270 research outputs found
The connexin43 carboxyl terminus and cardiac gap junction organization
AbstractThe precise spatial order of gap junctions at intercalated disks in adult ventricular myocardium is thought vital for maintaining cardiac synchrony. Breakdown or remodeling of this order is a hallmark of arrhythmic disease of the heart. The principal component of gap junction channels between ventricular cardiomyocytes is connexin43 (Cx43). Proteinâprotein interactions and modifications of the carboxyl-terminus of Cx43 are key determinants of gap junction function, size, distribution and organization during normal development and in disease processes. Here, we review data on the role of proteins interacting with the Cx43 carboxyl-terminus in the regulation of cardiac gap junction organization, with particular emphasis on Zonula Occludens-1. The rapid progress in this area suggests that in coming years we are likely to develop a fuller understanding of the molecular mechanisms causing pathologic remodeling of gap junctions. With these advances come the promise of novel approach to the treatment of arrhythmia and the prevention of sudden cardiac death. This article is part of a Special Issue entitled: The Communicating junctions, composition, structure and characteristics
Antiferrodistortive phase transition in EuTiO3
X-ray diffraction, dynamical mechanical analysis and infrared reflectivity
studies revealed an antiferrodistortive phase transition in EuTiO3 ceramics.
Near 300K the perovskite structure changes from cubic Pm-3m to tetragonal
I4/mcm due to antiphase tilting of oxygen octahedra along the c axis (a0a0c- in
Glazer notation). The phase transition is analogous to SrTiO3. However, some
ceramics as well as single crystals of EuTiO3 show different infrared
reflectivity spectra bringing evidence of a different crystal structure. In
such samples electron diffraction revealed an incommensurate tetragonal
structure with modulation wavevector q ~ 0.38 a*. Extra phonons in samples with
modulated structure are activated in the IR spectra due to folding of the
Brillouin zone. We propose that defects like Eu3+ and oxygen vacancies strongly
influence the temperature of the phase transition to antiferrodistortive phase
as well as the tendency to incommensurate modulation in EuTiO3.Comment: PRB, in pres
Orthorhombic versus monoclinic symmetry of the charge-ordered state of NaV2O5
High-resolution X-ray diffraction data show that the low-temperature
superstructure of alpha-NaV2O5 has an F-centered orthorhombic 2a x 2b x 4c
superlattice. A structure model is proposed, that is characterized by layers
with zigzag charge order on all ladders and stacking disorder, such that the
averaged structure has space group Fmm2. This model is in accordance with both
X-ray scattering and NMR data. Variations in the stacking order and disorder
offer an explanation for the recently observed devils staircase of the
superlattice period along c.Comment: REVTEX, 4 pages including 2 figures, shortened, submitted to PR
Ultra-low temperature structure determination of a Mn12 single-molecule magnet and the interplay between lattice solvent and structural disorder
We have determined the ultra-low temperature crystal structure of the archetypal single-molecule magnet (SMM) [Mn12O12(O2CMe)16(H2O)4]·4H2O·2MeCO2H (1) at 2 K, by using a combination of single-crystal X-ray and single-crystal neutron diffraction. This is the first structural study of any SMM in the same temperature regime where slow magnetic relaxation occurs. We reveal an additional hydrogen bonding interaction between the {Mn12} cluster and its solvent of crystallisation, which shows how the lattice solvent transmits disorder to the acetate ligands in the {Mn12} complex. Unusual quantum properties observed in 1 have long been attributed to disorder. Hence, we studied the desolvation products of 1, in order to understand precisely the influence of lattice solvent on the structure of the cluster. We present two new axially symmetric structures corresponding to different levels of desolvation of 1, [Mn12O12(O2CMe)16(H2O)4]·4H2O (2) and [Mn12O12(O2CMe)16(H2O)4] (3). In 2, removal of acetic acid of crystallisation largely resolves positional disorder in the affected acetate ligands, whereas removal of lattice water molecules further resolves the acetate ligand disorder in 3. Due to the absence of acetic acid of crystallisation, both 2 and 3 have true, unbroken S4 symmetry, showing for the first time that it is possible to prepare fully axial Mn12âacetate analogues from 1, via single-crystal to single-crystal transformations
Ethyl 1,6-dimethyl-2-oxo-4-(quinolin-4-yl)-1,2,3,4-tetraÂhydroÂpyrimidine-5-carboxylÂate
In the title compound, C18H19N3O3, the tetraÂhydroÂpyrimidone ring adopts a distorted boat conformation. In the crystal structure, interÂmolecular NâHâŻO hydrogen bonds link the molÂecules into centrosymmetric dimers, which are further linked via interÂmolecular CâHâŻÏ interÂactions. In addition, an intraÂmolecular CâHâŻO hydrogen bond occurs
Third structure determination by powder diffractometry round robin (SDPDRR-3)
The results from a third structure determination by powder diffractometry (SDPD) round robin are discussed. From the 175 potential participants having downloaded the powder data, nine sent a total of 12 solutions (8 and 4 for samples 1 and 2, respectively, a tetrahydrated calcium tartrate and a lanthanum tungstate). Participants used seven different computer programs for structure solution (ESPOIR, EXPO, FOX, PSSP, SHELXS, SUPERFLIP, and TOPAS), applying Patterson, direct methods, direct space methods, and charge flipping approach. It is concluded that solving a structure from powder data remains a challenge, at least one order of magnitude more difficult than solving a problem with similar complexity from single-crystal data. Nevertheless, a few more steps in the direction of increasing the SDPD rate of success were accomplished since the two previous round robins: this time, not only the computer program developers were successful but also some users. No result was obtained from crystal structure prediction expert
Study of the pressure effects in TiOCl by ab initio calculations
Electronic structure calculations on the low dimensional spin-1/2 compound
TiOCl were performed at several pressures in the orthorhombic phase, finding
that the structure is quasi-one-dimensional. The Ti3+ (d1) ions have one t2g
orbital occupied (dyz) with a large hopping integral along the b direction of
the crystal. The most important magnetic coupling is Ti-Ti along the b axis.
The transition temperature (Tc) has a linear evolution with pressure, and at
about 10 GPa this Tc is close to room temperature, leading to a room
temperature spin-Peierls insulator-insulator transition, with an important
reduction of the charge gap in agreement with the experiment. On the
high-pressure monoclinic phase, TiOCl presents two possible dimerized
structures, with a long or short dimerization. Long dimerized state occurs
above 15 GPa, and below this pressure the short dimerized structure is the more
stable phase.Comment: 3 pages, 3 embedded figures, 1 table. A. Pi\~neiro, et al.,J. Magn.
Magn. Mater. (2009) (accepted
The reductive activation of CO2 across a TiâTi double bond: synthetic, structural, and mechanistic studies
[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(â )(2) (1) (Pn(â ) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at â78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a ÎŒ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a ÎŒ-O dimer in which the TiâTi bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a âside-onâ bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(ÎŒ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(ÎŒ-S) complex 11 with a double-sandwich structure and bis(ÎŒ-S) dimer 12 in which the TiâTi bond has been cleaved
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