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21.
Friedericke S. Menke Dr. Barbara Wicher Dr. Victor Maurizot Prof. Ivan Huc 《Angewandte Chemie (International ed. in English)》2023,62(12):e202217325
Aromatic oligoamide sequences programmed to fold into stable helical conformations were designed to display a linear array of hydrogen-bond donors and acceptors at their surface. Sequences were prepared by solid-phase synthesis. Solution 1H NMR spectroscopic studies and solid-state crystallographic structures demonstrated the formation of stable hydrogen-bond-mediated dimeric helix bundles that could be either heterochiral (with a P and an M helix) or homochiral (with two P or two M helices). Formation of the hetero- or homochiral dimers could be driven quantitatively using different chlorinated solvents—exemplifying a remarkable case of either social or narcissistic chiral self-sorting or upon imposing absolute handedness to the helices to forbid PM species. 相似文献
22.
Structural analysis using powder X-ray diffraction data has overcome many obstacles and nowadays is readily applicable for structural analysis of all types of compounds and materials. Being less straightforward than single crystal diffraction, it requires significant users’ input and consequently, implementation of standardized tools to assess the accuracy of crystal structures. This article discusses potential errors in crystal structure solution and refinement of small-molecule structures obtained from PXRD data. Moreover, it proposes how accuracy of these structures can be improved by using high-quality PXRD data, complementary external analytical techniques, knowledge stored in crystal structure databases, as well as an approach to search the parameter space to avoid local minima in testing different sets of geometry restraints. 相似文献
23.
Mitchell D. Nothling John E. Daniels Yen Vo Ivan Johan Martina H. Stenzel 《Angewandte Chemie (International ed. in English)》2023,62(20):e202218955
Piezocatalysis offers a means to transduce mechanical energy into chemical potential, harnessing physical force to drive redox reactions. Working in the solid state, we show here that piezoelectric BaTiO3 nanoparticles can transduce mechanical load into a flux of reactive radical species capable of initiating solid state free radical polymerization. Activation of a BaTiO3 powder by ball milling, striking with a hammer, or repeated compressive loading generates highly reactive hydroxyl radicals (⋅OH), which readily initiate radical chain growth and crosslinking of solid acrylamide, acrylate, methacrylate and styrenic monomers. Control experiments indicate a critical role for chemisorbed water on the BaTiO3 nanoparticle surface, which is oxidized to ⋅OH via mechanoredox catalysis. The force-induced production of radicals by compressing dry piezoelectric materials represents a promising new route to harness mechanical energy for solid state radical synthesis. 相似文献
24.
Armando Berlanga-Vázquez Radu A. Talmazan Carlos A. Reyes-Mata Prof. Edmundo G. Percástegui Dr. Marcos Flores-Alamo Prof. Maren Podewitz Prof. Ivan Castillo 《欧洲无机化学杂志》2023,26(6):e202200596
Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L1,5 ), while substitution of positions 1 and 4 produces the Cs-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L1,4 ) described herein. [ Cu(L1,4)I ] was synthesized from L1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L1,4 regioisomer undergoes a deformation that does not occur with L1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L1,4 − H) (CH3CN)2] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework. 相似文献
25.
26.
Dr. Annalisa Arcella Dr. Jens Dreyer Dr. Emiliano Ippoliti Ivan Ivani Dr. Guillem Portella Dr. Valérie Gabelica Prof. Dr. Paolo Carloni Prof. Dr. Modesto Orozco 《Angewandte Chemie (International ed. in English)》2015,54(2):467-471
By combining ion‐mobility mass spectrometry experiments with sub‐millisecond classical and ab initio molecular dynamics we fully characterized, for the first time, the dynamic ensemble of a model nucleic acid in the gas phase under electrospray ionization conditions. The studied oligonucleotide unfolds upon vaporization, loses memory of the solution structure, and explores true gas‐phase conformational space. Contrary to our original expectations, the oligonucleotide shows very rich dynamics in three different timescales (multi‐picosecond, nanosecond, and sub‐millisecond). The shorter timescale dynamics has a quantum mechanical nature and leads to changes in the covalent structure, whereas the other two are of classical origin. Overall, this study suggests that a re‐evaluation on our view of the physics of nucleic acids upon vaporization is needed. 相似文献
27.
Impedimetric Detection of DNA Damage with the Sensor Based on Silver Nanoparticles and Neutral Red 下载免费PDF全文
Yury Kuzin Anna Porfireva Veronika Stepanova Vladimir Evtugyn Ivan Stoikov Gennady Evtugyn Tibor Hianik 《Electroanalysis》2015,27(12):2800-2808
Novel electrochemical DNA‐sensor based on glassy carbon electrode (GCE) modified with Ag nanoparticles, Neutral red covalently attached to its surface and native DNA adsorbed on modifier coating was developed for the estimation of DNA damage on example of model system based on Fenton reagent. As was shown, the oxidation process resulted in synchronous increase of electron transfer resistance and capacitance measured by electrochemical impedance spectroscopy (EIS). The contribution of each sensor component on the signal was specified and sensitivity estimated against similar surface coatings. The shift of EIS parameters was found to be higher than that of similar biosensors reported. The DNA sensor was tested on the estimation of antioxidant capacity of green tea infusions again the results of coulometric titration with electrogenerated bromine. 相似文献
28.
Ekaterina E. Stoikova Michail I. Sorvin Dmitry N. Shurpik Herman C. Budnikov Ivan I. Stoikov Gennady A. Evtugyn 《Electroanalysis》2015,27(2):440-449
A novel potentiometric sensor based on screen‐printed carbon electrode covered with electropolymerized polyaniline (PANI) and unsubstituted pillar[5]arene as ionophore has been developed and tested in potentiometric measurements of pH and metal ions. The introduction of pillar[5]arene improved the reversibility of the pH response in the range from 2.0 to 9.0 with the slope of 45 mV/pH. Among metal cations, the response to Fe3+ and Ag+ ions was referred to PANI redox conversion whereas the signal toward Cu2+ in the range from 1.0×10?6 to 1.0×10?2 M (limit of detection (LOD) 3.0×10?7 M) to specific interaction with the macrocycle. 相似文献
29.
Ivan Buslov Jeanne Becouse Simona Mazza Mickael Montandon‐Clerc Prof. Dr. Xile Hu 《Angewandte Chemie (International ed. in English)》2015,54(48):14523-14526
Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base‐metal catalysts. Reported herein is that well‐defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti‐Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83 000 per hour and turnover numbers of up to 10 000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts. 相似文献