English-Spanish bilingual learners of Portuguese as a third language: non-redundant acquisition and its typological nature

This chapter has two goals: (a) to discuss the Spanish-Portuguese interface in current formal language acquisition research and (b) to highlight the contributions of this language pairing in the emerging field of formal third language acquisition. The authors discuss two L3 acquisition studies (Montrul, Dias, & Santos, 2011; Giancaspro, Halloran, & Iverson, in press) examining Differential Object Marking, a morphological case marker present in Spanish but not in Portuguese, arguing that the results show how data from Spanish-English bilinguals learning Brazilian Portuguese as an L3 illuminate the deterministic role of structural and typological similarity in linguistic transfer. The data provide supportive evidence for only one of three existing L3 transfer models: the Typological Proximity Model (Rothman, 2010, 2011, 2013).

A new calibrated sunspot group series since 1749: statistics of active day fractions

Although the sunspot-number series have existed since the mid-19th century, they are still the subject of intense debate, with the largest uncertainty being related to the "calibration" of the visual acuity of individual observers in the past. Daisy-chain regression methods are applied to inter-calibrate the observers which may lead to significant bias and error accumulation. Here we present a novel method to calibrate the visual acuity of the key observers to the reference data set of Royal Greenwich Observatory sunspot groups for the period 1900-1976, using the statistics of the active-day fraction. For each observer we independently evaluate their observational thresholds [S_S] defined such that the observer is assumed to miss all of the groups with an area smaller than S_S and report all the groups larger than S_S. Next, using a Monte-Carlo method we construct, from the reference data set, a correction matrix for each observer. The correction matrices are significantly non-linear and cannot be approximated by a linear regression or proportionality. We emphasize that corrections based on a linear proportionality between annually averaged data lead to serious biases and distortions of the data. The correction matrices are applied to the original sunspot group records for each day, and finally the composite corrected series is produced for the period since 1748. The corrected series displays secular minima around 1800 (Dalton minimum) and 1900 (Gleissberg minimum), as well as the Modern grand maximum of activity in the second half of the 20th century. The uniqueness of the grand maximum is confirmed for the last 250 years. It is shown that the adoption of a linear relationship between the data of Wolf and Wolfer results in grossly inflated group numbers in the 18th and 19th centuries in some reconstructions.

Asymmetric oxidation of vinyl- and ethynyl terthiophene ligands in triruthenium complexes

A series of ruthenium(II) complexes [{RuCl(CO)(PMe3)3(–CHvCH–)}nX], 1a–1c (1a: n = 3, X = 3,3’’- dimethyl-2,2’:3’,2’’-terthiophene; 1b: n = 2, X = 2,2’-bithiophene; 1c: n = 2, X = 2,3-bis(3-methylthiophen- 2-yl)benzothiophene) and [{Cp*(dppe)2Ru(–CuC–)}3X], 1d (X = 3,3’’-dimethyl-2,2’:3’,2’’- terthiophene), were prepared and characterized by 1H, 13C and 31P NMR. Their redox, spectroscopic and bonding properties were studied with a range of spectro-electrochemical methods in combination with density functional theory calculations. The first two anodic steps observed for 1a and 1d are largely localized on the lateral frameworks of the molecular triangle, the direct conjugation between them being precluded due to the photostable open form of the dithienyl ethene moiety. The third anodic step is then mainly localized on the centerpiece of the triangular structure, affecting both bithiophene laterals. The experimental IR and UV-vis-NIR spectroelectrochemical data and, largely, also DFT calculations account for this explanation, being further supported by direct comparison with the anodic behavior of reference diruthenium complexes 1b and 1c.

Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene ligands

Four new diruthenium complexes [{(η5-C5Me5)Ru(dppe)}2(μ-CuC–L–CuC)] featuring different bridging isomeric diethynyl benzodithiophenes viz. L = benzo[1,2-b;4,5-b’]dithiophene (complex 1), benzo[2,1-b;4,5b’]dithiophene (complex 2), benzo[1,2-b;3,4-b’]dithiophene (complex 3) and benzo[1,2-b;4,3-b’]-dithiophene (complex 4), were synthesized and characterized by molecular spectroscopic and crystallographicmethods. The subtle changes in the molecular structure introduced by the diethynyl benzodithiophene isomers have a notable impact on the stability of the oxidized complexes and their absorption characteristics in the visible-NIR and IR spectral domains. Electronic properties of stable oxidized complexes[1]n+ and [4]n+ (n = 1, 2) were investigated by cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry as well as DFT and TDDFT calculations. The results document the largely bridgelocalized character of the oxidation of parents 1 and 4. Cations [2]+ and [3]+ are too unstable at ambient temperature to afford their unambiguous characterization. UV-vis-NIR absorption spectral data combined with TDDFT calculations (BLYP35) reveal that the broad electronic absorption of [1]+ and [4]+ in the NIR region has a mixed intraligand π–π* and MLCT character, with similar contribution from their spin-delocalized trans and cis conformers. A spin-localized (mixed-valence) rotamer was only observed for [1]+ at ambient temperature as a minor component on the time scale of IR spectroscopy.