Intermolecular Hydrogen Bonds and the Supramolecular Structure of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis(<Emphasis Type="Italic">p</Emphasis>-tolylsulfonyl)diethylenetriamine

Abstract  The title compound N,N′-bis(p-tolylsulfonyl)diethylenetriamine (1) was synthesized and its crystal structure determined by X-ray diffraction. Adjacent molecules of 1, symmetrically related through a c-glide, are linked by alternating hydrogen bonds that form molecular chains along [0 0 1]. Two molecular chains occur in each unit cell and pack to form alternating layers in a three-dimensional supramolecular structure. The compound crystallizes in the Pca2₁ space group stabilized by the inclusion of solvent dichloromethane molecules in structural voids between molecules of 1. The dichloromethane molecules are related through a twofold screw rotation axis and are not disordered. Index Abstract  Intermolecular hydrogen bonds involving sulfonamide moieties of title compound afford a supramoleular structure that accommodates the inclusion of dichloromethane in alternating layers.      

Transport properties near the magneto/structural transition of Tb5Si2Ge2

We report high resolution measurements of the electrical resistivity (ρ, dρ/dT) and thermopower (S, dS/dT) measurements near the magnetic and structural transition of the layered Tb₅Si₂Ge₂ compound, which are fairly close but not fully coupled. The analysis of the transport properties confirms a split magneto/structural transition, with T_S ～ 97 K and T_S ～ 107 K for the structural transition (on cooling and heating respectively; 1st-order transition). The magnetic transition occurs only at T_C ～ 112 K and without hysteresis (2nd-order transition). The magnetic critical behavior of resistivity is analyzed, obtaining an almost classical mean field exponent (α ～ 0.59) for T > T_C. For the structural phase, and below T_S, we obtain a rather different exponent (α ～ 1.06).     

Trivalent chromium conversion coating on AA2024-T3 used in aeronautical and aerospace industry

Significant research has been conducted to replace the chromium(VI)-based surface treatments, and some commercial substitute systems are now available and needs to be tested to evaluate their performance and to know how they comply with the required specifications. The anticorrosion properties provided by a commercially available trivalent chromium-based product—PreCoat A32—when applied to AA2024-T3 aluminium alloy substrates were evaluated in this work and compared with those obtained with a chromium(VI)-based pretreatment well-recognized reference (Alodine 1200S). The morphology and elemental composition of the conversion coatings were investigated by high-resolution microscopy and energy-dispersive X-ray analysis, respectively, being the wettability of the modified surface measured by contact angle goniometry. The data obtained reveal that PreCoat A32–treated surfaces are more apt to receive aqueous paint schemes than those healed with Alodine 1200S. The corrosion resistance of the treated samples was monitored by potentiodynamic polarisation assays and electrochemical impedance spectroscopy analysis, revealing that PreCoat A32 coatings provide improved corrosion protection for AA2024-T3. The corrosion resistance effectiveness of PreCoat A32 was also confirmed in trials realised in salt-spray chamber, humidity tests, and thermal cycling assays, where more severe exposure conditions were simulated. The gathered data clearly indicate that the PreCoat A32 brings together the mandatory qualities to successfully substitute the conventional and undesirable chromium(VI)-based treatments, in aeronautical and aerospace industry.     

Singlet oxygen‐induced protein aggregation: Lysozyme crosslink formation and nLC‐MS/MS characterization

Singlet molecular oxygen (¹O₂) has been associated with a number of physiological processes. Despite the recognized importance of ¹O₂‐mediated protein modifications, little is known about the role of this oxidant in crosslink formation and protein aggregation. Thus, using lysozyme as a model, the present study sought to investigate the involvement of ¹O₂ in crosslink formation. Lysozyme was photochemically oxidized in the presence of rose bengal or chemically oxidized using [¹⁸O]‐labeled ¹O₂ released from thermolabile endoperoxides. It was concluded that both ¹O₂ generating systems induce lysozyme crosslinking and aggregation. Using SDS‐PAGE and nano‐scale liquid chromatography coupled to electrospray ionization mass spectrometry, the results clearly demonstrated that ¹O₂ is directly involved in the formation of covalent crosslinks involving the amino acids histidine, lysine, and tryptophan.     

Characterization of yellow mombin biomass (Spondias mombin L.) for production of activated carbon

Journal of Thermal Analysis and Calorimetry - Large amounts of plant biomass generated daily and not harnessed for lack of adequate technologies. Based on this context, this study aimed to perform...     

Blend films based on biopolymers extracted from babassu mesocarp (Orbignya phalerata) for the electrochemical detection of methotrexate antineoplastic drug

Journal of Solid State Electrochemistry - Methotrexate (MTX) is an antineoplastic drug widely used in cancer therapies with potentially toxic activity. This paper describes the electrochemical...     

Measurement of relaxation times in extensional flow of weakly viscoelastic polymer solutions

The characterization of the extensional rheology of polymeric solutions is important in several applications and industrial processes. Filament stretching and capillary breakup rheometers have been developed to characterize the extensional properties of polymeric solutions, mostly for high-viscosity fluids. However, for low concentration polymer solutions, the measurements are difficult using available devices, in terms of the minimum viscosity and relaxation times that can be measured accurately. In addition, when the slow retraction method is used, solvent evaporation can affect the measurements for volatile solvents. In this work, a new setup was tested for filament breakup experiments using the slow retraction method, high-speed imaging techniques, and an immiscible oil bath to reduce solvent evaporation and facilitate particle tracking in the thinning filament. Extensional relaxation times above around 100 μs were measured with the device for dilute and semi-dilute polymer solutions. Particle tracking velocimetry was also used to measure the velocity in the filament and the corresponding elongation rate, and to compare with the values obtained from the measured exponential decay of the filament diameter.     

Three-dimensional flow of Newtonian and Boger fluids in square–square contractions

The flow of a Newtonian fluid and a Boger fluid through sudden square–square contractions was investigated experimentally aiming to characterize the flow and provide quantitative data for benchmarking in a complex three-dimensional flow. Visualizations of the flow patterns were undertaken using streak-line photography, detailed velocity field measurements were conducted using particle image velocimetry (PIV) and pressure drop measurements were performed in various geometries with different contraction ratios. For the Newtonian fluid, the experimental results are compared with numerical simulations performed using a finite volume method, and excellent agreement is found for the range of Reynolds number tested (Re₂ ≤ 23). For the viscoelastic case, recirculations are still present upstream of the contraction but we also observe other complex flow patterns that are dependent on contraction ratio (CR) and Deborah number (De₂) for the range of conditions studied: CR = 2.4, 4, 8, 12 and De₂ ≤ 150. For low contraction ratios strong divergent flow is observed upstream of the contraction, whereas for high contraction ratios there is no upstream divergent flow, except in the vicinity of the re-entrant corner where a localized atypical divergent flow is observed. For all contraction ratios studied, at sufficiently high Deborah numbers, strong elastic vortex enhancement upstream of the contraction is observed, which leads to the onset of a periodic complex flow at higher flow rates. The vortices observed under steady flow are not closed, and fluid elasticity was found to modify the flow direction within the recirculations as compared to that found for Newtonian fluids. The entry pressure drop, quantified using a Couette correction, was found to increase with the Deborah number for the higher contraction ratios.     

Laminar co-rotating Batchelor vortex merging

The dynamics of laminar co-rotating vortex pairs without axial flow have been recently thoroughly studied through theoretical, experimental and numerical studies, which revealed different instabilities contributing to the decay of the vortices. In this paper, the objective is to extend the analysis to the case of co-rotating vortices with axial flow at low Reynolds numbers. A high-order incompressible Navier–Stokes flow solver is used. The momentum equations are spatially discretized on a staggered mesh by finite differences and all derivatives are evaluated with 10th order compact finite difference schemes with RK-4 temporal discretization. The initial condition is a linear superposition of two co-rotating circular Batchelor vortices with q = 1. It is found that there is an initial evolution that resembles the evolution that single q = 1 vortices go through. Azimuthal disturbances grow and result in the appearance of large-scale helical sheets of vorticity. With the development of these instability waves, the axial velocity deficit is weakened. The redistribution of both angular and axial momentum between the core and the surroundings drives the vortex core to a more stable configuration, with a higher q value. After these processes, the evolution is somewhat similar to a pair of co-rotating Lamb–Oseen vortices. A three-dimensional instability develops, with a large band of unstable modes, with the most amplified mode corresponding scaling with the vortex initial separation distance. P. J. S. A. Ferreira de Sousa wishes to acknowledge the support of FCT—SFRH/BD/1129/2000 and SFRH/BPD/21778/2005.