Excited states of GFP chromophore and active site studied by the SAC-CI method: effect of protein-environment and mutations

Excited states of fluorescent proteins were studied using symmetry-adapted cluster-configuration interaction (SAC-CI) method. Protein-environmental effect on the excitation and fluorescence energies was investigated. In green fluorescent protein (GFP), the overall protein-environmental effect on the first excitation energy is not significant. However, glutamine (Glu) 94 and arginine (Arg96) have the red-shift contribution as reported in a previous study (Laino et al., Chem Phys 2004, 298, 17). The excited states of GFP active site (GFP-W22-Ser205-Glu222-Ser65) were also calculated. Such large-scale SAC-CI calculations were performed with an improved code containing a new algorithm for the perturbation selection. The SAC-CI results indicate that a charge-transfer state locates at 4.19 eV, which could be related to the channel of the photochemistry as indicated in a previous experimental study. We also studied the excitation and fluorescence energies of blue fluorescent protein, cyan fluorescent protein, and Y66F. The SAC-CI results are very close to the experimental ones. The protonation state of blue fluorescent protein was determined. Conformation of cyan fluorescent protein indicated by the present calculation agrees to the experimentally observed structure.     

Preferential intramolecular ring closure of aminoalcohols with diethyl carbonate to oxazolidinones

The closure by cyclization with diethyl carbonate (EtO)(2)CO from aminoalcohols 1 as starting material can lead to the oxazolidinones 2a, b and 2c, respectively. In the reaction of trans-isomer (6) and (EtO)(2)CO, isolated products were also only 5-membered oxazolidinone derivative (7), containing its dehydrated derivative 8. The preferential formation of the 5-membered oxazolidinone ring system apparently indicated that this process (5-Exo-Trig ring closure) is more favorable than that of 6- or 7-membered ring derivative (3 or 9) by 6- or 7-Exo-Trig ring closure.     

Lead zirconate titanate cantilever for noncontact atomic force microscopy

Noncontact atomic force microscopy with frequency modulation detection is a promising technique for surface observation with true atomic resolution. The piezoelectric material itself can be an actuator and sensor of the oscillating probe simultaneously, without the need for additional electro-mechanical transducers or other measurement systems. A vertical resolution of 0.01 nm rms has been achieved using a microfabricated cantilever with lead zirconate titanate thin film in noncontact mode frequency modulation detection. The cantilever also has a sharpened pyramidal stylus with a radius of about 10 nm for noncontact atomic force microscopy.     

Application of a novel photopolymer to a holographic head‐up display

A novel photopolymer for fabrication of high‐resolution volume holograms, which primarily are used on holographic optical elements such as head‐up display (HUD), is reported. This photopolymer consists of bisphenol‐type epoxy resin and radically polymerizable aliphatic monomer with diaryliodonium salt and 3‐ketocoumarin (KCD) as a complex initiator. The chemistry of imaging formation is based on the radical polymerization of the monomer initiated by a holographic exposure, following by the cationic polymerization of epoxy resin by UV‐exposure after post‐exposure baking. The yellowish color of hologram derived from KCD, the shape of peak of reconstructed light and the blue shift of wavelength of reconstructed light, were improved in order to satisfy the specifications for the combiner of HUD. A stand type holographic HUD system as an example of automotive display attached on the dashboard of an automobile is demonstrated. The display gives a high contrast image, and the combiner has good durability. Copyright © 1999 John Wiley & Sons, Ltd.     

A new general route to thiophenophanes: synthesis and properties of [n](2,5)thiophenophane-1,n-diones

A series of [n](2,5)thiophenophane-1,n-diones (5) (n = 9, 10, 12, 14, 16, and 20) were synthesized in a simple four-step route starting from the appropriate 1,omega-oligomethylenedicarboxylic acids. The bis(halomethylketones) (6), which were obtained by successive treatment of the diacids with SOCl2, diazomethane, and HBr or HCl, were cyclized by Na2S under high dilution conditions. The obtained monomeric cyclic diketosulfides (4) were condensed with glyoxal in MeOH by slowly adding dilute NaOMe affording 5. The thiophene-2,5-dicarbonyl moiety of 5 (n = 9) is significantly deformed as shown by X-ray crystallography, and the effect of the strain is reflected in the C=O stretching frequencies and the pi-pi* and the n-pi* absorptions.     

A novel quinoline alkaloid possessing a 7-benzyl group from the centipede, Scolopendra subspinipes.

The novel quinoline alkaloid scolopendrine was isolated from the centipede, Scolopendra subspinipes mutilans L. Koch. The structure was determined to be 2-hydroxy-7-[(4-hydroxy-3-methoxyphenyl)methyl]-3-methoxy-8-quinolyl sulfate on the basis of high-resolution electron-spray ionization mass spectroscopy and two-dimensional NMR spectral data. Unlike quinoline alkaloids so far reported, scolopendrine is unique in having a 7-benzyl moiety in the quinoline ring.     

Crystal‐to‐Crystal Photoinduced Electron Transfer Generating Photoacids to Formulate Water‐Borne Photopolymers

Casting a photopolymer solution to form a film, followed by imagewise photoirradiation and subsequent wet development, leads to photolithography. Whereas the wet development is achievable with aqueous alkali, the emission of an organic solvent as a volatile organic compound (VOC) is usually inevitable during the film casting because ingredients of common photopolymers are insoluble in water. We show here a prototype of water‐borne photopolymers dispersed with milled nanoparticles of poorly water‐soluble photoacid generators (PAGs), which undergo solid‐state photolysis to liberate a photoacid to make a poly(vinyl alcohol) film insoluble in water with the aid of an acid‐sensitive crosslinking reagent. The photolysis of onium‐type PAGs is sensitized in the solid state simply by comilling with water‐insoluble sensitizers to extend spectral sensitivity of this kind of photopolymers. Fluorescence quenching measurements revealed that the solid‐state sensitization occurs through exciton migration in sensitizer particles followed by electron transfer to PAG particles.

     

Steady-state and nanosecond spectroscopic studies of triplet sensitized reaction of K-region arene oxides

Photorearrangement reactions of K-region arene oxides, 9,10-epoxy-9,10-dihydrophenanthrene (1a), 3-acetyl-9,10-epoxy-9,10-dihydrophenanthrene (1b), and 3,4-epoxy-3,4-dihydropyrene (1c) in dichloroethane (DCE) solution were investigated by steady irradiation and nanosecond transient spectroscopy. Photorearrangements producing substituted oxepins, 2 occur via the singlet excited state of these compounds, while the phenolic products, 9-hydroxyphenanthrene (3a), 3-acetyl-9-hydroxyphenanthrene (3b), and 4-hydroxypyrene (3c) are formed via the triplet state. Phenol 3 formation from the triplet 1 sensitized by the triplet 3 (i.e. product sensitization) is proposed for the photorearrangement reactions of 1a and 1c, and this process is the only way phenol (3a) is formed because of the negligible intersystem crossing probability of 1a. No product sensitization occurs in the photorearrangement reaction of 1b.