Chitosan-based magnetite nanocomposites were synthesized using a versatile ultrasound assisted in situ method involving one quick step. This synthetic route approach results in the formation of spheroidal nanoparticles (Fe3O4) with average diameter between 10 and 24nm, which were found to be superparamagnetic with saturation magnetization (Ms) ranges from 32-57emug(-1), depending on the concentration. The incorporation of Fe3O4 into chitosan matrix was also confirmed by FTIR and TG techniques. This hybrid nanocomposite has the potential application as electrochemical sensors, since the electrochemical signal was excepitionally stable. In addition, the in situ strategy proposed in this work allowed us to synthesize the nanocomposite system in a short time, around 2min of time-consuming, showing great potential to replace convencional methods. Herein, the procedure will permit a further diversity of applications into nanocomposite materials engineering.

OBJECTIVE:To determine the safety and efficacy of a transdermal nanostructured formulation of progesterone (10%) combined with estriol (0.1%) + estradiol (0.25%) for relieving postmenopausal symptoms.METHODS:A total of 66 postmenopausal Brazilian women with climacteric symptoms of natural menopause received transdermal nanostructured formulations of progesterone and estrogens in the forearm daily for 60 months to mimic the normal ovarian secretory pattern. Confocal Raman spectroscopy of hormones in skin layers was performed. Clinical parameters, serum concentrations of estradiol and follicle-stimulating hormone, blood pressure, BI-RADS classification from bilateral mammography, and symptomatic relief were compared between baseline and 60 months post-treatment. Clinicaltrials.gov: NCT02033512.RESULTS:An improvement in climacteric symptoms was reported in 92.5% of women evaluated before and after 60 months of treatment. The serum concentrations of estradiol and follicle-stimulating hormone changed significantly (p<0.05) after treatment; the values of serum follicle-stimulating hormone decreased after 60 months from 82.04±4.9 to 57.12±4.1 IU/mL. A bilateral mammography assessment of the breasts revealed normal results in all women. No adverse health-related events were attributed to this hormone replacement therapy protocol.CONCLUSION:The nanostructured formulation is safe and effective in re-establishing optimal serum levels of estradiol and follicle-stimulating hormone and relieving the symptoms of menopause. This transdermal hormone replacement therapy may alleviate climacteric symptoms in postmenopausal women.

In this work, chitosan/magnetite nanoparticles (ChM) were quickly synthesized according to our previous report based on co-precipitation reaction under ultrasound (US) irradiation. Besides ChM was in-depth structurally characterized, showing a crystalline phase corresponding to magnetite and presenting a spheric morphology, a “nanorod”-type morphology was also obtained after increasing reaction time for eight minutes. Successfully, both morphologies presented a nanoscale range with an average particle size of approximately 5–30 nm, providing a superparamagnetic behavior with saturation magnetization ranging from 44 to 57 emu·g−1. As ChM nanocomposites have shown great versatility considering their properties, we proposed a comparative study using three different amine-based nanoparticles, non-surface-modified and surface-modified, for removal of azo dyes from aqueous solutions. From nitrogen adsorption–desorption isotherm results, the surface-modified ChMs increased the specific surface area and pore size. Additionally, the adsorption of anionic azo dyes (reactive black 5 (RB5) and methyl orange (MO)) on nanocomposites surface was pH-dependent, where surface-modified samples presented a better response under pH 4 and non-modified one under pH 8. Indeed, adsorption capacity results also showed different adsorption mechanisms, molecular size effect and electrostatic attraction, for unmodified and modified ChMs, respectively. Herein, considering all results and nanocomposite-type structure, ChM nanoparticles seem to be a suitable potential alternative for conventional anionic dyes adsorbents, as well as both primary materials source, chitosan and magnetite, are costless and easily supplied.

Functionalized Fe3O4 nanoparticles (NPs) have emerged as a promising contrast agent for magnetic resonance imaging (MRI). Their synthesis and functionalization methodology strongly affect their performance in vivo. The methodology most used in the literature for the synthesis of Fe3O4 NPs is thermal decomposition, which has proven to be time-consuming, expensive, and laborious, as it requires further ligand exchange strategies to transfer the as-synthesized nanoparticles from organic to aqueous solvents. This work describes a rapid and facile sonochemical methodology to synthesize and functionalize Fe3O4 NPs with excellent physicochemical properties for MRI. This sonochemistry approach was used to produce, in 12 min, Fe3O4 NPs functionalized with polysodium acrylate (PAANa), trisodium citrate (CIT), branched polyethylenimine (BPEI), and sodium oleate. X-ray diffraction and transmission electron microscopy demonstrated that the NPs were composed of a single inverse spinel phase with an average diameter of 9–11 nm and a narrow size distribution. Mössbauer spectroscopy and magnetic measurements confirmed that the obtained NPs were transitioning to the superparamagnetic regime and possessed excellent magnetization saturation values (59–77 emu/g). Fourier transform infrared spectroscopy proved that the sonochemistry approach provided conditions that induced a strong interaction between Fe3O4 and the coating agents. Furthermore, dynamic light-scattering experiments evidenced that samples coated with PAANa, CIT, and BPEI possess colloidal stability in aqueous solvents. Emphasis must be placed on PAANa-coated NPs, which also presented remarkable colloidal stability under simulated physiological conditions. Finally, the obtained NPs exhibited great potential to be applied as an MRI contrast agent. The transverse relaxivity values of the NPs synthesized in this work (277–439 mM–1 s–1) were greater than those of commercial NPs and those prepared using other methodologies. Therefore, this work represents significant progress in the preparation of Fe3O4 NPs, providing a method to prepare high-quality materials in a rapid, cost-effective, and facile manner.

Parque de Desenvolvimento Tecnológico do Ceará, Rua do Contorno, s/n, Fortaleza -CE. BrasilRecebido em 22/8/06; aceito em 18/5/07; publicado na web em 19/12/07 SIMPLE SYSTEM FOR PREPARATION OF CHITOSAN MICROSPHERES. This article describes the construction and optimization of an inexpensive apparatus for the production of uniform and porous chitosan microspheres. It also describes the control of the main operational parameters and strategies for the production of uniform chitosan microspheres.Keywords: porous beads; chitosan; chitosan microspheres. INTRODUÇÃOA quitosana é um derivado da quitina, biopolímero presente nas carapaças dos crustáceos, nos exoesqueletos dos insetos e nas paredes celulares de fungos 1,2 . A quitina é constituída de unidades 2-acetamido-2-desoxi-D-glicopiranose unidas por ligações β-(1→4) e quando desacetilada, quer seja por tratamento com bases fortes quer seja por métodos microbiológicos, resulta na estrutura β-(1→4)-2-amino-2-desoxi-D-glicopiranose, conhecida como quitosana 1,2 . As propriedades da quitosana, como viscosidade, grau de desacetilação, massa molar dependem das fontes de matéria-prima e métodos de fabricação. O grau de desacetilação, uma das mais importantes propriedades químicas desse polímero, determina a quantidade de grupos amínicos na cadeia polimérica, sendo que, uma extensão acima de 60% de desacetilação, define a entidade química quitosana 2,3 . A quitosana nas formas de pó ou de flocos tem sido muito utilizada em processos de adsorção de íons metálicos 3-10 e corantes [11][12][13] . Todavia, nestas formas a quitosana apresenta duas grandes desvantagens: solubilidade em meio ácido, que dificulta sua recuperação, e baixa área superficial, que limita o acesso aos sítios de adsorção (grupos amino) não expostos, diminuindo a velocidade e a capacidade de adsorção.. Estes problemas podem ser contornados, respectivamente, promovendo-se a reticulação da cadeia polimérica da quitosana e sua modificação física, da forma de pó ou floco para a forma de esferas [14][15][16][17][18][19] . A produção de esferas de quitosana juntamente com a sua funcionalização propiciam a obtenção de um material com elevada capacidade de adsorção de íons metálicos, como tem sido demonstrado em diversas pesquisas [20][21][22][23][24][25][26][27] . Na literatura, diferentes métodos descrevendo o processo de preparação de microesferas de quitosana têm sido publicados, tais como atomização 28,29 , emulsão 30,31 e inversão de fase 32 . Neste trabalho, as microesferas de quitosana foram preparadas pelo método de inversão de fase baseado no trabalho de Rorrer 32 . Entretanto, a confecção reprodutível de microesferas de quitosana porosas e uniformes por esse método depende do controle dos parâmetros: velocidade do fluxo de gotejamento da solução de quitosana, velocidade do fluxo de ar, diâmetro da agulha do gotejador, espaço anular (espaço entre ponta da agulha do tubo ao tubo de saída de ar) e a altura do gotejador em relação à superfície da solução coagulante, bem como da densidade da solução coagulant...