Negative Fukui functions: new insights based on electronegativity equalization

The occurrence of negative values for Fukui functions was studied through the electronegativity equalization method. Using algebraic relations between Fukui functions and different other conceptual DFT quantities on the one hand and the hardness matrix on the other hand, expressions were obtained for Fukui functions for several archetypical small molecules. Based on EEM calculations for large molecular sets, no negative Fukui functions were found

Critical thoughts on computing atom condensed Fukui functions

Different procedures to obtain atom condensed Fukui functions are described. It is shown how the resulting values may differ depending on the exact approach to atom condensed Fukui functions. The condensed Fukui function can be computed using either the fragment of molecular response approach or the response of molecular fragment approach. The two approaches are nonequivalent; only the latter approach corresponds in general with a population difference expression. The Mulliken approach does not depend on the approach taken but has some computational drawbacks. The different resulting expressions are tested for a wide set of molecules. In practice one must make seemingly arbitrary choices about how to compute condensed Fukui functions, which suggests questioning the role of these indicators in conceptual density-functional theory

Nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties by means of electrical property expansions: Application to HF, CH4, CF4, and SF6

Electrical property derivative expressions are presented for the nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties. For CF4 and SF6, as opposed to HF and CH4, a term that is quadratic in the vibrational anharmonicity (and not previously evaluated for any molecule) makes an important contribution to the static second vibrational hyperpolarizability of CF4 and SF6. A comparison between calculated and experimental values for the difference between the (anisotropic) Kerr effect and electric field induced second-harmonic generation shows that, at the Hartree-Fock level, the nuclear relaxation/infinite frequency approximation gives the correct trend (in the series CH4, CF4, SF6) but is of the order of 50% too small

Nuevo disipador para edificación sismorresistente. 1ª parte: caracterización y modelos de predicción

A new energy dissipator, based on yielding of steel under shear response, has been developed and recently tested. It is H shaped and web stiffened. Yielding moin part is mechanized from one piece of rectangular shoped steel bar. Its conception let obtain thin and well-stiffened web cross sections without welded parts. Main experimentally obtained charecteristics are a yielding point near 0.5 mm of displacement, yielding loads between 14 kN and 20 kN and a dissipated energy, before damage appears in the web, from 10 kJ to 21 kJ. All tested specimens have developed large deformations without web buckling. Whe web degradation appers, flanges and stiffeners keep dissipating an important amount of energy. Proposed numerical models and simple mathematical expressions offer well correlated results when compared to the experimental ones

Molecular changes underlying mammalian phenotypic innovation

Mammals are characterized by specific phenotypic traits that include lactation, hair, and relatively large brains with unique structures. Individual mammalian lineages have, in turn, evolved characteristic traits that distinguish them from others. These include obvious anatom¬ical differences but also differences related to reproduction, life span, cognitive abilities, be¬havior. and disease susceptibility. However, the molecular basis of the diverse mammalian phenotypes and the selective pressures that shaped their evolution remain largely unknown. In the first part of my thesis, I analyzed the genetic factors associated with the origin of a unique mammalian phenotype lactation and I studied the selective pressures that forged the transition from oviparity to viviparity. Using a comparative genomics approach and evolutionary simulations, I showed that the emergence of lactation, as well as the appear¬ance of the casein gene family, significantly reduced selective pressure on the major egg-yolk proteins (the vitellogenin family). This led to a progressive loss of vitellogenins, which - in oviparous species - act as storage proteins for lipids, amino acids, phosphorous and calcium in the isolated egg. The passage to internal fertilization and placentation in therian mam¬mals rendered vitellogenins completely dispensable, which ended in the loss of the whole gene family in this lineage. As illustrated by the vitellogenin study, changes in gene content are one possible underlying factor for the evolution of mammalian-specific phenotypes. However, more subtle genomic changes, such as mutations in protein-coding sequences, can also greatly affect the phenotypes. In particular, it was proposed that changes at the level of gene reg¬ulation could underlie many (or even most) phenotypic differences between species. In the second part of my thesis, I participated in a major comparative study of mammalian tissue transcriptomes, with the goal of understanding how evolutionary forces affected expression patterns in the past 200 million years of mammalian evolution. I showed that, while com¬parisons of gene expressions are in agreement with the known species phylogeny, the rate of expression evolution varies greatly among lineages. Species with low effective population size, such as monotremes and hominoids, showed significantly accelerated rates of gene expression evolution. The most likely explanation for the high rate of gene expression evolution in these lineages is the accumulation of mildly deleterious mutations in regulatory regions, due to the low efficiency of purifying selection. Thus, our observations are in agreement with the nearly neutral theory of molecular evolution. I also describe substantial differences in evolutionary rates between tissues, with brain being the most constrained (especially in primates) and testis significantly accelerated. The rate of gene expression evolution also varies significantly between chromosomes. In particular, I observed an acceleration of gene expression changes on the X chromosome, probably as a result of adaptive processes associated with the origin of therian sex chromosomes. Lastly, I identified several individual genes as well as co-regulated expression modules that have undergone lineage specific expression changes and likely under¬lie various phenotypic innovations in mammals. The methods developed during my thesis, as well as the comprehensive gene content analyses and transcriptomics datasets made available by our group, will likely prove to be useful for further exploratory analyses of the diverse mammalian phenotypes.

Estimation of inelastic seismic material properties of a surgical sea-bed from multi-component marine seismic data

To date, state-of-the-art seismic material parameter estimates from multi-component sea-bed seismic data are based on the assumption that the sea-bed consists of a fully elastic half-space. In reality, however, the shallow sea-bed generally consists of soft, unconsolidated sediments that are characterized by strong to very strong seismic attenuation. To explore the potential implications, we apply a state-of-the-art elastic decomposition algorithm to synthetic data for a range of canonical sea-bed models consisting of a viscoelastic half-space of varying attenuation. We find that in the presence of strong seismic attenuation, as quantified by Q-values of 10 or less, significant errors arise in the conventional elastic estimation of seismic properties. Tests on synthetic data indicate that these errors can be largely avoided by accounting for the inherent attenuation of the seafloor when estimating the seismic parameters. This can be achieved by replacing the real-valued expressions for the elastic moduli in the governing equations in the parameter estimation by their complex-valued viscoelastic equivalents. The practical application of our parameter procedure yields realistic estimates of the elastic seismic material properties of the shallow sea-bed, while the corresponding Q-estimates seem to be biased towards too low values, particularly for S-waves. Given that the estimation of inelastic material parameters is notoriously difficult, particularly in the immediate vicinity of the sea-bed, this is expected to be of interest and importance for civil and ocean engineering purposes.

Interplay of spectral efficiency, power and doppler spectrum for reference-signal-assisted wireless communication

Expressions relating spectral efficiency, power, and Doppler spectrum, are derived for Rayleigh-faded wireless channels with Gaussian signal transmission. No side information on the state of the channel is assumed at the receiver. Rather, periodic reference signals are postulated in accordance with the functioning of most wireless systems. The analysis relies on a well-established lower bound, generally tight and asymptotically exact at low SNR. In contrast with most previous studies, which relied on block-fading channel models, a continuous-fading model is adopted. This embeds the Doppler spectrum directly in the derived expressions, imbuing them with practical significance. Closed-form relationships are obtained for the popular Clarke-Jakes spectrum and informative expansions, valid for arbitrary spectra, are found for the low- and high-power regimes. While the paper focuses on scalar channels, the extension to multiantenna settings is also discussed.

High-SNR power offset in multiantenna communication

The analysis of the multiantenna capacity in the high-SNR regime has hitherto focused on the high-SNR slope (or maximum multiplexing gain), which quantifies the multiplicative increase as function of the number of antennas. This traditional characterization is unable to assess the impact of prominent channel features since, for a majority of channels, the slope equals the minimum of the number of transmit and receive antennas. Furthermore, a characterization based solely on the slope captures only the scaling but it has no notion of the power required for a certain capacity. This paper advocates a more refined characterization whereby, as function of SNRjdB, the high-SNR capacity is expanded as an affine function where the impact of channel features such as antenna correlation, unfaded components, etc, resides in the zero-order term or power offset. The power offset, for which we find insightful closed-form expressions, is shown to play a chief role for SNR levels of practical interest.

Multiuser detection in a dynamic environment — Part II: Joint user identification and parameter estimation

The problem of jointly estimating the number, the identities, and the data of active users in a time-varying multiuser environment was examined in a companion paper (IEEE Trans. Information Theory, vol. 53, no. 9, September 2007), at whose core was the use of the theory of finite random sets on countable spaces. Here we extend that theory to encompass the more general problem of estimating unknown continuous parameters of the active-user signals. This problem is solved here by applying the theory of random finite sets constructed on hybrid spaces. We doso deriving Bayesian recursions that describe the evolution withtime of a posteriori densities of the unknown parameters and data.Unlike in the above cited paper, wherein one could evaluate theexact multiuser set posterior density, here the continuous-parameter Bayesian recursions do not admit closed-form expressions. To circumvent this difficulty, we develop numerical approximationsfor the receivers that are based on Sequential Monte Carlo (SMC)methods (“particle filtering”). Simulation results, referring to acode-divisin multiple-access (CDMA) system, are presented toillustrate the theory.

Outage probability analysis for MRC in η-μ fading channels with co-channel interference

Exact closed-form expressions are obtained for the outage probability of maximal ratio combining in η-μ fadingchannels with antenna correlation and co-channel interference. The scenario considered in this work assumes the joint presence of background white Gaussian noise and independent Rayleigh-faded interferers with arbitrary powers. Outage probability results are obtained through an appropriate generalization of the moment-generating function of theη-μ fading distribution, for which new closed-form expressions are provided.

Spectral efficiency in reference-signal-assisted low-power wireless communication

Expressions relating spectral efficiency, power and Doppler spectrum are derived for low-power Rayleighfaded wireless channels with proper complex signaling. Noside information on the state of the channel is assumed at the receiver. Rather, periodic reference signals are postulated inaccordance with the functioning of most wireless systems. In contrast with most previous studies, which relied on block-fading channel models, a continuous-fading model is adopted. This embeds the Doppler spectrum directly in thederived expressions thereby imbuing them with practical significance.

Using qualia information to identify lexical semantic classes in an unsupervised clustering task

Acquiring lexical information is a complex problem, typically approached by relying on a number of contexts to contribute information for classification. One of the first issues to address in this domain is the determination of such contexts. The work presented here proposes the use of automatically obtained FORMAL role descriptors as features used to draw nouns from the same lexical semantic class together in an unsupervised clustering task. We have dealt with three lexical semantic classes (HUMAN, LOCATION and EVENT) in English. The results obtained show that it is possible to discriminate between elements from different lexical semantic classes using only FORMAL role information, hence validating our initial hypothesis. Also, iterating our method accurately accounts for fine-grained distinctions within lexical classes, namely distinctions involving ambiguous expressions. Moreover, a filtering and bootstrapping strategy employed in extracting FORMAL role descriptors proved to minimize effects of sparse data and noise in our task.

Teaching Literature in EFL through the Story Grammar and Reader Response Approach

La Literatura ha de ser implementada a les aules com a eina per a l’ensenyament i aprenentatge de la llengua anglesa, i hauria de complementar els llibres de text d’ensenyament d’aquesta llengua. D’aquesta manera els alumnes seran exposats encara més a una varietat de registres, expressions i vocabulari d’aquesta llengua. La metodologia d’ensenyar la gramàtica dels contes o històries coneguda en anglès com “Story Grammar Approach” (SGA) i la metodologia sobre la comprensió i reacció lectora o “Reader Response Approach” (RRA) són excel•lent vehicles per a implementar la Literatura com a eina a les aules per a ensenyar anglès.La metodologia sobre la gramàtica de contes o “SGA” només es pot posar en pràctica quan els textos són narratius perquè aquests posseeixen tots els següents elements:• Personatges• Ambient• Trama• Conflicte• Resolució• Tema La metodologia de la reacció lectiva o “RRA” es centra principalment en la comprensió subjectiva i reacció del lector sobre un text, en la qual el lector formula una hipòtesis i aporta les seves idees sobre el text a una conversa grupal. Els estudiants han de poder aportar les seves reaccions, idees i respostes sobre els textos. La metodologia “RRA” també enfoca les habilitats cognitives superiors i empenya a l’alumne a millorar la seva expressió oral.Aquestes dues metodologies aporten incomptable avantatges. Treballen totes les intel•ligències múltiples i totes les competències acadèmiques (menys la matemàtica), els alumnes aprenen a treballar i a escolar als altres (i valorar altres opinions), poden aprendre sobre diferents cultures, la història, geografia, són exposats a diferents gèneres, i fomenten i estimulen la lectura i escriptura, com també treballen les habilitats productives i receptives en l’aprenentatge del anglès.

Androgen dependence of hirsutism, acne, and alopecia in women: retrospective analysis of 228 patients investigated for hyperandrogenism.

Hirsutism, acne, alopecia, and oligo-amenorrhea are clinical expressions of hyperandrogenism, one of the most frequent endocrine disorders in women of reproductive age. Women referred to our endocrine clinics for skin symptoms of hyperandrogenism underwent a laboratory workup to evaluate hormone measurements and received antiandrogen therapy. We retrospectively analyzed the outcome of 228 consecutive patients investigated over 6 years.Patients with hirsutism had higher levels of androstenedione, dehydroepiandrosterone sulfate (DHEAS), and salivary testosterone; lower levels of sex hormone-binding globulin (SHBG); and a higher prevalence of oligo-amenorrhea than patients with alopecia, while patients with acne showed intermediate values. Hirsutism score correlated positively with androstenedione, DHEAS, and salivary testosterone, and correlated negatively with SHBG; salivary testosterone showed the highest correlation coefficient. Total testosterone was not significantly different among patients with hirsutism, alopecia, or acne, and did not significantly correlate with hirsutism score. Hirsutism and oligo-amenorrhea were the most sensitive symptoms of hyperandrogenism, and no androgenic parameter alone allowed us to identify all cases of hyperandrogenism.Patients of central European origin sought consultation with milder hirsutism scores than patients of southern European origin. There was, however, no difference in the clinical-biological correlation between these groups, arguing against differences in skin sensitivity to androgens.Polycystic ovary syndrome, defined as hyperandrogenism (hirsutism or elevated androgens) and oligo-amenorrhea, was diagnosed in 63 patients (27.6%), an underestimate compared with other reports that include systematic ovarian ultrasound studies. Neither pelvic ultrasound, used in a limited number of cases, nor the luteinizing hormone/follicle-stimulating hormone ratio helped to distinguish patients with polycystic ovary syndrome from the other diagnostic groups. These included hyperandrogenism (hirsutism or elevated androgens) and eumenorrhea (101 patients; 44.3%); normal androgens (acne or alopecia and eumenorrhea) (51 patients; 22.4%); isolated low SHBG (7 patients; 3.1%); nonclassical congenital adrenal hyperplasia (4 patients; 1.8% of total, 4.9% of patients undergoing cosyntropin stimulation tests); and ovarian tumor (2 patients; 0.9%).Ethinylestradiol and high-dose cyproterone acetate treatment lowered the hirsutism score to 53.5% of baseline at 1 year, and was also effective in treating acne and alopecia. The clinical benefit is ascribed to the peripheral antiandrogenic effect of cyproterone acetate as well as the hormone-suppressive effect of this combination. Salivary testosterone showed the most marked proportional decrease of all the androgens under treatment. Cost-effectiveness and tolerance of ethinylestradiol and high-dose cyproterone acetate compared well with other antiandrogenic drug therapies for hirsutism. The less potent therapy with spironolactone only, a peripheral antiandrogen without hormone-suppressive effect, was effective in treating isolated alopecia in patients with normal androgens.

Els Colors : estratègia i imatge empresarial

L’estudi presentat en aquest informe correspon a la investigació al voltant del paper del color al màrqueting empresarial. La seva influència, ja sigui com a eina comunicativa o identificadora d’un producte o empresa, es torna molt superior a la qualse li podria atribuir en un primer moment (fins al punt de convertir-se en un aspecte clau) quan s’observa la reacció dels consumidors davant les seves variacions i l’aplicació que en fan les companyies.La primera idea a confirmar pel treball és el caràcter inconscient de les reaccions generades per la percepció visual i les motivacions existents per explotarles.Un estudi sobre els precursors i les teories actuals de la psicologia del color condueix a una comparació entre allò que reflecteixen els estudis amb la realitat empresarial actual, mostrant una correlació evident entre valors de les organitzacions iles seves expressions pictòriques i exemplificant situacions de coincidència entre canvi de color i canvi d’estratègia corporativa. Aquest procés dóna lloc a la hipòtesi principal: el color és un element indispensable del procés de comercialització.Per tal de contrastar-la, inicialment s’acudirà a l’evidència recaptada mitjançant un qüestionari d’elaboració pròpia. A partir dels seus resultats, observarem com els consumidors no creuen estar tan influenciats per l’estètica i el color dels productes que compren com efectivament ho estan, i podrem seguir reafirmant la teoria exposada a la primera part amb paral·lelismes respecte les opinions mostrades.A continuació, es reflexionarà sobre quatre funcions del color aplicades a l’empresa de les quals aquestes es poden beneficiar: segmentador de mercats, indicador de canvi de tendència, identificador nacional i element associatiu immediat.Les determinacions preses a cada apartat a partir de reflexions teòriques i exemples formaran un entramat de conclusions que posarà fi al projecte en un apartat en el quals’ordenen les bases per a la correcta aplicació del color al món empresarial, en funció del rol de la companyia dins del seu mercat, els valors a transmetre, el tipus de producte a comerciar, etc.Finalment, els nombrosos fonaments que se li poden atribuir a favor fan que lahipòtesi inicial quedi ratificada com a certa, ja que es demostrarà una permanent voluntat per part de les empreses d’influir sobre el comportament dels destinataris del seu procés publicitari mitjançant aquest recurs, ja sigui de manera directa o indirecta.