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Double Helices (double + helice)
Selected AbstractsDevelopment of synthetic double helical polymers and oligomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2009Yoshio Furusho Abstract There is growing interest in the design and synthesis of artificial helical polymers and oligomers, in connection with biological importance as well as development of novel chiral materials. Since the discovery of the helical structure of isotactic polypropylene, a significant advancement has been achieved for synthetic polymers and oligomers with a single helical conformation for about half a century. In contrast, the chemistry of double helical counterparts is still premature. This short review highlights the recent advances in the synthesis, structures, and functions of double helical polymers and oligomers, featuring an important role of supramolecular chemistry in the design and synthesis of double helices. Although the artificial double helices reported to date are still limited in number, recent advancement of supramolecular chemistry provides plenty of structural motifs for new designs. Therefore, artificial double helices hold great promise as a new class of compounds. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5195,5207, 2009 [source] Agarose Sols and Gels RevisitedMACROMOLECULAR SYMPOSIA, Issue 1 2006Jean-Michel Guenet Abstract Agarose sols have been seen for long as solutions of flexible chains that, on cooling, produce thermoreversible gels through double-helix formation. Investigations of the chain conformation in the sol state by small-angle neutron scattering reveals instead a rigid chain with a very large persistence length (lp,>,9 nm). The chain cross-section radius and mass per unit length correspond to characteristics of helices as those described by Foord and Atkins. These results lead one to a reappraisal of the occurrence of double helices in the gelation process, as they rather suggest a transition of the type loose-single helix,tight single helix. Studies of gels from agarose/water/cosolvent where the cosolvent is Dimethyl Sulfoxide (DMSO), Dimethyl Formamide (DMF), and Methyl Formamide (MF) have led one to conclude on the formation of agarose/water/ cosolvent ternary complexes. The contrast variation method by neutron scattering gives further support to this assumption. Finally, determination of the gel nanostructure allows one to account for the two regimes observed for the variation of the elastic modulus vs concentration. [source] Molecular design and synthesis of artificial double helicesTHE CHEMICAL RECORD, Issue 1 2007Yoshio Furusho Abstract This account describes novel artificial double helices recently developed by our group. We have designed and synthesized the double helices consisting of two complementary, m -terphenyl-based strands that are intertwined through chiral amidinium,carboxylate salt bridges. Due to the chiral substituents on the amidine groups, the double helices adopted an excess one-handed helical conformation in solution as well as in the solid state. By extending the modular strategy, we have synthesized double helices bearing Pt(II) linkers, which underwent the double helix-to-double helix transformations through the chemical reactions of the Pt(II) complex moieties. In addition, artificial double-stranded metallosupramolecular helical polymers were constructed by combining the salt bridges and metal coordination. In contrast to the design-oriented double helices based on salt bridges, we have serendipitously developed a spiroborate-based double helicate bearing oligophenol strands. The optical resolution of the helicate was successfully attained by a diastereomeric salt formation. We have also unexpectedly found that oligoresorcinols consisting of a very simple repeating unit self-assemble into double helices with the aid of aromatic interactions in water. Furthermore, a bias in the twist sense of the double helices can be achieved by incorporating chiral substituents at both ends of the strands. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 1,11; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20097 [source] Building of RNA and DNA double helices into electron densityACTA CRYSTALLOGRAPHICA SECTION D, Issue 6 2008Frantisek Pavelcik A method has been developed that automatically fits double-helical regions into the electron density of nucleic acid structures. Rigid fragments consisting of two Watson,Crick base pairs and three pairs of phosphate groups in the A-type or B-type conformation are positioned into the electron density by phased rotation and translation functions. The position and orientation of the localized double-helical fragments are determined by phased refinement. The method has been tested by building double-helical regions of nine RNA structures of variable crystallographic resolution and polynucleotide length and is available for free use. [source] Crystallization and X-ray diffraction analysis of an `all-locked' nucleic acid duplex derived from a tRNASer microhelixACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 8 2009Katja Behling Modified nucleic acids are of great interest with respect to their nuclease resistance and enhanced thermostability. In therapeutical and diagnostic applications, such molecules can substitute for labile natural nucleic acids that are targeted against particular diseases or applied in gene therapy. The so-called `locked nucleic acids' contain modified sugar moieties such as 2,- O,4,- C -methylene-bridged ,- d -ribofuranose and are known to be very stable nucleic acid derivatives. The structure of locked nucleic acids in single or multiple LNA-substituted natural nucleic acids and in LNA,DNA or LNA,RNA heteroduplexes has been well investigated, but the X-ray structure of an `all-locked' nucleic acid double helix has not been described to date. Here, the crystallization and X-ray diffraction data analysis of an `all-locked' nucleic acid helix, which was designed as an LNA originating from a tRNASer microhelix RNA structure, is presented. The crystals belonged to space group C2, with unit-cell parameters a = 77.91, b = 40.74, c = 30.06,Å, , = 91.02°. A high-resolution and a low-resolution data set were recorded, with the high-resolution data showing diffraction to 1.9,Å resolution. The crystals contained two double helices per asymmetric unit, with a Matthews coefficient of 2.48,Å3,Da,1 and a solvent content of 66.49% for the merged data. [source] Solution Structure of a DNA Duplex Containing a Biphenyl PairCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2008Zeena Johar Abstract Hydrogen-bonding and stacking interactions between nucleobases are considered to be the major noncovalent interactions that stabilize the DNA and RNA double helices. In recent work we found that one or multiple biphenyl pairs, devoid of any potential for hydrogen bond formation, can be introduced into a DNA double helix without loss of duplex stability. We hypothesized that interstrand stacking interactions of the biphenyl residues maintain duplex stability. Here we present an NMR structure of the decamer duplex d(GTGACXGCAG), d(CTGCYGTCAC) that contains one such X/Y biaryl pair. X represents a 3,,,5,,-dinitrobiphenyl- and Y a 3,,,4,,-dimethoxybiphenyl C -nucleoside unit. The experimentally determined solution structure shows a B-DNA duplex with a slight kink at the site of modification. The biphenyl groups are intercalated side by side as a pair between the natural base pairs and are stacked head to tail in van der Waals contact with each other. The first phenyl rings of the biphenyl units each show tight intrastrand stacking to their natural base neighbors on the 3,-side, thus strongly favoring one of two possible interstrand intercalation structures. In order to accommodate the biphenyl units in the duplex the helical pitch is widened while the helical twist at the site of modification is reduced. Interestingly, the biphenyl rings are not static in the duplex but are in dynamic motion even at 294,K. [source] | |||||||||||||||||||||||||