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31.
We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.  相似文献   
32.
Flexible antibacterial materials have gained utmost importance in protection from the distribution of bacteria and viruses due to the exceptional variety of applications. Herein, we demonstrate a readily scalable and rapid single-step approach for producing durable ZnO nanoparticle antibacterial coating on flexible polymer substrates at room temperature. Substrates used are polystyrene, poly(ethylene-co-vinyl acetate) copolymer, poly(methyl methacrylate), polypropylene, high density polyethylene and a commercial acrylate type adhesive tape. The deposition was achieved by a spin-coating process using a slurry of ZnO nanoparticles in toluene. A stable modification layer was obtained when toluene was a solvent for the polymer substrates, namely polystyrene and poly(ethylene-co-vinyl acetate). These coatings show high antibacterial efficiency causing >5 log decrease in the viable counts of Gram-negative bacteria Escherichia. coli and Gram-positive bacteria Staphylococcus aureus in 120 min. Even after tapping these coated surfaces 500 times, the antibacterial properties remained unchanged, showing that the coating obtained by the presented method is very robust. In contrast to the above findings, the coatings are unstable when toluene is not a solvent for the substrate.  相似文献   
33.
The detailed reaction profiles of the neutral-neutral as well as the cation-neutral direct hydroamination reactions between ethylene and ammonia are analyzed using MP2 (Full)/6-31++G(2df,2p) and B3LYP/6-31++G(2df,2p) methodologies. Analysis shows that both neutral-neutral, as well as the cation-neutral reactions are exothermic and the latter is >100 kJ/mol more exothermic than the former. Calculations show that a very large barrier height (>200 kJ/mol), and very large negative reaction entropy prevent the neutral-neutral reaction from proceeding in the forward direction. Analysis of the cation-neutral reaction, which is barrierless (the transition state is more stable than the reactants) and highly exothermic, indicates that the direct hydroamination reaction is thermodynamically attainable via a cation-neutral reaction pathway without a catalyst. Our calculations also suggest that although the cation-neutral direct hydroamination reaction is very fast, the cation of either ethylene or ammonia goes through a structural relaxation process before reacting with the other neutral reactant.  相似文献   
34.
Kinase-mediated resistance to antibiotics is a significant clinical challenge. These enzymes share a common protein fold characteristic of Ser/Thr/Tyr protein kinases. We screened 14 antibiotic resistance kinases against 80 chemically diverse protein kinase inhibitors to map resistance kinase chemical space. The screens identified molecules with both broad and narrow inhibition profiles, proving that protein kinase inhibitors offer privileged chemical matter with the potential to block antibiotic resistance. One example is the flavonol quercetin, which inhibited a number of resistance kinases in vitro and in vivo. This activity was rationalized by determination of the crystal structure of the aminoglycoside kinase APH(2″)-IVa in complex with quercetin and its antibiotic substrate kanamycin. Our data demonstrate that protein kinase inhibitors offer chemical scaffolds that can block antibiotic resistance, providing leads for co-drug design.  相似文献   
35.
A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.  相似文献   
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37.
The synthesis of two phenylated bifunctional monomers, dimethyl 4-(4-(p-aminophenoxy)phenyl)-3,5,6-triphenylphthalate and dimethyl 4-(4-(4-(p-aminophenoxy)phenoxy)phenyl)-3,5,6-triphenylphthlate, was accomplished. Polymerization in solution or by a bulk polymerization procedure yielded a series of low molecular weight phenylated polyimides. The polymers were soluble in chlorinated hydrocarbons and exhibited thermal stabilities comparable to other polyimide systems.  相似文献   
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39.
The onset of COVID-19, coupled with the finer lens placed on systemic racial disparities within our society, has resulted in increased discussions around mental health. Despite this, mental health struggles in research are still often viewed as individual weaknesses and not the result of a larger dysfunctional research culture. Mental health interventions in the science, technology, engineering, and mathematics (STEM) academic community often focus on what individuals can do to improve their mental health instead of focusing on improving the research environment. In this paper, we present four aspects of research that may heavily impact mental health based on our experiences as research scientists: bullying and harassment; precarity of contracts; diversity, inclusion, and accessibility; and the competitive research landscape. Based on these aspects, we propose systemic changes that institutions must adopt to ensure their research culture is supportive and allows everyone to thrive.  相似文献   
40.
Sulfatases are ubiquitous enzymes that hydrolyze sulfate from sulfated organic substrates such as carbohydrates, steroids, and flavones. These enzymes can be exploited in the field of biotechnology to analyze sulfated metabolites in humans, such as steroids and drugs of abuse. Because genomic data far outstrip biochemical characterization, the analysis of sulfatases from published sequences can lead to the discovery of new and unique activities advantageous for biotechnological applications. We expressed and characterized a putative sulfatase (PyuS) from the bacterium Pedobacter yulinensis. PyuS contains the (C/S)XPXR sulfatase motif, where the Cys or Ser is post-translationally converted into a formylglycine residue (FGly). His-tagged PyuS was co-expressed in Escherichia coli with a formylglycine-generating enzyme (FGE) from Mycobacterium tuberculosis and purified. We obtained several crystal structures of PyuS, and the FGly modification was detected at the active site. The enzyme has sulfatase activity on aromatic sulfated substrates as well as phosphatase activity on some aromatic phosphates; however, PyuS did not have detectable activity on 17α-estradiol sulfate, cortisol 21-sulfate, or boldenone sulfate.  相似文献   
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