Rapid determination of mono and dinitrophenols by DPP, in the presence of lead and cadmium and using concentrated CaCl2 electrolyte

The contamination of drinking water and industrial wastewaters is a critical environmental problem. The nitrophenol, dinitrophenol, cadmium, and lead contaminants are classified as hazardous compounds. Their rapid determination may be obtained using differential pulse polarography with concentrated electrolyte. CaCl₂, which is very soluble to levels exceeding 5 mol l^–1, allows separation of coalescent peaks at 0.1 mol l^–1. A systematic study undertaken from 0.1 to 5 mol l^–1 shows good separation of lead and cadmium from the organic compounds, and optimization of the electrolyte concentration according to the objective is described. Preconcentration of real samples is necessary because pollution levels are usually very low.     

Ethics in OR/MS: Past,present and future

The pervasiveness and impact on society and on every day human life of technology has led to a growing awareness that science and technology cannot be considered above or beyond the realm of value judgements and hence of ethics. This is especially true for Operations Research / Management Science (OR/MS), that particular science which is concerned with methodologies for scientifically deciding how to design and operate man-machine systems in an optimal way, usually under conditions requiring the allocation of scarce resources. Here we try to give a historical account of the growing interest for ethics within the OR/MS community from its birth to present days. Starting from attempts to define models and codes of ethical behaviour in our profession, the OR/MS community has arrived at more fundamental questions about the ethical responsibility it faces in a world of growing inequalities and in which the ever greater stress that human activities impose on the environment puts at risk the very survival of human kind.     

Contact phase modulation method for acoustic nonlinear parameter measurement in solid

In this work, a new method to measure in contact the nonlinearity parameter beta of solid plates is presented. A high frequency (HF) tone-burst signal of 20 MHz is inserted in the material by a contact-transducer (with a suitable coupling). A low frequency (LF) pulse (2.5 MHz) is applied to the other face, in the opposite direction, so that the nonlinear interaction of the two waves takes place during the back propagation toward the HF transducer. This collinear interaction creates a phase modulation of the HF tone-burst which is proportional to the beta coefficient and the particle velocity of the LF wave. To determine this particle velocity, in time domain, an extended self-reciprocity calibration of the contact LF transducer is used. A numeric phase demodulation is then performed, giving the beta coefficient of the sample. The proposed method is validated by nonlinearity parameter measurements in Fused Silica. The nonlinear parameter of Fused Silica measured is found to be in good agreement with the literature, and specially the negative sign of this parameter.     

Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles

We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface.     

Plasma formation dynamics within a water microdroplet on femtosecond time scales

We demonstrate that a highly confined plasma inclusion is formed inside a micrometric water droplet that is excited by a femtosecond laser. An 800-nm laser pulse generates a plasma inclusion by laser-induced breakdown that is subsequently probed by the elastic scattering of a second (400-nm) time-delayed ultrashort pulse. For a 25-microm-radius droplet and an incident intensity of 7 x 10(12) W/cm2 the radius of the highly localized plasma is 1.9 +/- 0.4 microm. We probed the plasma formation dynamics on femtosecond time scales by varying the delay between the pump and the probe pulses. Good agreement with numerical simulations of the process was found.     

On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy

The applicability of Raman spectroscopy to characterize disordered and heterogeneous carbonaceous materials (CM) is discussed, by considering both natural and synthetic CM. First, different analytical mismatches during the measurement are discussed and technical indications are provided in order to eliminate them. Second, the accuracy and relevance of the different parameters obtained by the decomposition of spectra by conventional fitting procedure, is reviewed. Lastly, a new Raman technique (Raman area mode microspectroscopy) giving an homogeneous repartition of power within a large laser beam is presented, this technique being powerful to study strongly heterogeneous CM and/or photosensitive samples.     

MASSIS: a mass spectrum simulation system. 2: Procedures and performance

The use of the mass spectral simulation system, MASSIS, is reported and its performance has been evaluated. The search for substructures matching with fragments stored in four pivot databases was realised using the Ullmann algorithm. Special cleavage rules, such as the McLafferty rearrangement, the retro-Diels-Alder reaction, elimination of a neutral small molecule and oxygen migration, are processed through shortest path and depth-first search algorithms. For a search in the database of small fragments, the key step is to determine the tautomeric fragments; then a match can be obtained using a subgraph isomorphism algorithm. A string match is used to determine peak intensity. If the limited environment of an atom is the same as that found in the database of relationships between fragment and intensity, this intensity value is assigned to the query atom. Performance in a set of tests is very important in evaluating the system performance. A comparison of peaks with an intensity greater than 5% (relative) shows that our system has a very high performance figure (> 90% ) for routine organic compounds.     

MASSIS: a mass spectrum simulation system 1. Principle and method

A mass spectrum simulation system was developed. The simulated spectrum for a given target structure is computed based on the cleavage knowledge and statistical rules established and stocked in pivot databases: cleavage rule knowledge, function groups, small fragments and fragment-intensity relationships. These databases were constructed from correlation charts and statistical analysis of large population of organic mass spectra using data mining techniques. Since 1980, several systems were proposed for mass spectrum simulation, but in present there is no any commercial software available. This shows the complexity and difficulties in the development of a such system. The reported mass spectral simulation system in this paper could be the first general software for organic chemistry use     

Structural and magnetic properties of carboxylato-bridged manganese(II) complexes involving tetradentate ligands: discrete complex and 1D polymers. Dependence of J on the nature of the carboxylato bridge

The crystal structure of an inorganic linear polymer consisting of Mn(II) and an N-centered tripodal ligand N,N-bis(2-(6-methyl)pyridylmethyl)glycinate is presented (1, C(16)H(20)N(3)O(3)F(6)P(1)Mn(1), a = 9.993(2) A, b = 13.285(3) A, c = 16.040(3) A, orthorhombic, Pnam, Z = 4). The polymeric structure is ensured by carboxylato ligands connecting two Mn(II) in a rather rare syn-anti geometry. The magnetic properties of this infinite chain have been investigated, together with the magnetic properties of a dimeric Mn(II) compound (3) from a closely related ligand [N,N-bis[(1-methylimidazol-2-yl)-methyl)glycinate] involving an unusual bis(monatomic-carboxylato) bridge. The inorganic polymer 1 shows a pseudo-2D magnetic structure, with a major interaction pathway along the chain (J/k = -0.172 +/- 0.005 K) and an interchain minor one (zJ'/k = -0.006 +/- 0.004 K). These properties are reminiscent of those from a closely related previously reported inorganic Mn(II) polymer (2 obtained from manganese(II) and N,N-(2-pyridylmethyl)((1-methylimidazol-2-yl)methyl)glycinate). The dimer 3 shows a small antiferromagnetic coupling of J/k = -0.693 +/- 0.016 K. To address the influence of the carboxylato bridging mode on the magnetic properties, these complexes are compared to a series of compounds involving carboxylato bridges of several geometries between Mn(II) ions. Carboxylato bridges induce usually antiferromagnetic coupling, with the magnitude of the interaction (/J/) increasing with the number of bridges. The J value is dependent on the bridging mode. The syn-syn bridge is an efficient pathway, even by comparison with the monatomic [(mu-eta(1)-carboxylato)] bridge.     

Effects of the polydispersity on the viscoelasticity of low molecular weight polymers

The viscoelastic behavior of low molecular weight polymers exhibiting a fairly broad distribution has been deduced from the behavior of narrow samples by way of a linear law as a function of the density of the molecular weight distribution. Rheology of polydisperse linear polymers where the entire distribution of molecular weights is lower than 2 M _ehas been investigated using both binary mixtures and a broad sample of polystyrene. A decrease of the friction coefficient and of the viscosity compared to that of a narrow sample with the same M _w is observed. Therefore, the low components of broad samples play the role of plasticizers or lubricants which has been investigated in relation with the molecular weight distribution.