Solid-supported syntheses of 3-thio-1,2,4-triazoles

Two solid-supported synthesis strategies for the preparation of 3-thio-1,2,4-triazoles are described. In the first, Rink amide resin is combined with Fmoc-protected ω-amino acids, acid hydrazides, and alkyl halides to provide diverse sets of starting materials from which numerous triazoles may be prepared. The second employs t-alkylcarbamateresin (Boc resin) which permits the use of additional pools of starting materials, including isothiocyanates and α- and ω-amino esters, resulting in triazoles with patterns of functional groups that are not possible from the initial route. The combination of multiple resins and resin attachment sites allows the preparation of a diverse library based upon the3-thio-1,2,4-triazole scaffold and avoids the pitfallof having a single linker functionality present at the same position in all library members. General synthetic procedures and representative products from each route are presented. A similarity analysis of representative sublibraries from each synthesis strategy concludes that variation of the solid-phase linker chemistry and attachment site can enhance molecular diversity of the combined triazole library. This revised version was published online in August 2006 with corrections to the Cover Date.     

Aggregation and settling in aqueous polydisperse alumina nanoparticle suspensions

Nanoparticle suspensions (also called nanofluids) are often polydisperse and tend to settle with time. Settling kinetics in these systems are known to be complex and hence challenging to understand. In this study, polydisperse spherical alumina (Al₂O₃) nanoparticles in the size range of ~10–100 nm were dispersed in water and examined for aggregation and settling behaviour near its isoelectric point. A series of settling experiments were conducted and the results were analysed by photography and by small angle X-ray scattering (SAXS). The settling curve obtained from standard bed height measurement experiments indicated two different types of behaviour, both of which were also seen in the SAXS data. But the SAXS data were remarkably able to pick out the rapid settling regime as a result of the high temporal resolution (10 s) used. By monitoring the SAXS intensity, it was further possible to record the particle aggregation process for the first time. Optical microscopy images were produced on drying and dried droplets extracted from the suspension at various times. Dried deposits showed the rapid decrease in the number of very large particles with time which qualitatively validates the SAXS prediction, and therefore its suitability as a tool to study unstable polydisperse colloids.     

A simple and rapid hydride generation—atomic absorption method for the determination of arsenic in biological,environmental and geological samples

An inexpensive 50-ml disposable (hypodermic) syringe is used as the arsine generation vessel. The arsine is passed into a 10-cm long. 10-mm i.d. electrically heated silica tube atomizer with nitrogen carrier gas. Excess of hydrogen is burned off in a hydrogen diffusion flame at the ends of the tube. Samples containing appreciable silica are fused with KOH—MgO_XXX while organic samples are digested with H₂SO₄—H₂O₂. Parameters affecting the determination of arsenic as arsine have been investigated. Collaborative results on a variety of standard reference materials agree well with literature values. The advantages of the proposed method are that it is sensitive, selective, fast, simple, inexpensive, precise and accurate.     

Monitoring free silanols on reversed-phase supports with peptide standards

Summary A series of synthetic peptide HPLC standards has been designed for use in monitoring free silanols on silica-based reversed-phase supports. The four standards (+ 1 to + 4 net charge) showed great versatility in monitoring silanol activity over a pH range of 2.0 to 7.0. We have developed a silanol monitoring system based on the sensitivity of the standards to ionic interactions with reversed-phase packings at pH 7.0. This monitoring procedure involves chromatographing the peptides at pH 7.0 with a combined acetonitrile and sodium perchlorate linear AB gradient and is generally applicable to reversed-phase packings exhibiting a wide range of silanol concentrations. These standards not only demonstrate the presence and extent of free silanols, they also allow the researcher to determine what changes must be made to the mobile phase composition to minimize ionic interactions. In addition, the standards, in conjunction with the double gradient monitoring system at pH 7.0, will aid researchers and manufacturers in the improvement and development of reversed-phase matrices.     

Mössbauer absorption in some high Tc superconductors:170Yb in YbBa2Cu3O7−x,166Er in ErBa2Cu3O7−x,and57Fe in YBa2Cu3O7−x

For the high T_c compound YbBa₂Cu₃O_7−x, Mossbauer absorption measurements show that magnetic ordering occurs within the Yb³⁺ sublattice at 0.35K (μ_sat=1.7μ_B). For ErBa₂Cu₃O_7−x the Er³⁺ sublattice orders at 0.7K (μ_sat=4μ_B). Measurements on⁵⁷Fe diluted into YBa₂Cu₃O_7−x shows that no ordered magnetic moments exist within the Cu sublattices down to at least 4.2K. Instituto de Fisica, Porto-Alegre, Brasil (supported by CNPq)     

Anomalous surface diffusion of water compared to aprotic liquids in nanopores

1H nuclear magnetic relaxation dispersion experiments show remarkable differences between water and acetone in contact with microporous glass surfaces containing trace paramagnetic impurities. Analyzed with surface relaxation theory on a model porous system, the data obtained for water show that proton surface diffusion limited by chemical exchange with the bulk phase permits long-range effectively one-dimensional exploration along the pores. This magnetic-field dependence coupled with the anomalous temperature dependence of the relaxation rates permits a direct interpretation in terms of the proton translational diffusion coefficient at the surface of the pores. A universal rescaling applied to these data collected for different pore sizes and on a large variety of frequencies and temperatures, supports this interpretation. The analysis demonstrates that acetone diffuses more slowly, which increases the apparent confinement and results in a two-dimensional model for the molecular dynamics close to surface relaxation sinks. Surface-enhanced water proton diffusion, however, permits the proton to explore a greater spatial extent of the pore, which results in an apparent one-dimensional model for the diffusive motions of the water that dominate nuclear spin relaxation.     

Yb Mössbauer and neutron diffraction investigation of the antiferromagnetic phase in the Kondo lattices YbP and YbN

The Kondo lattices YbP and YbN (nonstoichiometric samples) have been investigated by ¹⁷⁰Yb Mössbauer spectroscopy, in the temperature range 0.085 K to 80 K in zero magnetic field in YbN and with an applied magnetic field at T=0.045 K in YbP and YbN, and by neutron diffraction in YbN. In both compounds, the antiferromagnetic transition at T_N0.7 K is first order and occurs through a progressive growth of paramagnetic domains as the temperature increases. The measured exchange interaction is much larger than k_BT_N in both compounds and it is found to be isotropic in YbP and anisotropic in YbN. The saturated magnetic moment in both compounds is reduced by 50% with respect to the value calculated from the crystal field and exchange interactions. These properties are interpreted in terms of the competition between the Kondo effect and the RKKY exchange interaction; using a model mean field NCA calculation to describe the magnetic phase, the Kondo temperatures T_K are found to be near 5–10 K.