Role of chain length and spacers in the organization of long chain Schiff base compounds at air/water and solid/liquid interfaces

Langmuir films of long chain Schiff base compounds: N-(4-fluorobenzylidene)hexadecanamine (compound 1), N-(4-fluorobenzylidene)octadecanamine (compound 2) and 4-{[(4-fluorobenzylidene)amino]methyl}-N-hexadecylaniline (compound 3) have been studied at air/water interface using the characteristic surface pressure-molecular area (π-A) and surface potential-molecular area (ΔV-A) isotherms. Photoelastic modulated Fourier transform infrared spectroscopy has been used to analyze the films of the three compounds at air/water interface. The Langmuir-Blodgett films of these compounds have been characterized using X-ray diffraction that shows layered structures, with interlayer distances of up to 4.4 nm for compound 3. The results show that the layer-to-layer distance can be easily and rationally designed by choosing alkyl chains of different lengths and spacer. Compound 3 packs in an interdigitated bilayer structure with longer lamellar spacing whereas compounds 1 and 2 show a noninterdigitated monolayer structure. Atomistic model calculations have been carried out on the three compounds and the dipole moment values obtained agreed well with the experimental results of surface potential in Langmuir films. Among the three compounds, compound 3 forms stable vesicles spontaneously at room temperature.     

Has the burden and distribution of PCBs and PBDEs changed in European background soils between 1998 and 2008? Implications for sources and processes

Background soils were collected from 70 locations on a latitudinal transect in the United Kingdom and Norway in 2008, ten years after they had first been sampled in 1998. The soils were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCs), to see whether there had been any change in the loadings or distributions of these persistent organic pollutants (POPs). The same transect has also been used to sample air between the mid-1990s and the present, so the air and soil spatial and temporal trends provide information on air-soil transfers, source-receptor relationships, long-range atmospheric transport (LRAT), and recycling phenomena. Comparisons of the 2008 and 1998 data sets show a general decline for PBDEs in surface soil, and a smaller averaged net decline of PCBs. Changes between the years were observed for total POP concentrations in soil and also for correlations with site and sample characteristics assumed to affect those concentrations. POP concentrations were correlated to distance and strength of possible sources, a relationship that became weaker in the 2008 data. Fractionation, a commonly discussed process for the global cycling of POPs was also lost in the 2008 data. As in 1998, soil organic matter content continues to have a strong influence on the loadings of POPs in surface soils, but changes in the PCB loads were noted. These factors indicate an approach to air-surface soil equilibrium and a lessening of the influence of primary sources on POP concentrations in soil between 1998 and 2008.     

Adsorption of arsenic on polyaluminum granulate

The kinetics and efficiencies of arsenite and arsenate removal from water were evaluated using polyaluminum granulates (PAG) with high content of aluminum nanoclusters. PAG was characterized to be meso- and macroporous, with a specific surface area of 35 ± 1 m(2) g(-1). Adsorption experiments were conducted at pH 7.5 in deionized water and synthetic water with composition of As-contaminated groundwater in the Pannonian Basin. As(III) and As(V) sorption was best described by the Freundlich and Langmuir isotherm, respectively, with a maximum As(V) uptake capacity of ~200 μmol g(-1) in synthetic water. While As(III) removal reached equilibrium within 40 h, As(V) was removed almost entirely within 20 h. Micro X-ray fluorescence and electron microscopy revealed that As(III) was distributed uniformly within the grain, whereas As(V) diffused up to 81 μm into PAG. The results imply that As(V) is adsorbed 3 times faster while being transported 10(5) times slower than As(III) in Al hydroxide materials.     

Effect of Pre-Induced Mesenchymal Stem Cell-Coated Cellulose/Collagen Nanofibrous Nerve Conduit on Regeneration of Transected Facial Nerve

(1) Objective: In order to evaluate the effect of a pre-induced mesenchymal stem cell (MSC)-coated cellulose/collagen nanofibrous nerve conduit on facial nerve regeneration in a rat model both in vitro and in vivo. (2) Methods: After fabrication of the cellulose/collagen nanofibrous conduit, its lumen was coated with either MSCs or pre-induced MSCs. The nerve conduit was then applied to the defective main trunk of the facial nerve. Rats were randomly divided into three treatment groups (n = 10 in each): cellulose/collagen nanofiber (control group), cellulose/collagen nanofiber/MSCs (group I), and cellulose/collagen nanofiber/pre-induced MSCs (group II). (3) Results Fibrillation of the vibrissae of each group was observed, and action potential threshold was compared 8 weeks post-surgery. Histopathological changes were also observed. Groups I and II showed better recovery of vibrissa fibrillation than the control group. (4) Conclusions: Group II, treated with the pre-induced MSC-coated cellulose/collagen nanofibrous nerve conduit, showed the highest degree of recovery based on functional and histological evaluations.     

Observer-based control for high order delayed systems with an unstable pole and a pole at the origin

Time delays in dynamical systems are challenging when trying to control them. One of the most common techniques consists in estimating one or more signals of interest before they are delayed, in order to use them in the control stage. In this work, an observer-based control strategy for unstable linear systems with a pole at the origin and delay is suggested. Also, the proposed observer is extended to be used in the case of a high order unstable delayed system. Likewise, the conditions to ensure the existence of the proposed observer-predictor are presented. A methodology is introduced to obtain the observer parameters. The proposed observer scheme makes use of a Proportional-Integral-Derivative control that makes it possible to ensure the tracking of step-type references and the rejection of disturbances of the same type in the closed-loop system.     

Recovery of Hydroxytyrosol from Olive Mill Wastewater Using the Promiscuous Hydrolase/Acyltransferase PestE

Olive mill wastewater (OMWW) is produced annually during olive oil extraction and contains most of the health-promoting 3-hydroxytyrosol of the olive fruit. To facilitate its recovery, enzymatic transesterification of hydroxytyrosol (HT) was directly performed in an aqueous system in the presence of ethyl acetate, yielding a 3-hydroxytyrosol acetate rich extract. For this, the promiscuous acyltransferase from Pyrobaculum calidifontis VA1 (PestE) was engineered by rational design. The best mutant for the acetylation of hydroxytyrosol (PestE_I208A_L209F_N288A) was immobilized on EziG² beads, resulting in hydroxytyrosol conversions between 82 and 89 % in one hour, for at least ten reaction cycles in a buffered hydroxytyrosol solution. Due to inhibition by other phenols in OMWW the conversions of hydroxytyrosol from this source were between 51 and 62 %. In a preparative scale reaction, 13.8 mg (57 %) of 3-hydroxytyrosol acetate was extracted from 60 mL OMWW.     

Additive Manufacturing of Tool Steels

The public funded project “AddSteel” aims to develop functionally adapted steel materials for additive manufacturing (AM). Based on the AM process laser powder bed fusion (LPBF), the holistic process chain, including alloy design, powder atomization, AM, and postheat treatment, is considered to achieve this objective. Tool steels are usually characterized by higher carbon content and limited weldability, leading to limited processability for LPBF. To extend these limitations, different approaches for tool steels are investigated: for high-carbon tool steels, the effects of lower martensite start temperature are investigated using the alloy 1.2842 as an example. A low martensite start temperature seems to be advantageous for crack-free processing with LPBF. In order to avoid a high hardness level after rapid cooling, the use of a hot work steel with a carbon content of 0.2 wt% is investigated. Due to the chemical composition of the material, a moderate preheating temperature <300 °C is required. In addition, very high scanning speeds are possible with an improved shielding gas flow. Finally, the experience along the process chain with the standard steels is used for a modification of the alloy 1.2344. The effects of this modification on AM and heat treatment are investigated.     

Formation of Supramolecular Gels from Host–Guest Interactions between PEGylated Chitosan and α-Cyclodextrin

Chitosan-based hydrogels are prepared via the formation of polypseudorotaxanes (PPR), by selectively threading α-cyclodextrin (α-CD) macrocycles onto polymeric chains, which, through the formation of microcrystalline domains, act as junction points for the network. Specifically, host–guest inclusion complexes are formed between α-CD and PEGylated chitosan (PEG-Ch), resulting in the formation of supramolecular gels. PEG-grafted chitosan is obtained with a reaction yield of 79.8%, a high degree of grafting (50.9% GW) and water solubility (≈16 mg mL⁻¹), as assessed by turbidimetry. A range of compositions for mixtures of PEG-Ch solutions (0.2–0.8% w/w) and α-CD solutions (2−12% w/w, or 0.04–0.2% mol) are studied. Regardless of PEG content, gels are not formed at low α-CD concentrations (<4%). Dynamic rheology measurements reveal stiff gels (G’ above 15k) and a narrow linear viscoelastic region, reflecting their brittleness. The highest elastic modulus is obtained for a hydrogel composition of 0.4% PEG-Ch and 6% α-CD. Steady-state measurements, cycling between low and high shear rates, confirm the thixotropic nature of the gels, demonstrating their capacity to fully recover their mechanical properties after being exposed to high stress, making them good candidates to use as in-situ gel-forming materials for drug delivery to topical or parenteral sites.