Iodine(III)-Mediated C–H Alkoxylation of Aniline Derivatives with Alcohols under Metal-Free Conditions

The development of a novel intermolecular oxidative C–H alkoxylation of aniline derivatives is described under metal-free conditions with high reaction rates at ambient temperature. In the presence of an I­(III) oxidant, a range of aldehydes, anilines, and alcohol substrates undergo three-component coupling to produce synthetically useful alkoxyl-substituted <i>N</i>-arylimines. The preliminary mechanism investigations revealed that the transformation proceeds via imines as intermediates

Prognostic and clinicopathological value of osteopontin expression in non-small cell lung cancer: a meta-analysis and systematic review

Although Osteopontin (OPN) has been reported to be associated with many different human cancers, the data on non-small cell lung cancer (NSCLC) are not definitive. This study aimed to explore the prognostic effect of OPN expression and clinicopathological characteristics in patients with NSCLC. This study followed all aspects of the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) report. PubMed, Embase and the Cochrane Library were searched to identify the relative studies. The pooled hazard ratios (HRs) and 95% confidence intervals (CIs) were calculated to estimate the prognostic value of the OPN in patients with NSCLC. The odds ratio (OR) was calculated to represent the relationship between OPN expression and clinicopathological parameters. A total of fifteen studies with 2173 participants were finally included. The results revealed that high expression of OPN was significantly associated with poorer overall survival (OS) (HR = 1.89; 95%CI = 1.68–2.11; p  This meta-analysis implies that OPN might be a valuable biomarker for a poor prognosis and poor clinicopathological outcomes for patients with NSCLC. Our findings suggest that osteopontin is an important biomarker for poor prognosis and poor clinicopathological outcome in Non-small cell lung cancer (NSCLC) patients.Increased expression of osteopontin in NSCLC patients is associated not only with poorer survival but also with tumor differentiation, lymph node metastasis, and distant metastasis.This may be due to that osteopontin promotes multiple pathological processes including cancer cell proliferation, invasion, tumor progression, and metastasis in NSCLC. Our findings suggest that osteopontin is an important biomarker for poor prognosis and poor clinicopathological outcome in Non-small cell lung cancer (NSCLC) patients. Increased expression of osteopontin in NSCLC patients is associated not only with poorer survival but also with tumor differentiation, lymph node metastasis, and distant metastasis. This may be due to that osteopontin promotes multiple pathological processes including cancer cell proliferation, invasion, tumor progression, and metastasis in NSCLC.</p

Phenyliodonium Diacetate Mediated Direct Synthesis of Benzonitriles from Styrenes through Oxidative Cleavage of CC Bonds

A metal-free PhI­(OAc)₂ mediated nitrogenation of alkenes through CC bond cleavage using inorganic ammonia salt as nitrogen source under mild conditions was developed, affording nitriles in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of an ammonium salt as nitrogen source. Based upon experimental observations, a plausible reaction mechanism is proposed

K₂S₂O₈-Mediated Difunctionalization of C≡C Bonds in Water: A Simple and Efficient Approach to α,α-Dihaloacetophenones from Phenylacetylenes and NaX

<div><p></p><p>A novel K₂S₂O₈-mediated oxy-1,1-dihalogenation of alkynes with NaX in the presence of water has been developed, affording α,α-dihaloacetophenones in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of pure water as reaction medium. A plausible reaction mechanism is proposed on the basis of mechanistic studies.</p> </div

Toward Tandem Photovoltaic Devices Employing Nanoarray Graphene-Based Sheets

Graphene quantum dots (GQDs) are promising photonic materials for light harvesting. However, only low photoelectron conversion efficiency can be generated in single-junction graphene-based solar cells when isolated GQDs with the edge bonding defects are used as semiconductors. To address this issue, a four-junction GQD-based tandem solar cell with high theoretical conversion efficiency was proposed in this paper. Instead of isolated GQDs, nanoarray GQDs embedded in hexagonal host materials, such as graphane or boron nitride, was adopted as the photoactive layer. Utilizing our universal thermodynamic approach to the gap openings in low-dimensional graphene, nanoarray armchair-interfaced GQDs embedded in graphane to achieve the maximal diameter of confined GQDs are found preferential for fabricating tandem solar cell devices. Besides these, the separation between GQDs and the thickness of GQD-based sheets were determined. This contribution is of benefit to the application of graphene for solar cell devices

CO₂ Reduction Mechanism on the Pb(111) Surface: Effect of Solvent and Cations

The Pb electrode is the most efficient and selective catalyst in reducing CO₂ into HCOOH; however, the reaction mechanism remains elusive. Herein, we have investigated the mechanism of CO₂ electroreduction to HCOOH on the Pb(111) surface using density functional theory calculations. We find that the effects of solvation and cations lead to different active intermediates for CO₂ electroreduction (HCOO in gas-phase condition, both HCOO and COOH in solvent condition, and COOH in cation solution). In particular, the size and hydrophilic/hydrophobic nature of the cations are found to significantly affect the reaction selectivity and efficiency of CO₂ electroreduction at different overpotentials. These findings rationalize several experimental observations and contribute to a thorough understanding of CO₂ electroreduction

Table_1_Immunotherapy strategies for EGFR-mutated advanced NSCLC after EGFR tyrosine-kinase inhibitors failure.docx

BackgroundThis study aimed to investigate the efficacy of immunotherapy, as monotherapy or in combination, comparing to chemotherapy with or without anti-angiogenesis for advanced non-small cell lung cancer (NSCLC) patients progressing to epidermal growth factor receptor (EGFR)-tyrosine kinase inhibitors (TKIs).MethodsWe retrospectively analyzed patients with advanced NSCLC harboring EGFR mutations who received immune checkpoint inhibitors (ICI) and/or chemotherapy after EGFR-TKIs failure at Shanghai Chest Hospital between Aug 2016 and Oct 2022. According to the subsequent immunotherapy regimen, the patients were assigned to ICI monotherapy (IM), IO plus anti-angiogenesis (IA), ICI plus chemotherapy (IC), ICI plus chemotherapy plus anti-angiogenesis (ICA). Eligible patients undergoing standard chemotherapy were assigned to chemotherapy plus anti-angiogenesis (CA) and chemotherapy alone (CM). Efficacy was evaluated according to the RECIST 1.1version, and calculated the objective response rate (ORR) and disease control rate (DCR). Survival curves were plotted using the Kaplan-Meier method, and the median progression-free survival (PFS) was calculated. Differences among survival curves of the six groups were assessed using the log-rank test.ResultsA total of 237 advanced NSCLC patients with EGFR mutations were included in this study. Of the 160 patients who received immunotherapy, 57 received ICI monotherapy, 27 received ICI plus anti-angiogenesis therapy, 43 received ICI plus chemotherapy, and 33 received ICI plus anti-angiogenesis plus chemotherapy. 77 patients received standard chemotherapy, of which 30 received chemotherapy plus anti-angiogenesis and 47 received chemotherapy alone. Patients in ICA group showed significant longer PFS than IM (7.2 vs 1.9 months, P=0.011), IA (7.2 vs 4.8 months, P=0.009) and CM group (7.2 vs 4.4 months, P=0.005). There was no significant difference in PFS between the ICA and IC (7.2 vs 5.6 months, P=0.104) or CA (7.2 vs 6.7 months, P=0.959) group. Meanwhile, the ICA group showed the highest ORR and DCR (36.4% and 90.9%) compared to the other five groups. The IC group had a higher ORR than the IA and CA group (32.6% vs 7.4% vs 10.0%, respectively), but the DCR was comparable (79.1% vs 74.1% vs 76.7%, respectively). The ORR of the CM group was 6.4% and the DCR was 66.0%. IM group showed the lowest ORR and DCR (1.8% and 36.8%). Treatment-related adverse events (TRAEs) of grade 3 or worse occurred in 9 (27.3%) patients in the ICA group, 6 (20.0%) in the CA group, 7 (14.9%) in the CM group, 5 (11.6%) in the IC group, 5 (8.8%) in the IM group, and 2 (7.4%) in the IA group.ConclusionNSCLC patients with positive EGFR mutations after EGFR-TKIs failure received subsequent immunotherapy plus anti-angiogenesis and chemotherapy are likely to have more benefits in ORR, DCR and mPFS.</p

Iron-Facilitated Oxidative Radical Decarboxylative Cross-Coupling between α‑Oxocarboxylic Acids and Acrylic Acids: An Approach to α,β-Unsaturated Carbonyls

The first Fe-facilitated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyls frequently found in bioactive compounds. The synthetic potential of the coupled products is also demonstrated in subsequent functionalization reactions. Preliminary mechanism studies suggest that a free radical pathway is involved in this process: the generation of an acyl radical from α-oxocarboxylic acid via the excision of carbon dioxide followed by the addition of an acyl radical to the α-position of the double bond in acrylic acid then delivers the α,β-unsaturated carbonyl adduct through the extrusion of another carbon dioxide

Enhanced Sodium-Ion Mobility and Electronic Transport of Hydrogen-Incorporated V₂O₅ Electrode Materials

Although α-V₂O₅ as an attractive electrode material for electrochemical energy storage devices exhibits a high theoretical capacity, its atomic structure with the confined size of channels for Na-ion transport and low electronic conductivity lead to the poor rate performance. Here we demonstrate that hydrogen incorporation in α-V₂O₅ is an effective way to improve the kinetics of ionic and electronic transports by using the density functional theory. Among various structures of hydrogen-incorporated α-V₂O₅, H₂V₂O₅ presents enlarged diffusion channels along the [010] and [001] directions where the diffusion energy barriers decrease to 0.844 eV (−34.93%) and 1.737 eV (−41.81%), respectively. Improved electronic conductivity is also achieved for H₂V₂O₅ due to the insulator–metal transition attributed by the high concentration of hydrogen atoms. As H₂V₂O₅ has smaller volume expansion occurring during the Na-intercalation process, H₂V₂O₅ at the comparable specific capacity exhibits higher rate capability and cyclability than α-V₂O₅

Enzymatic Synthesis of Poly(butylene-<i>co</i>-sebacate-<i>co</i>-glycolate) Copolyesters and Evaluation of the Copolymer Nanoparticles as Biodegradable Carriers for Doxorubicin Delivery

Aliphatic copolyesters consisting of diester, diol, and glycolate repeat units were enzymatically synthesized for the first time via lipase-catalyzed polycondensation reactions. Copolymerization of ethyl glycolate (EGA) with diethyl sebacate (DES) and 1,4-butanediol (BD) in the presence of Candida antarctica lipase B (CALB) resulted in the formation of poly­(butylene-<i>co</i>-sebacate-<i>co</i>-glycolate) (PBSG) copolyesters with molecular weight (<i>M</i>_w) up to 28000 and typical polydispersity between 1.2 and 1.8. The synthesized copolymers contained 10–40 mol % glycolate (GA) units depending on the monomer feed ratio employed. DSC analyses show that the copolyesters with 12–38% GA content are semicrystalline materials that melt between 43 and 59 °C. Free standing nanoparticles with an average size ranging from 250 to 400 nm were successfully fabricated from these PBSG copolymers using a single emulsification-solvent evaporation process. PBSG copolyesters were found to be hydrolytically degradable and doxorubicin- (DOX-) encapsulated PBSG nanoparticles exhibited slow and sustained release of the drug in PBS solution at 37 °C over an extended period of time (60 days). Cellular uptake studies indicate that the drug-loaded PBSG particles are absorbed by a large percentage (up to 95%) of Hela cancer cells within 4 h incubation time. <i>In vitro</i> cytotoxicity investigations reveal that at a same DOX concentration (0.125–2.0 μM), DOX-encapsulated PBSG nanoparticles possess either higher or comparable cytotoxicity toward Hela cells than the free drug DOX·HCl. These results suggest that the PBSG nanoparticles are promising carriers for controlled release delivery of DOX to treat cancers