Long range resonance energy transfer from a dye molecule to graphene has (distance)-4 dependence

In our previous report on resonance energy transfer from a dye molecule to graphene [J. Chem. Phys.129, 054703 (2008)], we had derived an expression for the rate of energy transfer from a dye to graphene. An integral in the expression for the rate was evaluated approximately. We found a Yuwaka-type dependence of the rate on the distance. We now present an exact evaluation of the integral involved, leading to very interesting results. For short distances (z < 20 A), the present rate and the previous rate are in good agreement. For larger distances, the rate is found to have a z(-4) dependence on the distance, exactly. Thus we predict that for the case of pyrene on graphene, it is possible to observe fluorescence quenching up to a distance of 300 A. This is in sharp contrast to the traditional fluorescence resonance energy transfer where the quenching is observable only up to 100 A.

Spectrally Resolved Resonance Energy Transfer from ZnO:MgO Nanocrystals

Resonance energy transfer (RET) from the visible emission of core−shell ZnO:MgO nanocrystals to Nile Red chromophores, following band gap excitation in the UV, has been investigated for four different nanocrystal sizes. With use of steady state and time-resolved fluorescence spectroscopic measurements the wavelength dependent RET efficiencies have been determined. The RET process in ZnO:MgO nanocrystals occurs from emissions involving trap state recombination. There are two such processes with different RET efficiencies for the same particle size. This is shown to be a consequence of the fact that the recombination processes giving rise to the two emissions are located at different distances from the center of the particle so that the donor−acceptor distances for the two are different, even for the same particle size.

Distance dependence of fluorescence resonance energy transfer

Deviations from the usual R (-6) dependence of the rate of fluorescence resonance energy transfer (FRET) on the distance between the donor and the acceptor have been a common scenario in the recent times. In this paper, we present a critical analysis of the distance dependence of FRET, and try to illustrate the non R (-6) type behaviour of the rate for the case of transfer from a localized electronic excitation on the donor, a dye molecule to three different energy acceptors with delocalized electronic excitations namely, graphene,two-dimensional semiconducting sheet and the case of such a semiconducting sheet rolled to obtain a nanotube. We use simple analytic models to understand the distance dependence in each case.

Construction of energy-level diagram of oriented benzene using connectivity information obtained by modified z-cosy experiment

Experiments involving selective perturbation of a transition yield information about the directly connected transitions, which in turn yield information for deriving the parameters of the spin Hamiltonian of oriented molecules. Problems involved with selective perturbation are removed by the use of a two-dimensional experiment, namely, the modified Z-COSY-experiment, The use of this experiment is demonstrated for obtaining the connectivity information and for determining the parameters of the spin Hamiltonian of oriented benzene, a strongly coupled six-spin system

Ricin-membrane interaction: membrane penetration depth by fluorescence quenching and resonance energy transfer

The entry of the plant toxin ricin and its A- and B-subunits in model membranes in the presence as well as absence of monosialoganglioside (GM(1)) has been studied. Dioleoylphosphatidylcholine and 5-, 10-, and 12-doxyl- or 9,10-dibromophosphatidylcholines serve as quenchers of intrinsic tryptophan fluorescence of the proteins. The parallax method of Chattopadhyay and London [(1987) Biochemistry 26, 39-45] has been employed to measure the average membrane penetration depth of tryptophans of ricin and its B-chain and the actual depth of the sole Trp 211 in the A-chain. The results indicate that both of the chains as well as intact ricin penetrate the membrane deeply and the C-terminal end of the A-chain is well inside the bilayer, especially at pH 4.5. An extrinsic probe N-(iodoacetyl)-N'-(5-sulfo-1-naphthyl) ethylenediamine (I-AEDANS) has been attached to Cys 259 of the A-chain, and the kinetics of penetration has been followed by monitoring the increase in AEDANS fluorescence at 480 nm. The insertion follows first-order kinetics, and the rate constant is higher at a lower pH. The energy transfer distance analysis between Trp 211 and AEDANS points out that the conformation of the A-chain changes as it inserts into the membrane. CD studies indicate that the helicity of the proteins increases after penetration, which implies that some of the unordered structure in the native protein is converted to the ordered form during this process. Hydrophobic forces seem to be responsible for stabilizing a particular protein conformation inside the membrane.

Lectin binding to complex carbohydrate at the interface: a study by resonance energy transfer

The binding affinity of the oligosaccharide moiety of a neutral glycosphingolipid, asialoGM1, towards Ricinus communis agglutinin (RCAI) was determined for the first time by fluorescence resonance energy transfer (RET). The asialoGM1 was incorporated into a phospholipid (DMPC) vesicle doped with dansylated DPPE and then titrated with an increasing amount of the galactose specific RCAI. The efficiency of RET was determined by a saturable increase in the quenching of 'donor' fluorescence, i.e. the 'trp' residue of RCAI, due to the energy transfer from the 'acceptor' dansyl group on the surface of the vesicle. The apparent binding constant was found to be in the range of 10(5)-10(6) M-1 at 27 degrees C.

Influence of the highest occupied molecular orbital energy level of the donor material on the effectiveness of the anode buffer layer in organic solar cells

Efficiency of organic photovoltaic cells based on organic electron donor/organic electron acceptor junctions can be strongly improved when the transparent conductive Anode is coated with a Buffer Layer (ABL). Here, the effects of a metal (gold) or oxide (molybdenum oxide) ABL are reported, as a function of the Highest Occupied Molecular Orbital (HOMO) of different electron donors. The results indicate that a good matching between the work function of the anode and the highest occupied molecular orbital of the donor material is the major factor limiting the hole transfer efficiency. Indeed, gold is efficient as ABL only when the HOMO of the organic donor is close to its work function Phi(Au). Therefore we show that the MoO(3) oxide has a wider field of application as ABL than gold. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be similar to 61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two component PY-PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from similar to 330 nm to similar to 600 nm in aqueous solution. (C) 2015 Elsevier B.V. All rights reserved.

Electronic energy transfer between long-range resonance states of 3-mercaptopropionic acid capped CdTe quantum dots in aqueous media

We demonstrate electronic energy transfer between resonance states of 2 and 2.8 nm CdTe quantum dots in aqueous media using steady-state photoluminescence spectroscopy without using any external linker molecule. With increasing concentration of larger dots, there is subsequent quenching of luminescence in smaller dots accompanied by the enhancement of luminescence in larger dots. Our experimental evidence suggests that there is long-range resonance energy transfer among electronic excitations, specifically from the electronically confined states of the smaller dots to the higher excited states of the larger dots.

Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-pi(1)*; S-1 state) and the shorter (1 pi-pi(1)*; S-2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S-2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C-2 nu symmetry constraint on the S-2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling. (C) 2015 AIP Publishing LLC.

Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Electron energy loss spectroscopic study of Cr(CO)6, Mo(CO)6 and W(CO)6 in the vapour phase

Electron energy loss spectra (EELS) of Cr, Mo and W hexacarbonyls in the vapour phase are reported. Most of the bands observed are similar to those in optical spectra, but the two high energy transitions in the 9·8–11·2 eV region are reported here for the first time. Based on the orbital energies from the ultraviolet photoelectron spectra and the electronic transition energies from EELS and earlier optical studies, the molecular energy level schemes of these molecules are constructed.

Smart applications for energy harvested WSNs

A Wireless Sensor Network (WSN) powered using harvested energies is limited in its operation by instantaneous power. Since energy availability can be different across nodes in the network, network setup and collaboration is a non trivial task. At the same time, in the event of excess energy, exciting node collaboration possibilities exist; often not feasible with battery driven sensor networks. Operations such as sensing, computation, storage and communication are required to achieve the common goal for any sensor network. In this paper, we design and implement a smart application that uses a Decision Engine, and morphs itself into an energy matched application. The results are based on measurements using IRIS motes running on solar energy. We have done away with batteries; instead used low leakage super capacitors to store harvested energy. The Decision Engine utilizes two pieces of data to provide its recommendations. Firstly, a history based energy prediction model assists the engine with information about in-coming energy. The second input is the energy cost database for operations. The energy driven Decision Engine calculates the energy budgets and recommends the best possible set of operations. Under excess energy condition, the Decision Engine, promiscuously sniffs the neighborhood looking for all possible data from neighbors. This data includes neighbor's energy level and sensor data. Equipped with this data, nodes establish detailed data correlation and thus enhance collaboration such as filling up data gaps on behalf of nodes hibernating under low energy conditions. The results are encouraging. Node and network life time of the sensor nodes running the smart application is found to be significantly higher compared to the base application.

Energy transfer efficiency distributions in polymers in solution during folding and unfolding

Distribution of fluorescence resonance energy transfer (FRET) efficiency between the two ends of a Lennard-Jones polymer chain both at equilibrium and during folding and unfolding has been calculated, for the first time, by Brownian dynamics simulations. The distribution of FRET efficiency becomes bimodal during folding of the extended state subsequent to a temperature quench, with the width of the distribution for the extended state broader than that for the folded state. The reverse process of unfolding subsequent to a upward temperature jump shows different characteristics. The distributions show significant viscosity dependence which can be tested against experiments.

Coalescence of magic sized CdSe into rods and wires and subsequent energy transfer

We report on the synthesis of CdSe magic-sized clusters (MSCs) and their evolution into 1D rod and wires retaining the diameter of the order of MSCs. At the beginning of the reaction, different classes of stable MSCs with band gaps of 3.02 eV and 2.57 eV are formed, which exhibit sharp band edge photoluminescence features with FWHM in the order of similar to 13 nm. Reaction annealing time was carried out in order to monitor the shape evolution of the MSCs. We find that magic sized CdSe evolve into 1D rod and wires retaining the same diameter upon increasing annealing time. We observed the gradual emergence of new red shifted emission peaks during this shape evolution process, which emerge as a result of one dimensional energy transfer within the magic sized clusters during their subsequent transformation into rods and wires. The smallest, the second smallest sized MSC and the wires sequentially act as donors and acceptors during the size evolution from small MSCs to larger ones, and then eventually to wires. Steady-state and time-resolved luminescent spectroscopy revealed Forster resonance energy transfer (FRET) between the MSCs to the rods and wires.