The first observed complex of 9-crown-3 ether: X-ray crystallographic and solid state C NMR study of naphtho-9-crown-3 ether and its 2:1 LiClO4 complex

The X-ray crystal structure of naphtho-9-crown-3 ether, 1 is reported. The molecule crystallizes in the monoclinic P2(1)/c space group with a=8.866(2) Å, b=6.451(1) Å, c=20.110(4) Å and β=91.055(4)°, with Z=4. The 2:1 naphtho-9-crown-3 LiClO₄ complex, 2 crystallizes in the triclinic P-1 space group with a=10.5075(10) Å, b=11.7283(11) Å, c=15.9921(15) Å and β=84.289(2)°, with Z=2. There are two distinct complexes found in the crystal, one ordered and one disordered in the crown portion of the molecule. ¹³C CPMAS NMR spectra for 1 and 2 are presented.     

The coordination chemistry of the hydrotris(3-diphenylmethylpyrazol-1-yl)borate (Tp(CHPh2)) ligand

The new ligand, hydrotris[3-(diphenylmethyl)pyrazol-1-yl]borate, Tp(CHPh2), has been synthesized and its coordination chemistry was compared with that of the analogous Tp(iPr). The new ligand was converted to a variety of complexes, such as M[Tp(CHPh2)]X (M = Co, Ni, Zn; X = Cl, NCO, NCS), Pd[Tp(CHPh2)][eta3-methallyl], Co[Tp(CHPh2)](acac), and Co[Tp(CHPh2)](scorpionate ligand). Compounds Tl[Tp(CHPh2)], 1, Co[Tp(CHPh2)]Cl, 2, Co[Tp(CHPh2)](NCS)(DMF), 3, Ni[Tp(CHPh2)](NCS)(DMF)2, 4, Co[Tp(CHPh2)](acac), 5, Co[Tp(CHPh2)][Ph2Bp], 6, Co[Tp(CHPh2)][Bp(Ph)], 7, Co[Tp(CHPh2)][Tp], 8, and (Ni[Tp(CHPh2)])2[C2O4](H2O)2, 9, were structurally characterized.     

A polynomial solution for the potato-peeling problem

The potato-peeling problem asks for the largest convex polygon contained inside a given simple polygon. We give anO(n ⁷) time algorithm to this problem, answering a question of Goodman. We also give anO(n ⁶) time algorithm if the desired polygon is maximized with respect to perimeter.Work in this paper has been supported in part by NSF grants #DCR-84-01898 and #DCR-84-01633, the Office of Naval Research Grant N00014-82-K-0381, and by grants from Digital Equipment Corporation, the Sloan Foundation, the System Development Foundation, and the IBM Corporation. This paper contains the main results of the paper A Polynomial Solution for Potato-Peeling and other Polygon Inclusion and Enclosure Problems presented in the 25th Foundation of Computer Science Conference, 1984, Florida. The second half of that paper is submitted for publication elsewhere [1].     

Encouraging problem-solving disposition in a Singapore classroom

In this article, we share our learning experience as a Lesson Study team. The Research Lesson was on Figural Patterns taught in Year 7. In addition to helping students learn the skills of the topic, we wanted them to develop a problem-solving disposition. The management of these two objectives was a challenge to us. From the lesson observation and the students’ classwork, it turned out better than we expected.     

Targeted guanine oxidation by a dinuclear copper(II) complex at single stranded/double stranded DNA junctions

A dinuclear copper(II) complex [Cu(II)2(PD'O-)(H2O)2](ClO4)3 (5) with terminal Cu(II)-H(2)O moieties and a Cu...Cu distance of 4.13 A (X-ray structure) has been synthesized and characterized by EPR spectroscopy (ferromagnetic coupling observed) and cyclic voltammetry. Dizinc(II) and mononuclear copper(II) analogues [Zn(II)2(PD'O-)(H2O)2]3+ (7) and [Cu(II)(mPD'OH)(H2O)]2+ (6), respectively, have also been synthesized and structurally characterized. Reacting 5/MPA/O(2) (MPA = 3-mercaptopropionic acid) with DNA leads to a highly specific oxidation of guanine (G) at a junction between single- and double-stranded DNA. Mass spectrometric analysis of the major products indicates a gain of +18 and +34 amu relative to initial DNA strands. The most efficient reaction requires G at the first and second unpaired positions of each strand extending from the junction. Less reaction is observed for analogous targets in which the G cluster is farther from the junction or contains less than four Gs. Consistent with our previous systems, the multinuclear copper center is required for selective reaction; mononuclear complex 6 is not effective. Hydrogen peroxide as a substitute for MPA/O2 also does not lead to activity. Structural analysis of a [Cu(II)2(PD'O-)(G)]3+ complex (8) and dizinc analogue [Zn(II)(2)(PD'O-)(G)](ClO4)3 (9) (G = guanosine) reveals coordination of the G O6 and N7 atoms with the two copper (or zinc) centers and suggests that copper-G coordination likely plays a role in recognition of the DNA target. The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed.     

Purification of His-tagged hepatitis B core antigen from unclarified bacterial homogenate using immobilized metal affinity-expanded bed adsorption chromatography

Hepatitis B core antigen (HBcAg) is used as a diagnostic reagent for the detection of hepatitis B virus infection. In this study, immobilized metal affinity-expanded bed adsorption chromatography (IMA-EBAC) was employed to purify N-terminally His-tagged HBcAg from unclarified bacterial homogenate. Streamline Chelating was used as the adsorbent and the batch adsorption experiment showed that the optimal binding pH of His-tagged HBcAg was 8.0 with a binding capacity of 1.8 mg per ml of adsorbent. The optimal elution condition for the elution of His-tagged HBcAg from the adsorbent was at pH 7 in the presence of 500 mM imidazole and 1.5 M NaCl. The IMA-EBAC has successfully recovered 56% of His-tagged HBcAg from the unclarified E. coli homogenate with a purification factor of 3.64. Enzyme-linked immunosorbent assay (ELISA) showed that the antigenicity of the recovered His-tagged HBcAg was not affected throughout the IMA-EBAC purification process and electron microscopy revealed that the protein assembled into virus-like particles (VLP).