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1.
Eur Biophys J ; 53(4): 183-192, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38647542

RESUMO

The sensitivity of cytosol water's microwave dielectric (MD) response to D-glucose uptake in Red Blood Cells (RBCs) allows the detailed study of cellular mechanisms as a function of controlled exposures to glucose and other related analytes like electrolytes. However, the underlying mechanism behind the sensitivity to glucose exposure remains a topic of debate. In this research, we utilize MDS within the frequency range of 0.5-40 GHz to explore how ionic redistributions within the cell impact the microwave dielectric characteristics associated with D-glucose uptake in RBC suspensions. Specifically, we compare glucose uptake in RBCs exposed to the physiological concentration of Ca2+ vs. Ca-free conditions. We also investigate the potential involvement of Na+/K+ redistribution in glucose-mediated dielectric response by studying RBCs treated with a specific Na+/K+ pump inhibitor, ouabain. We present some insights into the MD response of cytosol water when exposed to Ca2+ in the absence of D-glucose. The findings from this study confirm that ion-induced alterations in bound/bulk water balance do not affect the MD response of cytosol water during glucose uptake.


Assuntos
Citosol , Eritrócitos , Glucose , Micro-Ondas , Água , Citosol/metabolismo , Glucose/metabolismo , Água/metabolismo , Eritrócitos/metabolismo , Eritrócitos/efeitos dos fármacos , Eritrócitos/citologia , Cálcio/metabolismo , Humanos , Transporte Biológico , Íons/metabolismo , Ouabaína/farmacologia , Sódio/metabolismo
2.
Sensors (Basel) ; 24(9)2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38732847

RESUMO

The most reliable methods for pregnancy diagnosis in dairy herds include rectal palpation, ultrasound examination, and evaluation of plasma progesterone concentrations. However, these methods are expensive, labor-intensive, and invasive. Thus, there is a need to develop a practical, non-invasive, cost-effective method that can be implemented on the farm to detect pregnancy. This study suggests employing microwave dielectric spectroscopy (MDS, 0.5-40 GHz) as a method to evaluate reproduction events in dairy cows. The approach involves the integration of MDS data with information on milk solids to detect pregnancy and identify early embryonic loss in dairy cows. To test the ability to predict pregnancy according to these measurements, milk samples were collected from (i) pregnant and non-pregnant randomly selected cows, (ii) weekly from selected cows (n = 12) before insemination until a positive pregnancy test, and (iii) daily from selected cows (n = 10) prior to insemination until a positive pregnancy test. The results indicated that the dielectric strength of Δε and the relaxation time, τ, exhibited reduced variability in the case of a positive pregnancy diagnosis. Using principal component analysis (PCA), a clear distinction between pregnancy and nonpregnancy status was observed, with improved differentiation upon a higher sampling frequency. Additionally, a neural network machine learning technique was employed to develop a prediction algorithm with an accuracy of 73%. These findings demonstrate that MDS can be used to detect changes in milk upon pregnancy. The developed machine learning provides a broad classification that could be further enhanced with additional data.


Assuntos
Micro-Ondas , Leite , Animais , Feminino , Bovinos , Leite/química , Gravidez , Análise de Componente Principal , Espectroscopia Dielétrica/métodos , Indústria de Laticínios/métodos , Testes de Gravidez/métodos , Testes de Gravidez/veterinária , Algoritmos
3.
Mol Pharm ; 20(4): 2080-2093, 2023 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-36897219

RESUMO

Amorphous-Amorphous phase separation (AAPS) is an important phenomenon that can impede the performance of amorphous solid dispersions (ASDs). The purpose of this study was to develop a sensitive approach relying on dielectric spectroscopy (DS) to characterize AAPS in ASDs. This includes detecting AAPS, determining the size of the active ingredient (AI) discrete domains in the phase-separated systems, and accessing the molecular mobility in each phase. Using a model system consisting of the insecticide imidacloprid (IMI) and the polymer polystyrene (PS), the dielectric results were further confirmed by confocal fluorescence microscopy (CFM). The detection of AAPS by DS was accomplished by identifying the decoupled structural (α-)dynamics of the AI and the polymer phase. The α-relaxation times corresponding to each phase correlated reasonably well with those of the pure components, implying nearly complete macroscopic phase separation. Congruent with the DS results, the occurrence of the AAPS was detected by means of CFM, making use of the autofluorescent property of IMI. Oscillatory shear rheology and differential scanning calorimetry (DSC) detected the glass transition of the polymer phase but not that of the AI phase. Furthermore, the otherwise undesired effects of interfacial and electrode polarization, which can appear in DS, were exploited to determine the effective domain size of the discrete AI phase in this work. Here, stereological analysis of CFM images probing the mean diameter of the phase-separated IMI domains directly stayed in reasonably good agreement with the DS-based estimates. The size of phase-separated microclusters showed little variation with AI loading, implying that the ASDs have presumably undergone AAPS upon manufacturing. DSC provided further support to the immiscibility of IMI and PS, as no discernible melting point depression of the corresponding physical mixtures was detected. Moreover, no signatures of strong attractive AI-polymer interactions could be detected by mid-infrared spectroscopy within this ASD system. Finally, dielectric cold crystallization experiments of the pure AI and the 60 wt % dispersion revealed comparable crystallization onset times, hinting at a poor inhibition of the AI crystallization within the ASD. These observations are in harmony with the occurrence of AAPS. In conclusion, our multifaceted experimental approach opens new venues for rationalizing the mechanisms and kinetics of phase separation in amorphous solid dispersions.


Assuntos
Nitrocompostos , Polímeros , Cristalização/métodos , Polímeros/química , Neonicotinoides , Solubilidade , Varredura Diferencial de Calorimetria
4.
Biotechnol Lett ; 45(8): 931-938, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37227599

RESUMO

OBJECTIVES: Dielectric spectroscopy is commonly used for online monitoring of biomass growth. It is however not utilized for biomass concentration measurements due to poor correlation with Cell Dry Weight (CDW). A calibration methodology is developed that can directly measure viable biomass concentration in a commercial filamentous process using dielectric values, without recourse to independent and challenging viability determinations. RESULTS: The methodology is applied to samples from the industrial scale fermentation of a filamentous fungus, Acremonium fusidioides. By mixing fresh and heat-killed samples, linear responses were verified and sample viability could be fitted with the dielectric [Formula: see text] values and total solids concentration. The study included a total of 26 samples across 21 different cultivations, with a legacy at-line viable cell analyzer requiring 2 ml samples, and a modern on-line probe operated at-line with 2 different sample presentation volumes, one compatible with the legacy analyzer, a larger sample volume of 100 ml being compatible with calibration for on-line operation. The linear model provided an [Formula: see text] value of 0.99 between [Formula: see text] and viable biomass across the sample set using either instrument. The difference in ∆C when analyzing 100 mL and 2 mL samples with an in-line probe can be adjusted by a scalar factor of 1.33 within the microbial system used in this study, preserving the linear relation with [Formula: see text] of 0.97. CONCLUSIONS: It is possible to directly estimate viable biomass concentrations utilizing dielectric spectroscopy without recourse to extensive and difficult to execute independent viability studies. The same method can be applied to calibrate different instruments to measure viable biomass concentration. Small sample volumes are appropriate as long as the sample volumes are kept consistent.


Assuntos
Reatores Biológicos , Espectroscopia Dielétrica , Fermentação , Reatores Biológicos/microbiologia , Espectroscopia Dielétrica/métodos , Biomassa , Fungos
5.
Sensors (Basel) ; 23(5)2023 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-36904783

RESUMO

Microwave ablation is a technique used to treat tumorous tissue. Its clinical use has been greatly expanding in the last few years. Because the design of the ablation antenna and the success of the treatment greatly depend on the accurate knowledge of the dielectric properties of the tissue being treated, it is highly valuable to have a microwave ablation antenna that is also able to perform in-situ dielectric spectroscopy. In this work, an open-ended coaxial slot ablation antenna design operating at 5.8 GHz is adopted from previous work, and its sensing abilities and limitations are investigated in respect of the dimensions of the material under test. Numerical simulations were performed to investigate the functionality of the floating sleeve of the antenna and to find the optimal de-embedding model and calibration option for obtaining accurate dielectric properties of the area of interest. Results show that, as in the case of the open-ended coaxial probe, the accuracy of the measurement greatly depends on the likeness between the calibration standards' dielectric properties and the material under test. Finally, the results of this paper clarify to which extent the antenna can be used to measure dielectric properties and paves the way to future improvements and the introduction of this functionality into microwave thermal ablation treatments.

6.
Sensors (Basel) ; 23(5)2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36904601

RESUMO

Dielectric spectroscopy (DS) is the primary technique to observe the dielectric properties of biomaterials. DS extracts complex permittivity spectra from measured frequency responses such as the scattering parameters or impedances of materials over the frequency band of interest. In this study, an open-ended coaxial probe and vector network analyzer were used to characterize the complex permittivity spectra of protein suspensions of human mesenchymal stem cells (hMSCs) and human osteogenic sarcoma (Saos-2) cells in distilled water at frequencies ranging from 10 MHz to 43.5 GHz. The complex permittivity spectra of the protein suspensions of hMSCs and Saos-2 cells revealed two major dielectric dispersions, ß and γ, offering three distinctive features for detecting the differentiation of stem cells: the distinctive values in the real and imaginary parts of the complex permittivity spectra as well as the relaxation frequency in the ß-dispersion. The protein suspensions were analyzed using a single-shell model, and a dielectrophoresis (DEP) study was performed to determine the relationship between DS and DEP. In immunohistochemistry, antigen-antibody reactions and staining are required to identify the cell type; in contrast, DS eliminates the use of biological processes, while also providing numerical values of the dielectric permittivity of the material-under-test to detect differences. This study suggests that the application of DS can be expanded to detect stem cell differentiation.


Assuntos
Espectroscopia Dielétrica , Humanos , Suspensões , Diferenciação Celular
7.
Int J Mol Sci ; 24(2)2023 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-36674515

RESUMO

The progress of the automated industry has introduced many benefits in our daily life, but it also produces undesired electromagnetic interference (EMI) that distresses the end-users and functionality of electronic devices. This article develops new composites based on a polyetherimide (PEI) matrix and cobalt ferrite (CoFe2O4) nanofiller (10-50 wt%) by mixing inorganic phase in the poly(amic acid) solution, followed by film casting and controlled heating, to acquire the corresponding imide structure. The composites were designed to contain both electric and magnetic dipole sources by including highly polarizable groups (phenyls, ethers, -CN) in the PEI structure and by loading this matrix with magnetic nanoparticles, respectively. The films exhibited high thermal stability, having the temperature at which decomposition begins in the interval of 450-487 °C. Magnetic analyses indicated a saturation magnetization, coercitive force, and magnetic remanence of 27.9 emu g-1, 705 Oe, and 9.57 emu g-1, respectively, for the PEI/CoFe2O4 50 wt%. Electrical measurements evidenced an increase in the conductivity from 4.42 10-9 S/cm for the neat PEI to 1.70 10-8 S/cm for PEI/CoFe2O4 50 wt% at 1 MHz. The subglass γ- and ß-relaxations, primary relaxation, and conductivity relaxation were also examined depending on the nanofiller content. These novel composites are investigated from the point of view of their EMI shielding properties, showing that they are capable of attenuating the electric and magnetic parts of electromagnetic waves.


Assuntos
Anestésicos Gerais , Cobalto , Condutividade Elétrica
8.
Int J Mol Sci ; 24(24)2023 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-38138995

RESUMO

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4'-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4',4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4',4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari-Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.


Assuntos
Vidro , Simulação de Dinâmica Molecular , Animais , Temperatura de Transição , Temperatura , Vidro/química
9.
Molecules ; 28(21)2023 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-37959860

RESUMO

The formation of the nematic to twist-bend nematic (NTB) phase has emerged as a fascinating phenomenon in the field of supramolecular chemistry, based on complex intermolecular interactions. Through a careful analysis of molecular structures and dynamics, we elucidate how these intermolecular interactions drive the complex twist-bend modulation observed in the NTB. The study employs broadband dielectric spectroscopy spanning frequencies from 10 to 2 × 109 Hz to investigate the molecular orientational dynamics within the glass-forming thioether-linked cyanobiphenyl liquid crystal dimers, namely, CBSC7SCB and CBSC7OCB. The experimental findings align with theoretical expectations, revealing the presence of two distinct relaxation processes contributing to the dielectric permittivity of these dimers. The low-frequency relaxation mode is attributed to an "end-over-end rotation" of the dipolar groups parallel to the director. The high-frequency relaxation mode is associated with precessional motions of the dipolar groups about the director. Various models are employed to describe the temperature-dependent behavior of the relaxation times for both modes. Particularly, the critical-like description via the dynamic scaling model seems to give not only quite good numerical fittings, but also provides a consistent physical picture of the orientational dynamics in accordance with findings from infrared (IR) spectroscopy. Here, as the longitudinal correlations of dipoles intensify, the m1 mode experiences a sudden upsurge in enthalpy, while the m2 mode undergoes continuous changes, displaying critical mode coupling behavior. Interestingly, both types of molecular motion exhibit a strong cooperative interplay within the lower temperature range of the NTB phase, evolving in tandem as the material's temperature approaches the glass transition point. Consequently, both molecular motions converge to determine the glassy dynamics, characterized by a shared glass transition temperature, Tg.

10.
Molecules ; 28(10)2023 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-37241937

RESUMO

Two neutral copper(I) halide complexes ([Cu(BTU)2X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N'-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (1H and 13C), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH…X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 × 10-7 S·cm-1 was achieved at 430 K for the chloro-complex and 1.37 × 10-6 S·cm-1 at 440K for the related bromo-complex.

11.
Toxicol Appl Pharmacol ; 453: 116211, 2022 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-36037915

RESUMO

Cancer chemoprevention is an approach that offers huge potential for preventing/retarding carcinogenesis. MitoQ is well-known and extensively studied mitochondria-targeted antioxidants for its applications in diseases linked with oxidative stress. In the present study chemopreventive potential of mitoQ was studied with a focus on the role of gap-junctions and p53 at an advanced stage of HCC. BALB/c mice model of hepatocarcinogenesis was established using N-nitrosodiethylamine as a carcinogen (200 mg/kg b. w., cumulative dose, intraperitoneally). The chemopreventive effect of mitoQ was studied by pre-protecting animals with mitoQ (0.125 mg/kg b. w., orally once a week) till the termination of the study. The tumors developed in the course of the study were histopathologically analyzed and statistically evaluated. The mechanistic role of mitoQ was investigated in terms of mitochondrial oxidative stress, expression of 8-OHdG, Cx26, Cx32, p53 and status of gap-junctional intercellular communication (GJIC) in tumors. Chemopreventive activity of mitoQ was evident from improved survival of animals, significantly (p ≤ 0.05) lower tumor multiplicity, tumor incidence and a total number of tumors. MitoQ treatment significantly (p ≤ 0.05) decreased mitochondrial oxidative stress as indicated by reduced mtROS and mtLPO. Increased staining intensity of 8-OHdG and internalization of Cx26, Cx32 which was observed in hepatic tumors was reduced upon mitoQ treatment. Furthermore, the expression of Cx26, Cx32 and p53 was significantly increased along with improvement in GJIC in mitoQ treatment group. MitoQ demonstrated its chemopreventive potential probably by regulating mtROS, connexins and p53 in hepatocarcinogenesis.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Animais , Carcinogênese/induzido quimicamente , Quimioprevenção , Conexinas/metabolismo , Dietilnitrosamina/toxicidade , Neoplasias Hepáticas/induzido quimicamente , Neoplasias Hepáticas/prevenção & controle , Camundongos , Roedores , Proteína Supressora de Tumor p53
12.
Chemphyschem ; 23(10): e202100914, 2022 05 18.
Artigo em Inglês | MEDLINE | ID: mdl-35226788

RESUMO

This report describes the application of dielectric spectroscopy as a simple and fast way to guide protein adsorption experiments. Specifically, the polarization behavior of a layer of adsorbed lysozyme was investigated using a triangular-wave signal with frequencies varying from 0.5 to 2 Hz. The basic experiment, which can be performed in less than 5 min and with a single sample, not only allowed confirming the susceptibility of the selected protein towards the electric signal but also identified that this protein would respond more efficiently to signals with lower frequencies. To verify the validity of these observations, the adsorption behavior of lysozyme onto optically transparent carbon electrodes was also investigated under the influence of an applied alternating potential. In these experiments, the applied signal was defined by a sinusoidal wave with an amplitude of 100 mV and superimposed to +800 mV (applied as a working potential) and varying the frequency in the 0.1-10000 Hz range. The experimental data showed that the greatest adsorbed amounts of lysozyme were obtained at the lowest tested frequencies (0.1-1.0 Hz), results that are in line with the corresponding dielectric features of the protein.


Assuntos
Espectroscopia Dielétrica , Muramidase , Adsorção , Eletricidade , Eletrodos , Muramidase/química
13.
Biotechnol Bioeng ; 119(3): 857-867, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34927241

RESUMO

Cell death is one of the failure modes of mammalian cell culture. Apoptosis is a regulated cell death process mainly observed in cell culture. Timely detection of apoptosis onset allows opportunities for preventive controls that ensure high productivity and consistent product quality. Capacitance spectroscopy captures the apoptosis-related cellular properties changes and thus quantifies the percentage of dying cells. This study demonstrated a quantification model that measures the percentage of apoptotic cells using a capacitance spectrometer in an at-line setup. When predicting the independent test set collected from bench-scale bioreactors, the root-mean-squared error of prediction was 8.8% (equivalent to 9.9% of the prediction range). The predicted culture evolution trajectory aligned with measured values from the flow cytometer. Furthermore, this method alarms cell death onset earlier than the traditional viability test, that is, the trypan blue exclusion test. Compared to flow cytometry (the traditional early cell death detection method), this method is rapid, simple, and less labor-intensive. In addition, this at-line setup can be easily transferred between scales (e.g., lab-scale for development to manufacturing scale), which benefits process transfers between facilities, scale-up, and other process transitions.


Assuntos
Reatores Biológicos , Técnicas de Cultura de Células , Animais , Células CHO , Técnicas de Cultura de Células/métodos , Morte Celular , Cricetinae , Cricetulus , Capacitância Elétrica , Análise Espectral
14.
Biotechnol Bioeng ; 119(3): 922-935, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34964125

RESUMO

Real-time estimation of physiological properties of the cell during recombinant protein production would ensure enhanced process monitoring. In this study, we explored the application of dielectric spectroscopy to track the fed-batch phase of recombinant Escherichia coli cultivation for estimating the physiological properties, namely, cell diameter and viable cell concentration (VCC). The scanning capacitance data from the dielectric spectroscopy were pre-processed using moving average. Later, it was modeled through a nonlinear theoretical Cole-Cole model and further solved using a global evolutionary genetic algorithm (GA). The parameters obtained from the GA were further applied for the estimation of the aforementioned physiological properties. The offline cell diameter and cell viability data were obtained from particle size analyzer and flow cytometry measurements to validate the Cole-Cole model. The offline VCC was calculated from the cell viability % from flow cytometry data and dry cell weight concentration. The Cole-Cole model predicted the cell diameter and VCC with an error of 1.03% and 7.72%, respectively. The proposed approach can enable the operator to take real-time process decisions to achieve desired productivity and product quality.


Assuntos
Espectroscopia Dielétrica , Escherichia coli , Sobrevivência Celular , Espectroscopia Dielétrica/métodos , Escherichia coli/genética , Escherichia coli/metabolismo , Modelos Teóricos , Proteínas Recombinantes/genética , Proteínas Recombinantes/metabolismo
15.
Mol Pharm ; 19(5): 1586-1597, 2022 05 02.
Artigo em Inglês | MEDLINE | ID: mdl-35405077

RESUMO

Acetaminophen, nicotine, and lidocaine hydrochloride were investigated in their deeply supercooled liquid states using oscillatory shear rheology. The mechanical spectra of these drugs are presented in modulus, compliance, as well as fluidity formats. Their frequency profiles can be described via models adapted from the field of charge transport. Inspired by the success of this approach, the Barton-Nakajima-Namikawa relation, best known from the same field, was also tested. When adapted to rheology, this approach interrelates static and dynamic characteristics of viscous flow and was found to work excellently. The temperature dependence of the characteristic shear frequencies was checked against the shoving model, which relates them to the temperature-dependent instantaneous shear modulus and acceptable agreement was found. Combined with shear mechanical literature data on ibuprofen and indomethacin, a modified version of the phenomenological model by Gemant, DiMarzio, and Bishop (GDB) was employed to successfully predict the shape and amplitude of the dielectric spectra for all studied liquids, except for lidocaine hydrochloride. For the latter, the modified GDB model is suggested to aid in mapping out the reorientational part of the dielectric response, while the experimental results are strongly superimposed by ionic conduction phenomena. The reverse transformation, the calculation of rheological spectra based on dielectric ones, is also successfully demonstrated. For the example of acetyl salicylic acid, it is shown how dielectric spectra can be used to even predict rheological ones. The limits of the central parameter governing these mutual transformations, the electroviscoelastic material constant, and indications for its correlation with the dielectric relaxation strength are discussed. For pharmaceuticals characterized by a strong dynamical decoupling of the electrical from the mechanical degrees of freedom, the modified GDB model is not expected to be applicable.


Assuntos
Vidro , Lidocaína , Preparações Farmacêuticas , Reologia , Temperatura
16.
Mol Pharm ; 19(8): 2950-2961, 2022 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-35797094

RESUMO

Using sulfamethoxazole (SMZ) and trimethoprim (TMP) as model drugs, we designed amorphous solid dispersions (ASDs) for the simultaneous solubility enhancement of two active pharmaceutical ingredients (APIs) by exploiting the drug-drug and drug-polymer interactions. In order to make this approach broadly applicable and over a wide dose range, a mixture of SMZ and TMP at weight ratios of 5:1 and 1:5 (w/w) were formulated into ternary ASDs. Depending on the dose ratio of the two drugs, the polymer used was either an aminoalkyl methacrylate copolymer (Eudragit, EDE) or polyacrylic acid. The drug-drug and drug-polymer interactions were characterized to be ionic by infrared and solid-state nuclear magnetic resonance spectroscopy. The interactions resulted in a substantial reduction in molecular mobility, evident from the increase in the structural relaxation time determined by dielectric spectroscopy. The drug-drug interaction resulted in ∼3 orders of magnitude reduction in molecular mobility. The addition of a polymer led to a further decrease in molecular mobility of up to 4 orders of magnitude. The strength of intermolecular interactions was also estimated from the glass transition temperatures of the ASDs obtained by differential scanning calorimetry. The strong intermolecular interactions yielded highly stable ASDs with no evidence of crystallization, both at elevated temperatures and under accelerated storage conditions (40 °C/75% relative humidity; 6 weeks). The dissolution performances of the ASDs were evaluated using the area under the curve (AUC) obtained from the concentration-time profiles under the non-sink condition. SMZ and TMP in their ternary ASDs, when compared with their crystalline counterparts, exhibited up to 6.4- and 4.6-fold increases in AUC, respectively. Importantly, the synchronized release of the two drugs was observed, a desirable attribute in synergistic formulations. A single-phase ternary ASD, stabilized by drug-drug and drug-polymer interactions, is likely responsible for the unique release profile.


Assuntos
Polímeros , Cristalização , Combinação de Medicamentos , Composição de Medicamentos/métodos , Liberação Controlada de Fármacos , Polímeros/química , Solubilidade
17.
Eur Biophys J ; 51(4-5): 353-363, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35532810

RESUMO

Dielectric spectroscopy has been used in the study and development of non-invasive glucose monitoring (NIGM) sensors, including the range of microwave frequencies. Dielectric relaxation of red blood cell (RBC) cytosolic water in the microwave frequency band has been shown to be sensitive to variations in the glucose concentration of RBC suspensions. It has been hypothesized that this sensitivity stems from the utilization of D-glucose by RBCs. To verify this proposition, RBCs were pretreated with inhibitors of D-glucose uptake (cytochalasin B and forskolin). Then their suspensions were exposed to different D-glucose concentrations as measured by microwave dielectric spectroscopy (MDS) in the 500 MHz-40 GHz frequency band. After incubation of RBCs with either inhibitor, the dielectric response of water in the cytoplasm, and specifically its relaxation time, demonstrated minimal sensitivity to the change of D-glucose concentration in the medium. This result allows us to conclude that the sensitivity of MDS to glucose uptake is associated with variations in the balance of bulk and bound RBC cytosolic water due to intracellular D-glucose metabolism, verifying the correctness of the initial hypothesis. These findings represent a further argument to establish the dielectric response of water as a marker of glucose variation in RBCs.


Assuntos
Automonitorização da Glicemia , Micro-Ondas , Glicemia/análise , Glicemia/metabolismo , Espectroscopia Dielétrica , Eritrócitos/química , Glucose/metabolismo , Suspensões , Água/química
18.
J Dairy Sci ; 105(11): 8638-8649, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36055847

RESUMO

The nonhomogeneity of bovine colostrum leads to strong scattering effects for electromagnetic waves, which affects the application of electromagnetic spectroscopy in detecting colostrum. This work aimed to compare the performance of near-infrared spectroscopy (NIRS) and dielectric spectroscopy (DS) in quantitatively predicting the content of mature milk as an adulterant in colostrum. The near-infrared spectra in the range of 833 to 2,500 nm and the dielectric spectra in the range of 20 to 4,500 MHz of 150 adulterated colostrum samples containing 0 to 50% mature milk were analyzed. The different proportions of mature milk in colostrum significantly changed near-infrared and dielectric spectra. The principal component analysis score plot showed that both NIRS and DS could identify the proportion of mature milk in colostrum, but the 2 methods had different characteristics. Linear partial least squares regression and nonlinear least squares support vector machine (LSSVM) models based on near-infrared and dielectric spectra were established to identify doping proportions. The results showed that DS had better identification performance with a root-mean-square error of prediction of 4.9% and a residual prediction deviation of 3.441 by successive projection algorithm LSSVM, whereas NIRS was relatively weak with a root-mean-square error of prediction of 7.3% and a residual prediction deviation of 2.301 by full-spectra LSSVM. This work provides important insights for the quantitative prediction of nonhomogeneous liquid food by DS.


Assuntos
Colostro , Leite , Feminino , Gravidez , Bovinos , Animais , Leite/química , Contaminação de Alimentos/análise , Análise dos Mínimos Quadrados , Espectroscopia de Luz Próxima ao Infravermelho/veterinária
19.
Sensors (Basel) ; 22(3)2022 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-35161919

RESUMO

Recently, wideband microwave spectroscopy (WBMS) has been applied for material characterization. Blood glucose sensing through microwave spectroscopy is usually done with resonant frequency-domain methods. Time-domain (TD) WBMS is a low-cost and convenient technique that can be used for glucose sensing of the aqueous solution. In this paper, early research for the implementation of a TD dielectric spectroscopy setup for glucose concentration measurement is presented. TD reflected signals from water with different glucose content are calculated using inverse Laplace transform. The proposed setup is a quasi-monostatic setup in which measurements are done with two different devices in the frequency range of 0.1 to 6 GHz to make a comparison between frequency domain (FD) and TD methods. Frequency domain (FD) measurement is performed with VNA and two Vivaldi antennas. Then, TD data is obtained using the transforming option of VNA. Direct TD measurement is operated with a maximum length sequence (m-sequence) transceiver. Measurement and numerical results follow the same trend and show good agreement with each other. A monotonic relation between peaks of TD signals and the corresponding glucose concentration is achieved. The variation of the height of the reflected signal's peak is 0.00002 and 0.0005 for each 50 mg/dL glucose concentration with FD measurements and direct TD measurements, respectively. The glucose concentration range of 25 mg/dL to 400 mg/dL is investigated, and the worst repeatability of this method is 3.65% for 300 mg/dL.


Assuntos
Espectroscopia Dielétrica , Micro-Ondas , Estudos de Viabilidade , Glucose , Água
20.
Sensors (Basel) ; 22(3)2022 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-35161888

RESUMO

The As2S3-Cu interface was studied by dielectric spectroscopy measurements on Cu-As2S3-Cu thin film heterostructure samples to assess the charge carriers' contribution to the electrical properties of such an interface. Three-dimensional printed masks ensured good reproducibility during the PLD deposition of heterostructure samples. The samples were tested for electrical conductivity and AC photoconductivity by dielectric spectroscopy measurements. DC bias voltages and light were applied to the samples. The electrical capacity of the thin film heterostructure can be modified electrically and optically. We observed long-term photoconductivity with a time dependency that was not exponential, and a quick change of the electrical capacity, indicating the potential of the heterostructure cells as photodetector candidates.

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