Modulation of fluorescence through coassembly of molecules in organic nanostructures

This paper describes the fluorescence of bimolecular coassemblies that form one-dimensional nanostructures. One molecule is a fluorescent peptide amphiphile containing its branched stilbene chromophore covalently linked to the hydrophilic end of the amphiphile, and the second molecule is a shorter, nonfluorescent peptide amphiphile of complementary charge. Using circular dichroism we observe that mixing both molecules results in coassemblies that exhibit a beta-sheet signature in the peptide region indicative of these types of nanostructures. The nature of the coassembly is dependent on the molar ratio of each component, and the changing CD spectra suggest the formation of domains along the length of the nanofibers with decreasing concentrations of the fluorescent component. In coassemblies with dilute concentrations of the fluorophore, we observe an increase in fluorescence intensity and quantum yield, as well as chiral transfer to the achiral segment of the fluorescent peptide amphiphile. The coassemblies studied containing a fluorescent component at a low molar ratio exhibit fluorescence resonance energy transfer to fluorescent acceptors in solution. When the nonfluorescent peptide amphiphile component is designed to bind the important bioactive polysaccharide heparin, a selective transfer of energy is observed between fluorescein-tagged heparin and the coassemblies in both dilute solution and in macroscopic gels.     

Pendular-state spectroscopy of the S(1)-S(0) electronic transition of 9-cyanoanthracene

Fluorescence excitation spectra of the S(1)-S(0) origin band of 9-cyanoanthracene have been observed under a uniform electric field up to 200 kV/cm to explore pendular-state spectrum of an asymmetric-top molecule close to the strong field limit. The observed spectra exhibit distinct evolution of the band contour as a function of the applied electric field, which are much different from each other for different excitation configurations. An approximate method suitable for spectrum simulations of large asymmetric-top molecules in a pendular condition is developed for the analysis of the experimental results. The comparison of the observed and simulated spectra shows that the spectra are well ascribed in terms of the pendular-state selection rules, which have recently been derived from theoretical consideration of the pendular-limit representation of energy levels and spectra.     

Hydrogen scrambling in ethane induced by intense laser fields: statistical analysis of coincidence events

Two-body Coulomb explosion processes of ethane (CH(3)CH(3)) and its isotopomers (CD(3)CD(3) and CH(3)CD(3)) induced by an intense laser field (800 nm, 1.0 × 10(14) W/cm(2)) with three different pulse durations (40 fs, 80 fs, and 120 fs) are investigated by a coincidence momentum imaging method. On the basis of statistical treatment of the coincidence data, the contributions from false coincidence events are estimated and the relative yields of the decomposition pathways are determined with sufficiently small uncertainties. The branching ratios of the two body decomposition pathways of CH(3)CD(3) from which triatomic hydrogen molecular ions (H(3)(+), H(2)D(+), HD(2)(+), D(3)(+)) are ejected show that protons and deuterons within CH(3)CD(3) are scrambled almost statistically prior to the ejection of a triatomic hydrogen molecular ion. The branching ratios were estimated by statistical Rice-Ramsperger-Kassel-Marcus calculations by assuming a transition state with a hindered-rotation of a diatomic hydrogen moiety. The hydrogen scrambling dynamics followed by the two body decomposition processes are discussed also by using the anisotropies in the ejection directions of the fragment ions and the kinetic energy distribution of the two body decomposition pathways.     

Latex‐state NMR spectroscopy for quantitative analysis of epoxidized deproteinized natural rubber

Method of quantitative analysis through latex‐state ¹³C NMR spectroscopy was established for in situ determination of epoxy group content of epoxidized natural rubber in latex stage. The epoxidized natural rubber latex was prepared by epoxidation of deproteinized natural rubber with freshly prepared peracetic acid in latex stage. The resulting epoxidized deproteinized natural rubber (EDPNR) latex was characterized through latex‐state ¹³C NMR spectroscopy. Chemical shift values of signals of latex‐state ¹³C NMR spectrum for EDPNR were similar to those of solution‐state ¹³C NMR spectrum for EDPNR. Resolution of latex‐state ¹³C NMR spectrum was gradually improved as temperature for the nuclear magnetic resonance (NMR) measurement increased to 70°C. Signal‐to‐noise ratio of latex‐state ¹³C NMR measurement was similar to that of solution‐state ¹³C NMR measurement at temperature above 50°C. The epoxy group content determined through latex‐state NMR spectroscopy was proved to be the same as that determined through solution‐state NMR spectroscopy. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis and Properties of New Laser Dyes Containing 4-(2-Thienyl)Pyridine Skeleton

Abstract

Three 4-(oligothienyl)pyridines and four α,ω-di(4-pyridyl)oligo-thiophenes were prepared and the effect of conjugated thiophene rings on their fluorescence properties were examined. 4-(2,2′-Bithienyl-5-yl)pyridine and 2,5-di(4-pyridyl)thiophene exhibited laser dye emission upon pumping with a nitrogen laser and the conversion efficiency of the latter was 1.5 times as great as that of a commercial laser dye PBBO at 400 nm.     

FTMW spectroscopy of jet-cooled 9-cyanoanthracene

Rotational spectrum of jet-cooled 9-cyanoanthracene has been observed in the 4-8 GHz region with a Fourier-transform microwave spectrometer. The present observation of 25 low-J transitions with J^′′?11 has confirmed the previous results on the rotational constants of the ground state determined by rotational coherence spectroscopy [J. Phys. Chem. A. 105 (2001) 1131] and provided the values with significantly improved precision. An accurate set of hyperfine splitting constants is also reported for the ¹⁴N nuclear quadrupole coupling. The electric dipole moment was determined from Stark effect measurements on several split components: μ_b(=μ)=4.406(7) D.     

Multi-scale plasma simulation by the interlocking of magnetohydrodynamic model and particle-in-cell kinetic model

Many kinds of simulation models have been developed to understand the complex plasma systems. However, these simulation models have been separately performed because the fundamental assumption of each model is different and restricts the physical processes in each spatial and temporal scales. On the other hand, it is well known that the interactions among the multiple scales may play crucial roles in the plasma phenomena (e.g. magnetic reconnection, collisionless shock), where the kinetic processes in the micro-scale may interact with the global structure in the fluid dynamics. To take self-consistently into account such multi-scale phenomena, we have developed a new simulation model by directly interlocking the fluid simulation of the magnetohyrdodynamics (MHD) model and the kinetic simulation of the particle-in-cell (PIC) model. The PIC domain is embedded in a small part of MHD domain. The both simulations are performed simultaneously in each domain and the bounded data are frequently exchanged each other to keep the consistency between the models. We have applied our new interlocked simulation to Alfvén wave propagation problem as a benchmark test and confirmed that the waves can propagate smoothly through the boundaries of each domain.