Hydrogenation of carbon monoxide by ruthenium complexes with iodide promoters: catalytic and mechanistic investigations

Carbon monoxide and hydrogen are converted into organic products, including methanol, ethylene glycol, and ethanol, by halide-promoted ruthenium catalysts in organic solvents. Iodide salts are exceptionally good promoters for this system. Spectroscopic and reaction studies have shown that two ruthenium complexes, HRu₃(CO)₁₁^? and Ru(CO)₃I₃^?, are present during catalysis and essential for optimum activity. Possible roles for the involvement of these complexes in catalysis are considered.     

Interligand interactions controlling the mu-N7,N9-metal bonding of adenine (AdeH) to the N-benzyliminodiacetato(2-) copper(II) chelate and promoting the N9 versus N3 tautomeric proton transfer: molecular and crystal structure of [Cu2(NBzIDA)(2)(H2O)(2)(mu-N7,N9-Ade(N3)H)].(3)H2O

The reaction in water of the N-benzyliminodiacetate-copper(II) chelate ([Cu(NBzIDA)]) and the adenine:thymine base pair complex (AdeH:ThyH) with a Cu/NBzIDA/AdeH/ThyH molar ratio of 2:2:1:1 yields [Cu(2)(NBzIDA)(2)(H(2)O)(2)(mu-N7,N9-Ade(N3)H)].3H(2)O and free ThyH. The compound has been studied by thermal, spectral, and X-ray diffraction methods. In the asymmetric dinuclear complex units both Cu(II) atoms exhibit a square pyramidal coordination, where the four closest donors are supplied by NBzIDA in a mer-tridentate conformation and the N7 or N9 donors of AdeH, which is protonated at N3. The mu-N7,N9 bridge represents a new coordination mode for nonsubstituted AdeH, except for some adeninate(1-)-[methylmercury(II)] derivatives studied earlier. The dinuclear complex is stabilized by the Cu-N7 and Cu-N9 bonds and N6-H(exocyclic)...O(carboxyl) and N3-H(heterocyclic)...O(carboxyl) interligand interactions, respectively. The structure of the new compound differs from that of the mononuclear compound [Cu(NBzIDA)(Ade(N9)H)(H(2)O)].H(2)O, in which the unusual Cu-N3(AdeH) bond is stabilized by a N9-H...O(carboxyl) interligand interaction and where alternating benzyl-AdeH intermolecular pi,pi-stacking interactions produce infinite stacked chains. The possibility for ThyH to be involved in the molecular recognition between [Cu(NBzIDA)] and the AdeH:ThyH base pair is proposed.     

Statistical mechanical theory of liquid entropy

The multiparticle correlation expansion for the entropy of a classical monatomic liquid is presented. This entropy expresses the physical picture in which there is no free particle motion, but, rather, each atom moves within a cage formed by its neighbors. The liquid expansion, including only pair correlations, gives an excellent account of the experimental entropy of most liquid metals, of liquid argon, and of the hard-sphere liquid. The pair correlation entropy is well approximated by a universal function of temperature. Higher-order correlation entropy, due to n-particle irreducible correlations for n ≥ 3, is significant in only a few liquid metals, and its occurrence suggests the presence of n-body forces. When the liquid theory is applied to the study of melting, we discover the important classification of normal and anomalous melting, according to whether there is not or is a significant change in the electronic structure upon melting, and we discover the universal disordering entropy for melting of a monatomic crystal. Interesting directions for future research are extension to include orientational correlations of molecules, theoretical calculation of the entropy of water, application to the entropy of the amorphous state, and correlational entropy of compressed argon. We clarify the relation among different entropy expansions in the recent literature. © 1994 John Wiley & Sons, Inc.     

Leptonic decays of the Ω−

Branching ratios, widths, and lepton energy spectra are derived for the leptonic decays of the $\text{Ω}{}^{\mathrm{?}}$ into β⁰ and $\text{β}{}^{01}$. The calculations are made by hypothesizing that higher-order multipoles in an expansion of the baryon current are zero. The axial vector coupling is determined using the bag model.     

Measurement of the fragmentation of hadronic systems of different flavour and colour selected by lepton pairs

A lepton-pair trigger was used to select a hadronic system in different flavour and colour states: properties of the transformation of this system into hadrons were measured in terms of charge flow, multiplicity distribution, and fragmentation function. It is observed that, while the effects of flavour are clearly seen, the colour degrees of freedom are not observed in the region of low p_T.     

Synthesis of novel iodo derived bicalutamide analogs

A series of optically active nonsteroidal selective androgen receptor modulators with structures analogous to bicalutamide was prepared by replacing the trifluoromethyl group with iodine and the sulfonyl linker by oxygen.     

An automated instrument for human STR identification: design, characterization, and experimental validation

The microfluidic integration of an entire DNA analysis workflow on a fully integrated miniaturized instrument is reported using lab‐on‐a‐chip automation to perform DNA fingerprinting compatible with CODIS standard relevant to the forensic community. The instrument aims to improve the cost, duration, and ease of use to perform a “sample‐to‐profile” analysis with no need for human intervention. The present publication describes the operation of the three major components of the system: the electronic control components, the microfluidic cartridge and CE microchip, and the optical excitation/detection module. Experimental details are given to characterize the level of performance, stability, reliability, accuracy, and sensitivity of the prototype system. A typical temperature profile from a PCR amplification process and an electropherogram of a commercial size standard (GeneScan 500?, Applied Biosystems) separation are shown to assess the relevance of the instrument to forensic applications. Finally, we present a profile from an automated integrated run where lysed cells from a buccal swab were introduced in the system and no further human intervention was required to complete the analysis.     

A Teacher’s Conception of Definition and Use of Examples When Doing and Teaching Mathematics

To contribute to an understanding of the nature of teachers’ mathematical knowledge and its role in teaching, the case study reported in this article investigated a teacher’s conception of a metamathematical concept, definition, and her use of examples in doing and teaching mathematics. Using an enactivist perspective on mathematical knowledge, the authors give an account of the case of Lily, a prospective, then beginning, teacher who conceived of mathematical definition as an object with particular form and function and engaged in purposeful, specialized use of examples when doing and teaching mathematics. Lily’s case illustrates how a teacher’s interpretation of examples (as exemplifications or single instances) and conception of the form and function of definitions can influence her doing and teaching mathematics. An implication is that teacher preparation should foster teachers’ abilities to use examples purposefully to provide students with rich opportunities to engage in mathematical processes such as defining.     

NMR spectroscopic characterization of new 2,3‐dihydro‐1,3,4‐thiadiazole derivatives

The ¹H and ¹³C NMR resonances of twenty‐seven 2,2‐dimethyl‐5‐(2‐nitrophenyl‐5‐substituted)‐2,3‐dihydro‐1,3,4‐thiadiazoles, and twenty‐seven 3‐acyl‐5‐(2‐amino‐5‐substituted)‐2,2‐dimethyl‐2,3‐dihydro‐1,3,4‐thiadiazoles were assigned completely using the concerted application of one‐dimensional and two‐dimensional experiments (DEPT, HMQC and HMBC). NOESY experiments, X‐ray crystallography and conformational analysis confirm the preferred conformation of these compounds. Copyright © 2012 John Wiley & Sons, Ltd.