High-performance and scalable polarization splitter-rotator based on photonic crystal nanobeam reflection.

The polarization splitter-rotator (PSR) is a key device for polarization processing in polarization diversity systems, which has wide applications in achieving polarization independence and mixed multiplexing. However, it remains a significant challenge to simultaneously achieve a better balance in bandwidth, crosstalk (CT), polarization extinction ratio (PER), and compact footprint of the PSR. In this article, a photonic crystal nanobeam (PCN) structure is introduced to PSR for large bandwidth and compact size, with a device length of only 104 µm.

Unresectable hepatocellular carcinoma: Transarterial chemoembolization combined with lenvatinib in combination with programmed death-1 inhibition is a possible approach.

In this editorial, we review the article "Efficacy and predictive factors of transarterial chemoembolization combined with lenvatinib plus programmed cell death protein-1 inhibition for unresectable hepatocellular carcinoma". We specifically focused on whether transarterial chemoembolization combined with lenvatinib in combination with a programmed death 1 inhibitor could be used in patients with unresectable hepatocellular carcinoma. Since both transarterial chemoembolization as well as lenvatinib in combination with programmed death 1 inhibitors play an important role in the treatment of advanced liver cancer, but the combination of all three therapeutic approaches needs more research.

CDK4/6 inhibitors and the pRB-E2F1 axis suppress PVR and PD-L1 expression in triple-negative breast cancer.

Immune-checkpoint (IC) modulators like the poliovirus receptor (PVR) and programmed death ligand 1 (PD-L1) attenuate innate and adaptive immune responses and are potential therapeutic targets for diverse malignancies, including triple-negative breast cancer (TNBC). The retinoblastoma tumor suppressor, pRB, controls cell growth through E2F1-3 transcription factors, and its inactivation drives metastatic cancer, yet its effect on IC modulators is contentious. Here, we show that RB-loss and high E2F1/E2F2 signatures correlate with expression of PVR, CD274 (PD-L1 gene) and other IC modulators and that pRB represses whereas RB depletion and E2F1 induce PVR and CD274 in TNBC cells.

Conjugation of the glutelin hydrolysates-glucosamine by transglutaminase and functional properties and antioxidant activity of the products.

A novel mixture of glycopeptides was prepared from corn glutelin and glucosamine (GlcN). The functional properties and antioxidative activities of this mixture were investigated. Corn glutelin was limited hydrolyzed by Alcalase, and then its hydrolysates were glycosylated with GlcN by transglutaminase (TGase) to modify its main and side chain, respectively.

Palladium-Catalyzed -Difluoroallylation Reaction between Aryltributyltin and Bromodifluoromethylated Alkenes.

A robust Stille -difluoroallylation of arylstannanes with 3-bromo-3,3-difluoropropenes has been established. The catalyst was found to exert critical effect on the reaction chemoselectivity. By using Pd(OH)/C as the catalyst, a series of 3-(hetero)aryl/vinyl-3,3-difluoropropenes were obtained in high efficiency with α-substitution regioselectivity.

Preparation of Sulfamates and Sulfamides Using a Selective Sulfamoylation Agent.

Sulfamates and sulfamides are prevalent in biological molecules, but their universal synthetic methods are limited. We herein report a sulfamoylation agent with high solubility and shelf stability. Various sulfamates and sulfamides can be synthesized directly from alcohols or amines by employing this agent with high selectivity and high yields.

Modeling germline mutations in pineoblastoma uncovers lysosome disruption-based therapy.

Pineoblastoma is a rare pediatric cancer induced by germline mutations in the tumor suppressors RB1 or DICER1. Presence of leptomeningeal metastases is indicative of poor prognosis. Here we report that inactivation of Rb plus p53 via a WAP-Cre transgene, commonly used to target the mammary gland during pregnancy, induces metastatic pineoblastoma resembling the human disease with 100% penetrance.

Visible Light-Promoted Phosphine-Catalyzed Difluoroalkylation of Arenes and Heterocycles.

A visible light-promoted difluoroalkylation reaction of arenes or heterocycles, using triaryl phosphine as the catalyst and difluoroalkyl iodide as the alkylating agent, is presented. The strategy is highlighted by photocatalyst-free, mild reaction conditions and a broad substrate scope. Mechanistic experiments indicate that this reaction involves a radical-chain process that is initiated by an electron donor-acceptor complex formed from difluoroalkyl iodide and phosphine.

Molecular stratification within triple-negative breast cancer subtypes.

Triple-negative breast cancer (TNBC) has been subdivided into six distinct subgroups: basal-like 1 (BL1), basal-like 2 (BL2), mesenchymal (M), mesenchymal stem-like (MSL), immunomodulatory (IM), and luminal androgen receptor (LAR). We recently identified a subgroup of TNBC with loss of the tumor suppressor PTEN and five specific microRNAs that exhibits exceedingly poor clinical outcome and contains TP53 mutation, RB1 loss and high MYC and WNT signalling. Here, show that these PTEN-low/miRNA-low lesions cluster with BL1 TNBC.

Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage.

Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst.

Non-transition Metal-Mediated Diverse Aryl-Heteroatom Bond Formation of Arylammonium Salts.

Aryl-heteroatom (C-X) bonds ubiquitously exist in organic, medicinal, and material chemistry, but a universal method to construct diverse C-X bonds is lacking. Here we report our discovery of a convenient and efficient approach to construct various C-X bonds using arylammonium salts as the substrate via an SAr process. This strategy features mild reaction condition, no request of transition metal catalyst, and easy formation of various C-X bonds (C-S, C-Si, C-Sn, C-Ge, C-Se, C-N).

A subgroup of microRNAs defines PTEN-deficient, triple-negative breast cancer patients with poorest prognosis and alterations in RB1, MYC, and Wnt signaling.

Background: Triple-negative breast cancer (TNBC) represents a heterogeneous group of ER- and HER2-negative tumors with poor clinical outcome. We recently reported that Pten-loss cooperates with low expression of microRNA-145 to induce aggressive TNBC-like lesions in mice. To systematically identify microRNAs that cooperate with PTEN-loss to induce aggressive human BC, we screened for miRNAs whose expression correlated with PTEN mRNA levels and determined the prognostic power of each PTEN-miRNA pair alone and in combination with other miRs.

From Anilines to Aryl Ethers: A Facile, Efficient, and Versatile Synthetic Method Employing Mild Conditions.

We have developed a simple and direct method for the synthesis of aryl ethers by reacting alcohols/phenols (ROH) with aryl ammonium salts (ArNMe ), which are readily prepared from anilines (ArNR' , R'=H or Me). This reaction proceeds smoothly and rapidly (within a few hours) at room temperature in the presence of a commercially available base, such as KO Bu or KHMDS, and has a broad substrate scope with respect to both ROH and ArNR' . It is scalable and compatible with a wide range of functional groups.

Mapping genomic and transcriptomic alterations spatially in epithelial cells adjacent to human breast carcinoma.

Almost all genomic studies of breast cancer have focused on well-established tumours because it is technically challenging to study the earliest mutational events occurring in human breast epithelial cells. To address this we created a unique dataset of epithelial samples ductoscopically obtained from ducts leading to breast carcinomas and matched samples from ducts on the opposite side of the nipple. Here, we demonstrate that perturbations in mRNA abundance, with increasing proximity to tumour, cannot be explained by copy number aberrations.

Organozinc-Mediated Direct C-C Bond Formation via C-N Bond Cleavage of Ammonium Salts.

We report a direct cross-coupling reaction between diarylzinc (Ar Zn) and aryltrimethylammonium salts (ArNMe ⋅ OTf) in the presence of LiCl, via C-N bond cleavage. The reaction takes place smoothly upon heating in THF without any external catalyst, enabling an efficient and chemoselective formation of biaryl products. Mechanistic studies indicate that the reaction proceeds through a single electron transfer route.

Monomeric Octahedral Ruthenium(II) Complex Enabled meta-C-H Nitration of Arenes with Removable Auxiliaries.

A removable oxime-assisted meta-C-H nitration of arenes is reported. Mechanistic investigations and DFT calculations reveal a new monomeric octahedral ruthenium(II) complex is responsible for the meta-selective nitration. Dioxygen as a cooxidant is crucial for achieving high conversion and good yields.

Cross-Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C-O or C-N Bond Cleavage.

Various aryl-, alkenyl-, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C-O bond to afford cross-coupled products, catalyzed by commercially available [Ni(cod) ] (cod=1,5-cyclooctadiene) catalysts with N-heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C-N bond cleavage in the presence of a [Pd(PPh ) Cl ] catalyst. These methods enable selective sequential functionalizations of arenes having both C-N and C-O bonds in one pot.

Stille coupling via C-N bond cleavage.

Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C-N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R-NMe] react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod) and imidazole ligand together with 3.