Flavonoids and a neolignan glucoside from Guarea macrophylla (Meliaceae)

This work describes the phytochemical study of the methanol extract obtained from leaves of Guarea macrophylla, leading to the isolation and identification of three flavonoid glycosides (quercetin 3-O-β-D-glucopyranoside, quercetin 3-O-b-D-galactopyranoside, kaempferol 7-O-β-D-glucopyranoside) and a neolignan glucoside, dehydrodiconiferyl alcohol-4-β-D-glucoside. All compounds were identified by a combination of spectroscopic methods (¹H, 1D, 2D NMR, 13C and UV), ESI-MS and comparison with the literature data. This is the first report of flavonoids in the genus Guarea and of a neolignan glucoside in the Meliaceae family.

Silk and ink. What were silk wallets, and what can they, together with Jacobina Charlotta Munterhjelm’s diary, tell us about the gentry women’s lives in the 18th and 19th century?

The subject of this thesis is the elaborate silk wallets and what can they tell about the gentry women’s lives in the 18th and 19th century Finland together Jacobina Charlotta Munsterhjelm’s diary. Silk wallets were made of silk and decorated by embroidering, they were used to preserve memorabilia and letters. Making these lavish items took time, skills and materials, and the decorations usually contained symbols and messages. As main source there are silk wallets from the collections of the National Museum of Finland and Satakunta Museum, as well as the diary of Jacobina Munsterhjelm from 1799 to 1801. By interpreting these items we can build a picture of gentry women’s lives. The culture of silk wallets is European, the silk wallet phenomenon studied is Swedish-Finnish, and the research is limited mainly in Finland by its sources. This research has been carried out by constructing a cultural context to the silk wallets with the help of Ginzburg’s methods from his work Juusto ja madot - 1500-luvun myllärin maailmankuva. Silk wallets represent the gentry as well as the communication culture in the 18th and 19th centuries, but have remained unstudied. The thesis consists of two parts, the first focuses on the silk wallets, from where were they developed, how they were made, and to their decorations. The silk wallet culture developed among the gentry handicrafts during the 18th century and faded during the early 20th century. The making of the silk wallets demanded time, skills and materials. The decorations contain messages and symbols – they contain the possible affections the makers might have toward the receiver, and reflect the status and qualities of the receiver. The second part examines the makers, the gentry women, and the handicraft culture which played a big role in their lives, through silk wallets and the diary of Jacobina Munstehjelm. From there it continues to the affections and meanings which can be found from the silk wallets.

Synthesis of isotope-labelled methoxypyrazine compounds as internal standards and quantitative determination of aroma methoxypyrazines in water and wines by solid-phase extraction with isotope dilution-GC-MS /

An efficient way of synthesizing the deuterium labelled analogues of three methoxypyrazine compounds: 2-d3-methoxy-3-isopropylpyrazine, 2-d3-methoxy-3- isobutylpyrazine, and 2-d3-methoxy-3-secbutylpyrazine, has been developed. To confirm that the deuterium labels had been incorporated into the expected positions in the molecules synthesized, the relevant characterization by NMR, HRMS and GC/MS analysis was conducted. Another part of this work involved quantitative determination of methoxypyrazines in water and wines. Solid-phase extraction (SPE) proved to be a suitable means for the sample separation and concentration prior to GC/MS analysis.Such factors as the presence of ethanol, salt, and acid have been investigated which can influence the recovery by SPE for the pyrazines from the water matrix. Significantly, in this work comparatively simple fractional distillation was attempted to replace the conventional steam distillation for pre-concentrating a sample with a relatively large volume prior to SPE. Finally, a real wine sample spiked with the relevant isotope-labelled methoxypyrazines was quantitatively analyzed, revealing that the wine with 10 beetles per litre contained 138 ppt of 2-methoxy-3-isopropylpyrazine. Interestingly, we have also found that 2-methoxy-3-secbutylpyrazine exhibits an extremely low detection limit in GC/MS analysis compared with the detection limit of the other two methoxypyrazines: 2- methoxy-3-isopropylpyrazine and 2-methoxy-3-isobutylpyrazine.

The performance and strategies of adolescents in learning to read artificial words /

The present study explored processing strategies used by individuals when they begin to read c;l script. Stimuli were artificial words created from symbols and based on an alphabetic system. The words were.presented to Grade Nine and Ten students, with variations included in the difficulty of orthography and word familiarity, and then scores were recorded on the mean number of trials for defined learning variables. Qualitative findings revealed that subjects 1 earned parts of the visual a'nd auditory features of words prior to hooking up the visual stimulus to the word's name. Performance measures-which appear to affect the rate of learning were as follows: auditory short-term memory, auditory delayed short-term memory, visual delayed short- term memory, and word attack or decod~ng skills. Qualitative data emerging in verbal reports by the subjects revealed that strategies they pefceived to use were, graphic, phonetic decoding and word .reading.

Extending relAPS to first order logic

RelAPS is an interactive system assisting in proving relation-algebraic theorems. The aim of the system is to provide an environment where a user can perform a relation-algebraic proof similar to doing it using pencil and paper. The previous version of RelAPS accepts only Horn-formulas. To extend the system to first order logic, we have defined and implemented a new language based on theory of allegories as well as a new calculus. The language has two different kinds of terms; object terms and relational terms, where object terms are built from object constant symbols and object variables, and relational terms from typed relational constant symbols, typed relational variables, typed operation symbols and the regular operations available in any allegory. The calculus is a mixture of natural deduction and the sequent calculus. It is formulated in a sequent style but with exactly one formula on the right-hand side. We have shown soundness and completeness of this new logic which verifies that the underlying proof system of RelAPS is working correctly.

Molybdenum (IV) imido silylamido and hydride complexes : stoichiometric and catalytic reactivity, mechanistic aspects of hydrosilation reactions

This thesis describes the synthesis, structural studies, and stoichiometric and catalytic reactivity of novel Mo(IV) imido silylamide (R'N)Mo(R2)(173_RIN-SiR32-H)(PMe3)n (1: Rl = tBu, Ar', Ar; R2 = Cl; R32 = Me2, MePh, MeCl, Ph2, HPh; n = 2; 2: R' = Ar, R2 = SiH2Ph, n = 1) and hydride complexes (ArN)Mo(H)(R)(PMe3)3 (R = Cl (3), SiH2Ph (4». Compounds of type 1 were generated from (R'N)Mo(PMe3)n(L) (5: R' = tBu, Ar', Ar; L = PMe3, r/- C2H4) and chlorohydrosilanes by the imido/silane coupling approach, recently discovered in our group. The mechanism of the reaction of 5 with HSiCh to give (ArN)MoClz(PMe3)3 (8) was studied by VT NMR, which revealed the intermediacy of (ArN)MCh(172 -ArN=SiHCl)(PMe3)z (9). The imido/silyl coupling methodology was transferred to the reactions of 5 with chlorine-free hydrosilanes. This approach allowed for the isolation of a novel ,B-agostic compound (ArN)Mo(SiHzPh)(173 -NAr-SiHPhH)(PMe3) (10). The latter was found to be active in a variety of hydrosilation processes, including the rare monoaddition of PhSiH3 to benzonitrile. Stoichiometric reactions of 11 with unsaturated compounds appear to proceed via the silanimine intermediate (ArN)M(17z-ArN=SiHPh)(PMe3) (12) and, in the case of olefins and nitriles, give products of Si-C coupling, such as (ArN)Mo(R)(173 -NAr-SiHPh-CH=CHR')(PMe3) (13: R = Et, R' = H; 14: R = H, R' = Ph) and (ArN)Mo(172-NAr-SiHPh-CHR=N)(PMe3) (15). Compound 13 was also subjected to catalysis showing much improved activity in the hydrosilation of carbonyls and alkenes. Hydride complexes 3 and 4 were prepared starting from (ArN)MoCh(PMe3)3 (8). Both hydride species catalyze a diversity of hydrosilation processes that proceed via initial substrate activation but not silane addition. The proposed mechanism is supported by stoichiometric reactions of 3 and 4, kinetic NMR studies, and DFf calculations for the hydrosilation of benzaldehyde and acetone mediated by 4.

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

A System for Models of First Order Theories

If you want to know whether a property is true or not in a specific algebraic structure,you need to test that property on the given structure. This can be done by hand, which can be cumbersome and erroneous. In addition, the time consumed in testing depends on the size of the structure where the property is applied. We present an implementation of a system for finding counterexamples and testing properties of models of first-order theories. This system is supposed to provide a convenient and paperless environment for researchers and students investigating or studying such models and algebraic structures in particular. To implement a first-order theory in the system, a suitable first-order language.( and some axioms are required. The components of a language are given by a collection of variables, a set of predicate symbols, and a set of operation symbols. Variables and operation symbols are used to build terms. Terms, predicate symbols, and the usual logical connectives are used to build formulas. A first-order theory now consists of a language together with a set of closed formulas, i.e. formulas without free occurrences of variables. The set of formulas is also called the axioms of the theory. The system uses several different formats to allow the user to specify languages, to define axioms and theories and to create models. Besides the obvious operations and tests on these structures, we have introduced the notion of a functor between classes of models in order to generate more co~plex models from given ones automatically. As an example, we will use the system to create several lattices structures starting from a model of the theory of pre-orders.

A novel fluorescent bisazomethine dye derived from 3-hydroxyquinoxaline-2- carboxaldehyde and 2,3-diaminomaleonitrile

A novel bisazomethine Schiff base was synthesised by the condensation of 3-hydroxyquinoxaline-2- carboxaldehyde and 2,3-diaminomaleonitrile. 1H NMR, 13C NMR, HPLC and FT-IR studies revealed that the compound exists in two major tautomeric forms. The Schiff base exhibits positive absorption and fluorescent solvatochromism and displays dual fluorescence with large stoke shifts. Cyclic voltammetric analysis of the compound in 1:1 methanol–THF was influenced by scan rate. Thermal analysis of the compound was undertaken using TG–DTA and DSC

Synthesis, Spectral and Structural Studies of a Novel Semicarbazone Synthesized from Quinoline-2-Carboxaldehyde and N4-Phenyl-3-Semicarbazide

A new semicarbazone, HL has been synthesized from quinoline-2-carboxaldehyde and N4-phenyl-3- semicarbazide and structurally and spectrochemically characterized. 1H NMR, 13C NMR, IR and electronic spectra of the compound are studied. The existence of keto form in the solid state is supported by the crystal structure and IR data. The compound crystallizes into an orthorhombic space group P212121. Intra and intermolecular hydrogen bonding interactions facilitates unit cell packing in the crystal lattice

Synthesis and Properties of Polyurethanes of Hexamethylene Di-Isocyanate with Multifunctional Chromophores in the Main Chain

Various polyurethanes containing photoactive bis(azo) and bis(o-nitrobenzyl) groups in the main chain were synthesized by polyaddition reactions of diols such as bis(4-hydroxyphenylazo)-2,20-dinitrodiphenylmethane, 4-hydroxy-3-methylphenylazo- 40-hydroxyphenylazo-2,20-dinitrodiphenylmethane and bis(4-hydroxy-3- methylphenylazo)-2,20-dinitrodiphenylmethane with hexamethylene di-isocyanate (HMDI), in dimethyl acetamide (DMAc) in the presence of di-n-butyltin dilaurate (DBTDL) as catalyst. All of them were characterized by IR, UV-vis, 1H NMR and 13C NMR spectra and also by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC).

Restarting automata with restricted utilization of auxiliary symbols

The restarting automaton is a restricted model of computation that was introduced by Jancar et al. to model the so-called analysis by reduction, which is a technique used in linguistics to analyze sentences of natural languages. The most general models of restarting automata make use of auxiliary symbols in their rewrite operations, although this ability does not directly correspond to any aspect of the analysis by reduction. Here we put restrictions on the way in which restarting automata use auxiliary symbols, and we investigate the influence of these restrictions on their expressive power. In fact, we consider two types of restrictions. First, we consider the number of auxiliary symbols in the tape alphabet of a restarting automaton as a measure of its descriptional complexity. Secondly, we consider the number of occurrences of auxiliary symbols on the tape as a dynamic complexity measure. We establish some lower and upper bounds with respect to these complexity measures concerning the ability of restarting automata to recognize the (deterministic) context-free languages and some of their subclasses.

Modulsymbole und Bruhat-Tits-Gebäude der PGL(3) über Funktionenkörpern

Thema der vorliegenden Arbeit ist die Bestimmung von Basen von Räumen spezieller harmonischer 2-Koketten auf Bruhat-Tits-Gebäuden der PGL(3) über Funktionenkörpern. Hierzu wird der Raum der speziellen harmonischen 2-Koketten auf dem Bruhat-Tits-Gebäude der PGL(3) zunächst mit gewissen komplexen Linearkombinationen von 2-Simplizes des Quotientenkomplexes, sogenannten geschlossenen Flächen, identifiziert und anschließend durch verallgemeinerte Modulsymbole beschrieben. Die Darstellung der Gruppe der Modulsymbole durch Erzeuger und Relationen ermöglicht die Bestimmung einer endlichen Basis des Raums der speziellen harmonischen 2-Koketten. Die so gewonnenen Erkenntnisse können zur Untersuchung von Hecke-Operatoren auf speziellen harmonischen 2-Koketten genutzt werden. Mithilfe des hergeleiteten Isomorphismus zwischen dem Raum der speziellen harmonischen 2-Koketten und dem Raum der geschlossenen Flächen wird die Theorie der Hecke-Operatoren auf den Raum der geschlossenen Flächen übertragen. Dies ermöglicht die Berechnung von Abbildungsmatrizen der Hecke-Operatoren auf dem Raum der harmonischen 2-Koketten durch die Auswertung auf den geschlossenen Flächen.

Workforce Issues in the Greater Boston Health Care Industry: Implications for Work and Family

Interviews with more than 40 leaders in the Boston area health care industry have identified a range of broadly-felt critical problems. This document synthesizes these problems and places them in the context of work and family issues implicit in the organization of health care workplaces. It concludes with questions about possible ways to address such issues. The defining circumstance for the health care industry nationally as well as regionally at present is an extraordinary reorganization, not yet fully negotiated, in the provision and financing of health care. Hoped-for controls on increased costs of medical care – specifically the widespread replacement of indemnity insurance by market-based managed care and business models of operation--have fallen far short of their promise. Pressures to limit expenditures have produced dispiriting conditions for the entire healthcare workforce, from technicians and aides to nurses and physicians. Under such strains, relations between managers and workers providing care are uneasy, ranging from determined efforts to maintain respectful cooperation to adversarial negotiation. Taken together, the interviews identify five key issues affecting a broad cross-section of occupational groups, albeit in different ways: Staffing shortages of various kinds throughout the health care workforce create problems for managers and workers and also for the quality of patient care. Long work hours and inflexible schedules place pressure on virtually every part of the healthcare workforce, including physicians. Degraded and unsupportive working conditions, often the result of workplace "deskilling" and "speed up," undercut previous modes of clinical practice. Lack of opportunities for training and advancement exacerbate workforce problems in an industry where occupational categories and terms of work are in a constant state of flux. Professional and employee voices are insufficiently heard in conditions of rapid institutional reorganization and consolidation. Interviewees describe multiple impacts of these issues--on the operation of health care workplaces, on the well being of the health care workforce, and on the quality of patient care. Also apparent in the interviews, but not clearly named and defined, is the impact of these issues on the ability of workers to attend well to the needs of their families--and the reciprocal impact of workers' family tensions on workplace performance. In other words, the same things that affect patient care also affect families, and vice versa. Some workers describe feeling both guilty about raising their own family issues when their patients' needs are at stake, and resentful about the exploitation of these feelings by administrators making workplace policy. The different institutions making up the health care system have responded to their most pressing issues with a variety of specific stratagems but few that address the complexities connecting relations between work and family. The MIT Workplace Center proposes a collaborative exploration of next steps to probe these complications and to identify possible locations within the health care system for workplace experimentation with outcomes benefiting all parties.

Roles in construction projects: analysis and terminology

Standard form contracts are typically developed through a negotiated consensus, unless they are proffered by one specific interest group. Previously published plans of work and other descriptions of the processes in construction projects tend to focus on operational issues, or they tend to be prepared from the point of view of one or other of the dominant interest groups. Legal practice in the UK permits those who draft contracts to define their terms as they choose. There are no definitive rulings from the courts that give an indication as to the detailed responsibilities of project participants. The science of terminology offers useful guidance for discovering and describing terms and their meanings in their practical context, but has never been used for defining terms for responsibilities of participants in the construction project management process. Organizational analysis enables the management task to be deconstructed into its elemental parts in order that effective organizational structures can be developed. Organizational mapping offers a useful technique for reducing text-based descriptions of project management roles and responsibilities to a comparable basis. Research was carried out by means of a desk study, detailed analysis of nine plans of work and focus groups representing all aspects of the construction industry. No published plan of work offers definitive guidance. There is an enormous amount of variety in the way that terms are used for identifying responsibilities of project participants. A catalogue of concepts and terms (a “Terminology”) has been compiled and indexed to enable those who draft contracts to choose the most appropriate titles for project participants. The purpose of this terminology is to enable the selection and justification of appropriate terms in order to help define roles. The terminology brings an unprecedented clarity to the description of roles and responsibilities in construction projects and, as such, will be helpful for anyone seeking to assemble a team and specify roles for project participants.