Effects of ZnWO4 nanoparticles on growth, photosynthesis, and biochemical parameters of the green microalga Raphidocelis subcapitata.

Nanoparticles have applications in many sectors in the society. ZnWO4 nanoparticles (ZnWO4-NPs) have potential in the fabrication of sensors, lasers, and batteries, and in environmental remediation. Thus, these NPs may reach aquatic ecosystems. However, we still do not know their effects on aquatic biota and, to our knowledge, this is the first study that evaluates the toxicity of ZnWO4-NPs in a eukaryotic organism. We evaluated the toxicity of ZnWO4-NPs on the green microalga Raphidocelis subcapitata for 96 h, in terms of growth, cell parameters, photosynthesis, and biochemical analysis. Results show that most of Zn was presented in its particulate form, with low amounts of Zn2+, resulting in toxicity at higher levels. The growth was affected from 8.4 mg L-1, with 96h-IC50 of 23.34 mg L-1. The chlorophyll a (Chl a) content increased at 30.2 mg L-1, while the fluorescence of Chl a (FL3-H) decreased at 15.2 mg L-1. We observed increased ROS levels at 44.4 mg L-1. Regarding photosynthesis, the NPs affected the oxygen evolving complex (OEC) and the efficiency of the photosystem II at 22.9 mg L-1. At 44.4 mg L-1 the qP decreased, indicating closure of reaction centers, probably affecting carbon assimilation, which explains the decay of carbohydrates. There was a decrease of qN (non-regulated energy dissipation, not used in photosynthesis), NPQ (regulated energy dissipation) and Y(NPQ) (regulated energy dissipation via heat), indicating damage to the photoprotection system; and an increase in Y(NO), which is the non-regulated energy dissipation via heat and fluorescence. The results showed that ZnWO4-NPs can affect the growth and physiological and biochemical parameters of the chlorophycean R. subcapitata. Microalgae are the base of aquatic food chains, the toxicity of emerging contaminants on microalgae can affect entire ecosystems. Therefore, our study can provide some help for better protection of aquatic ecosystems.

Toxicity of α-Ag2WO4 microcrystals to freshwater microalga Raphidocelis subcapitata at cellular and population levels.

Silver-based materials have microbicidal action, photocatalytic activity and electronic properties. The increase in manufacturing and consumption of these compounds, given their wide functionality and application, is a source of contamination to freshwater ecosystems and causes toxicity to aquatic biota. Therefore, for the first time, we evaluated the toxicity of the silver tungstate (α-Ag2WO4), in different morphologies (cube and rod), for the microalga Raphidocelis subcapitata. To investigate the toxicity, we evaluated the growth rate, cell complexity and size, reactive oxygen species (ROS) production and chlorophyll a (Chl a) fluorescence. The α-Ag2WO4 - R (rod) was 1.7 times more toxic than α-Ag2WO4-C (cube), with IC10 and IC50 values of, respectively, 8.68 ± 0.91 µg L-1 and 13.72 ± 1.48 µg L-1 for α-Ag2WO4 - R and 18.60 ± 1.61 µg L-1 and 23.47 ± 1.16 µg L-1 for α-Ag2WO4-C. The release of silver ions was quantified and indicated that the silver ions dissolution from the α-Ag2WO4 - R ranged from 34 to 71%, while the Ag ions from the α-Ag2WO4-C varied from 35 to 97%. The α-Ag2WO4-C induced, after 24 h exposure, the increase of ROS at the lowest concentrations (8.81 and 19.32 µg L-1), whereas the α-Ag2WO4 - R significantly induced ROS production at 96 h at the highest concentration (31.76 µg L-1). Both microcrystal shapes significantly altered the cellular complexity and decreased the Chl a fluorescence at all tested concentrations. We conclude that the different morphologies of α-Ag2WO4 negatively affect the microalga and are important sources of silver ions leading to harmful consequences to the aquatic ecosystem.

Use of magnetic Fe3O4 nanoparticles coated with bovine serum albumin for the separation of lysozyme from chicken egg white.

Fe3O4 magnetic nanoparticles modified with tetraethyl orthosilicate and bovine serum albumin (Fe3O4@TEOS@BSA) were synthesized and efficiently used to separate lysozyme from egg white. Glutaraldehyde was used to crosslink the bovine serum albumine molecules around the nanoparticles. The surface modifications were attested by transmission electron microscopy, infrared spectroscopy, thermogravimetry analysis, and zeta potential. The material was thermally stable, and its surface charge was pH-dependent. The best lysozyme adsorption and desorption were obtained at pHs 10.0 and 5.0, respectively. The pseudo-second-order model fitted well into the lysozyme adsorption kinetic data and the time for the equilibrium was 15 min. The adsorption equilibrium results were best described by the Freundlich model. Fe3O4@TEOS@BSA particles were very efficient to extract lysozyme from chicken egg, according to the SDS-PAGE analyses. The extracted molecules maintained their enzymatic activity in about 90%. Fe3O4@TEOS@BSA particles were easily recycled, with their reuse being possible 5 times with the same performance.

Thermodynamic and kinetic insights into the interactions between functionalized CdTe quantum dots and human serum albumin: A surface plasmon resonance approach.

To explore in vivo application of quantum dots (QDs), it is essential to understand the dynamics and energetics of interactions between QDs and proteins. Here, surface plasmon resonance (SPR) and molecular docking were employed to investigate the kinetics and thermodynamics of interactions between human serum albumin (HSA) and CdTe QDs (~3 nm) functionalized with mercaptopropionic acid (MPA) or thioglycolic acid (TGA). Kinetic analysis showed that HSA-QD interactions involved transition-complex formation. Despite the structural similarities between MPA and TGA, the [HSA-CdTe@TGA]‡ formation by association of free HSA and QDs demanded 70% more energy and higher entropic gain (Ea-TGA‡= 65.10 and T∆Sa-TGA‡= 28.62 kJ mol-1) than the formation of [HSA-CdTe@MPA]‡ (Ea-MPA‡ = 38.13 and T∆Sa-MPA‡ = 0.53kJ mol-1). While the [HSA-CdTe@MPA]° dissociation required higher energy and lower entropy loss (Ed-MPA‡ = 49.96 and T∆Sd-MPA‡ = - 32.18kJ mol-1) than the [HSA-CdTe@TGA]° dissociation (Ed-TGA‡= 30.78 and T∆Sd-TGA‡= - 51.12 kJ mol-1). The stability of [HSA-QDs]° was independent of the temperature and functionalizing group. However, the enthalpic and entropic components were highly affected by the substitution of MPA (ΔH° = - 11.83 and TΔS° = 32.72 kJ mol-1) with TGA (ΔH° = 34.31 and TΔS° = 79.73 kJ mol-1). Furthermore, molecular docking results indicated that the metal site on the QDs contributes to the stabilization of [HSA-QDs]°. Therefore, differences in QD functionalization and surface coverage densities can alter the HSA-QD interaction, thus their application.

Fast and Efficient Method to Obtain Tagitinin F by Photocyclization of Tagitinin C.

There is some evidence in the literature of the photocyclization reaction of Tagitinin C (1) to Tagitinin F (2). Compound 2 has high pharmacological potential, but it is not easy to obtain, while compound 1 is easily obtained from a widespread plant, Tithonia diversifolia. Among different reaction conditions monitored, one was found that allowed the cyclization of 1 into 2 in <15 min in a photo-dependent reaction. Scaling-up the photocyclization of the pure compound 1 into 2 demonstrated 100% yield, and the isolation of 2 from a UV-irradiated extract was eight-fold higher than the quantity isolated from the non-UV-irradiated extract. We were also able to better understand the process of photoconversion and determine methods to isolate and quantify these compounds, which are known for their important antitumoral activities among other important pharmacological properties.

Influence of the ionic strength on the physicochemical properties of methotrexate-loaded chitosan polyelectrolyte complexes

Abstract Polyelectrolyte complexes (PECs) as drug delivery systems are widely explored since they are easily obtained by coacervation and biopolymers can be associated. However, particle distribution is a challenging critical parameter that has been infrequently focused. This work evaluated the effect of NaCl concentration on the physicochemical properties of PECs based on chitosan and hypromellose loaded with methotrexate. The particle size, zeta potential and polydispersity index (PdI) were determined by DLS, besides of drug entrapment efficiency (EE) and in vitro drug release profile determination. Particle size decreased while NaCl concentration rised, achieving a narrower size distribution of (345±79 nm) and PdI (0.285±0.067) with 200 mmol/L NaCl. The higher the NaCl concentration, the lower the zeta potential at acid pH. The EE was kept similar ((28.2±4.5) %) from 0 to 300 mmol/L NaCl, while 400 mmol/L NaCl impaired the drug entrapment. The addition of (200 and 300) mmol/L NaCl did not affect the drug release profile, but it was faster with (100 or 400) mmol/L. In conclusion, the addition of 200 mmol/L NaCl reduced particle size and PdI with no changes in the EE and drug release. Therefore, the ionic strength plays an important role on PECs development.

Synthesis of new phytogrowth-inhibitory substituted aryl-p-benzoquinones.

Reaction of [(2-alkyloxy)methyl]-1,4-dimethoxybenzene 10 (alkyl=butyl, hexyl, decyl, tridecyl, tetradecyl, hexadecyl, and octadecyl) with ceric ammonium nitrate in order to produce p-benzoquinones (=cyclohexa-2,5-diene-1,4-diones) afforded 5-[(alkyloxy)methyl]-2-(4-formyl-2,5-dimethoxyphenyl)benzo-1,4-quinones 12a-12g in yields that varied from 46 to 97%, accompanied by 2-[(alkyloxy)methyl]benzo-1,4-quinones 11a-11g in only small quantities (< or =5%). These quinones resemble the natural phytotoxic compound sorgoleone, found in Sorghum bicolor. This reaction exemplifies a general procedure for the synthesis of novel aryl-substituted p-benzoquinones. The selective effects of compounds 12a-12g, at the concentration of 5.5 ppm, on the growth of Cucumis sativus, Sorghum bicolor, Euphorbia heterophylla, and Ipomoea grandifolia were evaluated. All compounds caused some inhibition upon the aerial parts and root growth of the tested plants. The most active compound, 2-(4-formyl-2,5-dimethoxyphenyl)-5-[(tridecyloxy)methyl]-benzo-1,4-quinone (12d), caused between 3 and 18%, and 12 and 29% inhibition on the roots and aerial parts development of Cucumis sativus and Sorghum bicolor, respectively, and between 77 and 85%, and 34 and 52% inhibition on the roots and aerial parts growth of Euphorbia heterophylla and Ipomoea grandifolia, respectively.

Efeitos de rutina, colestiramina e betalaína no controle de lipídeos em soro de coelhos hiperlipidêmicos / Effects of rutin, colestiramin and betalain in the control of lipids in serum of hyperlipidaemics rabitts

O presente estudo teve como objetivo avaliar o efeito hipolipidêmico do flavonóide rutina, do medicamento colestiramina, do corante natural betalaína, bem como verificar o sinergismo entre o flavonóide rutina associado à betalaína investigando seus efeitos em coelhos. Os resultados foram significativos para o flavonóide e betalaína isoladamente e associados, ou seja, verificando-se o efeito hipolipidêmico e sinérgico destas substâncias nos parâmetros analisados de colesterol total, colesterol-DDL, colesterol-LDL e triacilgliceróis