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Keywords = structural breakup and recovery

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17 pages, 4336 KiB  
Article
New Supramolecular Hydrogels Based on Diastereomeric Dehydrotripeptide Mixtures for Potential Drug Delivery Applications
by Carlos B. P. Oliveira, André Carvalho, Renato B. Pereira, David M. Pereira, Loic Hilliou, Peter J. Jervis, José A. Martins and Paula M. T. Ferreira
Gels 2024, 10(10), 629; https://doi.org/10.3390/gels10100629 - 30 Sep 2024
Cited by 2 | Viewed by 2038
Abstract
Self-assembly of peptide building blocks offers unique opportunities for bottom-up preparation of exquisite nanostructures, nanoarchitectures, and nanostructured bulk materials, namely hydrogels. In this work we describe the synthesis, characterization, gelation, and rheological properties of new dehydrotripeptides, Cbz-L-Lys(Cbz)-L,D-Asp-∆Phe-OH [...] Read more.
Self-assembly of peptide building blocks offers unique opportunities for bottom-up preparation of exquisite nanostructures, nanoarchitectures, and nanostructured bulk materials, namely hydrogels. In this work we describe the synthesis, characterization, gelation, and rheological properties of new dehydrotripeptides, Cbz-L-Lys(Cbz)-L,D-Asp-∆Phe-OH and (2-Naph)-L-Lys(2-Naph)-L,D-Asp-∆Phe-OH, containing a N-terminal lysine residue Nα,ε-bis-capped with carboxybenzyl (Cbz) and 2-Naphthylacetyl (2-Naph) aromatic moieties, an aspartic acid residue (Asp), and a C-terminal dehydrophenylalanine (∆Phe) residue. The dehydrotripeptides were obtained as diastereomeric mixtures (L,L,Z and L,D,Z), presumably via aspartimide chemistry. The dehydrotripeptides afforded hydrogels at exceedingly low concentrations (0.1 and 0.04 wt%). The hydrogels revealed exceptional elasticity (G’ = 5.44 × 104 and 3.43 × 106 Pa) and self-healing properties. STEM studies showed that the diastereomers of the Cbz-capped peptide undergo co-assembly, generating a fibrillar 3D network, while the diastereomers of the 2-Naph-capped dehydropeptide seem to undergo self-sorting, originating a fibril network with embedded spheroidal nanostructures. The 2-Naph-capped hydrogel displayed full fast recovery following breakup by a mechanical stimulus. Spheroidal nanostructures are absent in the recovered hydrogel, as seen by STEM, suggesting that the mechanical stimulus triggers rearrangement of the spheroidal nanostructures into fibers. Overall, this study demonstrates that diastereomeric mixtures of peptides can be efficacious gelators. Importantly, these results suggest that the structure (size, aromaticity) of the capping group can have a directing effect on the self-assembly (co-assembly vs. self-sorting) of diastereomers. The cytotoxicity of the newly synthesized gelators was evaluated using human keratinocytes (HaCaT cell line). The results indicated that the two gelators exhibited some cytotoxicity, having a small impact on cell viability. In sustained release experiments, the influence of the charge on model drug compounds was assessed in relation to their release rate from the hydrogel matrix. The hydrogels demonstrated sustained release for methyl orange (anionic), while methylene blue (cationic) was retained within the network. Full article
(This article belongs to the Special Issue Recent Advances in Physical Gels and Their Applications)
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20 pages, 7378 KiB  
Article
The Influence of Oscillatory Frequency on the Structural Breakup and Recovery of Coastal Mud
by Hengye Gu, Shaohua Wang, Zhitong Su and Yuezhang Xia
J. Mar. Sci. Eng. 2023, 11(11), 2073; https://doi.org/10.3390/jmse11112073 - 30 Oct 2023
Cited by 1 | Viewed by 1275
Abstract
The structural breakup and recovery of coastal mud are closely related to wave propagation, mud transportation, and coastal morphology evolution. Due to the influence of climate, topography, and other factors, the wave frequency in marine environments is more variable than fixed. To investigate [...] Read more.
The structural breakup and recovery of coastal mud are closely related to wave propagation, mud transportation, and coastal morphology evolution. Due to the influence of climate, topography, and other factors, the wave frequency in marine environments is more variable than fixed. To investigate the mud structural breakup and recovery process under oscillatory shear loads with different frequencies, a series of oscillatory rheological experiments of the coastal mud collected from the tidal flats of Zhairuoshan Island, Zhejiang province, China, were carried out. The results revealed that the structural breakup of coastal mud had a two-step transition process. The fluidization occurs more rapidly at higher frequencies, but the influence of frequency on the two yield stresses is limited. In addition, frequency has a complex effect on the structural recovery of coastal mud. The normalized equilibrium storage modulus (G′/G0′) does not change monotonically with frequency. Moreover, the viscosity quickly approaches equilibrium when a shear load is applied. After that, when a low-frequency load is applied, G′/G0′ is no longer related to the pre-shear duration. However, when a high-frequency load is applied, G′/G0′ of the mud sample pre-sheared for 500 s is significantly larger than that of the sample pre-sheared to the minimum viscosity. This study is anticipated to provide reference and supplementary test data for understanding the interaction between waves of different frequencies and muddy seabed. Full article
(This article belongs to the Section Ocean Engineering)
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22 pages, 4642 KiB  
Article
Obtaining the Synthetic Fuels from Waste Plastic and Their Effect on Cavitation Formation in a Common-Rail Diesel Injector
by L. Kevorkijan, A. Palomar-Torres, E. Torres-Jiménez, C. Mata, I. Biluš and L. Lešnik
Sustainability 2023, 15(21), 15380; https://doi.org/10.3390/su152115380 - 27 Oct 2023
Cited by 4 | Viewed by 2735
Abstract
The presented paper addresses two significant issues of the present time. In general, the studies of the effect of synthetic fuels on cavitation formation and cavitation erosion prediction in the nozzle tip of common-rail diesel injectors were addressed. The first problem is plastic [...] Read more.
The presented paper addresses two significant issues of the present time. In general, the studies of the effect of synthetic fuels on cavitation formation and cavitation erosion prediction in the nozzle tip of common-rail diesel injectors were addressed. The first problem is plastic waste, which can have a significant negative environmental impact if not treated properly. Most plastic waste has high energy value, so it represents valuable material that can be used in resource recovery to produce various materials. One possible product is synthetic fuel, which can be produced using thermal and catalytic pyrolysis processes. The first issue addressed in the presented paper is the determination of fuel properties since they highly influence the fuel injection process, spray development, combustion, etc. The second is the prediction of cavitation development and cavitation erosion in a common-rail diesel injector when using pyrolytic oils from waste plastic. At first, pyrolytic oils from waste high- and low-density polyethylene were obtained using thermal and catalytic pyrolysis processes. Then, the obtained oils were further characterised. Finally, the properties of the obtained oils were implemented in the ANSYS FLUENT computational program and used in the study of the cavitation phenomena inside an injection nozzle hole. The cavitating flow in FLUENT was calculated using the Mixture Model and Zwart-Gerber-Belamri cavitation model. For the modelling of turbulence, a realisable k–ε model with Enhanced Wall Treatment was used, and an erosion risk indicator was chosen to compare predicted locations of cavitation erosion. The results indicate that the properties of the obtained pyrolytic oils have slightly lower density, surface tension and kinematic viscosity compared to conventional diesel fuel, but these minor differences influence the cavitation phenomenon inside the injection hole. The occurrence of cavitation is advanced when pyrolytic oils are used, and the length of cavitation structures is greater. This further influences the shift of the area of cavitation erosion prediction closer to the nozzle exit and increases its magnitude up to 26% compared to diesel fuel. All these differences have the potential to further influence the spray break-up process, combustion process and emission formation inside the combustion chamber. Full article
(This article belongs to the Section Energy Sustainability)
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22 pages, 28360 KiB  
Article
Structural Analysis and Paleostress Evolution in the Imiter Silver Mining Region, Eastern Anti Atlas, Morocco: Implications for Mineral Exploration
by Youssef Atif, Abderrahmane Soulaimani, Abdelhak Ait Lahna, Driss Yaagoub, Nasrrddine Youbi, Amin Beiranvand Pour and Mazlan Hashim
Minerals 2022, 12(12), 1563; https://doi.org/10.3390/min12121563 - 4 Dec 2022
Cited by 5 | Viewed by 3752
Abstract
Development and concentration of many ore deposits at the regional and district scales closely depend on structural geology, especially in polydeformed basements. The superposition of many deformation periods highlights the complexity of the structural context and expected potential location of mineralization zones. The [...] Read more.
Development and concentration of many ore deposits at the regional and district scales closely depend on structural geology, especially in polydeformed basements. The superposition of many deformation periods highlights the complexity of the structural context and expected potential location of mineralization zones. The formation and concentration of hydrothermal ore deposits is highly dependent on structural controls. On the NE flank of the Saghro massif (Eastern Anti-Atlas, Morocco), the Imiter silver mining region has been affected by multiple tectonic events since the Precambrian and throughout the Phanerozoic. In this investigation, a structural analysis of the different geological units revealed multi-stage deformation, beginning with the late Pan-African-Cadomian event, and ending with the last Cenozoic exhumation of the area. At least eight tectonic regimes have been identified. The Imiter basement, formed by the Cryogenian-early Ediacaran “flysch-like” Saghro Group, has been folded in low-grade metamorphic conditions, followed by an ENE-WSW brittle compressive event. These deformations occurred before to the early Ediacaran during the compressional and/or transpressional late Pan-African-Cadomian events (600–580 Ma). The unconformably overlaying deposition of the late Ediacaran Ouarzazate Group takes place in a WNW-ESE extensional setting and then involved in a NNW-SSE compressional event that occurred concurrently with a regional exhumation and erosion stages. A similar extensional event appears to have controlled the middle Cambrian sedimentation, the oldest Paleozoic deposits in this area. During the late Carboniferous, Variscan shortening was recorded by NW-SE transpressional deformation responsible for combined dextral strike-slip and southward thrusts. The Imiter silver mining region is part of the Moroccan Sub-Meseta Zone along with Paleozoic inliers of the Skoura and Tamlelt on the southern side of the High Atlas. The Mesozoic evolution began with the Late Triassic NNW-SSW transtensional tectonic regime with a northeast trending CAMP (Central Atlantic Magmatic Province) dyke during the Pangea breakup. Ultimately, the Imiter silver mining region experienced NNW-SSE Atlasic shortening during the uplift of the adjacent High Atlas. Over time, the direction of implemented tectonic stress and its effect on various geological units can elucidate the relationship between tectonism and hydrothermal silver mineralization in the Imiter region. In conclusion, structural analysis and investigation of paleostress development can be one of the most important factors for successful exploration plan and resource recovery in the Imiter region. An analysis of geological structures in determining feasible mineralization zones is crucial for future safe mining operation in the study area and can be extrapolated to other ore mining regions. Full article
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