Deep-Eutectic-Solvent-Based Self-Healing Polymer Electrolyte for Safe and Long-Life Lithium-Metal Batteries

The deployment of high-energy-density lithium-metal batteries has been greatly impeded by Li dendrite growth and safety concerns originating from flammable liquid electrolytes. Herein, we report a stable quasi-solid-state Li metal battery with a deep eutectic solvent (DES)-based self-healing polymer (DSP) electrolyte. This electrolyte was fabricated in a facile manner by in situ copolymerization of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA) and pentaerythritol tetraacrylate (PETEA) monomers in a DES-based electrolyte containing fluoroethylene carbonate (FEC) as an additive. The well-designed DSP electrolyte simultaneously possesses non-flammability, high ionic conductivity and electrochemical stability, and dendrite-free Li plating. When applied in Li metal batteries with a LiMn₂O₄ cathode, the DSP electrolyte effectively suppressed manganese dissolution from the cathode and enabled high-capacity and a long lifespan at room and elevated temperatures.     

Estimation of band alignment at CdS/Cu2ZnSnS4 hetero-interface by direct XPS measurements

This paper aims to estimate the band alignment to CdS/CZTS hetero-interface by direct X-ray photoelectron spectroscopy (XPS) measurements. XPS was used to determinate the valence-band offset (VBO) directly by determining the valence band positions at the hetero-interface. The conduction band offset (CBO) value was estimated based on the band gap measurements by UV/Visible spectroscopy and VBO measurements. The position of valence band (VB) changes close to the CdS-CZTS interface and the CBO is cliff-like. The band alignment diagram indicates that the CdS-CZTS interface heterojunction is type II.     

Chain transfer by addition-fragmentation mechanism. VII. Radical polymerization of vinyl monomers in the presence of ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoate and related compounds

Ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoate 1 , ethyl 2-[1-(dimethylvinylsilylperoxy)-ethyl]propenoate 2 , ethyl 2-[1-(1-(2-ethoxycarbonyl-1-methyl-2-propenylperoxysilyl)-1-methylethylperoxy)ethyl]propenoate 3 , and 2-phenyl-2-trimethylsilylperoxypropane 4 were synthesized and added to the free radical polymerization of vinylic monomers. 1 and 2 were found to show no homopolymerizability but act as effective chain transfer reagents in radical polymerizations of methyl methacrylate (MMA), styrene (St), and n-butyl acrylate (BA). The estimated chain transfer constants (C_tr) are as follows: C_tr ( 1 ) = 0.15 for MMA, 0.90 for St, and 2.03 for BA at 60°C; C_tr ( 2 ) = 0.12 for MMA, 1.16 for St, and 1.9 for BA at 60°C. ¹H–NMR spectra of poly(St) formed in the presence of 1 is consistent with the view that the polymers bear an oxirane at one terminal and an trimethylsilyloxy fragment at the other end. Moreover, peroxysilane 4 showed very low transfer properties by direct homolytic substitution (SH₂). These findings indicate that the ethyl 2-[1-(substituted dimethylsilylperoxy)ethyl]-propenoates 1–3 undergo chain transfer reaction via a intramolecular homolytic substitution (SHi) following an addition process. Preparation of poly(styrene) up to high conversion in the presence of 3 yielded to the formation of the corresponding polymeric structures bearing hydrolysable C(SINGLE BOND)O(SINGLE BOND)Si(SINGLE BOND)O(SINGLE BOND)C bonds. © 1996 John Wiley & Sons, Inc.     

Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations

Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]₂^2? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]₂^2? dimers form dissociated ion pairs with the NBu₄⁺ counterions, and their first solvation shell comprises approximately 20 CH₂Cl₂ molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE ^{. ?} in solution at 175 K is ?5.5 kcal mol^?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.     

Straightforward preparation of polymers based on oligodimethylsiloxane and alkylamine

Novel oligodimethylsiloxane‐based polymers with alkyl side chain were synthesized in bulk by step‐growth polymerization between α,ω‐glycidyl ether oligodimethylsiloxanes and a monoalkylamine in the absence of catalyst and at temperatures ranging between 80 and 180 °C. Matrix assisted laser desorption ionization time of flight results attested for the high reactivity of the amine functions with the glycidyl groups and revealed that the main polymer structure was (A₂B₂)_n type with alkyl moieties as dangling chains. No etherification was observed during the reaction even at high temperatures and the nature of the end groups strongly depended on the molar ratio between glycidyl and amine functions. Polymerization reactions were followed by ¹H NMR and the kinetics of the glycidyl‐amine reaction pointed out the dependence of temperature, molar ratio, and the molar mass of the oligodimethylsiloxane. High conversion rates were obtained, especially with the lowest molecular weight oligodimethylsiloxane. An optimized kinetic model derived from the Horie's model was discussed and permitted to correctly fit the experimental data. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Macrotricyclic quaternary tetraammonium receptors: halide anion recognition and interfacial activity at an aqueous interface. A molecular dynamics investigation

We report a molecular dynamics study of the halide inclusion complexes X(-) subset L(4+) of a macrotricyclic tetrahedral receptor L(4+) built from four quaternary ammonium sites connected by six (CH(2))(n) chains. The hydrophilic/hydrophobic character of the complexes is investigated at a water/chloroform interface, represented explicitly and, despite their +3 charge and "spherical" shape, they are found to display amphiphilic behavior and to concentrate at the interface. The more lipophilic N-substituted CH(2)phi derivative, as well as less charged models are more surface active than the N-Me substituted host. In relation with the Hofmeister series, I(-) exo neutralizing counterions are compared with Cl(-) anions and are found to sit closer to the interface, which becomes more neutral. The "macrocyclic interfacial effect" is investigated by a comparison of L(4+) complexes with their acyclic counterparts. Finally, we address the question of anion binding selectivity by L(4+) and its L(1) (4+) and L(2) (4+) topological isomers. F(-) is too small for these three hosts, while I(-) is too big. According to free energy perturbation calculations, Cl(-) is preferred to Br(-), but somewhat more by L(1) (4+) than by L(4+).     

Characterization of pure high-grade DCIS on magnetic resonance imaging using the evolving breast MR lexicon terminology: can it be differentiated from pure invasive disease?

Magnetic resonance imaging (MRI) is now a recognized method of imaging the breast. Unfortunately, there is lack of standardization in the MRI terminology used to characterize the appearance of breast lesions. Moreover, cases of mixed histologies are often imaged. We retrospectively identified cases of pure high-grade ductal carcinoma in situ (DCIS) using the recently introduced breast MRI lexicon and characterized the lesions in order to try and identify features that might distinguish high-grade DCIS from invasive disease. Five-year review of our institution's database revealed 637 patients underwent gadolinium-enhanced breast MRI examination. Twenty patients had histologically proven pure high-grade DCIS. After excluding patients with previous chemotherapy or inadequate MRI examination, 13 patients were analyzed and compared to the 13 most recent cases of pure invasive breast carcinoma. The morphological and dynamic features were then compared. High-grade DCIS cases were significantly more likely to show focal branching pattern (P=.03) and to have an irregular contour (P=.03), compared with invasive disease. Although of marginal statistical significance, DCIS lesions are more likely to have a lower morphological score than invasive carcinoma (P=.06), whilst the latter is more likely to show ring enhancement (P=.07). Use of breast MRI for staging at our institution shows that pure DCIS and pure invasive cancers are both rare entities. Despite the relatively limited numbers, we identified features that would help to differentiate high-grade DCIS from invasive carcinoma on MRI.     

A tandem metal carbene cyclization-cycloaddition approach to the pseudolaric acids

An approach toward the synthesis of the antifungal and cytotoxic pseudolaric acids based on the tandem metal carbene cyclization-cycloaddition reaction is described. Using this strategy, the advanced intermediate 3a bearing three of the four stereocenters of the target molecules has been synthesized. The substrate-controlled diastereoselectivity of the tandem carbene cyclization-cycloaddition was preferential for the undesired diastereomer, but reagent control through the use of Hashimoto's chiral rhodium catalyst Rh(2)(S-BPTV)(4) reversed the selectivity in favor of 3a. Ring opening of the oxabicyclic nucleus to give a hydroxycycloheptene has been demonstrated in a model study.     

Challenges associated with the synthesis of unusual o-carboxamido stilbenes by the Heck protocol: Intriguing substituent effects, their toxicological and chemopreventive implications

The syntheses of fourteen unusual o-carboxamido stilbenes by the Heck protocol revealed surprising complexity related to intriguing substituent effects with mechanistic implications. The unexpected cytotoxic and chemopreventive properties also seem to be substituent dependent. For example, although stilbene 15d (with a 4-methoxy substituent) showed cytotoxicity on HT29 colon cancer cells with an IC(50) of 4.9 μM, the 3,4-dimethoxy derivative (15c) is inactive. It is interesting to observe that the 3,5-dimethoxy derivative (15e) showed remarkable chemopreventive activity in WRL-68 fetal hepatocytes, surpassing the gold standard, resveratrol. The resveratrol concentration needed to be 5 times higher than that of 15e to produce comparable elevation of NQO1.