Synthesis and Reactions of Iron and Ruthenium Dinitrogen Complexes

This thesis is primarily concerned with the synthesis and reactions of iron and ruthenium dinitrogen complexes of tripodal phosphine ligands. Of particular interest is the cationic dinitrogen bridged iron complex [(FeH(PP3))2(μ-N2)]2+ 23, containing the tetradentate ligand P(CH2CH2PMe2)3, PP3 1, and its potential for facilitating the reduction of the bound dinitrogen upon treatment with acid. The synthesis of a selection of novel and known tripodal phosphine and amino phosphine ligands is described. New ligands N(CH2CH2CH2PMe2)3 N3P3 7 and P(CH2CH2CH2PiPr2)3 P3Pi3 11 were synthesised by nucleophilic displacement of bromide from the bromoalkylphosphine and bromoalkylamine precursors with the relevant phosphide. A new method for synthesis of known ligand P(CH2CH2CH2PMe2)3 P3P3 19 by the nucleophilic substitution of its chloroalkylphosphine oxide with dimethylphosphide and subsequent reduction is also reported. The reaction of [(FeH(PP3))2(μ-N2)]2+ 23 with base produced the singly deprotonated mixed valence species [(FeH(PP3))(μ-N2)(Fe(PP3))]+ 37 and subsequently the iron(0) dinuclear species (Fe(PP3))2(μ-N2) 38 and mononuclear complex Fe(N2)(PP3) 44. The 15N labelling of complexes has allowed the 15N NMR spectra of 23, 37 and 44 to be reported along with the observation of a long-range 5JP-P coupling across the bridging dinitrogen of 37. Complexes 23 and 37 were also structurally characterised by X-ray crystallography. The treatment of a variety of iron PP3 1 dinitrogen complexes, including the mononuclear species [(Fe(N2)H(PP3)]+ 22, with acid, or base then acid, did not result in the formation of ammonia from reduction of the complexed dinitrogen. The reactions of FeCl2(PP3) 24 and FeClH(PP3) 25 with ammonia and hydrazine afforded the complexes [FeCl(N2H4)(PP3)] 48, [FeH(N2H4)(PP3)] 47, [FeCl(NH3)(PP3)] 49 and [FeH(NH3)(PP3)] 46. Complexes 47 and 46 are considered potential intermediates in any reduction of the dinitrogen ligand of 23 to ammonia. Complexes 49 and 46 were also formed from the decomposition of the hydrazine complexes 48 and 47. The 15N NMR shifts, derived from both the 15N labelling of complexes and from 1H-15N 2D NMR experiments at natural abundance are reported. In addition, complex 47 was characterised by X-ray crystallography. The novel ligand P(CH2CH2PiPr2)3 PPi3 12 was used in the successful synthesis of [FeCl(PPi3)]+ 51 and [RuCl(PPi3)]+ 56. Reduction of 51 and 56 with potassium graphite under dinitrogen afforded the complexes Fe(N2)(PPi3) 52 and Ru(N2)(PPi3) 57 respectively. This is the first report of a Ru(0) dinitrogen complex. Treatment of 52 and 57 with lutidinium tetrafluoroborate resulted in protonation and oxidation of the metal centre to afford the hydrido complexes [Fe(N2)H(PPi3)]+ 53 and [Ru(N2)H(PPi3)]+ 58 respectively. 15N labelled analogues of 52, 53, 57 and 58 were achieved by exchange reactions with 15N2 gas, allowing for analysis by 15N NMR spectroscopy. Species 52, 57 and 58 have also been structurally characterised by X-ray crystallography. Treatment of 52 with excess acid in THF afforded both 53 and the dihydrogen complex [Fe(H2)H(PPi3)]+ 54. The mechanism of formation of 54 probably involves the C-H activation of the solvent THF. The complex cation [RuCl(P3Pi3)]+ 65 was synthesised using the novel ligand P3Pi3 11. A polymeric iron(II) complex, [Fe2Cl4(N3P3)2]n 66, of the tridentate ligand N3P3 7 was also synthesised. Characterisation of both 65 and 66 by X-ray crystallography is reported. (FeCl)2(μ-Cl)2(μ-Pi2)2 68, an unusual bridged dimer of the known ligand CH2(PiPr2)2 Pi2 67, and iron(II) and iron(0) tetramers of the PP3 1 ligand, namely [Fe4Cl4(PP3)5]4+ 71 and Fe4(PP3)5 72 were also characterised by X-ray crystallography

Structural basis of proton-coupled potassium transport in the KUP family

Potassium homeostasis is vital for all organisms, but is challenging in single-celled organisms like bacteria and yeast and immobile organisms like plants that constantly need to adapt to changing external conditions. KUP transporters facilitate potassium uptake by the co-transport of protons. Here, we uncover the molecular basis for transport in this widely distributed family. We identify the potassium importer KimA from Bacillus subtilis as a member of the KUP family, demonstrate that it functions as a K+/H+ symporter and report a 3.7 Å cryo-EM structure of the KimA homodimer in an inward-occluded, trans-inhibited conformation. By introducing point mutations, we identify key residues for potassium and proton binding, which are conserved among other KUP proteins

Legal Paradigm Shifts and Their Impacts on the Socio-Spatial Exclusion of Asylum Seekers in Denmark

This chapter discusses the genesis of Denmark’s asylum accommodation system and recent legal and socio-spatial changes as a reaction to the increase of arrivals. By elucidating the structures and objectives of asylum accommodation, I present that the state’s further tightening of restrictive reception and accommodation policies significantly impacts the socio-spatial configurations of accommodations, refugees’ access to housing and their well-being. I discuss the links between the tensioning of laws, the reduction of living conditions and the (re-)constitution of large accommodations as means of socio-spatial exclusion. Applying the case of Denmark’s Hovedstaden Region (Capital Region), I finally argue that asylum accommodation is a central instrument of Denmark’s approaches to strategically isolate forced migrants and to deter them from migrating to Denmark

Morphological evidences indicate that the interference of cimetidine on the peritubular components is responsible for detachment and apoptosis of Sertoli cells

Cimetidine, referred as antiandrogenic agent, has caused alterations in the seminiferous tubules, including alterations in the peritubular tissue and death of myoid cells by apoptosis. Regarding the structural and functional importance of the peritubular tissue for the maintenance of Sertoli cells (SC), we purpose to investigate the SC-basement membrane interface, focusing the morphological features of SC and their interaction with the basement membrane in the affected tubules by cimetidine. Ten animals were distributed into two groups, control (CG) and cimetidine (CmG) which received saline solution and 50 mg of cimetidine per kg of body weight, respectively, for 52 days. The testes were fixed, dehydrated and embedded for analyses under light and transmission electron microscopy. Paraffin sections were submitted to the TUNEL method; sections of testes embedded in glycol methacrylate were submitted to PAS method and stained by H&E for morphological and quantitative analyses of Sertoli Cells. In the CmG, the SC nuclei were positive to the TUNEL method and showed typical morphological alterations of cell death by apoptosis (from early to advanced stages). A significant reduction in the number of Sertoli Cells was probably due to death of these cells by apoptosis. A close relationship between SC nuclear alterations (including a high frequency of dislocated nuclei from the basal portion) and damage in the peritubular tissue was observed. The ultrastructural analysis showed a parallelism between the gradual advancement of apoptotic process in SC and detachment of the anchoring sites (hemidesmosomes) of SC plasma membrane from the lamina densa. The presence of portions of lamina densa underlying the detached hemidesmosomes indicates a continuous deposition of lamina densa, resulting in the thickening of the basal lamina. The results indicate a possible disarrangement of the SC cytoskeleton, including the focal adhesion structure. These alterations are related to SC apoptosis and probably result from disturbs induced by cimetidine on the peritubular tissue

Targeted disruption of Slc2a8 (GLUT8) reduces motility and mitochondrial potential of spermatozoa

GLUT8 is a class 3 sugar transport facilitator which is predominantly expressed in testis and also detected in brain, heart, skeletal muscle, adipose tissue, adrenal gland, and liver. Since its physiological function in these tissues is unknown, we generated a Slc2a8 null mouse and characterized its phenotype. Slc2a8 knockout mice appeared healthy and exhibited normal growth, body weight development and glycemic control, indicating that GLUT8 does not play a significant role for maintenance of whole body glucose homeostasis. However, analysis of the offspring distribution of heterozygous mating indicated a lower number of Slc2a8 knockout offspring (30.5:47.3:22.1%, Slc2a8+/+, Slc2a8+/−, and Slc2a8−/− mice, respectively) resulting in a deviation (p = 0.0024) from the expected Mendelian distribution. This difference was associated with lower ATP levels, a reduced mitochondrial membrane potential and a significant reduction of sperm motility of the Slc2a8 knockout in comparison to wild-type spermatozoa. In contrast, number and survival rate of spermatozoa were not altered. These data indicate that GLUT8 plays an important role in the energy metabolism of sperm cells

Cryptanalysis of GlobalPlatform Secure Channel Protocols

GlobalPlatform (GP) card specifications are the de facto standards for the industry of smart cards. Being highly sensitive, GP specifications were defined regarding stringent security requirements. In this paper, we analyze the cryptographic core of these requirements; i.e. the family of Secure Channel Protocols (SCP). Our main results are twofold. First, we demonstrate a theoretical attack against SCP02, which is the most popular protocol in the SCP family. We discuss the scope of our attack by presenting an actual scenario in which a malicious entity can exploit it in order to recover encrypted messages. Second, we investigate the security of SCP03 that was introduced as an amendment in 2009. We find that it provably satisfies strong notions of security. Of particular interest, we prove that SCP03 withstands algorithm substitution attacks (ASAs) defined by Bellare et al. that may lead to secret mass surveillance. Our findings highlight the great value of the paradigm of provable security for standards and certification, since unlike extensive evaluation, it formally guarantees the absence of security flaws

Reticular synthesis and the design of new materials

The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62718/1/nature01650.pd

cohesion and conflict in transnational merchant families

How do people negotiate the diversity of positionalities within kin groups? Through a diachronic approach, I investigate how Ali and Jalal, two merchants with Azeri and Gilaki ethnic identifications who came to Hamburg in the 1930s, mobilized kin to generate capital along the lines of generation, gender, and age. The reader simultaneously learns about the local history of Iranian immigration. Building on literature about historical merchant networks, the social organization of the Iranian marketplace (bazaar), the anthropology of kinship and transnational families, I question the social cohesion on which Aihwa Ong's study of flexible capital creation relies. The material suggests that the experience of family relations influences agents' positioning in the local Iranian social field