Lasermittauksen soveltaminen vesihydraulisessa sylinterissä

Työn tavoitteena on tutkia mahdollisuutta käyttää laser interferometripohjaista aseman mittausjärjestelmää vesihydraulisessa sylinterissä. Työ liittyy Lappeenrannan teknillisessä yliopistossa kehitetyn rinnakkaisrakenteisen robotin PENTA WH muuttamiseen öljyhydraulisesta vesihydrauliseksi. Öljyhydraulisen prototyypin käyttämä vanha kuularuuviin ja inkrementaaliseen enkooderiin perustuvamittausjärjestelmä ei sovellu vesihydrauliseen robottiin. Työn tavoitteena on esittää vaihtoehtoinen ratkaisu.

Novel Robot Solutions for Carrying out Field Joint Welding and Machining in the Assembly of the Vacuum Vessel of ITER

It is necessary to use highly specialized robots in ITER (International Thermonuclear Experimental Reactor) both in the manufacturing and maintenance of the reactor due to a demanding environment. The sectors of the ITER vacuum vessel (VV) require more stringent tolerances than normally expected for the size of the structure involved. VV consists of nine sectors that are to be welded together. The vacuum vessel has a toroidal chamber structure. The task of the designed robot is to carry the welding apparatus along a path with a stringent tolerance during the assembly operation. In addition to the initial vacuum vessel assembly, after a limited running period, sectors need to be replaced for repair. Mechanisms with closed-loop kinematic chains are used in the design of robots in this work. One version is a purely parallel manipulator and another is a hybrid manipulator where the parallel and serial structures are combined. Traditional industrial robots that generally have the links actuated in series are inherently not very rigid and have poor dynamic performance in high speed and high dynamic loading conditions. Compared with open chain manipulators, parallel manipulators have high stiffness, high accuracy and a high force/torque capacity in a reduced workspace. Parallel manipulators have a mechanical architecture where all of the links are connected to the base and to the end-effector of the robot. The purpose of this thesis is to develop special parallel robots for the assembly, machining and repairing of the VV of the ITER. The process of the assembly and machining of the vacuum vessel needs a special robot. By studying the structure of the vacuum vessel, two novel parallel robots were designed and built; they have six and ten degrees of freedom driven by hydraulic cylinders and electrical servo motors. Kinematic models for the proposed robots were defined and two prototypes built. Experiments for machine cutting and laser welding with the 6-DOF robot were carried out. It was demonstrated that the parallel robots are capable of holding all necessary machining tools and welding end-effectors in all positions accurately and stably inside the vacuum vessel sector. The kinematic models appeared to be complex especially in the case of the 10-DOF robot because of its redundant structure. Multibody dynamics simulations were carried out, ensuring sufficient stiffness during the robot motion. The entire design and testing processes of the robots appeared to be complex tasks due to the high specialization of the manufacturing technology needed in the ITER reactor, while the results demonstrate the applicability of the proposed solutions quite well. The results offer not only devices but also a methodology for the assembly and repair of ITER by means of parallel robots.

Variable temperature and pressure study of the aquation reactions of cobalt(III) and chromium(III) penta- and tetra-amines

Preparation of a series of specific penta- and tetra-amine derivatives of Co-III and Cr-III with a neutral leaving ligand has been carried out in order to accomplish a fine tuning of the associativeness/dissociativeness of their substitution reactions. Spontaneous aquation reactions of the neutral ligands have been studied at variable temperature and pressure. Although rate constants and thermal activation parameters show an important degree of scatter, the values determined for the activation volumes of the substitution process illustrate the mechanistic fine tuning that may be achieved for these reactions. In all cases, in the absence of important steric constraints in the molecule, electronic inductive effects seem to be the most important factor accounting for the dissociative shifts observed both for pentaamine (i.e.Delta V double dagger=+4.0 or +14.0 cm(3) mol(-1) and +5.2 or +16.5 cm(3) mol(-1) for the aquation of cis- or trans-[Co(MeNH2)(NH3)(4)(DMF)](3+) and cis- or trans-[CoL15(DMF)](3+) respectively, where L-15 represents a pentaamine macrocyclic ligand), and tetraamine systems (i.e.Delta V double dagger=+4.1 or +8.4 cm(3) mol(-1) and -10.8 or -7.4 cm(3) mol(-1) for the aquation of cis-[Co(NH3)(4)Cl(DMAC)](2+) (DMAC=dimethylacetamide) or cis-[Co(en)(2)Cl(DMAC)](2+) and cis-[Cr(NH3)(4)Cl(DMF)](2+) or cis -[Cr(en)(2)Cl(DMF)](2+)). From the results, clear evidence is obtained which indicates that, only when the situation is borderline I-a/I-d, or the steric demands are increased dramatically, dissociative shifts are observed; in all other cases electronic inductive effects seem to be dominant for such a tuning of the substitution process.

Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines

The pendent-arm macrocyclic hexaamine trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) may coordinate in tetra-, penta- or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo-octahedral cobalt(III) complexes of L, namely sodium trans-cyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)(3) or Na{trans-[CoL(CN)]}(ClO4)(3), (I), where L is coordinated as a pentadentate ligand, and trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) cobalt (III) trans-dicyano (trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)(2)(Cl4H32N6)][Co(CN)(2)(Cl4H30N6)](ClO4)(4)•-4H(2)O or trans-[CoL(CN)(2)]trans-[Co(H2L)(CN)(2)] (ClO4)(4)•-4H(2)O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C-bound cyano ligands. In (I), the secondary amine Co-N bond lengths lie within the range 1.944 (3)-1.969 (3) &ANGS;, while the trans influence of the cyano ligand lengthens the Co-N bond length of the coordinated primary amine [Co-N = 1.986 (3) &ANGS;]. The Co-CN bond length is 1.899 (3) &ANGS;. The complex cations in (11) are each located on centres of symmetry. The Co-N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)-1.982 (3) &ANGS;]. The two independent Co-CN bond lengths are similar [1.918 (4) and 1.926 (4) &ANGS;] but significantly longer than in the structure of (1), again a consequence of the trans influence of each cyano ligand.

4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes from the cane beetle Antitrogus parvulus - Cuticular hydrocarbons with unprecedented structure and stereochemistry

[GRAPHICS] The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus were deduced to be 4,6,8,10,16,18-hexa- and 4,6,8,10,16-pentamethyldocosanes 2 and 3, respectively. Isomers of 2,4,6,8-tetramethylundecanal 27, 36, and 37, derived from 2,4,6-trimethylphenol, were coupled with the phosphoranes 28 and 29 to furnish alkenes and, by reduction, diastereomers of 2 and 3. Chromatographic and spectroscopic comparisons confirmed 2 as either 6a or 6b and 3 as either 34a or 34b.

WH-Constructions in Cape Verdean Creole

This dissertation concerns two types of wh-constructions – interrogative and relative clauses – of Cape Verdean Creole (CVC), a Portuguese-based Creole language spoken on the archipelago of Cape Verde, specifically the variety spoken on Santiago Island, in the coast of West Africa. Chapter 2 focus on some aspects of the syntax of CVC, claiming that the possibilities of S-V inversion are very limited and that verbs stay in Vº, except for the Present tense form of the copula verb e ‘to be’, which is the spell out of the formal feature [Present] of T. It is proposed that CVC exhibits a clause functional structure that is similar to English: [CP [TP [NegP [AspP [VP … ]]]]]. In this chapter, it is also suggested that a non Split-CP, based on the formal features [±D, ±V, ±Q, ±Wh, ±T], correctly accounts for the distribution of the complementizers in CVC. Chapter 3 presents the wh-question formation strategies exhibited by CVC, showing that some of them involve Move, while others do not. Considering CVC data, it is said that the language has two clausal typing processes: an ambiguous complementizer ki ([±Q, ±Wh]), whose checking domain is strictly local; and an unambiguous complementizer Ø ([+Q, +Wh]), whose checking domain is not strictly local. The first one derives fronted wh-questions and the second one accounts for wh-in- -situ. Chapter 4 describes the relativization strategies displayed by CVC, focusing on the fact that PP pied-piping is ruled out and that resumption is possible both inside and outside syntactic islands. It is suggested a revision of Bianchi’s (2002a) head raising analysis for the structure of relative clauses. Chapter 5 discusses the properties of the defective copy strategy ([wh[+PL] … el]) and presents evidence in favor of a distinction between this type of wh-strategy and resumption ([wh[+PL] … es]). It is argued that the language requires an overt pronominal form (3SG) to occur in the complement position of the preposition because CVC types the clause with a complementizer ki [uCat +D] and does not allow for preposition incorporation. The set of formal features of the lower copy is ‘shrinked’, i.e. the features are deleted but not erased, being accessible to PF. This analysis of the defective copy xiv strategy predicts that it only applies to PPs and that it is an autonomous process involving wh-movement, which is distinct from resumption.

Wh-constructions in cape verdean creole: extensions of the copy theory of movement

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Yxi Wähä suomenkielinen Wirsikirja - arvokas harvinaiskirjahankinta

Virsikirjalöydön esittelytilaisuus Helsingin yliopiston kirjastossa 25.1.2005

Preparation of penta-azole containing cyclopeptides: challenges in macrocyclization

Herein is described the synthesis of several analogs of the natural product IB-01211 from concatenated azoles, via a biomimetic pathway based on cyclization-oxidation of serine containing peptides combined with the Hantzsch synthesis. The macrocyclization of rigid peptide compounds 1 and 2 to give IB-01211 and its epimer 12b was explored, and the results are compared here to those previously obtained for the macrocyclization of more flexible structures in the syntheses of YM-216391, telomestatin, and IB-01211. Lastly, the preliminary results of anti-tumor activity screening of the synthesized analogs are discussed.

La adquisición de la interrogación: las interrogativas parciales en catalán y castellano = The acquisition of interrogatives:Wh-questions in Catalan and Spanish

En este trabajo se describe la naturaleza y secuencia de adquisición de las preguntas interrogativas parcialesen niños de habla catalana y/o castellana dentro de un marco de análisis según el cual la adquisición de lasestructuras lingüísticas se construye gradualmente desde estructuras concretas hasta estructuras más abstractas.La muestra utilizada se compone de 10 niños y niñas procedentes de corpus longitudinales cuyas edades van delos 17 meses a los 3 años. El análisis se ha realizado atendiendo a la estructura sintáctica de la oración, loserrores, los pronombres y adverbios interrogativos, y la tipología verbal. Los resultados muestran que la secuenciade adquisición pasa por un momento inicial caracterizado por producciones estereotipadas o fórmulas,durante el cual sólo aparecen algunas partículas interrogativas en estructuras muy concretas. Posteriormente lainterrogación aparece con otros pronombres y adverbios y se diversifica a otros verbos, además, no se observanerrores en la construcción sintáctica. Estos resultados suponen un hecho diferencial respecto de estudios previos enlengua inglesa

Anti-trypanosomal activity of 1,2,3,4,6-penta-O-galloyl-β -D-glucose isolated from Plectranthus barbatus Andrews (Lamiaceae)

MeOH extract from the leaves of Plectranthus barbatus Andrews (Lamiaceae), showed in vitro anti-trypanosomal activity. The bioassay-guided fractionation resulted in the isolation of a gallic acid derivative, identified as 1,2,3,4,6-penta-O-galloyl-β-D-glucose (PGG), after thorough NMR and MS spectral analysis. Finally, this compound was tested against trypomastigote forms of T. cruzi and displayed an EC50 value of 67 µM, at least 6.6-fold more effective than the standard drug benznidazole. This is the first occurrence of PGG in the Plectranthus genus and the first anti-parasitic activity described for PGG in the literature.