Estudio cinético de la obtención de óxido de mesitilo a partir de diacetonalcohol catalizada por resinas de intercambio iónico

El objetivo de esta investigación es determinar las velocidades de formación de óxido de mesitilo y de acetona (producto secundario) a partir de diacetonalcohol, cuando se usa como catalizador una resina de intercambio iónico en forma ácida. Se eligió esta reacción debido a la importancia del óxido de mesitilo como disolvente de plásticos a vinílicos y celulósicos y como materia prima en la producción de sustancias de uso industrial. Así, por hidrogenación del mismo se obtiene metilisobutilcetona, solvente de gran utilidad. En la industria nacional se realiza esta hidrogenación en el mismo reactor en el que se obtiene el óxido de mesitilo, pues se parte de acetona y se catalizan las reacciones sucesivas con mezcla de resina de intercambio iónico ácida y paladio. El óxido de mesitilo se obtiene industrialmente a partir de acetona, y lo más efectivo es transformarla en diacetonalcohol con un catalizador básico y luego en óxido de mesitilo con uno ácido (1). Hasta el presente, en el único estudio cinético realizado sobre su formación (2) se parte de acetona usando como catalizador la resina Dowex 50 en forma ácida, pero de acuerdo a lo indicado más arriba es más importante conocer la cinética partiendo de diacetonalcohol. (1) Verkhovskaya, Z.N., Klimenko, N.A., Zalesskaya. E.M., Bychkova, I.N.- Khim. Prom. 43 (7), 500 (1967). (2) Klein, F.G. - Ph.D. Thesis, Univ. of Michigan, ann Arbor, Mich. (1955).Fil: Lemcoff, Norberto Oscar. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

Metabolomics demonstrates divergent responses of two Eucalyptus species to water stress

Past studies of water stress in Eucalyptus spp. generally highlighted the role of fewer than five “important” metabolites, whereas recent metabolomic studies on other genera have shown tens of compounds are affected. There are currently no metabolite profiling data for responses of stress-tolerant species to water stress. We used GC–MS metabolite profiling to examine the response of leaf metabolites to a long (2 month) and severe (Ψpredawn < −2 MPa) water stress in two species of the perennial tree genus Eucalyptus (the mesic Eucalyptus pauciflora and the semi-arid Eucalyptus dumosa). Polar metabolites in leaves were analysed by GC–MS and inorganic ions by capillary electrophoresis. Pressure–volume curves and metabolite measurements showed that water stress led to more negative osmotic potential and increased total osmotically active solutes in leaves of both species. Water stress affected around 30–40% of measured metabolites in E. dumosa and 10–15% in E. pauciflora. There were many metabolites that were affected in E. dumosa but not E. pauciflora, and some that had opposite responses in the two species. For example, in E. dumosa there were increases in five acyclic sugar alcohols and four low-abundance carbohydrates that were unaffected by water stress in E. pauciflora. Re-watering increased osmotic potential and decreased total osmotically active solutes in E. pauciflora, whereas in E. dumosa re-watering led to further decreases in osmotic potential and increases in total osmotically active solutes. This experiment has added several extra dimensions to previous targeted analyses of water stress responses in Eucalyptus, and highlights that even species that are closely related (e.g. congeners) may respond differently to water stress and re-waterin

Consideraciones geométrico cinéticas sobre reacciones solido-fluido

En este trabajo se muestra que, partiendo de un tratamiento cinético para la reacción entre un sólido poroso y un fluido, el orden de reacción aparente con respecto al sólido debe ser menor que uno. Esto a su vez implica otra conclusión de naturaleza exclusivamente geométrica acerca de la estructura porosa del reactivo sólido. Esta conclusión expresa que la superficie por unidad de volumen hecha adimensional tiene que ser mayor que la concentración adimensional del sólido, tomándose como condición de referencia para adimensionalizar a la del estado inicial.It is shown in this paper that from the kinetic treatment for a reaction between a fluid and a porous solid it can he concluded that the apparent order of reaction for the solid ought to he less than one. This in turn implies another conclusion of a purely geometric nature about the porous structure of the solid rèactant; this conclusion says that the dimensionless surface area of solid reactant per unit volume ought to he greater than the dimensionless concentration of that solid, the reference condition being those of the initial ones

Development of a High Latent Effectiveness Energy Recovery Ventilator with Integration into Rooftop Package Equipment

This Final Report covers the Cooperative Program carried out to design and optimize an enhanced flat-plate energy recovery ventilator and integrate it into a packaged unitary (rooftop) air conditioning unit. The project objective was to optimize the design of a flat plate energy recovery ventilator (ERV) core that compares favorably to flat plate air-to-air heat exchanger cores on the market and to cost wise to small enthalpy wheel devices. The benefits of an integrated unit incorporating an enhanced ERV core and a downsized heating/cooling unit were characterized and the design of an integrated unit considering performance and cost was optimized. Phase I was to develop and optimize the design of a membrane based heat exchanger core. Phase II was the creation and observation of a system integrated demonstrator unit consisting of the Enhanced Energy Recovery Ventilator (EERV) developed in Phase I coupled to a standard Carrier 50HJ rooftop packaged unitary air conditioning unit. Phase III was the optimization of the system prior to commercialization based on the knowledge gained in Phase II. To assure that the designs chosen have the possibility of meeting cost objectives, a preliminary manufacturability and production cost study was performed by the Center for Automation Technologies at RPI. Phase I also included a preliminary design for the integrated unit to be further developed in Phase II. This was to assure that the physical design of the heat exchanger designed in Phase I would be acceptable for use in Phase II. An extensive modeling program was performed by the Center for Building Performance & Diagnostics of CMU. Using EnergyPlus as the software, a typical office building with multiple system configurations in multiple climatic zones in the US was simulated. The performance of energy recovery technologies in packaged rooftop HVAC equipment was evaluated. The experimental program carried out in Phases II and III consisted of fabricating and testing a demonstrator unit using Carrier Comfort Network (CCN) based controls. Augmenting the control signals, CCN was also used to monitor and record additional performance data that supported modeling and conceptual understanding. The result of the testing showed that the EERV core developed in Phase I recovered energy in the demonstrator unit at the expected levels based on projections. In fact, at near-ARI conditions the core recovered about one ton of cooling enthalpy when operating with a three-ton rooftop packaged unit

Functionalizable Stereocontrolled Cyclopolyethers by Ring-Closing Metathesis as Natural Polymer Mimics

While complex stereoregular cyclic architectures are commonplace in biomacromolecules, they remain rare in synthetic polymer chemistry, limiting the potential to develop synthetic mimics or advanced materials for biomedical applications. Herein we disclose the formation of a stereocontrolled 1,4‐linked six‐membered cyclopolyether prepared by ring‐closing metathesis (RCM). Ru‐mediated RCM, with careful control of catalyst, concentration and temperature, selectively affords the six‐membered ring cyclopolymer. Under optimized reaction conditions, no metathetical degradation, macrocycle or crosslinking was observed. Post‐polymerization modification by dihydroxylation afforded a novel polymer family encompassing a poly(ethylene glycol) backbone and sugar‐like functionalities ("PEGose"). This strategy also paves the way for using RCM as an efficient method to synthesize other stereocontrolled cyclopolymers

Rationalizing the influence of small-molecule dopants on guanine crystal morphology

Many spectacular optical phenomena in animals are produced by reflective assemblies of guanine crystals. The crystals comprise planar H-bonded layers of π-stacked molecules with a high in-plane refractive index. By preferentially expressing the highly reflective π-stacked (100) crystal face and controlling its cross-sectional shape, organisms generate a diverse array of photonic superstructures. How is this precise control over crystal morphology achieved? Recently, it was found that biogenic guanine crystals are composites, containing high quantities of hypoxanthine and xanthine in a molecular alloy. Here, we crystallized guanine in the presence of these dopants and used computations to rationalize their influence on the crystal morphology and energy. Exceptional quantities of hypoxanthine are incorporated into kinetically favored solid solutions, indicating that fast crystallization kinetics underlies the heterogeneous compositions of biogenic guanine crystals. We find that weakening of H-bonding interactions by additive incorporation elongates guanine crystals along the stacking direction─the opposite morphology of biogenic crystals. However, by modulation of the strength of competing in-plane H-bonding interactions, additive incorporation strongly influences the cross-sectional shape of the crystals. Our results suggest that small-molecule H-bond disrupting additives may be simultaneously employed with π-stack blocking additives to generate reflective platelet crystal morphologies exhibited by organisms

Olefin cross metathesis and ring-closing metathesis in polymer chemistry

The use of olefin cross metathesis in preparing functional polymers, through either pre-functionalisation of monomers or post-polymerisation functionalisation is growing in both scope and breadth. The broad functional group tolerance of olefin metathesis offers a wealth of opportunities for introducing a broad range of functional groups into the polymer backbone, tuning polymer properties and expanding potential applications. Similarly, ring-closing metathesis offers the ability to tune the polymer macrostructure and microstructure to similar effect. In this review, we explore the importance of understanding selectivity in olefin cross metathesis in designing functional polymers, the manipulation of this reactivity to prepare (multi)functional polymers, and show how polymer systems can be constructed to favour ring closing and change backbone structure and properties