Iron oxide magnetic nanoparticles used as probing agents to study the nanostructure of mixed self-assembled monolayers

Self-assembled monolayers (SAMs) of organic molecules are of exceptional technological importance since they represent a convenient, flexible, and simple system for tuning the chemical and physical properties of surfaces. The fine control of surface properties is directly dependent on the structure of mixed SAMs which is difficult to characterize at the nanoscale with usual techniques such as scanning probe microscopies. In this study, we report on a general method to investigate at the nanoscale the structure of molecular patterns which consist in SAMs of two components. Iron oxide nanoparticles (NPs) have been used as probing agents to study indirectly the structure of mixed SAMs. Mixed SAMs were prepared by the replacement of mercaptododecane (MDD) adsorbed by mercaptoundecanoic acid (MUA) molecules on gold substrates. Therefore, the SAM surface displays both chelating carboxylic terminal groups and non-chelating methylene terminal groups. As NPs have been previously demonstrated to specifically interact with carboxylic acid groups, the increasing density in NPs was correlated with the evolution of the COOH/CH(3) terminal groups ratio. Therefore the structure of mixed SAMs was studied indirectly as well as the kinetic of the replacement reaction and its mechanism. With this aim, we took advantage of the SPR properties of the gold substrate and of the high refractive index of iron oxide nanoparticles to follow their assembling on mixed SAMs as a time resolved study. The high sensitivity and tuning of the SPR signal over a wide range of wavelengths are correlated with the NP density. Furthermore, SEM combined with image analysis has allowed studying the replacement rate of MDD by MUA in SAMs. We took also advantages of the magnetic properties of NPs to evaluate qualitatively the replacement of thiol molecules.     

NMR of insensitive nuclei enhanced by dynamic nuclear polarization

Despite the powerful spectroscopic information it provides, Nuclear Magnetic Resonance (NMR) spectroscopy suffers from a lack of sensitivity, especially when dealing with nuclei other than protons. Even though NMR can be applied in a straightforward manner when dealing with abundant protons of organic molecules, it is very challenging to address biomolecules in low concentration and/or many other nuclei of the periodic table that do not provide as intense signals as protons. Dynamic Nuclear Polarization (DNP) is an important technique that provides a way to dramatically increase signal intensities in NMR. It consists in transferring the very high electron spin polarization of paramagnetic centers (usually at low temperature) to the surrounding nuclear spins with appropriate microwave irradiation. DNP can lead to an enhancement of the nuclear spin polarization by up to four orders of magnitude. We present in this article some basic concepts of DNP, describe the DNP apparatus at EPFL, and illustrate the interest of the technique for chemical applications by reporting recent measurements of the kinetics of complexation of 89Y by the DOTAM ligand.     

Extrusion of Nanocellulose‐Reinforced Nanocomposites Using the Dispersed Nano‐Objects Protective Encapsulation (DOPE) Process

Cross‐linked alginate capsules a few millimeters in diameter have been formed by immersion in a CaCl₂ solution. When adding cellulose whiskers or microfibrillated cellulose to the aqueous alginate solution, nanocomposite capsules containing 40 wt.% cellulosic nanoparticles were obtained. The morphology and compression strength of these capsules were investigated by microscopic observations and crushing tests, respectively. The capsules were extruded with a thermoplastic polymer. Visual inspection of the ensuing films shows a nonhomogeneous dispersion of the capsules that kept their integrity after extrusion. It results in preliminary disappointing mechanical properties of the composite films. However, further investigation is in progress to optimize this simple and ecofriendly process.

     

Effect of processing procedures and conditions on structural,morphological, and rheological properties of polyethylene/polyamide/nanoclay blends

The article deals with the effect of processing procedures and conditions on structural, morphological, and rheological properties of ternary blends composed of polyethylene (PE), polyamide (PA)‐12, and organically modified montmorillonite nanoclay with selective affinity. Samples were prepared from PE/PA and PA/PE blends, either by simultaneous mixing or from a polymer/clay masterbatch, using two processing conditions. The results have shown the existence of a weight fraction threshold, above which no significant processing effect was observed. Below this weight fraction threshold, the results tend to underline the significant role of two parameters that depend on processing procedures and/or conditions: the contact time between PE and PA phases and the contact time between clay and PA. Clay structure, blend morphology, and rheological properties were all shown to depend on these two parameters, and also on the nature of the matrix (PE or PA), because of the selective affinity of clay toward polymer phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis and Surface-Active Properties of Uronic Amide Derivatives,Surfactants from Renewable Organic Raw Materials

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, ¹H-RMN and ¹³C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46–58% global yield. Surface-active properties (CMC, γ_cmc, Γ_max, A _min) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9–10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased γ_cmc at slower values than their counterpart’s glucuronic N-alkylamides.     

Electrochemical and spectroscopic characterization of lithium titanate spinel Li4Ti5O12

Herein we describe electrochemical and spectroscopic properties of lithium titanate spinel as well as an easy method based on colorimetry to determine the lithium content of electrodes containing lithium titanate spinel as active material. Raman microspectrometry measurements have been performed to follow lithium insertion into and extraction from the active material, respectively. The Raman signals display a pronounced fading of intensity already at low levels of lithium intercalation and disappear at a SOC higher than ∼10%. However, the colorimetric method can be used up to a SOC of 50%.     

Chitosan effects on glass matrices evaluated by biomaterial. MAS-NMR and biological investigations

Bioactive glass 46S6 and biodegradable therapeutic polymer (Chitosan: CH) have been elaborated to form 46S6-CH composite by freeze-drying process. The kinetics of chemical reactivity and bioactivity at the surface were investigated by using physicochemical techniques, particularly solid-state MAS-NMR. Immortalized cell line used to construct multicellular spheroids was employed as three-dimensional (3D) cell cultures for in vitro studies. Obtained results showed a novel structure of the composite; the chemical treatment (ultrasound, magnetic stirring, freeze drying process and lyophilization) led the bioactive glass particles to be loaded in the chitosan-based materials. ²⁹Si and ³¹P MAS-NMR results showed the emergence of two new species, Q _Si ³ (OH) and Q _Si ⁴ , which are characteristic of the vitreous network dissolution in simulated body fluid (SBF). MAS-NMR also confirmed the formation of amorphous calcium phosphate (ACP) at the surface of the initial 46S6-CH. Three-dimensional (3D) cell cultures highlighted the effect of chitosan, where the cell viability reached up to 78% in 46S6-CH composite and up to 67% in 46S6. The association of (CH) and bioactive glass (BG) matrix promotes a highly significant bioactivity, demonstrating surface bone formation and satisfactory behavior in biological environment.     

Estimates of N2O and CH4 fluxes from agricultural lands in various regions in Europe

According to the revised 1996 IPCC guidelines, several emission factors are needed to calculate national inventories of N₂O emissions from agriculture. To estimate the direct N₂O emissions from mineral soils, an emission factor of 0.0125 kg N₂O-N per kg N applied is currently being used. From recent literature data it was clearly shown that real N₂O emissions could differ substantially from this value. Based on the IPCC methodology an inventory of N₂O emission from agriculture in Europe (EU-15) has been made. In 1996, the N₂O emission was estimated at 672 Gg N₂O-N. The N₂O emission per country varied between 10 and 177 Gg N₂O-N. The N₂O emission per ha agricultural land in the various countries varied between 1.7 and 14.2 kg N₂O-N ha⁻¹. Highest N₂O emissions per ha were found in countries with a high agricultural intensity, such as the Netherlands, Belgium-Luxembourg, Denmark and Germany. Agricultural soils are a sink for atmospheric methane. An oxidation capacity of 2.5 and 1.5 kg CH₄ ha⁻¹ yr⁻¹ was put forward for grasslands and arable land, respectively. Based on land use data of 1993, the CH₄ sink of agricultural lands in EU-15 was estimated at 303.5 Gg CH₄. In general, it could be concluded that N₂O emissions from soils (327 Tg CO₂ equivalents) are far more important than its sink function for CH₄ (6.3 Tg CO₂ equivalents). This revised version was published online in August 2006 with corrections to the Cover Date.     

Polystyrene latex particles bearing primary amine groups via soap‐free emulsion polymerization

Polystyrene latexes were prepared in the presence of an amino‐containing functional comonomer, N‐(3‐aminopropyl)methacrylamide hydrochloride (APMH), via soap‐free batch emulsion polymerization initiated by the cationic initiator 2,2′‐azobis(2‐amidinopropane) dihydrochloride. These latexes were characterized by studying the influence of the ionic comonomers on the polymerization kinetics, particle size, surface charge density and colloidal properties. The synthesized latexes were monodisperse with a final size between 100 and 600 nm depending on the APMH concentration. The initial polymerization rate and the particle number increased in accordance with the Smith–Ewart theory for soap‐free styrene emulsion polymerization with a hydrophilic functional comonomer. The final functionalization rate of the particles has been particularly studied with the intention of fitting the prepared latexes to be used in the immobilization of biological molecules for biological sample preparation and diagnostic applications. © 2020 Society of Chemical Industry     

Nitrogen contributions of alley cropped Trifolium pratense may sustain short rotation woody crop yields on marginal lands

Nutrient Cycling in Agroecosystems - Incorporating nitrogen-fixing cover crops into short rotation woody crop (SWRC) plantations may increase soil and tree nitrogen while sustaining, or even...