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41.
42.
Vladimir P. Petrović Dušica Simijonović Zorica D. Petrović Svetlana Marković 《Chemical Papers》2015,69(9):1244-1252
One-pot anti-Mannich reaction of vanillin, aniline and cyclohexanone was successfully catalyzed by ionic liquid triethanolammonium chloroacetate, at room temperature. Yield of the obtained Mannich base was very good and excellent diastereoselectivity was achieved. Mechanism of the reaction was investigated using the density functional theory. The reaction started with a nucleophilic attack of aniline nitrogen at the carbonyl group of vanillin. The intermediate α-amino alcohol formed in this way was further subjected to protonation by the triethanolammonium ion yielding the imminium ion. Theoretically, the obtained imminium ion and the enol form of cyclohexanone can build the protonated Mannich base via the anti and syn pathways. The chloroacetic anion spontaneously abstracts the proton yielding the final product of the reaction anti 2-[1-(N-phenylamino)-1-(4-hydroxy-3-methoxyphenyl)]methylcyclohexanone (MB-H). The syn pathway requires lower activation energy but the anti pathway yields a thermodynamically more stable product, which implies that the examined Mannich reaction is thermodynamically controlled. 相似文献
43.
Using controlled radical polymerization to confirm the lower critical solution temperature of an N‐(alkoxyalkyl) acrylamide polymer in aqueous solution 下载免费PDF全文
Xeniya Savelyeva Lucia Li Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2015,53(1):59-67
N‐(3‐Methoxypropyl) acrylamide (MPAM) was polymerized by controlled radical polymerization (CRP) methods such as nitroxide‐mediated polymerization (NMP) and reversible addition–fragmentation chain‐transfer polymerization (RAFT). CRP was expected to yield well‐defined polymers with sharp lower critical solution temperature (LCST) transitions. NMP with the BlocBuilder (2‐([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropanoic acid) and SG1 ([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino] oxidanyl) initiating system revealed low yields and lack of control (high dispersity, ? ~ 1.5–1.6, and inhibition of chain growth). However, RAFT was far more effective, with linear number average molecular weight, , versus conversion, X, plots, low ? ~ 1.2–1.4 and the ability to form block copolymers using N,N‐diethylacrylamide (DEAAM) as the second monomer. Poly(MPAM) (with = 13.7–25.3 kg mol?1) thermoresponsive behavior in aqueous media revealed cloud point temperatures (CPT)s between 73 and 92 °C depending on solution concentration (ranging from 1 to 3 wt %). The and the molecular weight distribution were the key factors determining the CPT and the sharpness of the response, respectively. Poly(MPAM)‐b‐poly(DEAAM) block copolymer ( = 22.3 kg mol?1, ? = 1.41, molar composition FDEAAM = 0.38) revealed dual LCSTs with both segments revealing distinctive CPTs (at 75 and 37 °C for poly(MPAM) and poly(DEAAM) blocks, respectively) by both UV–Vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 59–67 相似文献
44.
Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes 下载免费PDF全文
Qing Ji Ha T. M. Le Dr. Xiqu Wang Dr. Yu‐Sheng Chen Dr. Tatyana Makarenko Prof. Allan J. Jacobson Prof. Ognjen Š. Miljanić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17205-17209
Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m2 g?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation. 相似文献
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46.
Under the influence of previously published and some new theoretical results, potential‐ dependent adsorption and desorption of model electroinactive surfactants Triton X‐100 (T‐X‐100 or polyethylene glycol p‐(1,1,3,3‐tetramethylbutyl)‐phenyl ether) and sodium dodecyl sulfate (SDS) on the static mercury drop electrode (SMDE) were studied by square‐wave voltammetry (SWV). Although (according to the theory) the resulting current – potential curve should consist of two highly separated peaks, only desorption signal could be seen on each experimentally obtained voltammogram, most probably because of the limitations concerning the available potential range. Different properties of the recorded peak are in good agreement with the theory indicating that square‐wave voltammetry could be treated as a potential tool for tensammetric studies of electroinactive surface active substances. 相似文献
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Dr. Aleksander Rebane Geoffrey Wicks Dr. Mikhail Drobizhev Dr. Thomas Cooper Aleksander Trummal Dr. Merle Uudsemaa 《Angewandte Chemie (International ed. in English)》2015,54(26):7582-7586
We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–107 V cm?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction. 相似文献
49.
Construction of a New Class of Tetracycline Lead Structures with Potent Antibacterial Activity through Biosynthetic Engineering 下载免费PDF全文
Dr. Urška Lešnik Dr. Tadeja Lukežič Dr. Ajda Podgoršek Dr. Jaka Horvat Dr. Tomaž Polak Dr. Martin Šala Branko Jenko Dr. Kirsten Harmrolfs Dr. Alain Ocampo‐Sosa Prof. Dr. Luis Martínez‐Martínez Dr. Paul R. Herron Dr. Štefan Fujs Dr. Gregor Kosec Prof. Dr. Iain S. Hunter Prof. Dr. Rolf Müller Prof. Dr. Hrvoje Petković 《Angewandte Chemie (International ed. in English)》2015,54(13):3937-3940
Antimicrobial resistance and the shortage of novel antibiotics have led to an urgent need for new antibacterial drug leads. Several existing natural product scaffolds (including chelocardins) have not been developed because their suboptimal pharmacological properties could not be addressed at the time. It is demonstrated here that reviving such compounds through the application of biosynthetic engineering can deliver novel drug candidates. Through a rational approach, the carboxamido moiety of tetracyclines (an important structural feature for their bioactivity) was introduced into the chelocardins, which are atypical tetracyclines with an unknown mode of action. A broad‐spectrum antibiotic lead was generated with significantly improved activity, including against all Gram‐negative pathogens of the ESKAPE panel. Since the lead structure is also amenable to further chemical modification, it is a platform for further development through medicinal chemistry and genetic engineering. 相似文献
50.
In the present paper, we study the propagation of acceleration and shock waves in a binary mixture of ideal Euler fluids, assuming that the difference between the atomic masses of the constituents is negligible. We evaluate the characteristic speeds, proving that they can be separated into two groups: one is related to the case of a single Euler fluid, provided that an average ratio of specific heats is introduced; the other is new and related to the propagation speed due to diffusion. We evaluate the critical time for sound acceleration waves and compare its value to that of a single fluid. We then study shock waves, showing that three types of shock waves appear: sonic and contact shocks, which have counterparts in the single fluid case, and the diffusive shock, which is peculiar to the mixture. We discuss the admissibility of the shock waves using the Lax-Liu conditions and the entropy growth criterion. It is proved that the sonic and the characteristic shock obey the same properties as in the single fluid case, while for the diffusive shock there exists a locally exceptional case that is determined by a particular value of the concentration of the constituents, for which the genuine nonlinearity is lost and no shocks are admissible. For other values of the unperturbed concentration, the diffusive shock is stable in a bounded interval of admissibility.Received: 15 December 2002, Accepted: 28 June 2003
Correspondence to: T. RuggeriS. Simi: On leave from the Department of Mechanics, Faculty of Technical Sciences, University of Novi Sad, Serbia 相似文献