Curtin-Hammett versus non-Curtin-Hammett frameworks is optimizing the enantioselective binolam/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 2

Extensive experimental and computational studies have been carried out on the enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:n Binolam:Ti(OiPr)4 mixtures as precatalysts, with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This, as well as the reaction’s response to the presence of an exogenous base, and the failure to react in the presence of Binol:Ti(OiPr)4 mixtures, led us to propose not a direct cyanobenzoylation but an indirect process involving enantioselective hydrocyanation followed by O-benzoylation. Computational work provided positive evidence for the intervention of both indirect and direct cyanobenzoylation routes, the former being faster. However, the standard Curtin–Hammett-based optimization search ended with unsatisfactory results. Experimental and computational DFT studies (B3LYP/6-31G*) led us to conclude that: (1) the overall cyanobenzoylation of aldehydes catalyzed by 1:n Binolam:Ti(OiPr)4 mixtures involves an enantioselective hydrocyanation followed by an stereochemically inert O-benzoylation; (2) the initial complexes prevailing in a 1:1 Binolam:Ti(OiPr)4 mixture are the solvated mononuclear monomer 5·2(iPrOH) and solvated dinuclear dimer 9·2(iPrOH), whereas 9·2(iPrOH) is the major component in a 1:2 or higher 1:n mixture; (3) since the slowest step is that of benzoylation of ligated iPrOH which yields the actual catalysts 5–9, the catalytic system fits into a non-Curtin–Hammett framework, the final products deriving from a kinetic quench of the competing routes; and (4) accordingly, catalysis by 1:1 Binolam:Ti(OiPr)4 mixtures should involve cyanobenzoylations promoted by mononuclear 5, contaminated with those promoted by some dinuclear open dimer 9, whereas cyanobenzoylations catalyzed by a 1:2 and higher 1:n mixtures should be the result of catalysis promoted by the large amounts of dinuclear open dimer 9.

Mathematical approach for predicting non-negative tristimulus values using the CAT02 chromatic adaptation transform

It has been reported that for certain colour samples, the chromatic adaptation transform CAT02 imbedded in the CIECAM02 colour appearance model predicts corresponding colours with negative tristimulus values (TSVs), which can cause problems in certain applications. To overcome this problem, a mathematical approach is proposed for modifying CAT02. This approach combines a non-negativity constraint for the TSVs of corresponding colours with the minimization of the colour differences between those values for the corresponding colours obtained by visual observations and the TSVs of the corresponding colours predicted by the model, which is a constrained non-linear optimization problem. By solving the non-linear optimization problem, a new matrix is found. The performance of the CAT02 transform with various matrices including the original CAT02 matrix, and the new matrix are tested using visual datasets and the optimum colours. Test results show that the CAT02 with the new matrix predicted corresponding colours without negative TSVs for all optimum colours and the colour matching functions of the two CIE standard observers under the test illuminants considered. However, the accuracy with the new matrix for predicting the visual data is approximately 1 CIELAB colour difference unit worse compared with the original CAT02. This indicates that accuracy has to be sacrificed to achieve the non-negativity constraint for the TSVs of the corresponding colours.

Non-porous reference carbon for N2 (77.4 K) and Ar (87.3 K) adsorption

A new non-porous carbon material from granular olive stones has been prepared to be used as a reference material for the characterization of the pore structure of activated carbons. The high precision adsorption isotherms of nitrogen at 77.4 K and argon at 87.3 K on the newly developed sample have been measured, providing the standard data for a more accurate comparative analysis to characterize disordered porous carbons using comparative methods such as t- and αS-methods.

Implementation of non-local boundary layer schemes in the Regional Atmospheric Modeling System and its impact on simulated mesoscale circulations

This paper proposes the implementation of different non-local Planetary Boundary Layer schemes within the Regional Atmospheric Modeling System (RAMS) model. The two selected PBL parameterizations are the Medium-Range Forecast (MRF) PBL and its updated version, known as the Yonsei University (YSU) PBL. YSU is a first-order scheme that uses non-local eddy diffusivity coefficients to compute turbulent fluxes. It is based on the MRF, and improves it with an explicit treatment of the entrainment. With the aim of evaluating the RAMS results for these PBL parameterizations, a series of numerical simulations have been performed and contrasted with the results obtained using the Mellor and Yamada (MY) scheme, also widely used, and the standard PBL scheme in the RAMS model. The numerical study carried out here is focused on mesoscale circulation events during the summer, as these meteorological situations dominate this season of the year in the Western Mediterranean coast. In addition, the sensitivity of these PBL parameterizations to the initial soil moisture content is also evaluated. The results show a warmer and moister PBL for the YSU scheme compared to both MRF and MY. The model presents as well a tendency to overestimate the observed temperature and to underestimate the observed humidity, considering all PBL schemes and a low initial soil moisture content. In addition, the bias between the model and the observations is significantly reduced moistening the initial soil moisture of the corresponding run. Thus, varying this parameter has a positive effect and improves the simulated results in relation to the observations. However, there is still a significant overestimation of the wind speed over flatter terrain, independently of the PBL scheme and the initial soil moisture used, even though a different degree of accuracy is reproduced by RAMS taking into account the different sensitivity tests.

The incorporation of construction and demolition wastes as recycled mixed aggregates in non-structural concrete precast pieces

Concern for the environment has lately heightened awareness about the need for recycling in the construction industry. However, some standards, such as the Spanish standard, only accept the recycling of aggregates derived from concrete, which limits the extensive use of construction and demolition waste, which are produced in much bigger volumes. The aim of this work was to explore the possibility of using recycled mixed aggregates (RMA) in the preparation of precast non-structural concretes. To that end different percentages of natural aggregate were replaced by RMA in non-structural elements (25, 50, 75 and 100%). Contents of cement, water, and the dosages commonly used by companies were unchanged by the introduction of RMA. The characterization of the prepared elements has been done using the specific tests for each type of non-structural element (terrazzo for indoor use, hollow tiles, kerbstones and paving blocks): compression and flexural strength, water absorption, dimensional tolerances, abrasion and slipping resistance. The paving blocks, kerbstones, and hollow tiles prepared were tested for 360 days. The stability of the tested properties confirmed the possibility of using these wastes on an industrial scale satisfying the standard requirements. However, the surface of terrazzo with RMA is not as good as that prepared with natural aggregate.