Quantum mechanical study of the nonbonded forces in water-methanol complexes

The water-methanol dimer can adopt two possible configurations (WdM or MdW) depending on whether the water or the methanol acts as the hydrogen bond donor. The relative stability between the two configurations is less than 1 kcal/mol, and as a result, this dimer has been a challenging system to investigate using either theoretical or experimental techniques. In this paper, we present a systematic study of the dependence of the geometries, interaction energies, and harmonic frequencies on basis sets and treatment of electron correlation for the two configurations. At the highest theory level, MP2/aug-cc-pVQZ//MP2/aug-cc-pVTZ, interaction energies of -5.72 and -4.95 kcal/mol were determined for the WdM and MdW configurations, respectively, after correcting for basis set superposition error using the Boys-Bernardi counterpoise scheme. Extrapolating to the complete basis set limit resulted in interaction energies of -5.87 for WdM and -5.16 kcal/mol for MdW. The energy difference between the two configurations is larger than the majority of previously reported values, confirming that the WdM complex is preferred, in agreement with experimental observations. The effects that electron correlation have on the geometry were investigated by performing optimization at the MP2(full), MP4, and CCSD levels of theory. The approach trajectories for the formation of each dimer configuration are presented and the importance of these trajectories in the development of parameters for use in classical force fields is discussed.     

Synthesis of oligopyridines and their metal complexes as precursors to topological stereoisomers

[structure: see text]. Palladium-based carbon-carbon coupling reactions in sequence with halogen-exchange chemistry on a series of heterocycles lead to an efficient synthetic strategy for oligopyridines that bind metal ions such as ruthenium to form coordination racks. The particular structures are designed to form terpyridine subunits for octahedral binding. Reaction of 4,6-diiodopyrimidine produces a "double-bay" terpyridine from which binuclear coordination complexes have been formed.     

Homodyne and heterodyne imaging through a scattering medium

We introduce a novel two-dimensional (2D) homodyne and heterodyne technique for imaging objects through or embedded in a scattering medium. Our imaging approach is based on heterodyning of light with different Doppler broadenings that is scattered from objects of two different textures or from an opaque object and a textured scattering medium. We report on the initial demonstration of pulling signals out of noise for an object hidden behind a scattering medium. Enhancements of signal-to-noise ratio of the order of 50 have been achieved by use of a 2D holographic phase-sensitive detector. We also discuss the experimental feasibility of this approach for objects embedded in a scattering medium.     

Direct investigation of superparamagnetism in Co nanoparticle films

A direct probe of superparamagnetism was used to determine the complete anisotropy energy distribution of Co nanoparticle films. The films were composed of self-assembled lattices of uniform Co nanoparticles of 3 or 5 nm in diameter, and a variable temperature scanning-SQUID microscope was used to measure temperature-induced spontaneous magnetic noise in the samples. Accurate measurements of anisotropy energy distributions of small volume samples will be critical to magnetic optimization of nanoparticle devices and media.     

Economy of proficiency testing: reference versus consensus values

Many proficiency tests are operated with a consensus value derived from the participants’ results. Apart from technical issues, one of the reasons often mentioned is that proficiency tests operated with consensus values would be cheaper than those using reference values obtained from a priori characterisation measurements. The economy of a proficiency test must of course be balanced by the need of the participants, and the quality of the comparison in general. The proficiency tests selected in this study had both a reference value and a consensus value, one of which was used for assessing the performance of the participating laboratories. In this work, both a technical and an economical assessment of how the comparisons were operated is made. From the evaluation, it follows that usually the use of consensus values does not necessarily reduce the costs of a proficiency test. However, frequently it may be observed that the quality of the assessment of the laboratories is better with a reference value. Received: 11 October 2000 Accepted: 3 January 2001     

Towards the stable chelation of radium for biomedical applications with an 18-membered macrocyclic ligand

Targeted alpha therapy is an emerging strategy for the treatment of disseminated cancer. [²²³Ra]RaCl₂ is the only clinically approved alpha particle-emitting drug, and it is used to treat castrate-resistant prostate cancer bone metastases, to which [²²³Ra]Ra²⁺ localizes. To specifically direct [²²³Ra]Ra²⁺ to non-osseous disease sites, chelation and conjugation to a cancer-targeting moiety is necessary. Although previous efforts to stably chelate [²²³Ra]Ra²⁺ for this purpose have had limited success, here we report a biologically stable radiocomplex with the 18-membered macrocyclic chelator macropa. Quantitative labeling of macropa with [²²³Ra]Ra²⁺ was accomplished within 5 min at room temperature with a radiolabeling efficiency of >95%, representing a significant advancement over conventional chelators such as DOTA and EDTA, which were unable to completely complex [²²³Ra]Ra²⁺ under these conditions. [²²³Ra][Ra(macropa)] was highly stable in human serum and exhibited dramatically reduced bone and spleen uptake in mice in comparison to bone-targeted [²²³Ra]RaCl₂, signifying that [²²³Ra][Ra(macropa)] remains intact in vivo. Upon conjugation of macropa to a single amino acid β-alanine as well as to the prostate-specific membrane antigen-targeting peptide DUPA, both constructs retained high affinity for ²²³Ra, complexing >95% of Ra²⁺ in solution. Furthermore, [²²³Ra][Ra(macropa-β-alanine)] was rapidly cleared from mice and showed low ²²³Ra bone absorption, indicating that this conjugate is stable under biological conditions. Unexpectedly, this stability was lost upon conjugation of macropa to DUPA, which suggests a role of targeting vectors in complex stability in vivo for this system. Nonetheless, our successful demonstration of efficient radiolabeling of the β-alanine conjugate with ²²³Ra and its subsequent stability in vivo establishes for the first time the possibility of delivering [²²³Ra]Ra²⁺ to metastases outside of the bone using functionalized chelators, marking a significant expansion of the therapeutic utility of this radiometal in the clinic.

The therapeutic alpha-emitter ²²³Ra can be stably complexed in vivo, creating opportunities for the development of targeted radiopharmaceutical agents with this radionuclide.     

Frequency and development of slugs in a horizontal pipe at large liquid flows

The generation of slugs was studied for air–water flow in horizontal 0.0763 m and 0.095 m pipes. The emphasis was on high liquid rates (u_LS ? 0.5 m/s) for which slugs are formed close to the entry and the time intervals between slugs are stochastic. A “fully developed” slug flow is defined as consisting of slugs with different sizes interspersed in a stratified flow with a height slightly larger than the height, h₀, needed for a slug to be stable. Properties of this “fully developed” pattern are discussed. A correlation for the frequency of slugging is suggested, which describes our data as well as the data from other laboratories for a wide range of conditions. The possibility is explored that there is a further increase of slug length beyond the “fully developed” condition because slugs slowly overtake one another.     

The biaxial loading response of powder aluminum at elevated temperature

Nuclear fuel can be fabricated using powder-metallurgy processes by compacting uranium-oxide powder with aluminum powder to form a cermet and then extruding the cermet to form fuel tubes. This method of production allows greater control of uranium-oxide particle size and distribution in the tube, making the production of fuel with greater concentrations of uranium oxide possible, and thus decreasing the volume of radioactive waste remaining after the fuel is spent. As the concentration of uranium oxide increases, however, there is an increase in failures during extrusion. To address this problem, an experimental procedure was developed to examine the response of powder aluminum, a material with a structure similar to that of the cermet fuel, to biaxial loadings such as those experienced during extrusion. Biaxial loadings can be varied from pure shear to simple tension or compression, or to combinations of these loadings in a numerically controlled ‘tension-torsion’ testing machine. Data obtained using this system were used to develop a model for the post-yield behavior in extruded powder aluminum which includes information derived both from the macroscopic stress-strain behavior of 1100 aluminum and extruded powder aluminum and from the observed microscopic structure of the extruded powder aluminum. This paper describes the development of the experimental system and shows the different biaxial mechanical behavior of the two materials. Test fixtures were developed and software was written to control constant strain-rate tension, compression, torsion, combined tension-torsion, and combined compression-torsion tests performed using a computer-controlled MTS biaxial testing machine. Extruded powder aluminum and 1100 aluminum specimens were tested at 427°C, the powder-aluminum extrusion temperature, under those loading conditions. Each specimen was subjected to only one loading cycle. Data were recorded during loading only. Tested specimens were also sectioned and examined microscopically.     

Mendeleev,the man and his matrix: Dmitri Mendeleev,aspects of his life and work: was he a somewhat fortunate man?

This article traces the life of Russian chemist Dmitri Mendeleev from childhood in Siberia, through education and training to become the first formulator of the Periodic Table, the logo of chemistry. His unique contribution is described and analysed; what factors helped him be the first formulator? What did he do after making his most famous discovery? In addition the article peeps into his personal life, his dealings with his family and the authorities. Finally we look at honours he received in later life.