Nonlinear optical properties of meso-Tetra(fluorenyl)porphyrins peripherally functionalized with one to four ruthenium alkynyl substituents

The synthesis of a series of four porphyrin derivatives based on a meso-tetrafluorenylporphyrin core functionalized with one to four trans-chlorobis(dppe)ruthenium alkynyl units (dppe = 1,2-bis(diphenylphosphino)ethane) at the periphery, together with cyclic voltammetry (CV) and UV–Vis absorption and emission spectroscopy studies, are reported. In these multipolar assemblies, the organoruthenium endgroups are potential electron-donors and the central porphyrin core is a potential electron-acceptor. The third-order nonlinear optical (NLO) responses have been assessed by Z-scan, revealing that these extended π-networks incorporating polarizable organometallic units behave as nonlinear absorbers in the near-IR range. The role of the peripheral transition metal centers on the third-order NLO properties is discussed

Asperities and barriers on the seismogenic zone in North Chile: state-of-the-art after the 2007 Mw 7.7 Tocopilla earthquake inferred by GPS and InSAR data

The Mw 7.7 2007 November 14 earthquake had an epicentre located close to the city of Tocopilla, at the southern end of a known seismic gap in North Chile. Through modelling of Global Positioning System (GPS) and radar interferometry (InSAR) data, we show that this event ruptured the deeper part of the seismogenic interface (30–50 km) and did not reach the surface. The earthquake initiated at the hypocentre and was arrested ~150 km south, beneath the Mejillones Peninsula, an area already identified as an important structural barrier between two segments of the Peru–Chile subduction zone. Our preferred models for the Tocopilla main shock show slip concentrated in two main asperities, consistent with previous inversions of seismological data. Slip appears to have propagated towards relatively shallow depths at its southern extremity, under the Mejillones Peninsula. Our analysis of post-seismic deformation suggests that small but still significant post-seismic slip occurred within the first 10 d after the main shock, and that it was mostly concentrated at the southern end of the rupture. The post-seismic deformation occurring in this period represents ~12–19 per cent of the coseismic deformation, of which ~30–55 per cent has been released aseismically. Post-seismic slip appears to concentrate within regions that exhibit low coseismic slip, suggesting that the afterslip distribution during the first month of the post-seismic interval complements the coseismic slip. The 2007 Tocopilla earthquake released only ~2.5 per cent of the moment deficit accumulated on the interface during the past 130 yr and may be regarded as a possible precursor of a larger subduction earthquake rupturing partially or completely the 500-km-long North Chile seismic gap

Resistance to autosomal dominant Alzheimer's disease in an APOE3 Christchurch homozygote: a case report.

We identified a PSEN1 (presenilin 1) mutation carrier from the world's largest autosomal dominant Alzheimer's disease kindred, who did not develop mild cognitive impairment until her seventies, three decades after the expected age of clinical onset. The individual had two copies of the APOE3 Christchurch (R136S) mutation, unusually high brain amyloid levels and limited tau and neurodegenerative measurements. Our findings have implications for the role of APOE in the pathogenesis, treatment and prevention of Alzheimer's disease

Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

Displaced Voices: A Journal of Migration, Archives and Cultural Heritage, Volume 3 Issue 2 (Autumn 2023)

Twentieth Century Histories of Civic Society’s Responses to Crises of Displacement: A Special Issue to mark the 70th Anniversary of Refugee Council Displaced Voices is a biannual digital magazine produced twice a year by the Living Refugee Archive team at the University of East London. Displaced Voices aims to provide a digital platform for activists, archivists, researchers, practitioners and academics to contribute to issues pertaining to refugee and migration history; refugee and migrant rights; social justice; cultural heritage and archives. We welcome a range of contributions to the magazine including articles of between 1000-2000 words; reports on fieldwork in archival collections; book recommendations and reviews; and more creative pieces including (but not limited too) cartoons; photography; and poetry. We would also welcome news on activities; publication of reports, projects; letters and news from your own networks. We welcome submissions from all writers whether you are a student, practitioner, activist or established academic. The Displaced Voices online magazine is born out of the collaborative and intersectional work that we have been undertaking through our work with the refugee and migration archives housed at the University of East London. Our work to date has explored the intersections of refugee and migration studies with narrative and life history research linked to oral history methods and archival approaches to the preservation, documentation and accessibility of archival resources recording the refugee experience. This magazine is a collaborative project between the Living Refugee Archive at the University of East London; the Oral History Society Migration Special Interest Group and the International Association for the Study of Forced Migration Working Group on the History of Forced Migration and Refugees. Thematically we are looking to engage with articles that explore the intersection of refugee and forced migration studies; history and cultural heritage studies; narrative research; oral history and archival science

Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)