Near-Ultraviolet Circular Dichroism and Two-Dimensional Spectroscopy of Polypeptides

A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. In contrast to intense bands in the far-ultraviolet, near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, which were realised through the consideration of the vibrational structure of the electronic transitions of aromatic side chains.     

Experimental investigation of an active open optical resonator in a turbulent atmosphere

The spectral densities of the time fluctuations of the amplitude of steady-state generation at two wavelengths ₁=0.63 and ₂=1.15 under conditions of turbulent fluctuations of the refractive index in the waveguide channel of an open optical resonator are studied. The frequency dependences of the spectral densities are analyzed at various states of atmospheric turbulence, including the state produced in an aerodynamic chamber. For wavelength ₂ the fluctuations of the water-vapor content form a random absorption field. The distinctive features of the frequency dependence of the spectral density are discussed and related to the time cross-correlation of random fields of the passive impurity of the water-vapor concentration, the temperature, and the turbulent velocity of the flow. The asymptotic behavior of the frequency dependences of the spectral density is analyzed from the standpoint of the self-similarity of the stochastic characteristics of the system consisting of the waveguide channel and the medium.Odessa Hydrometeorological Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 34, No. 2, pp. 111–118, February, 1991.     

Influence of the Caprolactam Quality on the Characteristics of Polycaproamide Thereof

The influence of the caprolactam quality on the characteristics of polycaproamide thereof was elucidated.     

Conical intersection seams in polyenes derived from their chemical composition

The knowledge of conical intersection seams is important to predict and explain the outcome of ultrafast reactions in photochemistry and photobiology. They define the energetic low-lying reachable regions that allow for the ultrafast non-radiative transitions. In complex molecules it is not straightforward to locate them. We present a systematic approach to predict conical intersection seams in multifunctionalized polyenes and their sensitivity to substituent effects. Included are seams that facilitate the photoreaction of interest as well as seams that open competing loss channels. The method is based on the extended two-electron two-orbital method [A. Nenov and R. de Vivie-Riedle, J. Chem. Phys. 135, 034304 (2011)]. It allows to extract the low-lying regions for non-radiative transitions, which are then divided into small linear segments. Rules of thumb are introduced to find the support points for these segments, which are then used in a linear interpolation scheme for a first estimation of the intersection seams. Quantum chemical optimization of the linear interpolated structures yields the final energetic position. We demonstrate our method for the example of the electrocyclic isomerization of trifluoromethyl-pyrrolylfulgide.     

On an Ulam's problem

The existence and the uniqueness (with respect to a filtration-equivalence) of a vector flowX on ? ⁿ ,n≥3, such that:

1. X has not any stationary points on ? ⁿ ;
2. all orbits ofX are bounded;
3. there exists a filtration forX are proved in the present note.

     

Molecular driving forces for Z/E isomerization mediated by heteroatoms: the example hemithioindigo

A combined experimental and theoretical investigation of photoinduced Z/E isomerizations is presented. Unsubstituted Hemithioindigo is selected as a representative minimal model to unravel the reaction mechanism in the presence of heteroatoms on an atomic level. Time-resolved spectroscopy reveals multiexponential reaction dynamics on the few picoseconds time scale, which are interpreted by quantum chemical calculations at the CASSCF/CASPT2 level of theory. Detailed insight into the processes governing the ultrafast decay from the first excited state, mediated by a number of conical intersections, is provided. Charge separation and charge balance recovery on the reaction pathway play the leading role and are controlled by the electron-donating or -withdrawing character of the heteroatoms. The electronic and geometric structures of the individual minimum energy conical intersections governing the reaction are rationalized, and an extended energetically low lying conical intersection seam is extracted. Comparison to the experimental results permits linking the observed time constants to molecular intermediates and pathways. An explanation is provided for the pronounced differences of Z → E and the E → Z photoreactions upon excitation to the first excited singlet state.     

Multiple Decay Mechanisms and 2D‐UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine‐Uracil Monophosphate

The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D‐UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine ¹L_a state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine ¹L_b and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter‐base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long‐lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the ¹L_b, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240 ps. We have also simulated the time evolution of the 2D‐UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25 000 and 38 000 cm^?1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D‐UV spectroscopy to disentangle the photophysics of multichromophoric systems.     

Reversibly Crosslinked Networks of Nanoparticles in Metallocene‐Catalyzed Olefin Polymerization

A hierarchic build‐up of functional nano‐ and microparticles allows the generation of smart organic supports for metallocene catalysts. Latices, well defined in size and surface structure, are made by emulsion polymerization using poly(ethylene oxide)‐containing surfactants. Micron‐sized catalyst beads are formed by reversible loading/crosslinking with a metallocene/methylaluminoxane complex. As a result of the network fragmentation during ethylene polymerization, the catalysts achieve very high productivities, hard polyethylene particles and homogeneous distributions of nanometer‐sized fragments in the product.