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81.
Chromatographia - The possibility of rare earth elements (REE) separation by ion interaction chromatography (IIC) employing their complexes with diglycolic acid (ODA) in anion exchange mode has... 相似文献
82.
Annalena Gärtner Matthäus Marek Dr. Merle Arrowsmith Dr. Dominic Auerhammer Krzysztof Radacki Dr. Dominic Prieschl Dr. Rian D. Dewhurst Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9694-9699
Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes. 相似文献
83.
Anna Hanft Dr. Krzysztof Radacki Priv.-Doz. Dr. Crispin Lichtenberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6230-6239
The behavior of the redox-active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)3] and [Bi(ATI)2Ln][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable-temperature) NMR spectroscopy, line-shape analysis, and single-crystal X-ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored. 相似文献
84.
Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds 下载免费PDF全文
Florian Hupp Dr. Mengtao Ma Franziska Kroll Dr. J. Oscar C. Jimenez‐Halla Dr. Rian D. Dewhurst Dr. Krzysztof Radacki Dr. Andreas Stasch Prof. Dr. Cameron Jones Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16888-16898
We present the isolation of the first mononuclear dihalogermylene, and mono‐ and dinuclear stannylene complexes of transition metals. These exhibit exceptionally pyramidalized Group 14 centers. Additionally, removal of the halide substituents from the Ge/Sn atom was successfully performed in two ways, halide abstraction and reduction, leading to a variety of unusual structural motifs. 相似文献
85.
Johannes Hoja Prof. Dr. Alexander F. Sax Prof. Dr. Krzysztof Szalewicz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2292-2300
The stability and geometry of a hydrogen‐bonded dimer is traditionally attributed mainly to the central moiety A?H???B, and is often discussed only in terms of electrostatic interactions. The influence of substituents and of interactions other than electrostatic ones on the stability and geometry of hydrogen‐bonded complexes has seldom been addressed. An analysis of the interaction energy in the water dimer and several alcohol dimers—performed in the present work by using symmetry‐adapted perturbation theory—shows that the size and shape of substituents strongly influence the stabilization of hydrogen‐bonded complexes. The larger and bulkier the substituents are, the more important the attractive dispersion interaction is, which eventually becomes of the same magnitude as the total stabilization energy. Electrostatics alone are a poor predictor of the hydrogen‐bond stability trends in the sequence of dimers investigated, and in fact, dispersion interactions predict these trends better. 相似文献
86.
The aim of this study was to determine the effect of different drying methods: convective (at 50, 60, 70 °C), vacuum-microwave (at 120, 240, 360, 480 W and 360 W with reduction to 120 W) and hybrid (convective pre-drying at 50, 60, 70 °C followed by vacuum-microwave drying at 120 W) on the quality parameters of novel red-fleshed apple fruit snacks (RFAs), such as phenolics, on-line antioxidant capacity, water activity and color. Drying kinetics, including a temperature profile of dried material, and modified Page model were determined. Freeze-drying was used as a control method. The highest content of bioactive compounds in the samples was retained following freeze-drying, then hybrid, vacuum-microwave and finally convection drying. The antioxidant capacity measured by on-line 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), identified anthocyanins, flavan-3-ols and phenolic acid as the main compounds responsible for this activity. Unfavorable changes in color, formation of hydroxymethylfurfural (HMF) and degradation of polyphenolics were noted along with increasing drying temperature and magnetron power. The red-fleshed apple snacks are a promising high-quality dehydrated food product belonging to functional foods category. 相似文献
87.
Dr. Adam Mames Dariusz Gołowicz Dr. Mariusz Pietrzak Dr. Krzysztof Kazimierczuk Prof. Sławomir Szymański Dr. Tomasz Ratajczyk 《Chemphyschem》2020,21(6):540-545
Triptycene derivatives are widely utilized in different fields of chemistry and materials sciences. Their physicochemical properties, often of pivotal importance for the rational design of triptycene-based functional materials, are influenced by noncovalent interactions between substituents mounted on the triptycene skeleton. Herein, a unique interaction between electron-rich substituents in the peri position and the silyl group located on the bridgehead sp3-carbon is discussed on the example of 1,4-dichloro-9-(p-methoxyphenyl)-silyltriptycene (TRPCl) which exists in solution in the form of two rotamers differing by dispositions, syn or anti, of the Si−CPh (the CPh atom is from the p-methoxyphenyl group) bond against the peri-Cl atom. For the first time, substantial differences between the Si−CPh bonds in these two dispositions are identified, based on indirect experimental and direct theoretical evidence. For these two orientations, the experimental 1J(Si,CPh) values differ by as much as 10 percent. The differences are explained in terms of effective electron density transfer from the peri-Cl atom to the antibonding σ* orbitals of the Si−X bonds (X=H, CPh) oriented anti to that atom. The electronic effects are revealed by an NBO analysis. Connections of these observations with the notion of blue-shifting hydrogen bonds are discussed. 相似文献
88.
Joanna Bojarska Milan Remko Izabela D. Madura Krzysztof Kaczmarek Janusz Zabrocki Wojciech M. Wolf 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):328-345
Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C29H31NO5, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42 , 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time. 相似文献
89.
Jerzy Chrusciel Krzysztof Matyjaszewski 《Journal of polymer science. Part A, Polymer chemistry》1996,34(11):2243-2252
Ring opening of 1,2,3,4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasilane in the presence of various transition metal catalysts has been studied. Pd and Pt compounds are most active. Compounds with bulky ligands [e.g., Pd(PPh3)4] lead to the formation of “dimeric” cyclooctasilanes. Compounds with less bulky groups convert monomer to dimers and mixture of oligomers and polymers. Reactions with the all-trans monomer, tttt-(MePhSi)4, result in the formation of stereoregular dimer, presumably all-trans, tttttttt-(MePhSi)8, in high yields. Reactions in the presence of oxygen lead to the formation of polymers with inserted oxygen atoms in the main chain. © 1996 John Wiley & Sons, Inc. 相似文献
90.
Konrad Skotnicki Ireneusz Janik Klaudia Sadowska Grazyna Leszczynska Krzysztof Bobrowski 《Molecules (Basel, Switzerland)》2022,27(1)
One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (●OH) and azide (●N3) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ●OH with 2-SeU are dominated by an absorption band with an λmax = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2●). The dimeric radical (2●) is formed in the reaction of a selenyl-type radical (6●) with 2-SeU, and both radicals are in equilibrium with Keq = 1.3 × 104 M−1 at pH 4 (below the pKa of 2-SeU). Similar equilibrium with Keq = 4.4 × 103 M−1 was determined for pH 10 (above the pKa of 2-SeU), which admittedly involves the same radical (6●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λmax = 390 nm, which was assigned to the ●OH adduct to the double bond at C5 carbon atom (3●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ●N3-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU. 相似文献