57 research outputs found
Collective excitations and low temperature transport properties of bismuth
We examine the influence of collective excitations on the transport
properties (resistivity, magneto- optical conductivity) for semimetals,
focusing on the case of bismuth. We show, using an RPA approximation, that the
properties of the system are drastically affected by the presence of an
acoustic plasmon mode, consequence of the presence of two types of carriers
(electrons and holes) in this system. We found a crossover temperature T*
separating two different regimes of transport. At high temperatures T > T* we
show that Baber scattering explains quantitatively the DC resistivity
experiments, while at low temperatures T < T* interactions of the carriers with
this collective mode lead to a T^5 behavior of the resistivity. We examine
other consequences of the presence of this mode, and in particular predict a
two plasmon edge feature in the magneto-optical conductivity. We compare our
results with the experimental findings on bismuth. We discuss the limitations
and extensions of our results beyond the RPA approximation, and examine the
case of other semimetals such as graphite or 1T-TiSe_2
Effects of thermal- and spin- fluctuations on the band structure of purple bronze LiMoO
The band structures of ordered and thermally disordered
LiMoO are calculated by use of ab-initio DFT-LMTO method. The
unusual, very 1-dimensional band dispersion obtained in previous band
calculations is confirmed for the ordered structure, and the overall band
structure agrees reasonably with existing photoemission data. Dispersion and
bandstructure perpendicular to the main dispersive direction is obtained. A
temperature dependent band broadening is calculated from configurations with
thermal disorder of the atomic positions within the unit cell. This leads a
band broadening of the two bands at the Fermi energy which can become
comparable to their energy separation. The bands are particularly sensitive to
in-plane movements of Mo sites far from the Li-sites, where the
density-of-states is highest. The latter fact makes the effect of Li vacancies
on the two bands relatively small. Spin-polarized band results for the ordered
structure show a surprisingly large exchange enhancement on the high DOS Mo
sites. Consequences for spin fluctuations associated with a cell doubling along
the conducting direction are discussed
Dynein Function and Protein Clearance Changes in Tumor Cells Induced by a Kunitz-Type Molecule, Amblyomin-X
Amblyomin-X is a Kunitz-type recombinant protein identified from the transcriptome of the salivary glands of the tick Amblyomma cajennense and has anti-coagulant and antitumoral activity. the supposed primary target of this molecule is the proteasome system. Herein, we elucidated intracellular events that are triggered by Amblyomin-X treatment in an attempt to provide new insight into how this serine protease inhibitor, acting on the proteasome, could be comparable with known proteasome inhibitors. the collective results showed aggresome formation after proteasome inhibition that appeared to occur via the non-exclusive ubiquitin pathway. Additionally, Amblyomin-X increased the expression of various chains of the molecular motor dynein in tumor cells, modulated specific ubiquitin linkage signaling and inhibited autophagy activation by modulating mTOR, LC3 and AMBRA1 with probable dynein involvement. Interestingly, one possible role for dynein in the mechanism of action of Amblyomin-X was in the apoptotic response and its crosstalk with autophagy, which involved the factor Bim; however, we observed no changes in the apoptotic response related to dynein in the experiments performed. the characteristics shared among Amblyomin-X and known proteasome inhibitors included NF-kappa B blockage and nascent polypeptide-dependent aggresome formation. Therefore, our study describes a Kunitz-type protein that acts on the proteasome to trigger distinct intracellular events compared to classic known proteasome inhibitors that are small-cell-permeable molecules. in investigating the experiments and literature on Amblyomin-X and the known proteasome inhibitors, we also found differences in the structures of the molecules, intracellular events, dynein involvement and tumor cell type effects. These findings also reveal a possible new target for Amblyomin-X, i.e., dynein, and may serve as a tool for investigating tumor cell death associated with proteasome inhibition.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Butantan Inst, Biochem & Biophys Lab, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biochem, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biochem, São Paulo, BrazilFAPESP: 2011/05969-4FAPESP: CAT/CEPID 1998/14307-9FAPESP: CETICs 2013/07467-1Web of Scienc
Metal Hydrides Form Halogen Bonds: Measurement of Energetics of Binding
The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η5-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η5-cyclopentadienyl) is demonstrated by 1H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = −10.9 ± 0.4 and −11.8 ± 0.3 kJ/mol; ΔS° = −38 ± 2 and −34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = −7.3 ± 0.1 kJ/mol, ΔS° = −24 ± 1 J/(mol·K)). For the more reactive complexes 2–5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M–1, respectively
Effects of Charge and Substituent on the S∙∙∙N Chalcogen Bond
Neutral complexes containing a S···N chalcogen bond are compared with similar systems in which a positive charge has been added to the S-containing electron acceptor, using high-level ab initio calculations. The effects on both XS···N and XS+···N bonds are evaluated for a range of different substituents X = CH3, CF3, NH2, NO2, OH, Cl, and F, using NH3 as the common electron donor. The binding energy of XMeS···NH3 varies between 2.3 and 4.3 kcal/mol, with the strongest interaction occurring for X = F. The binding is strengthened by a factor of 2–10 in charged XH2S+···NH3 complexes, reaching a maximum of 37 kcal/mol for X = F. The binding is weakened to some degree when the H atoms are replaced by methyl groups in XMe2S+···NH3. The source of the interaction in the charged systems, like their neutral counterparts, is derived from a charge transfer from the N lone pair into the σ*(SX) antibonding orbital, supplemented by a strong electrostatic and smaller dispersion component. The binding is also derived from small contributions from a CH···N H-bond involving the methyl groups, which is most notable in the weaker complexes
Expression of two endoplasmic reticulum stress markers, GRP78 and GADD153, is involved in the mechanism of action of the Amblyomin-X.
Inst Butantan, Biochem & Biophys Lab, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Bioquim, São Paulo, BrazilUniv São Paulo, Fac Med, Dept Radiol & Oncol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Bioquim, São Paulo, BrazilWeb of Scienc
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