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A novel family of functionalized styrenic copolymers that are susceptible to a base-catalyzed β-elimination reaction is reported. The reactive copolymers, poly-{(2-phenyl-2-cyanoethoxycarbonyloxystyrene)-co-(4-hydroxystyrene)}, are prepared by chemical modification of poly(4-hydroxystyrene) using 2-phenyl-2-cyanoethyl chloroformate. A photoresist material consisting of the copolymer and bis[[(2-nitrobenzyl)-oxy] carbonyl]-4,4′-trimethylenedipiperidine used as an amine photogenerator affords positive tone images by UV irradiation. The effect of copolymer structure and composition on imaging, thermal stability, and the ease of β-elimination reaction is discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3543–3552 1997
Our direct DFT decomposition of CO frequency shifts updates the paradigm for metal carbonyl binding.
A pesquisa socio-histórica sobre o corpo – sua configuração social, usos culturais e alterações físicas – passou por um crescimento sem precedentes nas duas últimas décadas, como demonstrado pela produção extraordinária de monografias historiográficas, tratados filosóficos, investigações antropológicas e estudos variados inspirados pelo feminismo, ou interessados em sexualidade, e os incontáveis números especiais de revistas que vão da literatura à psiquiatria, sem falar do lançamento, emblemático desse florescimento que torna-se tendência, do periódico inglês Body & Society que tem como obetivo agir como catalizador para a aplicação de teorias pós-estruturalistas e pós-modernas à esse objeto recentemente reabilitado e reconduzido ao centro das ciências sociais e humanas. Mas, ainda assim, essa profusão de trabalhos em múltiplas áreas apresenta uma característica notável e paradoxal que é esconder da vista corpos “verdadeiramente existentes” através da sua substituição por um corpo quase completamente virtual formado por signos, portador de códigos, e receptáculo passivo (ou recalcitrante) de forças sociais consideradas externas a ele, em resumo, um corpo mais ou menos reduzido ao nível de outro texto sujeito a uma tratamento essencialmente hermenêutico.
Alkali-ion intercalation compounds are widely used as cathode materials for rechargeable batteries, including Li-, Na-, and K-ion batteries. For many years, researchers have developed layered oxide cathode materials for Na- and K-ion batteries given that the layered oxides show high reversible capacity and high working voltage in Li-ion technology. However, our works have demonstrated that the layered oxide compounds may not be good cathode candidates for Na and K systems. There are two main issues: [1-4] (i) Na and K transition metal oxide compounds form non-stoichiometric composition ( x <1.0 in A x MO 2 , A= Na and K). It leads practical difficulty of realizing Na- and K-ion batteries because all the Na and K ions should come from the cathode in rocking-chair batteries. (ii) As the insertion ion size increases, the voltage curve becomes much sloped. The sloped voltage curves result in low specific capacity and average voltage. Both the problems are attributable to much stronger Na + -Na + and K + -K + interaction than Li + -Li + in the layered oxide structure. In this respect, polyanion compounds that have 3 dimensional arrangements of Na and K ions, resulting in longer Na + -Na + and K + -K + distance, will be better candidates. We proposed KVPO 4 F [5] as an example of polyanion compounds and it has stoichiometric composition and provides high average voltage of ~4.3 V ( vs. K/K + ) with a reversible capacity of ~105 mAh/g. We further investigated the effect of intercalation ion species in K x VPO 4 F ( x ~0). [6] Our work demonstrates the voltage for Na intercalation is even higher than that for Li insertion unlike the common belief that Li insertion voltage is always higher than Na insertion. The lower Li intercalation voltage is likely attributed to unstable Li site in large cavity, making less stable discharged product upon Li insertion vs. Na insertion. In addition, we found that Li intercalation is more sluggish than Na and K intercalation in K x VPO 4 F ( x ~0). Since Li ion is too small compared to cavity in the cathode, Li ions are undercoordinated in the transition state, in which a Li ion is coordinated by two anions only. Therefore, Li ion migration barrier is much higher than Na and K migration. This finding teaches us that large cavity size (or channel size) is not always good for fast alkali ion migration and we need to finely tune the cavity size suitable for each intercalating ion species. References [1] H. Kim, J. C. Kim, S.-H. Bo, T. Shi, D. –H. Kwon, G. Ceder. K‐Ion Batteries Based on a P2‐Type K 0.6 CoO 2 Cathode. Adv. Energy Mater. 7, (2017) 1700098 [2] H. Kim, D. –H. Seo, A. Urban, J. Lee, D. –H. Kwon, S. –H. Bo, T. Shi, J. Papp, B. McCloskey, G. Ceder. Stoichiometric Layered Potassium Transition Metal Oxide for Rechargeable Potassium Batteries. Chem. Mater. 30 (2018) 6532-6539. [3] H. Kim, D. –H. Seo, J. C. Kim, S. –H. Bo, L. Liu, T. Shi, G. Ceder. Investigation of Potassium Storage in Layered P3‐Type K 0.5 MnO 2 Cathode. Adv. Mater. 29 (2017) 1702480. [4] H. Kim, H. Ji, J. Wang, and G. Ceder. Trands in Chem. 1 (2019) 682. [5] H. Kim, D. –H. Seo, M. Bianchini, R. Clement, H. Kim, J. C. Kim, Y. Tian, T. Shi, W. –S. Yoon, G. Ceder. A New Strategy for High‐Voltage Cathodes for K‐Ion Batteries: Stoichiometric KVPO 4 F. Adv. Energy Mater. 8, (2018) 1801591. [6] H. Kim, Y. Ishado, Y. Tian, G. Ceder. Investigation of Alkali‐Ion (Li, Na, and K) Intercalation in K x VPO 4 F ( x ∼ 0) Cathode. Adv. Funct. Mater. 29 (2019) 1902392.
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Abstract The design and performance of reference electrodes for use in high subcritical and supercritical aqueous systems are reviewed. Particular attention is paid to the stability of the electrochemically active elements, to the contribution of the two irreversible thermodynamic potentials (the isothermal liquid junction potential and the thermal liquid junction potential) to the measured potential, to calibration of the reference electrode on to the standard hydrogen scale, and to the application of the electrodes in pH measurements and in potentiometry. Methods for estimating and suppressing the thermal diffusion potential and the isothermal liquid junction potential are also discussed. While significant progress has been made over the past several decades in developing viable reference electrodes for use in high temperature aqueous systems, particularly for potential monitoring in subcritical systems, no universally accepted reference electrode has emerged for potential monitoring in supercritical aqueous systems.
Neutral tetraazacyclophanes were prepared in a one-step palladium-catalyzed amination reaction. Simple oxidation of these materials creates dication diradicals that are stable at room temperature and that are geometrically well defined. The electronic and magnetic properties of the dications were investigated by CV, UV−vis, and EPR spectroscopy. These spectral data and solution phase magnetic susceptibility measurements indicate high spin ground states in certain media. EPR zero field splitting parameters for the diradical suggest that the distance between the two radical sites can be approximated simply by the distance between alternating nitrogens in the macrocycle.