S-Arylation of Thioic S-Acid Using Thianthrenium Salts via Photoactivation of Electron Donor-Acceptor Complex.

Thioesters make up an important class of bioactive compounds. Due to their chemoselectivity, they have been widely used in the synthesis of a wide range of complex bioactive molecules and natural products. At present, chemists have developed a variety of methods for the preparation of thioester compounds. However, these methods usually require the use of transition metal catalysis or harsh reaction conditions. The strategy of synthesizing thioester compounds via visible light-induced electron donor-acceptor (EDA) complex reactions avoids the problems associated with conventional methods through the development of photocatalysis. Here we report a sustainable method for thiocarbonylating aryl sulfonium salts via a visible light-induced EDA complex process without transition metals.

Visible Light-Accelerated Palladium-Catalyzed Thiocarbonylation Using Oxalic Acid Monothioester with Aryl/Alkenyl Sulfonium Salts.

Herein, we present a decarboxylative thiocarbonylation of aryl and alkenyl sulfonium salts with oxalic acid monothioethers (OAMs), which can be achieved by visible light-accelerated palladium catalysis. Sulfonium salts are widely available, and OAM is an easily accessible and stored reagent; this mild reaction method can also be used for the synthesis of different types of thioester compounds. The reaction represents a new application of visible light-accelerated palladium catalysis in catalytic decarboxylative cross-couplings.

Construction of A375·S2 Melanoma Cell Line with High Sensibility to IL-1 by Overexpressing IL-1 Receptor.

We described an operation that co-overexpress interleukin receptor 1 (IL-1R1) and its co-receptor (IL-1R1AcP) genes in wild-type A375·S2 cells in order to increase their sensibility to IL-1. Firstly, laser scanning confocal microscope observed that IL-1R1 could be expressed on the surface of A375·S2 cells. qPCR was performed to estimate the ratio of two genes and result showed the ratio was almost 4.57:1. Then two genes were linked to vectors and co-transfected into A375·S2 cells. qPCR and Western blotting showed the protein content improved markedly. Finally, MTS assay was executed and the sensitivity of A375·S2 cells that co-transfected receptors to IL-1ß increased significantly. Another MTS assay showed the cell activity variation changed significantly (P < 0.05) and the reliability of the experiment was high, indicating that cell line established in this study could be further used for the activity test of IL-1Ra. Supplementary Information: The online version contains supplementary material available at 10.1007/s12088-022-01027-8.

A stress-responsive transcription factor PeNAC1 regulating beta-D-glucan biosynthetic genes enhances salt tolerance in oat.

MAIN CONCLUSION: A Populus euphratica NAC gene regulates (1,3; 1,4)-ß-D-glucan content in oat developing seed and improves the spikelet number and grain number per spike in transgenic oat under salinity conditions Salinity is the major factor affecting the production and quality of oat, and improving oat salt tolerance to increase yield and quality is vital. (1,3;1,4)-ß-D-glucan in Gramineae is the key component in response to various environmental signals, and it is the most important functional ingredient in oat grain. The NAC transcription factors are important candidate genes used in genetic engineering to improve plant abiotic stress tolerance. In this study, we introduced Populus euphratica PeNAC1, controlled by its own promoter, into hexaploid cultivated oat and produced six transgenic lines. Compared to the non-transgenic control, the expression of PeNAC1 significantly improved the seed germination rate, seedling survival rate, and leaf chlorophyll content in the transgenic plants under salt stress. These physiological changes increased the spikelet number and grain number per spike in the transgenic oat under salinity conditions and reduced the yield loss per plant. The results indicated that the heterologous expression of PeNAC1 plays an effective role in improving the salt tolerance in transgenic oat. In addition, overexpressing PeNAC1 significantly increased the (1,3;1,4)-ß-D-glucan content as well as the expression level of the (1,3;1,4)-ß-D-glucan biosynthetic genes AsCslF3, AsCslF6, and AsCslF9 in the transgenic lines under salt stress, which suggested that PeNAC1 regulates the synthesis of (1,3;1,4)-ß-D-glucan. Our research should assist in the discovery of the diverse action modes of NAC proteins, while PeNAC1 will be useful for improving the salt tolerance and quality of oat through molecular breeding.

Exploration of Biaryl Carboxylic Acids as Proton Shuttles for the Selective Functionalization of Indole C-H Bonds.

A survey of diversely substituted 2-arylbenzoic acids were synthesized and tested for use as proton shuttle in the direct arylation of indoles with bromobenzenes. It was found that 3-ethoxy-2-phenylbenzoic acid gives superior yield and selectivity for this class of substrates.

Alterations of tau and VASP during microcystin-LR-induced cytoskeletal reorganization in a human liver cell line.

Previously, we have reported alterations to HSP27 during Microcystin-LR (MC-LR)-induced cytoskeletal reorganization in the human liver cell line HL7702. To further elucidate the detailed mechanism of MC-LR-induced cytoskeletal assembly, we focused on two cytoskeletal-related proteins, Tau and VASP. These two proteins phosphorylated status influences their ability to bind and stabilize cytoskeleton. We found that MC-LR markedly increased the level of Tau phosphorylation with the dissociation of phosphorylated Tau from the cytoskeleton. Furthermore, the phosphorylation of Tau induced by MC-LR was suppressed by an activator of PP2A and by an inhibitor of p38 MAPK. VASP was also hyperphosphorylated upon MC-LR exposure; however, its phosphorylation appeared to regulate its cellular localization rather than cytoskeletal dynamics, and its phosphorylation was unaffected by the PP2A activator. These data suggest that phosphorylated Tau is regulated by p38 MAPK, possibly as a consequence of PP2A inhibition. Tau hyperphosphorylation is likely an important factor leading to the cytoskeletal destabilization triggered by MC-LR and the role of VASP alteration upon MC-LR exposure needs to be studied further. To our knowledge, the finding that Tau is implicated in cytoskeletal destabilization in MC-LR-treated hepatocytes and MC-LR-induced VASP's alteration has not been reported previously.

Copper-catalyzed reductive cross-coupling of nonactivated alkyl tosylates and mesylates with alkyl and aryl bromides.

A copper-catalyzed reductive cross-coupling reaction of nonactivated alkyl tosylates and mesylates with alkyl and aryl bromides was developed. It provides a practical method for efficient and cost-effective construction of aryl-alkyl and alkyl-alkyl CC bonds with stereocontrol from readily available substrates. When used in an intramolecular fashion, the reaction enables convenient access to various substituted carbo- or heterocycles, such as 2,3-dihydrobenzofuran and benzochromene derivatives.

Expedient synthesis of chiral α-amino acids through nickel-catalyzed reductive cross-coupling.

A novel method for the synthesis of non-natural L- and D-amino acids by a Ni-catalyzed reductive cross-coupling reaction is described. This strategy enables the racemization-free cross-coupling of serine/homoserine- derived iodides with aryl/acyl/alkyl halides. It provides convenient access to varieties of enantiopure and functionalized amino acids, which are important building blocks in bioactive compounds and pharmaceuticals.

Risk Factors and Predictive Nomogram for Survival in Elderly Patients with Brain Glioma.

OBJECTIVE: To determine the factors that contribute to the survival of elderly individuals diagnosed with brain glioma and develop a prognostic nomogram. METHODS: Data from elderly individuals (age ≥65 years) histologically diagnosed with brain glioma were sourced from the Surveillance, Epidemiology, and End Results (SEER) database. The dataset was randomly divided into a training cohort and an internal validation cohort at a 6:4 ratio. Additionally, data obtained from Tangdu Hospital constituted an external validation cohort for the study. The identification of independent prognostic factors was achieved through the least absolute shrinkage and selection operator (LASSO) and multivariate Cox regression analysis, enabling the construction of a nomogram. Model performance was evaluated using C-index, ROC curves, calibration plot and decision curve analysis (DCA). RESULTS: A cohort of 20 483 elderly glioma patients was selected from the SEER database. Five prognostic factors (age, marital status, histological type, stage, and treatment) were found to significantly impact overall survival (OS) and cancer-specific survival (CSS), with tumor location emerging as a sixth variable independently linked to CSS. Subsequently, nomogram models were developed to predict the probabilities of survival at 6, 12, and 24 months. The assessment findings from the validation queue indicate a that the model exhibited strong performance. CONCLUSION: Our nomograms serve as valuable prognostic tools for assessing the survival probability of elderly glioma patients. They can potentially assist in risk stratification and clinical decision-making.

Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl Grignard reagents.

Practical catalytic cross-coupling of secondary alkyl electrophiles with secondary alkyl nucleophiles under Cu catalysis has been realized. The use of TMEDA and LiOMe is critical for the success of the reaction. This cross-coupling reaction occurs via an S(N)2 mechanism with inversion of configuration and therefore provides a general approach for the stereocontrolled formation of C-C bonds between two tertiary carbons from chiral secondary alcohols.

Alkylboronic esters from copper-catalyzed borylation of primary and secondary alkyl halides and pseudohalides.

Easy access: An unprecedented copper-catalyzed cross-coupling reaction of the title compounds with diboron reagents is described (see scheme; Ts = 4-toluenesulfonyl). This reaction can be used to prepare both primary and secondary alkylboronic esters having diverse structures and functional groups. The resulting products would be difficult to access by other means.

Effects of strip cropping with reducing row spacing and super absorbent polymer on yield and water productivity of oat (Avena sativa L.) under drip irrigation in Inner Mongolia, China.

With the serious shortage of water resources and the development of water-saving agriculture, the application of drip irrigation has been paid more and more attention. But there was lack of oat planting methods suitable for drip irrigation, currently. In order to establish an efficient oat planting method for drip irrigation, a study was conducted at Agriculture and Forestry Sciences of Ulanqab, Inner Mongolia during the season (2019-2020) to evaluate the effect of strip cropping with reducing row spacing and super absorbent polymer on the yield and water use efficiency of oat. To conduct the field trials, a split plot system in three replications was established. Three planting patterns were in the main plots, including conventional cropping with 20 cm equal row spacing (PA), strip cropping with the 15 cm row spacing (PB) and strip cropping with the 10 cm row spacing (PC), and two super absorbent polymer levels were in the subplots, including 22.5 kg ha-2 (Y) and 0 (N). The results showed that, compared with PA, PB and PC both decreased the irrigation volumes by 4.5-18.4 mm, and the irrigation volumes of PB was lower than that of PC. When super absorbent polymers were applied, compared with PA, PB significantly increased grain yield and above-ground biomass, but PC had the opposite effects. The grain yield and above-ground biomass of PB significantly increased by 16.65% and 7.31% on average in two years, respectively. And the increasing of grain yield was attributed by the significant increasing of pike number and kernel number per spike. But when super absorbent polymers were not applied, PB had no significant effects on grain yield and above-ground biomass. PB also had the significant effects on regulating water use of oats weather or not super absorbent polymers were applied, it significantly increased the precipitation ratio by 2.64% (PBY) and 2.13% (PBN) and decreased irrigation ration by 3.32% (PBY) and 5.28% (PBN) on average in two years. Although PB and PC both decreased the total evapotranspiration, but PB increased WUE and PC deceased WUE. The WUE of PB increased by 19.70% (PBY) and 9.87% (PBN) on average in two years. Also PB had the highest economic benefits in all treatments. In conclusion, a drip irrigation oat planting pattern was proposed, which the row spacing is 15 cm, adjusted the equal row spacing planting to 8-row strip planting, with a belt spacing of 30 cm, combined with the application of 22.5 kg ha-2 applying super absorbent polymers. And this oat planting pattern is a viable strategy to improve oat productivity.

Received anti-VEGF therapy in a patient with CRAO sparing the CLRA with subretinal fluid: A case report.

RATIONALE: Central retinal artery occlusion (CRAO) sparing the cilioretinal artery (CLRA) with severe subretinal fluid and non-characteristic cherry-red spot is uncommon. In the present case, the patient received an intravitreal injection of anti- vascular endothelial growth factor, which is very rare. PATIENT CONCERNS: A 59-year-old man underwent vitrectomy of the left eye for diabetic retinopathy and vitreous hemorrhage. Six months after the operation, the patient presented with sudden painless visual-acuity decline in his left eye and was diagnosed with CRAO; his best corrected visual acuity was weak light perception. Whole retinal edema was seen on the fundus, and macular gray retinal opacification was present without a characteristic cherry-red spot. Optical coherence tomography revealed subretinal fluid (SRF) in the papillomacular bundle and inner retinal thickening. Fundus fluorescein angiography confirmed that the central retinal artery was not filled at 40 seconds and that the CLRA supplied a part of the macular area. Eight months after the second intravitreal injection of ranibizumab, Optical coherence tomography showed a significant reduction in inner retinal hyperreflectivity and the thickness of the nasal macular retina. The SRF was clearly absorbed, and the visual acuity improved to 1.1 logMAR units. DIAGNOSIS: Atypical CRAO. INTERVENTIONS: The patient was treated with intravitreal injection of anti-VEGF in his left eye. The thickness of the nasal macular retina decreased. OUTCOMES: The SRF was clearly absorbed, and the patient's visual acuity significantly improved. LESSONS: When CRAO occurs in patients with diabetic retinopathy sparing the CLRA, the non-characteristic cherry-red spot may be due to macular inner retinal edema, SRF and other factors. According to the patient's condition, anti-vascular endothelial growth factor can be administered as appropriate to inhibit choroidal neovascularization, reduce SRF in the macular retina, and save some vision.

[Effects of moisture and humic acid on the metabolism of oat fructans]. / æ°´åˆ†å’Œè æ¤é ¸å¯¹ç‡•éº¦æžœèšç³–ä»£è°¢çš„å½±å“.

To provide theoretical guidance and technical support for oat production in dry farming area, we exa-mined the effects of moisture and humic acid (HA) on the accumulation and distribution of non-structural carbohydrates (NSC) in different organs of oat, as well as the mechanism of sugar metabolism and grain weight formation of oat. Two oat cultivars, 'Mengnong Dayan 1' and 'Neiyan 5', were used as experimental material. HA and clean water (CK) were foliar sprayed under dry framing (without irrigation) and limited irrigation (irrigated twice at jointing and heading stage). The dynamics of NSC components in stems, leaves and panicles, as well as the changes of carbon metabolism-related enzyme activities at different growth stages of oats after flowering were measured. Results showed that the trend of the contents of NSC in stems, leaves and panicles, in both two oat cultivars increased firstly and then decreased with the prolong of post-anthesis time. The contents of NSC in different organs were similar between two oat cultivars. Under irrigation treatment, the fructan content in panicle for Mengnong Dayan 1 of HA was higher than that of CK, with magnitude of enhancement being significantly greater than that corresponding treatment under dry farming. Under irrigation condition, the fructan, invertase activities in leaves and grain weight per panicle for Mengnong Dayan 1 of HA were increased by 27.1%, 30.6% and 55.9% compared with CK, respectively. Further, the increase trend under irrigation was stronger than that under dry farming condition. For Mengnong Dayan 1, the 1000-grain weight and grain weight per panicle were positively correlated with the content of fructan in leaves. In conclusion, the synergistic effect of moisture and humic acid could effectively regulate the accumulation of oat fructans and the activities of carbon metabolic enzymes, consequently promoting the formation of yield.

Real-World Implementation of Neurosurgical Enhanced Recovery After Surgery Protocol for Gliomas in Patients Undergoing Elective Craniotomy.

Objective: To design a multidisciplinary enhanced recovery after surgery (ERAS) protocol for glioma patients undergoing elective craniotomy and evaluate its clinical efficacy and safety after implementation in a tertiary neurosurgical center in China. Methods: ERAS protocol for glioma patients was developed and modified based on the best available evidence. Patients undergoing elective craniotomy for treatment of glioma between September 2019 to May 2021 were enrolled in a randomized clinical trial comparing a conventional neurosurgical perioperative care (control group) to an ERAS protocol (ERAS group). The primary outcome was postoperative hospital length of stay (LOS). Secondary outcomes were 30-day readmission rate, postoperative complications, duration of the drainage tube, time to first oral fluid intake, time to ambulation and functional recovery status. Results: A total of 151 patients were enrolled (ERAS group: n = 80; control group: n = 71). Compared with the control group, postoperative LOS was significantly shorter in the ERAS group (median: 5 days vs. 7 days, p<0.0001). No 30-day readmission or reoperation occurred in either group. The time of first oral intake, urinary catheter removal within 24 h and early ambulation on postoperative day (POD) 1 were earlier and shorter in the ERAS group compared with the control group (p<0.001). No statistical difference was observed between the two groups in terms of surgical- and nonsurgical-related complications. Functional recovery in terms of Karnofsky Performance Status (KPS) scores both at discharge and 30-day follow-up was similar in the two groups. Moreover, no significant difference was found between the two groups in the Hospital Anxiety and Depression Scale (HADS) scores. Conclusion: The implementation of the ERAS protocol for glioma patients offers significant benefits over conventional neurosurgical perioperative management, as it is associated with enhancing postoperative recovery, without additional perioperative complications and risks. Clinical Trial Registration: Chinese Clinical Trial Registry (http://www.chictr.org.cn/showproj.aspx?proj=42016), identifier ChiCTR1900025108.

Synthesis of dibenzofurans via palladium-catalyzed phenol-directed C-H activation/C-O cyclization.

A practical, Pd(0)/Pd(II)-catalyzed reaction was developed for phenol-directed C-H activation/C-O cyclization using air as an oxidant. The turnover-limiting step of the process was found to be C-O reductive elimination instead of C-H activation. This reaction can tolerate a variety of functional groups and is complementary to the previous methods for the synthesis of substituted dibenzofurans.

Clinical Features and Molecular Markers on Diffuse Midline Gliomas With H3K27M Mutations: A 43 Cases Retrospective Cohort Study.

PURPOSE: Diffuse midline gliomas (DMG) with H3K27M mutations have been identified as a rare distinctive entity with unique genetic features, varied molecular alterations, and poor prognosis. The current study aimed to evaluate the clinical characteristics and profile of molecular markers on patients with a DMG harboring H3K27M mutations, and explore the impact of this genetic makeup on overall survival. METHODS: We retrospectively analyzed 43 consecutive patients diagnosed with a DMG harboring H3K27M mutations (age range 3 to 75 years) and treated in a tertiary institution within China between January 2017 to December 2019. Various clinical and molecular factors were evaluated to assess their prognostic value in this unique patient cohort. RESULTS: The median overall survival (OS) was 12.83 months. Preoperative Karnofsky Performance Score (KPS) and adjuvant radiotherapy were found to be independent clinical parameters influencing the OS by multivariate analysis (p = 0.027 and p < 0.001 respectively). Whereas extent of tumor resection failed to demonstrate statistical significance. For molecular markers, P53 overexpression was identified as a negative prognostic factor for overall survival by multivariate analysis (p = 0.030). CONCLUSION: Low preoperative KPS, absence of radiotherapy and P53 overexpression were identified as predictors of a dismal overall survival in patients with DMG and H3K27M mutations.

Comparative analysis of a panel of biomarkers related to protein phosphatase 2A between laryngeal squamous cell carcinoma tissues and adjacent normal tissues.

Laryngeal squamous cell carcinoma (LSCC) is the most common type of head and neck squamous cell carcinoma (HNSCC) worldwide. Protein phosphatase 2A (PP2A) dysfunction has been widely reported in a broad range of malignancies due to its distinctive role in miscellaneous cellular processes. However, it is poorly understood whether aberrant alterations of PP2A are involved in the network of oncogenic events in LSCC. Here, we detected a panel of PP2A-associated proteins using western blot in both laryngeal squamous cell carcinoma tissues and paired adjacent normal tissues from patients (Data S1). We found that phospho-PP2A/C (Y307), α4, cancerous inhibitor of protein phosphatase 2A (CIP2A), Akt, ezrin, phospho-ezrin (T567), 14-3-3, and focal adhesion kinase (FAK) showed increased expression levels in carcinoma tissues relative to normal tissues, while phospho-Akt (T308) showed decreased levels. Our study, thus, provides a rationale for targeting PP2A to develop novel therapies and proposes a combination of interrelated biomarkers for the diagnostic evaluation and prognosis prediction in LSCC.

Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.