An interlaboratory study as useful tool for proficiency testing of chemical oxygen demand measurements using solid substrates and liquid samples with high suspended solid content

In 2008, the first Proficiency Testing Scheme of Chemical Oxygen Demand (1^stCOD-PT^ADG) was conducted to assess the results obtained for different research groups whose field work is mainly anaerobic digestion. This study was performed using four samples, two solid samples as raw materials and two solid samples to prepare high concentration suspended solid solutions. Invitations were sent to a large number of laboratories, mainly to anaerobic digestion research groups. Finally, thirty labs from sixteen countries agreed to participate, but for different reasons four participants could not send any data. In total, twenty-six results were reported to the COD-PT coordinator.This study showed the importance of continuous participation in proficiency testing (PT) schemes in order to compare the results obtained. Taking into account the lack of a general standard method and high quality certified reference materials (CRMs), the traceability of COD determination is not currently easy to check. In addition, the spread of participants’ results obtained was high and pointed to the advisability of using consensus values due to their unreliability. Therefore, the theoretical oxygen demand (ThOD) values were considered as assigned values for all the samples analysed. On the other hand, in this PT the established standard deviation (ESD) has been determined by the Horwitz modified function.Participants of this 1^stCOD-PT^ADG were asked to give a short report on the analytical method used. Although all the participants used potassium dichromate as their oxidant reagent, their experimental procedures were very different. With the purpose of comparing the results obtained, the different experimental conditions used were classified into five methods, corresponding to two main categories, open and closed reflux. The performance of laboratories was expressed by the z-score, whose value is considered satisfactory when z-score ≤±2. The overall analytical data evaluation showed that 64% of z-scores obtained were outside the accepted limits.     

Shape‐Selective Interception by Hydrocarbons of the O2‐Derived Oxidant of a Biomimetic Nonheme Iron Complex

Picky ferryl : The complex [Fe(Tp)(BF)] (Tp=hydrotris(3,5‐diphenylpyrazolyl)borate; BF=benzoylformate) reacts with O₂ to generate an oxidant (see picture; O red, pink; Fe yellow; N blue; C gray; H white) that oxidizes added hydrocarbons shape‐selectively. Discrimination derives from a cleft formed by two phenyl groups of the Tp ligand, favoring oblate spheroidal substrates.

     

Synthesis and preliminary investigations of the siRNA delivery potential of novel, single-chain rigid cationic carotenoid lipids

The success of nucleic acid delivery requires the development of safe and efficient delivery vectors that overcome cellular barriers for effective transport. Herein we describe the synthesis of a series of novel, single-chain rigid cationic carotenoid lipids and a study of their preliminary in vitro siRNA delivery effectiveness and cellular toxicity. The efficiency of siRNA delivery by the single-chain lipid series was compared with that of known cationic lipid vectors, 3β-[N-(N',N'-dimethylaminoethane)carbamoyl]-cholesterol (DC-Chol) and 1,2-dimyristoyl-sn-glyceryl-3-phosphoethanolamine (EPC) as positive controls. All cationic lipids (controls and single-chain lipids) were co-formulated into liposomes with the neutral co-lipid, 1,2-dioleolyl-sn-glycerol-3-phosphoethanolamine (DOPE). Cationic lipid-siRNA complexes of varying (+/-) molar charge ratios were formulated for delivery into HR5-CL11 cells. Of the five single-chain carotenoid lipids investigated, lipids 1, 2, 3 and 5 displayed significant knockdown efficiency with HR5-CL11 cells. In addition, lipid 1 exhibited the lowest levels of cytotoxicity with cell viability greater than 80% at all (+/-) molar charge ratios studied. This novel, single-chain rigid carotenoid-based cationic lipid represents a new class of transfection vector with excellent cell tolerance, accompanied with encouraging siRNA delivery efficiency.     

Ring‐Extended Gramicidin S Analogs Containing cis δ‐Sugar Amino Acid Turn Mimetics with Varying Ring Size

This article presents a series of ring‐extended gramicidin S derivatives, 9 – 14 , that have four ornithine residues as polar protonated side chains and one modified turn region containing a mono‐functionalized cis‐δ‐oxetane, δ‐furanoid, or δ‐pyranoid sugar amino acid residue. Of the GS analogs evaluated, we identified compound 7 , which contains the mono‐benzyloxy cis‐δ‐pyranoid sugar amino acid, as having a better biological profile than the clinically applied topical antibiotic gramicidin S.     

Foam films in the presence of functionalized gold nanoparticles

Dry aqueous foams made of anionic surfactant (SDS) and spherical gold nanoparticles are studied by small angle X-ray scattering and by optical techniques. To obtain stable foams, the surfactant concentration is well above the critical micelle concentration. The specular reflectivity signal obtained on a very thin film (thickness 20 nm) shows that functionalized nanoparticles (17 nm typical size) are trapped within the film in the form of a single monolayer. In order to isolate the film behavior, investigations are made on a single film confined in a tube. The film thinning according to the ratio of functionalized nanoparticle and SDS micelles (1:1, 1:10, 1:100) is mainly governed by the structural arrangement of SDS micelles. In thick films, nanoparticles tend to form aggregates that disappear during drainage. In particular self-organization of nanoparticles (with different surface charge) inside the film is not detected.     

Molecular Frame Photoemission： Probe of the Photoionization Dynamics for Molecules in the Gas Phase

Molecular frame photoemission is a very sensitive probe of the photoionization （PI） dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions （MFPADs）. We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ（χ, θe, Фe） MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and （θe, Фe） the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization （DPI） of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.     

The Manifold-Valued Dirichlet Problem for Symmetric Diffusions

Harmonic maps between two Riemannian manifolds M and N are often constructed as energy minimizing maps. This construction is extended for the Dirichlet problem to the case where the Riemannian energy functional on M is replaced by a more general Dirichlet form. We obtain weakly harmonic maps and prove that these maps send the diffusion to N-valued martingales. The basic tools are the reflected Dirichlet space and the stochastic calculus for Dirichlet processes.     

Nonlinear estimation in anisotropic multi-index denoising

In the framework of denoising a function depending of a multidimensional variable (for instance an image), we provide a nonparametric procedure which constructs a pointwise kernel estimation with a local selection of the multidimensional bandwidth parameter. Our method is a generalization of the Lepski's method of adaptation, and roughly consists in choosing the “coarsest” bandwidth such that the estimated bias is negligible. However, this notion becomes more delicate in a multidimensional setting. We will particularly focus on functions with inhomogeneous smoothness properties and especially providing a possible disparity of the inhomogeneous aspect in the different directions. We show, in particular that our method is able to exactly attain the minimax rate or to adapt to unknown degree of anisotropic smoothness up to a logarithmic factor, for a large scale of anisotropic Besov spaces. Received: 11 November 1999 / Revised version: 14 November 2000 / Published online: 24 July 2001     

Mössbauer Spectrometry as a Powerful Tool to Study Lithium Reactivity Mechanisms for Battery Electrode Materials

Hyperfine Interactions - The use of 57Fe as a local Mössbauer probe is of high interest for studying mechanisms induced by lithium insertion. In this way the substitutions Ti/Fe and Li/Fe have...     

Numerical and analytical study of high-resolution limb spectral radiance from nonequilibrium atmospheres

Emission line shapes are calculated numerically for isolated optically thick infrared lines in the earthlimb as a function of tangent height using a general nonlocal thermodynamic equilibrium (non-LTE), upper-atmospheric line-by-line radiation transport code. It is shown that the exact integral form of the transport equation can be written in a form that is easily amenable to analytical approximation of high accuracy. In this form, the limb spectral radiance I_v appears as a weighted average of n_u/n_l, the ratio of upper-state to lower-state population density, multiplied by the absorptivity 1 - exp[-τ(v)], where τ(v) is the total optical path along the line of sight. In the wings the variation of I_v is governed by the absorptivity; in the core of the optically thick line, I_v is determined by the averaged population ratio. The analytical forms enable us to calculate all of the important features of the self-absorbed line and agree remarkably well with more time-intensive numerical calculation. These results are illustrated by calculations on the 15-μm CO₂v₂ (01¹0-00⁰0) vibrational transition for tangent heights ranging through the mesosphere and lower thermosphere. Even though the collision linewidth is less than 1% of the Doppler width at these altitudes, it is shown that it is essential to use the Voigt line profile in this calculation rather than the Doppler profile. Failure to do so leads to a total band radiance that is in error by up to a factor of three, as well as incorrect band shapes and line shapes.