151 research outputs found
Structure of Metastable States in Phase Transitions with High-Spin Low-Spin Degree of Freedom
Difference of degeneracy of the low-spin (LS) and high-spin (HS) states
causes interesting entropy effects on spin-crossover phase transitions and
charge transfer phase transitions in materials composed of the spin-crossover
atoms. Mechanisms of the spin-crossover (SC) phase transitions have been
studied by using Wajnflasz model, where the degeneracy of the spin states (HS
or LS) is taken into account and cooperative natures of the spin-crossover
phase transitions have been well described. Recently, a charge transfer (CT)
phase transition due to electron hopping between LS and HS sites has been
studied by using a generalized Wajnflasz model. In the both systems of SC and
CT, the systems have a high temperature structure (HT) and a low temperature
structure (LT), and the change between them can be a smooth crossover or a
discontinuous first order phase transition depending on the parameters of the
systems. Although apparently the standard SC system and the CT system are very
different, it is shown that both models are equivalent under a certain
transformation of variables. In both systems, the structure of metastable state
at low temperatures is a matter of interest. We study temperature dependence of
fraction of HT systematically in a unified model, and find several structures
of equilibrium and metastable states of the model as functions of system
parameters. In particular, we find a reentrant type metastable branch of HT in
a low temperature region, which would play an important role to study the
photo-irradiated processes of related materials.Comment: 19 pages, 11 figure
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
Size dependence of the photoinduced magnetism and long-range ordering in Prussian blue analog nanoparticles of rubidium cobalt hexacyanoferrate
Nanoparticles of rubidium cobalt hexacyanoferrate
(RbCo[Fe(CN)]HO) were synthesized using different
concentrations of the polyvinylpyrrolidone (PVP) to produce four different
batches of particles with characteristic diameters ranging from 3 to 13 nm.
Upon illumination with white light at 5 K, the magnetization of these particles
increases. The long-range ferrimagnetic ordering temperatures and the coercive
fields evolve with nanoparticle size. At 2 K, particles with diameters less
than approximately 10 nm provide a Curie-like magnetic signal.Comment: 10 pages, 6 figures in text, expanded text and dat
New insights into how adipocytes sense their triglyceride stores. Is cholesterol a signal?
In recent years, our view of adipose tissue has evolved from a passive sink for energy storage to an active tissue producing multiple molecules acting on various tissues in different aspects of energy homeostasis. The production of adipose-derived secretory products is tightly regulated as a function of adipocyte lipid accumulation, but the mechanisms by which fat cells are able to sense the levels of their triglyceride stores still remains largely unknown. This paper reviews new insights into this question taking cholesterol as a potential intracellular signaling molecule
Reductions in all-cause, cancer, and coronary mortality in statin-treated patients with heterozygous familial hypercholesterolaemia: a prospective registry study
AIMS: To examine the changes in coronary, all-cause, and cancer mortality in patients with heterozygous familial hypercholesterolaemia (FH) before and after lipid-lowering therapy with statins. METHODS AND RESULTS: A total of 3382 patients (1650 men) aged <80 years were recruited from 21 lipid clinics in the United Kingdom and followed prospectively between 1980 and 2006 for 46 580 person-years. There were 370 deaths, including 190 from coronary heart disease (CHD) and 90 from cancer. The standardized mortality ratio (compared with the population in England and Wales) was calculated before and from 1 January 1992. In patients aged 20-79 years, CHD mortality fell significantly by 37% (95% CI = 7-56) from 3.4- to 2.1-fold excess. Primary prevention resulted in a 48% reduction in CHD mortality from 2.0-fold excess to none, with a smaller reduction of nearly 25% in patients with established disease. Coronary mortality was reduced more in women than in men. In patients without known CHD at registration, all-cause mortality from 1992 was 33% (21-43), lower than in the general population, mainly due to a 37% (21-50) lower risk of fatal cancer. CONCLUSION: The results emphasize the importance of early identification of FH and treatment with statins
Magnetization steps in a diluted Heisenberg antiferromagnetic chain: Theory and experiments on TMMC:Cd
A theory for the equilibrium low-temperature magnetization M of a diluted
Heisenberg antiferromagnetic chain is presented. The magnetization curve, M
versus B, is calculated using the exact contributions of finite chains with 1
to 5 spins, and the "rise and ramp approximation" for longer chains. Some
non-equilibrium effects that occur in a rapidly changing B, are also
considered. Specific non-equilibrium models based on earlier treatments of the
phonon bottleneck, and of spin flips associated with cross relaxation and with
level crossings, are discussed. Magnetization data on powders of TMMC diluted
with cadmium [i.e., (CH_3)_4NMn_xCd_(1-x)Cl_3, with 0.16<=x<=0.50 were measured
at 0.55 K in 18 T superconducting magnets. The field B_1 at the first MST from
pairs is used to determine the NN exchange constant, J, which changes from -5.9
K to -6.5 K as x increases from 0.16 to 0.50. The magnetization curves obtained
in the superconducting magnets are compared with simulations based on the
equilibrium theory. Data for the differential susceptibility, dM/dB, were taken
in pulsed magnetic fields (7.4 ms duration) up to 50 T, with the powder samples
in a 1.5 K liquid-helium bath. Non-equilibrium effects, which became more
severe as x decreased, were observed. The non-equilibrium effects are
tentatively interpreted using the "Inadequate Heat Flow Scenario," or to
cross-relaxation, and crossings of energy levels, including those of excited
states.Comment: 16 pages, 14 figure
Equivalence between non-bilinear spin- Ising model and Wajnflasz model
We propose the mapping of polynomial of degree 2S constructed as a linear
combination of powers of spin- (for simplicity, we called as spin-
polynomial) onto spin-crossover state. The spin- polynomial in general can
be projected onto non-symmetric degenerated spin up (high-spin) and spin down
(low-spin) momenta. The total number of mapping for each general spin- is
given by . As an application of this mapping, we consider a
general non-bilinear spin- Ising model which can be transformed onto
spin-crossover described by Wajnflasz model. Using a further transformation we
obtain the partition function of the effective spin-1/2 Ising model, making a
suitable mapping the non-symmetric contribution leads us to a spin-1/2 Ising
model with a fixed external magnetic field, which in general cannot be solved
exactly. However, for a particular case of non-bilinear spin- Ising model
could become equivalent to an exactly solvable Ising model. The transformed
Ising model exhibits a residual entropy, then it should be understood also as a
frustrated spin model, due to competing parameters coupling of the non-bilinear
spin- Ising model
Spectral sensitive phonon wipeout due to a fluctuating spin state in a Fe2+ coordination polymer
Raman scattering in the spin-crossover system [Fe(pmd)(H2O){Au(CN)2}2]*H2O
reveals a complex three-phase spin-state transition in contrast to earlier
observations in magnetization measurements. We observe different spin state
phases as function of temperature and electromagnetic radiation in the visible
spectral range. There exists a fluctuating spin state phase with an unexpected
wipeout of the low frequency phonon scattering intensity. Furthermore we
observe one phase with reduced symmetry that is attributed to a cooperative
Jahn-Teller effect. Pronounced electron-phonon interaction manifests itself as
a strong Fano-resonance of phonons related to {FeN6} and {FeN4O2} coordination
octahedra. Density functional theory supports this interpretation.Comment: 9 pages, 9 figures, 3 table
Exome sequencing in suspected monogenic dyslipidemias
Exome sequencing is a promising tool for gene mapping in Mendelian disorders. We used this technique in an attempt to identify novel genes underlying monogenic dyslipidemias
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