Laboratory study on heterogeneous decomposition of methyl chloroform on various standard aluminosilica clay minerals as a potential tropospheric sink

International audienceMethyl chloroform (1,1,1-trichloroethane, CH3CCl3) was found to decompose heterogeneously on seven types of standard clay minerals (23 materials) in dry air at 313 K in the laboratory. All reactions proceeded through the elimination of HCl; CH3CCl3 was converted quantitatively to CH2=CCl2. The activities of the clay minerals were compared via their pseudo-first-order reaction rate constants (k1). A positive correlation was observed between the k1 value and the specific surface area (S) of clay minerals, where the S value was determined by means of the general Brunauer-Emmett-Teller (BET) equation. The k1 value was anti-correlated with the value of n, which was a parameter of the general BET equation and related to the average pore size of the clay minerals, and correlated with the water content that can be removed easily from the clay minerals. The reaction required no special pretreatment of clay minerals, such as heating at high temperatures; hence, the reaction can be expected to occur in the environment. Photoillumination by wavelengths present in the troposphere did not accelerate the decomposition of CH3CCl3, but it induced heterogeneous photodecomposition of CH2=CCl2. The temperature dependence of k1, the adsorption equilibrium coefficient of CH3CCl3 and CH2=CCl2, and the surface reaction rate constant of CH3CCl3 were determined for an illite sample. The k1 value increased with increasing temperature. The amount of CH3CCl3 adsorbed on the illite during the reaction was proportional to the partial pressure of CH3CCl3. The reaction was sensitive to relative humidity and the k1 value decreased with increasing relative humidity. However, the reaction was found to proceed at a relative humidity of 22% at 313 K, although the k1 value was about one-twentieth of the value in non-humidified air. The conditions required for the reaction may be present in major desert regions of the world. A simple estimation indicates that the possible heterogeneous decomposition of CH3CCl3 on the ground surface in arid regions is worth taking into consideration when inferring the tropospheric lifetime of CH3CCl3 and global OH concentration from the global budget concentration of CH3CCl3

Anisotropic Superparamagnetism of Monodispersive Cobalt-Platinum Nanocrystals

Based on the high-temperature organometallic route (Sun et al. Science 287, 1989 (2000)), we have synthesized powders containing CoPt_3 single crystals with mean diameters of 3.3(2) nm and 6.0(2) nm and small log-normal widths sigma=0.15(1). In the entire temperature range from 5 K to 400 K, the zero-field cooled susceptibility chi(T) displays significant deviations from ideal superparamagnetism. Approaching the Curie temperature of 450(10) K, the deviations arise from the (mean-field) type reduction of the ferromagnetic moments, while below the blocking temperature T_b, chi(T) is suppressed by the presence of energy barriers, the distributions of which scale with the particle volumes obtained from transmission electron microscopy (TEM). This indication for volume anisotropy is supported by scaling analyses of the shape of the magnetic absorption chi''(T,omega) which reveal distribution functions for the barriers being also consistent with the volume distributions observed by TEM. Above 200 K, the magnetization isotherms M(H,T) display Langevin behavior providing 2.5(1) mu_B per CoPt_3 in agreement with reports on bulk and thin film CoPt_3. The non-Langevin shape of the magnetization curves at lower temperatures is for the first time interpreted as anisotropic superparamagnetism by taking into account an anisotropy energy of the nanoparticles E_A(T). Using the magnitude and temperature variation of E_A(T), the mean energy barriers and 'unphysical' small switching times of the particles obtained from the analyses of chi''(T,omega) are explained. Below T_b hysteresis loops appear and are quantitatively described by a blocking model, which also ignores particle interactions, but takes the size distributions from TEM and the conventional field dependence of E_A into account.Comment: 12 pages with 10 figures and 1 table. Version accepted for publication in Phys. Rev. B . Two-column layou

Identification of biomarkers in ductal carcinoma in situ of the breast with microinvasion

<p>Abstract</p> <p>Background</p> <p>Widespread use of mammography in breast cancer screening has led to the identification of increasing numbers of patients with ductal carcinoma <it>in situ </it>(DCIS). DCIS of the breast with an area of focal invasion 1 mm or less in diameter is defined as DCIS with microinvasion, DCIS-Mi. Identification of biological differences between DCIS and DCIS-Mi may aid in understanding of the nature and causes of the progression of DCIS to invasiveness.</p> <p>Methods</p> <p>In this study, using resected breast cancer tissues, we compared pure DCIS (52 cases) and DCIS-Mi (28 cases) with regard to pathological findings of intraductal lesions, biological factors, apoptosis-related protein expression, and proliferative capacity through the use of immunohistochemistry and the TdT-mediated dUTP-biotin nick end labeling (TUNEL) method.</p> <p>Results</p> <p>There were no differences in biological factors between DCIS and DCIS-Mi, with respect to levels of estrogen receptor, progesterone receptor, and human epidermal growth factor receptor type 2. The frequency of necrosis and positive expression ratio of survivin and Bax were significantly higher in DCIS-Mi than in DCIS. In addition, apoptotic index, Ki-67 index, and positive Bcl-2 immunolabeling tended to be higher in DCIS-Mi than in DCIS. Multivariate analysis revealed that the presence of necrosis and positive survivin expression were independent factors associated with invasion.</p> <p>Conclusion</p> <p>Compared with DCIS, DCIS-Mi is characterized by a slightly elevated cell proliferation capacity and enhanced apoptosis within the intraductal lesion, both of which are thought to promote the formation of cell necrotic foci. Furthermore, the differential expression of survivin may serve in deciding the response to therapy and may have some prognostic significance.</p

Breast cancer risk variants at 6q25 display different phenotype associations and regulate ESR1, RMND1 and CCDC170.

We analyzed 3,872 common genetic variants across the ESR1 locus (encoding estrogen receptor α) in 118,816 subjects from three international consortia. We found evidence for at least five independent causal variants, each associated with different phenotype sets, including estrogen receptor (ER(+) or ER(-)) and human ERBB2 (HER2(+) or HER2(-)) tumor subtypes, mammographic density and tumor grade. The best candidate causal variants for ER(-) tumors lie in four separate enhancer elements, and their risk alleles reduce expression of ESR1, RMND1 and CCDC170, whereas the risk alleles of the strongest candidates for the remaining independent causal variant disrupt a silencer element and putatively increase ESR1 and RMND1 expression.This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/ng.352