Effect of pH and salt concentration on the phase inversion of particle-stabilized foams

The effect of pH and salt concentration on the phase inversion of silica particle-stabilized foams is presented. Inversion from a water-in-air powder to an air-in-water foam can be achieved by increasing the pH of the aqueous phase. By contrast, an increase in the salt concentration causes a nonfoaming aqueous dispersion to foam. The results are rationalized in terms of changes in the hydrophobicity of the solid surfaces, probed by measurement of the contact angles of water drops on hydrophobized glass slides in air.     

Long-range 19F-15N distance measurements in highly-13C, 15N-enriched solid proteins with 19F-dephased REDOR shift (FRESH) spectroscopy

We present a novel rotational-echo double resonance (REDOR) method for detection of multiple (19)F-(15)N distances in solid proteins. The method is applicable to protein samples containing a single (19)F label, in addition to high levels of (13)C and (15)N enrichment. REDOR dephasing pulses are applied on the (19)F channel during an indirect constant time chemical shift evolution period on (15)N, and polarization is then transferred to (13)C for detection, with high-power (1)H decoupling throughout the sequence. This four-channel experiment reports site-specifically on (19)F-(15)N distances, with highly accurate determinations of approximately 5 A distances and detection of correlations arising from internuclear distances of at least 8 A. We demonstrate the method on the well-characterized 56-residue model protein GB1, where the sole tryptophan residue (Trp-43) has been labeled with 5-(19)F-Trp, in a bacterial growth medium also including (13)C-glucose and (15)N ammonium chloride. In GB1, 11 distances are determined, all agreeing within 20% of the X-ray structure distances. We envision the experiment will be utilized to measure quantitative long-range distances for protein structure determination.     

Modular syntheses of multidentate ligands with variable N-donors: applications to tri- and tetracopper(I) complexes

A general method for the preparation of multidentate ligands comprised of a multi-imine platform derived from 1,1,1-tris(aminomethyl)ethane or tris(aminoethyl)amine connected to bi- and tridentate N-donor chelates has been developed. The feasibility of the method has been demonstrated through the synthesis and characterization of a large set of these ligand types. Complexation to Cu(I) was accomplished for several cases, yielding tri- and tetracopper(I) complexes that have been characterized in solution by NMR spectroscopy and conductivity, and in the solid state by elemental analysis, mass spectrometry, and/or X-ray crystallography. These complexes are potentially useful for modeling multicopper protein active sites.     

Eta(1)-2-pyrone metal carbonyl complexes as CO-releasing molecules (CO-RMs): a delicate balance between stability and CO liberation

An evaluation of the CO releasing ability of iron(II) and molybdenum(II) complexes has facilitated the discovery of the most rapid CO releaser, namely [Mo(CO)(3)(eta(5)-C(5)H(5))(eta(1)-{O}-C{=O}-O-CMe=CH-COMe=CBr)]BF(4) (CORM-F10), reported to date. The rate of CO release is related to the overall solution phase stability of the transition metal carbonyl complex. The cytotoxicity and vasodilatory properties of CORM-F10 have been determined.     

Alternatives to pyridinediimine ligands: syntheses and structures of metal complexes supported by donor-modified alpha-diimine ligands

This report describes the synthesis and characterization of metal halide complexes (M = Mn, Fe, Co) supported by a new family of pendant donor-modified alpha-diimine ligands. The donor (N, O, P, S) substituent is linked to the alpha-diimine by a short hydrocarbon spacer forming a tridentate, mer-coordinating ligand structure. The tridentate ligands are assembled from monoimine precursors, the latter being synthesized by selective reaction with one carbonyl group of the alpha-dione. While attempts to separately isolate tridentate ligands in pure form were unsuccessful, metal complexes supported by the tridentate ligand are readily synthesized in-situ, by forming the ligand in the presence of the metal halide, resulting in a metal complex which subsequently crystallizes out of the reaction mixture. Metal complexes with NNN, NNO, NNP and NNS donor sets have been prepared and examples supported by NNN, NNP and NNS ligands have been structurally characterized. In the solid state, NNN and NNP ligands coordinate in a mer fashion and the metal complexes possess distorted square pyramidal structures and high spin (S = 2) electronic configurations. Compounds with NNS coordination environments display a variety of solid state structures, ranging from those with unbound sulfur atoms, including chloride bridged and solvent ligated species, to those with sulfur weakly bound to the metal center. The extent of sulfur ligation depends on the donor ability of the crystallization solvent and the substitution pattern of the arylthioether substituent.     

One-step synthesis of oxazoline and dihydrooxazine libraries

The reactions of 1,2- and 1,3-hydroxyalkyl azides and aldehydes in the presence of Lewis acid result in the one-step construction of oxazolines and dihydrooxazines, respectively. The reaction was adapted to parallel synthesis using a polymer-bound phosphine to scavenge excess hydroxyalkyl azide. Thus, a 60-member library of various disubstituted oxazolines and di- and trisubstituted dihydrooxazines was generated.     

Quasi-hopf algebras associated withsl 2 and complex curves

We construct quasi-Hopf algebras quantizing double extensions of the Manin pairs of Drinfeld, associated to a curve with a meromorphic differential, and the Lie algebrasl ₂. This construction makes use of an analysis of the vertex relations for the quantum groups obtained in our earlier work, PBW-type results and computation ofR-matrices for them; its key step is a factorization of the twist operator relating “conjugated” versions of these quantum groups.     

Basis- and partition identification for quadratic programming and linear complementarity problems

Optimal solutions of interior point algorithms for linear and quadratic programming and linear complementarity problems provide maximally complementary solutions. Maximally complementary solutions can be characterized by optimal partitions. On the other hand, the solutions provided by simplex–based pivot algorithms are given in terms of complementary bases. A basis identification algorithm is an algorithm which generates a complementary basis, starting from any complementary solution. A partition identification algorithm is an algorithm which generates a maximally complementary solution (and its corresponding partition), starting from any complementary solution. In linear programming such algorithms were respectively proposed by Megiddo in 1991 and Balinski and Tucker in 1969. In this paper we will present identification algorithms for quadratic programming and linear complementarity problems with sufficient matrices. The presented algorithms are based on the principal pivot transform and the orthogonality property of basis tableaus. Received April 9, 1996 / Revised version received April 27, 1998? Published online May 12, 1999