Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square‐Planar Copper(I) Complex

6,6′′‐Bis(2,4,6‐trimethylanilido)terpyridine (H2TpyNMes) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H2TpyNMes)copper(I)‐halide (Cl, Br and I) complexes is dictated by the strength of the NH–halide hydrogen bond. The CuICl and CuIICl complexes are nearly isostructural, the former presenting a highly unusual square‐planar geometry about CuI. The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid CuI/CuII electron‐transfer self‐exchange rates. Cu(H2TpyNMes)Cl shows similar fast electron transfer (≈105 m−1 s−1) which is the same order of magnitude as biological systems.Entatic state: Hydrogen bonds constrain the geometry of CuI and CuII complexes. A highly unusual square‐planar geometry about CuI (see structure) is shown to be nearly isostructural to the CuII core. The minimal reorganization energy between redox states allows for extremely rapid CuI/CuII electron‐transfer self‐exchange rates.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/134494/1/anie201511527_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134494/2/anie201511527-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134494/3/anie201511527.pd

Effects of electronic correlation on X-Ray absorption and dichroic spectra at L2,3_{2,3} edge

We present a new theoretical approach to describe X-Ray absorption and Magnetic Circular Dichroism spectra in the presence of e-e correlation. Our approach provides an unified picture to include correlations in both charged and neutral excitations, namely in direct / inversion photoemission where electrons are removed/added, and photo absorption where electrons are promoted from core levels to empty states. We apply this approach to the prototypical case of L$_{2,3}$ edge of 3$d$ transition metals and we show that the inclusion of many body effects in the core level excitations is essential to reproduce, together with satellite structures in core level photoemission, the observed asymmetric line shapes in X-ray absorption and dichroic spectra.Comment: 3 figures, 5 pages, submitted to Phys. Rev.

Excitation spectrum of a two-component Bose-Einstein condensate in a ring potential

A mixture of two distinguishable Bose-Einstein condensates confined in a ring potential has numerous interesting properties under rotational and solitary-wave excitation. The lowest-energy states for a fixed angular momentum coincide with a family of solitary-wave solutions. In the limit of weak interactions, exact diagonalization of the many-body Hamiltonian is possible and permits evaluation of the complete excitation spectrum of the system.Comment: 4 pages, 1 figur

Electronic structure of Co_xTiSe_2 and Cr_xTiSe_2

The results of investigations of intercalated compounds Cr_xTiSe_2 and Co_xTiSe_2 by X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES) are presented. The data obtained are compared with theoretical results of spin-polarized band structure calculations. A good agreement between theoretical and experimental data for the electronic structure of the investigated materials has been observed. The interplay between the M3d--Ti3d hybridization (M=Cr, Co) and the magnetic moment at the M site is discussed. A 0.9 eV large splitting of the core Cr2p{3/2} level was observed, which reveals a strong exchange magnetic interaction of 3d-2p electrons of Cr. In the case of a strong localization of the Cr3d electrons (for x<0.25), the broadening of the CrL spectra into the region of the states above the nominal Fermi level was observed and attributed to X-ray re-emission. The measured kinetic properties are in good accordance with spectral investigations and band calculation results.Comment: 14 pages, 11 figures, submitted to Phys.Rev.

Robust Digital Holography For Ultracold Atom Trapping

We have formulated and experimentally demonstrated an improved algorithm for design of arbitrary two-dimensional holographic traps for ultracold atoms. Our method builds on the best previously available algorithm, MRAF, and improves on it in two ways. First, it allows for creation of holographic atom traps with a well defined background potential. Second, we experimentally show that for creating trapping potentials free of fringing artifacts it is important to go beyond the Fourier approximation in modelling light propagation. To this end, we incorporate full Helmholtz propagation into our calculations.Comment: 7 pages, 4 figure

Лабораторна установка для дослідження ступеня очищення і пошкодження коренебульбоплодів

Патент України на корисну модель № 79083, МПК B65G 33/00, 2012.Лабораторна установка для дослідження ступеня очищення і пошкодження коренебульбоплодів, що містить раму, на якій з можливістю кутового та вертикального зміщення на підрамах встановлені секція пруткового транспортера-очисника та секція бітерних очисних валів, завантажувальний бункер, причому під секцією пруткового транспортера-очисника та секцією бітерних очисних валів на рамі розташовані поперечні лотки для відбору від сепарованих домішок, яка відрізняється тим, що кутовий зазор між центральною віссю барабана пруткового транспортера-очисника в зоні вивантаження коренебульбоплодів та центральною віссю першого бітерного очисного вала може змінюватись за рахунок використання різних отворів, які виконані на стійці та підрамі, а осьовий зазор – за рахунок кронштейна з отворами, причому над прутковим транспортером-очисником та секцією бітерних очисних валів встановлені вертикальні та похилі еластичні екрани, а для відбору очищених коренебульбоплодів в зоні вивантаження бітерних очисних валів розташована еластична ємність з можливістю вертикального переміщення та фіксації її задньої частини на вертикальному кронштейні

Influence of Compensating Defect Formation on the Doping Efficiency and Thermoelectric Properties of Cu_(2-y)Se_(1–x)Br_x

The superionic conductor Cu_(2−δ)Se has been shown to be a promising thermoelectric at higher temperatures because of very low lattice thermal conductivities, attributed to the liquid-like mobility of copper ions in the superionic phase. In this work, we present the potential of copper selenide to achieve a high figure of merit at room temperature, if the intrinsically high hole carrier concentration can be reduced. Using bromine as a dopant, we show that reducing the charge carrier concentration in Cu_(2−δ)Se is in fact possible. Furthermore, we provide profound insight into the complex defect chemistry of bromine doped Cu_(2−δ)Se via various analytical methods and investigate the consequential influences on the thermoelectric transport properties. Here, we show, for the first time, the effect of copper vacancy formation as compensating defects when moving the Fermi level closer to the valence band edge. These compensating defects provide an explanation for the often seen doping inefficiencies in thermoelectrics via defect chemistry and guide further progress in the development of new thermoelectric materials

Clinical and biomarker changes in dominantly inherited Alzheimer\u27s disease

BACKGROUND: The order and magnitude of pathologic processes in Alzheimer\u27s disease are not well understood, partly because the disease develops over many years. Autosomal dominant Alzheimer\u27s disease has a predictable age at onset and provides an opportunity to determine the sequence and magnitude of pathologic changes that culminate in symptomatic disease. METHODS: In this prospective, longitudinal study, we analyzed data from 128 participants who underwent baseline clinical and cognitive assessments, brain imaging, and cerebrospinal fluid (CSF) and blood tests. We used the participant\u27s age at baseline assessment and the parent\u27s age at the onset of symptoms of Alzheimer\u27s disease to calculate the estimated years from expected symptom onset (age of the participant minus parent\u27s age at symptom onset). We conducted cross-sectional analyses of baseline data in relation to estimated years from expected symptom onset in order to determine the relative order and magnitude of pathophysiological changes. RESULTS: Concentrations of amyloid-beta (Aβ) 42 in the CSF appeared to decline 25 years before expected symptom onset. Aβ deposition, as measured by positron-emission tomography with the use of Pittsburgh compound B, was detected 15 years before expected symptom onset. Increased concentrations of tau protein in the CSF and an increase in brain atrophy were detected 15 years before expected symptom onset. Cerebral hypometabolism and impaired episodic memory were observed 10 years before expected symptom onset. Global cognitive impairment, as measured by the Mini-Mental State Examination and the Clinical Dementia Rating scale, was detected 5 years before expected symptom onset, and patients met diagnostic criteria for dementia at an average of 3 years after expected symptom onset. CONCLUSIONS: We found that autosomal dominant Alzheimer\u27s disease was associated with a series of pathophysiological changes over decades in CSF biochemical markers of Alzheimer\u27s disease, brain amyloid deposition, and brain metabolism as well as progressive cognitive impairment. Our results require confirmation with the use of longitudinal data and may not apply to patients with sporadic Alzheimer\u27s disease. (Funded by the National Institute on Aging and others; DIAN ClinicalTrials.gov number, NCT00869817.

Photodegradation of Phenol over a Hybrid Organo-Inorganic Material: Iron(II) Hydroxyphosphonoacetate

Water treatment is a hot topic, and it will become much more important in the decades ahead. Advanced oxidation processes are being increasingly used for organic contaminant removal, for example using photo-Fenton reactions. Here we report the use of an organo-inorganic hybrid, Fe[HO3PCH(OH)COO]·2H2O, as Fenton photocatalyst for phenol oxidation with H2O2 under UVA radiation. Preactivation, catalyst content, and particle size parameters have been studied/optimized for increasing phenol mineralization. Upon reaction, iron species are leached from the catalyst making a homogeneous catalysis contribution to the overall phenol photo-oxidation. Under optimized conditions, the mineralization degree was slightly larger than 90% after 80 min of irradiation. Analysis by X-ray photoelectron spectroscopy revealed important chemical modifications occurring on the surface of the catalyst after activation and phenol photodegradation. The sustained slow delivery of iron species upon phenol photoreaction is advantageous as the mixed heterogeneous−homogeneous catalytic processes result in very high phenol mineralization.Proyecto nacional MAT2010-1517