Quencing of perylene fluorescence by Ag+ ions via exciplex formation

The fluorescence of perylene in alcoholic solution is dynamically quenched by AgClO₄ resulting in a new emission band with its maximum around 480 nm. Analysis of fluorescence decay curves at various emission wavelengths proves the formation of a perylene/Aa⁺ ion exciplex in the quenching reaction.     

A spectroscopic and thermoanalytical study of the mineral hoganite

A comprehensive spectroscopic analysis consisting of Raman, infrared (IR) and near infrared (NIR) spectroscopy was undertaken on the newly discovered mineral hoganite (copper(II) acetate monohydrate (Cu(CH(3)COO)(2) x H(2)O)). Assignments of vibrational bands due to the acetate anion have been made in all three forms of spectroscopy. Thermal analysis of the mineral was undertaken to follow its decomposition under a nitrogen atmosphere. Two major mass loss steps at 90 and approximately 220 degrees C were revealed. These mass losses correspond very well to firstly, the loss of a single water molecule, and then the loss of the acetate anion which quickly decomposes to form carbon dioxide and water.     

Factors affecting the market penetration of biomass-derived liquid transportation fuels

Applied Biochemistry and Biotechnology - The market for liquid transportation fuels in the United States is about 610×109 L (160×109 gal) annually, with gasoline accounting for about...     

Single-particle tracking of janus colloids in close proximity

We describe algorithms and an experimental method based on differential interference contrast microscopy to discriminate optically anisotropic colloidal spheres under situations where diffraction owing to their close proximity causes overlapping images. The data analysis is applied to modulated optical nanoprobes (MOONs) that are coated with metal on one hemisphere. These methods enable single-particle tracking of rotation in addition to translation not only in concentrated suspensions but also in dilute suspensions when particles come into transient hydrodynamic contact. An illustrative example is given.     

A re-investigation of [Fe(L-cysteinate)2(CO)2]2-: an example of non-heme CO coordination of possible relevance to CO binding to ion channel receptors

[Fe(L-cysteinate)(2)(CO)(2)](2-) is a CO releasing molecule which has low cytotoxicity to RAW264.7 macrophages. It provides an example of CO binding using ligands available to ion channels which use CO as a signalling molecule in the absence of heme. Previous work has shown that this compound consists of five isomers and it was proposed that the two isomers with trans-dicarbonyls are dominant. In this work the isomers are re-assigned and shown to be capable of releasing CO, albeit too slowly to act as a signalling receptor. It is shown that by linking the two L-cysteines together to form [Fe(SCH(2)CH{CO(2)H}NHCH(2))(2)(CO)(2)], only one isomer is isolated.     

Stereoselective alkylation of tartrate derivatives. A concise route to (+)-O-methylpiscidic acid and natural analogues

The lithium enolate of (2S,3S,5S,6S)-dimethoxy-2,3-dimethyl-1,4-dioxane-5,6-dithiocarboxylate undergoes stereoselective mono- and/or dialkylations to afford two new stereogenic centers. The alkylation products obtained possessed a cis stereochemistry, which was confirmed by the synthesis of natural 4'-O-methylpiscidic acid dimethyl ester .     

Hydroxamic acid polymers. II. Design of a polymeric chelating agent for iron

The iron chelating ability of hydroxamic acid polymers was studied as a function of the atomic chain spacing separating neighboring hydroxamic acid units. Two polymers were prepared, one having the hydroxamic acid group separated by 11 atoms and the other by three atoms. The iron binding of these polymers was compared with the model compound desferrioxamine B (DFO) and with a previously prepared polymer having a nine-atom spacing. Mole ratio plots indicated the following order of stability: DFO ≈ 11 atom > 9 atom > 3 atom. These results are in accordance with the picture derived from molecular models which shows that with a spacing of 11 atoms, three neighboring hydroxamic acids can fit the octahedral arrangement of the iron (III) complex without appreciable strain. Some strain is introduced when the spacing becomes only nine atoms, and with three atoms, complex formation between three neighboring groups becomes virtually impossible.     

Posaconazole (Noxafil, SCH 56592), a new azole antifungal drug, was a discovery based on the isolation and mass spectral characterization of a circulating metabolite of an earlier lead (SCH 51048)

Posaconazole (SCH 56592) is a novel triazole antifungal drug that is marketed in Europe and the United States under the trade name 'Noxafil' for prophylaxis against invasive fungal infections. SCH 56592 was discovered as a possible active metabolite of SCH 51048, an earlier lead. Initial studies have shown that serum concentrations determined by a microbiological assay were higher than those determined by HPLC from animals dosed with SCH 51048. Subsequently, several animals species were dosed with (3)H-SCH 51048 and the serum was analyzed for total radioactivity, SCH 51048 concentration and antifungal activity. The antifungal activity was higher than that expected based on SCH 51048 serum concentrations, confirming the presence of active metabolite(s). Metabolite profiling of serum samples at selected time intervals pinpointed the peak that was suspected to be the active metabolite. Consequently, (3)H-SCH 51048 was administered to a large group of mice, the serum was harvested and the metabolite was isolated by extraction and semipreparative HPLC. LC-MS/MS analysis suggested that the active metabolite is a secondary alcohol with the hydroxyl group in the aliphatic side chain of SCH 51048. All corresponding monohydroxylated diastereomeric mixtures were synthesized and characterized. The HPLC retention time and LC-MS/MS spectra of the diastereomeric secondary alcohols of SCH 51048 were similar to those of the isolated active metabolite. Finally, all corresponding individual monohydroxylated diasteriomers were synthesized and evaluated for in vitro and in vivo antifungal potencies, as well as pharmacokinetics. SCH 56592 emerged as the candidate with the best overall profile.     

NO-releasing zeolites and their antithrombotic properties

Transition metal-exchanged zeolite-A adsorbs and stores nitric oxide in relatively high capacity (up to 1 mmol of NO/g of zeolite). The stored NO is released on contact with an aqueous environment under biologically relevant conditions of temperature and pH. The release of the NO can be tuned by altering the chemical composition of the zeolite, by controlling the amount of water contacting the zeolite, and by blending the zeolite with different polymers. The high capacity of zeolite for NO makes it extremely attractive for use in biological and medical applications, and our experiments indicate that the NO released from Co-exchanged zeolite-A inhibits platelet aggregation and adhesion of human platelets in vitro.