CL

A palladium-catalyzed carbohalogenation of olefins with alkynyl oxime ethers has been described, which provides efficient and practical access to various chlorine-containing isoxazoles. This method exhibits excellent regioselectivity, good functional group compatibility, and mild reaction conditions. The mechanistic studies suggest that the reaction proceeds via a stabilized π-benzyl palladium intermediate, which is essential for the formation of C(sp3 )-Cl bonds.

Poly(vinylidene fluoride) (PVDF) shows excellent chemical and thermal resistance and displays high dielectric strength and unique piezoelectricity, which are enabling for applications in membranes, electric insulators, sensors, or power generators. However, its low polarity and lack of functional groups limit wider applications. While inert, PVDF has been modified by grafting polymer chains by atom transfer radical polymerization (ATRP), albeit via an unclear mechanism, given the strong C-F bonds. Herein, we applied eosin Y and green-light-mediated ATRP to modify PVDF-based materials...

Aqueous batteries, with the advantages of high safety and low cost, are highly promising for large-scale energy storage. However, freezing of the aqueous electrolyte limits the low-temperature operation. Here, we propose and achieve a highly dispersed solvation structure in the electrolyte by coupling nonaggregated Cl- anions, which reduces the water cluster size and prevents the solidification of the aqueous electrolyte until -136.3 °C. The low-temperature LiCl electrolyte exhibits a high ionic conductivity (1...

Contrastive learning (CL) has emerged as a powerful approach for self-supervised learning. However, it suffers from sampling bias, which hinders its performance. While the mainstream solutions, hard negative mining (HNM) and supervised CL (SCL), have been proposed to mitigate this critical issue, they do not effectively address graph CL (GCL). To address it, we propose graph positive sampling (GPS) and three contrastive objectives. The former is a novel learning paradigm designed to leverage the inherent properties of graphs for improved GCL models, which utilizes four complementary similarity measurements, including node centrality, topological distance, neighborhood overlapping, and semantic distance, to select positive counterparts for each node...

OBJECTIVE: To describe overall survival (OS) and disease-free survival (DFS) in a cohort of tongue cancer patients, together with the corresponding demographic, tumor and surgical characteristics. METHODS: A retrospective study was made of 205 consecutive patients with primary tongue cancer subjected to surgery and adjuvant therapy according to the stage of the disease, in Hospital Clínico Universitario Virgen de la Arrixaca (HUVA) (Murcia, Spain) during the period 2000-2020...

The E 1/2 potential associated with reduction of the linearly-functionalized 6,6'-biazulenic scaffold is accurately correlated to the combined σ p Hammett parameters of the substituents over >600 mV range. X-ray crystallographic analysis of the 2,2'-dichloro-substituted derivative revealed unexpectedly short C-Cl bond distances, along with other metric changes, suggesting a non-trivial cycloheptafulvalene-like structural contribution.

In this work, we propose and validate a generalization of the Helmholtz model that can account for both "bell-shaped" and "camel-shaped" differential capacitance profiles of concentrated electrolytes, the latter being characteristic of ionic liquids. The generalization is based on introducing voltage dependence of both the dielectric constant "ϵr(V)" and thickness "L(V)" of the inner Helmholtz layer, as validated by molecular dynamics (MD) simulations. We utilize MD simulations to study the capacitance profiles of three different electrochemical interfaces: (1) graphite/[BMIm+][BF4-] ionic liquid interface; (2) Au(100)/[BMIm+][BF4-] ionic liquid interface; (3) Au(100)/1M [Na+][Cl-] aqueous interface...

Sodium-based dual ion batteries (SDIBs) have garnered significant attention as novel energy storage devices offering the advantages of high-voltage and low-cost. Nonetheless, conventional electrolytes exhibit low resistance to oxidation and poor compatibility with electrode materials, resulting in rapid battery failure. In this study, for the first time, we propose a chlorination design of electrolytes for SDIB. Using ethyl methyl carbonate (EMC) as a representative solvent, chlorine-substituted EMC (Cl-EMC) not only demonstrates increased oxidative stability ascribed to the electron-withdrawing characteristics of chlorine atom, electrolyte compatibility with both the cathode and anode have also been greatly improved by forming Cl-containing interface layers...

BACKGROUND: Myopia management contact lenses have been shown to successfully decrease the rate of eye elongation in children by changing the peripheral refractive profile of the retina. Despite the efforts of the scientific community, the retinal response mechanism to defocus is still unknown. The purpose of this study was to evaluate the local electrophysiological response of the retina with a myopia control contact lens (CL) compared to a single-vision CL of the same material. METHODS: The retinal electrical activity and peripheral refraction of 16 eyes (16 subjects, 27...

Ultrathin MXene-based films exhibit superior conductivity and high capacitance, showing promise as electrodes for flexible supercapacitors. This work describes a simple method to enhance the performance of MXene-based supercapacitors by expanding and stabilizing the interlayer space between MXene flakes while controlling the functional groups to improve the conductivity. Ti3 C2 T x MXene flakes are treated with bacterial cellulose (BC) and NaOH to form a composite MXene/BC (A-M/BC) electrode with a microporous interlayer and high surface area (62...

The N3O1 tetradentate ligand, TriMeOBQMOA ( N , N -bis(5,6,7-trimethoxy-2-quinolylmethyl)-2-methoxyaniline), was developed as a Cd2+ -specific fluorescent sensor. The structure of TriMeOBQMOA is half of TriMeOBAPTQ ( N , N , N ', N '-tetrakis(5,6,7-trimethoxy-2-quinolylmethyl)-1,2-bis(2-aminophenoxy)ethane), which is a tetrakisquinoline derivative of the well-known calcium chelator BAPTA (1,2-bis(2-aminophenoxy)ethane- N , N , N ', N '-tetraacetic acid). The fluorescent Cd2+ selectivity of TriMeOBAPTQ ( I Zn / I Cd = 5...

Planar π-conjugated groups, like CO3 , NO3 , and BO3 triangles, are ideal functional units for designing birefringent materials due to their large optical anisotropy and wide band gap. The key point for designing birefringent crystals is to select appropriate functional building blocks (FBBs) and the proper arrangement mode. It is well known that the substitution strategy has proven to be a promising and accessible approach. In this work, alkali metals were chosen to regulate and control two different π-conjugated groups, CO3 and NO3 , to build new compounds with large birefringence...

Prevalence of F, Cl, S, P, Br, and I in pharmaceuticals and environmental contaminants has promoted standard-free quantitation using analyte-independent heteroatom responses in inductively coupled plasma (ICP)-MS. However, in-plasma ionization challenges and element-dependent isobaric interference removal methods have hampered the multielement nonmetal detection in ICP-MS. Here, we examine an alternative approach to enhance multielement detection capabilities. Analytes are introduced into an ICP leading to post-plasma formation of HF, HCl, H3 PO3 , H2 SO4 , HBr, and HI, which are then chemically ionized to BaF+ , BaCl+ , BaH2 PO3 + , BaHSO4 + , BaBr+ , and BaI+ via reactions with barium-containing ions supplied by a nanospray...

Autophagy supervises the proteostasis and survival of B lymphocytic cells. Trk-fused gene (TFG) promotes autophagosome-lysosome flux in murine CH12 B cells, as well as their survival. Hence, quantitative proteomics of CH12 tfg KO and WT B cells in combination with lysosomal inhibition should identify proteins that are prone to lysosomal degradation and contribute to autophagy and B cell survival. Lysosome inhibition via NH4 Cl unexpectedly reduced a number of proteins but increased a large cluster of translational, ribosomal, and mitochondrial proteins, independent of TFG...

BACKGROUND: Measuring spinal alignment with radiological parameters is essential in patients with spinal conditions likely to be treated surgically. These evaluations are not usually included in the radiological report. As a result, spinal surgeons commonly perform the measurement, which is time-consuming and subject to errors. We aim to develop a fully automated artificial intelligence tool to assist in measuring alignment parameters in whole-spine lateral radiograph (WSL X-rays). MATERIAL AND METHODS: We developed a tool called Vertebrai that automatically calculates the global spinal parameters (GSP): Pelvic incidence (PI), sacral slope (SS), pelvic tilt (PT), L1-L4 angle, L4-S1 lumbo-pelvic angle, T1 pelvic angle (TPA), sagittal vertical axis (SVA), cervical lordosis (CL), C1-C2 lordosis, lumbar lordosis (LL), mid-thoracic kyphosis (MTK), proximal thoracic kyphosis (PTK), global thoracic kyphosis (GTK), T1 slope (T1S), C2-C7 plummet (cSVA), spino-sacral angle (SSA), C7 tilt (C7T), global tilt (GT), spinopelvic tilt (T1SPi) and hip odontoid axis (OD-HA)...

BACKGROUND: Posaconazole is a vital drug to treat and prevent invasive fungal infections. Several factors, such as sex, body weight, total serum proteins, dietary intake, and severe mucositis, affect posaconazole pharmacokinetics (PKs). However, the relevance of other factors that affect the PKs of posaconazole in hematopoietic stem cell transplantation (HSCT) is unknown. This study explored factors influencing the PKs of posaconazole in HSCT recipients and nontransplant patients with hematological diseases...

The impact of non-Born-Oppenheimer couplings on the isotopic effects in the reaction of the Cl(2 P) atom with the HD ( v = 0, j = 0) molecule is investigated with our recently developed nonadiabatic time-independent quantum scattering methods, where the full open-shell characteristics are included in the six-state model, and also with the recently developed two-state model solving by time-independent methods, where part of the open-shell characteristic is included. The same reaction is also calculated with the simple adiabatic model using the lowest adiabatic potential energy surface...

The complex nature of the f-orbital electronic structures and their interaction with the chemical environment pose significant computational challenges. Advanced computational techniques that variationally include scalar relativities and spin-orbit coupling directly at the molecular orbital level have been developed to address this complexity. Among these, variational relativistic multiconfigurational multireference methods stand out for their high accuracy and systematic improvement in studies of f-block complexes...

The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long-standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2 -to-CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso-tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2 ] (2,2'-bipyridine)...

Direct coupling of benzotriazole to unsaturated substrates such as allenes represents an atom-efficient method for the construction of biologically and pharmaceutically interesting functional structures. In this work, the mechanism of the N 2 -selective Rh complex-catalyzed coupling of benzotriazoles to allenes was investigated in depth using a combination of experimental and theoretical techniques. Substrate coordination, inhibition, and catalyst deactivation was probed in reactions of the neutral and cationic catalyst precursors [Rh(μ-Cl)(DPEPhos)]2 and [Rh(DPEPhos)(MeOH)2 ]+ with benzotriazole and allene, giving coordination, or coupling of the substrates...