The structures of the hydrated lanthanoid(III) ions including lanthanum(III) have been characterized in aqueous solution and in the solid trifluoromethanesulfonate salts by extended X-ray absorption fine structure (EXAFS) spectroscopy. At ambient temperature the water oxygen atoms appear as a tricapped trigonal prism around the lanthanoid(III) ions in the solid nonaaqualanthanoid(III) trifluoromethanesulfonates. Water deficiency in the capping positions for the smallest ions starts at Ho and increases with increasing atomic number in the [Ln(H(2)O)(9-x)](CF(3)SO(3))(3) compounds with x=0.8 at Lu. The crystal structures of [Ho(H(2)O)(8.91)](CF(3)SO(3))(3) and [Lu(H(2)O)(8.2)](CF(3)SO(3))(3) were re-determined by X-ray crystallography at room temperature, and the latter also at 100 K after a phase-transition at about 190 K. The very similar Ln K- and L(3)-edge EXAFS spectra of each solid compound and its aqueous solution indicate indistinguishable structures of the hydrated lanthanoid(III) ions in aqueous solution and in the hydrated trifluoromethanesulfonate salt. The mean Ln--O bond lengths obtained from the EXAFS spectra for the largest ions, La-Nd, agree with estimates from the tabulated ionic radii for ninefold coordination but become shorter than expected starting at samarium. The deviation increases gradually with increasing atomic number, reaches the mean Ln-O bond length expected for eightfold coordination at Ho, and increases further for the smallest lanthanoid(III) ions, Er-Lu, which have an increasing water deficit. The low-temperature crystal structure of [Lu(H(2)O)(8.2)](CF(3)SO(3))(3) shows one strongly bound capping water molecule (Lu-O 2.395(4) A) and two more distant capping sites corresponding to Lu-O at 2.56(1) A, with occupancy factors of 0.58(1) and 0.59(1). There is no indication of a sudden change in hydration number, as proposed in the "gadolinium break" hypothesis.

We describe state-of-the-art experimental techniques using the beamline BM29 of the European Synchrotron Radiation Facility (ESRF). This station exploits the unique characteristics of an ESRF bending magnet source to provide a tunable, collimated, x-ray beam to perform high quality x-ray absorption spectroscopy within the energy range of E=5–75 keV using Si(111), Si(311), and Si(511) crystal pairs. Energy scans can be performed over this wide energy range with excellent reproducibility, stability and resolution, usually better than ΔE/E≃5×10−5. The experimental setup has been exploited to study condensed matter under extreme conditions. We describe here two sample environment devices; the L’ Aquila–Camerino oven for high-temperature studies up to 3000 K in high vacuum and the Paris–Edinburgh press suitable for high-pressure high-temperature studies in the range 0.1–7 GPa and temperatures up to 1500 K. These devices can be integrated in an experimental setup which combines various control and detection systems suitable to perform x-ray absorption spectroscopy, x-ray absorption temperature scans, and energy scanning x-ray diffraction (ESXD). The ESXD setup is based on a scintillator detector behind a fixed angle collimator aligned to the sample. The combination of these three measurements, which can be performed in rapid sequence on the sample during the experiment, provides an essential tool for structural investigations and in situ sample characterization.

The abundant, nuclear‐retained, metastasis‐associated lung adenocarcinoma transcript 1 (MALAT1) has been associated with a poorly differentiated and aggressive phenotype of mammary carcinomas. This long non‐coding RNA (lncRNA) localizes to nuclear speckles, where it interacts with a subset of splicing factors and modulates their activity. In this study, we demonstrate that oncogenic splicing factor SRSF1 bridges MALAT1 to mutant p53 and ID4 proteins in breast cancer cells. Mutant p53 and ID4 delocalize MALAT1 from nuclear speckles and favor its association with chromatin. This enables aberrant recruitment of MALAT1 on VEGFA pre‐mRNA and modulation of VEGFA isoforms expression. Interestingly, VEGFA‐dependent expression signatures associate with ID4 expression specifically in basal‐like breast cancers carrying TP53 mutations. Our results highlight a key role for MALAT1 in control of VEGFA isoforms expression in breast cancer cells expressing gain‐of‐function mutant p53 and ID4 proteins.

The structures of the N,N'-dimethylpropyleneurea (dmpu) solvated lanthanoid(III) ions have been studied in dmpu solution (La-Nd, Sm-Lu) and in solid iodide salts (La-Nd, Sm, Gd-Lu) by extended X-ray absorption fine structure (EXAFS), and single crystal X-ray diffraction (La, Pr, Nd, Gd, Tb, Er, Yb, and Lu); the EXAFS studies were performed on both K and L(III) absorption edges. Because of the space-demanding properties of dmpu upon coordination, dmpu solvated metal ions often show coordination numbers lower than those found in corresponding hydrates and solvates of oxygen donor solvents without steric requirements beyond the size of the donor atom. All lanthanoid(III) ions are seven-coordinate in solution, except lutetium(III) which is six-coordinated in regular octahedral fashion, whereas in the solid iodide salts the dmpu solvated lanthanoid(III) ions are all six-coordinate in regular octahedral fashion. A comparison of Ln-O bond lengths in a large number of lanthanoid(III) complexes with neutral oxygen donor ligands and different configurations shows that the metal ion-oxygen distance is specific for each coordination number with a narrow bond distance distribution. This also shows that the radius of the coordinated oxygen atom in these compounds can be assumed to be 1.34 A as proposed for coordinated water, while for ethers such as tetrahydrofuran (thf) it is somewhat larger. Using this atomic radius of oxygen in coordinated water molecules, we have calculated the ionic radii of the lanthanoid(III) ions in four- to nine-coordination and evaluated using the bond lengths reported for homo- and heteroleptic complexes in oxygen donor solvates in solution and solid state. This yields new and revised ionic radii which in some instances are significantly different from the ionic radii normally referenced in the literature, including interpolated values for the elusive promethium(III) ion.

A new experimental technique for time-resolved X-ray absorption studies in the sub-second range has been successfully tested on the dispersive XAS beamline (ID24) at the ESRF. It consists of a sequential acquisition of energy points using the dispersive optics scheme installed on the beamline. Turbo-XAS takes full advantage of the properties of third-generation radiation sources, overcoming many of the problems encountered in the classical dispersive XAS mode, based on position-sensitive detectors. The new technique bene®ts from the basic assets of the dispersive set-up, i.e. the absence of movement of the optics and the extremely small and stable horizontal focal spot. In addition, it features simultaneous recording of I 0 and I 1 and the possibility of performing¯uorescence and electron detection.