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1.
J Phys Chem B ; 2020 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-32628477

RESUMO

Against a sensible expectation that molecular mobility in fluids generally disrupts magnetic orderings that depend on intermolecular interactions, some molecular compounds with isolated electrons, which are called radicals, exhibit the increase of magnetic susceptibility in melting. Here we first propose a simple model to explain the thermomagnetic anomaly unique to fluids; the effect of the magnetic interactions in each of the contacts could be accumulated on each of the molecular spins as if the molecular motion amplified the first coordination number of each molecule hundredfold. The huge coordination number theoretically guarantees the retention of memory of interactions at equilibrium; molecules might be able to conserve the memory of molecular conformations, configurations, electric charges, energies as well as magnetic memory with each other.

2.
Aging (Albany NY) ; 12(6): 5516-5538, 2020 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-32224504

RESUMO

Alzheimer's disease (AD) has become a major world health problem as the population ages. There is still no available treatment that can stop or reverse the progression of AD. Human amnion epithelial cells (hAECs), an alternative source for stem cells, have shown neuroprotective and neurorestorative potentials when transplanted in vivo. Besides, studies have suggested that stem cell priming with plant-derived bioactive compounds can enhance stem cell proliferation and differentiation and improve the disease-treating capability of stem cells. Verbenalin is an iridoid glucoside found in medicinal herbs of Verbenaceae family. In the present study, we have conducted microarray gene expression profiling of verbenalin-treated hAECs to explore its therapeutic potential for AD. Gene set enrichment analysis revealed verbenalin treatment significantly enriched AD-associated gene sets. Genes associated with lysosomal dysfunction, pathologic angiogenesis, pathologic protein aggregation, circadian rhythm, age-related neurometabolism, and neurogenesis were differentially expressed in the verbenalin-treated hAECs compared to control cells. Additionally, the neuroprotective effect of verbenalin was confirmed against amyloid beta-induced neurotoxicity in human neuroblastoma SH-SY5Y cells. Our present study is the first to report the therapeutic potential of verbenalin for AD; however, further in-depth research in the in vitro and in vivo models are required to confirm our preliminary findings.

3.
Opt Express ; 27(17): 24426-24433, 2019 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-31510331

RESUMO

This paper first reports random laser action in dye-doped ferromagnetic nematic liquid crystals, which act as a randomly distributed cavity. The random laser intensity of the ferromagnetic nematic liquid crystals can be controlled by a weak magnetic field (∼1 mT). Moreover, the magnetic switching of random laser is attributed to the direction and polarization dependent emission of light in the ferromagnetic nematic liquid crystals in an external magnetic field.

4.
Front Neurosci ; 13: 779, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31396047

RESUMO

In the present study, we conducted microarray gene expression profiling to explore the direction of differentiation of human amnion epithelial cells (hAECs) treated with rosmarinic acid (RA). hAECs have several clinical advantages over other types of stem cells, including availability, low immunogenicity, low rejection rate, non-tumorigenicity, and less ethical constraint. On the other hand, RA is a phenolic compound having several health benefits, including neuroprotective and antidepressant-like activities. In this study, hAECs were isolated from discarded term placenta and were treated with 20 µM RA for 7 days. Microarray gene expression profiling was conducted for three biological replicates of RA-treated and untreated control cells on day 0 and day 7. Gene set enrichment analysis, and gene annotation and pathway analysis were conducted using online data mining tools GSEA and DAVID. Gene expression profiling showed that RA treatment biased hAECs toward ectodermal lineage progression, regulated transcription factors involved in neuronal differentiation, regulated neural specific epigenetic modifiers and several extracellular signaling pathways of neural induction, and significantly inhibited Notch signaling pathway. Gene expression profiling of RA-treated hAECs reveals for the first time a potential role of RA in neural induction and neuronal differentiation of hAECs. Having a naturally occurring compound as differentiation inducer as well as a readily available source of stem cells would have great advantages for the cell-based therapies. Findings from our genome-wide analysis could provide a foundation for further in-depth investigation.

5.
ACS Omega ; 4(6): 10031-10035, 2019 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-31460095

RESUMO

A liquescent salt based on an N-pentylphenothiazine radical cation (1 •+ ·NTf 2 - ) exhibited a unique crystal-crystal phase transition from a paramagnetic orange solid to a diamagnetic green solid induced by brief, weak, and pinpoint mechanostress. Electron spin resonance and electronic spectroscopies revealed that this unprecedented solid-state spin controllability was attributable to mechanostress-triggered sequential association of the highly mobile radical species occurring under neat conditions.

6.
J Am Chem Soc ; 141(25): 10033-10038, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31140278

RESUMO

Recently, we discovered a modular synthetic approach for constructing core-shell columnar liquid crystals (LCs) by supramolecular polymerization in LC media. In the present work, we successfully confirmed that our modular synthetic approach has the potential to be widely extended to the development of multifunctional columnar LCs. Herein, we constructed the first core-shell columnar LC that was proved to be orientable by both electric and magnetic fields by the supramolecular polymerization of NODiskNH* in a nematic LC medium of 4-cyano-4'-pentyloxybiphenyl (5OCB). NODiskNH* is a chiral benzenetricarboxamide derivative bearing 2,2,6,6-tetramethylpiperidine 1-oxyl termini, which is known to form a helical supramolecular polymer via a triple hydrogen-bonding array. NODiskNH* alone formed a hydrogen-bonded liquid phase without any long-range structural ordering. However, a nematic LC medium of 5OCB, when mixed with NODiskNH* at a molar ratio of 1:3, underwent a "structural order-increasing" mesophase transition, affording an optically active single LC phase with a hexagonally arranged core-shell columnar geometry in a temperature range from 113 to 51 °C. Unprecedentedly, this core-shell columnar LC can orient its columns both electrically and magnetically, resulting in unidirectional columnar ordering.

7.
Chemistry ; 24(65): 17293-17302, 2018 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-30378204

RESUMO

A unique superparamagnetic-like behavior and a large "positive magneto-LC effect" were observed in the solid phases and the hexagonal columnar (Colh ) liquid crystalline (LC) phase, respectively, of novel achiral non-π-delocalized nitroxide diradical compounds (R,S)-1, which showed polymorphism in the solid phases (solids I and II). The SQUID magnetization measurement revealed that (1) (R,S)-1 containing a small amount of racemic diastereomers (R*,R*)-1 possessed an unusual and large temperature-independent magnetic susceptibility (χTIM >0) component in the original nanocrystalline solid I that was responsible for the observed superparamagnetic-like behavior under low magnetic fields and did not arise from the contamination by extrinsic magnetic metal or metal ion impurities, besides ordinary temperature-dependent paramagnetic susceptibility (χpara >0) and temperature-independent diamagnetic susceptibility (χdia <0) components, (2) a large increase in molar magnetic susceptibility (χM ) (positive magneto-LC effect) that occurred at the solid I-to-liquid crystal transition upon heating was preserved as an additional χTIM increase in the resulting polymorphic nanocrystalline solid II by cooling, and (3) such unique magnetic phenomena were induced by thermal processing for (R,S)-1 or by adding a small amount of (R*,R*)-1 to (R,S)-1 as the impurity.

8.
J Vis Exp ; (138)2018 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-30176016

RESUMO

Materials showing coupling phenomena between magnetism and (ferro)electricity, i.e., magnetoelectric effects, have attracted a great deal of attention due to their potential applications for future device technologies such as sensors and storage. However, conventional approaches, which usually utilize materials containing magnetic metal ions (or radicals), have a major problem: only a few materials have been found to show the coupling phenomena at room temperature. Recently, we proposed a new approach to achieve room-temperature magnetoelectrics. In contrast to conventional approaches, our alternative proposal focuses on a completely different material, a "liquid crystal", free from magnetic metal ions. In such liquid crystals, a magnetic field can be utilized to control the orientational state of constituent molecules and the corresponding electric polarization through magnetic anisotropy of the molecules; it is an unprecedented mechanism of the magnetoelectric effect. In this context, this paper provides a protocol to measure ferroelectric properties induced by a magnetic field, that is, the direct magnetoelectric effect, in a liquid crystal. With the method detailed here, we successfully detected magnetically-tuned electric polarization in the chiral smectic C phase of a liquid crystal at room temperature. Taken together with the flexibility of constituent molecules, which directly affects the magnetoelectric responses, the introduced method will serve to allow liquid crystal cells to acquire more functions as room-temperature magnetoelectrics and associated optical materials.


Assuntos
Eletricidade , Cristais Líquidos/química , Magnetismo/métodos
9.
J Phys Chem B ; 122(29): 7409-7415, 2018 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-30001130

RESUMO

We synthesized new chiral all-organic liquid crystalline (LC) compounds with nitroxide (NO) and hydroxy (OH) groups, which form intermolecular hydrogen bonds between the NO and OH groups. The LC compounds show hexagonal columnar phases at room temperature, which solidify as LC glasses at low temperature. The experimental magnetic susceptibility of each of the compounds in the LC and isotropic phases is larger than that theoretically estimated on the simple assumption about the amount of the spins, whereas it accords with the theoretical one in the LC glass state. It is called magneto-LC effects. The difference between experimental and theoretical magnetic susceptibilities gradually increases as temperature increases through the LC glass state-to-LC phase transition. It suggests that molecular mobility is one of the origins of the magneto-LC effects.

10.
Chemistry ; 24(48): 12546-12554, 2018 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-29863759

RESUMO

The supramolecular chirality of aggregates consisting of achiral trans-bis(salicylaldiminato)NiII complex 1 bearing long alkyl chains can be generated and controlled precisely in a chiral nematic liquid-crystalline (LC) solvent, whereas the complex naturally forms achiral gel fibers in achiral nematic LC solvents and crystals in nonmesogenic solvents. The direction and intensity of the helicity of the gel fibers of 1 in the LC gel state can be adjusted by means of the nature of the helical twisting and the concentration of the chiral dopants. Helicity control was precisely detected in the circular dichroism (CD) spectra of LC gels and by direct SEM observation of the dried gel fibers. XRD analysis revealed that the flexibility of the herringbone-based lamellar alignment of this complex is the key to the LC-specific gelation and helicity control of the gel fibers.

11.
Langmuir ; 34(23): 6814-6819, 2018 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-29782797

RESUMO

Carbon dioxide (CO2) capture and storage (CCS) technologies have been attracting attention in terms of tackling with global warming. To date, various CO2 capture technologies including solvents, membranes, cryogenics, and solid adsorbents have been proposed. Currently, a liquid adsorption method for CO2 using amine solution (monoethanolamine) has been practically used. However, this liquid phase CO2 adsorption process requires heat regeneration, and it can cause many problems such as corrosion of equipment and degradation of the solution. Meanwhile, solid adsorption methods using porous materials are more advantageous over the liquid method at these points. In this context, we here evaluated if hydrogen titanate (H2Ti3O7) nanotubes and the surface modification effectively capture CO2. For this aim, we first developed a facile synthesis method of H2Ti3O7 nanotubes different from any conventional methods. Briefly, they were converted from the precursors-amorphous TiO2 nanoparticles at room temperature (25 °C). We then determined the outer and the inner diameters of the H2Ti3O7 nanotubes as 3.0 and 0.7 nm, respectively. It revealed that both values were much smaller than the reported ones; thus the specific surface area showed the highest value (735 m2/g). Next, the outer surface of H2Ti3O7 nanotubes was modified using ethylenediamine to examine if CO2 adsorption capacity increases. The ethylendiamine-modified H2Ti3O7 nanotubes showed a higher CO2 adsorption capacity (50 cm3/g at 0 °C, 100 kPa). We finally concluded that the higher CO2 adsorption capacity could be explained, not only by the high specific surface area of the nanotubes but also by tripartite hydrogen bonding interactions among amines, CO2, and OH groups on the surface of H2Ti3O7.

12.
Chemistry ; 23(62): 15713-15720, 2017 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-28815766

RESUMO

With a view to developing a theranostic nanomedicine for targeted drug delivery systems visible by magnetic resonance (MR) imaging, robust metal-free magnetic nanoemulsions (mean particle size less than 20 nm) consisting of a biocompatible surfactant and hydrophobic, low molecular weight 2,2,5-trimethyl-5-(4-alkoxy)phenylpyrrolidine-N-oxyl radicals were prepared in pH 7.4 phosphate-buffered saline (PBS). The structure of the nanoemulsions was characterized by electron paramagnetic resonance spectroscopy, and dynamic light scattering and small-angle neutron-scattering measurements. The nanoemulsions showed high colloidal stability, low cytotoxicity, enough reduction resistance to excess ascorbic acid, and sufficient contrast enhancement in the proton longitudinal relaxation time (T1 ) weighted MR images in PBS in vitro (and preliminarily in vivo). Furthermore, the hydrophobic anticancer drug paclitaxel could be encapsulated inside the nanoparticles, and the resulting paclitaxel-loaded nanoemulsions were efficiently incorporated into HeLa cells to suppress cell growth.


Assuntos
Antineoplásicos Fitogênicos/química , Portadores de Fármacos/química , Nanopartículas de Magnetita/química , Óxidos de Nitrogênio/química , Paclitaxel/química , Animais , Antineoplásicos Fitogênicos/toxicidade , Ácido Ascórbico/química , Encéfalo/diagnóstico por imagem , Proliferação de Células/efeitos dos fármacos , Difusão Dinâmica da Luz , Espectroscopia de Ressonância de Spin Eletrônica , Células HeLa , Humanos , Interações Hidrofóbicas e Hidrofílicas , Imagem por Ressonância Magnética , Camundongos , Peso Molecular , Difração de Nêutrons , Oxirredução , Paclitaxel/toxicidade , Tamanho da Partícula , Espalhamento a Baixo Ângulo
13.
Langmuir ; 33(15): 3802-3808, 2017 04 18.
Artigo em Inglês | MEDLINE | ID: mdl-28375635

RESUMO

The evaluation of the transport rates of hydrophilic substances is important in agricultural and pharmaceutical chemistry and in the cosmetics and food-processing industries. Although there are some estimation methods focusing on the diffusion of the substances through the oil phase of the W/O/W core-shell double emulsions (oil microcapsules), all of them take several hours or days. This long-time measurement has a risk of rupture of the oil microcapsules, which causes significant errors. If it were possible to measure the transport rate of substances in the oil phase of the oil microcapsules in real time, the risk of rupture could be reduced. Here, we propose a new estimation method for the transport rates of hydrogen peroxide (H2O2) in the oil phase of an oil microcapsule for real-time estimation by means of chemiluminescence (CL) emission of the luminol reaction. We theoretically give the relationship among the CL emission intensity, diffusion coefficient, microcapsule size, and experimental time and successfully estimate the diffusion coefficient of H2O2 in the oil phase of the oil microcapsule from the experimental data. Moreover, we discuss the dependence of the permeation of H2O2 through the oil phase on the concentration of the oil-soluble surfactant; the difference in the permeation rate is likely to be attributed not to the diffusion coefficient but to the partition coefficient of H2O2 in the oil microcapsule.

14.
J Neurosci Res ; 95(7): 1503-1512, 2017 07.
Artigo em Inglês | MEDLINE | ID: mdl-27704563

RESUMO

Peptidylarginine deiminases (PADs) are posttranslational modification enzymes that citrullinate (deiminate) protein arginine residues in a calcium-dependent manner, yielding citrulline residues. Enzymatic citrullination abolishes positive charges of native protein molecules, inevitably causing significant alterations in their structure and function. Previously, we reported the abnormal accumulation of citrullinated proteins and an increase of PAD2 content in hippocampi of patients with Alzheimer disease. In this study, we investigated PAD expression by using dibutyryl cAMP (dbcAMP) in human astrocytoma U-251MG cells. Under normal culture conditions, PAD2 and PAD3 mRNA expression is detectable with quantitative PCR in U-251MG cells. The addition of dbcAMP in a dose-dependent manner significantly increased this mRNA expression and protein levels. Moreover, PAD enzyme activity also increased significantly and dose-dependently. Furthermore, the expression of PAD2 and PAD3 mRNA was inhibited by the cAMP-dependent PKA inhibitor KT5720, suggesting that such expression of dbcAMP-induced PAD2 and PAD3 mRNA is mediated by the cAMP-PKA signaling pathway in U-251MG cells. This is the first report to document the PAD2 and PAD3 mRNA expression induced by dbcAMP and to attribute the induction of these genes to mediation by the cAMP-PKA signaling pathway in U-251MG cells. © 2016 Wiley Periodicals, Inc.


Assuntos
Astrocitoma/enzimologia , Proteínas Quinases Dependentes de AMP Cíclico/biossíntese , CMP Cíclico/análogos & derivados , Desiminases de Arginina em Proteínas/biossíntese , Transdução de Sinais/fisiologia , Linhagem Celular Tumoral , CMP Cíclico/farmacologia , Relação Dose-Resposta a Droga , Indução Enzimática/fisiologia , Humanos , Inibidores de Proteínas Quinases/farmacologia , Proteína-Arginina Desiminase do Tipo 2 , Proteína-Arginina Desiminase do Tipo 3 , Desiminases de Arginina em Proteínas/antagonistas & inibidores , Transdução de Sinais/efeitos dos fármacos
15.
Macromol Rapid Commun ; 38(1)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27775196

RESUMO

Microfluidic devices, which can continuously fabricate single emulsion with monodispersed droplets having a pore diameter of more than 100 µm in large numbers, can be applied to manufacture ordered macroporous films. 3D ordered macroporous films with a diameter of more than 100 µm can be fabricated using ordered arrays of the monodispersed droplets as templates of the macropores, which are self-assembled in the space between two parallel flat glass plates. As the gap between the glass plates increases, the number of the layer increases. Furthermore, in the case with two or more layers, the lattice structure of the macroporous films also changes due to the confinement effects.


Assuntos
Dispositivos Lab-On-A-Chip , Óleos/química , Emulsões/química , Estrutura Molecular , Tamanho da Partícula , Porosidade , Propriedades de Superfície , Água/química
16.
Chemistry ; 22(33): 11660-6, 2016 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-27406004

RESUMO

The kinetic/thermodynamic origin of preferential enrichment (PE), which is a spontaneous enantiomeric resolution phenomenon applicable to racemic crystals, is described. The mechanism of PE, which was unveiled with respect to the first-generation of chiral organic compounds showing PE, has been interpreted in terms of a nonlinear complexity phenomenon including two unique processes: a solvent-assisted solid-to-solid polymorphic transition and subsequent selective redissolution of the excess one enantiomer from the transformed disordered crystals into the mother liquor. The present works confirm that PE takes place because of the unique nonlinear solubility properties of the two enantiomers after the occurrence of a polymorphic transition under PE crystallization conditions at high supersaturation. Furthermore, a ternary phase diagram that is consistent with the mechanism of PE is proposed.

17.
Chem Commun (Camb) ; 52(20): 3935-8, 2016 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-26871609

RESUMO

The liquid crystalline chiral nitroxide biradical (S,S,S,S)-3 synthesized has shown much larger 'positive magneto-LC effects' in the chiral nematic (N*) phase than the monoradical (S,S)-1.

18.
J Am Chem Soc ; 138(4): 1103-5, 2016 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-26808362

RESUMO

Nanosheets (∼1 nm) are formed using a nonionic hyperswollen lyotropic lamellar phase as a template. The accumulation and reaction of ingredients in the highly separated (several hundred nm) bilayers in the hyperswollen lyotropic lamellar phase should result in very thin nanosheets. This method could be applied to the synthesis of a wide variety of two-dimensional organic and inorganic materials.

19.
Odontology ; 104(3): 282-90, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-26702624

RESUMO

The act of eating is a source of pleasure for people and is a major factor in maintaining a good quality of life. Several types of products for dysphagia patients are available to decrease aspiration of food that often accompanies daily food intake. The final goal of these products is to improve the ease of forming a food bolus and/or the safety of the swallowing process; however, tastes of products are not a major concern with initiation of swallowing. In the present study, we investigated the effect of bitter taste stimuli (quinine) and the combination of quinine and umami (monosodium glutamate: MSG) applied to the oropharynx on reflex swallows evoked by electrical stimulation to the oropharyngeal mucosa. Each of the distilled water (DW), quinine and quinine-MSG mixture solution (volume of each solutions, 100 µl) was applied 1 s prior to electrical stimulation. No swallow was evoked when each of the solutions was applied without electrical stimulation. The application of DW and lower concentration of quinine (<100 µM) did not affect the latency of reflex swallow, but 100 µM quinine application increased the latency of the reflex swallow. In addition, application of quinine-MSG mixture solution counteracted the increase in latency induced by quinine application alone. These findings suggest that MSG enhances the initiation of swallowing along with its well-known increase in appetite stimulation. Adding MSG might be effective when creating food to promote swallowing.


Assuntos
Deglutição/fisiologia , Estimulação Elétrica , Orofaringe/fisiologia , Reflexo/fisiologia , Paladar , Adulto , Feminino , Voluntários Saudáveis , Humanos , Masculino , Pessoa de Meia-Idade , Quinina , Glutamato de Sódio
20.
J Neurosci Res ; 93(11): 1664-74, 2015 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-26190193

RESUMO

Peptidylarginine deiminases (PADs) are posttranslational modification enzymes that convert protein arginine to citrulline residues in a calcium ion-dependent manner. Previously, we reported the abnormal accumulation of citrullinated proteins and the increase in the amount of PAD2 in hippocampi from Alzheimer's disease (AD) patients. Moreover, glial fibrillary acidic protein (GFAP), an astrocyte-specific marker protein, and vimentin were identified as citrullinated proteins by using two-dimensional gel electrophoresis and MALDI-TOF mass spectrometry. To clarify the substrate specificity of PADs against GFAP, we prepared recombinant human (rh)PAD1, rhPAD2, rhPAD3, rhPAD4, and rhGFAP. After incubation of rhGFAP with rhPAD1, rhPAD2, rhPAD3, and rhPAD4, citrullinated (cit-)rhGFAP was detected by Western blotting. The citrullination of rhGFAP by rhPAD2 was unique, specific, and time dependent; additionally, rhPAD1 slightly citrullinated rhGFAP. We then generated eight anti-cit-rhGFAP monoclonal antibodies, CTGF-125, -128, -129, -1212, -1213, -1221, -122R, and -1224R, which reacted specifically with cit-rhGFAP. Two of those eight monoclonal antibodies, CTGF-122R and -1224R, reacted with both cit-rhGFAP and rhGFAP in Western blots. By using the CTGF-1221 antibody and a tandem mass spectrometer, we identified the two independent citrullination sites (R270Cit and R416Cit) of cit-rhGFAP. Immunohistochemical analysis with CTGF-1221 antibody revealed cit-GFAP staining in the hippocampus of AD brain, and the cit-GFAP-positive cells appeared to be astrocyte-like cells. These collective results strongly suggest that PAD2 is responsible for the citrullination of GFAP in the progression of AD and that the monoclonal antibody CTGF-1221, reacting with cit-GFAP at R270Cit and R416Cit, is useful for immunohistochemical investigation of AD brains.


Assuntos
Doença de Alzheimer/patologia , Encéfalo/patologia , Proteína Glial Fibrilar Ácida/metabolismo , Western Blotting , Citrulina/metabolismo , Eletroforese em Gel Bidimensional , Proteína Glial Fibrilar Ácida/análise , Humanos , Hidrolases/metabolismo , Imuno-Histoquímica , Proteína-Arginina Desiminase do Tipo 2 , Desiminases de Arginina em Proteínas , Proteínas Recombinantes/metabolismo , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz
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