Évaluation économique des programmes de remplacement de la main d’oeuvre expatriée dans les pays en voie de développement : étude du cas de la Côte-d’Ivoire

This study addresses several problems of educational policy posed by the replacement of highly skilled expatriates in the Ivory Coast's labor force. Conceptualizing expatriate replacement as an import-substitution activity in which Ivorian labor substitutes for previously imported labor services, the authors apply a modified Domestic Resource Cost (DRC) analysis to evaluate Ivorian secondary and university educational programs necessary to train the local labor.This methodology, along with more conventional cost-benefit approach, confirms that education is economically desirable in the Ivory Coast and that resource allocation to the upper secondary level is especially warranted. Lower secondary education is useful in so far as it performs a conduit function for higher levels of training. The importance of university education will probably increase as the occupational-educational structure is upgraded through technological development. Finally, consideration should be given to instituting a system of tuition charges in order to equate social and private rates of return in upper secondary and university education

Adsorption of CO on Supported Gold Nanoparticle Catalysts: A Comparative Study

The adsorption of CO on three different gold nanoparticle catalysts supported on high surface area TiO2 was studied using infrared transmission spectroscopy at room temperature and CO pressures typically used in CO oxidation reactions. The three, real-world catalysts were Au catalysts synthesized in our laboratory from thiol monolayer protected clusters (MPCs) and two commercial catalysts from the World Gold Council (WGC and AuTEK). Within experimental reproducibility, the adsorption data for the three catalysts are indistinguishable. While showing approximately Langmuir behavior, the adsorption data also show coverage dependence, as others have observed for many catalyst systems. Two approaches were used to fit the data, a two-site model and a variable binding constant model. The two-site Langmuir model yielded strong (36%) and weak (64%) binding constants of 2740 and 146 atm-1, respectively. Alternatively, using a sliding-tangent Langmuir fit gave a variable binding constant of 2670-120 atm-1 at room temperature for coverage θ ) 0-0.8. The heat of adsorption was then extracted from the binding constants using a literature value for -TΔS. These values were determined as ΔH)-64 and -56 kJ/mol for strong and weak binding according to the two-site model and ΔH)-63 to -56 kJ/mol for coverage θ ) 0-0.8 for the variable binding constant model. These values agree well with literature values obtained (i) using supported catalysts under higher pressures and (ii) using model catalysts under higher pressures and ultrahigh vacuum conditions

Supramolecular Chemistry: A Capstone Course

A fourth-year capstone course offers students an opportunity to integrate topics covered in the core disciplinary courses, to learn an advanced interdisciplinary topic, and to approach unfamiliar problems and literature. This article describes a fourth-year capstone course designed to incorporate components of faculty lectures, student seminars, and original, hands-on research projects in order to cover the topic of supramolecular chemistry in one semester with unusual depth. This approach should be applicable to other advanced topics in chemistry

Acquired hypogammaglobulinemia in HIV ‐positive subjects after liver transplantation

Introduction As more solid organ transplantations are performed in patients infected with human immunodeficiency virus ( HIV ), post‐transplant complications in this population are becoming better defined. Methods Using serum samples from the Solid Organ Transplantation in HIV : Multi‐Site Study, we studied the epidemiology of acquired hypogammaglobulinemia ( HGG ) after liver transplantation ( LT ) in 79 HIV ‐infected individuals with a median CD 4 count at enrollment of 288 (interquartile range 200–423) cells/μL. Quantitative immunoglobulin G (IgG) levels before and after LT were measured, with moderate and severe HGG defined as IgG 350–500 mg/dL and <350 mg/dL, respectively. Incidence, risk factors, and associated outcomes of moderate or worse HGG were evaluated using K aplan– M eier estimator and proportional hazards ( PH ) models. Results The 1‐year cumulative incidence of moderate or worse HGG was 12% (95% confidence interval [ CI ]: 6–22%); no new cases were observed between years 1 and 2. In a multivariate PH model, higher pre‐transplant model for end‐stage liver disease score ( P  = 0.04) and treated acute rejection ( P  = 0.04) were both identified as significant predictors of moderate or worse HGG . There was a strong association of IgG levels <500 mg/dL with non‐opportunistic serious infection (hazard ratio [95% CI ]: 3.5 [1.1–10.6]; P  = 0.03) and mortality (3.2 [1.1–9.4]; P  = 0.04). These associations held after adjustment for important determinants of infection and survival among the entire cohort. Conclusion These results suggest that a proportion of HIV ‐positive LT recipients will develop clinically significant HGG after transplantation.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102205/1/tid12139.pd

CO Oxidation Over Au/TiO\u3csub\u3e2\u3c/sub\u3e Catalyst: Pretreatment Effects, Catalyst Deactivation, and Carbonates Production

A commercially available Au/TiO2 catalyst was subjected to a variety of thermal treatments in order to understand how variations in catalyst pretreatment procedures might affect CO oxidation catalysis. Catalytic activity was found to be inversely correlated to the temperature of the pretreatment. Infrared spectroscopy of adsorbed CO experiments, followed by a Temkin analysis of the data, indicated that the thermal treatments caused essentially no changes to the electronics of the Au particles; this, and a series of catalysis control experiments, and previous transmission electron microscopy (TEM) studies ruled out particle growth as a contributing factor to the activity loss. Fourier transform infrared (FTIR) spectroscopy showed that pretreating the catalyst results in water desorption from the surface, but the observable water loss was similar for all the treatments and could not be correlated with catalytic activity. A Michaelis–Menten kinetic treatment indicated that the main reason for deactivation is a loss in the number of active sites with little changes in their intrinsic activity. In situ FTIR experiments during CO oxidation showed extensive buildup of carbonate-like surface species when the pretreated catalysts were contacted with the feed gas. A semi-quantitative infrared spectroscopy method was developed for comparing the amount of carbonates present on each catalyst; results from these experiments showed a strong correlation between the steady-state catalytic activity and amount of surface carbonates generated during the initial moments of catalysis. Further, this experimental protocol was used to show that the carbonates reside on the titania support rather than on the Au, as there was no evidence that they poison Au–CO binding sites. The role of the carbonates in the reaction scheme, their potential role in catalyst deactivation, and the role of surface hydroxyls and water are discussed

The Critical Role of Water at the Gold-titania Interface in Catalytic CO Oxidation

We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be rate determining. These results provide a unified explanation to disparate literature results, clearly defining the mechanistic roles of water, support OH groups, and the metal-support interface

Enhanced Oxygen Activation over Supported Bimetallic Au-Ni Catalysts

New bimetallic Ni-Au supported nanoparticle catalysts were prepared by using dendrimer templated nanoparticles. Amine-terminated generation 5 polyamidoamine (PAMAM) dendrimers were anchored to a commercial silica with a siloxane linked anhydride. The dendrimer was then alkylated and used to template Ni-Au nanoparticles, which were subsequently extracted into organic solution as thiol monolayer protected clusters (MPCs). Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) indicated bimetallic nanoparticles of about 2 nm in size. Nanoparticles were deposited onto P-25 TiO2, and the capping thiol ligands were removed under flowing H2. DRIFTS infrared spectra of adsorbed CO showed only Au on the catalyst surface; no bands attributable to Ni or NiO were observed. Density functional theory (DFT) calculations showed that Au is substantially more stable than Ni on the surface of model slabs. DFT calculations also indicated that the incorporation of Ni into Au slabs results in stronger adsorption of O and CO on Au surfaces. Catalysts were evaluated with low-temperature CO oxidation. Kinetics studies indicated a substantial modification of Au catalysis through Ni incorporation. Apparent activation energies decreased by more than 50% and O2 reaction orders increased from 0.2 to 0.9. These results are placed in the context of the available literature regarding support effects for Au catalysts. The observed changes to Au chemistry in the current work are substantially larger than previous reports have attributed to support effects. A Michaelis-Menten (enzyme) treatment of the kinetics data indicated that the O2 reactivity constant increased by a factor of 40 for catalysts with high Ni content. This was in good qualitative agreement with the DFT calculations. At the same time, the introduction of Ni reduced the relative number of catalytically active sites

Kinetic Evaluation of Highly Active Supported Gold Catalysts Prepared from Monolayer-Protected Clusters: An Experimental Michaelis-Menten Approach for Determining the Oxygen Binding Constant during CO Oxidation Catalysis

Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the MPC-prepared Au and the standard WGC catalyst showed that these two catalyst systems have essentially the same reaction order and Arrhenius apparent activation energies (28 kJ/mol). However, the MPC-prepared Au catalyst shows 50% greater activity for CO oxidation. Using a Michaelis-Menten approach, the oxygen binding constants for the two catalyst systems were determined and found to be essentially the same within experimental error. To our knowledge, this kinetic evaluation is the first experimental determination of oxygen binding by supported Au nanoparticle catalysts under working conditions. The values for the oxygen binding equilibrium constant obtained from the Michaelis-Menten treatment (ca. 29-39) are consistent with ultra-high-vacuum measurements on model catalyst systems and support density functional theory calculations for oxygen binding at corner or edge atoms on Au nanoparticles and clusters

NaBr Poisoning of Au/TiO\u3csub\u3e2\u3c/sub\u3e Catalysts: Effects on Kinetics, Poisoning Mechanism, and Estimation of the Number of Catalytic Active Sites

Sodium bromide was used to intentionally poison a commercial Au/TiO2 catalyst with the goals of understanding the nature of halide poisoning and evaluating the number and nature of the catalytic active sites. A series of eight poisoned catalysts were prepared by impregnating the parent catalyst with methanolic solutions of NaBr. Each catalyst was tested with CO oxidation catalysis under differential reactor conditions; O2 reaction orders and Arrhenius activation energies were determined for each material. All of the kinetic data, including a Michaelis−Menten analysis, indicated that the primary effect of adding NaBr was to reduce the number of catalytically active sites. Density functional theory calculations, employed to evaluate likely binding sites for NaBr, showed that NaBr binds more strongly to Au corner and edge atoms than it does to the titania support or to exposed Au face atoms. Infrared spectroscopy of adsorbed CO, along with a Temkin analysis of the data, was also used to evaluate changes to the catalyst upon NaBr deposition. These studies suggested that NaBr addition induces some subtle changes in the coverage dependent properties of CO adsorption, but that these did not substantially impact the CO coverage of the CO binding sites. The experimental and computational results are discussed in terms of possible poisoning mechanisms (siteblocking vs off-site binding and modification); the nature and number of active sites are also discussed in the context of the results

Evaluating Differences in the Active-Site Electronics of Supported Au Nanoparticle Catalysts Using Hammett and DFT Studies

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles