Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.     

Evolution of Artificial Arginine Analogues—Fluorescent Guanidiniocarbonyl-Indoles as Efficient Oxo-Anion Binders

In this article, we present fluorescent guanidiniocarbonyl-indoles as versatile oxo-anion binders. Herein, the guanidiniocarbonyl-indole (GCI) and methoxy-guanidiniocarbonyl-indole (MGCI) were investigated as ethylamides and compared with the well-known guanidiniocarbonyl-pyrrole (GCP) concerning their photophysical properties as well as their binding behavior towards oxo-anions. Hence, a variety of anionic species, such as carboxylates, phosphonates and sulfonates, have been studied regarding their binding properties with GCP, GCI and MGCI using UV-Vis titrations, in combination with the determination of the complex stoichiometry using the Job method. The emission properties were studied in relation to the pH value using fluorescence spectroscopy as well as the determination of the photoluminescence quantum yields (PLQY). Density functional theory (DFT) calculations were undertaken to obtain a better understanding of the ground-lying electronic properties of the investigated oxo-anion binders. Additionally, X-ray diffraction of GCP and GCI was conducted. We found that GCI and MGCI efficiently bind carboxylates, phosphonates and sulfonates in buffered aqueous solution and in a similar range as GCP (K_ass ≈ 1000–18,000 M⁻¹, in bis-tris buffer, pH = 6); thus, they could be regarded as promising emissive oxo-anion binders. They also exhibit a visible fluorescence with a sufficient PLQY. Additionally, the excitation and emission wavelength of MGCI was successfully shifted closer to the visible region of the electromagnetic spectrum by introducing a methoxy-group into the core structure, which makes them interesting for biological applications.     

Wafer thickness optimization for silicon solar cells of heterogeneous material quality

In this Letter, we introduce a method of calculating the optimal wafer thickness for silicon solar cells with multicrystalline bulk material. The optimal thickness depends on the relation of bulk recombination to surface recombination and the light trapping. For multicrystalline silicon bulk recombination strongly varies laterally and with injection level, which complicates the calculations. A thickness optimization using the “Efficiency Limiting Bulk Recombination Analysis” (ELBA) takes all these effects correctly into account. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multivalency as a Chemical Organization and Action Principle

Multivalent interactions can be applied universally for a targeted strengthening of an interaction between different interfaces or molecules. The binding partners form cooperative, multiple receptor–ligand interactions that are based on individually weak, noncovalent bonds and are thus generally reversible. Hence, multi‐ and polyvalent interactions play a decisive role in biological systems for recognition, adhesion, and signal processes. The scientific and practical realization of this principle will be demonstrated by the development of simple artificial and theoretical models, from natural systems to functional, application‐oriented systems. In a systematic review of scaffold architectures, the underlying effects and control options will be demonstrated, and suggestions will be given for designing effective multivalent binding systems, as well as for polyvalent therapeutics.     

Light charged particle release in252Cf spontaneous fission: Tripartition versus fragment de-excitation

Double-differential emission probabilities P (E, θ) in angle θ and energy E of protons, tritons, and α-particles were measured in the case of spontaneous fission of²⁵²Cf. A detector system consisting of position-sensitive parallel-plate avalanche counters (PPAC) and ΔE?E-telescopes allowed a coincidence measurement of fission fragments (FF) and light charged particles (LCP) in the whole region from 0 deg. to 180 deg. with respect to the light-fragment direction. Previous results for α-particle emission were confirmed. The background contributions for protons are discussed in detail. For proton emission the background arising from (n, p)-reactions was measured and compared with a corresponding Monte-Carlo simulation of elastic (n, p)-clusions. Unlike for tritons and a-particles the P (E, θ) distribution for protons does not show equatorial peaking in 0 between 80 deg. and 90 deg. and contradicts classical scission point emission. The proton distribution, however, agrees with fragment de-excitation calculations in the framework of the cascade evaporation model (CEM) whereas an analogous calculation forα-particles completely fails. Upper limits for an additional scission component of proton emission are given.     

Assignment of h.f.s. constants of 1,4-benzosemiquinones by additivity rules. The free rotation of t-butyl groups

A set of equations for assigning hyperfine coupling constants of substituted 1,4-benzosemiquinones are presented. The equations, based on additivity rules, yield assignments for a range of substituents with a correlation between predicted and experimental constants to better than five per cent. The investigation shows that t-butyl groups in semiquinones rotate freely against prior assertions.     

Influence of the blend compatibility on the morphology of thin polymer blend films

Thin films of incompatible polymer blends can form a variety of structures on preparation. For the polymer blend system consisting of two poly(styrene-co-para-bromo-styrene)s at different degrees of bromination, PBr_xS/PBr_yS, the compatibility can be tuned through a variation of the difference in the degree of bromination. Within this blend system, two series of samples with different compatibilities were investigated at various blend compositions. The surface morphology of the thin films was investigated by atomic force microscopy (AFM) measurements, while diffuse X-ray scattering provided additional depth sensitivity at a comparable lateral resolution. The results are indicative for phase separation lateral, as well as perpendicular, to the sample surface.