STRUCTURE OF ORGANIC MOLECULES

Author: VAZ ARAÚJO M. ESTHER.
Year: 2003.
University: VIGO.
Place of preparation: FACULTADE DE QUÍMICA.

Summary: There has been determining configurations of the two centers estereogénicos (C3 and C3.) Metabolite present in the nitrogenous Etxionina. Here are the four stereoisomers have prepared potential, which has developed the synthetic approximation of beta-aminoácido chiral who are in the structure of etxionina by various routes, as well as better conditions for the formation of dicetopiperazinas. Finally, we compared the diastereomers synthetic and natural product derivatizado using NMR techniques mono and two-dimensional, circular dichroism and optical rotation, determining the absolute configuration as (3'S, 3R). Significant progress has been made towards the synthesis of the product itself naturally etzionina. It has also developed the synthesis of oligomers built from units beta-hidroxi-gamma-aminoácidos enantioméricamente pure stream homoquiral and hetreoquiral. About gamma-péptidos obtained, there has been a structural analysis using NMR techniques, circular dichroism and theoretical modeling (MM2), obtaining good indications of the existence of a novel helical conformation, bridges stabilized by hydrogen intrarresiduales and tensions estéricas that restricting the space conformacional. Finally, a study has been made on the distribution conformacional of uan oxazolidinin bicíclica by NMR, from scalar coupling proton neighbors and ecuaciónd and Karplus. It has also been determined quantitatively the effect of the solute interactions with different solvents on the balance conformacional based on the application of the model proposed by Kamlet and Taft.

Author: CHIVA TÁRREGA GEMMA MARÍA.
Year: 2004.
University: VALENCIA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA (UNIVESIDAD DE VALENCIA).

Summary: The peptides are of great interest in medicine and that can be used to treat diseases in which they are implicated. As a result of advances in chemistry Therapeutics and Molecular Biology, many active peptides have been prepared in large quantities and adapted for clinical and pharmacological experiments. Particularly interesting in the field of synthesis of peptidomiméticos farmacológicamanete active peptides are retro and retro-inversos. Moreover, in the field of synthesis of peptidomiméticos is growing interest in the a-and Ã-aminoácidos fluorinated. Given these two aspects, one of the objectives of the Doctoral Thesis has been the stereoselective synthesis of retro-peptidomiméticos? [NHCH2] modified partially fluorinated incorporating a substitute stable of trifluoroalanina in dissolution, solid phase and phase fluorosa. Another objective conducted in the realization of the Doctoral Thesis is a synthesis of two other families peptidomiméticos: peptidomiméticos with the grouping urea and peptidomiméticos with the grouping a-trifluorometil Ã2-alanina. The last of the objectives of this work was the determination of the mechanism through theoretical calculations and the origin of the diastereoselectividad of reaction aza-Michael used for the synthesis of these peptidomiméticos.

Author: HERRANZ RABANAL FERNANDO.
Year: 2005.
University: NACIONAL DE EDUCACIÓN A DISTANCIA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: UNED.

Summary: The main objectives of chemistry anfitrión-huésped (AH), encompassed within the field molecular recognition include imitation of biological processes, the study of the fundamental rules that govern the molecular interactions and the synthesis of new supramolecular systems with interesting properties in catalysis , transport, separation, etc. electronic. Our goal is framed in lso first two points mentioned above, namely mimicking biological processes and the study of the fundamental rules governing the molecular recognition. This work has focused on the study of the phenomena of molecular recognition of the analogs of urea and biotin presented in Figure 1. These compounds are the ésteer methyl biotin (1), N, N, dimetilurea (2), 2-imidazolidona (3), N, N trimetilenuerea (4), barbital (5) and tolbutamide ( 6). To study the chemical anfitrión-huésped of these substrates is needed, in addition to the substrates, with the hosts to be able to form complexes. It has summarized the number of receptors that are presented in Figure 2. With these compounds is carried out to quantify the continuing partnership Ka through assessments by NMR. In addition, molecular modeling is performed by Monte Carlo calculations in order to find the most likely structure and associated energy for each compound. This theoretical study has been conducted using two different camps AMBER force and OPLS, to determine which is the one that best describes the behavior of such systems, and also use the results of both in the generation of theoretical model. The study was completed with the characterization using Nuclear Magnetic Resonance in solid form, the technique CPMAS. Using the values of the constants of association and energy minimization of each complex can develop the theoretical model for the design of new hosts, not employed in the generation of this model. Lastly, we have made use of the model to design the hosts presented in Figure 3, remain particularly promising, for its value Ka theoretical with Me-biotina, hosts XI, XIII, XIV and XV.

Author: MARTIN MORENO CRISTINA.
Year: 2005.
University: ROVIRA I VIRGILI.
Place of defense: FACULTAT DE QUIMICA.
Place of preparation: FACULTAT DE QUIMICA.

Summary: Over the past few decades, the replacement of conventional materials for synthetic polymers has increased significantly due to the versatility, low density and better properties of the latter. While these synthetic polymers have been widely accepted in many applications, most of which are extremely flammable and in the presence of a heat source and oxygen are burned easily and quickly. The strategy most commonly used to minimize the flammability of material, is the incorporation of substances retardamtes the flame. Although in recent years there has been an increase in the number of heteroelementos used in flame retardant compounds to the flame, the market is still dominated by halogen-containing compounds, especially chlorine and bromine. These compounds are very effective either as an additive or as reactive but have a major drawback: increasing amounts of smoke and toxic decomposition products arising during combustion of the polymer. That's why, increasingly are devoting considerable efforts in research to the search for new flame retardants to halogen-free, to respect the environment and not be aggressive. The boric acid and its salts have been used as additives to the flame retardants since 1800, but have been less studied compounds of phosphorus, antimony and halogen. Most of the flame retardants containing boron decompose thermally generated boric acid releasing water in an endothermic reaction, therefore, can act as a flame retardant physicists to absorb heat in the process of decomposition, dilute volatile in the gas phase or form a water vapor layer on the solid phase. In addition, boric acid can act in a similar manner to phosphoric acid forming a coating intumescente which increases the effectiveness of the protective layer. These compounds of boron are the most used, as they are cheap and widely applied, but have, like all additives, multiple handicaps compared with reactive flame retardant on the blaze. Compounds organoborados acting as a reactive flame retardant on the blaze, have not been studied until relatively recently, however, the results obtained on the retardancia to the flame, in different polymers chemically modified with boron compounds, have been satisfactory. As a general objective of this work was raised obtaining new polymeric systems thermostable fire resistant, halogen-free, without detriment to the material properties and to respect the environment. This synthesized and characterized three new types of polymer-based systems:-Resins novolaca with boron, obtained by chemical modification of a resin novolaca commercial with two compounds organoborados bis (benzo-1 ,3,2-dioxaborolanilo) and oxide a (4,4,5,5-tetrametil-1 ,3,2-dioxaborolanilo). Subsequently, in order to improve their mechanical properties, these resins are entrecruzaron with hexametilentetraamina (HMTA) and diglicidil ether of bisphenol A (DGEBA). - Resins epoxi-novolaca modified compounds organoborados and subsequently entrecruzadas heat with a catalytic converter. Polymers estirénicos prepared from monomer containing boron. Finally, we assessed thermal properties, termodinamomecánicas and retardancia the flame of systems previously commented. Pudiéndose conclude that the intersecting of resins novolaca with HM 8 TA or EDM 576 BA and the epoxi-novolaca in the presence of a catalyst, it produces materials with good mechanical integrity, thus allowing establish relationships qualitative levels of intersecting. The thermal degradation of the resin modified with boron: resins novolaca and resins epoxi-novolaca and polymers estirénicos borados generates boric acid at high temperatures forming a residue intumescente that slows the degradation process and prevents it is total. The resins novolaca organoboradas with boron content between 2 and 4%, have excellent properties retardancia the flame. Instead, polymers estirénicos borados need content of at least 3% to manifest good properties to the flame retardants.

Author: BARRACHINA LE CUZIAT ISABEL.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: In this Doctoral Thesis studies were conducted concerning structure química-actividad biological molecules from "seeded" all of them belonging to the family Annonácea. On the one hand, acetogeninas (ACG) were isolated from the seeds of the species Annona cherimolia and A. Aff. Spraguei, preparing below sets of structural analogues through semisíntesis. On the other hand, were synthesized compounds with skeleton benzopirano prenilado (BP), belonging to a class of secondary metabolites isolated previously from our research group from the bark of the trunk of Polyalthia cerasoides. The pharmacological interest of all these compounds lies mainly in its ability to inhibit cellular respiration, through an unknown mechanism of action. Most of the ACG studied belong to the group of bis-tetrahidrofuránicas (THF) adjacent to, a'-dihidroxiladas, configuration relative threo / trans / threo / trans / erythro (type guanaconetins) and the ACG bis-THF configuration on threo / trans / threo / trans / threo (type tucumanin, with ACG? -lactona saturated Ã-hidroxilada). Tests have been conducted biological both inhibition of complex I of the mitochondrial respiratory chain, as cytotoxicity on a battery of tumor cell lines. The most relevant results for the ACG to the BP were published in 6 articles.

Author: PIÑOL LACAMBRA RAFAEL.
Year: 2005.
University: ZARAGOZA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The aim of the thesis was the development of thin films that can act as polarizers that can be completed and the interior of the cell liquid crystal device. These films are based on matrix liquid crystal material containing a dichroic dye. For the final application is criticizing a high order of the dichroic dye molecules in the liquid crystal matrix. Due to the high order introducing the study has focused on the stage SmB. Most of the polarizers are based on current layers PVAuniaxialmente incorporating iodine molecules or dichroic dye. Such polarization requires a series of protective layers of trietilcelulosa and it is necessary to use adhesive for lamination on the glass support. This type of polarizers are on the outside of the liquid crystal cell and are not stable under the conditions therefore construction of a liquid crystal device. Substitution of these polarizers traditional films polarizadoras based on liquid crystals reagents allow their incorporation into the cell. This involves a number of advantages including the obtaining of a minor devices thickness and weight, eliminating optical effects, securing devices more robust, and the exterior of the cell is now composed of the substrate glass. TA turn would allow the use of other types of substrates as previously excluded because of their high birefringencia and that would also allow the development of flexible devices. The films polarizadoras based on liquid crystals reagents can be prepared by deposition, which eliminates the use of adhesive whether applied in the home and abroad. The operation of a polarizer is determined largely mediated by the efficiency of the polarizer. One of the most simple ways to quantify this efficiency is the relationship dicroica in absorbance. The relationship dicroica in absorbance is defined as the ratio of absorbance in the direction where it is highest among the absorbance in the perpendicular direction. The films have been prepared from mixing guest-host, where a small percentage (0.5-2%) of a dichroic dye was dissolved in a liquid crystal matrix. If the liquid crystal molecules are oriented, for example by surface forces, the dye molecules yields due to a cooperative effect are aligned in a certain direction by the director of the stage. The order orientacional characteristic of a liquid crystal is quantified using the parameter of order. If the liquid crystal molecules reactive groups include acrylate groups as the existing order can be set using light curing situ by irradiation with ultraviolet light source. The light curing in the mesofase allows obtaining a network highly ordered and highly stable. As dichroic dye molecules have been used with cylindrical symmetry similar to that of liquid crystals and having a takeover anisótropa which is the basis dela obtaining the polarizers. We have used coloring with a dicroica positive. Ie absorption in the direction of the long axis of the molecule is greater than in the perpendicular direction. Through measures absorption of ultraviolet polarized light can be used to calculate the order of the matrix liquid crystal. It was designed and synthesized a wide range of compounds with different structures looking reactive monomers to submit a phase SmB stable at room temperature, which exhibiera a phase nematica fluid enabling alignment of the material by surface forces and include acrylate groups within its structure for 8 obtenci 78e engaging networks anisótropas oriented. It also study the effect of the spacer length of flexible liquid crystal properties. It was synthesized 34 monomers whose properties were studied using liquid crystal optical polarized light microscopy, differential scanning calorimetry and X-ray diffraction variable temperature. With materials that exhibited best properties were prepared mix that included a dichroic dye and a fotoiniciador. The liquid crystal properties and its homogeneity was studied using microscopy and calorimetry. Mixtures had better properties were studied by means of polarized light ultraviolet spectroscopy, determining the values of respect dicroica and order parameter at various temperatures in the mesofase SmB for mixtures lined by surface forces .. After determining the order mixtures were polimerizadas through light curing situ and study the order of the network and its stability with temperature. There have been films oriented and stable with a high order that present values suitable for application in liquid crystal devices.

Author: ARENAS BUSTO JESÚS ANDRÉS.
Year: 2005.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: The main problem in the prevention of meningococcal meningitis continues to be the development of an effective vaccine against serogroup B. Vaccines based on the capsular polysaccharide, but have been successful against other serogroups, have been unable to respond to the prevention of disease caused by the serogurpo, so that at present the research focuses on the study of other molecules as the outer membrane proteins. However, the features that must meet exacting an antigen ideal with a reduced antigenic variation, exposure and expression on the surface or generate functional antibodies requirements are difficult to meet the candidates nominated so far. In previous studies we found between different antigens common to the genre Neisseria, an antigen of 47 kDa (P47) capable of generating antibodies in humans after the invasion of meningococcus. In this Doctoral Thesis we raised identify and study their characteristics molecular, genetic and antigenic large number of strains, as well as conduct a preliminary assessment of their possible use in a universal vaccine against the disease. The antigen P47 corresponded with a lipoprotein located in the outer membrane of the bacterial pathogen involved and also present in N.lactamica, N.sicca and N.subflava (gene NMA0281, according strain Z2491 of N.meningitis). Although we do not use any strain N.gonorrhoeae in our studies this gene is also present in a strain sequence of this kind (FA1090). The use of different culture media, the genomic context where the gene and the similarity of domains with other proteins known to us indicated that it is a molecule involved in the metabolism of metals. The acquisition of a specific anti-serum protein denatured and cross-reactivity tests conducted by techniques western-blotting and FCM allowed valuing its high expression in N.meningitidis. Through the use of these techniques also note that it is accessible to antibodies in vitro studies while our international and intra-population variability, possibly by the presence or absence of structures of the external shell, its association with other OMPs or shaping the molecule in the membrane. Their eptopos Linear are highly conserved among all strains inlcuidas in the study (33) and antigenic both in humans and in various experimental animals and whether inmuniza as native (external membrane vesicles) and denatured. The complete sequencing of the gene that encodes and the use of bioinformatics tools indicated that the molecule is very structurally conserved and therefore meets the characteristics of an antigen genético - moleculares ideal. The antibodies generated by the lipoprotein P47 have been able to activate the classical pathway of full against homologous strain. The further testing will allow valuing definitely be included in a universal meningococcal vaccine, thus leaving open the study of this new alternative against the disease.

Author: LÓPEZ GRESA MARÍA DEL PILAR.
Year: 2006.
University: POLITÉCNICA DE VALENCIA.
Place of defense: Dep. Quimica.
Place of preparation: Universidad Politécnica de Valencia.

Summary: Nature is an inexhaustible source of secondary metabolites, many of whom become true pharmacological tools, which can both be useful as therapeutic help you understand how various metabolic processes. The biological properties of these compounds are very diverse: antitumour antibiotic citostática, inmunomodular, antifungal, antioxidant, anti-inflammatory or insecticide. Mainly are obtained from higher plants, marine organisms, microscopic fungi and bacteria. The variety of structures carbonadas, different therapeutic activities displayed and the elucidation of routes biosintéticas make the isolation, identification, chemical synthesis and testing of new substances continue to have a huge natural interest. In this sense, our research group worked for years in isolation, elucidation, chemical processing and synthesis of various compounds of natural origin, from terrestrial fungal extracts that have been highlighted by possessing activity insecticide, fungicide, bactericide, antioxidant and cytotoxic. Continuing with the methodology of work of the Center for Agricultural Chemical Ecology (CEQA) at the Technical University of Valencia, in this thesis has been studied organic extracts of various micro - fungi: Aspergillus ochraceus Wilhelm, Penicillium cluniae Quintanilla and Penicillium coalescens Quintanilla as a subject premium biometabolitos with potential pharmacological applications or insecticides. Starting extract broth A. Ochraceus, which showed activity citostática have been isolated four compounds: stephacidin A circumdatin E circumdatin Hy flavacol, the first of which was responsible for this activity. All these molecules have been isolated previously in this same species, except circumdatin H is the first time described in nature.

Author: ALZATE CANO MARÍA VICTORIA.
Year: 2006.
University: BURGOS.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE HUMANIDADES Y EDUCACIÓN.

Summary: This work plans prior knowledge of the inquiry as cognitive trends in terms of conceptos-en-acto and teoremas-en-acto, and discusses some breaks, challenges and affiliations as stages and aids cognitive, when a group of students from second-tier university interacts a sequence of situations: questionnaire, a collection of materials and materials potentially significant progress during the cognitive toward the goal of building a chemical classification. This research has been developed in the context of the theory of fields conceptual G. Vergnaud [1990, 1994; Barais and Vergnaud 1990; Moreira 2002] and describes, analyzes and interprets what is happening in a classroom learning process chemistry as significant (Ausubel, 2002; Moreira 2000, 2005) conceptual composition / structure, so in part, at the level of conceptualization and molecular molar, in particular the system of concepts: substance, simple and composite element, blending, mixing and homogeneous and heterogeneous chemical combination, and the representation lingüstica as chemical formulas relating and molecular. Field conceptually designed in a manner consistent with the epistemology of Bachelard (1976, 1993). From a qualitative approach participant observation, recognizes the pupil and communication between students, collaboration between students, concept maps, booklets classroom solutions to tasks, and daily charts qualifying field of the teacher as a means of investigating conceptions previous affiliations and ruptures and the possible construction of a new model of assimilation. The results suggest that possibly allow the pre-conceptions are formed as two triads of equivalence of conceptos-en-acto: elemento-sustancia simple-átomo and substance compuesta-mezcla homogénea-molécula, the first functional with the chemical symbol for elementary and second the association mechanics of these symbols. These potential equivalents in interaction with the collection of materials and educational materials, mediated by the teacher and language chemist, it seems progressing through bluntly, ruptures and affiliations, a scheme focusing on the immediate sensory perception and a natural language in terms of structure invariants operative close to the chemical knowledge and their respective significant chemical.

Author: BRANQUINHO OSÓRIO SARAIVA VENTURA NEVES MARGARIDA ALEXANDRINA.
Year: 2006.
University: BURGOS.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE HUMANIDADES Y EDUCACIÓN.

Summary: This research work intended to investigate the possibilities of transforming Experimental Work in a teaching-learning process of Physics, at the level of Secondary Education in Portugal, rendering it more effective in terms of learning for students. The analyzed results show the extent to which education centered on the Labor Experimental issues open or closed, and using instruments Metacognition, topic maps and diagrams V, favors Significant Learning in Physics. The theoretical references on which the research was taken from the Theory of Learning Significant Ausubel (1963, 1968, 2000) expanded and deepened by the work of Novak (1997, 2000a, 2000b), Gowin (1981), Novak & Gowin ( 1996) and Moreira (2000). The research methodology reflects a qualitative profile, and was conducted in three phases: 1) Study exploratory, to detect situations that, as teachers and students, facilitate learning when doing experimental work, and to collect suggestions for this methodology promotes learning. 2) Survey Central, it got goals characterize the type of work usually done Experimental class, detecting contributions to learning and difficulties in its implementation, find out what aspects of the three experimental work, implemented during this study, helped or hindered learning and if the use of instruments Metacognition facilitated or not learning. 3) Study supplementary, which was intended to verify whether the conduct of Labor Experimental using instruments Metacognition favored Significant Learning and promoted by students, modifications to epistemological level, with regard to the relationship between theory and experiment and its role in learning concepts of Physics. Subjects involved the investigation were teachers of the subject Sciences Físico- Chemical Education Secondary Education and their students. The data were recorded using questionnaires, surveys and observations of classrooms and analyzed maps and diagrams Concepts V, developed by the students during the course of experimental work as well as tests used to evaluate students on issues Experimental work with, and textbooks commonly used by the teachers who participated in the investigation. There has been a wide gap between the formal curriculum, which seeks to educate and empower the realization of Experimental Work in the classroom and the curriculum implemented by teachers involved in this study, since its implementation was not a priority, and although teachers developed experimental work, they did agree to a very traditional model. However, there is a degree of consistency between various components of the curriculum implemented: the type of class, the proposals of textbooks and the issues included in the assessment tests, which corresponded to a traditional model, giving the central role to theory and asking basically storage and applications of mathematical formulas. After the completion of the three experimental works, which were used instruments Metacognition, pupils and teachers recognize the potential of these tools to promote learning. The teachers had a very positive attitude towards the use of instruments in the conduct Metacognition Labor Experimental, especially the V diagram, as a report, because they are synthetic and complete. That attitude also was found in the students in using the V diagram, with 8 sideran 786 not only a good guide for planning Experimental Work, but contribute to the understanding. It happened with the same attitude when students use maps Concepts, and believe it is due to both the increased level of difficulty as they find the time spent to construct the maps considered excessive, although they recognize that the maps are tools Concepts to facilitate the organization of ideas. Teachers and students believe that the use of instruments Metacognition can promote the learning of students, especially those in a "medium level". It appears that maps concepts are most appropriate instruments to promote learning in the "best" students, however, students' low level "is the most effective use of diagrams V. There are indications Significant Learning at the performance of TE when using tools Metacognition, while appreciating changes in vision epistemological of students regarding the relationship theory and experimentation in learning gives Physics. It suggests some lines of research based on issues arising in the course of this work.

Author: ORTIZ GIL JORDI.
Year: 2006.
University: BARCELONA.
Place of defense: UNIVERSIDAD DE BARCELONA.
Place of preparation: UNIVERSITAT DE BARCELONA.

Summary: We have managed to optimize a method of obtaining 2-alquin, 1,4-dioles so enantioselectiva for adding a cetiluro zinc an aldehyde in the presence of N-metilefedrina. This process earned 1,4-dioles propargílicos not symmetrical with independent control of the settings. The application of this method has allowed some metabolites synthesize natural structure senzilla, musclidas. In this way we have managed the first stereoselective synthesis of these compounds. Moreover, it has shown the difficulty in obtaining relevant dicetonas symmetrical because of the low reactivity of dioles, disteres and diamidas intermediates. As for the method of Masamune-Abiko has achieved bis-aldol desired derivative metacroleína, with a high diastereoselectivida and a moderate performance. That was an intermediate product potential of lactacistina and leaves the door open for future research. We have managed to develop a method for generating a alilboranos through hidroboración of alenos and its subsequent addition to aldehydes to obtain compounds very funcionalizados containing two estereocentros consecutive, one of which is a quaternary carbon. Of the two possible diatereoisómeros only gets one very majority. This has opened an extraordinary way of obtaining oxazolidin-2-onas 4,4-disubstituídas so highly selective that often leads to a single distereoisómero.

Author: Rúa Nieri Federico.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: Universidad Autónoma de Barcelona.
Place of preparation: Facultad de Ciencias - UAB.

Summary: That argument has been made the synthesis and study structural solution and through theoretical calculations of 3 monomers acid peptidonucleicos. They incorporated the foundation nucleicas of thymine, adenine and cytosine to a waste alfa-aminoácido ciclobutánico derived pineno. Moreover, it has made the synthesis of beta-oligómeros consisting of a monomer unit ciclobutánica. Specifically a trímero a tetrámero and octámero. On these compounds has been carried out an extensive study structural solution based on proton nuclear magnetic resonance. It also -péptido has conducted a study to streamline structural theoretical experimental results. Based on these studies, it was concluded that the unit ciclobutánica is heavily inducing secondary structures, as it has been found that both the trímero as tetrámero adopt a conformation type tape not polar. In another vein, a study has been made based on the supramolecular transmission electron microscopy and atomic force microscopy, through which it has been observed that beta-tetrámero is autoagrega as fibrilas nano homogeneous and beta octámero makes forming miscelas or vesicles of varying sizes. It has also been encotrado it beta-tetrámero possesses the ability to form a organogel, whose properties are still under consideration.