Ligand Design for Dual Property Single Molecule Magnets

This thesis describes two different approaches for the preparation of polynuclear clusters with interesting structural, magnetic and optical properties. Firstly, exploiting p-tert-butylcalix[4]arene (TBC4) macrocycles together with selected Ln(III) ions for the assembly of emissive single molecule magnets, and secondly the preparation and coordination of a chiral mpmH ligand with selected 3d transition metal ions, working towards the discovery of chiral polynuclear clusters. In Project 1, the coordination chemistry of the TBC4 macrocycle together with Dy(III) and Tb(III) afforded two Ln6[TBC4]2 complexes that have been structurally, magnetically and optically characterized. X-ray diffraction studies reveal that both complexes contain an octahedral core of Ln6 ions capped by two fully deprotonated TBC4 macrocycles. Although the unit cells of the two complexes are very similar, the coordination geometries of their Ln(III) ions are subtly different. Variable temperature ac magnetic susceptibility studies reveal that both complexes display single molecule magnet (SMM) behaviour in zero dc field and the energy barriers and associated pre-exponential factors for each relaxation process have been determined. Low temperature solid state photoluminescence studies reveal that both complexes are emissive; however, the f-f transitions within the Dy6 complex were masked by broad emissions from the TBC4 ligand. In contrast, the Tb(III) complex displayed green emission with the spectrum comprising four sharp bands corresponding to 5D4 → 7FJ transitions (where J = 3, 4, 5 and 6), highlighting that energy transfer from the TBC4 macrocycle to the Tb(III) ion is more effective than to Dy. Examples of zero field Tb(III) SMMs are scarce in the chemical literature and the Tb6[TBC4]2 complex represents the first example of a Tb(III) dual property SMM assembled from a p-tert-butylcalix[4]arene macrocycle with two magnetically derived energy barriers, Ueff of 79 and 63 K. In Project 2, the coordination of both enantiomers of the chiral ligand, α-methyl-2-pyridinemethanol (mpmH) to Ni(II) and Co(II) afforded three polynuclear clusters that have been structurally and magnetically characterized. The first complex, a Ni4 cluster of stoichiometry [Ni4(O2CCMe3)4(mpm)4]·H2O crystallizes in a distorted cubane topology that is well known in Ni(II) cluster chemistry. The final two Co(II) complexes crystallize as a linear mixed valence trimer with stoichiometry [Co3(mpm)6]·(ClO4)2, and a Co4 mixed valence complex [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2], whose structural topology resembles that of a defective double cubane. All three complexes crystallize in chiral space groups and circular dichroism experiments further confirm that the chirality of the ligand has been transferred to the respective coordination complex. Magnetic susceptibility studies reveal that for all three complexes, there are competing ferro- and antiferromagnetic exchange interactions. The [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2] complex represents the first example of a chiral mixed valence Co4 cluster with a defective double cubane topology.

Medición de masa osea (MO) por densitometría dual (DXA) de la cadera en pacientes con síndrome de desgaste asociado con el virus de la inmunodeficiencia humana para determinar factor de riesgo de fractura osea.

Tesis (Doctor en Medicina) UANL, 2013.

Therapeutic potential of endothelin receptor type A and bradykinin receptor B1 dual antagonism in osteoarthritis treatment

Nous avons préalablement démontré que l'endothéline-1 (ET-1), un peptide vasoconstricteur de 21 acides aminés, joue un rôle central dans le métabolisme des tissus articulaires et a des fonctions cataboliques sur le cartilage articulaire dans l'ostéoarthrose, en liant son récepteur de type A (ETA). Suite à la relâche du nonapeptide vasodilatateur bradykinine (BK), et l'augmentation d'expression du récepteur B1 des kinines (BKB1), ces médiateurs engendrent un cycle d'inflammation, une destruction du cartilage, et une douleur articulaire. Lors de cette étude, l'efficacité thérapeutique des antagonistes spécifiques du ETA et/ou BKB1 dans un modèle animal d'ostéoarthrose a été testée. Notre hypothèse est que l'antagonisme va diminuer la progression de la pathologie et de la douleur articulaire. L'ostéoarthrose a été induite chez des rats par rupture chirurgicale du ligament croisé antérieur. Les animaux ont été traités par injections intra articulaire hebdomadaires des antagonistes peptidiques spécifiques du ETA et/ou BKB1. La douleur articulaire a été évaluée par le test d'incapacitance statique durant les deux mois postopératoires ; la morphologie articulaire a été examinée post mortem par radiologie et histologie. On constate que le traitement a diminué la douleur et a préservé la morphologie articulaire ; la double inhibition a été plus efficace que la simple inhibition. En conclusion, l'antagonisme double d'ETA et BKB1 améliore la douleur chronique et prévient la dégradation articulaire dans l'ostéoarthrose, ce qui suggère que ces récepteurs peuvent être des cibles thérapeutiques potentiels pour le traitement de cette pathologie.

Reconsidering the concept of ‘dual-use’ in the context of neuroscience research

Commentaire / Commentary

Resonant frequencies of circular-sided dual-port microstrip antenna

A dual-port microstrip antenna with a crescent shaped patch with excellent isolation betwecn the ports has been reportcd [I]. Since circular-sided geometries are inore compact than rectangular oncs, thcy find morc applications in microstrip arrays. The crcscent shaped antenna geometry [ I ] provides greater area rcductioii compared to other circular sided patches for broadband operation [2]. In this Lctter, formulac for calculating thc TM, I and TMZI mode resonant frequencies of this microstrip antenna, obtained by modifying the equations of a standard circular patch [3] are presentcd. Thcorctical results are compared with experimental observations aid the validity of the computation is established.

Broadband dual frequency microstrip antenna

A new dual port microstrip antenna geometry for dual frequency operation is presented. The structure consists of the intersection of two circles of the same radius with their centres displaced by a small fraction of the wavelength . This antenna provides wide impedance bandwidth and excellent isolation between its ports. The gain of the antenna is comparable to that of a standard circular microstrip antenna operating at the same resonant frequency. A theoretical analysis for calculating the resonant frequencies of the two ports is also presented

Single-Feed Dual-Band Circularly Polarised Microstrip Antenna

A novel technique for obtaining dual-hand circular polarization (CP) radiation of a single-feed circular microstrip antenna in proposed and demonstrated. By embedding two pain of arc shaped slots of proper lengths close to the boundary of a circular patch, and protruding one of the arc-shaped slots with a narrow slit, the circular microstrip antenna can perform dual-hand CP radiation using a single probe feed. Details of the antenna design

Single-feed dual-frequency dual-polarized slotted square microstrip antenna

A novel dual frequency dual-polarized square microstrip patch antenna embedded with a slot is presented. The proposed antenna offers tunability of the frequency ratio between the two frequencies by adjusting the slot dimensions. This configuration also provides a size reduction up to -51 and 35% for the two modes as compared to a square micro strip patch antenna

Dual-band dual-polarized compact microstrip antenna

Experimental studies on a compact dual frequency microstrip antenna are presented. This antenna configuration provides an area reduction of 40% compared to a standard rectangular antenna operating at the same frequency without much degradation of the gain. The antenna structure can be modified to achieve the desired ratio between the two resonant frequencies

A New Compact Dual-Band Dual-Polarized Microstrip Antenna

A new compact dual-band, dual-polarized microstrip antenna is presented. 7'iris antenna resonates at two frequencies with different polarizations: a linearly polarized one for terrestrial communication, and a circularly polarized one for satellite mobile communication. This antenna also provides an area reduction of 70% compared to a standard rectangular patch antenna

Slot-Loaded Compact Microstrip Antenna for Dual-Frequency Operation

Dual frequency operation is achieved from a compact microstrip antenna by loading a pair of narrow slots close to its radiating edges. The two frequencies have parallel polarization planes and similar radiation characteristics. The ratio between the two operating frequencies can be tuned in the range (1.14-1. 24), which is much smaller than that of similar designs. The above excellent radiation characteristics are achieved along with an area reduction of - 75% compared to the standard rectangular patch

Analytical Equations for Compact Dual Frequency Microstrip Antenna

Design equations are presented for calculating the resonance frequencies for a compact dual frequency arrow-shaped microstrip antenna. This provides a fast and simple way to predict the resonant frequencies of the antenna. The antenna is also analyzed using the IE3D simulation package. The theoretical predictions are found to be very close to the IE3D results and thus establish the validity of the design formulae

Slot coupled sqaure microstrip antenna for compact dual-frequency operation

A novel dual frequency design of a square microstrip antenna coaxially fed along the diagonal with a chip capacitor mounted at the bottom of the stub is introduced. This design provides enhanced area reduction and good cross-polarization levels. The antenna design can be used as a compact antenna system where limited size is a major requirement. The details of the antenna design and experimental results are presented