This paper is devoted to the steady-state rheological properties of two new kinds of ferrofluids. One of these was constituted by CoNi nanospheres of 24 nm in diameter, whereas the other by CoNi ...nanofibers of 56 nm in length and 6.6 nm in width. These ferrofluids were subjected to shear rate ramps under the presence of magnetic fields of different intensity, and the corresponding shear stress values were measured. From the obtained rheograms (shear stress vs shear rate curves) the values of both the static and the dynamic yield stresses were obtained as a function of the magnetic field. The magnetoviscous effect was also obtained as a function of both the shear rate and the magnetic field. The experimental results demonstrate that upon magnetic field application these new ferrofluids develop yield stresses and magnetoviscous effects much greater than those of conventional ferrofluids, based on nanospheres of approximately 10 nm in diameter. Besides some expected differences, such as the stronger magnetorheological effect in the case of ferrofluids based on nanofibers, some intriguing differences are found between the rheological behaviors of nanofiber ferrofluids and nanosphere ferrofluid. First, upon field application the rheograms of nanofiber ferrofluids present N-shaped dependence of the shear stress on the shear rate. The decreasing part of the rheograms takes place at low shear rate. These regions of negative differential viscosity, and therefore, unstable flow is not observed in the case of nanosphere ferrofluids. The second intriguing difference concerns the curvature of the yield stress vs magnetic field curves. This curvature is negative in the case of nanosphere ferrofluid, giving rise to saturation of the yield stress at medium field, as expected. However, in the case of nanofiber ferrofluid this curvature is positive, which means a faster increase of the yield stress with the magnetic field the higher the magnitude of the latter. These interesting differences may be due to the existence of strong interparticle solid friction in the case of nanofiber ferrofluids. Finally, theoretical models for the static yield stress of the ferrofluids were developed. These models consider that upon field application the ferrofluid nanoparticles are condensed in drops of dense phase. These drops tend to be aligned along the field direction, opposing the flow of the ferrofluids and being responsible for the static quasielastic deformation and the yield-stress phenomena. By considering the existence of interparticle dry friction only in the case of nanofiber ferrofluids, the developed models predicted quite well not only the magnitude of the static yield stress but also the differences in curvature of the yield stress vs magnetic field curves.
Suspensions of micrometer-sized iron particles (10 vol %) dispersed in kerosene and stabilized by addition of organoclay particles were prepared. The magnetization curves of these suspensions were ...measured, and their sedimentation and redispersion behaviors were analyzed as a function of clay concentration by means of optical and rheological methods. Furthermore, their magnetorheological properties were investigated using a controlled rate magnetorheometer and the effect of clay concentration on these properties was also analyzed. These experiments showed that the addition of clay slows down iron particle settling and eases the redispersion of the iron-based suspensions without masking their magnetorheological properties. Two mechanisms were found to be involved in this behavior: (i) the formation of a clay gel network and (ii) the presence of heterogeneous iron−clay adhesion.
Phagocytic cells capture and kill most invader microbes within the bactericidal phagosome, but some pathogens subvert killing by damaging the compartment and escaping to the cytosol. To prevent the ...leakage of pathogen virulence and host defence factors, as well as bacteria escape, host cells have to contain and repair the membrane damage, or finally eliminate the cytosolic bacteria. All eukaryotic cells engage various repair mechanisms to ensure plasma membrane integrity and proper compartmentalization of organelles, including the Endosomal Sorting Complex Required for Transport (ESCRT) and autophagy machineries. We show that during infection of Dictyostelium discoideum with Mycobacterium marinum, the ESCRT-I component Tsg101, the ESCRT-III protein Snf7/Chmp4/Vps32 and the AAA-ATPase Vps4 are recruited to sites of damage at the Mycobacterium-containing vacuole. Interestingly, damage separately recruits the ESCRT and the autophagy machineries. In addition, the recruitment of Vps32 and Vps4 to repair sterile membrane damage depends on Tsg101 but appears independent of Ca2+. Finally, in absence of Tsg101, M. marinum accesses prematurely the cytosol, where the autophagy machinery restricts its growth. We propose that ESCRT has an evolutionary conserved function to repair small membrane damage and to contain intracellular pathogens in intact compartments.
This article introduces a new and unobtrusive wearable monitoring device based on electrodermal activity (EDA) to be used in health-related computing systems. This paper introduces the description of ...the wearable device capable of acquiring the EDA of a subject in order to detect his/her calm/distress condition from the acquired physiological signals. The lightweight wearable device is placed in the wrist of the subject to allow continuous physiological measurements. With the aim of validating the correct operation of the wearable EDA device, pictures from the International Affective Picture System are used in a control experiment involving fifty participants. The collected signals are processed, features are extracted and a statistical analysis is performed on the calm/distress condition classification. The results show that the wearable device solely based on EDA signal processing reports around 89% accuracy when distinguishing calm condition from distress condition.
A novel torsional wave sensor designed to characterize mechanical properties of soft tissues is presented in this work. Elastography is a widely used technique since the 1990s to map tissue ...stiffness. Moreover, quantitative elastography uses the velocity of shear waves to achieve the shear stiffness. This technique exhibits significant limitations caused by the difficulty of the separation between longitudinal and shear waves and the pressure applied while measuring. To overcome these drawbacks, the proposed torsional wave sensor can isolate a pure shear wave, avoiding the possibility of multiple wave interference. It comprises a rotational actuator disk and a piezoceramic receiver ring circumferentially aligned. Both allow the transmission of shear waves that interact with the tissue before being received. Experimental tests are performed using tissue mimicking phantoms and cervical tissues. One contribution is a sensor sensitivity study that has been conducted to evaluate the robustness of the new proposed torsional wave elastography (TWE) technique. The variables object of the study are both the applied pressure and the angle of incidence sensor-phantom. The other contribution consists of a cervical tissue characterization. To this end, three rheological models have fit the experimental data and a static independent testing method has been performed. The proposed methodology permits the reconstruction of the mechanical constants from the propagated shear wave, providing a proof of principle and warranting further studies to confirm the validity of the results.
The generation of biomimetic and biocompatible artificial tissues is the basic research objective for tissue engineering (TE). In this sense, the biofabrication of scaffolds that resemble the ...tissues' extracellular matrix is an essential aim in this field. Uncompressed and nanostructured fibrin-agarose hydrogels (FAH and NFAH, respectively) have emerged as promising scaffolds in TE, but their structure and biomechanical properties must be improved in order to broaden their TE applications. Here, we generated and characterized novel membrane-like models with increased structural and biomechanical properties based on the chemical cross-linking of FAH and NFAH with genipin (GP at 0.1%, 0.25%, 0.5% and 0.75%). Furthermore, the scaffolds were subjected to rheological (G, G', G″ modulus), ultrastructural and ex vivo biocompatibility analyses. Results showed that all GP concentrations increased the stiffness (G) and especially the elasticity (G') of FAH and NFAH. Ultrastructural analyses demonstrated that GP and nanostructuration of FAH allowed us to control the porosity of FAH. In addition, biological studies revealed that higher concentration of GP (0.75%) started to compromise the cell function and viability. Finally, this study demonstrated the possibility to generate natural and biocompatible FAH and NFAH with improved structural and biomechanical properties by using 0.1%-0.5% of GP. However, further in vivo studies are needed in order to demonstrate the biocompatibility, biodegradability and regeneration capability of these cross-linked scaffolds.
To evaluate the influence of printing orientation on flexural strength (σf) and elastic modulus (E) of different 3D printing dental restorative resins.
Bar-shaped specimens (n = 20) were fabricated ...from two SLA-printed resins (FT- Formlabs Temporary, and FP- Formlabs Permanent) and two DLP-printed resins (DFT- Detax Freeprint Temp, and GCT- GC Temporary) using two building orientations (0º and 90º). The 3D-printed structures were aged (14 d) before submitted to three-point bending in 37ºC distilled water at a crosshead speed of 1.0 ± 0.3 mm/min until fracture to calculate the σf and the E values. The fractured surfaces were evaluated using stereomicroscopy and scanning electron microscopy (SEM) following fractography principles. Data were statistically analyzed using two-way ANOVA and Tukey post-hoc (α = 0.001).
FP and FT showed significantly higher E values than DFT and GCT, irrespectively of printing orientation (p < 0.001). There was no statistical difference between the building orientations (0º and 90º) for the mean σf and E values for the resin materials evaluated. Fractographic characteristics were similar for the surface fracture from all the materials evaluated, showing typical brittle fracture behavior.
Printing orientation did not influence of flexural strength and elastic modulus values for the 3D-printed resin structures evaluated. Surface topography was mostly governed by the 3D printer type.
•Mechanical properties such as flexural strength and elastic modulus were not affected by the printing angle.•The surface topography of the evaluated 3D-printing resins is mostly governed by the printer type.•Typical brittle fracture features were found for the evaluated 3D-printing resins.
As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress ...charge recombination. Here we investigate two series of in-chain donor–acceptor copolymers, PTPDnT and PBTInT, based on thieno3,4-cpyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengths scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with “outward” alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm2/(V s)). These characteristics contribute to the exceptional ∼80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1–4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.
Polycyclic aromatic hydrocarbons with an open-shell singlet biradical ground state are of fundamental interest and have potential applications in materials science. However, the inherent high ...reactivity makes their synthesis and characterization very challenging. In this work, a convenient synthetic route was developed to synthesize two kinetically blocked heptazethrene (HZ-TIPS) and octazethrene (OZ-TIPS) compounds with good stability. Their ground-state electronic structures were systematically investigated by a combination of different experimental methods, including steady-state and transient absorption spectroscopy, variable temperature NMR, electron spin resonance (ESR), superconducting quantum interfering device (SQUID), FT Raman, and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. All these demonstrated that the heptazethrene derivative HZ-TIPS has a closed-shell ground state while its octazethrene analogue OZ-TIPS with a smaller energy gap exists as an open-shell singlet biradical with a large measured biradical character (y = 0.56). Large two-photon absorption (TPA) cross sections (σ(2)) were determined for HZ-TIPS (σ(2) max = 920 GM at 1250 nm) and OZ-TIPS (σ(2) max = 1200 GM at 1250 nm). In addition, HZ-TIPS and OZ-TIPS show a closely stacked 1D polymer chain in single crystals.
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