294 research outputs found
Bulk and surface switching in Mn-Fe-based Prussian Blue Analogues
Many Prussian Blue Analogues are known to show a thermally induced phase
transition close to room temperature and a reversible, photo-induced phase
transition at low temperatures. This work reports on magnetic measurements,
X-ray photoemission and Raman spectroscopy on a particular class of these
molecular heterobimetallic systems, specifically on
Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and
Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition
phenomena both in the bulk of the material and at the sample surface. Results
indicate a high degree of charge transfer in the bulk, while a substantially
reduced conversion is found at the sample surface, even in case of a near
perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of
the charge transfer transition in these materials is found to be primarily due
to surface reconstruction. Substitution of a large fraction of charge transfer
active Mn ions by charge transfer inactive Cu ions leads to a proportional
conversion reduction with respect to the maximum conversion that is still
stoichiometrically possible and shows the charge transfer capability of metal
centers to be quite robust upon inclusion of a neighboring impurity.
Additionally, a 532 nm photo-induced metastable state, reminiscent of the high
temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The
efficiency of photo-excitation to the metastable state is found to be maximized
around 90 K. The photo-induced state is observed to relax to the low
temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.Comment: 12 pages, 8 figure
The effects of a plant proteinase inhibitor from Enterolobium contortisiliquum on human tumor cell lines
Supplementary to the efficient inhibition of trypsin, chymotrypsin, plasma kallikrein, and plasmin already described by the EcTI inhibitor from Enterolobium contortisiliquum, it also blocks human neutrophil elastase (K(iapp)=4.3 nM) and prevents phorbol ester (PMA)-stimulated activation of matrix metalloproteinase (MMP)-2 probably via interference with membrane-type 1 (MT1)-MMP. Moreover, plasminogen-induced activation of proMMP-9 and processing of active MMP-2 was also inhibited. Furthermore, the effect of EcTI on the human cancer cell lines HCT116 and HT29 (colorectal), SkBr-3 and MCF-7 (breast), K562 and THP-1 (leukemia), as well as on human primary fibroblasts and human mesenchymal stem cells (hMSCs) was studied. EcTI inhibited in a concentration range of 1.0-2.5 mu M rather specifically tumor cell viability without targeting primary fibroblasts and hMSCs. Taken together, our data indicate that the polyspecific proteinase inhibitor EcTI prevents proMMP activation and is cytotoxic against tumor cells without affecting normal tissue remodeling fibroblasts or regenerative hMSCs being an important tool in the studies of tumor cell development and dissemination
A Unified Theoretical Description of the Thermodynamical Properties of Spin Crossover with Magnetic Interactions
After the discovery of the phenomena of light-induced excited spin state
trapping (LIESST), the functional properties of metal complexes have been
studied intensively. Among them, cooperative phenomena involving low spin-high
spin (spin-crossover) transition and magnetic ordering have attracted
interests, and it has become necessary to formulate a unified description of
both phenomena. In this work, we propose a model in which they can be treated
simultaneously by extending the Wajnflasz-Pick model including a magnetic
interaction. We found that this new model is equivalent to
Blume-Emery-Griffiths (BEG) Hamiltonian with degenerate levels. This model
provides a unified description of the thermodynamic properties associated with
various types of systems, such as spin-crossover (SC) solids and Prussian blue
analogues (PBA). Here, the high spin fraction and the magnetization are the
order parameters describing the cooperative phenomena of the model. We present
several typical temperature dependences of the order parameters and we
determine the phase diagram of the system using the mean-field theory and Monte
Carlo simulations. We found that the magnetic interaction drives the SC
transition leading to re-entrant magnetic and first-order SC transitions.Comment: 30pages, 11figure
Magnetic Behavior of a Mixed Ising Ferrimagnetic Model in an Oscillating Magnetic Field
The magnetic behavior of a mixed Ising ferrimagnetic system on a square
lattice, in which the two interpenetrating square sublattices have spins +- 1/2
and spins +-1,0, in the presence of an oscillating magnetic field has been
studied with Monte Carlo techniques. The model includes nearest and
next-nearest neighbor interactions, a crystal field and the oscillating
external field. By studying the hysteretic response of this model to an
oscillating field we found that it qualitatively reproduces the increasing of
the coercive field at the compensation temperature observed in real
ferrimagnets, a crucial feature for magneto-optical applications. This behavior
is basically independent of the frequency of the field and the size of the
system. The magnetic response of the system is related to a dynamical
transition from a paramagnetic to a ferromagnetic phase and to the different
temperature dependence of the relaxation times of both sublattices.Comment: 10 figures. To be published in Phys.Rev
Electric-field-induced charge-transfer phase transition: a promising approach toward electrically switchable devices
Much research has been directed toward the development of electrically switchable optical materials for applications in memory and display devices. Here we present experimental evidence for an electric-field-induced charge-transfer phase transition in two cyanometalate complexes: Rb₀․₈Mn-[Fe(CN)₆]₀․₉₃•1.62H₂O and Co₃[W(CN)₈]₂(pyrimidine)₄•6H₂O, involving changes in their magnetic, optical, and electronic properties as well. Application of an electric field above a threshold value and within the thermal hysteresis region leads to a transition from the high- to the low-temperature phase in these compounds. A model is proposed to explain the main observations on the basis of a para-ferroelectric transition. Our observations suggest that this new concept of electrical switching, based on materials exhibiting charge-transfer phase transitions with large thermal hysteresis loops, may open up doors for novel electro-optical devices
Interplay between the Charge Transport Phenomena and the Charge-Transfer Phase Transition in RbxMn[Fe(CN)6]y · zH2O
Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y · zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (∼0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < ∼220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis
A single dividing cell population with imbalanced fate drives oesophageal tumour growth
Enforcing Multifunctionality: A Pressure-Induced Spin-Crossover Photomagnet
Photomagnetic compounds are usually
achieved by assembling preorganized
individual molecules into rationally designed molecular architectures
via the bottom-up approach. Here we show that a magnetic response
to light can also be enforced in a nonphotomagnetic compound by applying
mechanical stress. The nonphotomagnetic cyano-bridged Fe<sup>II</sup>–Nb<sup>IV</sup> coordination polymer {[Fe<sup>II</sup>(pyrazole)<sub>4</sub>]<sub>2</sub>[Nb<sup>IV</sup>(CN)<sub>8</sub>]·4H<sub>2</sub>O}<sub><i>n</i></sub> (<b>FeNb</b>) has been
subjected to high-pressure structural, magnetic and photomagnetic
studies at low temperature, which revealed a wide spectrum of pressure-related
functionalities including the light-induced magnetization. The multifunctionality
of <b>FeNb</b> is compared with a simple structural and magnetic
pressure response of its analog {[Mn<sup>II</sup>(pyrazole)<sub>4</sub>]<sub>2</sub>[Nb<sup>IV</sup>(CN)<sub>8</sub>]·4H<sub>2</sub>O}<sub><i>n</i></sub> (<b>MnNb</b>). The <b>FeNb</b> coordination polymer is the first pressure-induced spin-crossover
photomagnet
A single dividing cell population with imbalanced fate drives oesophageal tumour growth.
Understanding the cellular mechanisms of tumour growth is key for designing rational anticancer treatment. Here we used genetic lineage tracing to quantify cell behaviour during neoplastic transformation in a model of oesophageal carcinogenesis. We found that cell behaviour was convergent across premalignant tumours, which contained a single proliferating cell population. The rate of cell division was not significantly different in the lesions and the surrounding epithelium. However, dividing tumour cells had a uniform, small bias in cell fate so that, on average, slightly more dividing than non-dividing daughter cells were generated at each round of cell division. In invasive cancers induced by Kras(G12D) expression, dividing cell fate became more strongly biased towards producing dividing over non-dividing cells in a subset of clones. These observations argue that agents that restore the balance of cell fate may prove effective in checking tumour growth, whereas those targeting cycling cells may show little selectivity.Cancer Research UK (Grant ID: C609/A17257), Medical Research Council (Grant-in-Aid), DFG (Research Fellowship), Engineering and Physical Sciences Research Council (Critical Mass Grant), Wellcome Trust (Grant ID: 098357/Z/12/Z)This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/ncb340
- …