New base pairing motifs. The synthesis and thermal stability of oligodeoxynucleotides containing imidazopyridopyrimidine nucleosides with the ability to form four hydrogen bonds

The synthesis and thermal stability of oligodeoxynucleotides (ODNs) containing imidazo[5',4':4,5]pyrido[2,3-d]pyrimidine nucleosides 1-4 (N(N), O(O), N(O), and O(N), respectively) with the aim of developing two sets of new base pairing motifs consisting of four hydrogen bonds (H-bonds) is described. The proposed four tricyclic nucleosides 1-4 were synthesized through the Stille coupling reaction of a 5-iodoimidazole nucleoside with an appropriate 5-stannylpyrimidine derivative, followed by an intramolecular cyclization. These nucleosides were incorporated into ODNs to investigate the H-bonding ability. When one molecule of the tricyclic nucleosides was incorporated into the center of each ODN (ODN I and II, each 17mer), no apparent specificity of base pairing was observed, and all duplexes were less stable than the duplexes containing natural G:C and A:T pairs. On the other hand, when three molecules of the tricyclic nucleosides were consecutively incorporated into the center of each ODN (ODN III and IV, each 17mer), thermal and thermodynamic stabilization of the duplexes due to the specific base pairings was observed. The melting temperature (T(m)) of the duplex containing the N(O):O(N) pairs showed the highest T(m) of 84.0 degrees C, which was 18.2 and 23.5 degrees C higher than that of the duplexes containing G:C and A:T pairs, respectively. This result implies that N(O)and O(N) form base pairs with four H-bonds when they are incorporated into ODNs. The duplex containing N(O):O(N) pairs was markedly stabilized by the assistance of the stacking ability of the imidazopyridopyrimidine bases. Thus, we developed a thermally stable new base pairing motif, which should be useful for the stabilization and regulation of a variety of DNA structures.     

Convenient synthesis of 2-alkylamino-6-carboxy-5,7-diarylcyclopenteno[1,2-b]pyridines via direct acylamination with imidoyl chlorides

A robust synthetic method for 2-alkylamino-6-carboxy-5,7-diarylcyclopenteno[1,2-b]pyridines via acylamination at the alpha position of the functionalized pyridine system has been developed. The key step in this method was achieved by treatment of the corresponding pyridine N-oxides with 2.5 equiv of imidoyl chlorides in the presence of triethylamine, thus producing the desired 2-acylaminopyridines in good yields (74-96%).     

Rhodium-catalyzed oxidative alkynylation of acrylate esters with propargylic alcohols

Oxidative alkynylation of acrylate esters with propargylic alcohols giving conjugated enyne esters was realized by use of a diene-rhodium catalyst. Propargylic alcohols were found to be useful alkynylating reagents in the present reaction to produce alkynylrhodium species via carbon-carbon bond cleavage. An excess of the acrylate ester worked as a hydride acceptor to reproduce the active rhodium species.     

A Strategy for Neuraminidase Inhibitors Using Mechanism‐Based Labeling Information

A potent inhibitor for Vibrio cholerae neuraminidase (VCNA) was developed by using a novel two‐step strategy, a target amino acid validation using mechanism‐based labeling information, and a potent inhibitor search using a focused library. The labeling information suggested the hidden dynamics of a loop structure of VCNA, which can be a potential target of the novel inhibitor. A focused library composed of 187 compounds was prepared from a 9‐azide derivative of 2,3‐dehydro‐N‐acetylneuraminic acid (DANA) to interrupt the function of the loop of the labeled residues. Inhibitor 3c showed potent inhibition properties and was the strongest inhibitor with FANA, a N‐trifluoroacetyl derivative of DANA. Validation studies of the inhibitor with a detergent and a Lineweaver–Burk plot suggested that the 9‐substitution group would interact hydrophobically with the target loop moiety, adding a noncompetitive inhibition property to the DANA skeleton. This information enabled us to design compound 4 having the combined structure of 3c and FANA. Compound 4 showed the most potent inhibition (K_i=73 nM , mixed inhibition) of VCNA with high selectivity among the tested viral, bacterial, and mammal neuraminidases.     

Lipophilic aminimides possessing an additional ligating group as extractants for heavy metal cations

The title compounds were prepared in good yields by Slagel's method. All compounds obtained were used as agents for liquid-liquid extraction. They showed high affinity for certain heavy metal cations and their extractability depended to a great extent on the ligand structure. This dependence is believed to be due to the chelation of the metal cations between the imino nitrogens and the additional ligating site.     

Oriented and low‐density tin dioxide film by sol–gel mineralizing tin‐contained hydroxypropyl cellulose lyotropic liquid crystal for laser‐induced extreme ultraviolet emission

A series of tin‐doped hydroxypropyl cellulose (HPC) lyotropic liquid crystal (LC) was synthesized using a simple process and their properties were characterized using selective reflection, wide‐angle X‐ray diffraction (WAXD), and the band texture observed under polarized optical microscope. The present preparation is applicable for mass production using large substrate with low cost HPC. A cholesteric lyotropic LC phase was observed for the hybrid solution with higher than 40 wt % HPC. After sol–gel condensation, the HPC‐Sn hybrid LC films were calcined at 400 °C and the as‐prepared product was determined to obtain tin dioxide (SnO₂) which was characterized using WAXD. The iridescent color and ～2 nm structure seen after the condensation disappeared in the as‐prepared SnO₂. Scanning electronic microscope images of the SnO₂ showed that the HPC content in the HPC‐Sn hybrid played an important role in controlling the SnO₂ morphology. A spectrum of relatively monochromatic extreme ultraviolet (13.5 nm) emission was measured in the as‐prepared SnO₂ in comparison with bulk tin and inverse opal SnO₂. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4566–4576, 2009     

Interval Routing onk-Trees

A graph has an optimall-interval routing scheme if it is possible to direct messages along shortest paths by labeling each edge with at mostlpairwise-disjoint subintervals of the cyclic interval [1…n] (where each node of the graph is labeled by an integer in the range). Although much progress has been made forl = 1, there is as yet no general tight characterization of the classes of graphs associated with largerl. Bodlaenderet al. have shown that under the assumption of dynamic cost links, each graph with an optimall-interval routing scheme has treewidth of at most 4l. For the setting without dynamic cost links, this paper addresses the complementary question of the number of intervals required to label classes of graphs of treewidthk. Although it has been shown that there exist graphs of treewidth 2 that require a nonconstant number of intervals, our work demonstrates a class of graphs of treewidth 2, namely 2-trees, that are guaranteed to allow 3-interval routing schemes. In contrast, this paper presents a 2-tree that cannot have a 2-interval routing scheme. For generalk, anyk-tree is shown to have an optimal interval routing scheme using 2^{k + 1}intervals per edge.