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1.
Proc Natl Acad Sci U S A ; 121(41): e2407030121, 2024 Oct 08.
Article de Anglais | MEDLINE | ID: mdl-39356669

RÉSUMÉ

The ability of vitrification when crossing the glass transition temperature (Tg) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at ~136 K must be interpreted as an annealing prepeak, also referred to as the "shadow glass transition." Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.

2.
J Contemp Dent Pract ; 25(5): 486-493, 2024 May 01.
Article de Anglais | MEDLINE | ID: mdl-39364849

RÉSUMÉ

AIM AND OBJECTIVES: To characterize and analyze the structural presentation of a new denture base copolymer with a spiro-acetal cross-linker at 10 and 20 wt.% concentrations by nuclear magnetic resonance (NMR) and field emission scanning electron microscopy-energy-dispersive X-ray (FESEM-EDX) spectroscopies. Also, to evaluate the glass transition temperature (TG) of the new copolymer. MATERIALS AND METHODS: The investigational groups G10 and G20 were heat-cured with the new spiro-acetal cross-linker at the above-mentioned concentrations, respectively. The control group G0 was heat-cured without the new cross-linker. Nuclear magnetic resonance and EDX spectroscopies determined the copolymerization along with elemental composition. The surface characteristics were discerned by FESEM. Differential scanning calorimetry was employed to evaluate the TG of the resultant copolymer. Appropriate statistical operations were performed to compare the mean TG of the groups. RESULTS: The new copolymer's structure with the spiro-acetal cross-linker was configured with protons, carbons, aluminum, zirconium, yttrium, and silicon atoms. The TG of the resultant copolymer was high when compared with the G0. The 20 wt.% spiro-acetal cross-linker in the copolymer exhibited the highest TG. CONCLUSION: The spiro-acetal cross-linking comonomer incorporated in the heat-cure denture polymer produced a new denture base copolymer with elevated TG. The resultant configuration of the new copolymer was characterized, structurally presented, and confirmed. CLINICAL SIGNIFICANCE: The new copolymer might exhibit augmented strength due to the copolymerized spiro-acetal cross-linker. Moreover, the smooth and regular surface of the copolymer would have minimum or negligible microbial adhesion due to the hydrophobicity of the spiro-acetal comonomer incorporated in the denture base composition. How to cite this article: Ravivarman C, Ajay R, Saatwika L, et al. Structure, Surface Topography, and Glass Transition Temperature of Dental Poly (Methyl Methacrylate) Resin Conjugated with 3,9-bisethenyl-2,4,8,10-tetraoxaspiro [5,5] Undecane as Cross-linker: An In Vitro Research. J Contemp Dent Pract 2024;25(5):486-493.


Sujet(s)
Poly(méthacrylate de méthyle) , Propriétés de surface , Température de transition , Poly(méthacrylate de méthyle)/composition chimique , Test de matériaux , Verre/composition chimique , Bases d'appareil de prothèse dentaire , Techniques in vitro , Calorimétrie différentielle à balayage , Réactifs réticulants/composition chimique , Microscopie électronique à balayage , Matériaux dentaires/composition chimique , Spectroscopie par résonance magnétique , Spiranes/composition chimique
3.
Polymers (Basel) ; 16(17)2024 Aug 29.
Article de Anglais | MEDLINE | ID: mdl-39274097

RÉSUMÉ

Polymer materials have garnered significant attention due to their exceptional mechanical properties and diverse industrial applications. Understanding the glass transition temperature (Tg) of polymers is critical to prevent operational failures at specific temperatures. Traditional methods for measuring Tg, such as differential scanning calorimetry (DSC) and dynamic mechanical analysis, while accurate, are often time-consuming, costly, and susceptible to inaccuracies due to random and uncertain factors. To address these limitations, the aim of the present study is to investigate the potential of Simplified Molecular Input Line Entry System (SMILES) as descriptors in simple machine learning models to predict Tg efficiently and reliably. Five models were utilized: k-nearest neighbors (KNNs), support vector regression (SVR), extreme gradient boosting (XGBoost), artificial neural network (ANN), and recurrent neural network (RNN). SMILES descriptors were converted into numerical data using either One Hot Encoding (OHE) or Natural Language Processing (NLP). The study found that SMILES inputs with fewer than 200 characters were inadequate for accurately describing compound structures, while inputs exceeding 200 characters diminished model performance due to the curse of dimensionality. The ANN model achieved the highest R2 value of 0.79; however, the XGB model, with an R2 value of 0.774, exhibited the highest stability and shorter training times compared to other models, making it the preferred choice for Tg prediction. The efficiency of the OHE method over NLP was demonstrated by faster training times across the KNN, SVR, XGB, and ANN models. Validation of new polymer data showed the XGB model's robustness, with an average prediction deviation of 9.76 from actual Tg values. These findings underscore the importance of optimizing SMILES conversion methods and model parameters to enhance prediction reliability. Future research should focus on improving model accuracy and generalizability by incorporating additional features and advanced techniques. This study contributes to the development of efficient and reliable predictive models for polymer properties, facilitating the design and application of new polymer materials.

4.
Chemphyschem ; : e202400458, 2024 Sep 05.
Article de Anglais | MEDLINE | ID: mdl-39235149

RÉSUMÉ

In this work, the surface nature-dependent behaviors of magnetic deep eutectic solvents (MDES) and magnetic low-transition-temperature mixtures (MLTTM) are reported for the first time. It has been observed that the surface of material where the MDES or the MLTTM is placed could considerably affect the dispersion and the magnetic and structural properties of these magnetic mixtures. Several experiments have been carried out in order to point out the differences observed in the properties depending on the material on which these magnetic mixtures are placed. As a result, it has been shown that the MDESs or MLTTMs are retained and adhered to glass surfaces, resulting in a loss of magnetism in addition to a loss in the performance of synthesis carried out on the closeness of glass materials as the interaction between the glass and the mixture modify the composition and therefore the properties. As a preliminary result, when using these magnetic mixtures as extractant solvents in dispersive liquid-liquid microextraction, the MDES or MLTTM is retained on the walls of the glass tubes reducing the extraction efficiency, repeatability and the extraction recovery using an external magnetic field. For all these reasons, polypropylene materials should be recommended when handling MDES and MLTTMs.

5.
Anal Bioanal Chem ; 2024 Sep 12.
Article de Anglais | MEDLINE | ID: mdl-39264463

RÉSUMÉ

A column-free immunoaffinity purification (CFIP) technique for sample preparation of aflatoxin B1 (AFB1) was developed using an AFB1-specific nanobody (named G8) and an elastin-like polypeptide (ELP). The reversible phase transition between liquid and solid in response to temperature changes was exhibited by the ELP which was derived from human elastin. The G8 was tagged with ELPs of various lengths (20, 40, 60, and 80 repeat units) at the C-terminus using recursive directional ligation (RDL). Coding sequences were then subcloned into pET30a at the multiple cloning sites. Bioactive recombinant proteins were produced by expressing them as inclusion bodies in Escherichia coli BL21 (DE3), then dissolved and refolded. Analysis by indirect competitive enzyme-linked immunosorbent assay (icELISA) and transition temperature (Tt) measurement confirmed that the refolded G8-ELPs preserved the ability to recognize AFB1 as well as phase transition when the temperature rose above Tt. To establish the optimal conditions for cleaning AFB1, the effects of various parameters on recovery were investigated. The recovery in ELISA tests was 95 ± 3.67% under the optimized CFIP workflow. Furthermore, the CFIP-prepared samples were applied for high-performance liquid chromatography (HPLC) detection. The recovery in the CFIP-HPLC test ranged from 54 ± 1.86% to 98 ± 3.58% for maize, rice, soy sauce, and vegetable oil samples. To the best of our knowledge, this is the first report combining the function of both nanobody and ELP to develop a cleanup technique for small molecules in a complex matrix. The CFIP for the sample pretreatment was easy to use and inexpensive. In contrast to conventional immunosensitivity materials, the reagent utilized in the CFIP was entirely biosynthesized without any chemical coupling reactions. This suggests that the nanobody-ELP may serve as a useful dual-functional reagent for the development of sample cleaning or purification methods.

6.
Materials (Basel) ; 17(18)2024 Sep 23.
Article de Anglais | MEDLINE | ID: mdl-39336410

RÉSUMÉ

This work aims at the determination of the coefficient of thermal expansion (CTE) of parts manufactured through the Fused Deposition Modeling process, employing fiber Bragg grating (FBG) sensors. Pure thermoplastic and composite specimens were built using different commercially available filament materials, including acrylonitrile butadiene styrene, polylactic acid, polyamide, polyether-block-amide (PEBA) and chopped carbon fiber-reinforced polyamide (CF-PA) composite. During the building process, the FBGs were embedded into the middle-plane of the test specimens, featuring 0° and 90° raster printing orientations. The samples were then subjected to thermal loading for measuring the thermally induced strains as a function of applied temperature and, consequently, the test samples' CTE and glass transition temperature (Tg) based on the recorded FBG wavelengths. Additionally, the integrated FBGs were used for the characterization of the residual strain magnitudes both at the end of the 3D printing process and at the end of each of the two consecutively applied thermal cycles. The results indicate that, among all tested materials, the CF-PA/0° specimens exhibited the lowest CTE value of 14 × 10-6/°C. The PEBA material was proven to have the most isotropic thermal response for both examined raster orientations, 0° and 90°, with CTE values of 117 × 10-6/°C and 108 × 10-6/°C, respectively, while similar residual strains were also calculated in both printing orientations. It is presented that the followed FBG-based methodology is proven to be an excellent alternative experimental technique for the CTE characterization of materials used in 3D printing.

7.
Polymers (Basel) ; 16(18)2024 Sep 10.
Article de Anglais | MEDLINE | ID: mdl-39339016

RÉSUMÉ

The purpose of this study was to obtain information on the influence of the size factor on the climatic aging of circular fiber plastics produced by pultrusion. The kinetics of moisture transfer was obtained in humidification and drying modes at 60 °C in samples of epoxy basalt fiber reinforcement bars: after 28 months of exposure in the extremely cold climate of Yakutsk and 30 months of exposure in the moderately warm climate of Gelendzhik. It was shown that the 2D Langmuir model adequately describes the kinetics. The diffusion coefficients in the reinforcement direction for bars with diameters of 6, 8, 10, 16 and 20 mm turned out to be significantly higher than in the radial direction. To clarify the aging mechanism of the bars and the tensile, compressive and bending strength, the coefficient of linear thermal expansion and the glass transition temperature of the epoxy matrix of the bars with a diameter of 6, 8 and 10 mm after 51 months of exposure in Yakutsk and 54 months of exposure in Gelendzhik were measured. It was shown that after climatic exposure, the deformability of the bars decreased with increasing diameter of the bar; the glass transition temperature increased more significantly in the bar with a smaller diameter. In 6 mm diameter bars, the compressive and bending strength limits decreased by 10-25 % due to the plasticizing effect of moisture. With the same depth of moisture penetration into the volume of the samples, its effect on the strength of thin bars was significant, and for thick bars, it was insignificant. An increase in the glass transition temperature by 6 °C, associated with the additional curing of the polymer matrix, occurred in the surface layer of the epoxy basalt fiber reinforcement bars and was revealed in bars with a smaller diameter.

8.
Nano Lett ; 24(38): 11831-11838, 2024 Sep 25.
Article de Anglais | MEDLINE | ID: mdl-39283029

RÉSUMÉ

Topological superconductors (TSCs) offer a promising avenue for delving into exotic states of matter and fundamental physics. We propose a strategy for realizing high transition temperatures (high-Tc) in TSCs by leveraging nontrivial topology alongside a high carrier density near the Fermi level in metal-doped borophenes. We identified 39 candidates with exceptional thermodynamic stability from thousands of Be-intercalated borophenes (Be1-xBx) via extensive structural searches. Seven candidates exhibit high carrier densities, with B7Be2B7 emerging as a particularly promising candidate. This nanosheet displays both type-I and type-II Dirac fermions, indicative of Z2 topological metals, thereby positioning it as an ideal platform for high-Tc TSCs. The high-density π electrons of B7Be2B7 originating from type-II Dirac fermions, coupled with the out-of-plane vibrations of B and Be atoms, significantly enhance the electron-phonon coupling (λ = 1.42), resulting in a substantially high-Tc of 31.5 K. These findings underscore the potential of metal-doped borophenes as a cutting-edge material platform for achieving high-Tc TSCs.

9.
ACS Appl Mater Interfaces ; 16(35): 46332-46340, 2024 Sep 04.
Article de Anglais | MEDLINE | ID: mdl-39177447

RÉSUMÉ

Due to the slow diffusion of photovoltaic molecules, in particular, small-molecule acceptors (SMAs), under light and heating, the morphology of the active layer in organic solar cells (OSCs) prefers to deviate from the favorably metastable status, leading to the challenge of stability during long-term operation. Employing materials with a high glass transition temperature (Tg) as the third component to suppress molecular diffusion is an efficient method to achieve the balance of efficiency and stability of OSCs. Herein, a dimerized small-molecule acceptor denoted as F6D is synthesized by introducing a polyfluoride moiety as the linker to enhance the Tg. Benefitting from a rational molecular design, F6D not only exhibits a higher Tg, complementary absorption, and cascade energy levels with the host materials of the polymer donor PM6 and the SMA Y6 but also has excellent miscibility and multiple intermolecular interactions with Y6. As a result, a champion power conversion efficiency of 17.52% is achieved in the optimal PM6:Y6:F6D-based device. More importantly, the ternary device exhibits superior stability under continuous heating and lighting compared with the binary device.

10.
J Orofac Orthop ; 2024 Aug 27.
Article de Anglais | MEDLINE | ID: mdl-39190140

RÉSUMÉ

PURPOSE: The aim of this study was to evaluate the extent of property changes caused by heating the distal portion of heat-activated nickel-titanium (NiTi) wires. METHODS: Forty preformed heat-activated NiTi archwires (3M Unitek, Monrovia, CA, USA) with a nominal cross-section of 0.018″ were used in this study. The archwires were divided into a control group, not submitted to heat treatment and, thus, maintaining the as-received properties, and an experimental group, in which the archwires were submitted to heat treatment for distal bending at one end. Wire segments of control and experimental groups were submitted to differential scanning calorimetry (DSC) and Vickers microhardness measurements. RESULTS: The DSC results suggest local recrystallization and precipitate dissolution at the heat-treated tip, which decreases as the distance to the wire's tip increases. Vickers microhardness tests revealed significant changes for distances between 6 and 8 mm from the wire's tip. Heating the distal portion of heat-activated NiTi archwires should be performed with care since this clinical procedure may compromise the performance of these wires to a distance of 8 mm from the archwire end. CONCLUSION: Heat treatment for distal bending in heat-activated NiTi archwires may be performed, with little impact on the areas adjacent to heat treatment. In cases presenting molars requiring significant orthodontic corrections, it should be preferred to apply other techniques to avoid archwire sliding, such as crimpable stops, or to have flame control to avoid placing a heat-treated section in the tubes of these molars.

11.
Small Methods ; : e2400226, 2024 Aug 01.
Article de Anglais | MEDLINE | ID: mdl-39091063

RÉSUMÉ

Separation of equally sized particles distinguished solely by material properties remains still a very challenging task. Here a simple separation of differently charged, thermo-responsive polymeric particles (for example microgels) but equal in size, via the combination of pressure-driven microfluidic flow and precise temperature control is proposed. The separation principle relies on forcing thermo-responsive microgels to undergo the volume phase transition during heating and therefore changing its size and correspondingly the change in drift along a pressure driven shear flow. Different thermo-responsive particle types such as different grades of ionizable groups inside the polymer matrix have different temperature regions of volume phase transition temperature (VPTT). This enables selective control of collapsed versus swollen microgels, and accordingly, this physical principle provides a simple method for fractioning a binary mixture with at least one thermo-responsive particle, which is achieved by elution times in the sense of particle chromatography. The concepts are visualized in experimental studies, with an intend to improve the purification strategy of the broad distribution of charged microgels into fractioning to more narrow distribution microgels distinguished solely by slight differences in net charge.

12.
Polymers (Basel) ; 16(15)2024 Jul 29.
Article de Anglais | MEDLINE | ID: mdl-39125180

RÉSUMÉ

A previous related paper dealing with the density relaxation of polystyrene (PS) has shown that the equilibrium relaxation time (τeq) has a purely exponential temperature dependence (ETD) below ≈100 °C. Such an ETD is now also confirmed based upon available dielectric spectra data for PS. By combining the ETD behavior of τeq (or aT) at low temperatures with a VFTH behavior at higher temperatures (based mainly on available recoverable shear compliance data), a composite correlation for τeq (or aT) is developed, which is continuous with continuous slope at a crossover temperature that is found to be 99.22 °C, where τeq = 92.15 s. This composite representation is shown to describe (without any adjustable parameters) available independent data for the segmental relaxation time over a finite range both above and below Tcrossover (i.e., the glass transition temperature).

13.
Small ; : e2405573, 2024 Aug 06.
Article de Anglais | MEDLINE | ID: mdl-39104295

RÉSUMÉ

Volatile solid additives have emerged as a promising strategy for enhancing film morphology and promoting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, a series of novel polycyclic aromatic additives with analogous chemical structures, including fluorene (FL), dibenzothiophene (DBT), and dibenzofuran (DBF) derived from crude oils, are presented and incorporated into OSCs. All these additives exhibit strong interactions with the electron-deficient terminal groups of L8-BO within the bulk-heterojunction OSCs. Moreover, they demonstrate significant sublimation during thermal annealing, leading to increase free volumes for the rearrangement and recrystallization of L8-BO. This phenomenon leads to an improved film morphology and an elevated glass-transition temperature of the photoactive layers. Consequently, the PCE of the PM6:L8-BO blend has been boosted from 16.60% to 18.60% with 40 wt% DBF additives, with a champion PCE of 19.11% achieved for ternary PM6:L8-BO:BTP-eC9 OSCs. Furthermore, the prolonged shelf and thermal stability have been observed in OSCs with these additives. This study emphasizes the synergic effect of volatile solid additives on the performance and thermal stability of OSCs, highlighting their potential for advancing the field of photovoltaics.

14.
Int J Biol Macromol ; 279(Pt 4): 134595, 2024 Nov.
Article de Anglais | MEDLINE | ID: mdl-39122066

RÉSUMÉ

Biopolymers used to mitigate the environmental impact needed establish biodegradation percentage. The thermal and structural changes of two plastic materials, a flexible film based on cassava starch - Poly(lactic acid) (PLA) and a semi-rigid cassava flour-stay cellulose fique fiber, were evaluated biodegradation under ISO 4855-1 standard. The tests were carried out for four weeks at constant temperature and flow of 58 °C ±â€¯2 °C and 250 mL/h, using a mature compost as inoculum. The percentages of CO2, thermal, morphological, and structural changes, variation of degradation temperatures, glass transition temperatures (Tg), Melting temperatures (Tm) and enthalpies of fusion (Hm), were properly evaluated as indicators of the materials biodegradation of two materials. Scanning electron microscopy (SEM), showed the microorganisms colonization on the materials surface, evidencing the appearance of cracks and microbial population. The flexible film showed a biodegradation percentage of 98.24 %, the semi-rigid tray 89.06 %, and the microcrystalline cellulose, 81.37 %.


Sujet(s)
Dépollution biologique de l'environnement , Cellulose , Compostage , Amidon , Amidon/composition chimique , Amidon/métabolisme , Cellulose/composition chimique , Compostage/méthodes , Manihot/composition chimique , Température , Polyesters/composition chimique , Sol/composition chimique
15.
Polymers (Basel) ; 16(13)2024 Jul 06.
Article de Anglais | MEDLINE | ID: mdl-39000785

RÉSUMÉ

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material's surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

16.
Materials (Basel) ; 17(14)2024 Jul 14.
Article de Anglais | MEDLINE | ID: mdl-39063772

RÉSUMÉ

Traditional rock wool fibres are susceptible to crystallization and pulverization. To mitigate this, glass fibres were produced from iron ore waste (IOW). When the ratio of Fe2+ and Fe3+ is 1:3 and the Al2O3 content is 10 wt.%, increasing the FexOy content enhances the thermal stability.At an FexOy content of 17-19% and an Al2O3 content of 10-13%, the glass transition temperature (Tg) peaked. Increasing the FexOy content from 10% to 20% enhanced the stability of Si-O and Al-O bonds and increased bridged oxygen, stabilizing the structure. Here, Fe2+ balances structural charges, while Fe3+ replaces some Al atoms in the network. When the Al2O3 content is 10-13% and the FexOy content is 17-19%, the thermal stability of the IOW rock glass reaches its optimal level. At 20% FexOy content, the structure becomes three-dimensional and cyclic, increasing polymerization. Consequently, incorporating FexOy alongside a 10% Al2O3 content improves thermal stability, supporting the development of high-stability rock wool from IOW. This approach also enhances the refractory properties of rock wool fibres within the FexOy-Al2O3-SiO2-MgO-CaO system.

17.
Molecules ; 29(14)2024 Jul 09.
Article de Anglais | MEDLINE | ID: mdl-39064830

RÉSUMÉ

The performance and phase-separated microstructures of epoxy asphalt binders greatly depend on the concentration of epoxy resin or bitumen. In this paper, the effect of the epoxy resin (ER) concentration (10-90%) on the viscosity, thermo-mechanical properties, and phase-separated morphology of warm-mix epoxy asphalt binders (WEABs) was investigated using the Brookfield rotational viscometer, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and laser scanning confocal microscopy (LSCM). Due to the high reactivity of epoxy resin, the viscosity of WEABs increases with time. Furthermore, the initial viscosity of WEABs decreases with the ER concentration. Depending on the ER concentration, the viscosity-time behavior of WEABs is divided into three stages: slow (10-40%), fast (50-80%), and extremely slow (90%). In the slow stage, the viscosity slightly increases with the ER concentration, while the fast stage shows an opposite trend. DSC and DMA results reveal that WEABs with 10-80% ER exhibit two glass transition temperatures (Tgs) for cured epoxy resin and bitumen. Moreover, the Tgs of epoxy resin and bitumen increase with the ER concentration. However, WEAB with 90 % ER has only one Tg. LSCM observation shows that phase separation occurs in all WEABs. For WEABs containing 10-40% ER, spherical epoxy particles act as the discontinuous phase and disperse in the continuous bitumen phase. However, in WEABs with 50-90% ER, phase inversion takes place. Contrarily, bitumen particles disperse in the continuous epoxy phase. The damping properties of WEABs with the continuous epoxy phases increase with the ER concentration, while the crosslinking density shows an opposite trend. The occurrence of phase inversion results in a sharp increase in the tensile strength of WEABs. For WEABs with the continuous epoxy phases, the elongation at break increases with the ER concentration. The toughness first increases and then decreases with the ER concentration. A maximum toughness value shows at 70% ER.

18.
Adv Mater ; 36(35): e2311041, 2024 Aug.
Article de Anglais | MEDLINE | ID: mdl-39007252

RÉSUMÉ

2D single-phase multiferroic materials with the coexistence of electric and spin polarization offer a tantalizing potential for high-density multilevel data storage. One of the current limitations for application is the scarcity of the materials, especially those combine ferromagnetism and ferroelectricity at high temperatures. Here, robust ferrimagnetism and ferroelectricity in 2D ɛ-Fe2O3 samples with both single-crystalline and polycrystalline form are demonstrated. Interestingly, the polycrystalline nanosheets also exhibit easily switchable ferroelectric polarizations comparable to that of single crystals. The existence of grain boundary does not hinder the switching and retention of ferroelectric polarization. Furthermore, the ɛ-Fe2O3 nanosheets show ferrimagnetic and ferroelectric Curie temperatures up to 800 K, which reaches record highs in 2D single-phase multiferroic materials. This work provides important progress in the exploration of 2D high-temperature single-phase multiferroics for potentially compact high-temperature information nanodevices.

19.
Eur J Pharm Biopharm ; 202: 114395, 2024 Sep.
Article de Anglais | MEDLINE | ID: mdl-38971200

RÉSUMÉ

Drugs with poor water and lipid solubility are termed "brick dust." We previously successfully developed a co-amorphous system of a novel neuropeptide Y5 receptor antagonist (AntiY5R), a brick dust molecule, using sodium taurocholate (NaTC) as a co-former. However, the maximum improvement in AntiY5R dissolution by the co-amorphous system was only approximately 10 times greater than that of the crystals. Therefore, in the current study, other bile salts, including sodium cholate (NaC), sodium chenodeoxycholate (NaCC), and sodium glycocholate (NaGC), were examined as co-formers to further improve AntiY5R dissolution. NaC, NaCC, and NaGC have glass transition temperatures above 150°C. All three co-amorphous systems prepared successfully retained the amorphous form of AntiY5R for 3 months at 40°C, but the co-amorphous system with NaGC (AntiY5R-NaGC; 1:9 molar ratio) provided the highest improvement in AntiY5R dissolution, which was approximately 50 times greater than that of the crystals. Possible intermolecular interactions via the glycine moiety of NaGC more than the other bile salts would contribute to the highest dissolution enhancement with AntiY5R-NaGC. Thus, NaGC would be a promising co-former for formulating stable co-amorphous systems to enhance the dissolution behavior of brick dust molecules.


Sujet(s)
Stabilité de médicament , Acide glycocholique , Récepteur neuropeptide Y , Solubilité , Eau , Récepteur neuropeptide Y/antagonistes et inhibiteurs , Récepteur neuropeptide Y/métabolisme , Acide glycocholique/composition chimique , Eau/composition chimique , Neuropeptide Y/composition chimique , Cristallisation , Acides et sels biliaires/composition chimique
20.
Int J Pharm ; 662: 124486, 2024 Sep 05.
Article de Anglais | MEDLINE | ID: mdl-39033940

RÉSUMÉ

Cutaneous leishmaniasis, caused by Leishmania parasites, requires treatments with fewer side effects than those currently available. The development of a topical solution based on amphotericin B (AmB) was pursued. The considerable interest in deep eutectic solvents (DESs) and their remarkable advantages inspired the search for a suitable hydrophobic excipient. Various mixtures based on commonly used hydrogen bond donors (HBDs) and acceptors (HBAs) for DES preparations were explored. Initial physical and in-vitro screenings showed the potential of quaternary phosphonium salt-based mixtures. Through thermal analysis, it was determined that most of these mixtures did not exhibit eutectic behavior. X-ray scattering studies revealed a sponge-like nanoscale structure. The most promising formulation, based on a combination of trihexyl(tetradecyl)phosphonium chloride and 1-oleoyl-rac-glycerol, showed no deleterious effects through histological evaluation. AmB was fully solubilized at concentrations between 0.5 and 0.8 mg·mL-1, depending on the formulation. The monomeric state of AmB was observed by circular dichroism. In-vitro irritation tests demonstrated acceptable viability for AmB-based formulations up to 0.5 mg·mL-1. Additionally, an ex-vivo penetration study on pig ear skin revealed no transcutaneous passage, confirming AmB retention in healthy, unaffected skin.


Sujet(s)
Amphotéricine B , Antiprotozoaires , Interactions hydrophobes et hydrophiles , Leishmaniose cutanée , Amphotéricine B/administration et posologie , Amphotéricine B/composition chimique , Leishmaniose cutanée/traitement médicamenteux , Animaux , Antiprotozoaires/composition chimique , Antiprotozoaires/administration et posologie , Antiprotozoaires/pharmacologie , Antiprotozoaires/pharmacocinétique , Suidae , Peau/métabolisme , Peau/effets des médicaments et des substances chimiques , Excipients/composition chimique , Solubilité , Absorption cutanée , Solvants/composition chimique
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