Highly effective quenching of the ultrafast radiationless decay of photoexcited pyrimidine bases by covalent modification: photophysics of 5,6-trimethylenecytosine and 5,6-trimethyleneuracil

5,6-Trimethylenecytosine (TMC) and 5,6-trimethyleneuracil (TMU), in which the twist of the C5-C6 bond (or the pyrimidalization of C5) is strongly hindered, do not exhibit the subpicosecond excited-state lifetime characteristic of the naturally occurring pyrimidine bases. This result demonstrates the important role the out-of-plane deformation of the six-membered ring plays in the ultrafast (subpicosecond) internal conversion of photoexcited nucleobases. The dramatically shorter fluorescence lifetime of TMU ( approximately 30 ps) relative to TMC ( approximately 1.2 ns), in aqueous solution at room temperature, is attributed to the presence in TMU of an efficient, secondary nonradiative decay channel of S(1)(pipi*) involving a low-lying (1)npi* state.     

Multicolored electrochromism in 4,4'-biphenyl dicarboxylic acid diethyl ester

We investigated the properties of 4,4'-biphenyl dicarboxylic acid diethyl ester (PCE). The PCE underwent a 2-step reduction at -1.5 V and -2.2 V. The color of the PCE changed from colorless to yellow in the first step and consequently to red in the second reduction step. A PCE based EC cell using an NiO-modified electrode was also fabricated. The NiO electrode worked as a counter reaction material for PCE reduction. The PCE-NiO cell achieved multi-coloration ranging from colorless to yellow and red, and also achieved high coloration efficiency and long term switching stability.     

Preparation of imidazolinium salts by the Pd-catalyzed reduction of thioureas with triethylsilane and trialkylsilyl triflate

A Pd-catalyzed method for the preparation of imidazolinium salts from the corresponding thioureas that could then be used for the synthesis of imidazolium and amidinium salts is described. This method has great potential because all the required reagents are readily available and thioureas are safely converted to their corresponding precursors of NHCs under mild conditions.     

An optical-optical double resonance probe of the lowest triplet state of jet-cooled thiophosgene: rovibronic structures and electronic relaxation

The vibrational structure, rotational structure, and electronic relaxation of the "dark" T1 3A2(n,pi*) state of jet-cooled thiophosgene have been investigated by two-color S2<--T1<--S0 optical-optical double resonance (OODR) spectroscopy, which monitors the S2-->S0 fluorescence generated by S2<--T1 excitation. This method is capable of isolating the T1 vibrational structure into a1, b1, and b2 symmetry blocks. The fluorescence-detected vibrational structure of the Tz spin state of T1 shows that the CS stretching frequency as well as the barrier height for pyramidal deformation are significantly greater in the 3A2(n,pi*) state than in the corresponding 1A2(n,pi*) state. The differing vibrational parameters of the T1 thiophosgene relative to the S1 thiophosgene can be attributed to the motions of unpaired electrons that are better correlated when they are in the excited singlet state than when they are in the triplet state of same electron configuration. A set of T1 structural parameters and the information concerning the T1 spin states have been obtained from least-square fittings of the rotationally resolved T1<--S0 excitation spectrum. The nearly degenerate mid R:x and mid R:y spin states are well removed from mid R:z spin component, indicating that T1 thiophosgene is a good example of case (ab) coupling. The decay of the mid R:z spin state of T1 thiophosgene, obtained from time-resolved S2<--T1<--S0 OODR experiment, is characteristic of strong-coupling intermediate-case decay in which an initial rapid decay is followed by recurrences and/or a long-lived quasiexponential decay.     

Photocurrent enhancement in a porphyrin-gold nanoparticle nanostructure assisted by localized plasmon excitation

The nanostructured assembly of porphyrin and gold nano-particles exhibits distinct enhancement of photocurrents from porphyrin in the longer wavelength region, where the localized plasmon resonance was responsible     

Formation of nano‐dots of phenylazomethine dendrimers with Rhodamine 6G on mica

The phenylazomethine dendrimer (DPA) is associated with Rhodamine 6G in chloroform, which results in the chemical shift attributed to the aromatic protons of phenylazomethine being moved upfield in the ¹H‐NMR spectrum by increasing the Rhodamine 6G. The shift is saturated at the ratio of 1 : 1. On the basis of the NMR analysis, the association constant K of phenylazomethine with Rhodamine 6G was determined to be 1.4 × 10⁴ (l/mol) in CDCl₃ at 20°C. The association is also confirmed by UV‐vis spectroscopy, in which the absorption around 450 and 527 nm changes during the addition of Rhodamine 6G. The fluorescence intensity of the 1 : 1 complex of Rhodamine 6G and DPA G4 is stronger than that of the solution dissolved only in Rhodamine 6G at greater than 1 mM though it is generally known that the intermolecular interaction quenches the dye fluorescence in a concentrated solution. The association of DPA G4 with Rhodamine 6G suppresses the quenching at higher concentrations. Homogenous nano‐dots were observed on mica by casting the DPA G4 complex with Rhodamine 6G, in which the height and average area were 1.5–3 nm and 1.6 × 10³ nm² (the standard deviation σ = 3.7 nm²), respectively. Copyright © 2004 John Wiley & Sons, Ltd.     

A Non-Heme Iron(III) Complex with Porphyrin-like Properties That Catalyzes Asymmetric Epoxidation

In this report, we describe an iron(III) complex containing a carbazole-based tridentate ligand that catalyzes highly enantioselective asymmetric epoxidation of (E)-alkenes at room temperature. The non-heme iron(III) complex has a five-coordinated trigonal-bipyramidal structure, and its two-electron oxidized state has the similar electronic structure as that of iron porphyrins.     

Stereoselective total synthesis of nemorosone

The highly stereoselective total synthesis of nemorosone via a new approach to the bicyclo[3.3.1]nonane-2,4,9-trione core which features intramolecular cyclopropanation of an α-diazo ketone, stereoselective alkylation at the C8 position, and regioselective ring-opening of cyclopropane is described. The total synthesis of nemorosone includes chemo- and stereoselective hydrogenation directed by the internal alkene.     

Effect of light/dark cycle on bacterial hydrogen production by Rhodobacter sphaeroides RV

Hydrogen production by photosynthetic bacteria provides an efficient energy conversion method under low light intensity. However, under strong illumination, such as midday sunlight, the efficiency drops. This prevents the method from being applied industrially. To overcome this problem, we examined a method to thin out the excessive illumination. Light was given intermittently to reduce the total energy flux. The on/off ratio was set at 1/1 throughout the study, so that the time average of the light energy flux became half the continuous illumination. By keeping the time-average light flux constant (0.6 kW·m⁻²), the effects of the cycle period were examined in the range of hours to seconds. The hydrogen production rate was greatly affected by the cycle period, but cell growth and substrate consumption rates remained almost constant. The 30-min light/dark cycle (30 min on and 30 min off) provided the highest rate of hydrogen production (22 L·m⁻²·24 h⁻¹). At the shorter cycles, the rate decreased except that there was a suboptimum at about 40 s. Under excessive light intensity (1.2 kW·m⁻²), the light-to-hydrogen conversion efficiency was greatly enhanced. The hydrogen production rate during the 30-min cycle was twice as high as during a 12-h cycle under the same conditions.