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Kamlesh Madhusudan Makwana Dr. Radhakrishnan Mahalakshmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4147-4156
A popular strategy in the de novo design of stable β‐sheet structures for various biomedical applications is the incorporation of aromatic pairs at the non‐hydrogen‐bonding (NHB) position. However, it is important to explicitly understand how aryl pair packing at the NHB region is coordinated with backbone structural rearrangements, and to delineate the benefits and drawbacks associated with stereopositional choice of dissimilar aromatic pairs. Here, we probe the consequences of flipped Trp/Tyr pairs by using engineered permutants at the NHB position of dodecapeptide β‐hairpins, proximal and distal to the turn. Extensive conformational analysis of these peptides using NMR and CD spectroscopy reveal that a classic Edge‐to‐Face and Face‐to‐Edge geometry at the proximal and distal aromatic pairs, respectively, in YW‐WY, is the most stabilizing. Such a preferred packing geometry in YW‐WY results in a highly twisted β‐sheet backbone, with Trp always providing a ‘Face’ orientation to its dissimilar aromatic partner Tyr. Flipping the proximal and/or distal aromatic pair distorts the ideal T‐shaped geometry, and results in alternate aryl arrangements that can adversely affect strand twist and β‐sheet stability. Our study reveals the existence of a strong stereopositional influence on the packing of dissimilar aromatic pairs. Our findings highlight the importance of modeling physical interaction forces while designing protein and peptide structures for functional applications. 相似文献
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N,N-Dimethylaminoalkyl chalcogenolate Pd(II) complexes [PdCl(E∩NMe2)]n has been investigated as a moisture/air-stable and robust catalyst for Sonogashira cross-coupling reaction in the absence of copper and phosphine ligand. The dimeric palladium(II) complex of selenium containing ligand shows the best catalytic activity as compared with monomeric and trimeric complexes. The variety of functional groups are tolerated under optimized catalytic systems and provide excellent yields of the products. 相似文献
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Titanium‐Catalyzed Hydroalumination of Conjugated Dienes: Access to Fulvene‐Derived Allylaluminium Reagents and Their Diastereoselective Reactions with Carbonyl Compounds
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Dr. Jomy Joseph Dr. Florian Jaroschik Dr. Dominique Harakat Dr. K. V. Radhakrishnan Dr. Jean‐Luc Vasse Prof. Jan Szymoniak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5433-5438
The described titanium‐catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL‐H) and a catalytic amount of [Cp2TiCl2] (Cp=cyclopentadienyl). When applied to mono‐ and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react regio‐ and stereoselectively with both aldehydes and ketones to afford homoallylic alcohols that are suitable synthons for functionalized cyclopentanones. An extension of this methodology to simple dienes was also investigated. In the proposed mechanism, the initially formed bimetallic species (Ti/Al) are involved in the two possible catalytic cycles with a direct hydroalumination or/and a hydrotitanation followed by a titanium to aluminium transmetallation. 相似文献
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Structural Chemistry - In the present work, 2-substituted benzoxazole derivatives were synthesized from 2-(benzo[d]oxazol-2-yl) aniline. All the synthesized compounds were purified and... 相似文献
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Radhakrishnan Neeshma Thomas Shijo Sobhan C. B. 《Journal of Thermal Analysis and Calorimetry》2020,140(5):2471-2484
Journal of Thermal Analysis and Calorimetry - Nano-enhanced phase change materials (NEPCMs) have gained popularity as efficient thermal management and energy storage materials owing to their high... 相似文献
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Radhakrishnan M. Packianathan C. Sankaran B. Kandavelu P. Rosen B. P. 《Crystallography Reports》2021,66(7):1311-1315
Crystallography Reports - Exposure to environmental arsenic is associated with serious of health issues such as cancer, diabetes and developmental delays in infants and children. In human liver,... 相似文献
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Radhakrishnan TP Topiol S Biedermann PU Garten S Agranat I 《Chemical communications (Cambridge, England)》2002,(22):2664-2665
Ab initio calculations reveal chiral distinction in two-point contact CHFCIBr dimers, with chiral distinction energy of 1.5 kJ mol-1 between the SR and SS dimers fully optimized at the MP2/6-311++G** level. 相似文献