Analysis of size-classified fine and ultrafine particulate matter on substrates with laser-induced breakdown spectroscopy

Airborne particulate matter in the fine (0.1 µm–2.5 µm) and ultrafine (≤ 0.1 µm) size range is supposed to affect human health significantly. Smaller particles intrude more deeply into the lungs, so that an organism directly absorbs toxic compounds. Therefore, knowledge of the size-dependent composition of airborne particles is required to determine their health hazard. In this paper, we demonstrate the application of laser-induced breakdown spectroscopy to directly analyze size-classified particulate matter samples without any sample preparation. Samples analyzed are collected on filter substrates using a cascade impactor. Greased aluminum foils are used as filter substrate. To reduce ablation of the substrate material, low pulse energies of 0.6 mJ are used for plasma excitation. The plasma light is observed using an Echelle spectrometer. The effect of ambient gas and pressure on the line intensities is studied. Calibration samples for 14 elements relevant for human health were produced, and the system was calibrated for concentration ranges up to four orders of magnitude. Finally, the collected samples of particulate originating from steel-making processes were analyzed. The measurements show that the composition of these particles depends strongly on their size. For example, the elements lead, cadmium and copper are enriched within particles of about 200 nm diameter.     

Gold nanoparticles enhance the anti-leukemia action of a 6-mercaptopurine chemotherapeutic agent

6-mercaptopurine and its riboside derivatives are some of the most widely utilized anti-leukemic and anti-inflammatory drugs. Their short biological half-life and severe side effects limit their use. A new delivery method for these drugs based on 4-5 nm gold nanoparticles can potentially resolve these issues. We have found substantial enhancement of the antiproliferative effect against K-562 leukemia cells of Au nanoparticles bearing 6-mercaptopurine-9-beta-d-ribofuranoside compared to the same drug in typically administered free form. The improvement was attributed to enhanced intracellular transport followed by the subsequent release in lysosomes. Enhanced activity and nanoparticle carriers will make possible the reduction of the overall concentration of the drug, renal clearance, and, thus, side effects. The nanoparticles with mercaptopurine also showed excellent stability over 1 year without loss of inhibitory activity.     

Protein immobilization on epoxy-activated thin polymer films: effect of surface wettability and enzyme loading

A series of epoxy-activated polymer films composed of poly(glycidyl methacrylate/butyl methacrylate/hydroxyethyl methacrylate) were prepared. Variation in comonomer composition allowed exploration of relationships between surface wettability and Candida antartica lipase B (CALB) binding to surfaces. By changing solvents and polymer concentrations, suitable conditions were developed for preparation by spin-coating of uniform thin films. Film roughness determined by AFM after incubation in PBS buffer for 2 days was less than 1 nm. The occurrence of single CALB molecules and CALB aggregates at surfaces was determined by AFM imaging and measurements of volume. Absolute numbers of protein monomers and multimers at surfaces were used to determine values of CALB specific activity. Increased film wettability, as the water contact angle of films increased from 420 to 550, resulted in a decreased total number of immobilized CALB molecules. With further increases in the water contact angle of films from 55 degrees to 63 degrees, there was an increased tendency of CALB molecules to form aggregates on surfaces. On all flat surfaces, two height populations, differing by more than 30%, were observed from height distribution curves. They are attributed to changes in protein conformation and/or orientation caused by protein-surface and protein-protein interactions. The fraction of molecules in these populations changed as a function of film water contact angle. The enzyme activity of immobilized films was determined by measuring CALB-catalyzed hydrolysis of p-nitrophenyl butyrate. Total enzyme specific activity decreased by decreasing film hydrophobicity.     

Multicomponent polymer coating to block photocatalytic activity of TiO2 nanoparticles

Chemical grafting of anti-oxidant molecules with an additional hydrophobic polymer coating directly onto TiO(2) particle surfaces, using sonochemistry, is found to eliminate photocatalytic degradation enabling highly effective screening against UV radiation.     

Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme.     

Study of the Drying Behavior of Poly(vinyl alcohol) Aqueous Solution

This paper deals with the drying behavior of poly(vinyl alcohol) aqueous solution containing an active substance and placed into a Petri box. The objective is to reduce the drying time while respecting some constraints. To succeed, it is important to understand complex mechanisms governing heat and mass transfers. During the drying, the product thickness shrinks and its properties evolve. Drying kinetics in convective and infrared radiation are presented.     

A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON

This review article highlights part of the research activity of the C’Durable team at IRCELYON in the field of sustainable chemistry. This review presents a landscape of the work performed on the valorization of lignocellulosic biopolymers. These studies intend to transform cellulose, hemicellulose and lignin into valuable molecules. The methodology usually consists in evaluating the behavior of the biopolymers in the absence of catalyst under various conditions (solvent, temperature), and then to assess the influence of a catalyst, most often a heterogeneous catalyst, on the reactivity. The most significant results obtained on the upgrading of cellulose and lignin, which have been mainly investigated in the team, will be presented with an opening on studies involving raw lignocellulose.     

A doubly bridged isodicyclopentadienyl zirconium complex: bis{N‐(3,5‐dimethylphenyl)‐N‐[(η5‐isodicyclopentadien‐2‐yl)dimethylsilyl]amido‐κN}zirconium(II) diethyl ether solvate

Transmetallation of the dilithium salt of (3,5‐dimethyphenyl­amino)(isodicyclopentadienyl)dimethylsilane by treatment with zirconium tetrachloride in a 2:1 ratio leads to the substitution of all four chloride ligands. With the applied stoichiometry, the title complex, [Zr(C₂₀H₂₅NSi)₂]·C₄H₁₀O, was obtained and crystallized from diethyl ether. X‐ray diffraction characterization showed that both isodi­cyclo­penta­dienyl ligands (alternatively called 4,5,6,7‐tetrahydro‐4,7‐methano‐1H‐indene) are complexed to the metal on their exo face in a completely stereoselective manner and that they are η⁵‐bonded to the Zr atom.     

The Bending-Gradient Theory for Thick Plates: Existence and Uniqueness Results

This paper is devoted to the mathematical justification of the Bending-Gradient theory which is considered as the extension of the Reissner-Mindlin theory (or the First Order Shear Deformation Theory) to heterogeneous plates. In order to rigorously assess the well-posedness of the Bending-Gradient problems, we first assume that the compliance tensor related to the generalized shear force is positive definite. We define the functional spaces to which the variables of the theory belong, then state and prove the existence and uniqueness theorems of solutions of the Bending-Gradient problems for clamped and free plates, as well as for simply supported plates. The obtained results are afterward extended to the general case, i.e., when the compliance tensor related to generalized shear forces is not definite.     

Cellular rubber: Dependency between relaxation time and pretreatment

In this contribution we investigate experimentally a porous carbon-filled rubber. The main focus is on the dependency of the mechanical behaviour using different pretreatments. Therfore, cyclic tests and relaxation tests with different pretreatment are performed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)