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81.
Lydia A. Panther Dr. Daniel P. Guest Dr. Andrew McGown Hugo Emerit Dr. Raysa Khan Tareque Dr. Arathy Jose Mr. Chris M. Dadswell Dr. Simon J. Coles Dr. Graham J. Tizzard Dr. Ramón González-Méndez Dr. Charles A. I. Goodall Prof. Mark C. Bagley Prof. John Spencer Dr. Barnaby W. Greenland 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201444
Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br2-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)2) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs. 相似文献
82.
Dr. Giambattista Testolin Dr. Jana Richter Antje Ritter Dr. Hans Prochnow Prof. Dr. Jesko Köhnke Prof. Dr. Mark Brönstrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(54):e202201297
The rise of antibiotic resistance causes a serious health care problem, and its counterfeit demands novel, innovative concepts. The combination of photopharmacology, enabling a light-controlled reversible modulation of drug activity, with antibiotic drug design has led to first photoswitchable antibiotic compounds derived from established scaffolds. In this study, we converted cystobactamids, gyrase-inhibiting natural products with an oligoaryl scaffold and highly potent antibacterial activities, into photoswitchable agents by inserting azobenzene in the N-terminal part and/or an acylhydrazone moiety near the C-terminus, yielding twenty analogs that contain mono- as well as double-switches. Antibiotic and gyrase inhibition properties could be modulated 3.4-fold and 5-fold by light, respectively. Notably, the sensitivity of photoswitchable cystobactamids towards two known resistance factors, the peptidase AlbD and the scavenger protein AlbA, was light-dependent. While irradiation of an analog with an N-terminal azobenzene with 365 nm light led to less degradation by AlbD, the AlbA-mediated inactivation was induced. This provides a proof-of-principle that resistance towards photoswitchable antibiotics can be optically controlled. 相似文献
83.
Sebastian Scheidel Laurina Östreicher Isabelle Mark Ann-Christin Pöppler 《Magnetic resonance in chemistry : MRC》2022,60(6):572-582
Although solid-state nuclear magnetic resonance (NMR) is a versatile analytical tool to study polymorphs and phase transitions of pharmaceutical molecules and products, this work summarizes examples of spontaneous and unexpected (and unwanted) structural rearrangements and phase transitions (amorphous-to-crystalline and crystalline-to-crystalline) under magic angle spinning (MAS) conditions, some of them clearly being due to the pressure experienced by the samples. It is widely known that such changes can often be detected by X-ray powder diffraction (XRPD); here, the capability of solid-state NMR experiments with a special focus on 1H-13C frequency-switched Lee–Goldburg heteronuclear correlation (FSLG HETCOR)/MAS NMR experiments to detect even subtle changes on a molecular level not observable by conventional 1D NMR experiments or XRPD is presented. Furthermore, it is shown that a polymorphic impurity combined with MAS can induce a crystalline-to-crystalline phase transition. This showcases that solid-state NMR is not always noninvasive and such changes upon MAS should be considered in particular when compounds are studied over longer time spans. 相似文献
84.
Dr. Andreas A. Bastian Dr. Maria Bastian Dr. Manuel Jäger Mark Loznik Dr. Eliza M. Warszawik Xintong Yang Dr. Nabil Tahiri Dr. Peter Fodran Prof. Dr. Martin D. Witte Anne Thoma Dr. Jens Köhler Prof. Dr. Adriaan J. Minnaard Prof. Dr. Andreas Herrmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200883
The continuous emergence of antimicrobial resistance is causing a threat to patients infected by multidrug-resistant pathogens. In particular, the clinical use of aminoglycoside antibiotics, broad-spectrum antibacterials of last resort, is limited due to rising bacterial resistance. One of the major resistance mechanisms in Gram-positive and Gram-negative bacteria is phosphorylation of these amino sugars at the 3’-position by O-phosphotransferases [APH(3’)s]. Structural alteration of these antibiotics at the 3’-position would be an obvious strategy to tackle this resistance mechanism. However, the access to such derivatives requires cumbersome multi-step synthesis, which is not appealing for pharma industry in this low-return-on-investment market. To overcome this obstacle and combat bacterial resistance mediated by APH(3’)s, we introduce a novel regioselective modification of aminoglycosides in the 3’-position via palladium-catalyzed oxidation. To underline the effectiveness of our method for structural modification of aminoglycosides, we have developed two novel antibiotic candidates overcoming APH(3’)s-mediated resistance employing only four synthetic steps. 相似文献
85.
Ashley J. Basson Dr. Nathan R. Halcovitch Dr. Mark G. McLaughlin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202201107
A range of highly functionalized polycyclic fragments have been synthesized, employing a catalytic dehydrative cyclization. A range of nucleophiles are shown to be successful, with the reaction producing numerous high value motifs. 相似文献
86.
Mark J Cooker 《Wave Motion》1994,20(4):385-395
Analysis and experiments are carried out on a horizontal rectangular wave tank which swings at the lower end of a pendulum. The walls of the tank generate waves which affect the motion of the pendulum. For small displacements of the tank, linearised shallow water equations are used to model the motion, and there exist time-periodic solutions for the system whose periods are governed by a transcendental relation. Numerical and analytic solutions of this relation show that the fundamental period is greater than both the period of the empty tank (moving like a simple pendulum) and the fundamental period of the standing wave which occurs when the tank is removed from its supports and held fixed. For a rectangular tank the theory compares well with some experimental measurements. Qualitative observations are also made of the effect of breaking waves on the tank motion: for a tank which has a mass small compared with its load the energy dissipated by breaking waves can rapidly reduce the amplitude of swing of the tank. Potential flow theory is used with linearised free-surface boundary conditions to find time periodic motions for a tank with a hyperbolic cross section. 相似文献
87.
To study combustion chemistry at low temperatures in a shock tube, it is of great importance to increase experimental test times, and this can be done by tailoring the interface between the driver and driven gases. Using unconventional driver-gas tailoring with the assistance of tailoring curves, shock-tube test times were increased from 1 to 15 ms for reflected-shock temperatures below 1,000 K. Provided in this paper is the introduction of tailoring curves, produced from a one-dimensional perfect gas model for a wide range of driver gases and the production and demonstration of successful driver mixtures containing helium combined with either propane or carbon dioxide. The He/CO2 and He/C3H8 driver mixtures provide a unique way to produce a tailored interface and, hence, longer test times, when facility modification is not an option. The tailoring curves can be used to guide future applications of this technique to other configurations. Nonreacting validation experiments using driver mixtures identified from the tailoring curves were performed over a range of reflected-shock temperatures from approximately 800 to 1,400 K, and some examples of ignition-time experiments that could not have otherwise been erformed are presented. 相似文献
88.
89.
Application of an Itô-based approximation method to random vibration of a pinching hysteretic system
In this paper, an extension of the Cumulant-Neglect closure scheme is utilized for the random vibration analysis of a single degree of freedom system with a general pinching hysteresis restoring force. The hysteresis element used in the system model can simulate commonly observed forms of stiffness, strength and pinching degradations. The second order statistics of the system response to a stationary Gaussian white noise input are derived using an Itô-based approximation technique. The validity of these response statistics are then verified by comparing them to Monte Carlo simulation results. The numerical studies performed for different combinations of degradation parameters and excitation levels show that the response estimates obtained by this solution method are in good agreement with Monte Carlo simulation. These studies also indicate the applicability of this technique for response analysis of complicated forms of non-linearities. 相似文献
90.
The use of a sliding plate rheometer (SPR) to determine the first normal stress difference of molten polymers and elastomers
at high shear rates is demonstrated. The simple shear flow in this instrument is not subject to the flow instabilities that
limit the use of rotational rheometers to shear rates often below 1 s−1. However, issues of secondary flow and wall slip must be addressed to obtain reliable data using an SPR. A highly entangled,
monodisperse polybutadiene and a commercial polystyrene were the polymers studied. The inclusion of the polystyrene made it
possible to compare data with those obtained by Lodge using a stressmeter, which is an instrument based on the measurement
of the hole pressure. The data from the two instruments are in good agreement and are also close to the predictions of an
empirical equation of Laun based on the storage and loss moduli. 相似文献