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1.
Sensors (Basel) ; 23(3)2023 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-36772756

RESUMO

A multimode optical fiber supports excitation and propagation of a pure single optical mode, i.e., the field pattern that satisfies the boundary conditions and does not change along the fiber. When two counterpropagating pure optical modes are excited, they could interact through the stimulated Brillouin scattering (SBS) process. Here, we present a simple theoretical formalism describing SBS interaction between two individual optical modes selectively excited in an acoustically isotropic multimode optical fiber. Employing a weakly guiding step-index fiber approach, we have built an analytical expression for the spatial distribution of the sound field amplitude in the fiber core and explored the features of SBS gain spectra, describing the interaction between modes of different orders. In this way, we give a clear insight into the sound propagation effects accompanying SBS in multimode optical fibers, and demonstrate their specific contributions to the SBS gain spectrum.

2.
Molecules ; 28(4)2023 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-36838745

RESUMO

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]- was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]- and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]-. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]- was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.


Assuntos
Boratos , Boro , Boratos/química , Ânions/química , Boro/química , Isomerismo
3.
Int J Mol Sci ; 23(19)2022 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-36233323

RESUMO

A new series of compounds based on perbrominated disubstituted sulfonium derivatives of the closo-decaborate anion (n-Bu4N)[2-B10Br9SR2] (R = n-Pr, i-Pr, n-Bu, n-C8H17, n-C12H25, n-C18H37) was obtained, characterised by modern physicochemical methods of analysis. According to the results of an X-ray diffraction study, some of the anions and solvate molecules were disordered. The cations (n-Bu4N)+ and anions [2-B10Br9SR2]- were associated via C-H…Br and H…H contacts. In addition, Br…Br interactions between anions were revealed. The role of these contacts was analysed in terms of Hirshfeld surface analysis, QTAIM theory and the NCI method using quantum chemical calculations. An increase in the size of the alkyl R moiety led to significant strengthening of the total energy of H…H interactions. In the case of R = -n-C18H37, a parallel mutual orientation of alkyl moieties was established that was similar to the packing of salts of fatty acids. The nature of C-H…Br and Br…Br interionic interactions was found to be attractive, in contrast to the repulsive nature of intermolecular Br…Br interactions.


Assuntos
Ácidos Graxos , Sais , Ânions/química , Difração de Raios X
4.
Int J Mol Sci ; 23(8)2022 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-35457007

RESUMO

The process of protonation of [2,6-B10H8O2CCH3]- was investigated both theoretically and experimentally. The most suitable conditions for protonation of the derivative [2,6-B10H8O2CCH3]- were found. The process of protonation was carried out in the presence of an excess of trifluoromethanesulfonic acid CF3SO3H at room temperature in dichloromethane solution. The structure of the resulting complex [2,6-B10H8O2CCH3*Hfac]0 was established using NMR data and the results of DFT calculations. An additional proton atom Hfac was found to be localized on one of the facets that was opposite the boron atom in a substituted position, and which bonded mainly with one apical boron atom. The main descriptors of the B-Hfac bond were established theoretically using QTAIM and NBO approaches. In addition, the mechanism of [2,6-B10H8O2CCH3]- protonation was investigated.


Assuntos
Boro , Prótons , Espectroscopia de Ressonância Magnética , Modelos Moleculares
5.
Molecules ; 27(3)2022 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-35164015

RESUMO

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph3P, Ph2P-(CH2)2-PPh2 (dppe), Ph3As, Et3N, PhNH2, C5H5N, CH3CN, Ph2CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B3H7Nu] are obtained. It is found that the use of TiCl4, AlCl3, ZrCl4, HfCl4, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B3H7-HMXnx], which was detected by NMR spectroscopy. The structures of [Ph3P·B3H7] and [PhNH2·B3H7] were determined by X-ray diffraction.

6.
Inorg Chem ; 60(12): 8592-8604, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-34042435

RESUMO

A method for obtaining perchlorinated di-S,S-substituted derivatives of the closo-decaborate anion with various alkyl groups has been developed: [B10Cl9SR2]- (R= i-C3H7, n-C3H7, n-C4H9, n-C8H17, n-C12H25, n-C18H37, CH2Ph, and cyclo-S(CH2)4). The method is based on the preparation of the sulfonium-substituted anion [B10H9SR2]- by alkylation of the anion [B10H9SH]2- with bromoalkanes (i-C3H7Br, n-C3H7Br, n-C4H9Br, n-C8H17Br, n-C12H25Br, n-C18H37Br, PhCH2Br, and BrCH2(CH2)2CH2Br) followed by the cluster chlorination with sulfuryl chloride SO2Cl2 in acetonitrile. The process proceeds until the hydrogen atoms in the boron cluster are completely replaced with chlorine and completes within 60 h. It has been found that the melting point of salts ((C4H9)4N)[B10Cl9SR2] (R= i-C3H7, n-C3H7, n-C4H9, n-C8H17, n-C12H25, and n-C18H37) strongly depends on the length of the hydrocarbon chain of the substituent R.

7.
Int J Mol Sci ; 22(24)2021 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-34948186

RESUMO

In the present work, a convenient and straightforward approach to the preparation of borylated amidines based on the closo-dodecaborate anion [B12H11NCCH3NHR]-, R=H, Alk, Ar was developed. This method has two stages. A nitrile derivative of the general form [B12H11NCCH3]- was obtained, using a modified technique, in the first stage. On the second stage the resulting molecular system interacted with primary amines to form the target amidine products. This approach is characterised by a simple chemical apparatus, mild conditions and high yields of the final products. The mechanism of the addition of amine to the nitrile derivative of the closo-dodecaborate anion was studied, using quantum-chemical methods. The interaction between NH3 and [B12H11NCCH3]- ammonia was chosen as an example. It was found that the structure of the transition state determines the stereo-selectivity of the process. A study of the biological properties of borylated amidine sodium salts indicated that the substances had low toxicity and could accumulate in cancer cells in significant amounts.


Assuntos
Amidinas/síntese química , Terapia por Captura de Nêutron de Boro/métodos , Amidinas/química , Aminas , Ânions , Compostos de Boro/química , Desenho de Fármacos
8.
Molecules ; 26(12)2021 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-34207280

RESUMO

The interaction of hafnium(IV) salts (oxide-dichloride, chloride, and bromide) with nitrilotriacetic acid (NTA), diethylenetriamminepentaacetic acid (DTPA), 1,2-diaminocyclohexanetetraacetic acid (CDTA), 1,3-dipropylmino-2-hydroxy N,N,N',N'-tetraacetic acid (dpta), and N-(2-hydroxyethyl)ethylenediamine triacetic acid (HEDTA) has been studied. The corresponding complexes Na2[Hf(NTA)2]·3H2O (1), Na[HfDTPA]·3H2O (2), [HfCDTA(H2O)2] (3), and Na[Hf2(dpta)2]·7.5H2O·0.5C2H5OH (4) have been isolated and characterized and their structures have been determined by single crystal X-ray diffraction. Biological studies of [HfCDTA(H2O)2] have shown that in 5% glucose solution this complex has low toxicity and good contrasting ability.

9.
Molecules ; 26(1)2021 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-33466558

RESUMO

The novel members of the 1,2-diboraoxazoles family have been obtained. In the present work, we have carried out the intramolecular ring-closure reaction of borylated iminols of general type [B10H9N=C(OH)R]- (R = Me, Et, nPr, iPr, tBu, Ph, 4-Cl-Ph). This process is conducted in mild conditions with 83-87% yields. The solid-state structures of two salts of 1,2-diboraoxazoles were additionally investigated by X-ray crystallography. In addition, the phenomena of bonding interactions in the 1,2-diboraoxazole cycles have been theoretically studied by the Quantum Theory of Atoms in Molecules analysis. Several local and integral topological properties of the electron density involved in these interactions have been computed.


Assuntos
Ânions/química , Compostos de Boro/química , Compostos Heterocíclicos/química , Oxazóis/química , Teoria Quântica
10.
Appl Opt ; 58(34): 9398-9405, 2019 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-31873531

RESUMO

Recent advances in the development of ultra-compact semiconductor lasers and technology of printed flexible hybrid electronics have opened broad perspectives for the design of new pulse oximetry and photoplethysmography devices. Conceptual design of optical diagnostic devices requires careful selection of various technical parameters, including spectral range; polarization and intensity of incident light; actual size, geometry, and sensitivity of the detector; and mutual position of the source and detector on the surface of skin. In the current study utilizing a unified Monte Carlo computational tool, we explore the variations in diagnostic volume due to arterial blood pulsation for typical transmitted and back-scattered probing configurations in a human finger. The results of computational studies show that the variations in diagnostic volumes due to arterial pulse wave are notably (up to 45%) different in visible and near-infrared spectral ranges in both transmitted and back-scattered probing geometries. While these variations are acceptable for relative measurements in pulse oximetry and/or photoplethysmography, for absolute measurements, an alignment normalization of diagnostic volume is required and can be done by a computational approach utilized in the framework of the current study.


Assuntos
Artérias/fisiologia , Frequência Cardíaca/fisiologia , Oximetria/métodos , Oxigênio/sangue , Fotopletismografia/métodos , Fluxo Pulsátil/fisiologia , Humanos , Método de Monte Carlo
11.
Appl Opt ; 58(35): 9688, 2019 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-31873569

RESUMO

This publisher's note corrects several errors in Appl. Opt.58, 9398 (2019).APOPAI0003-693510.1364/AO.58.009398.

12.
Sensors (Basel) ; 19(3)2019 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-30717160

RESUMO

We present a low-frequency sensor for the detection of vibrations, with a sub-nm amplitude, based on a cantilever made of a single-crystalline lithium niobate (LiNbO3) plate, with a bidomain ferroelectric structure. The sensitivity of the sensor-to-sinusoidal vibrational excitations was measured in terms of displacement as well as of acceleration amplitude. We show a linear behavior of the response, with the vibrational displacement amplitude in the entire studied frequency range up to 150 Hz. The sensitivity of the developed sensor varies from minimum values of 20 µV/nm and 7 V/g (where g = 9.81 m/s² is the gravitational acceleration), at a frequency of 23 Hz, to peak values of 92.5 mV/nm and 2443 V/g, at the mechanical resonance of the cantilever at 97.25 Hz. The smallest detectable vibration depended on the excitation frequency and varied from 100 nm, at 7 Hz, to 0.1 nm, at frequencies above 38 Hz. Sensors using bidomain lithium niobate single crystals, as sensitive elements, are promising for the detection of ultra-weak low-frequency vibrations in a wide temperature range and in harsh environments.

13.
Opt Lett ; 43(16): 3921-3924, 2018 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-30106917

RESUMO

The adhesion of red blood cells (RBC) has been studied extensively in frame of cell-to-cell interaction induced by dextran macromolecules, whereas the data are lacking for native plasma solution. We apply optical tweezers to investigate the induced adhesion of RBC in plasma and in dextran solution. Two hypotheses, cross-bridges and depletion layer, are typically used to describe the mechanism of cell interaction; however, both mechanisms need to be confirmed experimentally. These interactions in fact are very much dependent on the size and concentration of dextran and proteins in plasma. The results show that in different dextran solutions, the interaction of adhering RBC agrees well with the quantitative predictions obtained based on the depletion-induced cells adhesion model, whereas the migrating cross-bridges model is more appropriate for plasma. Despite the different mechanisms of RBC interaction in a mixture of dextran with the size ranges and volume fraction proportional to plasma proteins, the dependence of RBC adhering tends to be close to the cross-bridges model. The induced aggregation of RBC in the dextran solutions and in native plasma are observed by direct visualization utilizing scanning electron microscopy.


Assuntos
Comunicação Celular , Eritrócitos/citologia , Microscopia Eletrônica de Varredura/métodos , Pinças Ópticas , Adesão Celular , Humanos
14.
Inorg Chem ; 56(6): 3421-3428, 2017 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-28256834

RESUMO

The first member, Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O, of a new family of boron-containing substances, closo-dodecaborate intercalated layered rare-earth hydroxides, was synthesized using a microwave-assisted hydrothermal method. The structure and composition of this compound were studied by X-ray diffraction, transmission and scanning electron microscopy, thermal analysis, inductively coupled plasma mass spectrometry, IR spectroscopy, and X-ray photoelectron spectroscopy. The title compound had the composition Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O and crystallized in a form of plate-like, aggregated particles less than 10 nm thick. The coordination of closo-dodecaborate anions with yttrium hydroxide host layers was demonstrated.

15.
Opt Lett ; 40(23): 5634-7, 2015 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-26625069

RESUMO

We show, through visible-range Mueller polarimetry, as well as numerical simulations, that the depolarization in a homogeneous turbid medium consisting of submicron spherical particles follows a parabolic law with the path-length traveled by light through the medium. This result is in full agreement with the phenomenological theory of the fluctuating medium within the framework of the differential Mueller matrix formalism. We further found that the standard deviations of the fluctuating elementary polarization properties of the medium depend linearly on the concentration of particles. These findings are believed to be useful for the phenomenological interpretation of polarimetric experiments, with special emphasis on biomedical applications.

16.
World J Microbiol Biotechnol ; 31(3): 535-7, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-25613548

RESUMO

Acidophilic thiobacilli are traditional biotechnological agents for metal recovery from sulfide ores. Major industrial strains belong to autotrophic bacteria which are used without any organic supplements to stimulate the process. The autotrophic strain Acidithiobacillus ferrooxidans ATCC 21834 is known to use formate as a source of energy under special laboratory conditions. We showed the presence of formate dehydrogenase in the type strain of another autotrophic species Halothiobacillus halophilus representing another genus of thiobacilli. This finding prompted studies of bioleaching stimulation by formate. Canadian sulfide nickel ore was chosen for model investigation as leached substrate and the moderate acidophilic strain H. halophilus DSM 6132 was used as the leaching agent. In bench-scale bioleaching experiments, inoculation of the ore with H. halophilus supplemented with 0.3 % formate increased the recovery of nickel 70-fold as compared with formate-free inoculation (1008.0 vs. 13.8 mg Ni/L per 34 days). Bacteria H. halophilus belong to moderate acidophilic microorganisms; thus, the results were obtained with initial pH 7.4 and final pH 5.4. The mechanism of formate stimulation is under discussion.


Assuntos
Meios de Cultura/química , Formiatos/metabolismo , Halothiobacillus/metabolismo , Níquel/metabolismo , Sulfetos/metabolismo , Halothiobacillus/crescimento & desenvolvimento , Concentração de Íons de Hidrogênio
17.
J Biomed Opt ; 29(5): 052913, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38089555

RESUMO

Significance: Phase retardation of circularly polarized light (CPL), backscattered by biological tissue, is used extensively for quantitative evaluation of cervical intraepithelial neoplasia, presence of senile Alzheimer's plaques, and characterization of biotissues with optical anisotropy. The Stokes polarimetry and Mueller matrix approaches demonstrate high potential in definitive non-invasive cancer diagnosis and tissue characterization. The ultimate understanding of CPL interaction with tissues is essential for advancing medical diagnostics, optical imaging, therapeutic applications, and the development of optical instruments and devices. Aim: We investigate propagation of CPL within turbid tissue-like scattering medium utilizing a combination of Jones and Stokes-Mueller formalisms in a Monte Carlo (MC) modeling approach. We explore the fundamentals of CPL memory effect and depolarization formation. Approach: The generalized MC computational approach developed for polarization tracking within turbid tissue-like scattering medium is based on the iterative solution of the Bethe-Salpeter equation. The approach handles helicity response of CPL scattered in turbid medium and provides explicit expressions for assessment of its polarization state. Results: Evolution of CPL backscattered by tissue-like medium at different conditions of observation in terms of source-detector configuration is assessed quantitatively. The depolarization of light is presented in terms of the coherence matrix and Stokes-Mueller formalism. The obtained results reveal the origins of the helicity flip of CPL depending on the source-detector configuration and the properties of the medium and are in a good agreement with the experiment. Conclusions: By integrating Jones and Stokes-Mueller formalisms, the combined MC approach allows for a more complete representation of polarization effects in complex optical systems. The developed model is suitable to imitate propagation of the light beams of different shape and profile, including Gaussian, Bessel, Hermite-Gaussian, and Laguerre-Gaussian beams, within tissue-like medium. Diverse configuration of the experimental conditions, coherent properties of light, and peculiarities of polarization can be also taken into account.


Assuntos
Dispositivos Ópticos , Espalhamento de Radiação , Análise Espectral , Anisotropia , Método de Monte Carlo
18.
J Biophotonics ; 17(7): e202400017, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38714530

RESUMO

We utilize Laser Speckle Contrast Imaging (LSCI) for visualizing cerebral blood flow in mice during and post-cardiac arrest. Analyzing LSCI images, we noted temporal blood flow variations across the brain surface for hours postmortem. Fast Fourier Transform (FFT) analysis depicted blood flow and microcirculation decay post-death. Continuous Wavelet Transform (CWT) identified potential cerebral hemodynamic synchronization patterns. Additionally, non-negative matrix factorization (NMF) with four components segmented LSCI images, revealing structural subcomponent alterations over time. This integrated approach of LSCI, FFT, CWT, and NMF offers a comprehensive tool for studying cerebral blood flow dynamics, metaphorically capturing the 'end of the tunnel' experience. Results showed primary postmortem hemodynamic activity in the olfactory bulbs, followed by blood microflow relocations between somatosensory and visual cortical regions via the superior sagittal sinus. This method opens new avenues for exploring these phenomena, potentially linking neuroscientific insights with mysteries surrounding consciousness and perception at life's end.


Assuntos
Encéfalo , Hemodinâmica , Animais , Camundongos , Encéfalo/irrigação sanguínea , Encéfalo/diagnóstico por imagem , Circulação Cerebrovascular , Imagem de Contraste de Manchas a Laser , Masculino , Autopsia
19.
J Biomed Opt ; 29(5): 052912, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38077500

RESUMO

Significance: The study of the effect of aging on the optical properties of biological tissues, in particular polarization, is important in the development of new diagnostic approaches. Aim: This work aims to provide a comprehensive analysis of the factors and mechanisms that contribute to the alteration of skin polarization properties caused by aging, using polarization-sensitive hyperspectral imaging measurements and Monte Carlo simulation. Approach: Our investigation involved both experimental studies of in vivo human skin of volunteers of different ages and computational modeling that accounted for changes in the absorption and scattering properties of the skin model. Specifically, we analyzed alterations in the degree of linear polarization (DOLP) to better understand the impact of aging on skin polarization properties. Results: A statistically significant increase in the DOLP was found for the elderly group. At the same time, there was no correlation between changes in polarization and the calculated blood volume fraction parameter for different ages. According to the simulation results, it was also found that a change in the scattering properties of biological tissues has a more significant effect on the change in polarizing light compared to the change in absorption. Conclusions: The results of the work prove that the sensitivity of polarization imaging to age- or pathological-related skin changes may be primarily due to changes in scattering, which in turn is associated with changes in the collagen fibers of the dermis. The proposed technique shows promise for in vivo non-invasive real-time assessment of age-associated skin changes and can also be extended to monitor changes associated with the development of age-related pathologies.


Assuntos
Luz , Pele , Humanos , Idoso , Pele/diagnóstico por imagem , Simulação por Computador , Diagnóstico por Imagem , Envelhecimento , Método de Monte Carlo , Espalhamento de Radiação
20.
Sci Rep ; 14(1): 13679, 2024 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-38871757

RESUMO

This study introduces a novel approach in the realm of liquid biopsies, employing a 3D Mueller-matrix (MM) image reconstruction technique to analyze dehydrated blood smear polycrystalline structures. Our research centers on exploiting the unique optical anisotropy properties of blood proteins, which undergo structural alterations at the quaternary and tertiary levels in the early stages of diseases such as cancer. These alterations manifest as distinct patterns in the polycrystalline microstructure of dried blood droplets, offering a minimally invasive yet highly effective method for early disease detection. We utilized a groundbreaking 3D MM mapping technique, integrated with digital holographic reconstruction, to perform a detailed layer-by-layer analysis of partially depolarizing dry blood smears. This method allows us to extract critical optical anisotropy parameters, enabling the differentiation of blood films from healthy individuals and prostate cancer patients. Our technique uniquely combines polarization-holographic and differential MM methodologies to spatially characterize the 3D polycrystalline structures within blood films. A key advancement in our study is the quantitative evaluation of optical anisotropy maps using statistical moments (first to fourth orders) of linear and circular birefringence and dichroism distributions. This analysis provides a comprehensive characterization of the mean, variance, skewness, and kurtosis of these distributions, crucial for identifying significant differences between healthy and cancerous samples. Our findings demonstrate an exceptional accuracy rate of over 90 % for the early diagnosis and staging of cancer, surpassing existing screening methods. This high level of precision and the non-invasive nature of our technique mark a significant advancement in the field of liquid biopsies. It holds immense potential for revolutionizing cancer diagnosis, early detection, patient stratification, and monitoring, thereby greatly enhancing patient care and treatment outcomes. In conclusion, our study contributes a pioneering technique to the liquid biopsy domain, aligning with the ongoing quest for non-invasive, reliable, and efficient diagnostic methods. It opens new avenues for cancer diagnosis and monitoring, representing a substantial leap forward in personalized medicine and oncology.


Assuntos
Holografia , Imageamento Tridimensional , Humanos , Imageamento Tridimensional/métodos , Anisotropia , Holografia/métodos , Masculino , Neoplasias da Próstata/patologia , Neoplasias da Próstata/sangue , Neoplasias da Próstata/diagnóstico , Neoplasias da Próstata/diagnóstico por imagem , Biópsia Líquida/métodos
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