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

Infrared Ellipsometry Analysis of Heritage Photographic Prints

[EN] Focusing on the photographic archive of Julian Carrillo (Mexico), we study and characterize the photographic processes of a set of 13 photographs dated between 1884 and 1925. By using infrared spectroscopic ellipsometry, we classified a selected set of photographs according to its kind of binder. Thus, we recognized for each photograph, the presence of proteins, and therefore, the particular photographic process. Furthermore, we have identified the presence of baryta layer, the use of plasticizer, and the eventual coating utilized to protect the photograph, whose composition was based in natural organic components, mainly shellac, beeswax, or camphorNieto-Villena, A.; Martinez, JR.; Flores-Camacho, JM.; Lastras-Martinez, A.; De La Cruz-Mendoza, JA.; Ortega-Zarzosa, G.; Valcarcel Andrés, JC.... (2018). Infrared Ellipsometry Analysis of Heritage Photographic Prints. Studies in Conservation. 63(8):466-476. https://doi.org/10.1080/00393630.2018.1476962S466476638Brambilla, L., Riedo, C., Baraldi, C., Nevin, A., Gamberini, M. C., D’Andrea, C., … Toniolo, L. (2011). Characterization of fresh and aged natural ingredients used in historical ointments by molecular spectroscopic techniques: IR, Raman and fluorescence. Analytical and Bioanalytical Chemistry, 401(6), 1827-1837. doi:10.1007/s00216-011-5168-zCasoli, A., & Fornaciari, S. (2014). An analytical study on an early twentieth-century Italian photographs collection by means of microscopic and spectroscopic techniques. Microchemical Journal, 116, 24-30. doi:10.1016/j.microc.2014.04.003Cattaneo, B., Chelazzi, D., Giorgi, R., Serena, T., Merlo, C., & Baglioni, P. (2008). Physico-chemical characterization and conservation issues of photographs dated between 1890 and 1910. Journal of Cultural Heritage, 9(3), 277-284. doi:10.1016/j.culher.2008.01.004Daher, C., Paris, C., Le Hô, A.-S., Bellot-Gurlet, L., & Échard, J.-P. (2010). A joint use of Raman and infrared spectroscopies for the identification of natural organic media used in ancient varnishes. Journal of Raman Spectroscopy, 41(11), 1494-1499. doi:10.1002/jrs.2693Edwards, H. G. M., Farwell, D. W., & Daffner, L. (1996). Fourier-transform Raman spectroscopic study of natural waxes and resins. I. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 52(12), 1639-1648. doi:10.1016/0584-8539(96)01730-8Fujiwara, H. (2007). Spectroscopic Ellipsometry. doi:10.1002/9780470060193Hendriks, K., & Ross, L. (1988). Chemical Treatments of Discoloured Photographic Prints: Image Manipulation or Legitimate Restoration? The Journal of Photographic Science, 36(3), 132-132. doi:10.1080/00223638.1988.11736990Mallégol, J., Gardette, J.-L., & Lemaire, J. (2000). Long-term behavior of oil-based varnishes and paints. Photo- and thermooxidation of cured linseed oil. Journal of the American Oil Chemists’ Society, 77(3), 257-263. doi:10.1007/s11746-000-0042-4Nieto-Villena, A., Martínez, J. R., de la Cruz-Mendoza, J. A., Valcárcel-Andrés, J. C., Ortega-Zarzosa, G., Solbes-García, Á., & Vázquez-Martínez, E. (2018). Atomic force microscopy as a tool for binder identification in ancient photographic processes. Surface and Interface Analysis, 50(4), 496-505. doi:10.1002/sia.6408Ostroff, Eugene. 1966. “Restoration of Photographs by Neutron Activation.” Science 154 (3745): 119–123. http://science.sciencemag.org/content/154/3745/119.Othmer, Kirk, ed. 2005. Encyclopedia of Chemical Technology. Vol. 17, 5th ed. New York: Wiley.Ricci, C., Bloxham, S., & Kazarian, S. G. (2007). ATR-FTIR imaging of albumen photographic prints. Journal of Cultural Heritage, 8(4), 387-395. doi:10.1016/j.culher.2007.07.002Sifontes, Á. B., Cañizales, E., Toro-Mendoza, J., Ávila, E., Hernández, P., Delgado, B. A., … Cruz-Barrios, E. (2015). Obtaining Highly Crystalline Barium Sulphate Nanoparticles via Chemical Precipitation and Quenching in Absence of Polymer Stabilizers. Journal of Nanomaterials, 2015, 1-8. doi:10.1155/2015/510376Stulik, Dusan, Herant Khanjian, Alberto de Tagle, and Alexandra M. Botelho. 2002. “Investigation of Jean-Louis-Marie-Eugene Durieu’s Toning and Varnishing Experiments: A Non-Destructive Approach.” ICOM Committee for Conservation 13th Triennial Meeting, Río de Janeiro, 658–663.Price, Beth A., and Boris Pretzel, eds. 2009. Infrared and Raman Users Group Spectral Database. 2007 ed. Vol. 1 & 2. Philadelphia: IRUG. Accessed June 20, 2014. http://www.irug.org/.Vila, A., & Centeno, S. A. (2013). FTIR, Raman and XRF identification of the image materials in turn of the 20th century pigment-based photographs. Microchemical Journal, 106, 255-262. doi:10.1016/j.microc.2012.07.01

Controlling the passage of light through metal microchannels by nanocoatings of phospholipids

The flow of polarized light through a metal film with an array of microchannels is controlled by the phase of an optically active, phospholipid nanocoating, even though the coating does not cover the open area of the microchannels. The molecular details of the assembly (DPPC phospholipid monolayer/bilayer on a hexadecanethiol monolayer on a copper-or nickel-coated microarray) were determined using the infrared, surfaceplasmon-mediated, extraordinary transmission of the metal microarrays. Infrared absorption spectra with greatly enhanced absorptions by comparison to literature were recorded and used as a diagnostic for the phase, composition, and molecular geometry of these nanocoatings. This approach presents new tools for nanoscale construction in constricted microspaces, which may ultimately be useful with individual microchannels

Crystal structure of rhodopsin bound to arrestin by femtosecond X-ray laser.

G-protein-coupled receptors (GPCRs) signal primarily through G proteins or arrestins. Arrestin binding to GPCRs blocks G protein interaction and redirects signalling to numerous G-protein-independent pathways. Here we report the crystal structure of a constitutively active form of human rhodopsin bound to a pre-activated form of the mouse visual arrestin, determined by serial femtosecond X-ray laser crystallography. Together with extensive biochemical and mutagenesis data, the structure reveals an overall architecture of the rhodopsin-arrestin assembly in which rhodopsin uses distinct structural elements, including transmembrane helix 7 and helix 8, to recruit arrestin. Correspondingly, arrestin adopts the pre-activated conformation, with a ∼20° rotation between the amino and carboxy domains, which opens up a cleft in arrestin to accommodate a short helix formed by the second intracellular loop of rhodopsin. This structure provides a basis for understanding GPCR-mediated arrestin-biased signalling and demonstrates the power of X-ray lasers for advancing the frontiers of structural biology

The PHENIX Experiment at RHIC

The physics emphases of the PHENIX collaboration and the design and current status of the PHENIX detector are discussed. The plan of the collaboration for making the most effective use of the available luminosity in the first years of RHIC operation is also presented.Comment: 5 pages, 1 figure. Further details of the PHENIX physics program available at http://www.rhic.bnl.gov/phenix

Effects of a physical education intervention on cognitive function in young children: randomized controlled pilot study

Randomized controlled trials (RCT) are required to test relationships between physical activity and cognition in children, but these must be informed by exploratory studies. This study aimed to inform future RCT by: conducting practical utility and reliability studies to identify appropriate cognitive outcome measures; piloting an RCT of a 10 week physical education (PE) intervention which involved 2hours per week of aerobically intense PE compared to 2 hours of standard PE (control). 64 healthy children (mean age 6.2 yrs SD 0.3; 33 boys) recruited from 6 primary schools. Outcome measures were the Cambridge Neuropsychological Test Battery (CANTAB), the Attention Network Test (ANT), the Cognitive Assessment System (CAS) and the short form of the Connor’s Parent Rating Scale (CPRS:S). Physical activity was measured habitually and during PE sessions using the Actigraph accelerometer. Test- retest intraclass correlations from CANTAB Spatial Span (r 0.51) and Spatial Working Memory Errors (0.59) and ANT Reaction Time (0.37) and ANT Accuracy (0.60) were significant, but low. Physical activity was significantly higher during intervention vs. control PE sessions (p <0.0001). There were no significant differences between intervention and control group changes in CAS scores. Differences between intervention and control groups favoring the intervention were observed for CANTAB Spatial Span, CANTAB Spatial Working Memory Errors, and ANT Accuracy. The present study has identified practical and age-appropriate cognitive and behavioral outcome measures for future RCT, and identified that schools are willing to increase PE time

Synthesis, Structures, and Optical Properties of Ruthenium(II) Complexes of the Tris(1-pyrazolyl)methane Ligand

Four new complex salts [Ru^(II)Cl(Tpm)(L^A)_2][PF_6]_n [Tpm = tris(1-pyrazolyl)methane; n = 1, L^A = pyridine (py) 1 or ethyl isonicotinate (EIN) 2; n = 3, L^A = N-methyl-4,4′-bipyridinium (MeQ^+) 3 or N-phenyl-4,4′-bipyridinium (PhQ^+) 4] have been prepared and characterized. Electronic absorption spectra show intense d → π^* metal-to-ligand charge-transfer (MLCT) absorption bands, while cyclic voltammetry reveals a reversible Ru^(III/II) wave, accompanied by quasireversible or irreversible L^A-based reductions for all except 1. Single crystal X-ray structures have been obtained for 1•Me_2CO, 2, and 3•Me_2CO. For 2–4, molecular first hyperpolarizabilities β have been measured in acetonitrile solutions via the hyper-Rayleigh scattering (HRS) technique at 800 nm. Stark (electroabsorption) spectroscopic studies on the MLCT bands in frozen butyronitrile allow the indirect estimation of static first hyperpolarizabilities β_0. The various physical data obtained for 3 and 4 are compared with those reported previously for related cis-{Ru^(II)(NH_3)_4}^(2+) species [Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845]. TD-DFT calculations on the complexes in 1–4 confirm that their lowest energy absorption bands are primarily Ru^(II) → L^A MLCT in character, while Ru^(II) → Tpm MLCT transitions are predicted at higher energies. DFT agrees with the Stark, but not the HRS measurements, in showing that β_0 increases with the electron-accepting strength of L^A. The 2D nature of the chromophores is evidenced by dominant β_(xxy) tensor components

The time-averaged paleomagnetic field

We review indications of persistent deviations from the geocentric axial dipole model of the time-averaged geomagnetic field and present a zonal harmonic model derived from 185 deep-sea sediment piston cores taken from low to middle latitudes (to approximately ±45°). Analysis of the paleomagnetic inclination recorded in these cores for the Brunhes (normal polarity; 0-73 Ma) and Matuyama (reverse polarity; 0.73-2.47 Ma) chrons, after plate motion correction, gives well-constrained estimates of the dominant long-term nondipole contributions (the axial quadrupole and axial octupole) and shows no significant deviation from axial symmetry. The amplitude of the axial quadrupole is found to vary with polarity (2.6% of the geocentric axial dipole for normal; 4.6% for reverse), while the axial octupole does not show appreciable change (-2.9% for normal; -2.1% for reverse). These estimates of the quadrupole contribution agree well with prior determinations for the Plio-Pleistocene (0-5 Ma); however, the octupole contribution we find is opposite in sign to previous estimates. We suggest that a negative octupole is representative of the actual time-averaged paleomagnetic field, while prior positive octupole estimates probably reflect spurious inclination shallowing. The lack of polarity asymmetry in the octupole suggests that this nondipole component may be more closely linked to the main dipole field than is the quadrupole and so supports models of the geodynamo in which dipole and quadrupole families do not interact

Strong gravitational lensing probes of the particle nature of dark matter

There is a vast menagerie of plausible candidates for the constituents of dark matter, both within and beyond extensions of the Standard Model of particle physics. Each of these candidates may have scattering (and other) cross section properties that are consistent with the dark matter abundance, BBN, and the most scales in the matter power spectrum; but which may have vastly different behavior at sub-galactic "cutoff" scales, below which dark matter density fluctuations are smoothed out. The only way to quantitatively measure the power spectrum behavior at sub-galactic scales at distances beyond the local universe, and indeed over cosmic time, is through probes available in multiply imaged strong gravitational lenses. Gravitational potential perturbations by dark matter substructure encode information in the observed relative magnifications, positions, and time delays in a strong lens. Each of these is sensitive to a different moment of the substructure mass function and to different effective mass ranges of the substructure. The time delay perturbations, in particular, are proving to be largely immune to the degeneracies and systematic uncertainties that have impacted exploitation of strong lenses for such studies. There is great potential for a coordinated theoretical and observational effort to enable a sophisticated exploitation of strong gravitational lenses as direct probes of dark matter properties. This opportunity motivates this white paper, and drives the need for: a) strong support of the theoretical work necessary to understand all astrophysical consequences for different dark matter candidates; and b) tailored observational campaigns, and even a fully dedicated mission, to obtain the requisite data.Comment: Science white paper submitted to the Astro2010 Decadal Cosmology & Fundamental Physics Science Frontier Pane