Die Carbonylierung acyclischer Diaminocarbene

Das Dissertationsprojekt befasst sich mit dem synthetischen Potential acyclischer Diaminocarbene (aDACs; Verbindungen des Typs (R2N)2C:) und prüft dabei insbesondere deren Reaktivität gegenüber Kohlenmonoxid (CO). Grundlage des Vorhabens ist eine Aufsehen erregende Beobachtung von SIEMELING et al. (Chem. Sci., 2010, 1, 697): Der Prototyp der aDACs, das Bis(diisopropylamino)carben, ist in der Lage CO zu aktivieren. Dabei wird zunächst ein intermediäres Keten des Typs (R2N)2C=C=O generiert, das in Folge einer intramolekularen Reaktion ein stabiles β-Lactamderivat ausbildet. Eine Sensation, schließlich ging man in der Fachwelt bis dato davon aus, dass cyclische und acyclische Diaminocarbene für derartige Reaktionen nicht elektrophil genug seien. Ziel der vorliegenden Arbeit war eine systematische Auslotung der aDAC-Reaktivität gegenüber CO. Im Rahmen der durchgeführten Untersuchungen ist es gelungen, das Feld der literaturbekannten aDACs von 12 auf 19 zu erweitern. Die Carbene, ihre Formamidiniumsalz-Vorstufen, sowie die korrespondierenden Carben–Metallkomplexe konnten in den meisten Fällen vollständig charakterisiert werden. Es konnte gezeigt werden, dass manche Isopropyl-substituierten aDACs in inertem Lösemittel einer β-Umlagerung unterliegen sowie, dass eine solche intramolekulare Reaktivität innerhalb dieser Substanzklasse nicht trivial ist: Zum Teil ganz ähnlich substituierte aDACs sind in Lösung unbegrenzt haltbar. Die Reaktivität gegenüber CO konnte an etwa einem Dutzend aDACs studiert werden. Lediglich in einem Fall zeigte sich das Carben inert. In einem sterisch überfrachteten Fall entstand in einer regio- und stereoselektiven Folgereaktion ein biologisch aktives bicyclisches β-Lactamderivat. In den meisten Fällen ergaben sich betainische Oxyallylspezies des Typs [(R2N)2C]2CO als intermolekulare Folgeprodukte. Die mechanistische Scheidelinie zwischen intra- und intermolekularer Keten-Folgereaktion konnte anhand der Carbonylierung sterisch ganz ähnlich substituierter aDACs aufgezeigt werden. Die gewonnenen Erkenntnisse liefern deutliche Hinweise darauf, dass das chemische Verhalten der aDACs gegenüber CO eher durch feinste elektronische Unterschiede als durch den sterischen Anspruch der Carben-Substituenten beeinflusst wird. Mit Hilfe von In-Situ-IR-Spektroskopie gelang es in manchen Fällen, bei denen eine Isolierung der Carbonylierungsprodukte nicht glückte, die Generierung hochreaktiver Oxyallylspezies zu belegen. Weiterhin konnte im Zuge der In-Situ-IR-Studien das zuvor nur postulierte Diaminoketen als primäres Carbonylierungsprodukt dingfest gemacht werden (ν(C=C=O) = 2085 1/cm): Es handelt sich hierbei um den ersten experimentellen Nachweis eines Diaminoketens überhaupt.

Viabilidad para una empresa dedicada a la producción de artesanías decorativas en la ciudad de Pasto. Amelí

Colombia es un país con diversas culturas, muchos de estos rasgos son aun arraigados y se conservan hasta el día de hoy intactos, entre estos se pueden encontrar, comida, vestuario, forma de hablar, herramientas y costumbres en general, una de las más fuertes expresiones culturales son las artesanías y Colombia es un país que tiene un gran potencial en este sector. El sector de las artesanías en Colombia tiene un gran apoyo de parte de diferentes entidades, privadas, mixtas y publicas las que se ocupan de brindar soporte a las empresas del sector con el fin de capacitar a los artesanos colombianos para que así puedan llegar a ofrecer productos que cumplan con las características, requerimientos y estándares requeridos por los clientes nacionales e internacionales. El siguiente documento plasma un estudio con el fin de conocer la viabilidad para crear una empresa dedicada a la producción y comercialización de artesanías decorativas ubicada en la ciudad de Pasto departamento de Nariño, donde existe la mayor cantidad de artesanos en Colombia, valiéndose del ingenio para crear artículos con alto valor agregado con técnicas novedosas plasmadas en los productos finales de la empresa denominada Amelí.

Estudio de las comunidades microbianas de embutidos fermentados ligeramente acidificados mediante técnicas moleculares. Estandarización, seguridad y mejora tecnológica.

Los embutidos fermentados ligeramente acidificados son un grupo de productos tradicionales mediterráneos, caracterizados por un pH superior a 5,3. Para un control eficiente de la seguridad microbiológica de los embutidos se necesitan técnicas rápidas para la identificación y recuento de los microorganismos patógenos a estudiar. En el presente trabajo, se desarrolló una técnica para la enumeración de L. monocytogenes que combinó el método del número más probable y la identificación mediante PCR específica. Para la detección de Salmonella spp. y L. monocytogenes se desarrolló un sistema de PCR-multiplex que permitió la identificación de ambos patógenos de forma simultánea en una sola reacción. El estudio de la calidad microbiológica de los embutidos fermentados ligeramente acidificados se completó con la caracterización de las comunidades microbianas más importantes en estos productos. Se identificaron a nivel de especie los aislados de bacterias del ácido láctico (BAL), de enterococos y de cocos gram-positivos catalasa-positivos (CGC+). Posteriormente se realizó una tipificación molecular de los mismos mediante RAPD y análisis del perfil plasmídico y se estudiaron las principales características de interés higiénico-sanitario y tecnológico de las cepas. Mediante PCR se identificó Lactobacillus sakei como la especie predominante (74%), seguida por Lactobacillus curvatus (21,2%). La actividad aminoácido-descarboxilasa se asoció a la especie L. curvatus (el 66% de los aislados presentaron esta actividad). La identificación de los enterococos se realizó mediante PCR-multiplex y por secuenciación del gen sodA. Enterococcus faecium fue la especie de enterococos predominante (51,9%) seguida por Enterococcus faecalis (14,2%). Todas las cepas de E. faecalis presentaron genes asociados a factores de virulencia. E. faecalis presentó mayor resistencia a antibióticos que el resto de las especies de enterococos estudiadas. Tan sólo una cepa de E. faecium presentó el genotipo vanA (que confiere resistencia de alto nivel a la vancomicina). La identificación de los aislados de CGC+ (mediante PCR específica y amplificación de la región intergénica 16S-23S ARNr) demostró que Staphylococcus xylosus es la especie predominante en los embutidos fermentados ligeramente acidificados (80,8%). La amina biógena más común en los CGC+ fue la feniletilamina, producida por un 10,8% de aislados. Un pequeño porcentaje de aislados fueron mecA+ (4,6%), presentando además resistencia a múltiples antibióticos. El potencial enterotoxigénico de las cepas de CGC+ fue muy reducido (3,3% de los aislados), detectándose únicamente el gen entC. El estudio pormenorizado de las comunidades bacterianas de interés permitió la selección de 2 cepas de L. sakei y 2 cepas de S. xylosus con características tecnológicas e higiénico-sanitarias óptimas. Para evaluar su efectividad como cultivos iniciadores se elaboraron dos tipos de embutidos ligeramente ácidos, chorizo y fuet, inoculados con microorganismos patógenos (Salmonella spp., L. monocytogenes y S. aureus). El uso de cultivos iniciadores permitió el control de L. monocytogenes, Enterobacteriaceae y Enterococcus así como del contenido en aminas biógenas. Los recuentos de Salmonella spp. disminuyeron de forma significante durante la maduración de los embutidos, independientemente del uso de cultivos iniciadores. El uso del tratamiento de alta presión (400 MPa) en los embutidos madurados consiguió la ausencia de Salmonella spp. en los lotes tratados.

Aproximacions sintètiques per a la preparació estereoselectiva de noves quinolil i pirazolilglicines i per a la preparació en fase sòlida de llibreries de benzotiazoles, 1,2,4-triazines i benzimidazoles

El treball experimental que ha permès redactar la present Tesi Doctoral ha estat dividit en dues parts. A la primera part es presenten els resultats referents a la síntesi estereocontrolada de noves heteroarilglicines (quinolil i pirazolilglicines) a partir de cetones acetilèniques, substrats quirals que permeten accedir a l'esquelet de diferents heterocicles (quinolines i pirazoles), la posterior obtenció dels corresponents quinolil i pirazolil--aminoalcohols i les diferents metodologies d'oxidació per tal d'accedir a les corresponents quinolil i priazolilglicines objectiu. A la segona part d'aquesta memòria s'ha estudiat, en dissolució, l'habilitat del grup alquilsulfona com a grup sortint eficaç en reaccions d'ipso-substitució nucleofilica. El desenvolupament d'aquesta reacció ha servit de punt de partida per a la creació de llibreries d'heterocicles amb alta diversitat molecular i potencial interès biològic sobre fase sòlida.

Síntesi en dissolució i fase sòlida de nous derivats primidínics amb una alta diversitat molecular

En aquest treball s'ha desenvolupat una metodologia eficaç envers la síntesi de diferents derivats pirimidínics amb un alt grau de diversitat molecular. Aquesta metodologia es basa en la S-alquilació selectiva dels 2-tiouracils (2) utilitzats com a material de partida. Aquesta reacció es realitza amb bromur de benzil quan es treballa en dissolució, o bé amb la reïna de Merrifield quan la química és sobre suport sòlid. Seguidament, s'alquila selectivament l'àtom d'oxigen de les benzilsulfanilpirimidinones (3) mitjançant la reacció de Mitsunobu, o bé utilitzant diferents halurs d'alquil en presència d'una base. Amb les 4-alcoxipirimidines (4) es realitzen diverses transformacions químiques, per exemple, addicions de Grignard, reducció i posterior metilació del grup carbonil (quan R2 = CH2COPh), etc. Posteriorment, s'oxida el grup sulfanil a sulfona utilitzant m-CPBA. Finalment es desplaça la funció sulfona amb diversos nucleòfils. Gràcies a aquesta metodologia s'han preparat diferents 2-amino-4-alcoxipirimidines (7, Nu = RR'N) en dissolució i sobre suport sòlid. Mitjançant algunes variacions s'han pogut obtenir altres derivats pirimidínics: - 4(3H)-pirimidinones 2,6-disubstituïdes (8, Nu = RR'N, ArO, RR'R''C), preparades a partir de la hidròlisi del grup alcòxid (OR5) dels compostos (7) en medi àcid. - imidazo[1,2-a]pirimidinones (9 o 10, n = 1) i pirimido[1,2-a]pirimidinones (9 o 10, n = 2). Els compostos (9) s'han obtingut selectivament a través d'una ciclació intramolecular de les pirimidines (7, Nu = aminoalcohols) utilitzant àcid sulfúric. Quan s'han ciclat els compostos (8, Nu = aminoalcohols) mitjançant una reacció de Mitsunobu intramolecular, s'han obtingut els regioisòmers (9) i (10) en diferents proporcions en funció dels grups presents en l'anell. - pirimidines funcionalitzades amb restes d'-arilglina (11). La funció arilglicina s'ha preparat mitjançant la condensació d'amines (4, R2 = CH2CHR3NHR4) amb àcid glioxàlic i àcids arilborònics (reacció de Petasis). L'oxidació del grup sulfanil dels compostos (11) a sulfona utilitzant m-CPBA ha provocat també l'oxidació de l'àtom de nitrogen de l'arilglicina. Alguns d'aquests derivats pirimidínics han mostrat ser inhibidors del Mycobacterium tuberculosis.

Monatin and its stereoisomers: chemoenzymatic synthesis and taste properties

The sweet natural compound monatin 1 has two stereogenic centres and the (2S,4S) absolute configuration has been attributed to the natural isomer. We obtained all four stereoisomers as pure compounds by a six-step synthetic sequence. The stereogenic centre at C-4 was introduced stereoselectively by a regio- and enantiospecific enzymatic hydrolysis of the racemic ethyl dicarboxylate 4 using a protease from Aspergillus oryzae. The absolute configuration of the intermediate products was assigned by X-ray diffraction of chiral derivatives. The stereogenic centre at C-2 was introduced non-specifically, and the resulting diastereomeric mixtures were separated by RP-HPLC. The absolute configurations of the final products were established by comparing retention times on a chiral HPLC column with those of known samples. The four stereoisomers were submitted to tasting trials and three of them, particularly the (2R,4R) isomer, were found to be intensely sweet. A sample of natural monatin analysed under the same conditions is shown to contain all the four stereoisomers. The relative stereoisomeric content in the plant, as well as the possible isomerisation of the chiral centres during extraction and manipulation of monatin samples, are important points that need to be clarified by extensive analysis of the natural extracts. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G′) and loss or viscous (G″) moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-δ-lactone (GDL) or calcium sulphate (CaSO4·2H2O), followed by either heat treatment (heated soymilk at 97 °C prior to coagulation and subsequently held at 70 °C for 60 min, HT) or high pressure treatment (400 MPa at 20 °C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4·2H2O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall “consistency” (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan δ). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more “open” structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required.

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G') and loss or viscous (G '') moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-delta-lactone (GDL) or calcium sulphate (CaSO4 center dot 2H(2)O), followed by either heat treatment (heated soymilk at >= 97 degrees C prior to coagulation and subsequently held at 70 degrees C for 60 min, HT) or high pressure treatment (400 MPa at 20 degrees C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4 center dot 2H(2)O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall "consistency" (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan delta). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more "open" structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required. (c) 2007 Elsevier Ltd. All rights reserved.

Fermentation of heated gluten systems by gut microflora

The Maillard reaction causes changes to protein structure and occurs in foods mainly during thermal treatment. Melanoidins, the final products of the Maillard reaction, may enter the gastrointestinal tract, which is populated by different species of bacteria. In this study, melanoidins were prepared from gluten and glucose. Their effect on the growth of faecal bacteria was determined in culture with genotype and phenotype probes to identify the different species involved. Analysis of peptic and tryptic digests showed that low molecular mass products are formed from the degradation of melanoidins. Results showed a change in the growth of bacteria. This in vitro study demonstrated that melanoidins, prepared from gluten and glucose, affect the growth of the gut microflora.

A linear optimization approach to the combined production planning model

Two fundamental processes usually arise in the production planning of many industries. The first one consists of deciding how many final products of each type have to be produced in each period of a planning horizon, the well-known lot sizing problem. The other process consists of cutting raw materials in stock in order to produce smaller parts used in the assembly of final products, the well-studied cutting stock problem. In this paper the decision variables of these two problems are dependent of each other in order to obtain a global optimum solution. Setups that are typically present in lot sizing problems are relaxed together with integer frequencies of cutting patterns in the cutting problem. Therefore, a large scale linear optimizations problem arises, which is exactly solved by a column generated technique. It is worth noting that this new combined problem still takes the trade-off between storage costs (for final products and the parts) and trim losses (in the cutting process). We present some sets of computational tests, analyzed over three different scenarios. These results show that, by combining the problems and using an exact method, it is possible to obtain significant gains when compared to the usual industrial practice, which solve them in sequence. (C) 2010 The Franklin Institute. Published by Elsevier Ltd. All rights reserved.

SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF 1:1 AND 2:3 LANTHANIDE(III) CITRATES

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL center dot xH(2)O] and [Ln(2)(LH)(3)center dot 2H(2)O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C6O7H5)(3-) and LH for (C6O7H6)(2-). Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL center dot xH(2)O]. The compounds [Ln(2)LH(3)center dot 2H(2)O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C-2v symmetry for the coordination polyhedron of [LnL center dot xH(2)O] and C-4v for [Ln(2)(LH)(3)center dot 2H(2)O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.

Value analysis of just-in-time demolition approach

The recent deconstruction approach for demolition projects promotes reusing and recycling materials. However, the demolition project is interrupted and slowed down while the project team wait for the waste exchange process. Wasted materials generated from the demolition project have to be stored on demolition site or extra depository. Cost and time might be lost for the inventory of wasted materials and products. Just-in-Time (JIT) is a matured method widely used in manufacture industry as well as construction industry. It is utilised to reduce the inventory of both raw materials and final products. It is also used to shorten production cycle and improve the quality of the products. The JIT philosophy can be applied into demolition project so that the inventory of wasted materials can be eliminated and the project time can be shortened. To implement JIT demolition, the waste exchange process can be performed before the wasted materials are generated from the project. Material owners and demanders can virtually plan for waste handling before the demolition project is physically implemented. As a result, waste materials can be sent to demanders through transportation right after they are produced from the project. Applying JIT philosophy in demolition projects can effectively reduce the inventory of wasted materials and the amount of demolition waste to be sent to landfills. Therefore the cost and time of the project are reduced, and the quality of final delivered materials is improved.

Bamboo : a distinctive green fibre

This article reports the preliminary findings on the morphology, chemical structure, antimicrobial and UV-screening properties of bamboo fibres. Bamboo fibres provide a very promising alternative to other natural fibres by virtue of their distinctive characteristics such as eco-friendly farming, inherent antimicrobial, UV-protective and highly· breathable properties. However, these novel properties are moslly claimed by fibre manufacturers, with little scientific evidence.  Moreover, those properties may largely depend on the manufacturing process, which is not widely disclosed by the manufacturers, Common manufacturing processes may require the use of a large amount of chemicals which would not make the product truly eco-friendly. Therefore, there is a strong need for unbiased laboratory experiments being conducted in a rigorous manner to elucidate the origin of those unique properties of bamboo fibres and to develop new processing methods to effectively utilise the properties in the final products. This research is aimed to prove the unique characteristics of bamboo fibres scientifically and to develop an efficient manufacturing process, in order to establish the place of bamboo fibres as a novel green material.

Synthesis and characterization of nanocrystalline hexagonal boron carbo-nitride under high temperature and high pressure

A study of the synthesis of hexagonal boron carbo-nitride (h-BCN) compounds via a two-step high-temperature and high-pressure (HTHP) technique using melamine (C 3N 6H 6) and boron oxide (B 2O 3) as raw materials is presented. An amorphous BCN precursor was prepared at 1000K under vacuum in a resistance furnace and then single-phase h-BCN nanocrystalline was synthesized at 1600K and 5.1GPa in a multi-anvil apparatus. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the final products were pure h-BCN crystals with the lattice constants a ≤ 0.2510nm and c ≤ 0.6690nm. The average grain size was about 150nm. X-ray photoelectron spectroscopy (XPS) results confirmed the occurrence of bonding between C-C, C-N, C-B and N-B atoms. Raman scattering analysis suggested that there were three strong Raman bands centered at 1359, 1596 and 1617cm -1, respectively. The band at 1617cm -1 was considered to be consistent with the characteristic Raman peak of h-BCN.

A facile synthesis of mesoporous silica nanoparticle and its morphology manipulation by varying pH value

 Mesoporous silica nanoparticles (MSNs) with particle size of20 nm have been synthesised through the template directed method at low temperature. The pH value of the reaction solution was found to have a great impact on the morphology of the final products. The morphology of resultant MSNs were investigated through transmission electron microscope. The mesoporous structure was examined by Brunauer-Emmett-Teller and Barrett-Joyner-Halenda methods. The results suggested that the high pH value had a great effect on the morphology of the final MSNs. Higher pH value intensified the interaction between particles. The pH value less than 10 is good for the formation of nanoparticles, while at pH 12, a silica framework with heterogeneous mesopore structure can be obtained.