The influence of different zeolitic supports on hydrogen production and waste degradation

The photocatalyst composition affects the chemical–physical properties and directly impacts photocatalytic activity, both in the hydrogen production and degradation of organic contaminants. In this work, the influence of zeolitic structures NaA, NaY, and ZSM-5 combined with a 10% active phase, TiO₂ catalyst doped with 1% copper, and cobalt cocatalysts was tested to mineralize the reactive blue dye (CI250) and to produce hydrogen by photocatalysis under ultraviolet radiation. The band gap energy was affected mainly by the cocatalyst, while the Brunauer-Emmett-Teller method (BET) area was affected by the zeolite structure as well as the X-ray diffraction (XRD). The most active catalyst was the Cu@TiO₂/NaY, which promoted a hydrogen production rate of 240 μmolH₂gcat⁻¹ using 10% ethanol (v/v) aqueous solution as a sacrificial agent and mineralization of 53% of the organic dye, followed by the catalysts impregnated on ZSM-5 zeolites, which had discolouration up to 50% and hydrogen evolution of 92.6 and 109.7 μmolH₂gcat⁻¹ for the catalyst doped with Cu and Co, respectively.     

Hydrophobization of hair to improve the interfacial adhesion between hair and high-density polyethylene

Concerned about environmental pollution, and aware of the comfort that polyethylene provides for daily human life, this work sought to replace a percentage of high-density polyethylene (HDPE) with human or bovine hair. Hair is natural, abundant, light weight, non-toxic, and disposed of as garbage. The main disadvantage of natural composites is the interfacial adhesion. To increase the interfacial adhesion between hair and HDPE, stearic acid or oleic acid was chemically anchored on the hair surface, which leads to an improved contact angle hysteresis and hydrophobicity. Dynamic-mechanical properties of the composites were investigated focusing on the type of carboxylic acid used (stearic or oleic acid), hair length, hair type (human or bovine) and amount of hair used in the composite. Taking 40°C as a reference, using 15% of hair with a length of 1 ± 0.15 mm, the highest storage modulus value was obtained with HDPE with human hair modified with oleic acid, exceeding the value of the storage modulus of HDPE by 67.64%. Increasing storage modulus on composites indicates of interfacial interaction and chemical affinity improvement between hair and polyethylene.     

Failure by slow crack growth of SiC fibers: Comparing the lifetime scatter for single filaments and multifilament tows

SiC-based fibers are subjected to slow crack growth, a crack growth mechanism activated by stresses and the chemical environment, as identified by static fatigue testing. Such tests can be performed on filaments or bundles. Although both types of specimens show a similar lifetime variation, testing of bundles is often preferred. This work compares the scatter of lifetimes predicted for filaments and for tows using a dedicated Monte Carlo simulation tool relying on the following hypotheses: The stress applied to a single filament can be defined, whereas the size of its most critical flaw cannot; on a bundle, neither the applied stress nor the strength of the critical filament (which triggers the cascade failure and the tow failure) can be defined. Depending on the parallelism of fibers inside the bundle and their strength dispersion, the lifetime scatter can be narrower for filaments compared to tows or vice versa.     

New Biocompatible β-Phosphorylated Linear Nitrones Targeting Mitochondria: Protective Effect in Apoptotic Cells

The mitochondrion, an essential organelle involved in cellular respiration, energy production, and cell death, is the main cellular source of reactive oxygen species (ROS), including superoxide. Mitochondrial diseases resulting from uncontrolled/excess ROS generation are an emerging public health concern and there is current interest in specific mitochondriotropic probes to get information on in-situ ROS production. As such, nitrones vectorized by the triphenylphosphonium (TPP) cation have recently drawn attention despite reported cytotoxicity. Herein, we describe the synthesis of 13 low-toxic derivatives of N-benzylidene-1-diethoxyphosphoryl-1-methylethylamine N-oxide (PPN) alkyl chain-grafted to a pyridinium, triethylammonium or berberinium lipophilic cation. These nitrones showed in-vitro superoxide quenching activity and EPR/spin-trapping efficiency towards biologically relevant free radicals, including superoxide and hydroxyl radicals. Their mitochondrial penetration was confirmed by ³¹P NMR spectroscopy, and their anti-apoptotic properties were assessed in Schwann cells treated with hydrogen peroxide. Two pyridinium-substituted PPNs were identified as potentially better alternatives to TPP nitrones conjugates for studying mitochondrial oxidative damage.     

Stereodivergent Biocatalytic Formal Reduction of α-Angelica Lactone to (R)- and (S)-γ-Valerolactone in a One-Pot Cascade

The formal asymmetric and stereodivergent enzymatic reduction of α-angelica lactone to both enantiomers of γ-valerolactone was achieved in a one-pot cascade by uniting the promiscuous stereoselective isomerization activity of Old Yellow Enzymes with their native reductase activity. In addition to running the cascade with one enzyme for each catalytic step, a bifunctional isomerase-reductase biocatalyst was designed by fusing two Old Yellow Enzymes, thereby generating an unprecedented case of an artificial enzyme catalyzing the reduction of nonactivated C=C bonds to access (R)-valerolactone in overall 41 % conversion and up to 91 % ee. The enzyme BfOYE4 could be used as single biocatalyst for both steps and delivered (S)-valerolactone in up to 84 % ee and 41 % overall conversion. The reducing equivalents were provided by a nicotinamide recycling system based on formate and formate dehydrogenase, added in a second step. This enzymatic system provides an asymmetric route to valuable chiral building blocks from an abundant bio-based chemical.     

A Facile and Green Microwave-Assisted Strategy to Induce Surface Properties on Complex-Shape Polymeric 3D Printed Structures

Light- induced polymeric 3D printing is becoming a well-established fabrication method, showing manifold advantages such as control of the local chemistry of the manufactured devices. It can be considered a green technology, since the parts are produced when needed and with minimum amount of materials. In this work 3D printing is combined with another green technology, microwave-assisted reaction, to fabricate objects of complex geometry with controllable surface properties, exploiting the presence of remaining functional groups on the surface of 3D printed specimens. In this context, surface functionalization with different amines is studied, optimizing formulations, reaction times, and avoiding surface deterioration. Then, two different applications are investigated. MW-functionalized filter-type structures have been tested against Staphylococcus aureus bacteria, showing high bactericidal activity on the surface along all areas of the complex-shaped structure. Second, a fluidic chip composed of three separated channels is 3D printed, filled with different amine-reactive dyes (dansyl and eosine derivatives), and made to react simultaneously. Complete and independent functionalization of the surface of the three channels is achieved only after 2 min of irradiation. This study demonstrates that light induced 3D printing and microwave-induced chemistry can be used together effectively, and used to produce functional devices.     

Quasi-Diamond Platelet-Shaped Zinc Oxide Nanostructures Display Enhanced Antibacterial Activity

The current study compares the antibacterial activity of zinc oxide nanostructures (neZnO). For this purpose, two bacterial strains, Escherichia coli (ATCC 4157) and Staphylococcus aureus (ATCC 29213) were challenged in room light conditions with the aforementioned materials. Colloidal and hydrothermal methods were used to obtain the quasi-round and quasi-diamond platelet-shape nanostructures. Thus, the oxygen vacancy (V_O) effects on the surface of neZnO are also considered to assess its effects on antibacterial activity. The neZnO characterization was achieved by X-ray diffraction (XRD), a selected area electron diffraction (SAED) and Raman spectroscopy. The microstructural effects were monitored by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Furthermore, optical absorption ultraviolet visible spectrophotometry (UV-Vis) and X-ray photoelectron spectroscopy (XPS) analyses complement the physical characterization of these nanostructures; neZnO caused 50 % inhibition (IC₅₀) at concentrations from 0.064 to 0.072 mg/mL for S. aureus and from 0.083 to 0.104 mg/mL for E. coli, indicating an increase in activity against S. aureus compared to E. coli. Consequently, quasi-diamond platelet-shaped nanostructures (average particle size of 377.6±10 nm) showed enhanced antibacterial activity compared to quasi-round agglomerated particles (average size of 442.8±12 nm), regardless of Vo presence or absence.     

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.     

Synthesis and ex-situ evaluation of quaternized polysulfone as an anion exchange ionomer for AEM technologies

Anion exchange ionomer (AEI) is a critical component used on anion exchange membrane fuel cell (AEMFC) and alkaline water electrolyzer (AWE). In this work, quaternized polysulfone with different functionalization degree were used as an ionomer to evaluate the performance in the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), both implied in the operation of AEMFC and AWE. The synthesized ionomer exhibited a better performance in both reactions in comparison to the commercial AEI Aemion®. PSf-130 exhibited better performance, since IEC and surface area increases twice regarding the same parameters in the PSf-60. The PSf-130 conductivity increases three times regarding the value exhibited by PSf-60. Finally, the J_lim and J_k increases 67% and 100% for ORR. On the other hand, the same catalytic parameter increased 44% and 35% for HOR comparing both polysulfone-based ionomers. The Tafel slope values do not showed drastically changes for different ionomers indicating the same rate determining step (RDS) and the same mechanism in both reactions for all the ionomers.     

Tight binding of the antitumor drug ditercalinium to quadruplex DNA

The structural selectivity of the DNA-binding antitumor drug ditercalinium was investigated by competition dialysis with a series of nineteen different DNA substrates. The 7H-pyridocarbazole dimer was found to bind to double-stranded DNA with a preference for GC-rich species but can in addition form stable complexes with triplex and quadruplex structures. The preferential interaction of the drug with four-stranded DNA structures was independently confirmed by electrospray mass spectrometry and a detailed analysis of the binding reaction was performed by surface plasmon resonance (SPR) spectroscopy. The BIAcore SPR study showed that the kinetic parameters for the interaction of ditercalinium with the human telomeric quadruplex sequence are comparable to those measured with a duplex sequence. Slow association and dissociation were observed with both the quadruplex and duplex structures. The newly discovered preferential binding of ditercalinium to the antiparallel quadruplex sequence d(AG(3)[T(2)AG(3)](3)) provides new perspectives for the design of drugs that can bind to human telomeres.