New gamma rays following the233U α-decay

²³³U -decay was reinvestigated using a radiochemically purified source and high efficiency HPGe coaxial detectors; the lowenergy -spectrum was also measured using a LEPS detector. The energy and intensity values of one hundred sixty three -lines were determined, from which forty eight are newly reported with respect to the last study of Canty et al. A revised²²⁹Th level scheme was built, using the Ritz combination principle, in which nine levels are newly observed, at 371.3, 381.8, 465.5, 569.2, 584.9, 605.1, 620.8, 656.9 and 749.9 keV.     

Thermodynamics of the URuC system

Thermodynamic measurements by the electromotive force method were made on the binary intermetallic phases URu₃ and U₃Ru₅ and on the ternary carbides URu₃C_0.7 and U₂RuC₂ of the URu and the URuC systems between 950 and 1200 K using galvanic cells with CaF₂ single crystal electrolytes: U, UF₃¦CaF₂¦UF₃, URu₃, Ru; U, UF₃¦CaF₂¦UF₃, U₃Ru₅, URu₃; Ru, URu₃, UF₃¦CaF₂¦UF₃, URu₃C_0.7, Ru, C; U, UF₃¦CaF₂¦UF₃, URu₃C_0.7, U₂RuC₂, C. The Gibbs energies of formation of URu₃, U₃Ru₅, URu₃C_0.7 and U₂RuC₂ were evaluated from the measured electromotive force which give ^fΔG^o〈URu₃〉 = −199 100 + 35.9 T J mol^−1fΔG^o〈U₃Ru₅〉 = −398 600 + 43.6 T J mol^−1fΔG^o〈URu₃C_0.7〉 = −192 600 + 2.5 T J mol^−1fΔG^o〈U₂RuC₂〉 = −380 200 + 52.5 T J mol⁻¹ The implications of these thermodynamic data for the behaviour of the fission product ruthenium in irradiated carbide fuels are discussed.     

[U(bipy)4]: A Mistaken Case of U0?

After more than 50 years, the synthesis and electronic structure of the first and only reported “U⁰ complex” [U(bipy)₄] ( 1 ) has been reinvestigated. Additionally, its one‐electron reduced product [Na(THF)₆][U(bipy)₄] ( 2 ) has been newly discovered. High resolution crystallographic analyses combined with magnetic and computational data show that 1 and its derivative 2 are best described as highly reduced species containing mid‐to‐high‐valent uranium ligated by redox non‐innocent ligands.     

Do collective atomic fluctuations account for cooperative effects? Molecular dynamics studies of the U1A-RNA complex

A complete understanding of gene expression relies on a comprehensive understanding of the protein-RNA recognition process. However, the study of protein-RNA recognition is complicated by many factors that contribute to both binding affinity and specificity, including structure, energetics, dynamical motions, and cooperative interactions. Several recent studies have suggested that energetic coupling between residues contributes to formation of the complex between the U1A protein and stem loop 2 of U1 snRNA as a consequence of a cooperative network of interactions. We have performed molecular dynamics simulations on the U1A-RNA complex, including explicit water and counterions, and analyzed the results based on the calculated positional cross-correlations of atomic fluctuations. The results indicate that cross-correlations calculated on a per residue basis agree well with the observed inter-residue cooperativity and predict that the networks identified to date may also be coupled into an extensive hyper-network that reflects the intrinsic rigidity of the RNA recognition motif. In addition, we report a comparison of the MD calculated correlations with the results of a positional covariance analysis based on the sequences of 330 RNA recognition motifs, including U1A. The calculated inter-residue cross-correlations agree very well with the results of the sites exhibiting positional covariance. Collectively, these results strongly support the hypothesis that collective fluctuations contribute to cooperativity and the corresponding observed thermodynamic coupling. Predictions of additional sites in U1A that may be involved in cooperative networks are advanced.     

Self-sorting: the exception or the rule?

In this paper, we pose the question of whether self-sorting in designed systems is exceptional behavior or whether it is likely to become a more general phenomenon governing molecular recognition and self-assembly. To address this question we prepared a mixture comprising two of Davis' self-assembled ionophores, Rebek's tennis ball and calixarene tetraurea capsule, Meijer's ureidopyrimidinone, Reinhoudt's calixarene bis(rosette), and two molecular clips in CDCl(3) solution and observed the behavior of this ensemble by (1)H NMR. As hypothesized, high-fidelity self-sorting behavior was observed. The influence of several key variables-temperature, concentration, equilibrium constants, and the presence of competitors-on the fidelity of self-sorting is described. These results show that self-sorting is neither the exception nor the rule. They suggest, however, that the subset of known molecular aggregates that exceed the criteria required for thermodynamic self-sorting is larger than previously appreciated and potentially quite broad.     

Refinement of the α-U4O9 crystalline structure: new insight into the U4O9 → U3O8 transformation

The oxidation reaction of UO(2) into U(3)O(8) is studied as a function of the crystalline distortion of interstitial oxygen clusters, named cuboctahedra, which appear in U(4)O(9) and U(3)O(7) intermediate phases. For that purpose, the refinement of α-U(4)O(9) was performed because this phase undergoes a trigonal distortion from cubic β-U(4)O(9) when the temperature is decreased. In α-U(4)O(9), the cuboctahedra can be described as crumpled sheets taken from a fragment of U(3)O(8). The manner by which the accumulation of crumpled sheets can lead to the formation of U(3)O(8) is discussed.     

Does the topological approach characterize the hydrogen bond?

 The topological analysis of the electron localization function has been applied to complexes representative of the weak, medium and strong hydrogen bond. For both the weak and the medium hydrogen bonds, the number of basins in the complexes is the sum of those of the moieties. In this case, the formation of a weak or a medium hydrogen-bonded complex does not involve a chemical reaction. In the weak hydrogen bond case, the reduction of the localization domain yields two domains in the first step, which can be partitioned afterwards into valence and core domains. In contrast, for medium complexes the core–valence separation is the first event which occurs during the reduction process and therefore the complex should be considered as a single molecular species. Moreover, the analysis of the basin population variance indicates in this case a noticeable delocalization between the V(A, H) and V(B) basins. Finally, the symmetrical strong hydrogen bond has a protonated basin V(H) at the bond midpoint. Such a topology corresponds to an incomplete proton transfer and to a rather covalent bond. Received: 19 April 1999 / Accepted: 22 July 1999 / Published online: 17 January 2000     

What is the structure of the RecA-DNA filament?

The bacterial RecA protein has been a model system for understanding how a protein can catalyze homologous genetic recombination. RecA-like proteins have now been characterized from many organisms, from bacteriophage to humans. Some of the RecA-like proteins, including human RAD51, appear to function as helical filaments formed on DNA. However, we currently have high resolution structures of inactive forms of the protein, and low resolution structures of the active complexes formed by RecA-like proteins on DNA in the presence of ATP or ATP analogs. Within a crystal of the E. coli RecA protein, a helical polymer exists, and it has been widely assumed that this polymer is quite similar to the active helical filament formed on DNA. Recent developments have suggested that this may not be the case.     

Is the Chandler Period Stable?

The problem on the Chandler period is an unsolved one. Several authors suggested a hypothesis that the Chandler wobble is only one free period which slightly changes in time and is amplitude-dependent. In this paper, we shall examine the hypothesis more rigorous than that which has been carried yet. A new deconvolution method for Fourier transform is suggested. Using this method, the polar motion data since 1900 are analysed and the varying process of the Chandlerian period and amplitude are given. The analytical results show that the Chandler period is not stable and is indeed amplitude-dependent. The probable explanation for this phenomenon is that it might be caused by non-equilibrium response of the ocean.     

Is the HCCS radical linear in the excited state?

The A (2)Pi-X (2)Pi 415 nm band system of the linear HCCS radical has been known since 1978, but the vibronic structure in this complex spectrum, which has both spin-orbit and Renner-Teller complications, has never been satisfactorily assigned, despite serious experimental and theoretical efforts. In a further attempt to understand the spectrum, we have studied the laser-induced fluorescence spectra of jet-cooled HCCS and DCCS, produced from thiophene precursors using the discharge jet technique. The 0(0) (0) bands of HCCS and DCCS have been rotationally analyzed, providing precise ground and excited state spin-orbit splittings. The energy levels of the v(')=0 (2)Pi(3/2) component of DCCS are found to be perturbed by a very low-lying (2)Sigma vibronic level, indicating that the HCC bending mode Renner-Teller effect is much larger than predicted by ab initio calculations with a linear excited state geometry. With this observation, the vibronic bands in the spectra of both isotopomers have been consistently assigned for the first time. Model calculations show that the large Renner-Teller effect and substantially different HCCS and DCCS excited state zero-point spin-orbit splittings can be explained with the assumption of a quasilinear excited state geometry.     

Where is the road to bio-water-saving for the globe?

The First International Conference on the Theory and Practices in Bio-water-saving (ICTPB) was held from May 21 to 25, 2006 in Beijing, China. This indicated that the work related to this hot topic on the globe has been paid more attention to. Most progress in this field has been presented from near 300 participating people worldwide, who were meeting together to discuss about the theory and practices of water-saving biology and how to serve global agricultural and ecological sustainable development. The work related to bio-water-saving has been involved in different scales and soil–plant root biointerfaces. On the basis of this background and in combination with the work from our laboratory and the center, we provided some ideas for global bio-water-saving in this paper, sharing the achievement in this field and advocating true bio-water-saving for the world and promoting the pace of global bio-water-saving.     

How to revise the GUM?

The announcement of a revision of the Guide to the expression of uncertainty in measurement has renewed the debate about the topic of measurement uncertainty. In this paper the author, chairman of Working Group 1 of the Joint Committee for Guides in Metrology, replies to the theses given in two recent papers by Semion Rabinovich. His opinions are personal, and are not necessarily shared by the JCGM/WG1. They are to be intended as a further contribution to the present discussion. Papers published in this section do not necessarily reflect the opinion of the Editors, the Editorial Board and the Publisher.     

Is the Cassie-Baxter formula relevant?

The utility of the Cassie-Baxter formula to predict the apparent contact angle of a drop on rough hydrophobic surfaces has been questioned recently. To resolve this issue, experimental and numerical data for advancing and receding contact angles are reported. In all cases considered it is seen that contact angles follow the overall trend of the Cassie-Baxter formula, except for the advancing front on pillar type roughness. It is shown that deviations from the Cassie-Baxter angle have a one-to-one correlation with microscopic distortions of the contact line with respect to its configuration in the Cassie-Baxter state.     

Why are hexavalent uranium cyanides rare while U–F and U–O bonds are common and short?

Relativistic small-core pseudopotential B3LYP and CCSD(T) calculations and frozen-core PW91–PW91 studies are reported for the series UF ₄X ₂ ( X=H, F, Cl, CN, NC, NCO, OCN, NCS and SCN). The bonding in UF ₆ is analyzed and found to have some multiple-bond character, approaching at a theoretical limit a bond order of 1.5. In addition to these s and p orbital interactions, the electrostatic attraction is important. Evidence for p bonding in the other systems studied was also found. The triatomic pseudohalides as well as fluorine and chlorine are in this sense better ligands than cyanide. The –CN group is a s donor and p acceptor, as uranium itself, and hence is unfit to bond to U(VI). The s-bonded UH ₆ is octahedral.