Biofilm Formation of Two Different Marine Bacteria on Modified PDMS Surfaces is Affected by Surface Roughness and Topography.

Different strategies were tested to reduce biofilm formation of the model marine bacteria Cobetia marina and Marinobacter hydrocarbonoclasticus on cross-linked polydimethylsiloxane (PDMS) coated aluminum and cellulose acetate surfaces modified by addition of multi-walled carbon nanotubes (MWCNT) or exposure of the surfaces to bromine vapors in the presence and absence of UV irradiation. The three surface modifications explored led to important reductions in biofilm formation for the two marine bacteria, up to 30% in the case of exposure to Br2(g). Biofouling reduction could be correlated to surface properties in all cases through the introduction of a quantitative theoretical model based on an effective roughness parameter, Raeff, that accounted for the different morphological changes observed. The model considers the possibility of bacterial inclusion into large surface wells, as observed by AFM in the case of Br2(g) + UV light treatment. In addition, a linear relationship was observed between biofouling reduction and the Raeff effective roughness parameter.

Liquid-Polymer Contact Electrification: Modeling the Dependence of Surface Charges and ξ-Potential on pH and Added-Salt Concentration.

Here, a mathematical model is presented, which accounts for the dependence of the surface electrical charge density (σ) on pH and the concentration of added salts (Cs), generated when a water drop rolls or slides on the surface of a hydrophobic polymer, a process known as liquid-polymer contact electrification (LPCE). The same model was successfully applied to fit the isotherms of ξ-potential as a function of pH, reported in the literature by other authors for water-poly(tetrafluoroethylene) (PTFE) interfaces. Hence, the dependence of σ and ξ on pH was described using the same concept: acid-base equilibria at the water-polymer interface. Equilibrium constants were estimated by fitting experimental isotherms. The experimental results and the model are consistent with a number of 10-100 acid-base sites/µm2. The model predicts the increase of |σ| and |ξ| with pH in the range of 2-10 and the existence of a zero-charge point at pHzcp ≅ 3 for PTFE (independent of Cs). Excellent fits were obtained with Ka/Kb ∼ 9 × 107, where Ka and Kb are the respective acid and base equilibrium constants. On the other hand, the observed decrease in |σ| and |ξ| with Cs at fixed pH is quantitatively described by introducing an activity factor associated with the quenching of water activity by the salt ions at the polymer-water interface, with quenching constant Kq. Additionally, the quenching predicts a decrease in |σ| and |ξ| at extreme pH, where I > (1/Kq) (I: ionic strength), in agreement with literature reports.

Liquid-polymer triboelectricity: chemical mechanisms in the contact electrification process.

Liquid-polymer contact electrification between sliding water drops and the surface of polytetrafluoroethylene (PTFE) was studied as a function of the pH and ionic strength of the drop as well as ambient relative humidity (RH). The PTFE surface was characterized by using SEM, water-contact-angle measurements, FTIR spectroscopy, XPS, and Raman spectroscopy. The charge acquired by the drops was calculated by detecting the transient voltage induced on a specifically designed capacitive sensor. It is shown that water drops become positively charged at pH > pHzch (pHzch being the zero charge point of the polymer) while they become negatively charged for pH < pHzch. The addition of non-hydrolysable salts (NaCl or CaCl2) to water decreases the electrical charge induced in the drop. The charge also decreases with increasing RH. These results suggest proton or hydroxyl transfer from the liquid to the hydrophobic polymer surface. A proposed thermodynamic model for the ion transfer process allows explaining the observed effects of RH, pH and ionic strength.

Modified ribavirin analogues as antiviral agents against Junín virus.

In this work, several ribavirin analogues were synthesized and incorporated into a multivalent arrangement. Both were subsequently modified by the addition of polyhydroxylated residues. Their antiviral activity was tested against Junín virus, etiological agent responsible of Argentine hemorrhagic fever. Some compounds inhibited Junín virus in the range of 13.2-389.1 µM. Two modified ribavirin analogues presented an effective concentration comparable to ribavirin but with a higher selectivity index.

Synthesis and in vitro antiproliferative activities of (5-aryl-1,2,4-oxadiazole-3-yl) methyl d-ribofuranosides.

The emergence of multidrug resistance cell lines is one of the major obstacles in the success of cancer chemotherapeutic treatment. Therefore, it remains a big challenge the development of new and effective drugs to defeat cancer. The presence of nitrogen heterocycles in the architectural design of drugs has led to the discovery of new leading compounds. Herein, we report the synthesis, characterization and in vitro antiproliferative activity against six cancer cell lines of d-ribofuranoside derivatives bearing a 1,2,4-oxadiazolic ring, with the aim of developing new active compounds. Most of these derivatives exhibit significant antiproliferative activities in the micromolar range. Noteworthy, the most potent compound of the series showed better selectivity towards the more resistant colon cancer cell line WiDr.

Antiviral activity of an N-allyl acridone against dengue virus.

BACKGROUND: Dengue virus (DENV), a member of the family Flaviviridae, is at present the most widespread causative agent of a human viral disease transmitted by mosquitoes. Despite the increasing incidence of this pathogen, there are no antiviral drugs or vaccines currently available for treatment or prevention. In a previous screening assay, we identified a group of N-allyl acridones as effective virus inhibitors. Here, the antiviral activity and mode of action targeted to viral RNA replication of one of the most active DENV-2 inhibitors was further characterized. RESULTS: The compound 10-allyl-7-chloro-9(10H)-acridone, designated 3b, was active to inhibit the in vitro infection of Vero cells with the four DENV serotypes, with effective concentration 50% (EC50) values in the range 12.5-27.1 µM, as determined by virus yield inhibition assays. The compound was also effective in human HeLa cells. No cytotoxicity was detected at 3b concentrations up to 1000 µM. Mechanistic studies demonstrated that virus entry into the host cell was not affected, whereas viral RNA synthesis was strongly inhibited, as quantified by real time RT-PCR. The addition of exogenous guanosine together with 3b rescued only partially the infectivity of DENV-2. CONCLUSIONS: The acridone derivative 3b selectively inhibits the infection of Vero cells with the four DENV serotypes without a direct interaction with the host cell or the virion but interfering specifically with the intracellular virus multiplication. The mode of antiviral action for this acridone apparently involves the cellular enzyme inosine-monophospahe dehydrogenase together with another still unidentified target related to DENV RNA synthesis.

Quantification of Enzymatic Biofilm Removal Using the Sauerbrey Equation: Application to the Case of Pseudomonas protegens.

A methodology for the quantitative analysis of enzymatic removal of biofilms (BF) was developed, based on a quartz crystal microbalance (QCM) under stationary conditions. This was applied to the case of Pseudomonas protegens (PP) BFs, through a series of five enzymes, whose removal activity was screened using the presented methodology. The procedure is based on the following: when BFs can be modeled as rigid materials, QCM can be used as a balance under stationary conditions for determining the BFs mass reduction by enzymatic removal. For considering a BF as a rigid model, energy dissipation effects, associated with viscoelastic properties of the BF, must be negligible. Hence, a QCM system with detection of dissipation (referred to as QCM with dissipation) was used for evaluating the energy losses, which, in fact, resulted in negligible energy losses in the case of dehydrated PP BFs, validating the application of the Sauerbrey equation for the change of mass calculations. The stationary methodology reduces operating times and simplifies data analysis in comparison to dynamic approaches based on flow setups, which requires the incorporation of dissipation effects due to the liquid media. By carrying out QCM, glycosidase-type enzymes showed BF removal higher than 80% at enzyme concentration 50 ppm, reaching removal over 90% in the cases of amylase and cellulase/xylanase enzymes. The highest removal percentage produced a reduction from about 15 to 1 µg in the BF mass. Amylase enzyme was tested from below 50 to 1 ppm, reaching around 60% of removal at 1 ppm. The obtained results were supported by other instrumental techniques such as Raman spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, atomic force microscopy, high performance anion exchange chromatography, thermogravimetric analysis, and differential scanning calorimetry. The removal quantifications obtained with QCM were compared with those obtained by well-established screening techniques (UV-vis spectrophotometry using crystal violet and agar diffusion test). The proposed methodology expands the possibility of using a quartz microbalance to perform enzymatic activity screening.

From the Lab to the Field: Organic Materials for Industrial Applications and Environmental Remediation.

Many new developments for different industries have their origin in basic science. In recent years, this trend has gained attention due to the increasing interaction between academic science and industry. This article presents some rational materials for chemical modifications that were developed by the basic science, then transferred to the productive sector. Conducting hydrophobic coatings for aerospace applications, hydrogels for the oil and gas industry, as well as polymers for removal of heavy metal, were some of the topics approached in the lab to solve industrial problems. Many times, nature is a great source of inspiration to produce new materials. In this sense, superhydrophobicity and superhydrophilicity (concepts closely related to our everyday life) were the bioinspiration for the development of membranes. These membranes were able to separate hydrocarbons and water, which found application in the treatment of subterranean water for the oil and gas industry.

Hemicelluloses hydrogel: Synthesis, characterization, and application in dye removal.

Novel materials using biowaste as adsorbents in wastewater treatment have been allocated considerable interest. Herein, we present the synthesis of different hydrogels of crosslinked polyacrylamide in presence of hemicelluloses with/ without bentonite, using a soft reaction condition. The structure of new hydrogels was characterized by spectroscopic, thermal and microscopic experiments. The semi-interpenetrated network with hemicelluloses: 10 %; acrylamide 79 %; bentonite 10 %; N,N,N',N'-tetramethylethylenediamine: 1 % allows reducing 20 % the use of non-renewable acrylamide, without changing its decomposition temperatures and keeping its water absorption capacity. This hydrogel was applied to dye removals, such as rhodamine B, methylene red and methylene blue in aqueous solutions. In the case of methylene blue, highest removal is observed with maximum adsorption of qmax = 140.66 mg/g, compared to material without hemicelluloses that only a qmax = 88.495 mg/g. The adsorption kinetics and equilibrium adsorption isotherms are in accordance with the pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The developed hydrogel from hemicelluloses represents a potential alternative adsorbent for a sustainable system of sewage treatment.

Alternative modification by grafting in bamboo cellulose nanofibrils: A potential option to improve compatibility and tunable surface energy in bionanocomposites.

Chemical modification in surface of cellulose nanofibrils CNFs (20 nm) from an endemic and non-significant value-added, Argentine bamboo, was developed. The modification in the CNFs was carried out with three simple routes using a low molecular weight polylactic acid synthesized in our laboratory (PLA1). The first step comprises of protection of the hydroxyl groups of PLA1 through a benzoylation (PLA1Bz). The next step consisted of the activation of carboxyl groups using thionyl chloride and the last reaction was the grafting of the modified PLA onto the CNFs (PLA1Bz-g-CNF). The covalently functionalization is confirmed by spectroscopically techniques as well as PLA1Bz-g-CNFs were characterized by thermal analyses. The PLA1Bz-g-CNFs were taken up such as nanocharges to improve properties of compatibilization and changing surface properties in films based on PLA. The comparison between the films with PLA1Bz-g-CNFs with respect to the physic mixture of the components (PLA1Bz/CNF), shows an improvement in the thermal, mechanical, and surface properties of the material, particularly when 5% of PLA1Bz-g-CNFs was added. The dispersive (γS D) component of film is increased in 36.1 mN/m respect to 29.3 mN/m from the films obtained with the physic mixture nanofibrils without modification and a plasticizing effect was noticed in the final material.

Antiviral activity against Zika virus of a new formulation of curcumin in poly lactic-co-glycolic acid nanoparticles.

OBJECTIVES: In the search of an effective antiviral formulation, the natural product curcumin (CUR) was encapsulated into poly(lactic-co-glycolic acid) nanoparticles, a non-toxic bioresorbable and biocompatible copolymer. The resulting CUR containing particles (PLGA-CUR NPs) were characterized and analysed for antiviral activity against Zika virus (ZIKV) infection. METHODS: The PLGA-CUR NPs were characterized by Fourier transform infrared, differential scanning calorimetry, dynamic light scattering, scanning electron microscopy and thermogravimetric analysis and release profile. Cytotoxicity of PLGA-CUR and the antiviral activity against ZIKV were determined in Vero cells. The effect of PLGA-CUR NPs on viral RNA synthesis and protein expression was analysed by RT-qPCR and immunofluorescence staining, respectively. KEY FINDINGS: The PLGA-CUR NPs showed an appropriate in vitro drug release profile. Our studies of the antiviral activity of PLGA-CUR NPs and CUR against ZIKV by virus yield reduction as well as viral RNA synthesis and protein expression have shown that PLGA-CUR formulation is more effective than free CUR to inhibit ZIKV infection of Vero cells. CONCLUSIONS: Our results demonstrate for the first time the antiviral activity against ZIKV of PLGA nanoparticles charged with CUR, suggesting that PLGA-CUR NPs are promising candidates for a drug formulation against human pathogenic flaviviruses.

Application of Crosslinked Polybenzimidazole-Poly(Vinyl Benzyl Chloride) Anion Exchange Membranes in Direct Ethanol Fuel Cells.

Crosslinked membranes have been synthesized by a casting process using polybenzimidazole (PBI) and poly(vinyl benzyl chloride) (PVBC). The membranes were quaternized with 1,4-diazabicyclo[2.2.2]octane (DABCO) to obtain fixed positive quaternary ammonium groups. XPS analysis has showed insights into the changes from crosslinked to quaternized membranes, demonstrating that the crosslinking reaction and the incorporation of DABCO have occurred, while the 13C-NMR corroborates the reaction of DABCO with PVBC only by one nitrogen atom. Mechanical properties were evaluated, obtaining maximum stress values around 72 MPa and 40 MPa for crosslinked and quaternized membranes, respectively. Resistance to oxidative media was also satisfactory and the membranes were evaluated in single direct ethanol fuel cell. PBI-c-PVBC/OH 1:2 membrane obtained 66 mW cm-2 peak power density, 25% higher than commercial PBI membranes, using 0.5 bar backpressure of pure O2 in the cathode and 1 mL min-1 KOH 2M EtOH 2 M aqueous solution in the anode. When the pressure was increased, the best performance was obtained by the same membrane, reaching 70 mW cm-2 peak power density at 2 bar O2 backpressure. Based on the characterization and single cell performance, PBI-c-PVBC/OH membranes are considered promising candidates as anion exchange electrolytes for direct ethanol fuel cells.

Advances in drug delivery, gene delivery and therapeutic agents based on dendritic materials.

Dendrimers are synthetic polymers that grow in three dimensions into well-defined structures. Their morphological appearance resembles a number of trees connected by a common point. Dendritic nanoparticles have been studied for a large number of pharmaceutical and biomedical applications including gene and drug delivery, clinical diagnosis and MRI. Despite the application of dendrimers, research is still in its childhood in comparison with liposomes and other nanomaterials. They are now playing a key role in several therapeutic strategies, with dendrimer-based products in clinical trials. The aim of this review is to describe the state-of-the-art of biomedical applications of dendrimers - and dendrimer conjugates - such as drug and gene delivery and antiviral activity.

Synthesis and antiviral activity of some imidazo[1,2-b][1,3,4]thiadiazole carbohydrate derivatives.

Herein we describe the synthesis of imidazo[2,1-b][1,3,4]thiadiazoles from carbohydrates with D-ribo and D-xylo configuration. The antiviral activity of these compounds was tested against Junín virus (the etiological agent of Argentine hemorrhagic fever). The p-chlorophenyl derivatives showed antiviral activity in a range of micromolar concentration.

Development of carbohydrate functionalized magnetic nanoparticles for aminoglycosides magnetic solid phase extraction.

Magnetic nanoparticles decorated with d-galactose and galactitol (Fe3O4@SiN-galactose and Fe3O4@SiN-galactitol) were synthesized and employed as sorbent in a magnetic solid phase extraction (MSPE) procedure prior the analysis of aminoglycosides (AGs) in honey samples by LC-MS/MS. AGs are broad spectrum antibiotics, characterized by aminosugars, widespread used in therapeutic and veterinary applications. AGs can be found in the environment and food of animal origin. Fe3O4@SiN-galactose and Fe3O4@SiN-galactitol were synthesized via copper catalyzed alkyne azide cycloaddition and the synthesis was efficiently followed by infrared spectroscopy. They were characterized by electron microscopy, thermogravimetric analysis and magnetization curves. The nature of the loading (acetonitrile:water, 50:50 v/v) and elution solution (formic acid 190 mM) were studied in order to optimize the MSPE. Quantitative difference between MSPE with Fe3O4@SiN-galactose and MSPE with Fe3O4@SiN-galactitol in terms of recovery was found. The final optimized method using Fe3O4@SiN-galactose and Fe3O4@SiN-galactitol was applied in the determination of AGs in honey. The MSPE performance of Fe3O4@SiN-galactitol was found to be superior to that of MSPE with Fe3O4@SiN-galactose. The limits of quantification were between 2 and 19 µg kg-1 for amikacin, dihydrostreptomycin, tobramicyn and gentamycin. A good correlation between predicted and nominal values of AGs in honey was found (trueness from 84% to 109%). This MSPE procedure not only requires a minimum amount of sorbent (1 mg) and sample (0.2 g), but it can also be accomplish in a rather short time.

Effect of radiant exposure and UV accelerated aging on physico-chemical and mechanical properties of composite resins.

Currently, there is no consensus in terms of defining the minimum radiant exposure values necessary for achieving adequate properties of composite resin. In addition, the long-term influence that radiant exposure has on the properties of composite resins is still questionable. OBJECTIVE: The objective of this study was to evaluate the effect of radiant exposure and UV accelerated aging on the physico-chemical and mechanical properties of micro-hybrid and nanofilled composite resins. MATERIAL AND METHODS: A nanofilled (Filtek Supreme; 3M ESPE) and a micro-hybrid composite resin (Filtek Z250; 3M ESPE) were investigated under different radiant exposures (3.75, 9, and 24 J/cm2) and UV accelerated aging protocols (0, 500, 1000, and 1500 aging hours). The degree of conversion (DC), flexural strength (FS), modulus (M), water sorption (WS), and solubility (WL) were evaluated. The results obtained were analyzed using two-way ANOVA and Tukey's test. Comparisons were performed using a significance level of α=0.05. RESULTS: The DC, FS, and M were found to be significantly influenced by both radiant exposure and accelerated aging time. The DC and EM increased with radiant exposure in the no-aging group (0-hour aging) for both micro-hybrid and nanofilled composites, whereas no correlation was found after accelerated aging protocols. WS and WL of micro-hybrid and nanofilled composite resins were scarcely affected by radiant exposure (p>0.05), whereas they were significantly reduced by accelerated aging (p<0.001). CONCLUSIONS: Although increasing radiant exposure affected the degree of conversion and mechanical properties of micro-hybrid and nanofilled composites, no influence on the hydrolytic degradation of the material was observed. In contrast, UV accelerated aging affected both the physico-chemical and mechanical properties of the composites.

Synthesis and evaluation of N-substituted acridones as antiviral agents against haemorrhagic fever viruses.

BACKGROUND: In the present study, a series of N-substituted acridone derivatives was synthesized and evaluated against two haemorrhagic fever viruses (HFV). METHODS: Compounds were tested against Junin virus (JUNV), an arenavirus agent of Argentine haemorrhagic fever, and dengue virus (DENV), a flavivirus agent of the most prevalent arthropod-borne viral disease in humans. RESULTS: Among tested compounds, two N-allyl acridones (derivatives 3c and 3f) elicited a potent and selective antiviral activity against JUNV (strain 1V4454) and DENV-2 (strain NGC) with 50% effective concentration values between 2.5 and 5.5 microM, as determined by virus yield inhibition. No cytotoxicity was detected at concentrations up to 1,000 microM, resulting in selectivity indices >181.8-400.0. Both acridones were effective against a wide spectrum of arenaviruses and the four serotypes of DENV. Furthermore, 3c and 3f failed to inactivate virus before cell infection as well as to induce a refractory state by cell pretreatment, indicating that the inhibitory effect was exerted through a blockade in virus multiplication during the infectious process. CONCLUSION: These data are the first demonstration that acridone derivatives have a potent antiviral activity that block in vitro multiplication of HFV belonging to Arenaviridae and Flaviviridae, such as JUNV and DENV.

Synthesis and antiviral activity of azoles obtained from carbohydrates.

Herein we describe the synthesis of 1,2,4-triazolyl-3-thione;1,3,4-oxadiazole, and imidazo[2,1-b]thiazole derivatives from carbohydrates. The antiviral activity of these compounds was tested against Dengue and Junin virus (the etiological agent of Argentine hemorrhagic fever). The 3-(p-bromobenzoyl)-5-(1,2-O-isopropylidene-3-O-methyl-alpha-d-xylofuranos-5-ulos-5-yl)imidazo[2,1-b]thiazole was able to inhibit the replication of both viruses in Vero cells at concentration significantly lower than the CC(50).

Effect of energy density on color stability in dental resin composites under accelerated aging.

The effects of the energy density that is used for polymerization on properties of dental resin composites are well known. However, few studies relate color stability to this factor. The aim of this study was to assess color changes (deltaE*), in vitro, in terms of accelerated aging under UV exposure of specimens prepared with different energy densities. Four commercial dental resin composites were included in the study. Thirty six specimens were prepared for each one of them, following the procedure established by ISO 4049 Standard, and assigned to three groups: A (3.75 J/cm2), B (9 J/cm2), C (24 J/cm2). Each group was further subdivided into four subgroups: 1 (no aging), 2 (500 hours aging), 3 (1000 hours aging) and 4 (1500 hours aging). The results were analyzed by means of ANOVA and Tukey's test (alpha = 0.05) to determine the effect of the factors. Correlation was performed in order to determine the possible relationship among variables. Energy density is not a significant factor in color stability. However aging is directly proportional to color changes. deltaE* depends on filler size; hybrid material presented deltaE* of 2.1(0.5), 2.4(0.6) and 3.3(0.3) at 500, 1000 and 1500 hours of accelerated aging respectively, and nanofilled material showed deltaE* of 3.0(0.6), 4.5(1.2) and 5.9(0.6) at the same times respectively. It can be concluded that deltaE* does not depend on energy density; however other factors are involved in color change. Further studies in this area are warranted.

Game-changing restraint of Ros-damaged phenylalanine, upon tumor metastasis.

An abrupt increase in metastatic growth as a consequence of the removal of primary tumors suggests that the concomitant resistance (CR) phenomenon might occur in human cancer. CR occurs in murine tumors and ROS-damaged phenylalanine, meta-tyrosine (m-Tyr), was proposed as the serum anti-tumor factor primarily responsible for CR. Herein, we demonstrate for the first time that CR happens in different experimental human solid tumors (prostate, lung anaplastic, and nasopharyngeal carcinoma). Moreover, m-Tyr was detected in the serum of mice bearing prostate cancer (PCa) xenografts. Primary tumor growth was inhibited in animals injected with m-Tyr. Further, the CR phenomenon was reversed when secondary implants were injected into mice with phenylalanine (Phe), a protective amino acid highly present in primary tumors. PCa cells exposed to m-Tyr in vitro showed reduced cell viability, downregulated NFκB/STAT3/Notch axis, and induced autophagy; effects reversed by Phe. Strikingly, m-Tyr administration also impaired both, spontaneous metastasis derived from murine mammary carcinomas (4T1, C7HI, and LMM3) and PCa experimental metastases. Altogether, our findings propose m-Tyr delivery as a novel approach to boost the therapeutic efficacy of the current treatment for metastasis preventing the escape from tumor dormancy.