1-Alkyl-5-((di)alkylamino) tetrazoles: building blocks for peptide surrogates

An approach to the synthesis of 1-alkyl-5-((di)alkylamino)tetrazoles by nucleophilic substitution in 1-alkyl-5-sulfonyltetrazoles with anions generated from the primary or secondary amines was developed. Tolerance of the method to the presence of some functional groups (i.e., protected amine) in both components of the reaction was demonstrated. Obtained tetrazoles are promising building blocks for the design of peptide surrogates, in particular, for replacement approaches of alkyl urea derivatives.     

Advanced Mass Calibration and Visualization for FT-ICR Mass Spectrometry Imaging

Mass spectrometry imaging by Fourier transform ion cyclotron resonance (FT-ICR) yields hundreds of unique peaks, many of which cannot be resolved by lower performance mass spectrometers. The high mass accuracy and high mass resolving power allow confident identification of small molecules and lipids directly from biological tissue sections. Here, calibration strategies for FT-ICR MS imaging were investigated. Sub-parts-per-million mass accuracy is demonstrated over an entire tissue section. Ion abundance fluctuations are corrected by addition of total and relative ion abundances for a root-mean-square error of 0.158?ppm on 16,764 peaks. A new approach for visualization of FT-ICR MS imaging data at high resolution is presented. The ??Mosaic Datacube?? provides a flexible means to visualize the entire mass range at a mass spectral bin width of 0.001?Da. The high resolution Mosaic Datacube resolves spectral features not visible at lower bin widths, while retaining the high mass accuracy from the calibration methods discussed.     

Measuring the quality of discrete representations of efficient sets in multiple objective mathematical programming

One way of solving multiple objective mathematical programming problems is finding discrete representations of the efficient set. A modified goal of finding good discrete representations of the efficient set would contribute to the practicality of vector maximization algorithms. We define coverage, uniformity and cardinality as the three attributes of quality of discrete representations and introduce a framework that includes these attributes in which discrete representations can be evaluated, compared to each other, and judged satisfactory or unsatisfactory by a Decision Maker. We provide simple mathematical programming formulations that can be used to compute the coverage error of a given discrete representation. Our formulations are practically implementable when the problem under study is a multiobjective linear programming problem. We believe that the interactive algorithms along with the vector maximization methods can make use of our framework and its tools. Received April 7, 1998 / Revised version received March 1999?Published online November 9, 1999     

Copper(II)–lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platforms with Lewis amphoteric nature

Reaction of copper(II) acetate, lanthanium(III) or gadolinium(III) nitrate (1/5 equiv.) with pyrazinohydroxamic acid (H₂Pyzha) in DMF led to a series of new heterobimetallic 15-metallacrown-5 complexes. In a MeOH/H₂O solution the complexes exist as molecular unassociated metallacrowns. In solid state their structures are more complicated as it has been confirmed by X-ray analysis: discrete molecular metallacrowns [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(NO₃)] · 0.5C₆H₆ · H₂O (1), [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅](NO₃) · 1.5DMF · 0.5H₂O (2), [La(NO₃)₂{Cu(pyzha)}₅(DMF)₅]NO₃ · 1.5DMF · 2C₆H₆ (3) are solvates, whereas compound [{La(NO₃)₂{Cu(pyzha)}₅(DMF)₅}₂(μ²-NO₃)](NO₃) · 3DMF (4) is a dimer, where μ-bridged nitrate links two copper centres of the adjacent metallamacrocycles. Complex [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₂(H₂O)(NO₃)] · CH₂Cl₂ · DMF (5) self-associates into a polymer chain by means of one pyrazine moiety and the copper ring atom. Reaction of the molecular metallacrowns with excess of inorganic salts CdBr₂ or Cu(OAc)₂ proceeds as anion methathesis process affording heteroanionic metallacrowns: molecular [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅] [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(H₂O)][CdBr₄] · 1.5DMF (6), and 3D hydrogen bonded polymer [La(μ²-OAc)(H₂O)₃{Cu(pyzha)}₅ (H₂O)₄(NO₃)](NO₃) · 4H₂O (7).     

Synthesis and evaluation of antitrypanosomal activity of some thiosemicarbazide derivatives of 1-butyl-6-fluoro-7-morpholino-4-oxo-1,4-dihydroquinoline-3-carboxylic acid

The synthesis of thiosemicarbazide of 1-butyl-6-fluoro-7-morpholino-4-oxo-1,4-dihydroquinoline-3-carboxylic acid as well as its heterocyclic derivatives – 1,3,4-thiadiazole and 1,2,4-triazole are described; the modification of proper 1,2,4-triazole derivative by maleimides is also presented. Spectral properties of the prepared compounds and X-ray analysis for the selected compounds were studied. For the compounds antitrypanosomal potential and the toxicity were determined.     

Isomorphisms of Some Complex Poisson Brackets

Given a complex manifold M_i, structures of Poisson algebras on (M_i)=C(M_i,C) which are associated with a nondegenerate -closed (2,0)-form _i on M_i are considered. It is shown that every isomorphism of Poisson structures (M₁) (M₂) is generated by a biholomorphic map :M₂ M₁ such that ₂ = *₁     

Helical rosette nanotubes with tunable stability and hierarchy

The design of nanostructured materials with tunable dimensions and properties that maintain their structural integrity under physiological conditions is a major challenge in biomedical engineering and nanomedicine. Helical rosette nanotubes (HRN) are a new class of materials produced through a hierarchical self-assembly process of low molecular weight synthetic organic modules in water. Here, we describe a synthetic strategy to tune their stability and hierarchy by preorganization of the self-assembling units, control of net charge per unit of nanotube surface area, amphiphilicity, and number of H-bonds per self-assembling module, and through peripheral steric (de)compression. Using these criteria, HRNs with tunable stability and hierarchical architecture were produced from self-assembling modules that (a) persist as individual molecules in solution, (b) self-assemble into HRN but denature at high temperature (<85 degrees C), (c) self-assemble into HRN whose structural integrity persists even in boiling water (>95 degrees C), and (d) self-assemble into well-dispersed short nanotubes, long nanotubes, ribbons, or superhelices. Given the biocompatibility, synthetic accessibility, and chemical and physical tunability of these materials, numerous applications in biomedical engineering, materials science, and nanoscience and technology are envisioned.