Modélisation tridimensionnelle des ARN par exploration de l'espace conformationnel et satisfaction de contraintes

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Modélisation tridimensionnelle des ARN par exploration de l'espace conformationnel et satisfaction de contraintes

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Statistical analysis and reduction of multiple access interference in MC-CDMA systems

Multicarrier code division multiple access (MC-CDMA) is a very promising candidate for the multiple access scheme in fourth generation wireless communi- cation systems. During asynchronous transmission, multiple access interference (MAI) is a major challenge for MC-CDMA systems and significantly affects their performance. The main objectives of this thesis are to analyze the MAI in asyn- chronous MC-CDMA, and to develop robust techniques to reduce the MAI effect. Focus is first on the statistical analysis of MAI in asynchronous MC-CDMA. A new statistical model of MAI is developed. In the new model, the derivation of MAI can be applied to different distributions of timing offset, and the MAI power is modelled as a Gamma distributed random variable. By applying the new statistical model of MAI, a new computer simulation model is proposed. This model is based on the modelling of a multiuser system as a single user system followed by an additive noise component representing the MAI, which enables the new simulation model to significantly reduce the computation load during computer simulations. MAI reduction using slow frequency hopping (SFH) technique is the topic of the second part of the thesis. Two subsystems are considered. The first sub- system involves subcarrier frequency hopping as a group, which is referred to as GSFH/MC-CDMA. In the second subsystem, the condition of group hopping is dropped, resulting in a more general system, namely individual subcarrier frequency hopping MC-CDMA (ISFH/MC-CDMA). This research found that with the introduction of SFH, both of GSFH/MC-CDMA and ISFH/MC-CDMA sys- tems generate less MAI power than the basic MC-CDMA system during asyn- chronous transmission. Because of this, both SFH systems are shown to outper- form MC-CDMA in terms of BER. This improvement, however, is at the expense of spectral widening. In the third part of this thesis, base station polarization diversity, as another MAI reduction technique, is introduced to asynchronous MC-CDMA. The com- bined system is referred to as Pol/MC-CDMA. In this part a new optimum com- bining technique namely maximal signal-to-MAI ratio combining (MSMAIRC) is proposed to combine the signals in two base station antennas. With the applica- tion of MSMAIRC and in the absents of additive white Gaussian noise (AWGN), the resulting signal-to-MAI ratio (SMAIR) is not only maximized but also in- dependent of cross polarization discrimination (XPD) and antenna angle. In the case when AWGN is present, the performance of MSMAIRC is still affected by the XPD and antenna angle, but to a much lesser degree than the traditional maximal ratio combining (MRC). Furthermore, this research found that the BER performance for Pol/MC-CDMA can be further improved by changing the angle between the two receiving antennas. Hence the optimum antenna angles for both MSMAIRC and MRC are derived and their effects on the BER performance are compared. With the derived optimum antenna angle, the Pol/MC-CDMA system is able to obtain the lowest BER for a given XPD.

Donor properties of metallomacrocyclic tetrapyrrole pigments with sym-trinitrobenzene

The interactions of metallo derivatives of macrocyclic tetrapyrrole pigments, pheophytin a (pheo), phthalocyanin (phth), and tetraphenylporphyrin (TPP) with sym-trinitrobenzene (TNB) have been studied with use of spectroscopic methods. These macrocyles form 1:l molecular complexw with the acceptor. The association constants (K) for the interactions follow the decreasing order of binding as pheo > phth > TPP. The divalent metal ions influence the values of K for the various metallo TPP derivatives, and the relative order of stabilities decrease as Co > Cu = VO > Ni > Zn. The stereochemistry of M(TPP) and the electronic configuration of the metal ions are shown to contribute to the magnitudes of K. The acceptor strongly quenches the fluorescence of the metallo macrocycles, and the quenching constant decreases as pheo > phth > TPP. The formation of exciplexes is postulated on the basis of the rate of bimolecular quenching constants and solvent effects.

Enzymic synthesis of sym-homospermidine in Lathyrus sativus (grass pea) seedlings

An enzyme catalysing the synthesis of sym-homospermidine from putrescine and NAD+ with concomitant liberation of NH3 was purified 100-fold from Lathyrus sativus (grass pea) seedlings by affinity chromatography on Blue Sepharose. This thiol enzyme had an apparent mol.wt. of 75000 and exhibited Michelis-Menten kinetics with Km 3.0mM for putrescine. The same enzyme activity could also be demonstrated in the crude extracts of sandal (Santalum album) leaves, but with a specific activity 15-fold greater than that in L. sativus seedlings.

Mies, talli ja moottoripyörä : Etnografinen tutkimus Misfit MC:stä ja bikerkulttuurin eetoksesta

Tutkimuksen punaisena lankana kulkee kysymys siitä, millainen on bikerkulttuurin eetos? Miten se on syntynyt, miten sitä ylläpidetään ja miten Misfit MC:n jäsenet sitä tulkitsevat ja toteuttavat omassa elämässään? Tarkastelen eetosta kahdenlaisen aineiston valossa. i) Kenttätyöllä (vuosina 1995-1998 ja 2000-2001) kerätyn aineiston valossa tarkastelen yhtä pääkaupunkiseudulla toimivaa HD-moottoripyöräkerhoa, vuonna 1989 toimintansa aloittanutta Misfit MC:tä. Jäsenet kutsuvat kerhoaan useimmiten talliksi, joskus pajaksi, kerhoksi tai klubiksi. Puhuessaan tallista, miehet voivat viitata kerhorakennukseen ("tuut sä tallille?") mutta myös ryhmään ("meidän talli") ja sen olemassaoloon ajallisesti ja paikallisesti. Aloittaessani kenttätyön vuonna 1995 Misfit MC:n kuului kymmenen 25-30-vuotiasta miestä. ii) Kenttätyöllä kerätyn aineiston lisäksi käytän materiaalia, joka koostuu Harley-Davidson-moottoripyörän ympärille rakentuneen bikerkulttuurin historiasta ja kulttuurituotteista, kuten kertomuksista, elokuvista, musiikista, kuvataiteesta ja moottoripyörälehdistä. Aineiston avulla valotan bikerkulttuurin eetoksen syntyä, alkuvaiheita, leviämistä ja keskeisiä elementtejä. Lähdeaineiston monimuotoisuus ja runsaus palautuu kenttätyöhöni jolloin vakuutuin siitä, että tutkimusmatka bikerkulttuurin historiaan, perinteisiin ja median välittämiin (mieli)kuviin on välttämätöntä, sillä menneisyys ja Harrikkaan ajan kuluessa varastoituneet merkitykset vaikuttavat ja ovat vahvasti läsnä Misfit MC:n toiminnassa ja talliin kuuluvien miesten elämäntyylissä. Tutkimus etenee seuraavanlaisesti. Luku I on Johdanto. Luvussa II Etnografia käsittelen etnografisen tiedon luonnetta niin tutkimusasenteena kuin kenttätyön valossa. Pohdin kenttätyötä ja sen suhdetta etnografian kirjoittamiseen eli miten kenttätyöllä kerätty aineisto muuntuu etnografiseksi monografiaksi. Käsittelen myös kenttätyöni reunaehtoja, kuten tyttöystävyyden ja sukupuolen merkitystä, ja tarkastelen tutussa kulttuurissa tehdyn kenttätyön ominaispiirteitä. Reunaehtojen kuvailu toimii myös johdatuksena bikerkulttuuriin sellaisena kuin se ilmenee Misfit MC:n tallielämässä ja käytänteissä. Lopuksi pohdin "tiheän kuvauksen" mahdollisuuksia ja vaateita aineistoni puitteissa. Luvussa III Bikerkulttuurin eetosta kartoittamassa, kuvailen Harley-Davidson-moottoripyörän ympärille rakentuneen elämäntavan syntyä, levittäytymistä ja keskeisiä elementtejä. Tarkastelen media- ja populaarikulttuurisia tekstejä (elokuvien kertomat tarinat, musiikkikappaleiden sanoitukset ja HD- ja bikerlehtien artikkelit) ja kuvia (elokuvien audiovisuaaliset aspektit, kuvataide ja HD- ja bikerlehtien kuvitus), jotka ovat vaikuttaneet bikerkulttuurin eetokseen. Luvun keskeisiä - aineistosta nousevia ja miessukupuoleen vahvasti sidoksissa olevia - käsitteitä ovat biker, outlaw ja chopper, jotka ovat bikerkulttuurissa säilyneet alkuperäisessä muodossa maantieteellisestä tai kielialueesta riippumatta. Luvussa IV Misfit MC ja bikerkulttuurin eetos temaattinen painopiste siirtyy Suomeen ja Misfit MC:hen. Aluksi käyn läpi suomalaisen bikerkulttuurin muotoutumista ja ominaispiirteitä. Alkukappaleiden jälkeen keskityn Misfit MC:n jäsenten elämäntyylin sävyihin ja heidän käsityksiinsä bikerkulttuurin eetoksesta. Analyysin kiintopisteitä ovat Misfit MC:n jäsenten näkemys bikeriydestä ja tallitoiminnasta, miesten elämäntyylin moraaliset ja esteettiset sävyt, tallirakennus miesyhteisöllisyyttä ja bikerkulttuurin eetosta luovana ja ylläpitävänä sosiaalisena tilana ja Misfit MC miesten yhteisönä. Luvussa V Eetoksen ytimessä: mies ja Harley-Davidson keskityn bikerkulttuurin ytimeen: miehen ja Harley-Davidson-moottoripyörän väliseen suhteeseen. Luvun alussa esittelen ruotsalaisen yhteiskuntatieteilijä Lars Lagergrenin moottoripyörään soveltamaa työkalu - leikkikalu - toteemi - välittäjä -typologiaa ja tarkastelen moottoripyörän olemusta sukupuolittavana ja sukupuolittuvana artefaktina. Johdanto-osion jälkeen siirryn kuvailemaan Misfit MC:n jäsenten suhdetta Harley-Davidson-moottoripyörään. Lähestyn miesten ja moottoripyörien suhdetta kahden toiminnan - moottoripyörän kunnostamisen ja rakentamisen sekä moottoripyörällä ajamisen - kautta. Avainsanat: aineellinen kulttuuri, arvot, biker, bikerkulttuuri, chopper, eetos, elämäntapa, etnografia, Harley-Davidson-moottoripyörä, Harley-Davidson-moottoripyöräkerho, kenttätyö, maskuliinisuus, mieskulttuuri, mieskuva, moottoripyöräily, osakulttuurit, outlaw, populaarikulttuuri, sukupuoliroolit, yhteisöt

Crystal and molecular structure of sym-homospermidine monohydrate

Sym-homospermidine, [formula; see text] is a naturally occurring rare-polyamine found in relatively large concentration in sandal leaves. As part of our studies on structure and interactions of polyamines, ym-homospermidine was purified from sandal leaves and its structure was determined by single crystal X-ray diffraction technique. The phosphate salt of the molecule crystallized in the triclinic space group P1- with a = 8.246(1)A, b = 8.775(1)A, c = 15.531(2)A, alpha = 74.20(1) degrees, beta = 88.36(1) degrees and gamma = 65.41(1) degrees. The structure was determined by direct methods and refined to a final R factor of 5.4% for 2087 reflections with magnitude of F(obs) greater than 5 sigma [F(obs)]. The amine exists in its most favourable all trans conformation. For each amine molecule three phosphate groups exist in the crystal structure, suggesting that two of the oxygens of each phosphate group are protonated. There is also a single water molecule in the asymmetric unit in contrast to that of spermidine phosphate which has 3 water molecules. These differences probably reflect the hydrogen bonding properties of mono-ionic and di-ionic phosphate groups. The structure is predominantly stabilized by a network of hydrogen bonds.

Dual Role of Acetate as a Nucleophile and as an Internal Base in Cycloplatination Reaction of sym-N,N `,N `'-Triarylguanidines

Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of sym-N,N',N `'-triarylguanidines, ArN=C(NHAr)(2) (sym = symmetrical; Ar = 2-MeC6H4 (LH22-tolyl), 2-(MeO)C6H4 (LH22-anisyl), 4-MeC6H4 (LH24-tolyl), 2,5-Me2C6H3 (LH22,5-xylyl), and 2,6-Me2C6H3 (LH22,6-xylyl)) in toluene under reflux condition for 3 h afforded cis- or trans-Cl2Pt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (1), 2-(MeO)C6H4 (2), 4-MeC6H4 (3), 2,5-h Me2C6H3 (4), and 2,6-Me2C6H3 (5), respectively) in 83-96% yield. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-tolyl and LH24-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 h afforded acetate-substituted products, cis-(AcO)ClPt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (6) and 4-MeC6H4 (7)) in 83% and 84% yields, respectively. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-anisyl and LH22-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 and 12 h afforded six-membered C,N] platinacycles, Pt{kappa(2)(C,N)-C6H3R-3(NHC(NHAr)(=NAr))-2}Cl(S(O)Me-2)] (Ar = 2-RC6H4; R = OMe (8) and Me (9)), in 92% and 79% yields, respectively. The new complexes have been characterized by analytical and spectroscopic techniques, and further the molecular structures of 1, 2, 4, 5, 6, and 8 have been determined by single-crystal X-ray diffraction. The platinum atom in 1, 4, and 5 exhibited the trans configuration, while that in 2, 6, and 8 exhibited the cis configuration. Complex 6 is shown to be the precursor for 9, and the former is suggested to transform to the latter possibly via an intramolecular C-H activation followed by elimination of AcOH. The solution behavior of new complexes has been studied by multinuclear NMR (H-1, Pt-195, and C-13) spectroscopy. The new complexes exist exclusively as a single isomer (trans (1 and 5) and cis (6 and 7)), a mixture of cis and trans isomers with the former isomer being predominant in the case of 2 and the latter isomer being predominant in the case of 3. Complex 5 in the trans form revealed the presence of one isomer at 0.007 mM concentration and two isomers in about 1.00:0.12 ratio at 0.154 mM concentration as revealed by H-1 NMR spectroscopy, and this has been ascribed to the restricted Pt-S bond rotation at higher concentration. Platinacycle 8 exists as one isomer, while 9 exists as a mixture of seven isomers in solution. The influence of steric factor, pi-acceptor property of the guanidine, subtle solid-state packing forces upon the configuration of the platinum atom, and the number of isomers in solution have been outlined. Factors that accelerate or slow down the cycloplatination reaction, the role of NaOAc, and a plausible mechanism of this reaction have been discussed.

Durability of Pt/C and Pt/MC-PEDOT catalysts under simulated start-stop cycles in polymer electrolyte fuel cells

A composite of mesoporous carbon (MC) with poly(3,4-ethylenedioxythiophene) (PEDOT) is studied as catalyst support for platinum nanoparticles. The durability of commercial Pt/carbon and Pt/MC-PEDOT as cathode catalyst is investigated by invoking air-fuel boundary at the anode side so as to foster carbon corrosion at the cathode side of a polymer electrolyte fuel cell (PEFC). Pt/MC-PEDOT shows higher resistance to carbon corrosion in relation to Pt/C. Electrochemical techniques such as cyclic voltammetry (CV) and impedance measurements are used to evaluate the extent of degradation in the catalyst layer. It is surmised that the resistance of MC-PEDOT as catalyst support toward electrochemical oxidation makes Pt/MC-PEDOT a suitable and stable cathode catalyst for PEFCs.

Six-membered C,N] cyclopalladated sym N,N `,N `'-tri(4-tolyl) guanidines: Synthesis, reactivity studies and structural aspects

Six-membered C,N] cyclopalladated sym N,N',N `'-tri(4-tolyl)guanidines, (ArNH)(2)C=NAr] (sym = symmetrical; Ar = 4-MeC6H4; LH24-tolyl) of the types (C,N)Pd(mu-OC(O)R)](2) (1 and 2), (C,N)Pd(mu-Br)](2) (3), cis-(C,N)PdLBr] (4-7), and (C,N)Pd(acac)] (8) were prepared in high yield by established methods with a view aimed at understanding the influence of the 4-tolyl substituent of the guanidine moiety upon the solution behaviour of 1-8. The composition of 1-8 was confirmed by elemental analysis, IR, and NMR spectroscopy, and mass spectrometry. The molecular structures of 1-6 were determined by single-crystal X-ray diffraction. Palladacycles 1-3 exist as a dimer in transoid conformation in the solid state while 4-6 exist as a monomer with cis configuration around the palladium atom as the Lewis base is placed cis to the Pd-C bond due to antisymbiosis. The NMR spectra of 1-8 revealed the presence of a single isomer in solution and this spectral feature is ascribed to the rapid inversion of the six-membered ``C,N]Pd'' ring due to the presence of sterically less hindered and more symmetrical 4-tolyl substituent in the =NAr unit of the guanidine moiety. (C) 2013 Elsevier B.V. All rights reserved.

Interlaboratory comparison of magnesium isotopic compositions of 12 felsic to ultramafic igneous rock standards analyzed by MC-ICPMS

To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3 parts per thousand in Mg-26/Mg-24, > 4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.

Eutectic MC Carbide Growth Morphologies of a Laser Clad TiC/FeAl Composite Coating

In this paper, eutectic MC carbide growth morphology and its evolution with laser scanning speed were studied comprehensively of a laser clad MC carbide reinforced FeAl intermetallic matrix composite coating. As the laser scanning speed increased, the growth morphology of eutectic MC carbide was found to be needle-aligned annulation, butterfly-like and well-developed dendrite.