Brittle porous material mesovolume structure models and simulation of their mechanical properties

To study the mechanical response of brittle porous materials at mesoscale, porous samples were generated and their deformation was numerically modelled. Two types of pore space morphology such as overlapping spherical pores and overlapping spherical solids were explicitly considered. For deformation modelling, an evolutionary approach including the nonlinear constitutive equations used to describe damage accumulation and its impact on the degradation of the solid frame strength properties was applied. The numerical results have shown that an average stress-strain diagram is sensitive to pore morphology as well as porosity

Oil spill problems and sustainable response strategies through new technologies

Crude oil and petroleum products are widespread water and soil pollutants resulting from marine and terrestrial spillages. International statistics of oil spill sizes for all incidents indicate that the majority of oil spills are small (less than 7 tonnes). The major accidents that happen in the oil industry contribute only a small fraction of the total oil which enters the environment. However, the nature of accidental releases is that they highly pollute small areas and have the potential to devastate the biota locally. There are several routes by which oil can get back to humans from accidental spills, e.g. through accumulation in fish and shellfish, through consumption of contaminated groundwater. Although advances have been made in the prevention of accidents, this does not apply in all countries, and by the random nature of oil spill events, total prevention is not feasible. Therefore, considerable world-wide effort has gone into strategies for minimising accidental spills and the design of new remedial technologies. This paper summarizes new knowledge as well as research and technology gaps essential for developing appropriate decision-making tools in actual spill scenarios. Since oil exploration is being driven into deeper waters and more remote, fragile environments, the risk of future accidents becomes much higher. The innovative safety and accident prevention approaches summarized in this paper are currently important for a range of stakeholders, including the oil industry, the scientific community and the public. Ultimately an integrated approach to prevention and remediation that accelerates an early warning protocol in the event of a spill would get the most appropriate technology selected and implemented as early as possible-the first few hours after a spill are crucial to the outcome of the remedial effort. A particular focus is made on bioremediation as environmentally harmless, cost-effective and relatively inexpensive technology. Greater penetration into the remedial technologies market depends on the harmonization of environment legislation and the application of modern laboratory techniques, e.g. ecogenomics, to improve the predictability of bioremediation

Synthesis and properties of the heterospin (S1 = S2 = 1/2) radical-ion salt bis(mesitylene)molybdenum(I) [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

The authors are grateful to the Presidium of the Russian Academy of Sciences (Project 8.14), the Royal Society (RS International Joint Project 2010/R3), the Leverhulme Trust (Project IN-2012-094), the Siberian Branch of the Russian Academy of Sciences (Project 13), the Ministry of Education and Science of the Russian Federation (Project of Joint Laboratories of Siberian Branch of the Russian Academy of Sciences and National Research Universities), and the Russian Foundation for Basic Research (Projects 13-03-00072 and 15-03-03242) for financial support of various parts of this work. N.A.S. thanks the Council for Grants of the President of Russian Federation for postdoctoral scholarship (grant MK-4411.2015.3). B.E.B. is grateful for an EaStCHEM Hirst Academic Fellowship. A.V.Z. thanks the Foundation named after D. I. Mendeleev, Tomsk State University, for support of his work.Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene / 1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]– (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2−300 K, the molar magnetic susceptibility of 2 is well-described by the Curie-Weiss law with parameters C and θ equal to 0.78 cm3⋅K⋅mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]– and [CrCp*2]+[1]–, i.e. changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.PostprintPostprintPeer reviewe

31st Annual Meeting and Associated Programs of the Society for Immunotherapy of Cancer (SITC 2016) : part two

Background The immunological escape of tumors represents one of the main ob- stacles to the treatment of malignancies. The blockade of PD-1 or CTLA-4 receptors represented a milestone in the history of immunotherapy. However, immune checkpoint inhibitors seem to be effective in specific cohorts of patients. It has been proposed that their efficacy relies on the presence of an immunological response. Thus, we hypothesized that disruption of the PD-L1/PD-1 axis would synergize with our oncolytic vaccine platform PeptiCRAd. Methods We used murine B16OVA in vivo tumor models and flow cytometry analysis to investigate the immunological background. Results First, we found that high-burden B16OVA tumors were refractory to combination immunotherapy. However, with a more aggressive schedule, tumors with a lower burden were more susceptible to the combination of PeptiCRAd and PD-L1 blockade. The therapy signifi- cantly increased the median survival of mice (Fig. 7). Interestingly, the reduced growth of contralaterally injected B16F10 cells sug- gested the presence of a long lasting immunological memory also against non-targeted antigens. Concerning the functional state of tumor infiltrating lymphocytes (TILs), we found that all the immune therapies would enhance the percentage of activated (PD-1pos TIM- 3neg) T lymphocytes and reduce the amount of exhausted (PD-1pos TIM-3pos) cells compared to placebo. As expected, we found that PeptiCRAd monotherapy could increase the number of antigen spe- cific CD8+ T cells compared to other treatments. However, only the combination with PD-L1 blockade could significantly increase the ra- tio between activated and exhausted pentamer positive cells (p= 0.0058), suggesting that by disrupting the PD-1/PD-L1 axis we could decrease the amount of dysfunctional antigen specific T cells. We ob- served that the anatomical location deeply influenced the state of CD4+ and CD8+ T lymphocytes. In fact, TIM-3 expression was in- creased by 2 fold on TILs compared to splenic and lymphoid T cells. In the CD8+ compartment, the expression of PD-1 on the surface seemed to be restricted to the tumor micro-environment, while CD4 + T cells had a high expression of PD-1 also in lymphoid organs. Interestingly, we found that the levels of PD-1 were significantly higher on CD8+ T cells than on CD4+ T cells into the tumor micro- environment (p < 0.0001). Conclusions In conclusion, we demonstrated that the efficacy of immune check- point inhibitors might be strongly enhanced by their combination with cancer vaccines. PeptiCRAd was able to increase the number of antigen-specific T cells and PD-L1 blockade prevented their exhaus- tion, resulting in long-lasting immunological memory and increased median survival

Light-Controlled Multiphase Structuring of Perovskite Crystal Enabled by Thermoplasmonic Metasurface

Halide perovskites belong to an important family of semiconducting materials with electronic properties that enable a myriad of applications, especially in photovoltaics and optoelectronics. Their optical properties, including photoluminescence quantum yield, are affected and notably enhanced at crystal imperfections where the symmetry is broken and the density of states increases. These lattice distortions can be introduced through structural phase transitions, allowing charge gradients to appear near the interfaces between phase structures. In this work, we demonstrate controlled multiphase structuring in a single perovskite crystal. The concept uses cesium lead bromine (CsPbBr3) placed on a thermoplasmonic TiN/Si metasurface and enables single-, double-, and triple-phase structures to form on demand above room temperature. This approach promises application horizons of dynamically controlled heterostructures with distinctive electronic and enhanced optical properties

Minimal Zn2+ Binding Site of Amyloid-β

Zinc-induced aggregation of amyloid-β peptide (Aβ) is a hallmark molecular feature of Alzheimer's disease. Here we provide direct thermodynamic evidence that elucidates the role of the Aβ region 6–14 as the minimal Zn2+ binding site wherein the ion is coordinated by His6, Glu11, His13, and His14. With the help of isothermal titration calorimetry and quantum mechanics/molecular mechanics simulations, the region 11–14 was determined as the primary zinc recognition site and considered an important drug-target candidate to prevent Zn2+-induced aggregation of Aβ