosis in CRC patients. Overexpression of miR-7-5p led to a rescue of radioresistance and an increase in radiation-induced apoptosis, and attenuated the stem cell-like properties in HCT116-R and RKO-R cells. Conversely, knocking down miR-7-5p in parental HCT116 and RKO cells suppressed the sensitivity to radiation treatment and enhance cancer cell stemness. Stemness-associated transcription factor KLF4 was demonstrated as a target of miR-7-5p. Rescue experiments revealed that miR-7-5p/KLF4 axis could induce radiosensitivity by regulating CSCs in colorectal cancer cells. Furthermore, we used CRC tumor tissues which exhibited resistance to neoadjuvant radiotherapy to establish a patient-derived xenograft (PDX) mouse model. Tail vein injection of magnetic nanoparticles carrying miR-7-5p mimics into the PDX mice significantly inhibited tumor growth with or without irradiation treatment in vivo. Our current studies not only demonstrate an anti-cancer function of miR-7-5p in regulating CSC properties and radiosensitivity in colorectal cancer, but also provide a novel potential strategy for delaying or reverse radiation resistance in preoperative radiotherapy of CRC patients.

Effect of Anterograde Lavage via Temporary Loop Ileostoma on the Recovery of Bowel Function in Patients Receiving Stoma Closure: A Retrospective Cohort Study.

BACKGROUND: The effect of anterograde lavage in patients with rectal cancer who underwent anterior resection and plan to receive stoma closure is unclear. OBJECTIVE: This study aimed to investigate the effect of anterograde lavage on postoperative bowel function recovery in patients who underwent temporary loop ileostomy and stoma closure. DESIGN: This was a hospital-based retrospective cohort study. SETTINGS: This study was conducted at a tertiary referral center. PATIENTS: All consecutive patients who underwent anterior resection for rectal cancer and were planning to receive stoma closure from March through December 2019 were included. INTERVENTIONS: The enrolled patients were divided into 2 groups according to whether they received anterograde lavage before stoma closure. MAIN OUTCOME MEASURES: Short-term functional outcomes, including time to first passing of flatus, first defecation time, and recovery time to first meal, were compared between the groups. Secondary outcomes included length of hospital stay, total cost of hospitalization, and postoperative complications. RESULTS: A total of 222 eligible participants were included in the analysis, including 114 in the lavage group and 108 in the nonlavage group. No statistically significant differences were found in age, sex ratio, or distance between the anastomotic line and dentate line. In the lavage group, patients' time to first passing of flatus (38 vs 42 h; p = 0.006), first defecation time (42 vs 48 h; p < 0.001), recovery time to first meal (48 vs 55.5 h; p < 0.001), and length of hospital stay (5 vs 7 d; p < 0.001) were significantly shorter than those in the nonlavage group, and the total cost of hospitalization was significantly lower than that of the nonlavage group (25,000 vs 28,000 RMB; p < 0.001). No significant difference was found in the incidence of postoperative complications between the 2 groups (p = 0.067). LIMITATIONS: This study is limited by its relatively small sample size and retrospective design with single-center participants. CONCLUSIONS: Anterograde lavage before stoma closure is safe and noninvasive. For patients receiving anterior resection and planning to have stoma closure, this procedure can potentially help recover bowel function more rapidly. See Video Abstract at http://links.lww.com/DCR/C51. EFECTO DEL LAVADO ANTERGRADO MEDIANTE ILEOSTOMA TEMPORAL EN ASA SOBRE LA RECUPERACIN DE LA FUNCIN INTESTINAL EN PACIENTES QUE RECIBEN CIERRE DE ESTOMA UN ESTUDIO DE COHORTE RETROSPECTIVO: ANTECEDENTES:No está claro el efecto del lavado anterógrado en pacientes con cáncer de recto con resección anterior que planean recibir el cierre del estoma.OBJETIVO:Investigar el efecto del lavado anterógrado en la recuperación de la función intestinal posoperatoria en pacientes que se sometieron a ileostomía en asa temporal y cierre de estoma.DISEÑO:Estudio de cohorte retrospectivo basado en el hospital.AJUSTES:Centro de referencia terciario.PACIENTES:Todos los pacientes que se sometieron a una resección anterior por cáncer de recto y que planeaban recibir el cierre del estoma desde marzo hasta diciembre de 2019.INTERVENCIONES:Los pacientes inscritos se dividieron en dos grupos según si recibieron lavado anterógrado antes del cierre del estoma.PRINCIPALES MEDIDAS DE RESULTADO:Los resultados funcionales a corto plazo, incluido el tiempo de la primera evacuación de flatos, tiempo de la primera defecación y tiempo de recuperación hasta la primera comida, se compararon entre los grupos. Resultados secundarios incluyeron duración de la estancia hospitalaria, costo total de la hospitalización y complicaciones posoperatorias.RESULTADOS:Se incluyeron en el análisis un total de 222 participantes elegibles, incluidos 114 en el grupo de lavado y 108 en el grupo de no lavado. No hubo diferencias estadísticamente significativas en la edad, la proporción de sexos o la distancia entre la línea de anastomosis y la línea dentada. En el grupo de lavado, el tiempo de la primera evacuación de flatos de los pacientes (38 vs 42 h; p = 0,006), el tiempo de la primera defecación (42 vs 48 h; p < 0,001), el tiempo de recuperación hasta la primera comida (48 vs 55,5 h; p < 0,001) y la duración de la estancia hospitalaria (5 vs 7 días; p < 0,001) fueron significativamente más cortos que los del grupo de no lavado, y el costo total de la hospitalización fue significativamente menor que el del grupo de no lavado (25000 vs 28000 RMB; p < 0,001). No hubo diferencia significativa en la incidencia de complicaciones postoperatorias entre los dos grupos (p = 0,067).LIMITACIONES:Este estudio está limitado por su tamaño de muestra relativamente pequeño y su diseño retrospectivo con participantes de un solo centro.CONCLUSIONES:El lavado anterógrado antes del cierre del estoma es seguro y no invasivo. Para los pacientes que se someten a una resección anterior y planean cerrar el estoma, este procedimiento puede ayudar potencialmente a recuperar la función intestinal más rápidamente. Consulte Video Resumen en http://links.lww.com/DCR/C51. (Traducción-Dr. Francisco M. Abarca-Rendon).

The transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines: access to (Z)-3-(silylmethylene)indolin-2-ones.

A new method involving mild acryl transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines with CO and silanes is presented for producing (Z)-3-(silylmethylene)indolin-2-ones. Upon using an acryl transient chelating group, 2-alkynylanilines undergo an unprecedented alkyne cis-silylrhodation followed by aminocarbonylation to assemble (Z)-3-(silylmethylene)indolin-2-ones. Mechanistic studies show that acryl transient chelating effects result in the key alkyne cis-silylrhodation process.

Effect of Multimedia Health Education on Psychological Burden, Quality of Life Ability, and Self-Efficacy of Congenital Microtia.

Aims: To investigate the effects of multimedia health education on psychological burden, quality of life, and self-efficacy of patients with congenital microtia. Materials and Methods: Eighty cases of patients with congenital microtia treated and cared for in our hospital from June 2018 to June 2022 were selected according to the numerical table method as retrospective study subjects and divided into 40 cases each in the comparison group and the observation group. The comparison group implemented conventional health education and discharge instruction, and the observation group implemented multimedia health education care to compare the effects of self-efficacy, self-care ability and psychological burden of patients in the two groups. Results: Before care, the two groups had no statistically significant difference in the quality of life scores (P > 0.05). Aftercare, the mental vitality scores, social interaction scores, emotional limitation scores, and mental status of patients in the observation group were significantly higher than those in the comparison group (P < 0.05). Before nursing care, there was no statistically significant difference in the nursing ability and anxiety-depression scores between the two groups (P > 0.05). After nursing care, the health knowledge level, self-care skills, self-care responsibility, and self-concept of the observation group were higher than the comparison group, while the depression-emotional disorder scores were significantly lower than the comparison group (P < 0.05). Conclusion: Routine health education and discharge instruction combined with multimedia health education care can effectively improve the quality of life of patients with congenital microtia, reduce adverse emotions, and improve patients' sense of self-efficacy.

Nickel-Catalyzed C-S Reductive Cross-Coupling of Alkyl Halides with Arylthiosilanes toward Alkyl Aryl Thioethers.

A nickel-catalyzed C-S reductive cross-coupling of alkyl halides with arylthiosilanes for producing alkyl aryl thioethers is developed. This reaction is initiated by umpolung transformations of arylthiosilanes followed by C-S reductive cross-coupling with alkyl halides to manage an electrophilic alkyl group onto the electrophilic sulfur atom and then construct a C(sp3)-S bond, and features exquisite chemoselectivity, excellent tolerance of diverse functional groups, and wide applications for late-stage modification of biologically relevant molecules.

Divergent functionalization of terminal alkynes enabled alkynylative [5+1] benzannulation of 3-acetoxy-1,4-enynes.

We here describe an alkynylative [5+1] benzannulation of 3-acetoxy-1,4-enynes with terminal alkynes, which enables both the construction of a benzene ring skeleton and intermolecular incorporation of an alkynyl group in a single reaction using Pd and Cu cooperative catalysts. The method represents efficient access to internal aryl alkynes through divergent functionalization of two terminal alkyne components: one alkyne serves as the one-carbon unit to realize the [5+1] benzannulation and the other alkyne as a nucleophile terminates the reaction.

Relay Palladium/Copper Catalysis Enabled Silylative [5 + 1] Benzannulation Using Terminal Alkynes as One-Carbon Units.

Using terminal alkyne as a nontraditional one-carbon (C1) unit and silylborane as an external silicon pronucleophile, a relay palladium/copper-catalyzed silylative [5 + 1] benzannulation of 3-acetoxy-1,4-enynes for producing polysubstituted arylsilanes, especially including bioactive motif-based analogues, in a single reaction step through benzene ring skeleton assembly and silyl intermolecular incorporation cascades is developed. Mechanistic studies show that this reaction allows the terminal sp-hybridized carbon atom in terminal alkynes as a C1 unit via cleavage of two π-bonds and one C(sp)-H bond.

Photocatalytic dual decarboxylative alkenylation mediated by triphenylphosphine and sodium iodide.

An efficient photocatalytic dual decarboxylative alkenylation of α,ß-unsaturated carboxylic acids and alkyl N-hydroxyphthalimide (NHP) esters mediated by triphenylphosphine and sodium iodide has been developed. This protocol proceeds under 456-nanometer irradiation by visible blue light in the absence of transition metals or organic dye based photoredox catalysts. The reaction is successfully applied to a wide range of redox-active esters derived from aliphatic carboxylic acids (1°, 2° and 3°) and α-amino acids, enabling transformations of diverse α,ß-unsaturated carboxylic acids to α,ß-alkylated styrenes with high efficiency and excellent selectivity under mild conditions.

Molecular Characterization of the Oncogene BTF3 and Its Targets in Colorectal Cancer.

Colorectal cancer (CRC) is one of the most commonly diagnosed and leading causes of cancer mortality worldwide, and the prognosis of patients with CRC remains unsatisfactory. Basic transcription factor 3 (BTF3) is an oncogene and hazardous prognosticator in CRC. Although two distinct functional mechanisms of BTF3 in different cancer types have been reported, its role in CRC is still unclear. In this study, we aimed to molecularly characterize the oncogene BTF3 and its targets in CRC. Here, we first identified the transcriptional targets of BTF3 by applying combined RNA-Seq and ChIP-Seq analysis, identifying CHD1L as a transcriptional target of BTF3. Thereafter, we conducted immunoprecipitation (IP)-MS and E3 ubiquitin ligase analysis to identify potential interacting targets of BTF3 as a subunit of the nascent-polypeptide-associated complex (NAC). The analysis revealed that BTF3 might also inhibit E3 ubiquitin ligase HERC2-mediated p53 degradation. Finally, miRNAs targeting BTF3 were predicted and validated. Decreased miR-497-5p expression is responsible for higher levels of BTF3 post-transcriptionally. Collectively, we concluded that BTF3 is an oncogene, and there may exist a transcription factor and NAC-related proteolysis mechanism in CRC. This study provides a comprehensive basis for understanding the oncogenic mechanisms of BTF3 in CRC.

Performance of carbon aerogels particle electrodes for the aqueous phase electro-catalytic oxidation of simulated phenol wastewaters.

In this paper, the feasibility of using carbon aerogels (CAs) as bed electrodes in a three-dimensional electrode reactor for the electrochemical treatment was studied. It was found that the removal efficiency depended on the airflow, the feed phenol concentration, pH, the ratio of aerogels mass to solution volume, and repeated times. Compared with commercial carbon particle electrodes, the CAs prepared exhibited stronger and longer-term activity to remove phenol simulated wastewater. For 250mgL(-1) of phenol solution, 98% of the initial phenol chemical oxygen demand (COD) can be removed after treatment for 20min. Moreover, high removal efficiency can be kept basically after being reused many times (e.g. 93% and 82% after 20 times and 50 times, respectively).

Preparation of activated ordered mesoporous carbons with a channel structure.

Activated ordered mesoporous carbons with a channel structure (AOMCs-CS) were successfully prepared by imposing CO(2) activation on ordered mesopore carbon C-FDU-15. It is found that the continuous carbon framework of the precursor C-FDU-15 plays an important role in keeping the order structure of the resulting AOMCs-CS. The mild activation (e.g., 31 wt % burnoff) does not impair the order degree. After that, the order degree gradually decreases with further increasing burnoff. However, the basic hexagonal mesostructure of C-FDU-15 can still be found in the AOMCs-CS when the burnoff is up to 73 wt %, although many carbon walls are punched and thus many larger mesopores and marcropores are generated. With increasing burnoff, the surface area and volume of micropores increase first and then decrease, and the surface area and volume of mesopores continuously increase. The highest measured Brunaruer-Emmett-Teller (BET) surface area, micropore volume, and total pore volume of the AOMCs-CS reach 2004 m(2)/g, 0.50 cm(3)/g, and 1.22 cm(3)/g, respectively.