Snapshots of the fluctuating hydrogen bond network in liquid water on the sub-femtosecond timescale with vibrational resonant inelastic x-ray scattering.

Liquid water molecules interact strongly with each other, forming a fluctuating hydrogen bond network and thereby giving rise to the anomalous phase diagram of liquid water. Consequently, symmetric and asymmetric water molecules have been found in the picosecond time average with IR and optical Raman spectroscopy. With subnatural linewidth resonant inelastic x-ray scattering (RIXS) at vibrational resolution, we take sub-femtosecond snapshots of the electronic and structural properties of water molecules in the hydrogen bond network. We derive a strong dominance of nonsymmetric molecules in liquid water in contrast to the gas phase on the sub-femtosecond timescale of RIXS and determine the fraction of highly asymmetrically distorted molecules.

Rydberg-resolved resonant inelastic soft x-ray scattering: dynamics at core ionization thresholds.

Resonant inelastic x-ray scattering spectra excited in the immediate vicinity of the core-level ionization thresholds of N2 have been recorded. Final states of well-resolved symmetry-selected Rydberg series converging to valence-level ionization thresholds with vibrational excitations are observed. The results are well described by a quasi-two-step model which assumes that the excited electron is unaffected by the radiative decay. This threshold dynamics simplifies the interpretation of resonant inelastic x-ray scattering spectra considerably and facilitates characterization of low-energy excited final states in molecular systems.

Interference between resonant and nonresonant inelastic x-ray scattering.

A detailed study of inelastic x-ray scattering from the ground state to the 3Σg(3σ(g)(-1)3s(g)1) state of the O2 molecule is presented. The observed angular anisotropy shows that the vibrational excitations within this final state are strongly dependent on the polarization of the incident radiation. The analysis demonstrates that this is a manifestation of interference between resonant and direct nonresonant inelastic x-ray scattering. This interference provides a new tool to monitor nuclear dynamics by relative rotation of the polarization vectors of the incident and scattered photons.

Comparative structural and electronic studies of hydrogen interaction with isolated versus ordered silicon nanoribbons grown on Ag(110).

We have investigated the geometry and electronic structure of two different types of self-aligned silicon nanoribbons (SiNRs), forming either isolated SiNRs or a self-assembled 5 × 2/5 × 4 grating on an Ag(110) substrate, by scanning tunnelling microscopy and high resolution x-ray photoelectron spectroscopy. At room temperature we further adsorb on these SiNRs either atomic or molecular hydrogen. The hydrogen absorption process and hydrogenation mechanism are similar for isolated or 5 × 2/5 × 4 ordered SiNRs and are not site selective; the main difference arises from the fact that the isolated SiNRs are more easily attacked and destroyed faster. In fact, atomic hydrogen strongly interacts with any Si atoms, modifying their structural and electronic properties, while molecular hydrogen has first to dissociate. Hydrogen finally etches the Si nanoribbons and their complete removal from the Ag(110) surface could eventually be expected.

Spatial quantum beats in vibrational resonant inelastic soft x-ray scattering at dissociating states in oxygen.

Resonant inelastic soft x-ray scattering (RIXS) spectra excited at the 1σ(g) → 3σ(u) resonance in gas-phase O2 show excitations due to the nuclear degrees of freedom with up to 35 well-resolved discrete vibronic states and a continuum due to the kinetic energy distribution of the separated atoms. The RIXS profile demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the atoms separate. Thomson scattering strongly affects both the spectral profile and the scattering anisotropy.

Reaction patterns of cell organelles in vitamin B6 deficiency. Ultrastructural-morphometric analysis of the liver parenchymal cell.

Under the influence of seven weeks of vitamin B6-free nutrition, the hepatocyte single volume is diminished in the face of an unchanged nuclear single volume, posing the question of whether there is proportional atrophy of all cell organelles or single organelle atrophy with counter-regulatory hyperplasia in other cellular compartments. The nucleoli hypertrophy, as the result of segregation and protein synthesis inhibition. The rough endoplasmic reticulum experiences hypoplasia, but the ultrastructural-morphometric analysis does not determine which metabolic steps are attacked. By contrast one observes hyperplasia in the smooth endoplasmic reticulum, which may be regarded as a counter-regulatory mechanism to the choking of protein synthesis. As with the rough endoplasmic reticulum, the mitochondria also show hypoplasia. This is due to the dependency of the mitochondria upon the endoplasmic protein synthesis. The disturbed functional output of the endoplasmic reticulum is seen in the reduced number of orthoperoxisomes as well. The Golgi apparatus experiences hypoplasia as a result of B6 hypovitaminosis, and this must be considered in the context of fatty change in the liver.

Spin-orbit mediated interference in the radiative and nonradiative channels of the La 4d core resonances.

Symmetrical fluorescence yield profiles and asymmetrical electron yield profiles of the preresonances at the La N_{IV,V} x-ray absorption edge are experimentally observed in LaPO_{4} nanoparticles. Theoretical studies show that they are caused by interference effects. The spin-orbit interaction and the giant resonance produce symmetry entangled intermediate states that activate coherent scattering and alter the spectral distribution of the oscillator strength. The scattering amplitudes of the electron and fluorescence decays are further modified by the spin-orbit coupling in the final 5p;{5}epsilonl and 5p;{5}4f;{1} states.

Geometric and electronic structure of lanthanide orthophosphate nanoparticles determined with X-rays.

The evolution of the geometric and electronic structures within the entire series of lanthanide orthophosphate nanoparticles ( approximately 2- approximately 5 nm) has been determined experimentally with X-ray diffraction and near edge X-ray absorption fine structure spectroscopy. In particular, the interplay between electronic structure, crystal morphology, and crystal phase has been systematically studied. A missing local order in the crystal structure accompanied by multiple ion sites in the nanoparticles was revealed to be due to the small crystal size and large surface contribution. All lanthanide ions were found to be in "3+" configuration and accommodated in three different crystallization states: the larger lanthanide ions (La, Ce, Pr, Nd, Sm) in the monoclinic phase, the smaller ones (Er, Tm, Yb, Lu) in the tetragonal phase, and the intermediate lanthanide ions (Eu, Gd, Tb, Dy, Ho) in a "mixed phase" between monoclinic and tetragonal phases.

Nonadiabatic effects in resonant inelastic x-ray scattering.

We have studied the spectral features of resonant inelastic x-ray scattering of condensed ethylene with vibrational selectivity both experimentally and theoretically. Purely vibrational spectral loss features and coupled electronic and vibrational losses are observed. The one-step theory for resonant soft x-ray scattering is applied, taking multiple vibrational modes and vibronic coupling into account. Our investigation of ethylene underlines that the assignment of spectral features observed in resonant inelastic x-ray scattering of polyatomic systems requires an explicit description of the coupled electronic and vibrational loss features.

Genomic organization, promoter cloning, and chromosomal localization of the Dif-2 gene.

We describe the genomic organization and the functional promoter of the monocyte specific gene Dif-2, the human homologue to genes in mouse (gly96) and rat (PRG1), that is downregulated during cell differentiation. The Dif-2 gene consists of two exons and a single intron of 112 bp in length. RNase protection assay indicates one major transcription start site. Sequence analysis reveals several consensus sequences for transcription factors including NF-kappa B, C/EBP, SP1, and the lack of a classical TATA-box. To demonstrate promoter activity, DNA fragments of the Dif-2 5'-flanking region were ligated upstream to the luciferase gene and transfected into HepG2 and HeLa cells. A minimal promoter element between nt -158 and nt +74 containing NF-kappa B and SP1 binding sites was shown to be sufficient for basal activity. These transcription factor binding sites, which are conserved between Dif-2, gly96, and PRG1 promoter regions, indicate a significant role for Dif-2 expression and may explain LPS and C2-ceramide sensitivity. The Dif-2 gene was mapped to chromosome 6p21.3 using in situ hybridization technique.

Identification and characterization of a novel monocyte/macrophage differentiation-dependent gene that is responsive to lipopolysaccharide, ceramide, and lysophosphatidylcholine.

A novel differentiation-dependent cDNA (DIF-2) has been isolated from human mononuclear phagocytes by differential display. The full-length cDNA was cloned and sequenced. DIF-2 consists of 156 amino acids and has a predicted isoelectric point of 8.84. The mRNA is expressed in freshly isolated monocytes and is downregulated significantly when monocytes are subjected to differentiation. A similar differentiation-dependent downregulation is observed in normal hepatocytes compared to undifferentiated HepG2 cells. The mRNA expression in monocytes is sensitive to lipopolysaccharide and ceramide which both strongly increase DIF-2 transcription, while lysophosphatidylcholine results in a weaker upregulation of DIF-2 expression. A DIF-2 homologous gene has been previously isolated from mouse fibroblasts and was shown to be a serum growth factor-inducible immediate early gene. Our results indicate that DIF-2 represents a gene which is regulated in differentiation processes and strongly responsive to lipopolysaccharide, ceramide and lysophosphatidylcholine.