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81.
For the first time, high-level structural and rovibrational data are provided for the hyroxyethynyl anion, CCOH?. CCOH? is a promising molecule for interstellar detection even though no new anions have been observed in the interstellar medium for the past half-decade. The large dipole moment of the corresponding neutral radical may be key for its creation as has been hypothesised and supported for other anions known to exist in various astronomical environments. Highly accurate quartic force fields are employed where previous benchmarks have produced spectroscopic constants and anharmonic vibrational frequencies within 20 MHz and 1 cm?1, respectively, of experiment. This same approach is applied here for CCOH? and its deuterated isotopologue with the goal of assisting laboratory experiments and/or astronomical observers in the potential detection of this anion. 相似文献
82.
Toru Minami Ryoji Kouno Tatsuo Okauchi Mitsuharu Nakamura Junji Ichikawa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):689-692
The α-phosphonovinyl anions, generated in situ from treatment of β-hetero-substituted vinyl-phosphonates 1a-c with LDA (or LTMP), were trapped with various electrophiles such as chlorotriorganosilanes, chlorotrimethylgermane, chlorotriorganotins, dimethyl disulfide, and halogen to afford the corresponding β-hetero-substituted α-functionalized vinylphosphonates 2–14 in good to excellent yields. The Friedel-Crafts reaction of α-(silyl) or α-(germyl)phosphonoketene dithioacetals 2, 9 or 4 with acid chlorides gave α-acylated phosphonoketene dithioacetals 15–19 in 53–91 % yields. The palladium-catalyzed cross-coupling reaction of β-ethoxy-α-(tributylstannyl)vinylphosphonate 13 with a variety of organic halides (R = acyl, allyl, aryl etc.) provided β-ethoxy-α-substituted vinylphosphonates 20–25 in good to moderate yields. The palladium-mediated cross-coupling reaction of α-(iodo)-vinyl-phosphonates 7, 14 with terminal acetylenes afforded α-alkynylated vinylphosphonates 26–29 in 69–83 % yields. 相似文献
83.
Four novel derivatives of 1,1′-bi-2-naphthol have been prepared and the structures of these compounds characterised by IR, MS, 1H and 13C NMR spectroscopy and elemental analysis. The enantioselective recognition of these sensors has been studied by fluorescence titration and 1H NMR spectroscopy. The sensors exhibited different chiral recognition abilities towards N-Boc-protected amino acid anions and formed 1:1 complexes between the host and the guest. Sensors exhibit excellent enantioselective fluorescent recognition ability towards the amino acid derivatives. 相似文献
84.
The synthesis and photophysical evaluation of three diaryl thiourea-based anion receptors (4–6) for comparison with their urea counterparts (1–3) is outlined. These anion receptors posses an acetamide functionality on one of the aryl groups and an electron-withdrawing CF3 group on the other. By varying the position of the acetamide group, in the o-, m- and p-positions of 4–6, respectively, the anion binding ability was both tuneable and found to be, in some cases, significantly different from that seen for the urea analogues 1–3. The binding affinities of the receptors 4–6, as well as the binding stoichiometries, were evaluated using UV–vis absorption spectroscopy in MeCN. However, these receptors were not sufficiently emissive to quantify the anion recognition using fluorescence. The results confirmed strong binding of these receptors to anions such as fluoride, acetate, phosphate, pyrophosphate and chloride. Nevertheless, the overall results obtained did not conform to the anticipated trends seen for 1–3, which is most likely due to the enhanced binding affinity of the thiourea analogues 4–6. The binding interactions were also investigated by using 1H NMR which confirmed that these receptors interacted with the anions in a stepwise manner, where the primary anion binding interaction occurred at the thiourea side, which led to an activation of the acetamide moiety towards the second anion binding interaction, an example of an allosteric activation mode. 相似文献
85.
86.
Ireneusz Sowa Magdalena Wójciak-Kosior Piotr Drączkowski Maciej Strzemski Ryszard Kocjan 《Analytica chimica acta》2013
The new sorbent for non-suppressed ion chromatography based on silica gel coated with a film of polyaniline (PANI) was obtained in a process of in situ polymerization of aniline by oxidation with ammonium peroxydisulfate. Raman analyses performed using a Thermo Scientific DXR confocal Raman Microscope equipped with the Omnic 8 software from Thermo Fisher Scientific have proved a uniform distribution of PANI on the surface of chromatographic beads and in the pores of the particle. 相似文献
87.
Sergei V. Kostjuk Hui Yee Yeong Brigitte Voit 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):471-486
This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
88.
89.
Prof. Pavel Anzenbacher Jr. Dr. Yuanli Liu Dr. Manuel A. Palacios Dr. Tsuyoshi Minami Dr. Zhuo Wang Dr. Ryuhei Nishiyabu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8497-8506
As the demand for probes suitable for sensor development increases, investigation of approaches that utilize known successful receptors gains in general importance. This study describes a two‐prong approach that can be used as a guide to developing sensors from known receptors. First, the conversion of a simple receptor, calix[4]pyrrole, into a fluorescent probe to establish a ratiometric signal is described. Secondly, the sensors that employ an output from a single ratiometric calix[4]pyrrole probe are fabricated by using poly(ether‐urethane) hydrogel copolymers. These hydrogels are designed to absorb, internalize and transport aqueous electrolytes. A sensor array of ten different poly(ether‐urethane) matrices with varying comonomer proportions were doped with a single probe and were exposed to eight different anions: acetate, benzoate, fluoride, chloride, phosphate, pyrophosphate, hydrogen sulfide, and cyanide, eight urine samples and anti‐inflammatory drugs (NSAIDs). The poly(ether‐urethane) matrices comprise different proportions of anion‐binding urethane moieties and different hydrophilicity given by the ratio between ethylene glycol ether and butylene glycol ether. This diversity in the hydration behavior provides different environment polarity, in which the recognition and self‐assembly processes display enough diverse behavior to allow for unique response of the probe to the analytes. Furthermore, a single probe is shown to recognize eight different aqueous anions and eight urine samples when embedded in ten different polyurethanes in an array that displays 100 % classification accuracy. To demonstrate the potential of the concept for quantitative studies, an estimation of non‐steroidal anti‐inflammatory drugs ibuprofen and diclofenac in water and in saliva was performed. A limit of detection of 0.1 ppm and a dynamic range of 0.1–0.6 and 0.05–60 ppm was observed, respectively. Given the general difficulty of chemosensors to recognize aqueous anions, the fact that one probe recognizes eight different analytes attests to an enormous effect of the polymer environment on the recognition process. This method could be used to generate a variety of sensor arrays for various analyses including species that are difficult to recognize, such as small‐molecule‐ and inorganic anions. 相似文献
90.
Prof. Evgeny A. Kataev Dr. Grigory V. Kolesnikov Rene Arnold Herman V. Lavrov Prof. Victor N. Khrustalev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3710-3714
Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields. 相似文献