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91.
92.
The fundamental aspects of charging in electrospray ionization (ESI) are hotly debated. In the present study, ESI charging of DNA oligonucleotides was explored in both positive (ESI+) and negative (ESI?) polarity using mass spectrometry detection. Single‐stranded 12‐mer CCCCAATTCCCC in buffer solution (aqueous NH4Ac, 100 mM) produced similar charge state distribution (CSD) in either ESI+ or ESI?. Similarity of CSD in ESI+ and ESI? was also observed for the double‐stranded 12‐mer CGCGAATTCGCG. By adding typical low‐vapor reagents (e.g. m‐nitro benzyl alcohol, m‐NBA; sulfolane) into the same buffer solution (<0.5% w/v), both CCCCAATTCCCC and CGCGAATTCGCG revealed strong supercharging (SC) effect in ESI?, while very little or no SC effect was observed in ESI+. With either sulfolane or m‐NBA, the CGCGAATTCGCG duplex dissociated into single strands in ESI?. No SC was observed in both ESI+ and ESI? for thermally denatured CGCGAATTCGCG duplex in NH4Ac buffer without the reagents. These findings are difficult to reconcile with the earlier model, which attributes SC in aqueous buffer solution to the conformational changes of analytes. Our observations suggest that the ionic strength of ESI droplets strongly affects the CSD of biopolymers such as DNA oligonucleotides and that SC effect is related to the depletion of ionic strength during the ESI process. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
93.
Marcos A. Kettner Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Thomas M. Klapötke Dr. Muhamed Sućeska Swetlana Wunder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7622-7631
Here we report on the preparation of two hydrogen atom free 3,3′‐bi(1,2,4‐oxadiazole) derivatives. 5,5′‐Bis(fluorodinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole) was synthesised by fluorination of diammonium 5,5′‐bis(dinitromethanide)‐3,3′‐bi(1,2,4‐oxadiazole). For our previously reported analogue 5,5′‐bis(trinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole), a new synthetic route starting from new 3,3′‐bi(1,2,4‐oxadiazolyl)‐5,5′‐diacetic acid was developed. In this course also hitherto unknown 5,5′‐dimethyl‐3,3′‐bi(1,2,4‐oxadiazole) was isolated. The compounds were characterised by multinuclear NMR spectroscopy, IR and Raman spectroscopy, elemental analysis as well as mass spectrometry. X‐ray diffraction studies were performed and the crystal structures for the 5,5'‐dimethyl and 5,5'‐(fluorodinitromethyl) derivatives are reported. The energetic 5,5'‐(fluorodinitromethyl) and 5,5'‐(trinitromethyl) compounds do not contain any hydrogen atoms and show remarkable high densities. Furthermore, the thermal stabilities and sensitivities were determined by differential scanning calorimetry (DSC) and standardised impact and friction tests. The heats of formation were calculated by the atomisation method based on CBS‐4M enthalpies. With these values and the room‐temperature X‐ray densities, several detonation and propulsion parameters, such as the detonation velocity and pressure as well as the specific impulse of mixtures with aluminium, were computed using the EXPLO5 code. 相似文献
94.
Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes
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Konstantin Junold Johannes A. Baus Dr. Christian Burschka Dr. Célia Fonseca Guerra Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Reinhold Tacke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12411-12415
Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt3 and BPh3 leads to the formation of the Lewis acid/base complexes 2 and 3 , respectively, which are the first five‐coordinate silicon compounds with an Si?B bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies. 相似文献
95.
Alexander Bujotzek Ole Schütt Adam Nielsen Konstantin Fackeldey Marcus Weber 《Journal of mathematical chemistry》2014,52(3):781-804
Obtaining a sufficient sampling of conformational space is a common problem in molecular simulation. We present the implementation of an umbrella-like adaptive sampling approach based on function-based meshless discretization of conformational space that is compatible with state of the art molecular dynamics code and that integrates an eigenvector-based clustering approach for conformational analysis and the computation of inter-conformational transition rates. The approach is applied to three example systems, namely $n$ -pentane, alanine dipeptide, and a small synthetic host-guest system, the latter two including explicitly modeled solvent. 相似文献
96.
Joachim W. Heinicke Nidhi Gupta Peter Mayer Konstantin Karaghiosoff 《无机化学与普通化学杂志》2020,646(13):959-963
NH-Functional 1H-1,3-benzazaphospholes 1a–1c and o-chloranil (tetrachloro-o-benzoquinone - TCBQ) undergo rapid [1+4]-cycloaddition in a 1:2 molar ratio to give 2a – 2c as high-melting zwitterionic σ6λ5-phosphorus compounds. In the case of 2a the yield is high (rel. to TCBQ) even if the reactants were used in a 1:0.5 molar ratio. For the 2-tert-butyl-substituted compounds 2b and 2c the yields were significantly lower, in part by unidentified byproducts. Addition of excess TCBQ to crude 2c containing unconverted 1c did not increase but strongly decrease the amount of 2c . Crystallization and XRD analysis led to detection of a minor side or consecutive product 3c , formally corresponding to P=C bond cleavage and [1+4] cycloaddition of three equivalents TCBQ, two at the phosphinidene and one at the carbene end. NMR spectroscopic data of 2a – 2c including conclusive 13C data for 2a give evidence of the structures of the new compounds. 相似文献
97.
Aleksei S. Pronin Spartak S. Yarovoy Yakov M. Gayfulin Aleksey A. Ryadun Konstantin A. Brylev Denis G. Samsonenko Ilia V. Eltsov Yuri V. Mironov 《Molecules (Basel, Switzerland)》2020,25(24)
Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2–, trans-[{Mo6I8}(CN)4(MeO)2]2– and trans-[{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands. 相似文献
98.
Alexander A. Larin Dmitry M. Bystrov Leonid L. Fershtat Alexey A. Konnov Nina N. Makhova Konstantin A. Monogarov Dmitry B. Meerov Igor N. Melnikov Alla N. Pivkina Vitaly G. Kiselev Nikita V. Muravyev 《Molecules (Basel, Switzerland)》2020,25(24)
In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid. 相似文献
99.
Marco Reichel Konstantin Karaghiosoff 《Angewandte Chemie (International ed. in English)》2020,59(30):12268-12281
The introduction of a monofluoromethyl moiety has undoubtedly become a very important area of research in recent years. Owing to the beneficial properties of organofluorine compounds, such as their metabolic stability, the incorporation of the CH2F group as a bioisosteric substitute for various functional groups is an attractive strategy for the discovery of new pharmaceuticals. Furthermore, the monofluoromethyl unit is also widely used in agrochemistry, in pharmaceutical chemistry, and in fine chemicals. The problems associated with climate change and the growing need for environmentally friendly industrial processes mean that alternatives to the frequently used CFC and HFBC fluoromethylating agents (CH2FCl and CH2FBr) are urgently needed and also required by the Montreal Protocol. This has recently prompted many researchers to develop alternative fluoromethylation agents. This Minireview summarizes both the classical and new generation of fluoromethylating agents. Reagents that act via electrophilic, nucleophilic, and radical pathways are discussed, in addition to their precursors. 相似文献
100.
Han Bing-yuan Khoroshilov Andrey V. Tyurin Alexander V. Baranchikov Alexander E. Razumov Mikhail I. Ivanova Olga S. Gavrichev Konstantin S. Ivanov Vladimir K. 《Journal of Thermal Analysis and Calorimetry》2020,142(4):1533-1543
Journal of Thermal Analysis and Calorimetry - Thermodynamic properties (heat capacity Cp, entropy S°, enthalpy change ΔH° and reduced Gibbs energy ΔΦ°) of crystalline... 相似文献