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1.
Nano Lett ; 24(38): 11831-11838, 2024 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-39283029

RESUMO

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.

2.
Anal Bioanal Chem ; 2024 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-39264463

RESUMO

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.

3.
Polymers (Basel) ; 16(17)2024 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-39274097

RESUMO

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.
Artigo em Inglês | MEDLINE | ID: mdl-39235149

RESUMO

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.
Int J Biol Macromol ; 279(Pt 4): 134595, 2024 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-39122066

RESUMO

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 %.

6.
J Orofac Orthop ; 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-39190140

RESUMO

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.

7.
ACS Appl Mater Interfaces ; 16(35): 46332-46340, 2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39177447

RESUMO

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.

8.
Small ; : e2405573, 2024 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-39104295

RESUMO

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.

9.
Small Methods ; : e2400226, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-39091063

RESUMO

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.

10.
Polymers (Basel) ; 16(15)2024 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-39125180

RESUMO

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).

11.
Materials (Basel) ; 17(14)2024 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-39063772

RESUMO

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.

12.
Molecules ; 29(14)2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-39064830

RESUMO

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.

13.
Polymers (Basel) ; 16(13)2024 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-39000785

RESUMO

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.

14.
Adv Mater ; 36(35): e2311041, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39007252

RESUMO

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.

15.
Int J Pharm ; 662: 124486, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39033940

RESUMO

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.


Assuntos
Anfotericina B , Antiprotozoários , Interações Hidrofóbicas e Hidrofílicas , Leishmaniose Cutânea , Anfotericina B/administração & dosagem , Anfotericina B/química , Leishmaniose Cutânea/tratamento farmacológico , Animais , Antiprotozoários/química , Antiprotozoários/administração & dosagem , Antiprotozoários/farmacologia , Antiprotozoários/farmacocinética , Suínos , Pele/metabolismo , Pele/efeitos dos fármacos , Excipientes/química , Solubilidade , Absorção Cutânea , Solventes/química
16.
Int J Biol Macromol ; 276(Pt 2): 133881, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39029822

RESUMO

Thermochromic wood (TW), a smart material that can respond to temperature changes and store thermal energy, holds broad potential for application in the construction industry. This study fabricated thermochromic poplar (TP) by encapsulating a thermochromic phase change material (TPCM), consisting of tetradecyl myristate and methyl red, within a full poplar-based cellulose/lignin/SiO2 framework. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicate that the poplar matrix and the incorporated SiO2 formed an integrated cellulose/lignin/SiO2 framework, which encapsulated the TPCM within the poplar ducts. The TP exhibits a color change from light purple to dark purple within the temperature range of 30-48 °C, with a pronounced shift at approximately 42 °C, correlating with the sensation of scalding. Thus, TP-based products can alert users to the risk of scalding through a noticeable color change. The full poplar-based framework mitigates the impact of ultraviolet (UV) radiation on the TP and prevents the loss of TPCM during thermal processing. The mechanical properties of TP are enhanced to a strength grade comparable to that of Manchurian ash wood, making it suitable for load-bearing components in wooden structures. Additionally, the average temperature of TP is around 10 °C higher than that of untreated poplar within 25 min after the same thermal treatment. Consequently, TP can serve as a building material with capabilities for temperature response, thermal energy storage, and structural load-bearing.


Assuntos
Celulose , Lignina , Populus , Dióxido de Silício , Temperatura , Madeira , Lignina/química , Madeira/química , Celulose/química , Populus/química , Dióxido de Silício/química , Cor , Compostos Azo/química
17.
Int J Pharm ; 661: 124470, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39004294

RESUMO

The influence of different preparation methods on the physicochemical properties of amorphous solid forms have gained considerable attention, especially with recent publications on pharmaceutical polyamorphism. In the present study, we have investigated the possible occurrence of polyamorphism in the drug celecoxib (CEL) by investigating the thermal behavior, morphology, structure, molecular mobility and physical stability of amorphous CEL obtained by quench-cooling (QC), ball milling (BM) and spray drying (SD). Similar glass transition temperatures but different recrystallization behaviors were observed for CEL-QC, CEL-BM and CEL-SD using modulated differential scanning calorimetry analysis. A correlation between the different recrystallization behaviors of the three CEL amorphous forms and the respective distinct powder morphologies, was also found. Molecular dynamics simulations however, reveal that CEL presents similar molecular conformational distributions when subjected to QC and SD. Moreover, the obtained molecular conformational distributions of CEL are different from the ones found in its crystal structure and also from the ones found in the lowest-energy structure obtained by quantum mechanical calculations. The type and strength of CEL hydrogen bond interactions found in CEL-QC and CEL-SD systems are almost identical, though different from the ones presented in the crystal structure. Pair distribution function analyses and isothermal microcalorimetry show similar local structures and structural relaxation times, respectively, for CEL-QC, CEL-BM and CEL-SD. The present work shows that not only similar physicochemical properties (glass transition temperature, and structural relaxation time), but also similar molecular conformational distributions were observed for all prepared CEL amorphous systems. Hence, despite their different recrystallization behaviors, the three amorphous forms of CEL did not show any signs of polyamorphism.


Assuntos
Varredura Diferencial de Calorimetria , Celecoxib , Cristalização , Simulação de Dinâmica Molecular , Temperatura de Transição , Celecoxib/química , Estabilidade de Medicamentos , Ligação de Hidrogênio , Química Farmacêutica/métodos , Composição de Medicamentos/métodos , Pós/química
18.
Eur J Pharm Biopharm ; 202: 114395, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38971200

RESUMO

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.


Assuntos
Estabilidade de Medicamentos , Ácido Glicocólico , Receptores de Neuropeptídeo Y , Solubilidade , Água , Receptores de Neuropeptídeo Y/antagonistas & inibidores , Receptores de Neuropeptídeo Y/metabolismo , Ácido Glicocólico/química , Água/química , Neuropeptídeo Y/química , Cristalização , Ácidos e Sais Biliares/química
19.
Appl Microbiol Biotechnol ; 108(1): 361, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38837050

RESUMO

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47-85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage. KEY POINTS: • Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress • Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only • Activation energy revealed chemically limited reactions ruled the activity loss in storage.


Assuntos
Liofilização , Liofilização/métodos , Espectroscopia de Infravermelho com Transformada de Fourier , Secagem por Atomização , Viabilidade Microbiana , Lactobacillus plantarum/metabolismo , Lactobacillus plantarum/fisiologia , Lactobacillus delbrueckii/metabolismo , Lactobacillus delbrueckii/fisiologia , Lactobacillales/metabolismo , Lactobacillales/fisiologia , Dessecação
20.
Polymers (Basel) ; 16(11)2024 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-38891440

RESUMO

The frontal polymerization (FP) of carbon/epoxy (C/Ep) composites is investigated, considering FP as a viable route for the additive manufacturing (AM) of thermoset composites. Neat epoxy (Ep) resin-, short carbon fiber (SCF)-, and continuous carbon fiber (CCF)-reinforced composites are considered in this study. The evolution of the exothermic reaction temperature, polymerization frontal velocity, degree of cure, microstructures, effects of fiber concentration, fracture surface, and thermal and mechanical properties are investigated. The results show that exothermic reaction temperatures range between 110 °C and 153 °C, while the initial excitation temperatures range from 150 °C to 270 °C. It is observed that a higher fiber content increases cure time and decreases average frontal velocity, particularly in low SCF concentrations. This occurs because resin content, which predominantly drives the exothermic reaction, decreases with increased fiber content. The FP velocities of neat Ep resin- and SCF-reinforced composites are seen to be 0.58 and 0.50 mm/s, respectively. The maximum FP velocity (0.64 mm/s) is observed in CCF/Ep composites. The degree of cure (αc) is observed to be in the range of 70% to 85% in FP-processed composites. Such a range of αc is significantly low in comparison to traditional composites processed through a long cure cycle. The glass transition temperature (Tg) of neat epoxy resin is seen to be approximately 154 °C, and it reduces slightly to a lower value (149 °C) for SCF-reinforced composites. The microstructures show significantly high void contents (12%) and large internal cracks. These internal cracks are initiated due to high thermal residual stress developed during curing for non-uniform temperature distribution. The tensile properties of FP-cured samples are seen to be inferior in comparison to autoclave-processed neat epoxy. This occurs mostly due to the presence of large void contents, internal cracks, and a poor degree of cure. Finally, a highly efficient and controlled FP method is desirable to achieve a defect-free microstructure with improved mechanical and thermal properties.

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