Colossal magnetostriction and negative thermal expansion in the frustrated antiferromagnet ZnCr2Se4

A detailed investigation of ZnCr2Se4 is presented which is dominated by strong ferromagnetic exchange but orders antiferromagnetically at T_N = 21 K. Specific heat C and thermal expansion Delta L/L exhibit sharp first-order anomalies at the antiferromagnetic transition. T_N is strongly reduced and shifted to lower temperatures by external magnetic fields and finally is fully suppressed suggesting a field induced quantum critical behavior close to 60 kOe. Delta L/L(T) is unusually large and exhibits negative thermal expansion below 75 K down to T_N indicating strong frustration of the lattice. Magnetostriction Delta L/L(H) reveals colossal values (0.5x10^{-3}) comparable to giant magnetostriction materials. Electron-spin resonance, however, shows negligible spin-orbital coupling excluding orbitally induced Jahn-Teller distortions. The obtained results point to a spin-driven origin of the structural instability at T_N explained in terms of competing ferromagnetic and antiferromagnetic exchange interactions yielding strong bond frustration.Comment: 5 pages 4 figure

Spin-driven Phonon Splitting in Bond-frustrated ZnCr2S4

Utilizing magnetic susceptibility, specific heat, thermal expansion and IR spectroscopy we provide experimental evidence that the two subsequent antiferromagnetic transitions in ZnCr_2S_4 at T_N1 = 15 K and T_N2= 8 K are accompanied by significant thermal and phonon anomalies. The anomaly at T_N2 reveals a strong temperature hysteresis typical for a first-order transformation. Due to strong spin-phonon coupling both magnetic phase transitions induce a splitting of phonon modes, where at T_N1 the high-frequency and at T_N2 the low-frequency modes split. The anomalies and phonon splitting observed at T_N2 are strongly suppressed by magnetic field. Regarding the small positive Curie-Weiss temperature Theta= 8 K, we argue that this scenario of two different magnetic phases with concomitant different magneto-elastic couplings results from the strong competition of ferromagnetic and antiferromagnetic exchange of equal strength.Comment: 4 pages, 4 figure

Spin-driven Phase Transitions in ZnCr2_2Se4_4 and ZnCr2_2S4_4 Probed by High Resolution Synchrotron X-ray and Neutron Powder Diffraction

The crystal and magnetic structures of the spinel compounds ZnCr$_2$S$_4$ and ZnCr$_2$Se$_4$ were investigated by high resolution powder synchrotron and neutron diffraction. ZnCr$_2$Se$_4$ exhibits a first order phase transition at $T_N=21$ K into an incommensurate helical magnetic structure. Magnetic fluctuations above $T_N$ are coupled to the crystal lattice as manifested by negative thermal expansion. Both, the complex magnetic structure and the anomalous structural behavior can be related to magnetic frustration. Application of an external magnetic field shifts the ordering temperature and the regime of negative thermal expansion towards lower temperatures. Thereby, the spin ordering changes into a conical structure. ZnCr$_2$S$_4$ shows two magnetic transitions at $T_{N1}=15$ K and $T_{N2}=8$ K that are accompanied by structural phase transitions. The crystal structure transforms from the cubic spinel-type (space group $Fd$\={3}$m$) at high temperatures in the paramagnetic state, via a tetragonally distorted intermediate phase (space group $I4_1$ / $amd$) for $T_{N2} < T < T_{N1}$ into a low temperature orthorhombic phase (space group $I m m a$) for $T < T_{N2}$. The cooperative displacement of sulfur ions by exchange striction is the origin of these structural phase transitions. The low temperature structure of ZnCr$_2$S$_4$ is identical to the orthorhombic structure of magnetite below the Verwey transition. When applying a magnetic field of 5 T the system shows an induced negative thermal expansion in the intermediate magnetic phase as observed in ZnCr$_2$Se$_4$.Comment: 11 pages, 13 figures, to be published in PR

Spin Driven Jahn-Teller Distortion in a Pyrochlore system

The ground-state properties of the spin-1 antiferromagnetic Heisenberg model on the corner-sharing tetrahedra, pyrochlore lattice, is investigated. By breaking up each spin into a pair of 1/2-spins, the problem is reduced to the equivalent one of the spin-1/2 tetrahedral network in analogy with the valence bond solid state in one dimension. The twofold degeneracy of the spin-singlets of a tetrahedron is lifted by a Jahn-Teller mechanism, leading to a cubic to tetragonal structural transition. It is proposed that the present mechanism is responsible for the phase transition observed in the spin-1 spinel compounds ZnV$_2$O$_4$ and MgV$_2$O$_4$.Comment: 4 pages, 3 eps figures, REVTeX, to appear in Phys. Rev. Let

Magnetic properties of the frustrated AFM spinel ZnCr_2O_4 and the spin-glass Zn_{1-x}Cd_xCr_2O_4 (x=0.05,0.10)

The $T$-dependence (2- 400 K) of the electron paramagnetic resonance (EPR), magnetic susceptibility, $\chi (T)$, and specific heat, $C_{v}(T)$, of the $normal$ antiferromagnetic (AFM) spinel ZnCr$_{2}$O$_{4}$ and the spin-glass (SG) Zn$_{1-x}$Cd$_{x}$Cr$_{2}$O$_{4}$ ($x=0.05,0.10$) is reported. These systems behave as a strongly frustrated AFM and SG with $$ $\approx T_{G}\approx 12$ K and -400 K $\gtrsim \Theta_{CW}\gtrsim -500$ K. At high-$T$ the EPR intensity follows the $\chi (T)$ and the $g$-value is $T$-independent. The linewidth broadens as the temperature is lowered, suggesting the existence of short range AFM correlations in the paramagnetic phase. For ZnCr$_{2}$O$_{4}$ the EPR intensity and $\chi (T)$ decreases below 90 K and 50 K, respectively. These results are discussed in terms of nearest-neighbor Cr$^{3+}$ (S $=3/2$%) spin-coupled pairs with an exchange coupling of $| J/k| \approx$ 50 K. The appearance of small resonance modes for $T\lesssim 17$ K, the observation of a sharp drop in $\chi (T)$ and a strong peak in $C_{v}(T)$ at $T_{N}=12$ K confirms, as previously reported, the existence of long range AFM correlations in the low-$T$ phase. A comparison with recent neutron diffraction experiments that found a near dispersionless excitation at 4.5 meV for $T\lesssim T_{N}$ and a continuous gapless spectrum for $T\gtrsim T_{N}$, is also given.Comment: 17 pages, 8 figures, 1 Table. Submitted to Physical Review

Expression of the 60 kDa and 71 kDa heat shock proteins and presence of antibodies against the 71 kDa heat shock protein in pediatric patients with immune thrombocytopenic purpura

BACKGROUND: Immune thrombocytopenic purpura (ITP) is an autoimmune disease characterized by platelet destruction resulting from autoantibodies against platelet proteins, particularly platelet glycoprotein IIb/IIIa. Heat shock proteins (Hsp) have been shown to be major antigenic determinants in some autoimmune diseases. Antibodies to Hsps have also been reported to be associated with a number of pathological states. METHODS: Using western blot, we measured the levels of the 60 kDa heat shock protein (Hsp60) and of the inducible 71 kDa member of the Hsp70 family (Hsp71) in lymphocytes and the presence of antibodies against these hsps in plasma of 29 pediatric patients with ITP before the treatment and in 6 other patients before and after treatment. RESULTS: Interestingly only one out of 29 patients showed detectable Hsp60 in lymphocytes while this heat shock protein was detected in the 30 control children. Hsp71 levels were slightly lower in lymphocytes of patients with ITP than in controls (1567.8 ± 753.2 via 1763.2 ± 641.8 integrated optical density (IOD) units). There was a small increase of Hsp71 after recovery from ITP. The titers of plasma antibodies against Hsp60 and Hsp71 were also examined. Antibodies against Hsp71 were more common in ITP patients (15/29) than in control children (5/30). The titer of anti-Hsp71 was also higher in children patients with ITP. The prevalence of ITP children with antibodies against Hsp71 (51.7%) was as high as those with antibodies against platelet membrane glycoproteins (58.3%). CONCLUSIONS: In summary, pediatric patients with ITP showed no detectable expression of Hsp60 in lymphocytes and a high prevalence of antibody against Hsp71 in plasma. These changes add to our understanding of the pathogenesis of ITP and may be important for the diagnosis, prognosis and treatment of ITP

Plasma antibodies against heat shock protein 70 correlate with the incidence and severity of asthma in a Chinese population

BACKGROUND: The heat shock proteins (Hsps) are induced by stresses such as allergic factors and inflammatory responses in bronchi epithelial cells and therefore may be detectable in patients with asthma. However, the etiologic link between anti-Hsps and asthma (its severity and related inflammatory responses such as interleukin-4 and immunoglobulin E) has not been established. We determined whether antibodies against Hsp60 and Hsp70 were present in patients with asthma and evaluated their associations with risk and severity of asthma. METHODS: We determined the levels of anti-Hsp60 and anti-Hsp70 by immunoblot and their associations with risk and symptom severity of asthma in 95 patients with asthma and 99 matched non-symptomatic controls using multivariate logistic regression analysis. RESULTS: Compared to the controls, asthma patients were more likely to have detectable anti-Hsp60 (17.2% vs 5.1%) and anti-Hsp70 (33.7% vs 8.1%) (p ≤ 0.001). In particular, the presence of anti-Hsp70 was associated with a greater than 2 fold risk for asthma (adjusted OR = 2.21; 95% CI = 1.35~3.59). Furthermore, both anti-Hsp60 and anti-Hsp70 levels were positively correlated with symptom severity (p < 0.05) as well as interleukin-4 and immunoglobulin E (p < 0.05). Individuals with antibodies against anti-Hsp60 and anti-Hsp70 were more likely to have a family history of asthma (p < 0.001) and higher plasma concentrations of total immunoglobulin E (p = 0.001) and interleukin-4 (p < 0.05) than those without antibodies. CONCLUSIONS: These data suggest that anti-Hsp60 and especially anti-Hsp70 correlate with the attacks and severity of asthma. The underlying molecular mechanisms linking antibodies to heat shock proteins and asthma remain to be investigated