Electrospinning is a promising technique for the fabrication of bioscaffolds in tissue engineering applications. Pertaining issues of multiple polymer jets and bending instabilities result in random paths which lend poor controllability over scaffolds morphology for affecting the porosity and mechanical stability. The present study alleviates these challenges by demonstrating a novel self-directing single jet taking a specifically patterned path to deposit fibers into circular and uniform scaffolds without tuning any externally controlled parameters. High-speed camera observation revealed that the charge retention and dissipation on the collected fibers caused rapid autojet switching between the two jetting modes, namely, a microcantilever-like armed jet motion and a whipping motion, which sequentially expand the area and thickness of the scaffolds, respectively, in a layered-like fashion. The physical properties showed that the self-switching dual-jet modes generated multilayered microfibrous scaffolds (MFSs) with dual morphologies and varied fiber packing density, thereby establishing the gradient porosity and mechanical strength (through buckled fibers) in the scaffolds. In vitro studies showed that as-spun scaffolds are cell-permeable hierarchical 3D microporous structures enabling lateral cell seeding into multiple layers. The cell proliferation on days 6 and 9 increased 21% and 38% correspondingly on MFSs than on nanofibrous scaffolds (NFSs) done by conventional multijets electrospinning. Remarkably, this novel and single-step process is highly reproducible and tunable for developing fibrous scaffolds for tissue engineering applications.
The ability of band offsets at multiferroic/metal and multiferroic/electrolyte interfaces in controlling charge transfer and thus altering the photoactivity performance has sparked significant attention in solar energy conversion applications. Here, we demonstrate that the band offsets of the two interfaces play the key role in determining charge transport direction in a downward self-polarized BFO film. Electrons tend to move to BFO/electrolyte interface for water reduction. Our experimental and first-principle calculations reveal that the presence of neodymium (Nd) dopants in BFO enhances the photoelectrochemical performance by reduction of the local electron-hole pair recombination sites and modulation of the band gap to improve the visible light absorption. This opens a promising route to the heterostructure design by modulating the band gap to promote efficient charge transfer.
Transition metal chalcogenides (TMCs) have gained worldwide interest owing to their outstanding renewable energy conversion capability. However, the poor mechanical flexibility of most existing TMCs limits their practical commercial applications. Herein, triggered by the recent and imperative synthesis of highly ductile α-Ag2S, an effective approach based on evolutionary algorithm and ab initio total-energy calculations for determining stable, ductile phases of bulk and two-dimensional Ag x Se1-x and Ag x Te1-x compounds was implemented. The calculations correctly reproduced the global minimum bulk stoichiometric P212121-Ag8Se4 and P21/c-Ag8Te4 structures. Recently reported metastable AgTe3 was also revealed but it lacks dynamical stability. Further single-layered screening unveiled two new monolayer P4/nmm-Ag4Se2 and C2-Ag8Te4 phases. Orthorhombic Ag8Se4 crystalline has a narrow, direct band gap of 0.26 eV that increases to 2.68 eV when transforms to tetragonal Ag4Se2 monolayer. Interestingly, metallic P21/c-Ag8Te4 changes to semiconductor when thinned down to monolayer, exhibiting a band gap of 1.60 eV. Present findings confirm their strong stability from mechanical and thermodynamic aspects, with reasonable Vickers hardness, bone-like Young's modulus (E) and high machinability observed in bulk phases. Detailed analysis of the dielectric functions ε(ω), absorption coefficient α(ω), power conversion efficiency (PCE) and refractive index n(ω) of monolayers are reported for the first time. Fine theoretical PCE (SLME method ∼11-28%), relatively high n(0) (1.59-1.93), and sizable α(ω) (104-105 cm-1) that spans the infrared to visible regions indicate their prospects in optoelectronics and photoluminescence applications. Effective strategies to improve the temperature dependent power factor (PF) and figure of merit (ZT) are illustrated, including optimizing the carrier concentration. With decreasing thickness, ZT of p-doped Ag-Se was found to rise from approximately 0.15-0.90 at 300 K, leading to a record high theoretical conversion efficiency of ∼12.0%. The results presented foreshadow their potential application in a hybrid device that combines the photovoltaic and thermoelectric technologies.
With increased awareness on the importance of gloves arising from the COVID-19 pandemic, people are expected to continue using them even after the pandemic recedes. This scenario in a way increased the rubber solid waste disposal problem; therefore, the production of biodegradable gloves may be an option to overcome this problem. However, the need to study the shelf life of biodegradable gloves is crucial before commercialization. There are well-established models to address the failure properties of gloves as stated in the American Society for Testing and Material (ASTM) D7160. In this study, polysaccharide-based material-filled natural rubber latex (PFNRL) gloves, which are biodegradable gloves, were subjected to an accelerated aging process at different temperatures of 50-80 °C for 1-120 days. Prediction models based on Arrhenius and shift factors were used to estimate the shelf life of the PFNRL gloves. Based on the results obtained, the estimated time for the PFNRL gloves to retain 75% of their tensile strength at shelf temperature (30 °C) based on Arrhenius and shift factor models was 2.8 years. Verification on the activation energy based on the shift factor model indicated that the shelf life of PFNRL gloves is 2.9 years, which is only a 3.6% difference. The value obtained is aligned with the requirement in accordance with ASTM D7160, which states that only up to a maximum of 3 years' shelf life is allowed for the gloves under accelerated aging conditions.
Many studies have investigated natural convection heat transfer from the outside surface of horizontal and vertical cylinders in both constant heat flux and temperature conditions. However, there are poor studies in natural convection from inclined cylinders. In this study, free convection heat transfer was examined experimentally from the outside surface of a cylinder for glycerol and water at various heat fluxes. The tests were performed at 10 different inclination angles of the cylinder, namely, φ = 0°, 10°, 20°, 30°, 40°, 50°, 60°, 70°, 80°, and 90°, measured from the horizon. Our results indicated that the average Nusselt number reduces with the growth in the inclination of the cylinder to the horizon at the same heat flux, and the average Nusselt number enhanced with the growth in heat flux at the same angle. Also, the average Nusselt number of water is greater than that of glycerol. A new experimental model for predicting the average Nusselt number is suggested, which has a satisfactory accuracy for experimental data.
The K2NiF6 catalytic effect on the NaAlH4 dehydrogenation properties was studied in this work. The desorption temperature was studied using temperature-programmed desorption and exhibited a lower onset hydrogen release after doped with different wt % of K2NiF6 (5, 10, 15 and 20 wt %). It was found that the NaAlH4 doped with 5 wt % K2NiF6 showed the optimal value that can reduce the onset desorption temperature of about 160 °C compared to 190 °C for the milled NaAlH4. The NaAlH4 + 5 wt % K2NiF6 sample showed faster desorption kinetics where 1.5 wt % of hydrogen was released in 30 min at 150 °C. In contrast, the milled NaAlH4 only released about 0.2 wt % within the same time and temperature. From the Kissinger analysis, the apparent activation energy was 114.7 kJ/mol for the milled NaAlH4 and 89.9 kJ/mol for the NaAlH4-doped 5 wt % K2NiF6, indicating that the addition of K2NiF6 reduced the activation energy for hydrogen desorption of NaAlH4. It is deduced that the new phases of AlNi, NaF, and KH that were formed in situ during the dehydrogenation process are the key factors for the improvement of dehydrogenation properties of NaAlH4.
Hydrate formation is a common challenge in the oil and gas industry when natural gas is transported under cold conditions in the presence of water. Coatings are one of the solutions that have shown to be a promising approach to address this challenge. However, this strategy suffers from the intrinsic existence of a solid-liquid interface causing a high rate of hydrate nucleation and high hydrate adhesion strength. This proof-of-concept study highlights the performance of a magnetic slippery surface to prevent hydrate adhesion at atmospheric pressure using tetrahydrofuran hydrates. The coating consisted of a hydrocarbon-based magnetic fluid, which was applied to a metal surface to create an interface that lowered the hydrate adhesion strength on the surface. The performance of these new surfaces under static and dynamic (under fluid flow) conditions shows that the magnetic coating gel can be a potential inhibitor for hydrate adhesion as it reduced the torque value after the formation of hydrates.
This study presents the electromagnetic (EM) characterization of a multiwalled carbon nanotubes (MWCNT)-silver nanoparticles (AgNP)-reinforced poly(vinyl alcohol) (PVA) hybrid nanocomposite fabricated via the solution mixing technique. Primarily, the structure and morphological properties of the PVA/MWCNT-AgNP hybrid nanocomposite are confirmed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The complex permittivity (ε*) and permeability (μ*), as well as the electromagnetic scattering parameters are measured using a PNA network analyzer equipped with X-band waveguide. The results showed an enhanced permittivity (ε' ≈ 25) value of the hybrid nanocomposite in the frequency range of 8-12 GHz. However, the permeability decreased to almost zero (μ' ≈ 0.4) since the inclusion of AgNP with an average particle size of 40 nm is not susceptible to magnetization and causes higher magnetic losses (tan δμ) than dielectric losses (tan δε). Remarkably, the hybrid nanocomposite reduced transmission of electromagnetic (EM) wave by nearly 60% in comparison to PVA/MWCNT. This is attributed to the enhanced absorption and reflection at the nanotubes, and metal-dielectric interfaces have induced multiple internal reflections owing to the porous structure of the nanocomposite. The prospect of the PVA/MWCNT-AgNP hybrid nanocomposite is favorable as a thin absorbing material for EM shielding applications.
A series of novel α-furfuryl-2-alkylaminophosphonates have been efficiently synthesized from the one-pot three-component classical Kabachnik-Fields reaction in a green chemical approach by addition of an in situ generated dialkylphosphite to Schiff's base of aldehydes and amines by using environmental and eco-friendly silica gel supported iodine as a catalyst by microwave irradiation. The advantage of this protocol is simplicity in experimental procedures and products were resulted in high isolated yields. The synthesized α-furfuryl-2-alkylaminophosphonates were screened to in vitro antioxidant and plant growth regulatory activities and some are found to be potent with antioxidant and plant growth regulatory activities. These in vitro studies have been further supported by ADMET (absorption, distribution, metabolism, excretion, and toxicity), quantitative structure-activity relationship, molecular docking, and bioactivity studies and identified that they were potentially bound to the GLN340 amino acid residue in chain C of 1DNU protein and TYR597 amino acid residue in chain A of 4M7E protein, causing potential exhibition of antioxidant and plant growth regulatory activities. Eventually, title compounds are identified as good blood-brain barrier (BBB)-penetrable compounds and are considered as proficient central nervous system active and neuroprotective antioxidant agents as the neuroprotective property is determined with BBB penetration thresholds.
Oil and grease remain the dominant contaminants in the palm oil mill effluent (POME) despite the conventional treatment of POME. The removal of residual oil from palm oil-water mixture (POME model) using the progressive freezing process was investigated. An optimization technique called response surface methodology (RSM) with the design of rotatable central composite design was applied to figure out the optimum experimental variables generated by Design-Expert software (version 6.0.4. Stat-Ease, trial version). Besides, RSM also helps to investigate the interactive effects among the independent variables compared to one factor at a time. The variables involved are coolant temperature, XA (4-12 °C), freezing time, XB (20-60 min), and circulation flow, XC (200-600 rpm). The statistical analysis showed that a two-factor interaction model was developed using the obtained experimental data with a coefficient of determination (R2) value of 0.9582. From the RSM-generated model, the optimum conditions for extraction of oil from the POME model were a coolant temperature of 6 °C in 50 min freezing time with a circulation flowrate of 500 rpm. The validation of the model showed that the predicted oil yield and experimental oil yield were 92.56 and 93.20%, respectively.
An increase of nucleate pool boiling with the use of different fluid properties has received much attention. In particular, the presence of nanostructures in fluids to enhance boiling was given special consideration. This study compares the effects of graphene nanoplatelet (GNP), functionalized GNP with polyethylene glycol (PEG), and multiwalled carbon nanotube (CNT) nanofluids on the pool boiling heat transfer coefficient and the critical heat flux (CHF). Our findings showed that at the same concentration, CHF for functionalized GNP with PEG (GNP-PEG)/deionized water (DW) nanofluids was higher in comparison with GNP- and CNT-based nanofluids. The CHF of the GNP/DW nanofluids was also higher than that of CNT/DW nanofluids. The CHF of GNP-PEG was 72% greater than that of DW at the concentration of 0.1 wt %. There is good agreement between measured critical heat fluxes and the Kandlikar correlation. In addition, the current results proved that the GNP-PEG/DW nanofluids are highly stable over 3 months at a concentration of 0.1 wt %.
The main purpose of this study is to determine shoreline change in Bengkalis Cape, Riau Province, Indonesia using sediment samples analysis, satellite images, and oceanographic parameters. The samples were collected at five stations by using sediment grab and oceanographic observation was also carried out at each station in November 2015. The southern part of Bengkalis Cape is characterised by fine-grain sediments (mud) and high rate of accretion that reaches 29.77 metre/year, and is influenced by weak tidal currents with a velocity of less than 0.06 m/s and low wave energy. In contrast, the northern part is occupied by coarse-grain sediments (sand) which is characterised by high rate of abrasion as shown in the image data for 20 years; 1995-2015 reaches 38.02 metre/year, and is under the influence of strong tidal current (0.16 m/s) and high wave energy. The major contributing factor for the shoreline change is the current system which flowing from Malacca strait to the shore area and sediments deposition in the area.
The title compound, [Sn(CH(3))(2)(C(5)H(10)NO(2)S(2))(2)], has crystallographic mirror symmetry (C-Sn-C on mirror plane) and the coordination polyhedron around the Sn atom is a tetrahedron [C-Sn-C 139.3 (2) degrees and S-Sn-S 82.3 (1) degrees ] distorted towards a skew-trapezoidal bipyramid owing to an intramolecular Sn.S contact [3.0427 (6) A]. The molecules are linked into a linear chain by intermolecular O-H.O hydrogen bonds [O.O 2.646 (3) A].
The title compound, C17H15N3O2, is a monoclinic polymorph (P21/c with Z' = 1) of the previously reported triclinic (P-1 with Z' = 2) form [Gajera et al. (2013 ▸). Acta Cryst. E69, o736-o737]. The mol-ecule in the monoclinic polymorph features a central pyrazolyl ring with an N-bound p-tolyl group and a C-bound 1,3-benzodioxolyl fused-ring system on either side of the C atom bearing the amino group. The dihedral angles between the central ring and the N- and C-bound rings are 50.06 (5) and 27.27 (5)°, respectively. The angle between the pendent rings is 77.31 (4)°, indicating the mol-ecule has a twisted conformation. The five-membered dioxolyl ring has an envelope conformation with the methyl-ene C atom being the flap. The relative disposition of the amino and dioxolyl substituents is syn. One of the independent mol-ecules in the triclinic form has a similar syn disposition but the other has an anti arrangement of these substituents. In the crystal structure of the monoclinic form, mol-ecules assemble into supra-molecular helical chains via amino-pyrazolyl N-H⋯N hydrogen bonds. These are linked into layers via C-H⋯π inter-actions, and layers stack along the a axis with no specific inter-actions between them.
In the title compounds, (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(2-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (I), (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (II) and (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3,4-di-meth-oxy-phen-yl)prop-2-en-1-one], C28H26O6 (III), the asymmetric unit consists of a half-mol-ecule, completed by crystallographic inversion symmetry. The dihedral angles between the central and terminal benzene rings are 56.98 (8), 7.74 (7) and 7.73 (7)° for (I), (II) and (III), respectively. In the crystal of (I), mol-ecules are linked by pairs of C-H⋯π inter-actions into chains running parallel to [101]. The packing for (II) and (III), features inversion dimers linked by pairs of C-H⋯O hydrogen bonds, forming R2(2)(16) and R2(2)(14) ring motifs, respectively, as parts of [201] and [101] chains, respectively.
The crystal and mol-ecular structures of the two title organotin di-thio-carbamate compounds, [Sn(C4H9)2(C7H14NO2S2)2], (I), and [Sn(C6H5)3(C5H10NOS2)], (II), are described. Both structures feature asymmetrically bound di-thio-carbamate ligands leading to a skew-trapezoidal bipyramidal geometry for the metal atom in (I) and a distorted tetra-hedral geometry in (II). The complete mol-ecule of (I) is generated by a crystallographic twofold axis (Sn site symmetry 2). In the crystal of (I), mol-ecules self-assemble into a supra-molecular array parallel to (10-1) via methyl-ene-C-H⋯O(meth-oxy) inter-actions. In the crystal of (II), supra-molecular dimers are formed via pairs of weak phenyl-C-H⋯π(phen-yl) contacts. In each of (I) and (II), the specified assemblies connect into a three-dimensional architecture without directional inter-actions between them. Hirshfeld surface analyses confirm the importance of H⋯H contacts in the mol-ecular packing of each of (I) and (II), and in the case of (I), highlight the importance of short meth-oxy-H⋯H(but-yl) contacts between layers.
A new polymorphic form of the title compound, C8H8O3, is described in the centrosymmetric monoclinic space group P21/c with Z' = 1 as compared to the first polymorph, which crystallizes with two conformers (Z' = 2) in the asymmetric unit in the same space group. In the crystal of the second polymorph, inversion dimers linked by O-H⋯O hydrogen bonds occur and these are linked into zigzag chains, propagating along the b-axis direction by C-H⋯O links. The crystal structure also features a weak π-π inter-action, with a centroid-to-centroid distance of 3.8018 (6) Å. The second polymorph of the title compound is less stable than the reported first polymorph, as indicated by its smaller calculated lattice energy.
The asymmetric unit of the title 1:2 co-crystal, C14H10O4S2·2C7H6O2, comprises half a mol-ecule of di-thiodi-benzoic acid [systematic name: 2-[(2-carb-oxy-phen-yl)disulfan-yl]benzoic acid, DTBA], as the mol-ecule is located about a twofold axis of symmetry, and a mol-ecule of benzoic acid (BA). The DTBA mol-ecule is twisted about the di-sulfide bond [the C-S-S-C torsion angle is -83.19 (8)°] resulting in a near perpendicular relationship between the benzene rings [dihedral angle = 71.19 (4)°]. The carb-oxy-lic acid group is almost co-planar with the benzene ring to which it is bonded [dihedral angle = 4.82 (12)°]. A similar near co-planar relationship pertains for the BA mol-ecule [dihedral angle = 3.65 (15)°]. Three-mol-ecule aggregates are formed in the crystal whereby two BA mol-ecules are connected to a DTBA mol-ecule via hy-droxy-O-H⋯O(hydroxy) hydrogen bonds and eight-membered {⋯HOC=O}2 synthons. These are connected into a supra-molecular layer in the ab plane through C-H⋯O inter-actions. The inter-actions between layers to consolidate the three-dimensional architecture are π-π stacking inter-actions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) Å] and parallel DTBA-hy-droxy-O⋯π(BA) contacts [O⋯ring centroid separation = 3.9049 (14) Å]. The importance of the specified inter-actions as well as other weaker contacts, e.g. π-π and C-H⋯S, are indicated in the analysis of the calculated Hirshfeld surface and inter-action energies.
The crystal and mol-ecular structures of C14H12Cl2, (I), and C14H12Br2, (II), are described. The asymmetric unit of (I) comprises two independent mol-ecules, A and B, each disposed about a centre of inversion. Each mol-ecule approximates mirror symmetry [the Cb-Cb-Ce-Ce torsion angles = -83.46 (19) and 95.17 (17)° for A, and -83.7 (2) and 94.75 (19)° for B; b = benzene and e = ethyl-ene]. By contrast, the mol-ecule in (II) is twisted, as seen in the dihedral angle of 59.29 (11)° between the benzene rings cf. 0° in (I). The mol-ecular packing of (I) features benzene-C-H⋯π(benzene) and Cl⋯Cl contacts that lead to an open three-dimensional (3D) architecture that enables twofold 3D-3D inter-penetration. The presence of benzene-C-H⋯π(benzene) and Br⋯Br contacts in the crystal of (II) consolidate the 3D architecture. The analysis of the calculated Hirshfeld surfaces confirm the influence of the benzene-C-H⋯π(benzene) and X⋯X contacts on the mol-ecular packing and show that, to a first approximation, H⋯H, C⋯H/H⋯C and C⋯X/X⋯C contacts dominate the packing, each contributing about 30% to the overall surface in each of (I) and (II). The analysis also clearly differentiates between the A and B mol-ecules of (I).
The common feature of the title compounds, [Zn(C5H10NO2S2)2(C10H8N2)]·2H2O, (I), and [Zn(C6H12NOS2)2(C10H8N2)], (II), is the location of the Zn(II) atoms on a twofold rotation axis. Further, each Zn(II) atom is chelated by two symmetry-equivalent and symmetrically coordinating di-thio-carbamate ligands and a 2,2'-bi-pyridine ligand. The resulting N2S4 coordination geometry is based on a highly distorted octa-hedron in each case. In the mol-ecular packing of (I), supra-molecular ladders mediated by O-H⋯O hydrogen bonding are found whereby the uprights are defined by {⋯HO(water)⋯HO(hy-droxy)⋯} n chains parallel to the a axis and with the rungs defined by 'Zn[S2CN(CH2CH2)2]2'. The water mol-ecules connect the ladders into a supra-molecular layer parallel to the ab plane via water-O-H⋯S and pyridyl-C-H⋯O(water) inter-actions, with the connections between layers being of the type pyridyl-C-H⋯S. In (II), supra-molecular layers parallel to the ab plane are sustained by hy-droxy-O-H⋯S hydrogen bonds with connections between layers being of the type pyridyl-C-H⋯S.