The good and the bad: Acquisition of likes and dislikes in affective learning

Affective learning, the acquisition of likes and dislikes, was investigated in two experiments using verbal ratings and affective priming as indices of affective change. In both experiments, neutral geometric shapes were paired with pleasant or unpleasant pictures in a picture-picture conditioning procedure to acquire positive and negative valence. Experiment 1 found the acquisition of positive valence; however, this valence change was lost after extinction training. Experiment 2 used more salient pictures as unconditioned stimuli. Positive and negative valence was acquired during paired presentations and retained across extinction training. The results of Experiment 2 are consistent with dual process accounts, which claim that evaluative conditioning is distinct from Pavlovian conditioning because it is resistant to extinction.

The effects of unconditional stimulus valence and conditioning paradigm on verbal, skeleto-motor, and autonomic indices of human Pavlovian conditioning

The effects of unconditional stimulus (US) valence (aversive electro-tactile stimulus vs. nonaversive imperative stimulus of a RT task) and conditioning paradigm (delay vs. trace) on affective learning as indexed by verbal ratings of conditional stimulus (CS) pleasantness and blink startle modulation and on relational learning as indexed by electrodermal responses were investigated. Affective learning was not affected by the conditioning paradigm; however, electrodermal responses and blink latency shortening indicated delayed learning in the trace procedure. Changes in rated CS pleasantness were found with the aversive US, but not with the non-aversive US. Differential conditioning as indexed by electrodermal responses and startle modulation was found regardless of US valence. The finding of significant differential blink modulation and electrodermal responding in the absence of a change in rated CS pleasantness as a result of conditioning with a non-aversive US was replicated in a second experiment. These results seem to indicate that startle modulation during conditioning is mediated by the arousal level of the anticipated US, rather than by the valence of the CS. (C) 2002 Elsevier Science (USA). All rights reserved.

Oxidation of mixed-valence CoIII/FeII complexes reversed at high pH: A kinetico-mechanistic study of water oxidation

The outer-sphere oxidation of Fell in the mixed-valence complex trans-[(LCoNCFeII)-Co-14S-N-III(CN)(6)](-), being L-14S an N3S2 macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N-5 macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S2O82- and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(double dagger) and DeltaV(double dagger). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[(LCoNCFeIII)-Co-14S-N-III(CN)(6)], as well as the analogous N-5 systems trans-[(LCoNCFeIII)-Co-14-N-III(CN)(6)], trans-[(LCoNCFeIII)-Co-15-N-III-(CN)(6)], and cis-[(LCoNCFeIII)-Co-n-N-III(CN)(6)], Oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [(LCoNCFeIII)-Co-n-N-III(CN)(5)] + OH- - [(LCoNCFeII)-Co-n-N-III(CN)(5)](-) + 1/2H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH- adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(double dagger) and DeltaV(double dagger) (-76 to -113 J K-1 mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O2- to Fe-III.

Dinuclear cyano-bridged Co-III-Fe-II complexes as precursors for molecular mixed-valence complexes of higher nuclearity

The preparation and characterization of a series of trinuclear mixed-valence cyano-bridged Co-III-Fe-II-Co-III compounds derived from known dinuclear [{LnCoIII(mu-NC)}Fe-II(CN)(5)](-) complexes (L-n = N-5 or N3S2 n-membered pendant amine macrocycle) are presented. All of the new trinuclear complexes were fully characterized spectroscopically (UV-vis, IR, and C-13 NMR). Complexes exhibiting a trans and cis arrangement of the Co-Fe-Co units around the [Fe(CN)(6)](4-) center are described (i.e., cis/trans-[{LnCoIII(mu-NC)}(2)Fe-II(CN)(4)](2+)), and some of their structures are determined by X-ray crystallography. Electrochemical experiments revealed an expected anodic shift of the Fe-III/II redox potential upon addition of a tripositively charged {(CoLn)-L-III} moiety. The Co-III/II redox potentials do not change greatly from the di- to the trinuclear complex, but rather behave in a fully independent and noncooperative way. In this respect, the energies and extinction coefficients of the MMCT bands agree with the formal existence of two mixed-valence Fe-II-CN-Co-III units per molecule. Solvatochromic experiments also indicated that the MMCT band of these compounds behaves as expected for a class II mixed-valence complex. Nevertheless, its extinction coefficient is dramatically increased upon increasing the solvent donor number.

The effects of assessment type on verbal ratings of conditional stimulus valence and contingency judgments: Implications for the extinction of evaluative learning

Recent research on causal learning found (a) that causal judgments reflect either the current predictive value of a conditional stimulus (CS) or an integration across the experimental contingencies used in the entire experiment and (b) that postexperimental judgments, rather than the CS's current predictive value, are likely to reflect this integration. In the current study, the authors examined whether verbal valence ratings were subject to similar integration. Assessments of stimulus valence and contingencies responded similarly to variations of reporting requirements, contingency reversal, and extinction, reflecting either current or integrated values. However, affective learning required more trials to reflect a contingency change than did contingency judgments. The integration of valence assessments across training and the fact that affective learning is slow to reflect contingency changes can provide an alternative interpretation for researchers' previous failures to find an effect of extinction training on verbal reports of CS valence.