Excited state interactions between the chiral Au 38 L 24 cluster and covalently attached porphyrin

A protected S-acetylthio porphyrin was synthesized and attached to the Au38(2-phenylethanethiolate)24 cluster in a ligand exchange reaction. Chiral high performance liquid chromatography of the functionalized cluster yielded enantiomeric pairs of clusters probably differing in the binding site of the porphyrin. As proven by circular dichroism, the chirality was maintained. Exciton coupling between the cluster and the chromophore is observed. Zinc can be incorporated into the porphyrin attached to the cluster, as evidenced by absorption and fluorescence spectroscopy, however, the reaction is slow. Quenching of the chromophore fluorescence is observed, which can be explained by energy transfer from the porphyrin to the cluster. Transient absorption spectra of Au38(2-phenylethanethiolate)24 and the functionalized cluster probe the bleach of the gold cluster due to ground state absorption and the characteristic excited state absorption signals. Zinc incorporation does not have a pronounced effect on the photophysical behaviour. Decay times are typical for the molecular behaviour of small monolayer protected gold clusters.

Femtosecond cluster studies of the solvated 7-azaindole excited state double-proton transfer

Presented here are femtosecond pump-probe studies on the water-solvated 7-azaindole dimer, a model DNA base pair. In particular, studies are presented that further elucidate the nature of the reactive and nonreactive dimers and also provide new insights establishing that the excited state double-proton transfer in the dimer occurs in a stepwise rather than a concerted manner. A major question addressed is whether the incorporation of a water molecule with the dimer results in the formation of species that are unable to undergo excited state double-proton transfer, as suggested by a recent study reported in the literature [Nakajima, A., Hirano, M., Hasumi, R., Kaya, K., Watanabe, H., Carter, C. C., Williamson, J. M. & Miller, T. (1997) J. Phys. Chem. 101, 392–398]. In contrast to this earlier work, our present findings reveal that both reactive and nonreactive dimers can coexist in the molecular beam under the same experimental conditions and definitively show that the clustering of water does not induce the formation of the nonreactive dimer. Rather, when present with a species already determined to be a nonreactive dimer, the addition of water can actually facilitate the occurrence of the proton transfer reaction. Furthermore, on attaining a critical hydration number, the data for the nonreactive dimer suggest a solvation-induced conformational structure change leading to proton transfer on the photoexcited half of the 7-azaindole dimer.

The nature of the excited state of the reaction center of photosystem II of green plants: A high-resolution fluorescence spectroscopy study

We studied the electronically excited state of the isolated reaction center of photosystem II with high-resolution fluorescence spectroscopy at 5 K and compared the obtained spectral features with those obtained earlier for the primary electron donor. The results show that there is a striking resemblance between the emitting and charge-separating states in the photosystem II reaction center, such as a very similar shape of the phonon wing with characteristic features at 19 and 80 cm−1, almost identical frequencies of a number of vibrational modes, a very similar double-Gaussian shape of the inhomogeneous distribution function, and relatively strong electron-phonon coupling for both states. We suggest that the emission at 5 K originates either from an exciton state delocalized over the inactive branch of the photosystem or from a fraction of the primary electron donor that is long-lived at 5 K. The latter possibility can be explained by a distribution of the free energy difference of the primary charge separation reaction around zero. Both possibilities are in line with the idea that the state that drives primary charge separation in the reaction center of photosystem II is a collective state, with contributions from all chlorophyll molecules in the central part of the complex.

Excited-state dynamics in photosystem II: Insights from the x-ray crystal structure

The heart of oxygenic photosynthesis is photosystem II (PSII), a multisubunit protein complex that uses solar energy to drive the splitting of water and production of molecular oxygen. The effectiveness of the photochemical reaction center of PSII depends on the efficient transfer of excitation energy from the surrounding antenna chlorophylls. A kinetic model for PSII, based on the x-ray crystal structure coordinates of 37 antenna and reaction center pigment molecules, allows us to map the major energy transfer routes from the antenna chlorophylls to the reaction center chromophores. The model shows that energy transfer to the reaction center is slow compared with the rate of primary electron transport and depends on a few bridging chlorophyll molecules. This unexpected energetic isolation of the reaction center in PSII is similar to that found in the bacterial photosystem, conflicts with the established view of the photophysics of PSII, and may be a functional requirement for primary photochemistry in photosynthesis. In addition, the model predicts a value for the intrinsic photochemical rate constant that is 4 times that found in bacterial reaction centers.

Problems of state life. A sermon delivered before His Excellency John D. Long, His Honor Byron Weston, the honorable Council, and the legislature of Massachusetts, at the annual election, King's chapel, Boston, Wednesday, January 3, 1883.

Printed by order of the Massachusetts General Court.

A life time in South Africa; being the recollections of the first premier of Natal,

Mode of access: Internet.

Thirty-one years on the plains and in the mountains, or, The last voice from the plains : an authentic record of a life time of hunting, trapping, scouting and Indian fighting in the far West /

Mode of access: Internet.

Energy level decay and excited state absorption processes in erbium-doped tellurium glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy level decay and excited state absorption processes in dysprosium-doped fluoride glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy transfer rates and population inversion of sup(4)Isub(11/2) excited state of Ersup(3+) investigated by means of numerical solutions of the rate equations system in Er:LiYFsub(4) crystal

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On Queueinginventory Models – product form solution; reservation, Cancellation and common life time

Queueing theory is the mathematical study of ‘queue’ or ‘waiting lines’ where an item from inventory is provided to the customer on completion of service. A typical queueing system consists of a queue and a server. Customers arrive in the system from outside and join the queue in a certain way. The server picks up customers and serves them according to certain service discipline. Customers leave the system immediately after their service is completed. For queueing systems, queue length, waiting time and busy period are of primary interest to applications. The theory permits the derivation and calculation of several performance measures including the average waiting time in the queue or the system, mean queue length, traffic intensity, the expected number waiting or receiving service, mean busy period, distribution of queue length, and the probability of encountering the system in certain states, such as empty, full, having an available server or having to wait a certain time to be served.