Enantioselective Synthesis of Succinimides by Michael Addition of Aldehydes to Maleimides Organocatalyzed by Chiral Primary Amine-Guanidines

The monoguanylation of (1S,2S)- and (1R,2R)-cyclohexane-1,2-diamine affords chiral primary amine-guanidines that are used as chiral organocatalysts in the enantioselective Michael addition of aldehydes, particularly α,α-disubstituted aldehydes, to maleimides. The reaction is carried out in the presence of imidazole, as an additive, in aqueous N,N-dimethylformamide, as the solvent, and affords the corresponding enantioenriched succinimides in high or quantitative yields with enantioselectivities up to 96 % ee. Theoretical calculations (DFT and M06–2X) suggest a different hydrogen-bonding coordination pattern between the maleimide (C=O) and the catalyst (NH groups) is responsible for the enantioinduction switch that is observed when the reaction is carried out using primary amine-guanidines versus primary amine-thioureas as the organocatalysts.

A new technique for recovering energy in thermally coupled distillation using vapor recompression cycles

Even though it has been proved that a fully thermally coupled distillation (TCD) system minimizes the energy used by a sequence of columns, it is well-known that vapor/liquid transfers between different sections produce an unavoidable excess of vapor (liquid) in some of them, increasing both the investment and operating costs. It is proposed here to take advantage of this situation by extracting the extra vapor/liquid and subjecting it to a direct/reverse vapor compression cycle. This new arrangement restores the optimal operating conditions of some of the affected sections with energy savings of around 20–30% compared with conventional TCD columns. Various examples, including the direct and reverse vapor recompression cycles, are presented. Furthermore, in each example, all possible modes of distillation (direct, indirect and Petlyuk distillation) with and without vapor recompression cycles (VRC) are compared to ensure that this approach delivers the best results.

An alternative disjunctive optimization model for heat integration with variable temperatures

This paper presents an alternative model to deal with the problem of optimal energy consumption minimization of non-isothermal systems with variable inlet and outlet temperatures. The model is based on an implicit temperature ordering and the “transshipment model” proposed by Papoulias and Grossmann (1983). It is supplemented with a set of logical relationships related to the relative position of the inlet temperatures of process streams and the dynamic temperature intervals. In the extreme situation of fixed inlet and outlet temperatures, the model reduces to the “transshipment model”. Several examples with fixed and variable temperatures are presented to illustrate the model's performance.

Mathematical programming model for heat exchanger design through optimization of partial objectives

Mathematical programming can be used for the optimal design of shell-and-tube heat exchangers (STHEs). This paper proposes a mixed integer non-linear programming (MINLP) model for the design of STHEs, following rigorously the standards of the Tubular Exchanger Manufacturers Association (TEMA). Bell–Delaware Method is used for the shell-side calculations. This approach produces a large and non-convex model that cannot be solved to global optimality with the current state of the art solvers. Notwithstanding, it is proposed to perform a sequential optimization approach of partial objective targets through the division of the problem into sets of related equations that are easier to solve. For each one of these problems a heuristic objective function is selected based on the physical behavior of the problem. The global optimal solution of the original problem cannot be ensured even in the case in which each of the sub-problems is solved to global optimality, but at least a very good solution is always guaranteed. Three cases extracted from the literature were studied. The results showed that in all cases the values obtained using the proposed MINLP model containing multiple objective functions improved the values presented in the literature.

Multi-objective optimization of environmentally conscious chemical supply chains under demand uncertainty

In this work, we analyze the effect of demand uncertainty on the multi-objective optimization of chemical supply chains (SC) considering simultaneously their economic and environmental performance. To this end, we present a stochastic multi-scenario mixed-integer linear program (MILP) with the unique feature of incorporating explicitly the demand uncertainty using scenarios with given probability of occurrence. The environmental performance is quantified following life cycle assessment (LCA) principles, which are represented in the model formulation through standard algebraic equations. The capabilities of our approach are illustrated through a case study. We show that the stochastic solution improves the economic performance of the SC in comparison with the deterministic one at any level of the environmental impact.

Rigorous Design of Complex Distillation Columns Using Process Simulators and the Particle Swarm Optimization Algorithm

We present a derivative-free optimization algorithm coupled with a chemical process simulator for the optimal design of individual and complex distillation processes using a rigorous tray-by-tray model. The proposed approach serves as an alternative tool to the various models based on nonlinear programming (NLP) or mixed-integer nonlinear programming (MINLP) . This is accomplished by combining the advantages of using a commercial process simulator (Aspen Hysys), including especially suited numerical methods developed for the convergence of distillation columns, with the benefits of the particle swarm optimization (PSO) metaheuristic algorithm, which does not require gradient information and has the ability to escape from local optima. Our method inherits the superstructure developed in Yeomans, H.; Grossmann, I. E.Optimal design of complex distillation columns using rigorous tray-by-tray disjunctive programming models. Ind. Eng. Chem. Res.2000, 39 (11), 4326–4335, in which the nonexisting trays are considered as simple bypasses of liquid and vapor flows. The implemented tool provides the optimal configuration of distillation column systems, which includes continuous and discrete variables, through the minimization of the total annual cost (TAC). The robustness and flexibility of the method is proven through the successful design and synthesis of three distillation systems of increasing complexity.

Simultaneous environmental and economic process synthesis of Isobutane Alkylation

This multidisciplinary study concerns the optimal design of processes with a view to both maximizing profit and minimizing environmental impacts. This can be achieved by a combination of traditional chemical process design methods, measurements of environmental impacts and advanced mathematical optimization techniques. More to the point, this paper presents a hybrid simulation-multiobjective optimization approach that at once optimizes the production cost and minimizes the associated environmental impacts of isobutane alkylation. This approach has also made it possible to obtain the flowsheet configurations and process variables that are needed to manufacture isooctane in a way that satisfies the above-stated double aim. The problem is formulated as a Generalized Disjunctive Programming problem and solved using state-of-the-art logic-based algorithms. It is shown, starting from existing alternatives for the process, that it is possible to systematically generate a superstructure that includes alternatives not previously considered. The optimal solution, in the form a Pareto curve, includes different structural alternatives from which the most suitable design can be selected. To evaluate the environmental impact, Life Cycle Assessment based on two different indicators is employed: Ecoindicator 99 and Global Warming Potential.

Monitoring an earthfill dam using differential SAR interferometry: La Pedrera dam, Alicante, Spain

Surface displacement at the dykes of La Pedrera reservoir (SE Spain) has been measured by satellite differential Synthetic Aperture Radar (SAR) interferometry. At the main dyke, a displacement of about 13 cm along the satellite line of sight has been estimated between August 1995 and May 2010, from a dataset composed by ERS-1, ERS-2 and Envisat-ASAR images. Two independent short-term processing tasks were also carried out with ERS-2/Envisat-ASAR (from June 2008 to May 2010) and TerraSAR-X (from August 2008 to June 2010) images which have shown similar spatial and temporal displacement patterns. The joint analysis of historical instrument surveys and DInSAR-derived data has allowed the identification of a long-term deformation process which is reflected at the dam's surface and is also clearly recognizable in the inspection gallery. The plausible causes of the displacements measured by DInSAR are also discussed in the paper. Finally, DInSAR data have been used to compute the long-term settlement of La Pedrera dam, showing a good agreement with external studies. Consequently, this work demonstrates the integration of DInSAR with in-situ techniques which helps provide a complete spatial vision of the displacements in the dam thereby helping to differentiate the causal mechanisms.

The role of nutrients for improving seedling quality in drylands

Forest plantations have been extensively used to combat desertification. In drylands, harsh climate conditions and unfertile soils often preclude seedling establishment. The improvement in seedling quality by manipulating nutrient availability could contribute to increase planting success. However, morpho-functional traits defining optimum seedling quality in drylands, and the fertilization schemes to achieve them, are still under discussion. Several studies suggest that well fertilized seedlings may perform better than nutrient limited seedlings in these environments. However, recent works have shown opposite results. In this review, we discuss the concept of seedling quality in drylands based on an evaluation of the effects of nutrient manipulation on seedling morpho-functional traits and field performance. According to existing data, we hypothesize that nutrient-limited small seedlings may be better adapted to arid environments and unfavorable microsites, where access to water is uncertain and a conservative water use strategy may be advantageous. In contrast, in dry sub-humid areas, areas with deep soils, protected from excess radiation, and areas where irrigation is feasible, well-fertilized big seedlings with high root growth potential may have more chances of success. We discuss this theory in the context of the multiple objectives of dryland restoration and the environmental constrains posed by these areas, and identify knowledge gaps that should be targeted to test our hypothesis.

Environment and health with respect to a poverty-related disease: the epidemiology of trachoma in Spain, 1925-1941

Trachoma currently represents one of the three main causes of ‘avoidable' blindness and reaches intolerable dimensions in many developing countries. It was endemic in many regions of eastern Spain until well into the twentieth century. The aim of this paper is to analyze the epidemiological development of this disease in contemporary Spain; to examine its determining factors, particularly environmental and sanitary/health factors, and, finally, to study the health care, environmental and socio-economic measures that led to its control and eradication. We believe that the historical approach not only highlights the role of environmental factors in the development of trachoma, but may also aid in understanding the current epidemiology of trachoma.

Screening Subclinical Keratoconus With Placido-Based Corneal Indices

Purpose. To assess in a sample of normal, keratoconic, and keratoconus (KC) suspect eyes the performance of a set of new topographic indices computed directly from the digitized images of the Placido rings. Methods. This comparative study was composed of a total of 124 eyes of 106 patients from the ophthalmic clinics Vissum Alicante and Vissum Almería (Spain) divided into three groups: control group (50 eyes), KC group (50 eyes), and KC suspect group (24 eyes). In all cases, a comprehensive examination was performed, including the corneal topography with a Placidobased CSO topography system. Clinical outcomes were compared among groups, along with the discriminating performance of the proposed irregularity indices. Results. Significant differences at level 0.05 were found on the values of the indices among groups by means of Mann-Whitney-Wilcoxon nonparametric test and Fisher exact test. Additional statistical methods, such as receiver operating characteristic analysis and K-fold cross validation, confirmed the capability of the indices to discriminate between the three groups. Conclusions. Direct analysis of the digitized images of the Placido mires projected on the cornea is a valid and effective tool for detection of corneal irregularities. Although based only on the data from the anterior surface of the cornea, the new indices performed well even when applied to the KC suspect eyes. They have the advantage of simplicity of calculation combined with high sensitivity in corneal irregularity detection and thus can be used as supplementary criteria for diagnosing and grading KC that can be added to the current keratometric classifications.

Sol–Gel Coordination Chemistry: Building Catalysts from the Bottom-Up

The development of synthetic routes for the tailoring of efficient silica-based heterogeneous catalysts functionalized with coordination complexes or metallic nanoparticles has become a important goal in chemistry. Most of these techniques have been based on postsynthetic treatments of preformed silicas. Nevertheless, there is an emerging approach, so-called sol–gel coordination chemistry, based on co-condensation during the sol–gel preparation of the hybrid material of the corresponding complex or nanoparticle modified with terminal trialkoxysilane groups with a silica source (such as tetraethoxysilane) and in the presence of an adequate surfactant. This method leads to the production of new mesoporous metal complex-silica materials, with the metallic functionality incorporated homogeneously into the structure of the hybrid material, improving the stability of the coordination complex (which is protected by the silica network) and reducing the leaching of the active phase. This technique also offers the actual possibility of functionalizing silica or other metal oxides for a wider range of applications, such as photonics, sensing, and biochemical functions.

Metal-complex ionosilicas: Cationic mesoporus silica with Ni(II) and Cu(II) complexes in their framework

Metal-complex ionosilicas with cationic complexes into the mesoporous silica framework were prepared using anionic surfactants. The electrostatic interaction between the anionic surfactant and the cationic metal complexes incorporated in the silica framework allows for the fine tuning of the mesoporous structure. The gentle procedure of synthesis developed and mild ion-exchange extraction of the surfactant, allowed a cleaner route for the immobilization of homogeneous cationic catalysts in mesoporous silica, while protecting the structural and chemical integrity of the metal complexes.

Microwave-assisted catalysis by iron oxide nanoparticles on MCM-41: Effect of the support morphology

Catalytically active heterogeneous catalysts have been prepared via microwave deposition of iron oxide nanoparticles (0.5–1.2 wt%) on MCM-41 type silica materials with different morphologies (particles, helical and spheres). This methodology leads to iron oxide nanoparticles composed by a mixture of FeO and Fe2O3 species, being the Fe(II)/Fe(III) peak ratio near to 1.11 by XPS. DRUV spectroscopy indicates the presence of tetrahedral coordinated Fe3+ in the silica framework of the three catalysts as well as some extraframework iron species in the catalysts with particle and sphere-like morphologies. The loading of the nanoparticles does neither affect the mesopore arrangement nor the textural properties of the silica supports, as indicated by SAXS and nitrogen adsorption/desorption isotherms. A detailed investigation of the morphology of the supports in various microwave-assisted catalyzed processes shows that helical mesostructures provide optimum catalytic activities and improved reusabilities in the microwave-assisted redox (selective oxidation of benzyl alcohol) catalyzed process probably due to a combination of lower particle size and higher acidity in comparison with the supports with particle and sphere morphology.

Handling of Uncertainty in Life Cycle Inventory by Correlated Multivariate Lognormal Distributions: Application to the Design of Supply Chain Networks

Poster presented in the 24th European Symposium on Computer Aided Process Engineering (ESCAPE 24), Budapest, Hungary, June 15-18, 2014.