The thesis entitled "Pushing the Limits of NMR Sensitivity and Chiral Analysis: Design of New NMR Methods and Bio-molecular Tools" consists of six chapters. The research work reported in this thesis is focused on the development of novel chemical and NMR methodological approaches for enantiomeric analysis and mea- surement of residual dipolar couplings (RDCs), and the development of sensitivity enhanced slice selective NMR experiments for obtaining pure shift 1H spectra and the measurement of scalar couplings. The thesis is divided into two parts. The Part I comprises chapters 2-4, where the enantiomeric analysis is discussed, which includes newly developed chiral reagents, two new weak chiral aligning media and design of novel NMR techniques. Part II comprises chapters 5 and 6, which discusses new sensitivity enhanced slice selective NMR techniques. Chapter 1 gives a general introduction to NMR and the problems investigated in the remaining chapters of the thesis. The chapter starts with a brief discussion on the introduction, advancements and general applications of NMR, discussion is also given on the NMR approaches for enantiomeric analysis both in isotropic and anisotropic phases and the measurement of RDCs, including the benefits and limitations associated with each approach. The chapter sets the tone by discussing limitations of the existed NMR enantiomeric approaches and slice-selective techniques, and builds the bridge for the rest of the chapters by addressing these limitations. The chapter also introduces slice selective experiments, their benefits over other conventional methods and limitations. Additional introductory notes are also given on some related concepts. Part I : NMR Chiral analysis and RDCs measurements Chapter 2 discusses chiral sensing properties of RNA nucleosides and their utility as chiral derivatizing agents for the enantio-discrimination of 1o-amines using one dimensional 1H NMR. A three component protocol has been proposed for the complexation of nucleosides with amines, which is rapid, economical and provides maximum diastereomeric conversion. The chiral differentiating ability of nucleosides are examined for different amines based on the 1H NMR chemical shift differences between the diastereomers (∆δ R, S ). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. It is observed that adenosine and guanosine exhibit large chiral differentiation (∆δ R, S ) due to the presence of a purine ring. The comparison of the diastereomeric excess (de) measured by NMR with those of the gravimetrically prepared ratios are in excellent agreement with each other confirming the robustness of these RNA nucleosides in discriminating primary amines. Chapter 3 establishes the smooth connectivity with the chapter 2 by discussing the limitations of the enantiomeric discrimination using NMR in isotropic solutions. This chapter discusses two new water compatible aligning media that were developed based on self-assembling strategy of small bio-molecules. The self-assembled folic acid, and the binary mixture of 50-GMP and guanosine are introduced as two novel weak aligning media. The properties of these low ordered media have been systematically studied for their easy preparation, physical parameter dependent tunability of their degree of alignment, mesosphere sustainability over a broad range of temperature and the concentration of the ingredients, and the phase reproducibility. The applications of both these new media are demonstrated for chiral and pro-chiral discrimination and also for the measurement of RDCs. Both these liquid crystalline media could be tuned to very low degree of alignment (order parameter of the order of 10−4), which provides simple first order spectra of molecules aligned in them, the analysis provide order dependent NMR spectral parameters. The 50-GMP:guanosine orienting medium can be prepared in less than 1 hour, and has been demonstrated to be an ideal medium for the determination of RDCs that are used as restraints in the structure calculations of small molecules. Chapter 4 describes 1H NMR spectral complexity in isotropic and anisotropic phases and its consequences on enantiomeric analysis. In circumventing such problems, new NMR techniques have been developed and the spin dynamics involved in the designed sequences are discussed. The newly developed 2D 1H NMR experimental method termed as RES-TOCSY, and its applicability for resolving R and S enantiomeric or diastereomeric peaks of all the coupled proton spins in isotropic phase is discussed. The utility of the developed method is demonstrated in diverse situations, such as, for suppressing impurities peaks, resolving the severely overlapped peaks and unraveling the peaks masked due to severe line broadening when metal complexes are used as chiral auxiliaries. The advantages and limitations of the method over other methods available in the literature are discussed and the significant advantage of the present method is illustrated by spectral comparison with J-resolved experiment. The appli- cation of the method for the accurate measurement of enantiomeric excess has also been demonstrated. The chapter also introduces another NMR experimental technique developed for resolving enantiomeric peaks and complete unraveling of R and S spectra in anisotropic phase. The developed 2D NMR method is cited in the literature as CH-RES-TOCSY. In addition to spectroscopic visualization of R and S spectra, the method also yields C-H RDCs. The applicability of the new experiment has been demonstrated on a chosen example. The wide utility of the method has also been demonstrated for the assignment of symmetric cis- and trans- isomers. Part II : Sensitivity Enhancement of Slice selective NMR Experiments Chapter 5 describes applications of slice selective NMR experiments over conven tional NMR methods and their limitations as far as the sensitivity of signal detection is concerned, especially in low concentrated samples. The chapter introduces the implementation of Acceleration by Sharing Adjacent Polarization (ASAP) technique in slice selective experiments. It is convincingly demonstrated that ASAP helps in reducing inter scan relaxation delay and consequently permits acquisition of more number of scans in a given time, resulting in the gain in signal enhancement by a factor of two. The pulse sequences have been suitably designed for obtaining the pure shift 1H spectra and in G-SERF experiment for the measurement of 1H-1H couplings, both with significantly enhanced signal intensities. Chapter 6 describes new sensitivity enhanced slice selective NMR methods for mea- surement of scalar couplings. A new experiment has been developed which is named as Quick G-SERF (QG-SERF). It is a 1D NMR slice selective method developed based on real time spin manipulation technique. The method gives multiple scalar couplings of a selected spin with simplified multiplets, which is analogous to the 2D G-SERF but with considerable saving in instrument time by 1-2 orders of magnitude. The rapidness of the experiment arises due to reduced dimensionality. The spin dynamics involved in the pulse sequence and its working principle have been described. The application of the method is illustrated for the measurement of 1H-1H couplings. The sequence has been further improved to obtain the heteronuclear couplings between two abundant spins in an orchestrated manner and has been demonstrated for measurement of 1H-19F couplings. This sequence cited as HF-QG-SERF has been implemented on the molecules containing number of chemically non-equivalent fluorine atoms.

Made available in DSpace on 2014-12-17T14:19:53Z (GMT). No. of bitstreams: 1 MariaSOE.pdf: 2714563 bytes, checksum: 2334cc432788b4b14ffbd7c43b7d713a (MD5) Previous issue date: 2005-07-16 / Nowdays, recycling became a relevant social and educational aim among many other factors, which involve balance between man and nature. This study relates the experiences with the production of recycled handmade paper directed at the teaching in Universidade Federal do Rio Grande do Norte UFRN, and through workshops of carnauba recycled handcrafts papers as a pioneer activity accomplished at the Felix Rodrigues Foundation, in the city of Pend?ncias, A?u Valley, Rio Grande do Norte. A bibliographic review was done about the history of handmade paper and a discussion about carnauba?s paper artistic possibilities in art-education. Analyses within the context of art teaching, accordingly to Ana Mae Barbosa?s triangle propose and, also, Buoro, Ostrower and Nachmanovitch?s pedagogy of art. It deals with a group of artisans in order to establish the nature of their relationship and the possibilities of achieving more ecological awareness. Finally, we intend to realize a dialogue with Morin and other authors / Na contemporaneidade, a quest?o da reciclagem tem se destacado pela sua import?ncia social e educativa, entre tantos outros fatores que envolvem o equil?brio do homem e da natureza. Relata-se a experi?ncia de ensino de arte na Extens?o Universit?ria com a produ??o de papel reciclado artesanal, direcionado ao ensino no laborat?rio de artes pl?sticas da UFRN e em oficinas de papel artesanal com fibras de carna?ba, como atividade pioneira realizada na Funda??o F?lix Rodrigues, na cidade de Pend?ncias, munic?pio do Vale do A?u, no Rio Grande do Norte. Recomp?e-se a hist?ria do papel artesanal e um di?logo reflexivo sobre as possibilidades art?sticas do papel de carna?ba. Elabora-se ainda, uma discuss?o sobre o aproveitamento desse papel para a cria??o art?stica como elemento complementar no ensino da arte, conforme sugest?es das propostas de ensino de Ana Mae Barbosa, e outros autores da pedagogia do ensino de artes como Buoro, Ostrower, Nachmanovitch. Analisa-se a natureza das rela??es sociais estabelecidas nesses grupos numa perspectiva de renova??o da consci?ncia ecol?gica. Pretende-se trilhar os caminhos de religa??o entre saberes cient?ficos e da tradi??o, ? luz de um di?logo com Edgar Morin e outros autores

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-06-14T19:53:37Z No. of bitstreams: 1 LechWalesaOliveiraSoares_DISSERT.pdf: 2473726 bytes, checksum: d7a80c7eeaba135cb9b0bb6355b7a8c2 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-15T23:04:07Z (GMT) No. of bitstreams: 1 LechWalesaOliveiraSoares_DISSERT.pdf: 2473726 bytes, checksum: d7a80c7eeaba135cb9b0bb6355b7a8c2 (MD5) / Made available in DSpace on 2016-06-15T23:04:07Z (GMT). No. of bitstreams: 1 LechWalesaOliveiraSoares_DISSERT.pdf: 2473726 bytes, checksum: d7a80c7eeaba135cb9b0bb6355b7a8c2 (MD5) Previous issue date: 2015-04-10 / A cimenta??o de po?os de petr?leo tem como fun??o b?sica promover a estabilidade mec?nica e selar hidraulicamente o po?o impedindo a comunica??o entre os diferentes tipos de fluidos. Materiais pozol?nicos s?o adicionados ao cimento, pois reagem com o hidr?xido de c?lcio formando silicatos e aluminatos de c?lcio hidratado, melhorando a estabilidade qu?mica dos produtos das fases hidratadas. A utiliza??o da cinza da casca de arroz, um rejeito da agroind?stria, na substitui??o parcial ou em adi??o ao cimento ? uma alternativa sustent?vel, na qual ? poss?vel reduzir os ?ndices de emiss?o de CO2 no processo de fabrica??o do cimento. Nesse trabalho foi avaliada a atividade pozol?nica da cinza da casca de arroz (RHA e WRHA) em pastas de cimento para po?os de petr?leo em adi??es de 10% e 20% com rela??o ? massa de cimento (BWOC). As pastas foram curadas por 28 dias a 38?C. As cinzas foram caracterizadas pelas t?cnicas de Microscopia Eletr?nica de Varredura (MEV), Infravermelho com Transformada de Fourier (FTIR), Energia Dispersiva de Raios X (EDX) e ?rea superficial (BET). A atividade pozol?nica foi avaliada pelas t?cnicas de An?lise Termogravim?trica (TGA), Difra??o de Raios X (DRX) e Resist?ncia ? Compress?o. Os resultados de TGA demonstraram que a adi??o da WRHA promoveu uma redu??o de aproximadamente 73% da fase Portlandita com rela??o ? pasta padr?o. A partir dos resultados de DRX foi poss?vel se evidenciou a redu??o da intensidade dos picos de Portlandita. Com base nos resultados apresentados podemos concluir que a cinza da casca do arroz reagiu quimicamente com a Portlandita produzindo C-S-H confirmando seu efeito como agente pozol?nico. / Pozzolanic materials such as rice husk ash are widely used to substitute part of cement, because they react with calcium hydroxide (CH) producing calcium silicate hydrate (C-S-H), which aggregate better physical, chemical and mechanical properties to the cement slurry. The usage of rice husk biomass ash from agribusiness in addition to or partially replacing cement is a noble purpose and a good way of sustainable development which currently is an obsession around the world. The ashes utilized in this study were characterized by: scanning electron microscopy technique (SEM), Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX) and BET method. The pozzolanic activity of RHA and WRHA in cement slurries was evaluated by: thermal-gravimetric technique and derivative thermogravimetry (TGA/DTG), X-ray diffraction (XRD) and Compressive Strength. The slurries formulated with additions of 10% and 20% of RHA and WRHA were cured for 28 days at 58 ?C. The results of thermal analysis demonstrated that a 20% WRHA addition caused a reduction of approximately 73% of Portlandite (calcium hydroxide ? CH) phase related to standard slurry (STD). The XRD scans also demonstrated the reduction of the Portlandite peaks? intensity for each slurry compared with STD slurry. The RHA and WRHA react chemically with Portlandite producing calcium silicate hydrate (C-S-H), confirming their effect as a pozzolanic agent. The WRHA presented the best results as a pozzolanic material.

Der erste Teil der Aktivitäten dieser Arbeit bestand in der Entwicklung einer modernen Ionenspeicher Apparatur zur Untersuchung chemischer Prozesse mit atomarem Wasserstoff. Die Integration eines differentiell gepumpten Radikalenstrahls in eine vorhandene temperaturvariable 22-Pol Speicherapparatur erforderte größere Änderungen an dieser. Da astrophysikalische Fragestellungen im Vordergrund standen, führt die Einleitung zunächst in das Gebiet der Astrophysik und -chemie ein. Die Grundlagen der Ionenspeicherung in temperaturvariablen Hf-Speichern sind ausführlich in der Literatur dokumentiert. Daher ist die Beschreibung der Apparatur (Kapitel 2) relativ kurz gehalten. Viel Mühe wurde in die Entwicklung einer intensiven und stabilen Quelle für Wasserstoffatome aufgewandt, deren kinetische Energie variiert werden kann. Das Kapitel 3 beschreibt dieses Modul in vielen Details, wobei der Einsatz von magnetischen Hexapolen zum Führen der Atome und die chemische Behandlung der Oberflächen zur Reduzierung der H-H Rekombination einen wesentlichen Platz einnimmt. Durch die außergewöhnliche Empfindlichkeit der Speichertechnik kann das neue Instrument zur Untersuchung von vielen Reaktionen eingesetzt werden, die von astrochemischer und fundamentaler Bedeutung sind. Die Ergebnisse dieser Arbeit sind im Kapitel 4 zusammengestellt, einige Reprints und Entwürfe von Publikationen findet man im Anhang. Die Reaktionen von CO2+ mit Wasserstoffatomen und -molekülen erwiesen sich als sehr geeignet, um in situ H and H2 Dichten über den gesamten Temperaturbereich der Apparatur zu bestimmen (10 K - 300 K). Zum ersten mal wurden Reaktionen von H- and D-Atomen mit den Kohlenwasserstoffionen CH+, CH2+, and CH4+ bei Temperaturen des interstellaren Raums untersucht. Ein sehr interessantes, noch nicht ganz verstandenes Stoßsystem ist die Wechselwirkung von protoniertem Methan mit H-Atomen. Im Ausblick der Arbeit werden einige Ideen aufgezeigt, wie man das Instrument verbessern kann, und es werden einige Reaktionen erwähnt, die man als nächste untersuchen könnte. Diese Dissertation ist einen Beitrag zum Projekt 5 der Forschergruppe Laboratory Astrophysics: Structure, Dynamics and Properties of Molecules and Grains in Space, die von der DFG im Zeitraum von 2000 bis 2006 unterstützt wurde. / The first part of the activities of this thesis was to develop a sophisticated ion storage apparatus dedicated to study chemical processes with atomic hydrogen. The integration of a differentially pumped radical beam source into an existing temperature variable 22-pole trapping machine has required major modifications. Since astrophysical questions have been in the center of our interest, the introduction first gives a short overview of astrophysics and -chemistry. The basics of ion trapping in temperature variable rf traps is well-documented in the literature; therefore, the description of the basic instrument (Chapter 2) is kept rather short. Much effort has been put into the development of an intense and stable source for hydrogen atoms the kinetic energy of which can be changed. Chapter 3 describes this module in detail with emphasis on the integration of magnetic hexapoles for guiding the atoms and special treatments of the surfaces for reducing H-H recombination. Due to the unique sensitivity of the rf ion trapping technique, this instrument allows one to study a variety of reactions of astrochemical and fundamental interest. The results of this work are summarized in Chapter 4, some reprints and drafts are reproduced in the appendix. Reactions of CO2+ with hydrogen atoms and molecules have been established as calibration standard for in situ determination of H and H2 densities over the full temperature range of the apparatus (10 K - 300 K). For the first time, reactions of H- and D-atoms with the ionic hydrocarbons CH+, CH2+, and CH4+ have been studied at temperatures of interstellar space. A very interesting, not yet fully understood collision system is the interaction of protonated methane with H. The outlook presents some ideas, how to improve the new instrument and a few reaction systems are mentioned which may be studied next. This thesis is a contribution to the project 5 of the research unit Laboratory Astrophysics: Structure, Dynamics and Properties of Molecules and Grains in Space which has been supported by the DFG from 2000 to 2006.

English abstract The present dissertation Spirituality of Presence: the Significance of R. Voillaume s Work focuses on the life and work of R. Voillaume (1905-2003). His work is understood as spirituality of presence , or to be more precise of double presence: presence to God and presence to man. After the introductory part dealing with Voillaume s life, historical context and a survey of his work, the dissertation continues with an analysis of his literary work. The main theme is a relecture of Foucauld s spirituality of Nazareth in the light of the mentioned concept of presence: the hidden and silent presence in the midst of men refers not only to the significance of hidden life in Catholic spirituality, it also points out to the deep openness to the situation of modern man and to the search of an authentic Christian life as a life of presence trying to make the life of faith accessible to a contemporary man in a creative and nonconformist way. The conclusion puts Foucauldian spirituality (whose main interpreter is R. Voillaume) into the context of Catholic spirituality and confronts his spirituality of presence with the findings of biblical theology. Theoretically, the dissertation combines personalistic and systematic approaches. Voillaume s work is understood as a major manifestation of Catholic...

Thermostated time evolutions are on a firm ground and widely used in classical molecular dynamics (MD) simulations. Hamilton´s equations of motion are supplemented by time-dependent pseudofriction terms that convert the microcanonical isoenergetic time evolution into a canonical isothermal time evolution, thus permitting the calculation of canonical ensemble averages by time averaging. However, similar methods for quantum MD schemes are still lacking. Given the rich dynamical behavior of ultracold trapped quantum gases depending on the value of the s-wave scattering length, it is timely to investigate how classical thermostating methods can be combined with powerful approximate quantum dynamics schemes to deal with interacting quantum systems at finite temperature. In this work, the popular method of Nose and Hoover to create canonically distributed positions and momenta in classical MD simulations is generalized to a genuine quantum system of infinite dimensionality. We show that for the quantum harmonic oscillator, the equations of motion in terms of coherent states may be modified in a Nose-Hoover manner to mimic the coupling of the system to a thermal bath and create a quantum canonical ensemble. The method is developed initially for a single particle and then generalized to the case of an arbitrary number of identical quantum particles, involving entangled distribution functions. The resulting isothermal equations of motion for bosons and fermions contain additional terms leading to Bose-attraction and Pauli-blocking, respectively. Questions of ergodicity are discussed for different coupling schemes. In the many-particle case, the superiority of the Nose-Hoover technique to a Langevin approach is demonstrated. In addition, the work contains an investigation of the Grilli-Tosatti thermostating method applied to the harmonic oscillator, and calculations for quantum wavefunctions moving with a time-invariant shape in a harmonic potential.

The adsorption and coadsorption of sulfur and oxygen on the Ir(110) surface was investigated by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES). The clean Ir(110) surface forms alternating (331) and (33-1) minifacets, resulting in a mesoscopically rippled surface. Upon chemisorption of sulfur or oxygen and subsequent annealing, the surface structure is changed. In the following, the results concerning sulfur and oxygen adsorption will be summarized before addressing the coadsorption system. Sulfur adsorption: At sulfur coverages of 0.1-0.2 ML, the Ir(110) surface adopts a (1x2) missing-row configuration similar to clean Au(110) and Pt(110). The sulfur-stabilized Ir(110)-(1x2) does not show any evidence for the preference of (111) faceted steps, and consequently does not form a mesoscopic fish-scale pattern. The latter was observed on the (110) surfaces of Au and Pt, and was found to be driven by the preference for (111) step facets. On Ir(110), no such preference seems to exist, since (331) step facets are frequently observed. With respect to the adsorbed sulfur, no extended islands are observed, indicating repulsive adsorbate-adsorbate interactions. At sulfur coverages near 0.5 ML, a p(2x2) structure with p2mg (glide-plane) symmetry is observed. The adsorption site and structural model derived by STM are compatible with an earlier LEED analysis of that structure: S adsorbs in threefold coordinated fcc hollow sites above the (111) facets formed by the non-missing substrate rows. At coverages higher than 0.5 ML, a c(2x4) LEED pattern with additional faint streaks in the [-110] azimuth is observed. STM reveals that the streaks are due to pairs of sulfur atoms (dimers, for brevity) in a second adsorbate layer, that can be desorbed by heating to 1100 K. A structural model is derived on the basis of the STM results, showing the dimer atoms in on-top positions over sulfur atoms of the first adsorbate layer. When the surface is completely covered by the dimers, the surface is saturated at 0.75 ML. Oxygen adsorption: In agreement with earlier reports, oxygen adsorption and subsequent annealing to 700-900 K results in an unreconstructed (1x1) surface, covered by a c(2x2)-O overlayer at 0.5 ML coverage. Coadsorption of oxygen on an S-precovered surface (S-coverage below 0.5 ML) leads to a phase separation of the adsorbates (competitive adsorption). At low coverages, oxygen forms a p(2x2)-O phase, whereas at higher O-coverages a compression into a (1x2)-O phase is observed. Postannealing the (1x2)-O phase at 900 K in vacuum leads to a reduction of the sulfur concentration, indicating sulfur oxidation. Interestingly, the p(2x2)-O phase does not seem to be reactive, according to the AES results. A possible explanation may be that the more densely packed (1x2)-O phase can be regarded as an activated structure. This is also supported by the STM results. At S-coverages above 0.5 ML, the surface is completely poisoned with respect to oxygen adsorption. Nevertheless, heating the sulfur saturated Ir(110)-c(2x4)-S structure in an oxygen atmosphere, the sulfur concentration gradually drops to zero. At intermediate stages of this oxidation process, island formation is observed by STM, but the underlying formation processes remain to be resolved.

No description available.

No description available.

Au cours de cette thèse, nous nous sommes intéressés à l'activation de liaisons C-H catalysée par des catalyseurs au palladium pour la préparation de biaryles portant un groupement SO₂R. De très nombreux composés biologiques possèdent une fonction SO₂R. Nous avons donc choisi d'étudier activation de liaisons C-H de ce type de substrat. L'activation de liaisons C-H est considérée comme attractive pour l'environnement par rapport à d'autres types de couplages tels que Suzuki, Stille, ou Negishi. D'abord, nous avons démontré qu'il est possible d'appliquer la méthode d'activation de liaisons C-H pour l'arylation directe de thiophènes portant un substituant SO₂R. Nous avons ensuite établi un système catalysé au palladium pour l'arylation sélective en C2 de dérivés N-tosylpyrrole. Nous avons constaté que le N-tosylpyrrole est plus réactif comparé au pyrrole non protégé. Nous avons également étudié l'arylation directe d'hétéroarènes par des bromobenzènes possédant un substituant SO₂R soit en C2 ou C4 par catalyse au palladium. Cette méthode fournit un accès simple à des dérivés de ArSO₂R. Enfin, nous avons développé la première méthode de déshydrogénation de liaisons sp³ C-H catalysée au palladium de N-alkyl-benzènesulfonamides pour produire des N-alcényle benzènesulfonamides. / During this Ph.D. period, we were interested in the C-H bonds activation catalysed by palladium catalysts for the preparation of biaryls units bearing SO₂R group. Many biological compounds present a SO₂R function and thus we chose to activate this family of substrates. This method is considered as cost effective and environmentally attractive compared to other types of couplings such as Suzuki, Stille, or Negishi. First, we demonstrated that it is possible to apply C-H bond activation method for the direct arylation of thiophene derivatives bearing a SO₂R substituent. We then established palladium-catalysed system for the selective C2 arylation of N-tosylpyrrole derivatives. We found that N-tosylpyrrole is more reactive than free NH-pyrrole. We also studied the direct arylation of heteroarenes using bromobenzenes bearing SO₂R substituents either at C2 or C4 via palladium-catalysed C-H activation. This method provides a simpler access to substituted SO₂R derivatives. Finally we developed the first palladium-catalysed dehydrogenative sp³ C-H bond functionalization/activation of N-alkyl-benzenesulfonamides to produce N-alkenyl-benzenesulfonamides. The reaction proceeds with easily accessible ligand-free Pd(OAc)₂ catalyst for aryl bromides bearing electron-withdrawing groups or PdCl(C₃H₅)(dppb) catalyst for aryl bromides with electron-donating substituents. We found that the reaction tolerates a variety of substituents both on nitrogen and on the bromobenzene moiety.