Electronic Structure and Anion Photoelectron Spectroscopy of Uranium-Gold Clusters UAun-, n = 3-7.

A collaborative effort between experiment and theory toward elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAun-(n = 3-7) were taken at the third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193 nm) photon energies, where the experimental adiabatic electron affinities and vertical detachment energies values were measured. Complementary first-principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu6 where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAun clusters (n = 3-7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UFn species, but significant deviations are seen starting with UAu5 where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu6 system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are calculated to be nearly isoenergetic. With UAu7, only ring-like structures are calculated. Overall, the calculated electron detachment energies are in good agreement with the experimental values.

Au as a Surrogate for F: The Case of UAu6 vs UF6.

Here, anion photoelectron spectroscopy and first-principles quantum chemistry are used to demonstrate to what degree Au can act as a surrogate for F in UF6 and its anion. Unlike UF6, UAu6 exhibits strong ligand-ligand, i.e., Au-Au, interactions, resulting in three low-lying isomers, two of which are three-dimensional while the third isomer has a ring-like quasi two-dimensional structure. Additionally, all the UAu6 isomers have open-shell electrons, which in nearly all cases are localized on the central U atom. The adiabatic electron affinity and vertical detachment energy are measured to be 3.05 ± 0.05 and 3.28 ± 0.05 eV, respectively, and are in very good agreement with calculations.

Experimental and Computational Description of the Interaction of H and H- with U.

The results of ab initio correlated molecular orbital theory electronic structure calculations for low-lying electronic states are presented for UH and UH- and compared to photoelectron spectroscopy measurements. The calculations were performed at the CCSD(T)/CBS and multireference CASPT2 including spin-orbit effects by the state interacting approach levels. The ground states of UH and UH- are predicted to be 4Ι9/2 and 5Λ6, respectively. The spectroscopic parameters Te, re, ωe, ωexe, and Be were obtained, and potential energy curves were calculated for the low energy Ω states of UH. The calculated adiabatic electron affinity is 0.468 eV in excellent agreement with an experimental value of 0.462 ± 0.013 eV. The lowest vertical detachment energy was predicted to be 0.506 eV for the ground state, and the adiabatic ionization energy (IE) is predicted to be 6.116 eV. The bond dissociation energy (BDE) and heat of formation values of UH were obtained using the IE calculated at the Feller-Peterson-Dixon level. For UH, UH-, and UH+, the BDEs were predicted to be 225.5, 197.9, and 235.5 kJ/mol, respectively. The BDE for UH is predicted to be ∼20% lower in energy than that for ThH. The analysis of the natural bond orbitals shows a significant U+H- ionic component in the bond of UH.

Interaction of Th with H0/-/+: Combined Experimental and Theoretical Thermodynamic Properties.

High-level electronic structure calculations of the low-lying energy electronic states for ThH, ThH-, and ThH+ are reported and compared to experimental measurements. The inclusion of spin-orbit coupling is critical to predict the ground-state ordering as inclusion of spin-orbit switches the coupled-cluster CCSD(T) ordering of the two lowest energy states for ThH and ThH+. At the multireference spin-orbit SO-CASPT2 level, the ground states of ThH, ThH-, and ThH+ are predicted to be the 2Δ3/2, 3Φ2, and 3Δ1 states, respectively. The adiabatic electron affinity is calculated to be 0.820 eV, and the vertical detachment energy is calculated to be 0.832 eV in comparison to an experimental value of 0.87 ± 0.02 eV. The observed ThH- photoelectron spectrum has many transitions, which approximately correlate with excitations of Th+ and/or Th. The adiabatic ionization energy of ThH including spin-orbit corrections is calculated to be 6.181 eV. The natural bond orbital results are consistent with a significant contribution of the Th+H- ionic configuration to the bonding in ThH. The bond dissociation energies for ThH, ThH-, and ThH+ using the Feller-Peterson-Dixon approach were calculated to be similar for all three molecules and lie between 259 and 280 kJ/mol.

NEUROLOGICAL MANIFESTATIONS OF PROLACTINOMA (CASE REPORT).

This article describes a clinical case of prolactinoma, the onset of which was diagnosed after long-term use of eglonil, after the appearance of such side effects as galactorrhea. This clinical case is a unique one because of the peculiarities of diagnostic search. The first complaints of the patient were anxiety and fear, fatigue, frequent mood swings, memory disoders. She was examined by a family physician and prescribed eglonil (sulpiride) 200mg for 7 days. Because of the positive effect the patient decided on her own to continue treatment for another several weeks. But suddenly she revealed a leakage of milk from the mammary glands. The family physician assessed galactorrhea as a side effect of long-term use of eglonil, and cancelled this prescription. Simultaneously the family doctor canceled COCs, that the patient used for the last several years, because of pregnancy planning. But three months later the mensis didn't occur. The menstrual cycle did not resume and pregnancy did not occur even 6 months later. Thus the doctor started to perform complete examination of the patient. Unfortunately, during the diagnostic search the patient rejected to do the contrast and primarily was performed MRI without contrast. The doctor revealed abnormal prolactin level - 423 ng/ml (normal range <25 ng/ml). Finally MRI of the pitutary including dynamic contrast was done. It has demonstrated an 8 x 11 mm mass in pituitary gland. The patient was prescribed conservative treatment according to the protocol. As a result, subsequent monthly control laboratory tests of prolactin levels in blood indicated gradual decrease of its level. Thus the first symptoms of prolactinoma may be atypical and can be detected only by a detailed survey and observation of the patient. It is also known that the severity of symptoms depends on the size of prolactinomas. Large prolactinomas cause symptoms of central nervous system lesion: headaches, depression, anxiety, irritability, emotional instability but in our clinical case, the prolactinoma was small but manifests with severe symptoms of the central nervous system lesion (according to the results of HADScale and MoCA scale). The presence of concomitant pathology can mask or distort the symptoms of another disease that complicates the diagnosis. On the other hand, treatment of one of the comorbidities and improving its course leads to a reduction in the manifestations of the others.

On the performance of the variance ratio unit root tests with flexible Fourier form.

This article introduces a new unit root test that combines the variance ratio framework with the Flexible Fourier Form under the generalized least squares detrending mechanism. The advantage of the proposed method against its alternatives can be listed as: (1) it suggests a non-parametric procedure that does not require any parametric or semi-parametric model to remove serial correlation in the innovation process; (2) it can reasonably adapt itself to deal with the multiple structural breaks with various functional specifications. In the simulation exercises, we show that the proposed method exhibits satisfactory performance in the size and size-adjusted power analysis.

Effect of chitosan on sealer penetration into the dentinal tubules.

OBJECTIVE: The objective of this study is to compare the effectiveness of final irrigation with chitosan, ethylenediaminetetraacetic acid (EDTA), and citric acid (CA) on a resin-based sealer (AH plus sealer [Dentsply DeTrey, Konstanz, Germany]) penetration into dentinal tubules using confocal laser scanning microscopy. MATERIALS AND METHODS: Seventy recently extracted human mandibular premolars were instrumented and irrigated with sodium hypochlorite (NaOCl), then divided into four groups according to the final irrigation regimen used: (1) the EDTA group: 17% EDTA + 2.5% NaOCl, (2) the CA group: 10% CA + 2.5% NaOCl, (3) the chitosan group: 0.2% chitosan + 2.5% NaOCl, and (4) the control group: 2.5% NaOCl. All teeth were obturated using the cold lateral condensation technique with gutta-percha and AH Plus sealer labeled with fluorescent dye. The apical 2 mm of specimen was discarded, and slices were obtained for apical, middle, and coronal thirds of the root with 1 mm intervals. Maximum, mean, and percentage of sealer penetration (SP) inside tubules were measured using confocal laser scanning microscopy. RESULTS: The percentage of SP was significantly higher in chitosan, EDTA, and CA group than control group for coronal thirds (P < 0.05), whereas there was no significant difference among all groups for middle and apical thirds. Chitosan and EDTA showed increased mean values of SP depth for middle thirds (P < 0.05). In all sections, the maximum depth of SP was significantly lower in EDTA group than other groups (P < 0.05). CONCLUSIONS: Chitosan, EDTA, and CA significantly improved the percentage of SP for coronal thirds.

Stimulation of Protein Expression Through the Harmonic Resonance of Frequency-Specific Music.

PURPOSE: The use of specific frequencies for specific individual amino acids may increase the potential energy of protein molecules in the medium [1]. The resonance would also increase the movement of particles in the cytosol, increasing the collisions necessary for the conduction of protein expression. METHODS: The clash of two waves that share frequencies will exhibit an increase in energy through an increase in amplitude [2]. The increase in energy would in turn increase the number of collisions forming the tRNA-amino acid, increasing the amino acid acquiry for ribosomes to improve intracellular efficiency in gene expression. To test the hypothesis, Red Fluorescent Protein (RFP) in transformated BL-21 strains of E. coli and p53 protein of MCF-7 were examined after exposure to sounds of specific frequencies. RESULTS: Through the exposure of the experimental systems to a sequence of sounds that match the frequencies of specific amino acids, the levels of RFP exhibition respective to the control groups in the bacterial medium increased two-fold in terms of RFU. The experiments that targeted the p53 protein with the 'music' showed a decrease in the cell prevalence in the MCF-7 type breast cancer cells by 28%, by decreasing the speed of tumour formation. CONCLUSION: Exposure to 'music' that was designed through assigning a musical note for every single one of the twenty unique amino acids, produced both an analytical and a visible shift in protein synthesis, making it as potential tool for reducing procedural time uptake.

Concentration and vertical distribution of 137Cs in the undisturbed soil of southwestern Nigeria.

The results of measurements of 137Cs in soil profiles that were sampled in undisturbed soil in Ondo, Ekiti, and Oyo states in the southwestern area of Nigeria are presented in this paper. Samples were collected from nine soil profiles. The vertical distributions of 137Cs in the soil profiles have been determined. Cesium concentration ranged from 0.31 +/- 0.10 Bq kg(-1) in the 0-2 cm depth to a maximum of 1.25 +/- 0.21 Bq kg(-1) in the 6-8 cm depth at some sites and from 3.16 +/- 0.16 Bq kg(-1) in 0-5 cm depth to below detection limit (BDL) at 20-25 cm at another site. 137Cs total deposition in 0-10 cm depth was found to be greatest at Ikogosi site with a value of 90.30 Bq m(-2). The results generally showed that more than 40 y after the first nuclear weapon tests, 137Cs still remains within the 25 cm upper layer of soil in the region with a migration velocity of 0.17-0.18 cm y(-1). The mean value of effective dose commitment due to the presence of cesium in soil in the entire region was found to be 10.77 microSv.

Object-based and environment-based inhibition of return of visual attention.

Efficient search for an object often requires that attention be prevented from returning to recently examined environmental loci. M. I. Posner and Y. A. Cohen (1984) proposed that inhibition of return (IOR) of visual attention is a search mechanism that prevents such attentional perservation. The internal representations upon which IOR functions were examined and the following conclusions were drawn: First, IOR mechanisms have access to both object- and environment-based representations. Second, environment-based inhibition can be associated with a featureless environmental location, whereas the object-based mechanism requires that attention be oriented to a visible object. These findings are discussed in terms of physiological pathways that may mediate location- and object-based effects.