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.

Enantioselective 1,3-dipolar cycloadditions of azlactones and electrophilic alkenes catalyzed by dimeric BinapAuTFA complexes

Glycine-derived azlactones react with maleimides using (S)- or (R)-dimeric BinapAuTFA complexes affording the corresponding cycloadducts in good yields and high enantioselections (up to 99% ee). The intermediate carboxylic acids are treated with trimethylsilyldiazomethane and isolated as Δ¹-pyrroline methyl esters. These cycloadducts are transformed into exo-proline derivatives by reduction with NaBH3CN in acidic media. On the other hand, N-benzoylalanine-derived oxazolone reacts with tert-butyl acrylate providing the cycloadduct with the ester group at the 3-position with a trans-relative configuration with respect to the methyl ester group.

Testing reference dependence, loss aversion and diminishing sensitivity in Spanish tourism

Based on Tversky and Kahneman’s Prospect Theory, we test the existence of reference dependence, loss aversion and diminishing sensitivity in Spanish tourism. To do this, we incorporate the reference-dependent model into a Multinomial Logit Model with Random Parameters -which controls for heterogeneity- and apply it to a sample of vacation choices made by Spaniards. We find that the difference between reference price and actual price is considered to make decisions, confirming that reference dependence exists; that people react more strongly to price increases than to price decreases relative to their reference price, which represents evidence in favor of the loss aversion phenomenon; and that there is diminishing sensitivity for losses only, showing convexity for these negative values.

NaOH and KOH for preparing activated carbons used in energy and environmental applications

Alkaline hydroxides, especially sodium and potassium hydroxides, are multi-million-ton per annum commodities and strong chemical bases that have large scale applications. Some of them are related with their consequent ability to degrade most materials, depending on the temperature used. As an example, these chemicals are involved in the manufacture of pulp and paper, textiles, biodiesels, soaps and detergents, acid gases removal (e.g., SO2) and others, as well as in many organic synthesis processes. Sodium and potassium hydroxides are strong and corrosive bases, but they are also very stable chemicals that can melt without decomposition, NaOH at 318ºC, and KOH at 360ºC. Hence, they can react with most materials, even with relatively inert ones such as carbon materials. Thus, at temperatures higher than 360ºC these melted hydroxides easily react with most types of carbon-containing raw materials (coals, lignocellulosic materials, pitches, etc.), as well as with most pure carbon materials (carbon fibers, carbon nanofibers and carbon nanotubes). This reaction occurs via a solid-liquid redox reaction in which both hydroxides (NaOH or KOH) are converted to the following main products: hydrogen, alkaline metals and alkaline carbonates, as a result of the carbon precursor oxidation. By controlling this reaction, and after a suitable washing process, good quality activated carbons (ACs), a classical type of porous materials, can be prepared. Such carbon activation by hydroxides, known since long time ago, continues to be under research due to the unique properties of the resulting activated carbons. They have promising high porosity developments and interesting pore size distributions. These two properties are important for new applications such as gas storage (e.g., natural gas or hydrogen), capture, storage and transport of carbon dioxide, electricity storage demands (EDLC-supercapacitors-) or pollution control. Because these applications require new and superior quality activated carbons, there is no doubt that among the different existing activating processes, the one based on the chemical reaction between the carbon precursor and the alkaline hydroxide (NaOH or KOH) gives the best activation results. The present article covers different aspects of the activation by hydroxides, including the characteristics of the resulting activated carbons and their performance in some environment-related applications. The following topics are discussed: i) variables of the preparation method, such as the nature of the hydroxide, the type of carbon precursor, the hydroxide/carbon precursor ratio, the mixing procedure of carbon precursor and hydroxide (impregnation of the precursor with a hydroxide solution or mixing both, hydroxide and carbon precursor, as solids), or the temperature and time of the reaction are discussed, analyzing their effect on the resulting porosity; ii) analysis of the main reactions occurring during the activation process, iii) comparative analysis of the porosity development obtained from different activation processes (e.g., CO2, steam, phosphoric acid and hydroxides activation); and iv) performance of the prepared activated carbon materials on a few applications, such as VOC removal, electricity and gas storages.

Glutaraldehyde in bio-catalysts design: a useful crosslinker and a versatile tool in enzyme immobilization

Glutaraldehyde is one of the most widely used reagents in the design of biocatalysts. It is a powerful crosslinker, able to react with itself, with the advantages that this may bring forth. In this review, we intend to give a general vision of its potential and the precautions that must be taken when using this effective reagent. First, the chemistry of the glutaraldehyde/amino reaction will be commented upon. This reaction is still not fully clarified, but it seems to be based on the formation of 6-membered heterocycles formed by 5 C and one O. Then, we will discuss the production of intra- and inter-molecular enzyme crosslinks (increasing enzyme rigidity or preventing subunit dissociation in multimeric enzymes). Special emphasis will be placed on the preparation of cross-linked enzyme aggregates (CLEAs), mainly in enzymes that have low density of surface reactive groups and, therefore, may be problematic to obtain a final solid catalyst. Next, we will comment on the uses of glutaraldehyde in enzymes previously immobilized on supports. First, the treatment of enzymes immobilized on supports that cannot react with glutaraldehyde (only inter and intramolecular cross-linkings will be possible) to prevent enzyme leakage and obtain some enzyme stabilization via cross-linking. Second, the cross-linking of enzymes adsorbed on aminated supports, where together with other reactions enzyme/support crosslinking is also possible; the enzyme is incorporated into the support. Finally, we will present the use of aminated supports preactivated with glutaraldehyde. Optimal glutaraldehyde modifications will be discussed in each specific case (one or two glutaraldehyde molecules for amino group in the support and/or the protein). Using preactivated supports, the heterofunctional nature of the supports will be highlighted, with the drawbacks and advantages that the heterofunctionality may have. Particular attention will be paid to the control of the first event that causes the immobilization depending on the experimental conditions to alter the enzyme orientation regarding the support surface. Thus, glutaraldehyde, an apparently old fashioned reactive, remains the most widely used and with broadest application possibilities among the compounds used for the design of biocatalyst.

Clinical and quality of life data correlation with a single-optic accommodating intraocular lens

Purpose: To examine a single-optic accommodating intraocular lens (IOL) visual performance by correlating IOL implanted eyes’ defocus curve with the intraocular aberrometric profile and the impact on the quality of life (QOL). Methods: Prospective consecutive case series study including a total of 25 eyes of 14 patients with ages ranging between 52 and 79 years old. All cases underwent cataract surgery with implantation of the single-optic accommodating IOL Crystalens HD (Bausch & Lomb). Distance and near visual acuity outcomes, intraocular aberrations, the defocus curve and QOL (NEI VFQ-25) were evaluated 3 months after surgery. Results: A significant improvement in distance visual acuity was found postoperatively (p = 0.02). Mean postoperative LogMAR uncorrected near visual acuity was 0.44 ± 0.23 (20/30). 60% of eyes had a postoperative addition between 0 and 1.5 diopters (D). The defocus curve showed an area of maximum visual acuity for the levels of defocus corresponding to distance and intermediate vision (−1 to +0.5 D). Postoperative intermediate visual acuity correlated significantly some QOL indices (r ≥ 0.51, p ≤ 0.03; difficulty in going down steps or seeing how people react to things that patient says) as well as with J0 component of manifest cylinder. Postoperative distance-corrected near visual acuity correlated significantly with age (r = 0.65, p < 0.01). Conclusions: This accommodating IOL seems to be able to restore the distance visual function as well as to provide an improvement in intermediate and near vision with a significant impact on patient's QOL, although limited by age and astigmatism. Future studies with larger sample sizes should confirm all these trends.

Isotopic study of ceria-catalyzed soot oxidation in the presence of NOx

The ceria-catalyzed soot oxidation mechanism has been studied by a pulse technique with labeled O2 in the absence and presence of NO, using ceria–soot mixtures prepared in the loose contact mode. In the absence of soot, the ceria-catalyzed oxidation of NO to NO2 takes place with ceria oxygen and not with gas-phase O2. However, the oxygen exchange process between gas-phase O2 and ceria oxygen (to yield back O2, but with oxygen atoms coming from ceria) prevailed with regard to the ceria-catalyzed oxidation of NO to NO2. Gas-phase O2 did not react directly with soot when pulsed to a soot–ceria loose contact mixture. Instead, ceria oxygen is transferred to soot (this step does not require gas-phase molecular oxygen to be present), and gas-phase O2 fills up the vacancies created on the oxide in a further step. The transfer of oxygen between ceria and soot occurred directly in the absence of NO. However, in the presence of NO, NO2 is expected to be additionally generated by ceria oxygen oxidation, which also reacts with soot. The main reaction products of the ceria-catalyzed soot oxidation reaction with NO/O2 were CO2 and NO. Additionally, evidence of the reduction of NOx to N2 was found.

Heterofunctional Supports in Enzyme Immobilization: From Traditional Immobilization Protocols to Opportunities in Tuning Enzyme Properties

A heterofunctional support for enzyme immobilization may be defined as that which possesses several distinct functionalities on its surface able to interact with a protein. We will focus on those supports in which a final covalent attachment between the enzyme and the support is achieved. Heterofunctionality sometimes has been featured in very old immobilization techniques, even though in many instances it has been overlooked, giving rise to some misunderstandings. In this respect, glutaraldehyde-activated supports are the oldest multifunctional supports. Their matrix has primary amino groups, the hydrophobic glutaraldehyde chain, and can covalently react with the primary amino groups of the enzyme. Thus, immobilization may start (first event of the immobilization) via different causes and may involve different positions of the enzyme surface depending on the activation degree and immobilization conditions. Other “classical” heterofunctional supports are epoxy commercial supports consisting of reactive covalent epoxy groups on a hydrophobic matrix. Immobilization is performed at high ionic strength to permit protein adsorption, so that covalent attachment may take place at a later stage. Starting from these old immobilization techniques, tailor-made heterofunctional supports have been designed to permit a stricter control of the enzyme immobilization process. The requirement is to find conditions where the main covalent reactive moieties may have very low reactivity toward the enzyme. In this Review we will discuss the suitable properties of the groups able to give the covalent attachment (intending a multipoint covalent attachment), and the groups able to produce the first enzyme adsorption on the support. Prospects, limitations, and likely pathways for the evolution (e.g., coupling of site-directed mutagenesis and thiol heterofunctional supports of enzyme immobilization on heterofunctional supports) will be discussed in this Review.

1,3-Dipolar cycloadditions of azomethine imines

Azomethine imines are considered 1,3-dipoles of the aza-allyl type which are transient intermediates and should be generated in situ but can also be stable and isolable compounds. They react with electron-rich and electron-poor olefins as well as with acetylenic compounds and allenoates mainly by a [3 + 2] cycloaddition but they can also take part in [3 + 3], [4 + 3], [3 + 2 + 2] and [5 + 3] with different dipolarophiles. These 1,3-dipolar cycloadditions (1,3-DC) can be performed not only under thermal or microwave conditions but also using metallo- and organocatalytic systems. In recent years enantiocatalyzed 1,3-dipolar cycloadditions have been extensively considered and applied to the synthesis of a great variety of dinitrogenated heterocycles with biological activity. Acyclic azomethine imines derived from mono and disubstituted hydrazones could be generated by prototropy under heating or by using Lewis or Brønsted acids to give, after [3 + 2] cycloadditions, pyrazolidines and pyrazolines. Cyclic azomethine imines, incorporating a C–N bond in a ring, such as isoquinolinium imides are the most widely used dipoles in normal and inverse-electron demand 1,3-DC allowing the synthesis of tetrahydro-, dihydro- and unsaturated pyrazolo[1,5-a]isoquinolines in racemic and enantioenriched forms with interesting biological activity. Pyridinium and quinolinium imides give the corresponding pyrazolopyridines and indazolo[3,2-a]isoquinolines, respectively. In the case of cyclic azomethine imines with an N–N bond incorporated into a ring, N-alkylidene-3-oxo-pyrazolidinium ylides are the most popular stable and isolated dipoles able to form dinitrogen-fused saturated and unsaturated pyrazolopyrazolones as racemic or enantiomerically enriched compounds present in many pharmaceuticals, agrochemicals and other useful chemicals.

Silica Microparticles Supported Gold and Copper Ferrite Nanoparticles: A Magnetically Recyclable Bimetallic Catalyst for Sonogashira Reaction

Novel silica supported gold and copper ferrite nanoparticles (NPs) have been synthesized, characterized and used as a separable dual catalyst in Sonogashira type reaction. These Au.CuFe2O4@Silica NPs show a high efficiency as catalyst in the alkynylation not only of aryl iodides but also aryl bromides. By using only 0.5 mol% loading and t-BuOK as base in N,N-dimethylacetamide as solvent, aryl iodides react at 115 ºC in 1 d, whereas for aryl bromides the cross-coupling takes place at 130 ºC in 2 d. The catalyst can be successfully recycled using an external magnet for four consecutive runs.

The Virtual Interactive Relationship Between BIM Project Teams: Effective Communication to aid Collaboration in the Design Process

Building Information Modelling (BIM) provides a shared source of information about a built asset, which creates a collaborative virtual environment for project teams. Literature suggests that to collaborate efficiently, the relationship between the project team is based on sympathy, obligation, trust and rapport. Communication increases in importance when working collaboratively but effective communication can only be achieved when the stakeholders are willing to act, react, listen and share information. Case study research and interviews with Architecture, Engineering and Construction (AEC) industry experts suggest that synchronous face-to-face communication is project teams’ preferred method, allowing teams to socialise and build rapport, accelerating the creation of trust between the stakeholders. However, virtual unified communication platforms are a close second-preferred option for communication between the teams. Effective methods for virtual communication in professional practice, such as virtual collaboration environments (CVE), that build trust and achieve similar spontaneous responses as face-to-face communication, are necessary to face the global challenges and can be achieved with the right people, processes and technology. This research paper investigates current industry methods for virtual communication within BIM projects and explores the suitability of avatar interaction in a collaborative virtual environment as an alternative to face-to-face communication to enhance collaboration between design teams’ professional practice on a project. Hence, this paper presents comparisons between the effectiveness of these communication methods within construction design teams with results of further experiments conducted to test recommendations for more efficient methods for virtual communication to add value in the workplace between design teams.

Implementation Feasibility of a Digital Nervous System for the Construction Industry: For Efficient and Effective Information Management across the Project Lifecycle

The construction industry has long been considered as highly fragmented and non-collaborative industry. This fragmentation sprouted from complex and unstructured traditional coordination processes and information exchanges amongst all parties involved in a construction project. This nature coupled with risk and uncertainty has pushed clients and their supply chain to search for new ways of improving their business process to deliver better quality and high performing product. This research will closely investigate the need to implement a Digital Nervous System (DNS), analogous to a biological nervous system, on the flow and management of digital information across the project lifecycle. This will be through direct examination of the key processes and information produced in a construction project and how a DNS can provide a well-integrated flow of digital information throughout the project lifecycle. This research will also investigate how a DNS can create a tight digital feedback loop that enables the organisation to sense, react and adapt to changing project conditions. A Digital Nervous System is a digital infrastructure that provides a well-integrated flow of digital information to the right part of the organisation at the right time. It provides the organisation with the relevant and up-to-date information it needs, for critical project issues, to aid in near real-time decision-making. Previous literature review and survey questionnaires were used in this research to collect and analyse data about information management problems of the industry – e.g. disruption and discontinuity of digital information flow due to interoperability issues, disintegration/fragmentation of the adopted digital solutions and paper-based transactions. Results analysis revealed efficient and effective information management requires the creation and implementation of a DNS.

Capacidad predictiva de la ira sobre la ansiedad escolar en estudiantes chilenos de Educación Secundaria

La ira y la ansiedad están relacionadas a través de la vulnerabilidad biológica subyacente en ambos constructos, ya que los individuos reaccionan ante una amenaza con ira o ansiedad. Pero ¿tiene la ira la capacidad para predecir la ansiedad? En este estudio nos hemos propuesto analizar esta capacidad predictiva de la ira sobre la ansiedad escolar en una muestra de 1131 estudiantes chilenos de Educación Secundaria, 560 chicos y 571 chicas (49,51% y 51,49%, respectivamente) todos ellos con edades comprendidas entre los 13 y los 18 años (M=15.30; DE=1.10). La expresión de la ira se midió con el State-Trait Anger Expression Inventory for Children and Adolescents (STAXINA) y la Ansiedad Escolar con el Inventario de Ansiedad Escolar (IAES). Los análisis de regresión logística revelaron que altas puntuaciones en sentimientos de ira, temperamento de ira, expresión interna de ira, ira-estado e ira-rasgo predicen la alta ansiedad. Estos resultados sugieren la necesidad de diseñar y desarrollar programas educativos que ayuden a los estudiantes a canalizar la expresión de la ira y disminuyan los niveles de ansiedad escolar.

The impact of demographic change and its challenges for the workforce in the European public sectors. Three priority areas to invest in future HRM. EIPA Working Paper 2012/W/01

European public sectors are particularly affected by the demographic challenge and an ageing and shrinking workforce. According to OECD statistics, over 30% of public employees of central government in 13 countries will leave during the next 15 years. Moreover, the public sector has as compared to the private sector to rely on a much older workforce, who will have to work longer in future. Against this background, European governments need to react and re-think major elements of current HR and organisational management in the public sector. Particularly the skills in age management should be improved in order to also maintain in future a highly productive, competent and efficient public sector and to ensure that public employees stay longer ‘employable’, ‘healthy’, ‘fit for the job’ and ‘up to the task’. The survey suggests some solutions by investing more in three priority areas in the field of HRM.

The twenty-first century needs a better G20 and a new G7+. Bruegel Policy Contribution 2014/13, 14 November 2014

During the 2008 financial crisis, the G20 was hastily elevated to ‘global economic steering committee’. In the early stages of the crisis, the G20 was an effective forum for crisis containment. As the crisis has eased, however, the G20 has lost both direction and momentum. Governments and policymakers have felt less need to act in unison and have rather refocused on their national agendas, as is their duty and primary function. However, effective global governance is needed permanently, not just in crisis times. It is desirable to have more representative and effective global governance that, among other things, is equipped to prevent crises rather than just react to them. In an environment of rapid change in global patterns of trade and wealth creation, a new revamped (but highly representative) grouping should be created within the G20, to provide leadership on key economic policy matters. Euro-area members should give up their individual seats in this G7+, allowing room for China and other large emerging economies. Without euro-area countries taking such a step, it would be impossible to reconcile effectiveness and representation in this new G7+, which would take charge of decision making on global economic imbalances, financial and monetary issues. All existing G20 countries, including individual euro-area countries, would however remain in the G20, which could potentially expand and would remain the prime forum for discussion on all remaining matters at global level.