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1.
Heliyon ; 10(11): e32147, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38947480

RESUMO

Barrier layers against intermetallic diffusion are a fundamental part on engineering electroplated coatings as they improve the lifetime of goods reducing wastes and improving the sustainability of the production chain. This study aims to set a cost-effective methodology to characterize barrier systems by evaluating the effectiveness with a recent approach based on XRF and EDS and characterize the kinetic of diffusion processes with X-ray diffractometry. Several high fashion barrier systems were tested highlighting that anticorrosion systems are not automatically suited as barrier layers for intermetallic diffusion, as opposed to industrial practice. Investigations on gold coatings obtained varying the current density revealed a correlation between the activation energy of the diffusion process, roughness, and crystallite size.

2.
Polymers (Basel) ; 16(10)2024 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-38794552

RESUMO

Nanotechnology is one of the newest directions for plant-based therapies. Chronic venous disease often predisposes to long-term and invasive treatment. This research focused on the inclusion of vegetal extracts from Sophorae flos (SE), Calendulae flos (CE), and Ginkgo bilobae folium (GE) in formulations with PHB and PLGA polymers and their physicochemical characterization as a preliminary stage for possible use in the development of a complex therapeutic product. The samples were prepared by an oil-water emulsification and solvent evaporation technique, resulting in suspensions with high spreadability and a pH of 5.5. ATR-FTIR analysis revealed bands for stretching vibrations (O-H, C=O, and C-H in symmetric and asymmetric methyl and methylene) in the same regions as the base components, but switched to high or low wavenumbers and absorbance, highlighting the formation of adducts/complexes between the extracts and polymers. The obtained formulations were in the amorphous phase, as confirmed by XRD analysis. AFM analysis emphasized the morphological peculiarities of the extract-polymer nanoformulations. It could be noticed that, in the case of SE-based formulations, the dominant characteristics for SE-PHB and SE-PLGA composition were the formation of random large (SE-PHB) and smaller uniform (SE-PLGA) particles; further on, these particles tended to aggregate in the case of SE-PHB-PLGA. For the CE- and GE-based formulations, the dominant surface morphology was their porosity, generally with small pores, but larger cavities were observed in some cases (CE- and GE-PHB). The highest roughness values at the (8 µm × 8 µm) scale were found for the following samples and succession: CE-PHB < SE-PLGA < SE-PHB-PLGA. In addition, by thermogravimetric analysis, impregnation in the matrix of compression stockings was evaluated, which varied in the following order: CE-polymer > SE-polymer > GE-polymer. In conclusion, nine vegetal extract-polymer nanoformulations were prepared and preliminarily characterized (by advanced physicochemical methods) as a starting point for further optimization, stability studies, and possible use in complex pharmaceutical products.

3.
Mol Pharm ; 21(5): 2555-2564, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38551918

RESUMO

Poloxamer 188 (P188) was hypothesized to be a dual functional excipient, (i) a stabilizer in frozen solution to prevent ice-surface-induced protein destabilization and (ii) a bulking agent to provide elegant lyophiles. Based on X-ray diffractometry and differential scanning calorimetry, sucrose, in a concentration-dependent manner, inhibited P188 crystallization during freeze-drying, while trehalose had no such effect. The recovery of lactate dehydrogenase (LDH), the model protein, was evaluated after reconstitution. While low LDH recovery (∼60%) was observed in the lyophiles prepared with P188, the addition of sugar improved the activity recovery to >85%. The secondary structure of LDH in the freeze-dried samples was assessed using infrared spectroscopy, and only moderate structural changes were observed in the lyophiles formulated with P188 and sugar. Thus, P188 can be a promising dual functional excipient in freeze-dried protein formulations. However, P188 alone does not function as a lyoprotectant and needs to be used in combination with a sugar.


Assuntos
Varredura Diferencial de Calorimetria , Excipientes , Liofilização , Poloxâmero , Trealose , Liofilização/métodos , Poloxâmero/química , Excipientes/química , Trealose/química , Varredura Diferencial de Calorimetria/métodos , Sacarose/química , Difração de Raios X , L-Lactato Desidrogenase/metabolismo , L-Lactato Desidrogenase/química , Cristalização/métodos , Química Farmacêutica/métodos , Proteínas/química , Composição de Medicamentos/métodos , Congelamento
4.
Int J Pharm ; 652: 123855, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38280497

RESUMO

Tioconazole is an effective antifungal agent with very low solubility in aqueous media, which limits its bioavailability and efficacy. Aiming to overcome the drug limitations by improving the solubility of this active pharmaceutical ingredient, solution precipitation techniques were employed to prepare four new crystalline salts, namely the mesylate, tosylate, maleate (1:1), and fumarate (1:1) hemihydrate. The thermal stabilities, dissolution properties, and structural characteristics of the solids were determined, and the study was extended to compare their properties with the already-known oxalate salt. The structural characterization of the new phases was carried out using a multi-method approach, which included thermal (differential scanning calorimetry and thermogravimetry), diffractometric (powder X-ray diffraction), and spectroscopic (near-infrared and mid-infrared) methodologies. The determination of the melting point of the salts confirmed the findings made by thermal methods. Functional characteristics of the salts, involving their intrinsic dissolution rates were also determined. It was found that the salts exhibited improved thermal stability and that the nature of the counterion modulated their dissolution characteristics. The salts displayed better intrinsic dissolution rates than the free base, to the point of being "highly soluble" according to the Biopharmaceutical Classification System. At pH 4.3, the sulfonic acid derivatives exhibited better dissolution rates than their carboxylic acid-derived counterparts, greatly improved regarding bare tioconazole. The results suggest that the salts have great potential to be used as replacements for the free base; in principle, careful salt selection may help to fulfill each solubility need for the different scenarios where the drug may be used.


Assuntos
Imidazóis , Sais , Sais/química , Difração de Raios X , Oxalatos , Solubilidade , Varredura Diferencial de Calorimetria
5.
Mol Pharm ; 20(12): 6380-6390, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37947441

RESUMO

Freezing is commonly encountered during the processing and storage of biomacromolecule products. Therefore, understanding the phase and state transitions in pharmaceutical frozen solutions is crucial for the rational development of biopharmaceuticals. Solid-state nuclear magnetic resonance spectroscopy (ssNMR) was used to analyze solutions containing sodium phosphate buffer, histidine, and trehalose. Upon freezing, crystallization of disodium phosphate hydrogen dodecahydrate (Na2HPO4·12H2O, DPDH) and histidine was identified using 31P and 13C ssNMR, respectively, and confirmed by synchrotron X-ray diffractometry (SXRD). Using histidine as a molecular probe and based on the chemical shifts of atoms of interest, the pH of the freeze concentrate was measured. The unfrozen water content in freeze concentrates was quantified by 1H single pulse experiments. 13C-insensitive nuclei enhancement by polarization transfer (INEPT) and cross-polarization (CP) experiments were used as orthogonal tools to characterize the solutes in a "mobile" and a more "solid-like" state in the freeze-concentrated solutions, respectively. The above analyses were applied to a commercial monoclonal antibody (mAb) formulation of dupilumab. This work further establishes ssNMR spectroscopy as a highly capable biophysical tool to investigate the attributes of biopharmaceuticals and thereby provide insights into process optimization and formulation development.


Assuntos
Produtos Biológicos , Histidina , Congelamento , Difração de Raios X , Soluções , Espectroscopia de Ressonância Magnética , Liofilização
6.
J Pharm Sci ; 112(12): 3233-3239, 2023 12.
Artigo em Inglês | MEDLINE | ID: mdl-37716530

RESUMO

This study aimed to investigate the polymorphism of 1-(4-acetamide-benzenesulfonyl)-benzimidazole (PABZI), a newly developed compound with significant activity against Trypanosoma cruzi, the parasite which causes American trypanosomiasis (Chagas disease). Three different crystalline forms of PABZI [a solvent-free form (form I), three isostructural solvates (from isopropanol; acetonitrile-dichloromethane, and methanol-benzene) and a non-isostructural solvate from methanol] were isolated and characterized. The crystal structure of form I was resolved at 173 K and 300 K by single crystal X-ray diffraction. Physicochemical properties, including solubility, dissolution rate, wettability, and solid-state stability were assessed for the two most viable solid forms of PABZI, viz. form I and the isopropanol solvate (PABZI-isoOH). Form I exhibited a higher solubility and dissolution rate, and superior stability towards moisture (40 °C/75 % relative humidity) and UV-Visible light than PABZI-isoOH. Based on the solid-state stability results, form I was selected over PABZI-isoOH for further preclinical studies.


Assuntos
2-Propanol , Metanol , Cristalização , Solventes/química , Solubilidade , Acetamidas , Benzimidazóis , Difração de Raios X , Varredura Diferencial de Calorimetria
7.
Mol Pharm ; 20(9): 4587-4596, 2023 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-37535010

RESUMO

The phase behavior of poloxamer 188 (P188) in aqueous solutions, characterized by differential scanning calorimetry (DSC) and synchrotron X-ray diffractometry, revealed solute crystallization during both freezing and thawing. Sucrose and trehalose inhibited P188 crystallization during freeze-thawing (FT). While trehalose inhibited P188 crystallization only during cooling, sucrose completely suppressed P188 crystallization during both cooling and heating. Lactate dehydrogenase (LDH) served as a model protein to evaluate the stabilizing effect of P188. The ability of P188, over a concentration range of 0.003-0.800% w/v, to prevent LDH (10 µg/mL) destabilization was evaluated. After five FT cycles, the aggregation behavior (by dynamic light scattering) and activity recovery were evaluated. While LDH alone was sensitive to interfacial stress, P188 at concentrations of ≥0.100% w/v stabilized the protein. However, as the surfactant concentration decreased, protein aggregation after FT increased. The addition of sugar (1.0% w/v; sucrose or trehalose) improved the stabilizing function of P188 at lower concentrations (≤0.010% w/v), possibly due to the inhibition of surfactant crystallization. Based on a comparison with the stabilization effect of polysorbate (both 20 and 80), it was evident that P188 could be a promising alternative surfactant in frozen protein formulations. However, when the surfactant concentration is low, the potential for P188 crystallization and the consequent compromise in its functionality warrant careful consideration.


Assuntos
Gelo , Poloxâmero , Congelamento , Trealose/química , Proteínas , L-Lactato Desidrogenase/química , Tensoativos , Sacarose/química , Liofilização , Varredura Diferencial de Calorimetria
8.
Beilstein J Org Chem ; 19: 736-751, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37284588

RESUMO

The past decade witnessed remarkable success in synthetic molecular nanographenes. Encouraged by the widespread application of chiral nanomaterials, the design, and construction of chiral nanographenes is a hot topic recently. As a classic nanographene unit, hexa-peri-hexabenzocoronene generally serves as the building block for nanographene synthesis. This review summarizes the representative examples of hexa-peri-hexabenzocoronene-based chiral nanographenes.

9.
J Appl Crystallogr ; 56(Pt 3): 776-786, 2023 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-37284267

RESUMO

Two wafers of one 4H-silicon carbide (4H-SiC) bulk crystal, one cut from a longitudinal position close to the crystal's seed and the other close to the cap, were characterized with synchrotron white-beam X-ray topography (SWXRT) in back-reflection and transmission geometry to investigate the dislocation formation and propagation during growth. For the first time, full wafer mappings were recorded in 00012 back-reflection geometry with a CCD camera system, providing an overview of the dislocation arrangement in terms of dislocation type, density and homogeneous distribution. Furthermore, by having similar resolution to conventional SWXRT photographic film, the method enables identification of individual dislocations, even single threading screw dislocations, which appear as white spots with a diameter in the range of 10 to 30 µm. Both investigated wafers showed a similar dislocation arrangement, suggesting a constant propagation of dislocations during crystal growth. A systematic investigation of crystal lattice strain and tilt at selected wafer areas with different dislocation arrangements was achieved with high-resolution X-ray diffractometry reciprocal-space map (RSM) measurements in the symmetric 0004 reflection. It was shown that the diffracted intensity distribution of the RSM for different dislocation arrangements depends on the locally predominant dislocation type and density. Moreover, the orientation of specific dislocation types along the RSM scanning direction has a strong influence on the local crystal lattice properties.

10.
Pharm Res ; 40(6): 1459-1477, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36959413

RESUMO

The present review summarizes the use of differential scanning calorimetry (DSC) and scattering techniques in the context of protein formulation design and characterization. The scattering techniques include wide angle X-ray diffractometry (XRD), small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). While DSC is valuable for understanding thermal behavior of the excipients, XRD provides critical information about physical state of solutes during freezing, annealing and in the final lyophile. However, as these techniques lack the sensitivity to detect biomolecule-related transitions, complementary characterization techniques such as small-angle scattering can provide valuable insights.


Assuntos
Espalhamento a Baixo Ângulo , Difração de Raios X
11.
Int J Pharm ; 637: 122869, 2023 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-36948477

RESUMO

Tioconazole is an effective antifungal agent, which has a very low solubility in aqueous media, that limits its bioavailability and efficacy. In an effort to overcome the drug limitations by improving its solubility, the hydrochloride salt was prepared in methanolic 1 M HCl and obtained as the hemihydrate, as demonstrated by elemental analysis. Single crystals were grown by slow evaporation from an aqueous 1 M HCl solution and their structure was determined using single-crystal X-ray diffraction at 302 K. The structures resulting from dehydration and further rehydration were also assessed, at 333 and 283 K, respectively. The morphology of the crystal, which exhibited birefringence under polarized light, was verified by hot stage microscopy. The solid was characterized by additional means, including thermal analysis (melting point, differential scanning calorimetry and thermogravimetry), spectroscopic methods (mid infrared, near infrared, 1H, 13C and 15N nuclear magnetic resonance in solution, as well as 13C and 15N solid state with spinning at the magic angle) and X-ray diffraction techniques. Functional evaluation tests, including the intrinsic dissolution rate and the dissolution of powders were also performed. In the intrinsic dissolution rate test, the salt proved to dissolve over 2000 times faster than tioconazole. The results suggest that the new salt has physicochemical and performance properties which may support its use as a replacement of the free base in certain applications, especially where improved dissolution rate, solubility or bioavailability of the drug would be desired.


Assuntos
Antifúngicos , Cloreto de Sódio , Difração de Raios X , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Varredura Diferencial de Calorimetria , Água/química , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
12.
Eur J Pharm Sci ; 183: 106397, 2023 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-36736465

RESUMO

The characterization of cytisine (CYT) and its blends with poly(lactic acid) was performed using thermal analysis, elemental analysis, infrared spectroscopy, and powder X-ray diffractometry. The heat capacities, total enthalpy, and phase transitions of CYT were established from 1.8 to 448.15 K (-271.35 - 175 °C) by advanced thermal analysis. Data were obtained using a Quantum Design Physical Property Measurement System (PPMS) and a differential scanning calorimetry (DSC). The low-temperature heat capacity of the crystalline CYT in the range of 1.8 to 300 K (-271.35 - 26.86 °C) was measured by PPMS and fitted to a theoretical model in the low temperature region below 11 K (-262.15 °C), to orthogonal polynomials in the middle range 5 K < T < 60 K (-268.15 °C < t < -213.15 °C) and to the Debye and Einstein functions in the high range of temperature above 60 K (-213.15 °C). The liquid heat capacity was calculated based on the approximated linear regression data above the molten state of the experimental heat capacity of CYT obtained by the standard DSC measurements, and it was expressed as Cpliquid = 0.0838T + 346.78 J·K-1·mol-1. The calculated heat capacity in the solid state was extended to a higher temperature and was used, together with liquid heat capacity, as the reference baselines for the advanced thermal analysis of CYT. The PPMS and DSC/TMDSC methods are complementary methods for thermal analysis of cytisine. The PPMS method allowed determination of the equilibrium heat capacity in the solid state, which together with the equilibrium heat capacity in the liquid state allowed to analyze of the experimental apparent heat capacity of cytisine obtained based on DSC. The melting temperature and the total heat of fusion of crystalline material were established as 431.8 K (158.65 °C) and 26.5 kJ·mol-1, respectively. The solid and liquid heat capacities and transition parameters of CYT were applied to calculate total enthalpies for fully amorphous and crystalline states. Analyses of DSC and X-ray confirmed the presence of the solid-solid transition linking with not so far described a polymorphism phenomenon of CYT. Based on the thermogravimetric analysis the temperature of degradation of CYT was determined as 460.5 K (187.35 °C). Also, a preliminary thermal analysis of the blends of cytisine and poly(lactic acid) as a new candidate for drug delivery system was presented.


Assuntos
Temperatura Alta , Abandono do Hábito de Fumar , Preparações Farmacêuticas , Temperatura , Varredura Diferencial de Calorimetria
13.
Angew Chem Int Ed Engl ; 62(6): e202214599, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36409199

RESUMO

Commercially available stock solutions of organolithium reagents are well-implemented tools in organic and organometallic chemistry. However, such solutions are inherently contaminated with lithium halide salts, which can complicate certain synthesis protocols and purification processes. Here, we report the isolation of chloride-free methyllithium employing K[N(SiMe3 )2 ] as a halide-trapping reagent. The influence of distinct LiCl contaminations on the 7 Li-NMR chemical shift is examined and their quantification demonstrated. The structural parameters of new chloride-free monomeric methyllithium complex [(Me3 TACN)LiCH3 ], ligated by an azacrown ether, are assessed by comparison with a halide-contaminated variant and monomeric lithium chloride [(Me3 TACN)LiCl], further emphasizing the effect of halide impurities.

14.
Acta Pharm Sin B ; 12(3): 1432-1446, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35530160

RESUMO

In the microscale, bacteria with helical body shapes have been reported to yield advantages in many bio-processes. In the human society, there are also wisdoms in knowing how to recognize and make use of helical shapes with multi-functionality. Herein, we designed atypical chiral mesoporous silica nano-screws (CMSWs) with ideal topological structures (e.g., small section area, relative rough surface, screw-like body with three-dimension chirality) and demonstrated that CMSWs displayed enhanced bio-adhesion, mucus-penetration and cellular uptake (contributed by the macropinocytosis and caveolae-mediated endocytosis pathways) abilities compared to the chiral mesoporous silica nanospheres (CMSSs) and chiral mesoporous silica nanorods (CMSRs), achieving extended retention duration in the gastrointestinal (GI) tract and superior adsorption in the blood circulation (up to 2.61- and 5.65-times in AUC). After doxorubicin (DOX) loading into CMSs, DOX@CMSWs exhibited controlled drug release manners with pH responsiveness in vitro. Orally administered DOX@CMSWs could efficiently overcome the intestinal epithelium barrier (IEB), and resulted in satisfactory oral bioavailability of DOX (up to 348%). CMSWs were also proved to exhibit good biocompatibility and unique biodegradability. These findings displayed superior ability of CMSWs in crossing IEB through multiple topological mechanisms and would provide useful information on the rational design of nano-drug delivery systems.

15.
Food Sci Technol Int ; 28(2): 144-156, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33653148

RESUMO

The preservation of Andean roots and tubers (ART) depends on the recognition of their health-promoting and nutritional metabolites and their transformation into other products such as starches. The objective of this study was to determine the physicochemical and structural properties of native starches obtained from Canna edulis K., Oxalis tuberosa M., and Ipomoea batatas L. from the Colombian Andean agroecosystem. The physicochemical properties of starches were determined by traditional methods of analysis. The thermal properties were determined by gravimetric thermal analysis (TGA) and differential scanning calorimetry (DSC), while the structural characteristics were studied with X-ray diffractometry and infrared spectrometry. The ART showed a starch yield of between 53.3% and 75.4% (dry basis) and amylose content between 28.4% and 35.6%. Starches from I. batatas showed the highest percentage of amylose, lowest gel clarity, lowest water absorption index, and highest gel temperature. X-ray diffractograms showed a type A crystallographic pattern for I. batatas starch, and a type B pattern for C. edulis and O. tuberosa starches, while infrared spectra (FTIR-ATR) corroborated the structural characteristics of each type of starch. The results suggest that starches from Andean resources can be used as a substitute for traditional starches from corn and potato. In addition, their amylose content makes them potential sources of resistant starch and dietary fiber.


Assuntos
Ipomoea batatas , Amido , Amilose/análise , Colômbia , Ipomoea batatas/química , Tubérculos/química , Amido/química , Difração de Raios X
16.
Materials (Basel) ; 14(11)2021 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-34073430

RESUMO

This paper presents domain and structure studies of bonded magnets made from nanocrystalline Nd-(Fe, Co)-B powder. The structure studies were investigated using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Mössbauer spectroscopy and X-ray diffractometry. On the basis of performed qualitative and quantitative phase composition studies, it was found that investigated alloy was mainly composed of Nd2(Fe-Co)14B hard magnetic phase (98 vol%) and a small amount of Nd1.1Fe4B4 paramagnetic phase (2 vol%). The best fit of grain size distribution was achieved for the lognormal function. The mean grain size determined from transmission electron microscopy (TEM) images on the basis of grain size distribution and diffraction pattern using the Bragg equation was about ≈130 nm. HRTEM images showed that over-stoichiometric Nd was mainly distributed on the grain boundaries as a thin amorphous border of 2 nm in width. The domain structure was investigated using a scanning electron microscope and metallographic light microscope, respectively, by Bitter and Kerr methods, and by magnetic force microscopy. Domain structure studies revealed that the observed domain structure had a labyrinth shape, which is typically observed in magnets, where strong exchange interactions between grains are present. The analysis of the domain structure in different states of magnetization revealed the dynamics of the reversal magnetization process.

17.
Carbohydr Polym ; 265: 118079, 2021 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-33966843

RESUMO

The goal of the study was to evaluate the influence of the solvent properties on the crystal characteristics of ß-cyclodextrin (ß-CD) recrystallized from alcohol-water solvent mixtures, with possible applications for the preparation, purifying and complexation of ß-CD. For the first time, structure-property relationships (QSPRs) between the hydrophobicity of alcohols or dielectric constant of solvents used for recrystallization of ß-CD and its properties (such as crystallinity index, CI) have been obtained. Recrystallized ß-CD from water and C1-C4 alcohol-water solutions provide ß-CD with higher CI values of 99.4(±5.9)% for ethanol-water (1:4, v/v) as recrystallizing system. This property has a parabolic variation with the logP (octanol/water partition coefficient) of the alcohol (r2 = 0.998). Solvent parameters also influence the ß-CD crystal characteristics, as was demonstrated by X-ray diffractometry refinement, infrared spectroscopy and thermal analyses.


Assuntos
Solventes/química , beta-Ciclodextrinas/química , Varredura Diferencial de Calorimetria/métodos , Cristalização/métodos , Etanol/química , Interações Hidrofóbicas e Hidrofílicas , Solubilidade , Espectrofotometria Infravermelho/métodos , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Termogravimetria/métodos , Água/química , Difração de Raios X/métodos
18.
Materials (Basel) ; 14(9)2021 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-33921972

RESUMO

Success of total knee replacement (TKR) depends on the prosthetic design and materials. The use of metal components is well established with the disadvantage of allergic reactions. Ceramics have been recently proposed because of high wear resistance, excellent biocompatibility, wettability, and suitable mechanical properties. This study was aimed at investigating in vitro wear resistance of Zirconia Toughened Alumina (ZTA)/Ultra-high-molecular-weight polyethylene (UHMWPE) of TKR femoral components. An in vitro protocol was designed with the application of relevant load profile, 6-degrees-of-freedom knee simulator, and 8 × 105 cycles on the ZTA/UHMWPE configuration under bovine calf serum. Before and after wear test, the femoral components were investigated by using the Scanning Electron Microscope (SEM) and the X-Ray Diffraction (XRD) analyses, and stylus surface roughness measurements. The proposed pre-clinical test yielded repeatable results. In particular, gravimetric results showed that, after 8 × 105 cycles, the mean weight loss of the polyethylene mobile components is 5.3 ± 1.1 mg. The surface roughness measurements (Ramax) performed after the wear test showed no significant variation on the UHMWPE menisci. A slight increase of roughness has been found on the ZTA (0.02 µm before wear test, 0.28 µm after the test). SEM observations did not show significant modification of the surface morphology. Tetragonal to monoclinic phase ratio was measured by XRD before and after wear test to evaluate stability of tetragonal ZrO2 phase. Minimal conversion of tetragonal to monoclinic phase was found from 5.4 to 8%. Although this study is a preliminary evaluation limited to in vitro tests, it provides novel pre-clinical indications about the potential of ceramic TKR femoral components.

19.
Vet Med Sci ; 7(1): 240-250, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-32776458

RESUMO

The carcass of a critically endangered, juvenile female grey nurse shark (Carcharias taurus, Rafinesque 1810) was recovered from a south-eastern Australian beach and subjected to necropsy. The 1.98-m-long shark exhibited advanced cachexia with its total weight (19.0 kg) and liver weight (0.37 kg) reduced by 60% and 89%, respectively, compared with a healthy individual of the same length. Marked tissue decomposition was evident preventing histopathology and identification of a definitive cause of death. At necropsy, the abdominal organs were abnormally displaced and showed marked reductions in size compared with a healthy individual of the same size. Importantly, a hook-shaped enterolith (HSE), with a rough surface and cream in colour, was found within the spiral valve of the intestine and is to the authors' knowledge, the first description of such in any marine animal. X-ray diffractometry showed that the HSE comprised the minerals monohydrocalcite (Ca[CO3].H2O; ~70 wt%) and struvite (Mg [NH4 ] [PO4 ]. [H2 O]6 ; ~30 wt%). A CT scan showed concentric lamellate concretions around a 7/o offset J-hook that formed the nidus of the HSE. Nylon fishing line attached to the hook exited the HSE and was evident in the abdominal cavity through a perforation in the intestinal wall where the posterior intestinal artery merges. The most parsimonious reconstruction of events leading to enterolithiasis and secondary cachexia in this shark was the consumption of a hooked fish and subsequent hook migration causing perforations of the cardiac stomach wall followed by the thin, muscular wall of the apposed, sub-adjacent intestine.


Assuntos
Caquexia/diagnóstico , Cálculos/complicações , Doenças dos Peixes/diagnóstico , Tubarões , Animais , Caquexia/etiologia , Caquexia/patologia , Cálculos/diagnóstico , Cálculos/etiologia , Cálculos/patologia , Feminino , Doenças dos Peixes/etiologia , Doenças dos Peixes/patologia , New South Wales
20.
Small ; 17(27): e2001439, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32696588

RESUMO

Atomically precise gold/silver clusters protected by organic ligands L, [(Au/Ag)x Ly ]z , have gained increasing interest as building units of functional materials because of their novel photophysical and physicochemical properties. The properties of [(Au/Ag)x Ly ]z are intimately associated with the quantized electronic structures of the metallic cores, which can be viewed as superatoms from the analogy of naked Au/Ag clusters. Thus, establishment of the correlation between the geometric and electronic structures of the superatomic cores is crucial for rational design and improvement of the properties of [(Au/Ag)x Ly ]z . This review article aims to provide a qualitative understanding on how the electronic structures of [(Au/Ag)x Ly ]z are affected by geometric structures of the superatomic cores with a focus on three factors: size, shape, and composition, on the basis of single-crystal X-ray diffraction data. The knowledge accumulated here will constitute a basis for the development of ligand-protected Au/Ag clusters as new artificial elements on a nanometer scale.

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