Packing as a probe of structure in alkaline earth glass systems

Packing is an intrinsic property of glass, defined as the ratio of ionic volume to molar volume, and is a useful parameter for analyzing structural changes with composition. Alkali based glasses show two trends in packing, one dominated by the oxygen covalent network for the small ions, Li and Na, and one ionically dominated by the metal cations for the large, K, Rb and Cs cases [S. Giri, C. Gaebler, J. Helmus, M. Affatigato, S.A. Feller, J. Non-Cryst. Solids 347 (2004) 87]. We have found that alkaline earth glasses do not display these behaviors, and in this paper we determined the packing fractions of these glasses and compared them with the alkali case. Further, we considered the structural implications of the packing trends.     

A combinatorial method for solution-phase synthesis of labeled bivalent beta-turn mimics

Piperidine-functionalized, 1,4-disubstituted-1,2,3-triazoles of generic structure 1 were conceived as "minimalist" mimics of peptidic beta-turn structures. Key features of these molecules include (i) the possibility of incorporating amino acid side chains corresponding to many of the protein amino acids; (ii) a close correspondence of separations of these side chains to i + 1 to i + 2 residues in turns; (iii) facile adjustment of the side-chain vectors on docking while only influencing two critical degrees of freedom; and (iv) some electrostatic polarity. Fifteen monomers of this type were made via copper-mediated cycloaddition reactions. Solution-phase methodologies were devised to assemble these monomers into bivalent compounds in high purity states (typically >85%) so that they could be used in first-pass biological assays without further purification. The skeleton for forming these bivalent compounds is triazine-based. There is a third site which allowed for introduction of a fluorescent label (library of compounds 2) or an alkyne-functionalized triethylene glycol chain (library of compounds 3) included to promote water-solubility and to allow incorporation of probes via copper-mediated cycloaddition reactions. In the event, two 135-membered libraries were prepared, one consisting of compounds 2 and the other of 3. No protecting groups or coupling agents were required; these attributes of the method were important to allow most of the products to be obtained in over 85% purities. The fluorescein-tagged library of compounds 2 was screened in a fluorescence-activated cell sorting (FACS) assay using cells transfected to overexpress one of the following neurotrophin receptors: TrkA, TrkC, and p75. Preliminary findings indicate four compounds 2gm, 2gn, 2gi, and 2gj bound the TrkA receptor selectively; all of these contain a threonine-lysine turn mimic. Thus, a pharmacological probe for the TrkA receptor has been developed.     

Heterovalent selectivity and the combinatorial advantage

Libraries of monovalent compounds can be reacted with each other to give libraries of bivalent ones. If those reactions are efficient, and if the products do not need to be purified, large numbers of bivalent compounds can be produced rapidly, and one might say there is a "combinatorial advantage" to doing so. However, selective formation of heterobivalent products must be possible otherwise statistical mixtures will form. This tutorial review describes methods that will give heterobivalent compounds almost exclusively. Although there are relatively few methods that will give that desired selectivity, such methods are becoming increasingly important as the potential applications of bi- and multivalent compounds emerge.     

Syntheses and properties of water-soluble Nile Red derivatives

Nile Red (compound A) fluoresces at about 530 nm with good quantum yields in apolar solvents. In more polar ones its fluorescence emission shows a dramatic, and potentially useful, shift to about 640 nm, but its quantum yield is significantly reduced. Further, Nile Red has a very poor solubility in aqueous media. The hypothesis tested in this paper is that Nile Red derivatives that incorporate water-solubilizing groups will tend to fluoresce with good quantum yields in aqueous media, and in the more useful wavelength range around 640 nm. Thus three Nile Red derivatives, 1-3, were prepared. Compound 1 had three hydroxyl groups more than Nile Red, but was surprisingly insoluble in aqueous media. However, the dicarboxylic acid 2 and carboxylic/sulfonic acid derivative 3 showed excellent water solubilities. Spectral data for 2 and 3 showed that they do indeed fluoresce with good quantum yields in the 640 nm region in aqueous media. These properties of compounds 2 and 3 might be useful in the development of fluorescent probes for biotechnology.     

New N-Substituted (±)-Dehydronorglaucine Analogs

The aporphine alkaloid N-carbethoxydehydronorglaucine (1) was found to have promising in vitro antitumor activity, but poor water solubility. We report the synthesis of 1, the efficient hydrolysis of its urethane group and the further transformation into several new dehydronorglaucine analogs.     

The platinumolefin bond strength in Pt(PPh3)2(η-3-phenylcyclobutene-1,2-dione)

The enthalpy, ΔH = ?64.7 ± 4 kJ mol^?1, for the reaction Pt(PPh₃)₂(η-C₂H₄)(s) + pcbd(g) → Pt(PPh₃)₂(η-pcbd)(s) + C₂H₄(g) where pcbd is 3-phenylcyclobutene-1,2-dione,

, has been measured calorimetrically. The Ptolefin bond in this complex is slightly stronger than that in Pt(PPh₃)₂(η-PhCHCH₂).     

The enthalpy of formation of tungsten thiotetrafluoride

The enthalpy of hydrolysis of solid tungsten thiotetrafluoride, WF(in4)S, in aqueous sodium hydroxide solution is -528.2 kJ mo1^-1. Hence its standard enthalpy of formation has been calculated to be -1150.5 kJ mo1^-1.