Effect of Poly(methacrylic acid) on the Cytokine Level in an In Vivo Tumor Model

Cancer is a leading cause of mortality globally. Despite remarkable improvements in cancer-treatment approaches, disease recurrence and progression remain major obstacles to therapy. While chemotherapy is still a first-line treatment for a variety of cancers, the focus has shifted to the development and application of new approaches to therapy. Nevertheless, the relationship between immune response, neoplastic diseases and treatment efficiency is not fully understood. Therefore, the aim of the study was to investigate the immunopharmacological effects of methacrylic acid homopolymer in an in vivo tumor model. Materials and methods: Monomeric methacrylic acid was used to synthesize polymers. Methacrylic acid was polymerized in dioxane in the presence of 4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid. To study the molecular weight characteristics of PMAA by GPC, carboxyl groups were preliminarily methylated with diazomethane. An experimental cancer model was obtained by grafting RMK1 breast cancer cells. The serum levels of IL-6, IL-10, IL-17, transforming growth factor β1 (TGF-β1), and tumor necrosis factor α (TNF-α) were measured by ELISA. Results: The effect of PMAA on the serum concentrations of several cytokines was studied upon its single administration to laboratory animals in early neoplastic process. The IL-6, IL-17 and TGF-β1 concentrations were found to change significantly and reach the level observed in intact rats. The IL-10 concentration tended to normalize. Conclusion: The positive results obtained are the basis for further studies on the effect of methacrylic-acid polymers with different molecular-weight characteristics on the neoplastic process.     

Bulk and surface electron transport in topological insulator candidate YbB6–δ

We report the study of transport and magnetic properties of the YbB_6–δsingle crystals grown by inductive zone melting. A strong disparity in the low temperature resistivity, Seebeck and Hall coefficients is established for the samples with the different level of boron deficiency. The effective parameters of the charge transport in YbB_6–δ are shown to depend on the concentration of intrinsic defects, which is estimated to range from 0.09% to 0.6%. The pronounced variation of Hall mobility μ_H found for bulk holes is induced by the decrease of transport relaxation time from τ ≈ 7.7 fs for YbB_5.994 to τ ≈ 2.2 fs for YbB_5.96. An extra contribution to conductivity from electrons with μ_H≈ –1000 cm² V^–1 s^–1 and the very low concentration n /n_Yb≈ 10^–6 discovered below 20 K for all the single crystals under investigation is suggested to arise from the surface electron states appeared in the inversion layer due to the band bending. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Axial Site Occupancy by the Least Electronegative Ligands in Trigonal Bipyramidal Tetraoxyphosphoranes(1)

Analogous to the formation of CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(Ph)(O(2)C(6)Cl(4)) (1), the new bicyclic tetraoxyphosphoranes CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(Et)(O(2)C(6)Cl(4)) (3) and CH(2)[ClC(6)H(3)O](2)P(Ph)(O(2)C(6)Cl(4)) (4) were synthesized by the oxidative addition of the appropriate cyclic phosphines with o-tetrachlorobenzoquinone. For the formation of CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(Ph)(O(2)C(2)Ph(2)) (2), a similar reaction was followed with the use of benzil (PhCOCOPh) in place of o-tetrachlorobenzoquinone. X-ray analysis of 1-3 revealed trigonal bipyramidal geometries and provided evidence for the first series of complexes in the absence of ring strain in which the least electronegative group, ethyl or phenyl, is located in an axial position, in violation of the electronegativity rule. Thus, the two oxygen-containing ring systems occupied two different sets of positions in the trigonal bipyramid (TBP) with the eight-membered rings at diequatorial sites. X-ray analysis of 4 revealed a trigonal bipyramidal geometry with electron-withdrawing chlorine substituents on each ring assumed the more conventional geometry with the rings occupying axial-equatorial positions and the phenyl group located in the remaining equatorial site. The fact that molecular mechanics calculations favorably reproduced the observed geometries suggests that a steric contribution associated with the ring tert-butyl groups for 1-3 is partly responsible in favoring diequatorial ring occupancy for the eight-membered ring. NMR data supported rigid pentacoordinated structures in solution at 23 degrees C. Phosphorane 1 crystallizes in the orthorhombic space group Fdd2 with a = 44.787(5) ?, b = 34.648(8) ?, c = 10.3709(9) ?, and Z = 16. Phosphorane 2 crystallizes in the orthorhombic space group Pna2(1) with a = 20.658(8) ?, b = 10.342(2) ?, c = 19.879(6) ?, and Z = 4. Phosphorane 3 crystallizes in the orthorhombic space group Pcmn with a = 9.807(2) ?, b = 16.632(4) ?, c = 23.355(3) ?, and Z = 4. Phosphorane 4 crystallizes in the monoclinic space group C2/c with a = 35.699(5) ?, b = 12.187(2) ?, c = 14.284(3) ?, beta = 107.08(1) degrees, and Z = 8. The final conventional unweighted residuals are 0.0395 (1), 0.0518 (2), 0.0540 (3), and 0.0868 (4).     

Ionic liquid matrices for MALDI mass spectrometry of lignin

Analytical and Bioanalytical Chemistry - The use of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry for the study of lignin is still extremely limited due to its low...     

Monasnicotinic acid,a novel pyridine alkaloid of the fungus Aspergillus cavernicola: isolation and structure elucidation

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Calorimetric study of poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K

For the first time, the heat capacity $ C_{\text{p}}^{^\circ } $ of poly(2-ethylhexyl acrylate) has been studied in an adiabatic vacuum calorimeter between 7 and 350 K, the standard thermodynamic functions: heat capacity $ C_{\text{p}}^{^\circ } $ (T), enthalpy H°(T) ? H°(0), entropy S°(T) ? S°(0), Gibbs function G°(T) ? H°(0) have been calculated from T → 0 to 350 K. The energy of combustion Δ_c U of the compound under study has been measured in a calorimeter with a stationary bomb and an isothermal shell. The standard enthalpy of combustion Δ_c H° and thermodynamic parameters of formation—enthalpy Δ_f H°, entropy Δ_f S°, Gibbs function Δ_f G°—at T = 298.15 K have been calculated. The results have been used to calculate the thermodynamic characteristics of 2-ethylhexyl acrylate bulk polymerization into poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K.     

Critical Effect of Film Thickness on Preconcentration Electroanalysis with Oriented Mesoporous Silica Modified Electrodes

Electrogenerated silica thin films exhibiting a regular hexagonal packing of vertically‐aligned mesopore channels are promising for preconcentration electroanalysis. This work demonstrates the critical role of film thickness on their sensing performance using paraquat as a model analyte, based on mesoporous silica films prepared by electrochemically assisted self‐assembly performed for various deposition times. Films prepared with too short synthesis times (<10 s) led to deposits covering partially the electrode surface and suffered from rather poor sensing performance. Then, uniformly deposited films were obtained (between 10 and 15 s), and sensitivity rose up by increasing deposition times, whereas some limitations started to occur with much thicker films (>15 s deposition times) as a result of less electrochemically accessible paraquat accumulated far away from the electrode surface and restricted mass transport through the whole film thickness. These limitations were also confirmed on the basis of multi‐layered mesoporous silica films, suggesting a behavior that might be typical for other types of film‐modified electrodes.     

Two dimorphs of 5‐methyl­sulfanyl‐1H‐tetrazole

5‐Methyl­sulfanyl‐1H‐tetrazole, C₂H₄N₄S, crystallizes in dimor­phic forms; the α‐form crystallizes at room temperature in the monoclinic crystal system, space group P2₁/m, and the β‐form crystallizes by sublimation at 423 K in the orthorhombic crystal system, space group Pbcm. In both forms, the mol­ecules occupy crystallographic mirror planes and are connected to one another via N—H⋯N hydrogen bonds, the amino H atoms being disordered. The two forms differ from one another in their packing; there are polar layers in the α‐form and non‐polar layers in the β‐form.     

Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.