Special Issue: Design of Bioreactor Systems for Tissue Engineering

Ye

Spectral energy distributions of a large sample of BL Lacertae objects

We have collected a large amount of multifrequency data for the objects in the Metsahovi Radio Observatory BL Lacertae sample and computed their spectral energy distributions (SED). This is the first time the SEDs of BL Lacs have been studied with a sample of over 300 objects. The synchrotron components of the SEDs were fitted with a parabolic function to determine the synchrotron peak frequency. We checked the dependence between luminosities at several frequency bands and synchrotron peak frequency to test the blazar sequence scenario, which states that the source luminosity depends on the location of the synchrotron peak. We also calculated broad band spectral indices and plotted them against each other and the peak frequency. The range of peak frequencies in our study was considerably extended compared to previous studies. There were 22 objects for which log\nu_{peak}>19. The data shows that at 5 GHz, 37 GHz and 5500 A there is negative correlation between luminosity and nu_{peak}. There is no significant correlation between source luminosity at synchrotron peak and peak frequency. Several low radio luminosity-low energy peaked BL Lacs were found. The negative correlation between broad band spectral indices and nu_{peak} is also significant, although there is substantial scatter. Therefore we find that neither alpha_{rx} nor alpha_{ro} can be used to determine the synchrotron peak of BL Lacs. On the grounds of our results we conclude that the blazar sequence scenario is not valid. In all our results the BL Lac population is continuous with no hint of the bimodality of the first BL Lac samples.Comment: 10 + 27 pages, 13 figures, accepted to A&

VLBI observations of seven BL Lac objects from RGB sample

We present EVN observations of seven BL Lac objects selected from the RGB sample. To investigate the intrinsic radiation property of BL Lac objects, we estimated the Doppler factor with the VLA or MERLIN core and the total 408 MHz luminosity for a sample of 170 BL Lac objects. The intrinsic (comoving) synchrotron peak frequency was then calculated by using the estimated Doppler factor. Assuming a Lorentz factor of 5, the viewing angle of jets was constrained. The high-resolution VLBI images of seven sources all show a core-jet structure. We estimated the proper motions of three sources with the VLBI archive data, and find that the apparent speed increases with the distance of components to the core for all of them. In our BL Lacs sample, the Doppler factor of LBLs is systematically larger than that of IBLs and HBLs. We find a significant anti-correlation between the total 408 MHz luminosity and the intrinsic synchrotron peak frequency. However, the scatter is much larger than for the blazar sequence. Moreover, we find a significant positive correlation between the viewing angle and the intrinsic synchrotron peak frequency. The BL Lac objects show a continuous distribution on the viewing angle. While LBLs have a smaller viewing angle than that of IBLs and HBLs, IBLs are comparable to HBLs. We conclude that the intrinsic synchrotron peak frequency is not only related to the intrinsic radio power (though with a large scatter), but also to the viewing angle for the present sample.Comment: 22 pages,15figures, published by A&

Mechanistic Basis for Red Light Switching of Azonium Ions

Azonium ions formed by the protonation of tetra-ortho-methoxy-substituted aminoazobenzenes photoisomerize with red light under physiological conditions. This property makes them attractive as molecular tools for the photocontrol of physiological processes, for example, in photopharmacology. However, a mechanistic understanding of the photoisomerization process and subsequent thermal relaxation is necessary for the rational application of these compounds as well as for guiding the design of derivatives with improved properties. Using a combination of sub-ps/ns transient absorption measurements and quantum chemical calculations, we show that the absorption of a photon by the protonated E-H+ form of the photoswitch causes rapid (ps) isomerization to the protonated Z-H+ form, which can also absorb red light. Proton transfer to solvent then occurs on a microsecond time scale, leading to an equilibrium between Z and Z-H+ species, the position of which depends on the solution pH. Whereas thermal isomerization of the neutral Z form to the neutral E form is slow (∼0.001 s-1), thermal isomerization of Z-H+ to E-H+ is rapid (∼100 s-1), so the solution pH also governs the rate at which E/E-H+ concentrations are restored after a light pulse. This analysis provides the first complete mechanistic picture that explains the observed intricate photoswitching behavior of azonium ions at a range of pH values. It further suggests features of azonium ions that could be targeted for improvement to enhance the applicability of these compounds for the photocontrol of biomolecules.</p

Iminothioindoxyl as a molecular photoswitch with 100 nm band separation in the visible range

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, lminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.</p

Solvent Effects on the Actinic Step of Donor-Acceptor Stenhouse Adduct Photoswitching

Donor-acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD-DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time-resolved visible pump-probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent-dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media