Organometallic catalysis in biological media and living settings

Organometallic catalysis has allowed the development of an impressive number of chemical transformations that could not be achieved using classical methodologies. Most of these reactions have been accomplished in organic solvents, and in many cases in the absence of water, and under air-free conditions. The increasing pressure to develop more sustainable transformations has stimulated the discovery of metal-catalyzed reactions that can take place in water. A particularly attractive extension of this chemistry consists of the use of biological relevant aqueous solvents, as this might set the basis to translate catalytic metal complexes to biological settings. While this research field is in its infancy, along the last ten years there have been an increasing number of reports demonstrating the viability of achieving metal-promoted transformations in biologically relevant contexts. In this review, that does not intend to be comprehensive, we summarize the most significant advances in the area, and highlight some of the more important difficulties that must be faced when trying to design biocompatible organometallic catalysts, such us stability, cell uptake, bioorthogonality and toxicity. We will manly focus on transition metal systems which have been shown to keep their activity in complex aqueous buffers and inside living cellsWe are thankful for the financial support from the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2016–2019) and the European Union (European Regional Development Fund – ERDF). We also thank support given by the Spanish grantsSAF2013-41943-R and SAF2016-76689-R, the Xunta de Galicia (GRC2013-041 and 2015-CP082), the ERDF, and the European Research Council (Advanced Grant No. 340055). MMC thanks the Ministerio de Economía y Competitividad for the Postdoctoral fellowship (IJCI-2014-19326)S

Uplink (Reverse Link) Capacity of An Air-Ground W-CDMA System

In this work, the uplink capacity and the interference statistics are given for an W-CDMA 3-D Airto- Ground (AG) cellular like network assuming imperfect power control and finite transmitted power. The free space model of propagation is used to calculate the intercellular interference. The uplink capacity has been studied for different frequencies and scenarios. It has been shown that, the effect of rain is to reduce the uplink capacity and the maximum allowable cell radius. Also it is shown that, the frequency of operation should be lower or equal to 2 GHz. For a frequency of operation of 2 GHz, the cell capacity can reach 70 voice users or 46 data users when the cell radius is 350km. The new contribution of the paper is the study of the effect of the imperfect power control and the finite transmitted power on the uplink capacity of the Air-Ground system for different values of outage

On the Impact of Ultra Wide Band (UWB) On Downlink Range of GSM-900 and DCS-1800 Systems

The effect of the UWB interference on the GSM-900 and DCS-1800 downlink is studied for different UWB power densities. For relatively high UWB power density (-60 dBm/MHz), the effect of the UWB signals is very high when the distance between the UWB transmitter and the GSM-900 or DCS-1800 receiver is less than 1 m. For low UWB power density (-91 dBm/MHz), the effect of the UWB signals is very small if the distance between the UWB transmitter and the GSM-900 or DCS-1800 receiver is 1 m or higher. It is found that the spectrum mask proposed by the FCC for indoor application (-53 dBm/MHz in the DCS-1800 band and -41 dBm/MHz in the GSM-900 band) is too high to be tolerated by the two mobile system

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(III) and Eu(III)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral selfassemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (glum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes

Differences Between and Within Genders in Gender Role Orientation According to Age and Level of Education

This study analyses the masculinity and femininity in a Spanish simple made upof 164 adult workers (88menand 76 women). To be specific, the objective was to demonstrate whether age and level of education were related to differences in masculinity and femininity, both when comparing between the two genders and when the comparisons are made within the same gender. The results indicated that the two variables predicted differences in women, but not in men. There were only differences between genders in masculinity and femininity between the ages of 20 and 39, and when the level of education is low. The results appear to support Hofstede’s hypothesis that there are fewer differences between genders in gender role orientation in feminine countries

DIFFERENCES BETWEEN MEN AND WOMEN WITH A DISMISSING ATTACHMENT STYLE REGARDING THEIR ATTITUDES AND BEHAVIOUR IN ROMANTIC RELATIONSHIPS.

R esearch to date has revealed that the association between gender, attachment and the quality and functioning of intimate relationships is complex. This study examined the relationship between gender and attachment styles in attitudes to communication with one’s partner and in the number of past relationships in a sample of 746 Spanish undergraduates. The Relationship Questionnaire was administered to them to determine the adult attachment style. The results revealed the existence of differences according to the adult attachment style and gender with regard to the two measured variables, and a significant effect of the interaction between gender and attachment. Dismissing men reported the highest average scores in the number of past relationships, with significant differences appearing when they were compared with secure and preoccupied men. However, dismissing women did not differ from the rest of the women with other attachment styles. When men and women with the same attachment styles were compared in this variable, the only significant differences were found between dismissing men and women (with the latter reporting fewer partners). In the case of attitudes to expressing feelings to one’s partner, dismissing men reported the most negative attitudes, compared with secure and preoccupied men. Dismissing women, unlike the men, did not differ in their attitudes either from preoccupied or fearful women. Moreover, clear differences were shown between dismissing men and women in these attitudes (more negative in the case of men)

PERCEIVED BENEFITS AND COSTS OF ROMANTIC RELATIONSHIPS FOR YOUNG PEOPLE:DIFFERENCES BY ADULT ATTACHMENT STYLE

Bowlby’s attachment theory suggested that the attachment experiences of early childhood influence adult approaches to close relationships. As a result of these experiences, the child develops typical mental schemas or internal working models. The aim of this study was to analyze how young people with different attachment styles perceive the benefits and costs involved in spending as much time as possible with their partner, and to determine whether their beliefs reflect the internal working models associated with their attachment style. A sample of 1,539 university students responded to the Relationship Questionnaire (Bartholomew & Horowith, 1991), and to a questionnaire about behavioral beliefs (perceived benefits and costs). Results show that young people with different attachment styles hold different beliefs about the consequences derived from engaging in a specific behavior in romantic relationships. Secure and preoccupied individuals perceived more benefits than costs associated with the behavior, whereas dismissing and fearful individuals perceived more costs than benefits. Furthermore, secure and preoccupied individuals rated those behavioral consequences leading to enhanced intimacy or closeness more positively than avoidant individuals, whereas dismissing individuals rated more negatively those consequences that involved a loss of independence. These results confirm that a congruity exists between the beliefs associated with the behavior studied and the internal working models related to each adult attachment style

Novel Gravity Distortion Evaluation on Large Antenna Array for Deep Space Communication

This paper presents a simple gravity evaluation model for large reflector antennas and the experimental example for a case study of one uplink array of 4x35-m antennas at X and Ka band. This model can be used to evaluate the gain reduction as a function of the maximum gravity distortion, and also to specify this at system designer level. The case study consists of one array of 35-m antennas for deep space missions. Main issues due to the gravity effect have been explored with Monte Carlo based simulation analysis

On the dynamics of buoyant and heavy partióles in a periodic Stuart vortex flow

In this paper, we study the dynamics of small, spherical, rigid particles in a spatially periodic array of Stuart vórtices given by a steady-state solution to the two-dimensional incompressible Euler equation. In the limiting case of dominant viscous drag forces, the motion of the particles is studied analytically by using a perturbation scheme. This approach consists of the analysis of the leading-order term in the expansión of the 'particle path function' <P, which is equal to the stream function evaluated at the instantaneous particle position. It is shown that heavy particles which re-main suspended against gravity all move in a periodic asymptotic trajectory located above the vórtices, while buoyant particles may be trapped by the stable equilibrium points located within the vórtices. In addition, a linear map for <P is derived to describe the short-term evolution of particles moving near the boundary of a vortex. Next, the assumption of dominant viscous drag forces is relaxed, and linear stability analyses are carried out to investígate the equilibrium points of the five-parameter dynamical system governing the motion of the particles. The five parameters are the free-stream Reynolds number, the Stokes number, the fluid-to-particle mass density ratio, the distribution of vorticity in the flow, and a gravitational parameter. For heavy particles, the equilibrium points, when they exist, are found to be unstable. In the case of buoyant particles, a pair of stable and unstable equilibrium points exist simultaneously, and undergo a saddle-node bifurcation when a certain parameter of the dynamical system is varied. Finally, a computational study is also carried out by integrating the dynamical system numerically. It is found that the analytical and computational results are in agreement, provided the viscous drag forces are large. The computational study covers a more general regime in which the viscous drag forces are not necessarily dominant, and the effects of the various parametric inputs on the dynamics of buoyant particles are investigated