Microwave-hydrothermal synthesis and characterization of nanostructured copper substituted ZnM2O4 (M = Al, Ga) spinels as precursors for thermally stable Cu catalysts

Nanostructured Cu(x)Zn(1-x)Al(2)O(4) with a Cu:Zn ratio of ?:? has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al(2)O(3)-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m(2) g(-1)). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen and the accessible metallic Cu(0) surface area of the reduced catalyst was 8 m(2) g(-1). The catalytic performance of the material in CO(2) hydrogenation and methanol steam reforming was compared with conventionally prepared Cu/ZnO/Al(2)O(3) reference catalysts. The observed lower performance of the spinel-based samples is attributed to a lack of synergetic interaction of the Cu nanoparticles with ZnO due to the incorporation of Zn(2+) in the stable spinel lattice. Despite its lower performance, however, the nanostructured nature of the spinel catalyst was stable after thermal treatment up to 500 °C in contrast to other Cu-based catalysts. Furthermore, a large fraction of the re-oxidized copper migrates back into the spinel upon calcination of the reduced catalyst, thereby enabling a regeneration of sintered catalysts after prolonged usage at high temperatures. Similarly prepared samples with Ga instead of Al exhibit a more crystalline catalyst with a spinel particle size around 20 nm. The slightly decreased Cu(0) surface area of 3.2 m(2) g(-1) due to less copper incorporation is not a significant drawback for the methanol steam reforming.     

Production of 2,3-butanediol from diverse saccharides via fermentation

The present study aimed to evaluate the potential use of whey to produce 2,3-BD via the fermentation of lactose and its monosaccharides, glucose and galactose, in a synthetic culture medium (medium 9, M9) using a modified strain of Escherichia coli K12 MG1655 (E. coli JFR12) at a 0.1 L/L (10 vol%) inoculum ratio, 37 °C, atmospheric pressure, an initial pH 7.4, and 100 rpm for 72 h varying the saccharide concentration from 12.5, 25, and 50 g/L. The 2,3-BD yield was ∼80 % of the theoretical yield using 25 g/L of glucose and lactose, corresponding to 0.38 g/g saccharides at a fermentation time of 48 h (glucose) and 72 h (lactose). However, the 2,3-BD yield was halved (0.19 g/g galactose), fermenting 25 g/L of galactose at 48 h. Taking into account these results, two important conclusions were determined: i) E. coli JFR12 could transform galactose into 2,3-BD although its yield was half of the yield observed with glucose at 48 h; and ii) E. coli JFR12 was as efficient as other natural 2,3-BD producers such as Klebsiella species fermenting lactose. However, the E. coli strain has the advantage of being an innocuous strain. To the best of our knowledge, there is no other study presenting the production of 2,3-BD from galactose and lactose with a genetically modified E. coli strain.     

Aerobic Granular Sludge: Perspectives for Excess Sludge Management and Resource Recovery

Aerobic granular sludge (AGS) technology is gaining increasing interest globally. However, several aspects are still challenging its installation, as the integration into existing municipal wastewater treatment plants. The operation of AGS units in continuous flow mode could facilitate that integration; yet has only been experienced at lab and pilot scales. Further, handling of excess granular sludge constitutes a prominent challenge. Even that, adopting effective strategies for its management holds promising contributions to the circular economy by fostering the reuse and recovery of valuable resources. The recovery of phosphorus and alginate-like polymers holds significant commercial potential worldwide, with broad applications in agriculture, food, pharmaceuticals, and biotechnology.     

Additive Manufacturing-Enabled Architected Nanocomposite Lattices Coated with Plasmonic Nanoparticles for Water Pollutants Detection

Novel low-cost materials to uptake and detect vestigial amounts of pesticides are highly desirable for water quality monitoring. Herein, are demonstrated, for the first time, surface-enhanced Raman scattering (SERS) sensors enabled via additively manufactured lattices coated with plasmonic nanoparticles (NPs) for detecting pesticides in real water samples. The architected lattices comprising polypropylene (PP) and multiwall carbon nanotubes (MWCNTs) are realized via fused filament fabrication (FFF). In the first stage, the SERS performance of the PP/MWCNT filaments coated with distinct metallic NPs (Ag NPs and Au NPs) is evaluated using methylene blue (MB) as molecular probe. Thereafter, distinctly architected hybrid SERS sensors with periodic porous and fully dense geometries are investigated as adsorbents to uptake MB from aqueous solutions and subsequent detection using SERS. The spatial distribution of MB and Ag NPs on the FFF-printed lattices is accomplished by SERS imaging. The best hybrid composite is used as SERS probing system to detect low amounts of pesticides (thiram and paraquat) and offers a detection limit of 100 nm for both pesticides. As a proof-of-concept, FFF-enabled test strips are used to detect in loco paraquat molecules spiked on real water samples (Estuary Aveiro water and tap water) using a portable Raman spectrometer.     

A 4-Arm PEG-Thiodepsipeptide Precursor Enables Gelatinase-Promoted Hydrogel Formation

In situ hydrogelation of injectable precursors upon biological stimulus is relevant to generate hydrogels under mild conditions and, potentially, at a biological side of interest. Here, it is shown that hydrolytic enzymes can be used to initiate the formation of covalent hydrogel networks, realizing a cleavage-leading-to-gelation strategy. For this purpose, a two-component system is used, consisting of a 4-arm polyethylene glycol-thiodepsipeptide conjugate, PEG4TDP_o containing the matrix metalloproteinases MMP-2- and MMP-9-cleavable Ac-Pro-Leu-Gly#SLeu-Leu-Gly- thiodepsipeptide sequence releasing a thiol upon hydrolysis, and a maleimide functionalized 4-armed PEG (PEG4MAL). PEG4TDP_o is synthesized in a PEG-functionalization protocol involving convergent and divergent synthetic steps without the need for rigorous purification procedures. In a fluorometric assay, it is shown that the construct is in fact cleaved by both investigated MMPs. PEG4TDP_o in the presence of 10 wt.% PEG4MAL formed hydrogels upon addition of MMP-2 or -9 with average gelation times of 28 and 40 min, respectively, as is investigated by rheology. The much faster gelation times compared to the enzyme-free system showed the specific input of the enzymatic reactions. The MMP-assisted activation and crosslinking strategy can potentially become useful by targeting tissues showing an increased expression of MMPs, such as cancers, or to detect MMPs.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

Site-selective substitution and resulting magnetism in arc-melted perovskite ATiO3-δ (A = Ca,Sr, Ba)

Magnetic properties in perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba) were investigated before and after arc melting. Crystal structure analysis was conducted by powder synchrotron X-ray diffraction with Rietveld refinements. Quantitative chemical element analysis was carried out by X-ray photoelectron spectroscopy. Magnetic measurements were conducted by vibrating sample magnetometer and X-ray magnetic circular dichroism (XMCD). The magnetic properties are found to be affected by impurities of 3d elements such as Fe, Co, and Ni. Depending on the composition and crystal structure, the occupation of the magnetic ions in perovskite titanates is selectively varied, which is interpreted to be the origin of the different magnetic behaviors in arc-melted perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba). In addition, both formation of oxygen vacancies and the reduction of Ti⁴⁺ to Ti³⁺ during arc-melting also play a role as proven by XMCD. Nevertheless, preferential site occupation of magnetic impurities is dominant in the magnetic properties of arc-melted perovskite ATiO_3-δ (A = Ca, Sr, Ba).     

Adsorption of mercaptopropionic acid onto Au(1 1 1): Part II. Effect on copper electrodeposition

Copper deposition in the presence of an organic additive (3-mercaptopropionic acid, MPA) was studied by cyclic voltammetry and in situ scanning tunneling microscopy (STM) and the results are compared to those for additive-free solutions. It is shown that underpotential deposition (upd) of copper onto a fully MPA-covered electrode produces a defect-rich substrate, but the defects are blocked by the dense organic film for bulk deposition, resulting in a low number of nuclei. A grain-refining effect of MPA, however, was found, when Cu deposition was initiated shortly after addition of MPA to the solution, i.e., for a low-coverage MPA adlayer.     

A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate)

The theory and implementation of reactive molecular dynamics (RMD) are presented. The capabilities of RMD and its potential use as a tool for investigating the mechanisms of thermal transformations in materials are demonstrated by presenting results from simulations of the thermal degradation of poly(methyl methacrylate) (PMMA). While it is known that depolymerization must be the major decomposition channel for PMMA, there are unanswered questions about the nature of the initiation reaction and the relative reactivities of the tertiary and primary radicals formed in the degradation process. The results of our RMD simulations, performed directly in the condensed phase, are consistent with available experimental information. They also provide new insights into the mechanism of the thermally induced conversion of this polymer into its constituent monomers.