Graphene oxide-gelatin aerogels as wound dressings with improved hemostatic properties

Graphene oxide (GO)-gelatin (G) aerogels were synthesized via the physical interactions between GO-oxygenated groups and G amine groups to obtain potential hemostatic devices. The influence of the aerogel synthesis conditions—acid and basic GO suspensions—was used to evaluate their clotting performance. These materials were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis, and their properties of absorption, stiffness, porosity, surface charge, and pore size were measured and compared. The clotting activity of the materials was evaluated by prothrombin time, activated partial thromboplastin time, soluble human P-selectin, and in vitro dynamic clotting assays, as well as their cytotoxicity. GO-G aerogels presented heterogeneous microporous structures with porosities higher than 90% and a high PBS absorption capacity, 49.6 ± 3.8 g_PBS/g_aerogel for positively charged aerogels (15.63 ± 0.5 mV) and 42.75 ± 2.38 g_PBS/g_aerogel for negatively charged aerogels (?20.53 ± 1.07 mV). Comparatively, positively charged aerogels had superior structural properties to negatively charged aerogels, such as stiffness, porosities, and pore sizes, because they promote H bonding. In regard to hemostatic activity, negatively charged aerogels had higher clotting performance, reaching 95.6% clotted blood, and therefore provide a suitable structure for the coagulation process and promote clot formation without using common mechanisms. In addition, negatively charged aerogels were not cytotoxic and promoted fibroblast proliferation. Therefore, negatively charged GO-G aerogels may be a potential hemostatic device that can be used as a wound dressing.     

Predictions of the excess pressure drop of Boger fluids through a 2:1:2 contraction–expansion geometry using non-equilibrium molecular dynamics

Non-equilibrium molecular dynamics are used to generate the flow of polymer solutions, specifically of Boger fluids, through a planar 2:1:2 contraction–expansion geometry. The solvent molecules are represented by Lennard–Jones particles, while linear molecules are described by spring-monomers with a finite extensible non-linear elastic spring potential. The equations for Poiseuille flow are solved using a multiple time-scale algorithm extended to non-equilibrium situations. Simulations are performed at constant temperature using Nose–Hoover dynamics. At simulation conditions, changes in concentration show no significant effect on molecular conformation, velocity profiles, and stress fields, while variations in the Deborah number have a strong influence on fluid response. Increasing the magnitude of the Deborah number (De), larger deformation rates are developed in the flow region. For a Deborah number of one, the non-dimensional pressure drop presents values lower than the correspondent Newtonian case. However, for large Deborah numbers, the pressure drop increases above the Newtonian reference. An effective excess pressure drop above the Newtonian value is predicted for Boger fluids along this geometry.     

Biogenic Sulfur-Based Chalcogenide Nanocrystals: Methods of Fabrication,Mechanistic Aspects,and Bio-Applications

Bio-nanotechnology has emerged as an efficient and competitive methodology for the production of added-value nanomaterials (NMs). This review article gathers knowledge gleaned from the literature regarding the biosynthesis of sulfur-based chalcogenide nanoparticles (S-NPs), such as CdS, ZnS and PbS NPs, using various biological resources, namely bacteria, fungi including yeast, algae, plant extracts, single biomolecules, and viruses. In addition, this work sheds light onto the hypothetical mechanistic aspects, and discusses the impact of varying the experimental parameters, such as the employed bio-entity, time, pH, and biomass concentration, on the obtained S-NPs and, consequently, on their properties. Furthermore, various bio-applications of these NMs are described. Finally, key elements regarding the whole process are summed up and some hints are provided to overcome encountered bottlenecks towards the improved and scalable production of biogenic S-NPs.     

Open-framework copper adeninate compounds with three-dimensional microchannels tailored by aliphatic monocarboxylic acids

A series of isostructural copper(II) coordination polymers containing the nucleobase adenine and different monocarboxylic acids as bridging ligands, [Cu(2)(μ(3)-ade)(2)(μ(2)-OOC(CH(2))(n)CH(3))(2)]·xH(2)O (n from 0 to 5), have been prepared. Single-crystal X-ray analysis of acetate (n = 0) and butanoate (n = 2) compounds shows a covalent three-dimensional network in which the copper(II) centers are bridged by μ-N3,N7,N9-adeninato and μ-O,O'-carboxylato ligands, with crystallization water molecules trapped in the pores, which are decorated by the Watson-Crick faces of the adenine. The tunable permanent porosity of guest-free compounds was confirmed by gas adsorption measurements.     

Combined Ex and In Situ Measurements Elucidate the Dynamics of Retained Species in ZSM-5 and SAPO-18 Catalysts Used in the Methanol-to-Olefins Reaction

The dynamics of the retained species on ZSM-5 and SAPO-18 catalysts are studied by using a combination of temperature-programmed desorption/oxidation, ex situ analysis, and in situ FTIR spectroscopic measurements over the entire conversion range, using fixed-bed and spectroscopic cell reactors, in continuous and discontinuous mode. The results point to the appropriateness of the combined methodologies to track the interconversion of active into deactivating species. A statistically relevant (supported by linear regression and multivariate analysis) association of the observations is found by using the different complementary methodologies. The kinetics of this interconversion depends on the initial conversion (tuned by acidity and space time) and microporous topology, and involve: (i) in the ZSM-5 catalysts, the diffusion of monocyclic aromatics toward the exterior of the zeolite to form coke, and (ii) in the SAPO-18 catalysts, the obstruction of the cavities by aromatics that grow into tetracyclic aromatic islands.     

A generalized inductive limit strict topology on the space of bounded continuous functions

A generalized inductive limit strict topology β_∞ is defined on C_b(X, E), the space of all bounded, continuous functions from a zero-dimensional Hausdorff space X into a locally -convex space E, where is a field with a nontrivial and nonarchimedean valuation, for which is a complete ultrametric space. Many properties of the topology β_∞ are proved and the dual of (C_b (X, E), β_∞) is studied.     

Why Ni3Al is an itinerant ferromagnet but Ni3Ga is not

Ni3Al and Ni3Ga are closely related materials on opposite sides of a ferromagnetic quantum critical point. The Stoner factor of Ni is virtually the same in both compounds and the density of states is larger in Ni3Ga. Thus in Stoner theory it should be more magnetic, and in local-density approximation (LDA) calculations it is. However, experimentally it is a paramagnet, while Ni3Al is an itinerant ferromagnet. We show that critical spin fluctuations are stronger in Ni3Ga, due to weaker q dependence of the susceptibility, and this effect is enough to reverse the trend. The approach combines LDA calculations with Landau theory and the fluctuation-dissipation theorem using the same momentum cutoff for both compounds. The calculations provide evidence for strong, beyond LDA, spin fluctuations associated with the critical point in both materials, but stronger in Ni3Ga than in Ni3Al.     

Kinetics and mechanism of the pyridinolysis of S-2,4-dinitrophenyl 4-substituted thiobenzoates

[reaction: see text] The reactions of S-2,4-dinitrophenyl 4-methyl (1), S-2,4-dinitrophenyl 4-H (2), S-2,4-dinitrophenyl 4-chloro (3), and S-2,4-dinitrophenyl 4-nitro (4) thiobenzoates with a structurally homogeneous series of pyridines are subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M (KCl). The reactions are studied spectrophotometrically (420 nm) by monitoring the appearance of 2,4-dinitrobenzenethiolate anion. Pseudo-first-order rate coefficients (k(obsd)) are obtained for all the reactions, employing excess of amine. The plots of k(obsd) vs [free pyridine] at constant pH are linear with the slopes (k(N)) independent of pH. The Br?nsted-type plots (log k(N) vs pK(a) of the conjugate acid of the pyridines) are curved for all the reactions. The Br?nsted curves are in accordance with stepwise mechanisms, through a zwitterionic tetrahedral intermediate (T(+/-)), and a change in the rate-limiting step. An equation based on this hypothesis accounts well for the experimental points. The Br?nsted lines were calculated with the following parameters: Reactions of thiolbenzoate 1: beta(1) 0.33 (slope at high pK(a)), beta(2) 0.95 (slope at low pK(a)), and pK(a)(0) = 8.5 (pK(a) at the curvature center); thiolbenzoate 2: beta(1) 0.30, beta(2) 0.88, and pK(a)(0) = 8.9; thiolbenzoate 3: beta(1) 0.33, beta(2) 0.89, and pK(a)(0) = 9.5; thiolbenzoate 4: beta(1) 0.21, beta(2) 0.97, and pK(a)(0) = 9.9. The increase of the pK(a)(0) value with the increase of the electron-withdrawing effect of the acyl substituent is explained by the argument that the rate of pyridine expulsion from T(+/-) (k(-)(1)) is favored over that of 2,4-dinitrobenzenethiolate leaving (k(2)), i.e., k(-)(1)/k(2) increases, as the acyl group becomes more electron withdrawing. The pK(a)(0) values for the title reactions are smaller than those for the reactions of the corresponding 4-nitrophenyl 4-substituted thiolbenzoates with the same pyridine series. This is explained by the larger k(2) value for 2,4-dinitrobenzenethiolate leaving from T(+/-) compared with 4-nitrobenzenethiolate, which results in lower k(-)(1)/k(2) ratios for the dinitro derivatives. The pK(a)(0) value obtained for the pyridinolysis of thiolbenzoate 2 (pK(a)(0) = 8.9) is smaller than that found for the same aminolysis of 2,4-dinitrophenyl benzoate (pK(a)(0) = 9.5). This is attributed to the greater nucleofugality from T(+/-) of 2,4-dinitrobenzenethiolate (pK(a) of conjugate acid 3.4) relative to 2,4-dinitrophenoxide (pK(a) of conjugate acid 4.1). The title reactions are also compared with the aminolysis of similar esters to assess the effect of the amine nature and leaving and acyl groups on the kinetics and mechanism.     

Carbon-13 Nuclear Magnetic Resonance Spectroscopy Study of the Glucose Stress of Human Lenses

The sorbitol theory in diabetic cataractogenesis was based on sorbitol accumulation under glucose stress. Sorbitol accumulation was examined by ¹³C nuclear magnetic resonance spectroscopy (NMR) for the first time in matched human lenses incubated in 5.5 mM and 35.5 mM C-1 ¹³C-enriched glucose up to 28 hours. The results showed that sorbitol and lactate in human tens can be detected at 35.5 mM, but not in 5.5 mM glucose solution. The glycolysis metabolic pathway of human lenses may be quite different from that of animals. The accumulation of metabolites can be traced and quantified by the intensities of ¹³C NMR peaks. Therefore, ¹³C NMR spectroscopy can be used as a valuable tool to investigate human lens carbohydrate metabolism non-interventionally.