New insights on surface-enhanced Raman scattering based on controlled aggregation and spectroscopic studies, DFT calculations and symmetry analysis for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine adsorbed onto citrate-stabilized gold nanoparticles

Asystematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a(1) and b(2) representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright (C) 2010 John Wiley & Sons, Ltd.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Crystal structure and theoretical calculations of Julocrotine, a natural product with antileishmanial activity

Julocrotine, N-(2,6-dioxo-l-phenethyl-piperidin-3-yl)-2-methyl-butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X-ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6-311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data. (C) 2007 Wiley Periodicals, Inc.

A Unified Load Generator for Geographically Distributed Generation ofNetwork Traffic

During the last decade, the Internet usage has been growing at an enormous rate which has beenaccompanied by the developments of network applications (e.g., video conference, audio/videostreaming, E-learning, E-Commerce and real-time applications) and allows several types ofinformation including data, voice, picture and media streaming. While end-users are demandingvery high quality of service (QoS) from their service providers, network undergoes a complex trafficwhich leads the transmission bottlenecks. Considerable effort has been made to study thecharacteristics and the behavior of the Internet. Simulation modeling of computer networkcongestion is a profitable and effective technique which fulfills the requirements to evaluate theperformance and QoS of networks. To simulate a single congested link, simulation is run with asingle load generator while for a larger simulation with complex traffic, where the nodes are spreadacross different geographical locations generating distributed artificial loads is indispensable. Onesolution is to elaborate a load generation system based on master/slave architecture.

A tool for standardized collector performance calculations including PVT

A tool for standardized calculation of solar collector performance has been developed in cooperation between SP Technical Research Institute of Sweden, DTU Denmark and SERC Dalarna University. The tool is designed to calculate the annual performance of solar collectors at representative locations in Europe. The collector parameters used as input in the tool are compiled from tests according to EN12975, without any intermediate conversions. The main target group for this tool is test institutes and certification bodies that are intended to use it for conversion of collector model parameters (derived from performance tests) into a more user friendly quantity: the annual energy output. The energy output presented in the tool is expressed as kWh per collector module. A simplified treatment of performance for PVT collectors is added based on the assumption that the thermal part of the PVT collector can be tested and modeled as a thermal collector, when the PV electric part is active with an MPP tracker in operation. The thermal collector parameters from this operation mode are used for the PVT calculations. © 2012 The Authors.

Semantic Distributed Messaging Middleware

Messaging middleware provides asynchronous communication between services in distributed environments. However, security, reliability and performance issues compel such middleware to be distributed, and distribution throws up its own problems such as identifying messaging channels which could then be subscribed to. In particular, interested parties need to identify channels defined in remote locations while not knowing details of how they are defined. A common vocabulary using semantic descriptions offers a solution to this problem. In this paper, we describe the design and implementation of federated messaging middleware using semantic description of channels.

Chained Negotiation for Distributed Notification Services

Distributed notification services allow consumers and publishers of notifications to interact with different notification services. However, such a distributed infrastructure makes it difficult to share notifications between consumers when consumers are allowed to specify Quality of Service levels. In this paper, we present a chained negotiation engine, enabling distributed notification services to support negotiation and to reuse existing subscriptions. We demonstrate the benefit to the system as a whole by reducing load on service providers and enabling content to be shared.