scholarly journals A double helix of opposite charges to form channels with unique CO2 selectivity and dynamics

2019 ◽  
Vol 10 (3) ◽  
pp. 730-736 ◽  
Author(s):  
Guolong Xing ◽  
Irene Bassanetti ◽  
Silvia Bracco ◽  
Mattia Negroni ◽  
Charl Bezuidenhout ◽  
...  

Electrostatic charges patterning along crystalline channels recognize CO2 with high selectivity and promote its fast screwing dynamics through the crystal at one million steps per second, strongly reminiscent of trans-membrane transport in biological channels.

Author(s):  
D.P. Bazett-Jones ◽  
F.P. Ottensmeyer

Dark field electron microscopy has been used for the study of the structure of individual macromolecules with a resolution to at least the 5Å level. The use of this technique has been extended to the investigation of structure of interacting molecules, particularly the interaction between DNA and fish protamine, a class of basic nuclear proteins of molecular weight 4,000 daltons.Protamine, which is synthesized during spermatogenesis, binds to chromatin, displaces the somatic histones and wraps up the DNA to fit into the small volume of the sperm head. It has been proposed that protamine, existing as an extended polypeptide, winds around the minor groove of the DNA double helix, with protamine's positively-charged arginines lining up with the negatively-charged phosphates of DNA. However, viewing protamine as an extended protein is inconsistent with the results obtained in our laboratory.


Author(s):  
Mark Hannibal ◽  
Jacob Varkey ◽  
Michael Beer

Workman and Langmore have recently proposed a procedure for isolating particular chromatin fragments. The method requires restriction endonuclease cutting of the chromatin and a probe, their digestion with two exonucleases which leave complimentary single strand termini and low temperature hybridization of these. We here report simple electron microscopic monitoring of the four reactions involved.Our test material was ϕX-174 RF DNA which is cut once by restriction endonuclease Xho I. The conversion of circles to linear molecules was followed in Kleinschmidt spreads. Plate I shows a circular and a linear DNA molecule. The rate of cutting is shown in Figure 1.After completion of the endonuclease cutting, one portion of the DNA was treated with exonuclease III, an enzyme known to digest the 3' terminals of double helical DNA. Aliquots when examined in the electron microscope reveal a decreasing length of double helix and increasing bushes at the ends.


2020 ◽  
Vol 44 (21) ◽  
pp. 8710-8717
Author(s):  
André L. D. Lima ◽  
Humberto V. Fajardo ◽  
André E. Nogueira ◽  
Márcio C. Pereira ◽  
Luiz C. A. Oliveira ◽  
...  

Nb-peroxo@iron oxides show high selectivity and activity in aniline conversion to azoxybenzene.


2020 ◽  
Author(s):  
Yunzhong Wang ◽  
Saixing Tang ◽  
Yating Wen ◽  
Shuyuan Zheng ◽  
Bing Yang ◽  
...  

<div>Persistent room-temperature phosphorescence (p-RTP) from pure organics is attractive </div><div>due to its fundamental importance and potential applications in molecular imaging, </div><div>sensing, encryption, anticounterfeiting, etc.1-4 Recently, efforts have been also made in </div><div>obtaining color-tunable p-RTP in aromatic phosphors5 and nonconjugated polymers6,7. </div><div>The origin of color-tunable p-RTP and the rational design of such luminogens, </div><div>particularly those with explicit structure and molecular packing, remain challenging. </div><div>Noteworthily, nonconventional luminophores without significant conjugations generally </div><div>possess excitation-dependent photoluminescence (PL) because of the coexistence of </div><div>diverse clustered chromophores6,8, which strongly implicates the possibility to achieve </div><div>color-tunable p-RTP from their molecular crystals assisted by effective intermolecular </div><div>interactions. Here, inspirited by the highly stable double-helix structure and multiple </div><div>hydrogen bonds in DNA, we reported a series of nonconventional luminophores based on </div><div>hydantoin (HA), which demonstrate excitation-dependent PL and color-tunable p-RTP </div><div>from sky-blue to yellowish-green, accompanying unprecedentedly high PL and p-RTP </div><div>efficiencies of up to 87.5% and 21.8%, respectively. Meanwhile, the p-RTP emissions are </div><div>resistant to vigorous mechanical grinding, with lifetimes of up to 1.74 s. Such robust, </div><div>color-tunable and highly efficient p-RTP render the luminophores promising for varying </div><div>applications. These findings provide mechanism insights into the origin of color-tunable </div><div>p-RTP, and surely advance the exploitation of efficient nonconventional luminophores.</div>


2018 ◽  
Author(s):  
Jiajun Wang ◽  
Jayesh Arun Bafna ◽  
Satya Prathyusha Bhamidimarri ◽  
Mathias Winterhalter

Biological channels facilitate the exchange of small molecules across membranes, but surprisingly there is a lack of general tools for the identification and quantification of transport (i.e., translocation and binding). Analyzing the ion current fluctuation of a typical channel with its constriction region in the middle does not allow a direct conclusion on successful transport. For this, we created an additional barrier acting as a molecular counter at the exit of the channel. To identify permeation, we mainly read the molecule residence time in the channel lumen as the indicator whether the molecule reached the exit of the channel. As an example, here we use the well-studied porin, OmpF, an outer membrane channel from <i>E. coli</i>. Inspection of the channel structure suggests that aspartic acid at position 181 is located below the constriction region (CR) and we subsequently mutated this residue to cysteine, where else cysteine free and functionalized it by covalent binding with 2-sulfonatoethyl methanethiosulfonate (MTSES) or the larger glutathione (GLT) blockers. Using the dwell time as the signal for transport, we found that both mono-arginine and tri-arginine permeation process is prolonged by 20% and 50% respectively through OmpF<sub>E181C</sub>MTSES, while the larger sized blocker modification OmpF<sub>E181C</sub>GLT drastically decreased the permeation of mono-arginine by 9-fold and even blocked the pathway of the tri-arginine. In case of the hepta-arginine as substrate, both chemical modifications led to an identical ‘blocked’ pattern observed by the dwell time of ion current fluctuation of the OmpF<sub>wt</sub>. As an instance for antibiotic permeation, we analyzed norfloxacin, a fluoroquinolone antimicrobial agent. The modulation of the interaction dwell time suggests possible successful permeation of norfloxacin across OmpF<sub>wt</sub>. This approach may discriminate blockages from translocation events for a wide range of substrates. A potential application could be screening for scaffolds to improve the permeability of antibiotics.


2017 ◽  
Author(s):  
Jeremy Roach ◽  
Yusuke Sasano ◽  
Cullen Schmid ◽  
Saheem Zaidi ◽  
Vsevolod Katritch ◽  
...  

Salvinorin A (SalA) is a plant metabolite that agonizes the human <i>kappa</i>-opioid receptor (κ-OR) with high affinity and high selectivity over <i>mu- </i>and <i>delta-</i>opioid receptors. Its therapeutic potential has stimulated extensive semi-synthetic studies and total synthesis campaigns. However, structural modification of SalA has been complicated by its instability, and efficient total synthesis has been frustrated by its dense, complex architecture. Treatment of strategic bonds in SalA as dynamic and dependent on structural perturbation enabled the identification of an efficient retrosynthetic pathway. Here we show that deletion of C20 simultaneously stabilizes the SalA skeleton, simplifies its synthesis and retains its high affinity and selectivity for the κ-OR. The resulting 10-step synthesis now opens the SalA scaffold to deep-seated property modification.


2020 ◽  
Author(s):  
Thomas Louis-Goff ◽  
Huu Vinh Trinh ◽  
Eileen Chen ◽  
Arnold L. Rheingold ◽  
Christian Ehm ◽  
...  

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF<sub>3</sub> as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF<sub>2</sub> in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF<sub>2</sub>-recombination side-reactions.


2019 ◽  
Author(s):  
Idriss Curbet ◽  
Sophie Colombel-Rouen ◽  
Romane Manguin ◽  
Anthony Clermont ◽  
Alexandre Quelhas ◽  
...  

<div> <div> <div> <div> <p>The synthesis of conjugated triynes by molybdenum-catalyzed alkyne metathesis is reported. Strategic to the success of this approach is the utilization of sterically-hindered diynes that allowed for the site- selective alkyne metathesis to produce the desired con- jugated triyne products. The steric hindrance of alkyne moiety was found to be crucial in preventing the for- mation of diyne byproducts. This novel synthetic strategy was amenable to self- and cross-metathesis providing straightforward access to the corresponding symmetrical and dissymmetrical triynes with high selectivity. </p> </div> </div> </div> </div>


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