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81.
Grand canonical Monte Carlo simulation is used to study the adsorption of nitrogen at 77 K and ammonia at 240 K to represent weakly polar and polar molecules, respectively, on infinite and finite graphite surfaces. These graphite surfaces were modeled with different percentages of carbons removed (defects) from the top graphite layer. Increasing the number of defects increases the adsorption and the isosteric heat of nitrogen at low pressure. At moderate pressures the amount adsorbed is less due to the disruption in the packing of the nitrogen in the first layer. In contrast, the adsorption of ammonia at all pressures is reduced as the percentage of defects is increased. This is due to the disruption in ammonia bonding caused by the defects. The condensation-like step change in the ammonia isotherm on the perfect graphite surface is not observed for any of these surfaces with defects even for the case of only 10% defects. At high percentage of defects the adsorption isotherm is close to Henry law behavior for much of the pressure range. The adsorption on finite surfaces shows that the amount adsorbed for both molecules decreases compared with that of the infinite surfaces, resulting from interaction potentials with the surface and other fluid molecules at the edge. The decrease is much greater for the ammonia adsorption because the bonding between ammonia molecules is disrupted, meaning that the adsorption cannot follow the mechanism of condensation seen for the infinite surface. 相似文献
82.
A. Lerf F. E. Wagner L. K. Herrera A. Justo A. Mu noz-Páez J. L. Pérez-Rodríguez 《Hyperfine Interactions》2016,237(1):55
From the beginning of the 16 th until the end of the 19 th century the most widely used mirrors consisted of a pane of glass backed with a reflecting layer of tin-mercury amalgam. They were made by sliding the glass pane over a tin foil covered with liquid mercury. After removal of the superfluous mercury, tin amalgam formed slowly at ambient temperature and yielded a reflecting layer adhering to the surface of the glass. Such mirrors often deteriorate in the course of time by oxidation of the tin in the amalgam to stannous or stannic oxide. 119Sn Mössbauer spectroscopy, scanning electron microscopy, micro-XRF and X-ray diffraction have been used to study this deterioration process. The studied specimens were a modern mirror made for the reconstruction of the Green Vault in Dresden in the early 2000s, two rather well preserved German mirrors from the 17 th and 19 th centuries and several strongly deteriorated specimens of Baroque mirrors from the south of Spain. The modern mirror consists mainly of a Sn0.9Hg0.1 amalgam with only 2 % of SnO2. The older German mirrors showed more pronounced oxidation, containing 12 and 15 % of SnO2, which did not noticeably impair their reflectivity. In the samples from the Spanish mirrors at best a few percent of metallic phase was left. The majority of the tin had oxidised to SnO2, but between 8 and 20 % of the tin was present as SnO. X-ray diffraction yielded similar results and micro-XRF mapping using synchrotron radiation for excitation gave information on the distribution of Sn and Hg in the reflecting layer of the mirrors. 相似文献
83.
Santiago Herrera Catherine Adam Alejandra Ricci Ernesto J. Calvo 《Journal of Solid State Electrochemistry》2016,20(4):957-967
The electrochemical study of electron transport between Au electrodes and the redox molecule Os[(bpy)2(PyCH2 NH2CO-]ClO4 tethered to molecular linkers of different length (1.3 to 2.9 nm) to Au surfaces has shown an exponential decay of the rate constant k ET 0 with a slope β = 0.53 consistent with through bond tunneling to the redox center. Electrochemical gating of single osmium molecules in an asymmetric tunneling nano-gap between a Au(111) substrate electrode modified with the redox molecules and a Pt-Ir tip of a scanning tunneling microscope was achieved by independent control of the reference electrode potential in the electrolyte, E ref ? E s, and the tip-substrate bias potential, E bias. Enhanced tunneling current at the osmium complex redox potential was observed as compared to the off resonance set point tunneling current with a linear dependence of the overpotential at maximum current vs. the E bias. This corresponds to a sequential two-step electron transfer with partial vibration relaxation from the substrate Au(111) to the redox molecule in the nano-gap and from this redox state to the Pt-Ir tip according to the model of Kuznetsov and Ulstrup (J Phys Chem A 104: 11531, 2000). Comparison of short and long linkers of the osmium complex has shown the same two-step ET (electron transfer) behavior due to the long time scale in the complete reduction-oxidation cycle in the electrochemical tunneling spectroscopy (EC-STS) experiment as compared to the time constants for electron transfer for all linker distances, k ET 0. 相似文献
84.
85.
Bulk Free Radical Polymerization of Methyl Methacrylate and Vinyl Acetate: A Comparative Study 下载免费PDF全文
David Victoria‐Valenzuela Jorge Herrera‐Ordonez Gabriel Luna‐Barcenas George D. Verros Dimitris S. Achilias 《大分子反应工程》2016,10(6):577-587
The model and methodology for estimating diffusion‐controlled rate coefficients for the methyl methacrylate (MMA) polymerization system is extended to the vinyl acetate (VAc) case. Comparison of the kinetic behavior and termination rate coefficients (kt) of both monomers suggests that at low conversions the termination reaction is controlled by the chemical step, whereas at moderate and high conversions it is controlled by the diffusive step which in turn is determined by the segmental diffusion of the long radicals and not by the center of mass diffusion of short radicals. It is found that, for most of the conversion range, diffusion coefficient for VAc is lower than the one for MMA notwithstanding that ktVAc > ktMMA. An explanation of this apparent inconsistency on the base of the model results and in terms of segmental mobility is proposed.
86.
(1S,2R)-1-Aminoindan-2-ol-derived thioureas behave as efficient H-bonding organocatalysts for the nucleophilic conjugate addition of formaldehyde hydrazones to beta,gamma-unsaturated alpha-keto esters as enoate surrogates, affording the corresponding adducts in good yields and enantioselectivities. 相似文献
87.
A theoretical study of the intermolecular double proton transfer in the adenine-uracil base pair has been performed to model the double proton transfer in the adenine-thymine dimer. The mechanism is analyzed in terms of the reaction force profile, which indicates that the activation of the transfer occurs via structural rearrangements to bring the interacting molecules close to each other to let the donor and acceptor atoms in the right position to achieve the transfer. It is found that only when the first proton transfer is partially completed does the second proton get activated, thus illustrating the asynchronous nature of the double proton-transfer process in base pair systems. 相似文献
88.
Jorge Herrera‐Ordez Roberto Olayo 《Journal of polymer science. Part A, Polymer chemistry》2000,38(12):2201-2218
A detailed mathematical model of the kinetics of styrene emulsion polymerization has been proposed. Its main features/assumptions are compartmentalization, micellar and homogeneous nucleation, particle formation by both initiator‐derived and desorbed radicals, dependence on the particle size of the rate coefficients, thermodynamic considerations, and aqueous phase kinetics. The model predicts that micellar nucleation dominates over homogeneous nucleation and that the evolution of the nucleation rate reaches a maximum, where desorbed radicals have an important contribution. Initiator‐derived radicals with only one monomeric unit have also a significant contribution on the rate of capture in particles. The results suggest that the correctness of the instantaneous termination approach depends not only on the size of the particle, but also on the type of entering radical (initiator‐derived or monomeric). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2201–2218, 2000 相似文献
89.
Nicola Zerbinati Sabrina Sommatis Cristina Maccario Serena Di Francesco Maria Chiara Capillo Giulia Grimaldi Raffaele Rauso Martha Herrera Pier Luca Bencini Roberto Mocchi 《Molecules (Basel, Switzerland)》2021,26(24)
(1) Background: Cosmeceuticals are topical products applied to human skin to prevent skin ageing and maintain a healthy skin appearance. Their effectiveness is closely linked to the compounds present in a final formulation. In this article, we propose a panel of in vitro tests to support the efficacy assessment of an anti-ageing cream enriched with functional compounds. (2) Methods: biocompatibility and the irritant effect were evaluated on reconstructed human epidermis (RHE) and corneal epithelium (HCE) 3D models. After a preliminary MTT assay, normal human dermal fibroblasts (NHDF) and keratinocytes (HaCaT) were used to evaluate the extracellular matrix (ECM) protein synthesis, and interleukin-6 (IL-6) and metalloproteinase-1 (MMP-1) production. (3) Results: data collected showed good biocompatibility and demonstrated the absence of the irritant effect in both 3D models. Therefore, we demonstrated a statistical increase in collagen and elastin productions in NHDF cells. In HaCaT cells, we highlighted an anti-inflammatory effect through a reduction in IL-6 levels in inflammatory stimulated conditions. Moreover, the reduction of MMP-1 production after UV-B radiation was demonstrated, showing significant photo-protection. (4) Conclusion: a multiple in vitro assays approach is proposed for the valid and practical assessment of the anti-ageing protection, anti-inflammatory and biocompatible claims that can be assigned to a cosmetic product containing functional compounds. 相似文献
90.
Ismael Herrera Rodolfo G. Camacho 《Numerical Methods for Partial Differential Equations》1997,13(1):1-18
Here, it is shown that the “traditional approach” to variable bubble-point problems, using black-oil models, is not consistent, because it violates the “bubble-point conservation law.” In order to have a consistent approach, it is necessary to incorporate shocks—discussed in previous papers—in which the bubble-point is discontinuous. A “consistent approach” is applied to specific examples, and results compared with those of the “traditional” one. The conclusion that the “traditional approach” generally yields large errors for the production rates and other parameters of interest in the oil industry, is reached. © 1997 John Wiley & Sons, Inc. 相似文献