Triplet-triplet energy-transfer coupling: theory and calculation

Triplet-triplet (TT) energy transfer requires two molecular fragments to exchange electrons that carry different spin and energy. In this paper, we analyze and report values of the electronic coupling strengths for TT energy transfer. Two different methods were proposed and tested: (1) Directly calculating the off-diagonal Hamiltonian matrix element. This direct coupling scheme was generalized from the one used for electron transfer coupling, where two spin-localized unrestricted Hartree-Fock wave functions are used as the zero-order reactant and product states, and the off-diagonal Hamiltonian matrix elements are calculated directly. (2) From energy gaps derived from configuration-interaction-singles (CIS) scheme. Both methods yielded very similar results for the systems tested. For TT coupling between a pair of face-to-face ethylene molecules, the exponential attenuation factor is 2.59 A(-1)(CIS6-311+G(**)), which is about twice as large as typical values for electron transfer. With a series of fully stacked polyene pairs, we found that the TT coupling magnitudes and attenuation rates are very similar irrespective of their molecular size. If the polyenes were partially stacked, TT couplings were much reduced, and they decay more rapidly with distance than those of full-stacked systems. Our results showed that the TT coupling arises mainly from the region of close contact between the donor and acceptor frontier orbitals, and the exponential decay of the coupling with separation depends on the details of the molecular contacts. With our calculated results, nanosecond or picosecond time scales for TT energy-transfer rates are possible.     

Dimethyl multiplexed labeling combined with microcolumn separation and MS analysis for time course study in proteomics

Stable-isotope labeling coupled with liquid-phase separation and MS analysis is a powerful technique for comparative proteomics. We developed a dimethyl labeling strategy (Anal. Chem. 2003, 75, 6843-6852 and J. Proteome Res. 2005, 4, 101-108) to label peptide N-terminus and epsilon-amino groups of Lys with water-soluble formaldehyde via reductive methylation, and an isotopic pair of formaldehyde is used for binary labeling on two sets of samples. In this study, this approach is extended to a four sample labeling by combining the binary isotopic reagents of formaldehyde (d0, d2) and the binary isotopic reducing reagents, sodium cyanoborohydride (d0, d3). To ensure sufficient mass difference, this multiplexed labeling is coupled with endoproteinase Lys-C instead of trypsin for digestion, resulting in at least two labeling sites with a mass difference of 4 Da for each pair of peptide digest. Moreover, multiplex dimethyl labeling was proved to have no significant isotopic effect during RP LC elution. This method was further applied for monitoring Lys-C digestion using hemoglobin as a model. Dimethyl labeled digests derived from seven time points (1-30 h) were grouped into two sets of sample mixtures, separated by nano-LC to reduce the complexity, and then analyzed by ESI-MS/MS. The temporal study reveals that Lys-C digestion was completed in 10-15 h for all detected peptides. The multiplex dimethyl method has not only provided a simultaneous detection mean for four sample sets but has also conserved all the advantages associated with the original binary method.     

Discrimination of basal cell carcinoma from normal dermal stroma by quantitative multiphoton imaging

We performed multiphoton fluorescence (MF) and second-harmonic generation (SHG) imaging on human basal cell carcinoma samples. In the dermis, basal cell carcinomas can be identified by masses of autofluorescent cells with relatively large nuclei and marked peripheral palisading. In the normal dermis, SHG from dermal collagen contributes largely to the multiphoton signal. However, within the cancer stroma, SHG signals diminish and are replaced by autofluorescent signals, indicating that normal collagen structures responsible for SHG have been altered. To better delineate the cancer cells and cancer stroma from the normal dermis, a quantitative MF to SHG index is developed. We demonstrate that this index can be used to differentiate cancer cells and adjacent cancer stroma from the normal dermis. Our work shows that MF and SHG imaging can be an alternative for Mohs' surgery in the real-time guidance of the secure removal of basal cell carcinoma.     

Al Schottky contact on p-GaSe

A new Schottky diode, Al/p-GaSe, was presented in this study. It shows an effective barrier height of 0.96 eV with an ideality factor of 1.24 over five decades and a reverse leakage current density of 4.12×10⁻⁷ A/cm² at −2 V after rapid thermal annealing at 400 C for 30 s. The generation–recombination effect of the Schottky diode was decreased as the annealing temperature was increased. The formation of Al_1.33Se₂ was observed by X-ray diffraction analysis after the diode was annealed at 400 C for 30 s. Owing to the grains’ growth, the surface morphology of the 400 C-annealed diode was rougher than that of the unannealed diode, which was observed both by the AFM and the SEM analysis.     

A secure biometric-based remote user authentication with key agreement scheme using extended chaotic maps

Recently, biometric-based remote user authentication schemes along with passwords have drawn considerable attention in research. In 2011, Das proposed an improvement on an efficient biometric-based remote user authentication scheme using smart cards and claimed his scheme could resist various attacks. However, there are some weaknesses in Das’s scheme such as the privileged insider attack and the off-line password guessing attack. Besides, Das’s scheme also cannot provide user anonymity. To overcome these weaknesses, we shall propose a secure biometric-based remote user authentication with key agreement scheme using extended chaotic maps. The proposed scheme not only can resist the above-mentioned attacks, but also provide user anonymity.     

iPTT: peer‐to‐peer push‐to‐talk for VoIP

This paper proposes iPTT, a peer‐to‐peer (P2P) Push‐to‐Talk (PTT) service for Voice over IP (VoIP). In iPTT, a distributed and mobile‐operator independent network architecture is presented to accelerate the deployment of the PTT service. Based on the serverless architecture, we develop two mechanisms, that is, flooding‐based floor control mechanism (FFC) and tree‐based floor control mechanism (TFC), for real‐time talk‐burst determination. The determination algorithms and the corresponding message flows for these two mechanisms are designed to show the feasibility of FFC and TFC. The performance of FFC and TFC is investigated through our analytical and simulation models in terms of the determination latency and the number of floor‐control message exchanges. Copyright © 2008 John Wiley & Sons, Ltd.     

A contrastive study on the influences of radial and three-dimensional satellite gravity gradiometry on the accuracy of the Earth's gravitational field recovery

The accuracy of the Earth’s gravitational field measured from the gravity field and steady-state ocean circulation explorer(GOCE),up to 250 degrees,influenced by the radial gravity gradient V zz and three-dimensional gravity gradient V ij from the satellite gravity gradiometry(SGG) are contrastively demonstrated based on the analytical error model and numerical simulation,respectively.Firstly,the new analytical error model of the cumulative geoid height,influenced by the radial gravity gradient V zz and three-dimensional gravity gradient V ij are established,respectively.In 250 degrees,the GOCE cumulative geoid height error measured by the radial gravity gradient V zz is about 2 1/2 times higher than that measured by the three-dimensional gravity gradient V ij.Secondly,the Earth’s gravitational field from GOCE completely up to 250 degrees is recovered using the radial gravity gradient V zz and three-dimensional gravity gradient V ij by numerical simulation,respectively.The study results show that when the measurement error of the gravity gradient is 3×10 12 /s 2,the cumulative geoid height errors using the radial gravity gradient V zz and three-dimensional gravity gradient V ij are 12.319 cm and 9.295 cm at 250 degrees,respectively.The accuracy of the cumulative geoid height using the three-dimensional gravity gradient V ij is improved by 30%-40% on average compared with that using the radial gravity gradient V zz in 250 degrees.Finally,by mutual verification of the analytical error model and numerical simulation,the orders of magnitude from the accuracies of the Earth’s gravitational field recovery make no substantial differences based on the radial and three-dimensional gravity gradients,respectively.Therefore,it is feasible to develop in advance a radial cold-atom interferometric gradiometer with a measurement accuracy of 10 13 /s 2-10 15 /s 2 for precisely producing the next-generation GOCE Follow-On Earth gravity field model with a high spatial resolution.     

Intelligent tracking control of a DC motor driver using self-organizing TSK-type fuzzy neural networks

In this paper, a self-organizing Takagi–Sugeno–Kang (TSK) type fuzzy neural network (STFNN) is proposed. The self-organizing approach demonstrates the property of automatically generating and pruning the fuzzy rules of STFNN without the preliminary knowledge. The learning algorithms not only extract the fuzzy rule of STFNN but also adjust the parameters of STFNN. Then, an adaptive self-organizing TSK-type fuzzy network controller (ASTFNC) system which is composed of a neural controller and a robust compensator is proposed. The neural controller uses an STFNN to approximate an ideal controller, and the robust compensator is designed to eliminate the approximation error in the Lyapunov stability sense without occurring chattering phenomena. Moreover, a proportional-integral (PI) type parameter tuning mechanism is derived to speed up the convergence rates of the tracking error. Finally, the proposed ASTFNC system is applied to a DC motor driver on a field-programmable gate array chip for low-cost and high-performance industrial applications. The experimental results verify the system stabilization and favorable tracking performance, and no chattering phenomena can be achieved by the proposed ASTFNC scheme.     

A New Lagrangian Asymptotic Solution for Gravity–Capillary Waves in Water of Finite Depth

A third-order Lagrangian asymptotic solution is derived for gravity–capillary waves in water of finite depth. The explicit parametric solution gives the trajectory of a water particle and the wave kinematics for Lagrangian points above the mean water level, and in a water column. The water particle orbits and mass transport velocity as functions of the surface tension are obtained. Some remarkable trajectories may contain one or multiple sub-loops for steep waves and large surface tension. Overall, an increase in surface tension tends to increase the motions of surface particles including the relative horizontal distance travelled by a particle as well as the time-averaged drift velocity