Effects of chemical aging on carbonaceous materials: Stability of water-dispersible colloids and their influence on the aggregation of natural-soil colloid.

Although hydrochar and biochar have been used as soil conditioners, there is not a clear understanding of how their properties changes due to aging impacts their colloidal particles behavior on the soil system. From this premise, we produced hydrochar and biochar from the same feedstock (cashew bagasse) and aged with different chemical methods: (i) using hydrogen peroxide, (ii) a mixture of nitric and sulfuric acids, and (iii) hot water. It was analyzed the effects of aging on the stability of the carbonaceous materials (CMs) colloids in aqueous medium with different ionic strength (single systems), as well as the stability of the natural-soil colloid when interacting with biochar and hydrochar colloids (binary systems). A chemical composition (C, H, N, and O content) change in CMs due to the chemically induced aging was observed along with minor structural modifications. Chemical aging could increase the amount of oxygen functional groups for both biochar and hydrochar, though in a different level depending on the methodology applied. In this sense, hydrochar was more susceptive to chemical oxidation than biochar. The effectiveness of chemical aging treatments for biochar increased in the order of water < acid < hydrogen peroxide, whereas for hydrochar the order was water < hydrogen peroxide < acid. While the increase in surface oxidation improved the biochar colloidal stability in water medium at different ionic strengths (single systems), the stability and critical coagulation concentration (CCC) slightly changed for hydrochar. Natural-soil clay (NSC) interactions with oxidized carbonaceous material colloids (binary systems) enhanced NSC stability, which is less likely to aggregate. Therefore, the aging of carbonaceous materials modifies the interaction and dynamics of soil small particles, requiring far more attention to the environmental risks due to their application over time.

"Attacking-Attacking" Anti-biofouling Strategy Enabled by Cellulose Nanocrystals-Silver Materials.

The development of high-performance anti-biofouling surfaces is paramount for controlling bacterial attachment and biofilm growth in biomedical devices, food packing, and filtration membranes. Cellulose nanocrystals (CNCs), a carbon-nanotube-like nanomaterial, have emerged as renewable and sustainable antimicrobial agents. However, CNCs inactivate bacteria under contact-mediated mechanisms, limiting its antimicrobial property mostly to the attached bacteria. This study describes the combination of CNCs with silver nanoparticles (CNC/Ag) as a strategy to increase their toxicity and anti-biofouling performance. CNC/Ag-coated surfaces inactivated over 99% of the attached Escherichia coli and Bacillus subtilis cells compared to 66.9 and 32.9% reduction shown by the pristine CNC, respectively. CNC/Ag was also very toxic to planktonic cells, displaying minimal inhibitory of 25 and 100 µg/mL against B. subtilis and E. coli, respectively. CNC/Ag seems to inactivate bacteria through an "attacking-attacking" mechanism where CNCs and silver nanoparticles play different roles. CNCs can kill bacteria by piercing the cell membrane. This physical membrane stress-mediated mechanism is demonstrated as lipid vesicles release their encapsulated dye upon contact with CNCs. Once the cell membrane is punctured, silver ions can enter the cell passively and compromise the integrity of DNA and other organelles. Inside the cells, Ag+ may damage the cell membrane by selectively interacting with sulfur and nitrogen groups of enzymes and proteins or by harming DNA via accumulation of reactive oxygen species. Therefore, CNC/Ag toxicity seems to combine the puncturing effect of the needle-like CNC and the silver's ability to impair the cell membrane and DNA functionalities.

Dynamics of bacterial population growth in biofilms resemble spatial and structural aspects of urbanization.

Biofilms develop from bacteria bound on surfaces that grow into structured communities (microcolonies). Although surface topography is known to affect bacterial colonization, how multiple individual settlers develop into microcolonies simultaneously remains underexplored. Here, we use multiscale population-growth and 3D-morphometric analyses to assess the spatiotemporal development of hundreds of bacterial colonizers towards submillimeter-scale microcolony communities. Using an oral bacterium (Streptococcus mutans), we find that microbial cells settle on the surface randomly under sucrose-rich conditions, regardless of surface topography. However, only a subset of colonizers display clustering behavior and growth following a power law. These active colonizers expand three-dimensionally by amalgamating neighboring bacteria into densely populated microcolonies. Clustering and microcolony assembly are dependent on exopolysaccharides, while population growth dynamics and spatial structure are affected by cooperative or antagonistic microbes. Our work suggests that biofilm assembly resembles certain spatial-structural features of urbanization, where population growth and expansion can be influenced by type of settlers, neighboring cells, and further community merging and scaffolding occurring at various scales.

Catalytic antimicrobial robots for biofilm eradication.

Magnetically driven robots can perform complex functions in biological settings with minimal destruction. However, robots designed to damage deleterious biostructures could also have important impact. In particular, there is an urgent need for new strategies to eradicate bacterial biofilms as we approach a post-antibiotic era. Biofilms are intractable and firmly attached structures ubiquitously associated with drug-resistant infections and destruction of surfaces. Existing treatments are inadequate to both kill and remove bacteria leading to reinfection. Here we design catalytic antimicrobial robots (CARs) that precisely and controllably kill, degrade and remove biofilms with remarkable efficiency. CARs exploit iron oxide nanoparticles (NPs) with dual catalytic-magnetic functionality that (i) generate bactericidal free radicals, (ii) breakdown the biofilm exopolysaccharide (EPS) matrix, and (iii) remove the fragmented biofilm debris via magnetic field driven robotic assemblies. We develop two distinct CAR platforms. The first platform, the biohybrid CAR, is formed from NPs and biofilm degradation products. After catalytic bacterial killing and EPS disruption, magnetic field gradients assemble NPs and the biodegraded products into a plow-like superstructure. When driven with an external magnetic field, the biohybrid CAR completely removes biomass in a controlled manner, preventing biofilm regrowth. Biohybrid CARs can be swept over broad swathes of surface or can be moved over well-defined paths for localized removal with microscale precision. The second platform, the 3D molded CAR, is a polymeric soft robot with embedded catalytic-magnetic NPs, formed in a customized 3D printed mold to perform specific tasks in enclosed domains. Vane-shaped CARs remove biofilms from curved walls of cylindrical tubes, and helicoid-shaped CARs drill through biofilm clogs, while simultaneously killing bacteria. In addition, we demonstrate applications of CARs to target highly confined anatomical surfaces in the interior of human teeth. These 'kill-degrade-and-remove' CARs systems could have significant impact in fighting persistent biofilm-infections and in mitigating biofouling of medical devices and diverse surfaces.

On the formation of protein corona on colloidal nanoparticles stabilized by depletant polymers.

To counter the undesired colloidal destabilization of nanoparticles in biologically-compatible media of high ionic strength (i.e. NaCl, phosphate buffer), polymers can be added to nanoparticle suspensions that will be used in biomedical applications. In these suspensions, polymers can promote high colloidal stability by manifestation of steric and/or depletion forces. However, little is known about the influence of these polymers on the interactions between nanoparticles and the biological components of the organism, such as proteins and cells. In this work, it was shown that the addition of the polymers (i) Pluronic-F127 (PF127), (ii) polyethylene glycol (PEG) of different molecular weights - 1.5, 12 and 35 kDa - and (iii) the protein bovine serum albumin (BSA) on colloidal silica nanoparticles (CSNPs; 135 nm) dispersed in phosphate-buffered saline (PBS) largely alter their colloidal stability through different mechanisms. Although all polymers were adsorbed on the CSNP surface, BSA maintained the CSNP dispersion in the medium by electrosteric stabilization mechanisms, while PEG and PF127 led to the occurrence of depletion forces between the particles. In addition, it was found that the interactions between polymers and CSNPs did not prevent proteins to access the nanoparticles' surface and have minimal effect on the formation of the protein corona when they were incubated in human blood plasma. On the other hand, BSA had a greater effect on the CSNP protein corona profile compared to other polymers (PEG and PF127). Together, these results confirm that biocompatible polymers PEG and PF127 can be used as colloidal stabilizing agents for nanoparticles since they preserve the accessibility of biomolecules to the nanoparticle surface, and they have little effect on the protein corona composition.

Biogenic synthesis of multifunctional silver nanoparticles from Rhodotorula glutinis and Rhodotorula mucilaginosa: antifungal, catalytic and cytotoxicity activities.

Silver nanoparticles (AgNPs) have several technological applications and may be synthetized by chemical, physical and biological methods. Biosynthesis using fungi has a wide enzymatic range and it is easy to handle. However, there are few reports of yeasts with biosynthetic ability to produce stable AgNPs. The purpose of this study was to isolate and identify soil yeasts (Rhodotorula glutinis and Rhodotorula mucilaginosa). After this step, the yeasts were used to obtain AgNPs with catalytic and antifungal activity evaluation. Silver Nanoparticles were characterized by UV-Vis, DLS, FTIR, XRD, EDX, SEM, TEM and AFM. The AgNPs produced by R. glutinis and R. mucilaginosa have 15.45 ± 7.94 nm and 13.70 ± 8.21 nm (average ± SD), respectively, when analyzed by TEM. AgNPs showed high catalytic capacity in the degradation of 4-nitrophenol and methylene blue. In addition, AgNPs showed high antifungal activity against Candida parapsilosis and increase the activity of fluconazole (42.2% for R. glutinis and 29.7% for R. mucilaginosa), while the cytotoxicity of AgNPs was only observed at high concentrations. Finally, two yeasts with the ability to produce AgNPs were described and these particles showed multifunctionality and can represent a technological alternative in many different areas with potential applications.

Cellulose nanocrystals as carriers in medicine and their toxicities: A review.

Cellulose nanocrystals (CNCs) are crystalline nanoparticles that present myriad applications. CNCs are produced from a variety of renewable sources, and they can be chemically modified. Although there are promising perspectives for introducing CNCs into pharmaceutical formulations, prior to achieving commercial products the influence of many parameters such as extraction and toxicity of the resulting products must be revealed. Since there is great physicochemical flexibility in the steps of obtaining and conjugating CNCs, there are uncountable and complex outcomes from the interactions of those parameters. We present a discussion that helps to unveil the whole panorama on the use of CNCs as drug delivery systems. The methods of producing CNCs are correlated to the resulting nanotoxicity from the cellular to organism level. This review points to relevant concerns that must be overcome to attain safe use of these nanostructures. We also discuss the patents and commercially available products based on CNCs.

Silver nanoparticles in dentistry.

OBJECTIVE: Silver nanoparticles (AgNPs) have been extensively studied for their antimicrobial properties, which provide an extensive applicability in dentistry. Because of this increasing interest in AgNPs, the objective of this paper was to review their use in nanocomposites; implant coatings; pre-formulation with antimicrobial activity against cariogenic pathogens, periodontal biofilm, fungal pathogens and endodontic bacteria; and other applications such as treatment of oral cancer and local anesthesia. Recent achievements in the study of the mechanism of action and the most important toxicological aspects are also presented. METHODS: Systematic searches were carried out in Web of Science (ISI), Google, PubMed, SciFinder and EspaceNet databases with the keywords "silver nano* or AgNP*" and "dentist* or dental* or odontol*". RESULTS: A total of 155 peer-reviewed articles were reviewed. Most of them were published in the period of 2012-2017, demonstrating that this topic currently represents an important trend in dentistry research. In vitro studies reveal the excellent antimicrobial activity of AgNPs when associated with dental materials such as nanocomposites, acrylic resins, resin co-monomers, adhesives, intracanal medication, and implant coatings. Moreover, AgNPs were demonstrated to be interesting tools in the treatment of oral cancers due to their antitumor properties. SIGNIFICANCE: The literature indicates that AgNPs are a promising system with important features such as antimicrobial, anti-inflammatory and antitumor activity, and a potential carrier in sustained drug delivery. However, there are some aspects of the mechanisms of action of AgNPs, and some important toxicological aspects arising from the use of this system that must be completely elucidated.

Doxorubicin-Functionalized Silica Nanoparticles Incorporated into a Thermoreversible Hydrogel and Intraperitoneally Administered Result in High Prostate Antitumor Activity and Reduced Cardiotoxicity of Doxorubicin.

Described here is an anticancer material based on colloidal mesoporous silica nanoparticles (MSNs) functionalized with doxorubicin (DOX), and incorporated into Pluronic F127 hydrogels for prolonged release, with a potential therapeutic application for prostate cancer treatment. The MSNs have spherical morphology, size of about 60 nm, surface area of 970 cm2 g-1 and average pore width of 2.0 nm. A high colloidal stability for the MSNs in the physiological medium used for in vivo administration (NaCl 0.9% w/v) could be attained in the presence of PF127 (from 5 to 18 wt %), where depletion repulsion forces prevent MSN agglomeration. By conjugating DOX, MSN and PF127 (18 wt %) in NaCl 0.9%, the hybrid system has a gelation temperature of 21 °C, which allowed its in vivo administration in the liquid form and further in situ gelation, generating a drug depot system inside the animals after peritoneal injection. The systems were tested in rats with chemically induced prostate cancer and, after this treatment, histopathological analyses confirmed (i) a reduction in the frequency of aggressive tumors; (ii) that the antitumor effect was dependent on MSN concentration; and most importantly (iii) the reduction of DOX intrinsic cardiotoxicity, indicating that the MSNs play a cardioprotective effect.

Advances in Dental Materials through Nanotechnology: Facts, Perspectives and Toxicological Aspects.

Nanotechnology is currently driving the dental materials industry to substantial growth, thus reflecting on improvements in materials available for oral prevention and treatment. The present review discusses new developments in nanotechnology applied to dentistry, focusing on the use of nanomaterials for improving the quality of oral care, the perspectives of research in this arena, and discussions on safety concerns regarding the use of dental nanomaterials. Details are provided on the cutting-edge properties (morphological, antibacterial, mechanical, fluorescence, antitumoral, and remineralization and regeneration potential) of polymeric, metallic and inorganic nano-based materials, as well as their use as nanocluster fillers, in nanocomposites, mouthwashes, medicines, and biomimetic dental materials. Nanotoxicological aspects, clinical applications, and perspectives for these nanomaterials are also discussed.

Large-field electron imaging and X-ray elemental mapping unveil the morphology, structure, and fractal features of a Cretaceous fossil at the centimeter scale.

We used here a scanning electron microscopy approach that detected backscattered electrons (BSEs) and X-rays (from ionization processes) along a large-field (LF) scan, applied on a Cretaceous fossil of a shrimp (area ∼280 mm(2)) from the Araripe Sedimentary Basin. High-definition LF images from BSEs and X-rays were essentially generated by assembling thousands of magnified images that covered the whole area of the fossil, thus unveiling morphological and compositional aspects at length scales from micrometers to centimeters. Morphological features of the shrimp such as pleopods, pereopods, and antennae located at near-surface layers (undetected by photography techniques) were unveiled in detail by LF BSE images and in calcium and phosphorus elemental maps (mineralized as hydroxyapatite). LF elemental maps for zinc and sulfur indicated a rare fossilization event observed for the first time in fossils from the Araripe Sedimentary Basin: the mineralization of zinc sulfide interfacing to hydroxyapatite in the fossil. Finally, a dimensional analysis of the phosphorus map led to an important finding: the existence of a fractal characteristic (D = 1.63) for the hydroxyapatite-matrix interface, a result of physical-geological events occurring with spatial scale invariance on the specimen, over millions of years.

Topography-driven bionano-interactions on colloidal silica nanoparticles.

We report here that the surface topography of colloidal mesoporous silica nanoparticles (MSNs) plays a key role on their bionano-interactions by driving the adsorption of biomolecules on the nanoparticle through a matching mechanism between the surface cavities characteristics and the biomolecules stereochemistry. This conclusion was drawn by analyzing the biophysicochemical properties of colloidal MSNs in the presence of single biomolecules, such as alginate or bovine serum albumin (BSA), as well as dispersed in a complex biofluid, such as human blood plasma. When dispersed in phosphate buffered saline media containing alginate or BSA, monodisperse spherical MSNs interact with linear biopolymers such as alginate and with a globular protein such as bovine serum albumin (BSA) independently of the surface charge sign (i.e. positive or negative), thus leading to a decrease in the surface energy and to the colloidal stabilization of these nanoparticles. In contrast, silica nanoparticles with irregular surface topographies are not colloidally stabilized in the presence of alginate but they are electrosterically stabilized by BSA through a sorption mechanism that implies reversible conformation changes of the protein, as evidenced by circular dichroism (CD). The match between the biomolecule size and stereochemistry with the nanoparticle surface cavities characteristics reflects on the nanoparticle surface area that is accessible for each biomolecule to interact and stabilize any non-rigid nanoparticles. On the other hand, in contact with variety of biomolecules such as those present in blood plasma (55%), MSNs are colloidally stabilized regardless of the topography and surface charge, although the identity of the protein corona responsible for this stabilization is influenced by the surface topography and surface charge. Therefore, the biofluid in which nanoparticles are introduced plays an important role on their physicochemical behavior synergistically with their inherent characteristics (e.g., surface topography).

Nanotoxicity of graphene and graphene oxide.

Graphene and its derivatives are promising candidates for important biomedical applications because of their versatility. The prospective use of graphene-based materials in a biological context requires a detailed comprehension of the toxicity of these materials. Moreover, due to the expanding applications of nanotechnology, human and environmental exposures to graphene-based nanomaterials are likely to increase in the future. Because of the potential risk factors associated with the manufacture and use of graphene-related materials, the number of nanotoxicological studies of these compounds has been increasing rapidly in the past decade. These studies have researched the effects of the nanostructural/biological interactions on different organizational levels of the living system, from biomolecules to animals. This review discusses recent results based on in vitro and in vivo cytotoxicity and genotoxicity studies of graphene-related materials and critically examines the methodologies employed to evaluate their toxicities. The environmental impact from the manipulation and application of graphene materials is also reported and discussed. Finally, this review presents mechanistic aspects of graphene toxicity in biological systems. More detailed studies aiming to investigate the toxicity of graphene-based materials and to properly associate the biological phenomenon with their chemical, structural, and morphological variations that result from several synthetic and processing possibilities are needed. Knowledge about graphene-based materials could ensure the safe application of this versatile material. Consequently, the focus of this review is to provide a source of inspiration for new nanotoxicological approaches for graphene-based materials.

Influence of protein corona on the transport of molecules into cells by mesoporous silica nanoparticles.

Although there are several studies reporting the promising biological efficiency of mesoporous silica nanoparticles (loaded with antitumoral drugs) against cancer cells and tumors, there are no reports on the influence of the bio-nano interface interactions on the molecular diffusion process occurring along their pores. In this context, we show here that the protein coating formed on multifunctionalized colloidal mesoporous silica nanoparticles (MSNs) dispersed in a cell culture medium decreases the release of camptothecin (CPT, a hydrophobic antitumoral drug) from the pores of MSNs. This effect is related to the adsorption of biomolecules on the nanoparticle surface, which partially blocks the pores. Parallely, the hydrophobic functionalization inside the pores can offer suitable sites for the adsorption of other molecules present in the cell culture medium depending on the hydrophobicity, size, and conformation aspects of these molecules and adsorption sites of MSNs. Thus, the molecular cargo loaded in the pores (i.e. CPT) can be replaced by specific molecules present in the dispersion medium. As a consequence, we show that a non-permeable cellular staining molecule such as SYTOX green can be incorporated in MSNs through this mechanism and internalized by cells in an artificial fashion. By extrapolating this phenomenon for applications in vivo, one has to consider now the possible manifestation of unpredicted biological effects from the use of porous silica nanoparticles and others with similar structure due to these internalization aspects.

Redox-enzymes, cells and micro-organisms acting on carbon nanostructures transformation: a mini-review.

Carbon nanotubes, graphene and fullerenes are actual nanomaterials with many applications in different industrial areas, with increasing potentialities in the field of nanomedicine. Recently, different proactive approaches on toxicology and safety management have become the focus of intense interest once the industrial production of these materials had a significant growth in the last years, even though their short- and long-term behaviors are not yet fully understood. The most important concerns involving these carbon-based nanomaterials are their stability and potential effects of their life cycles on animals, humans, and environment. In this context, this mini review discuss the biodegradability of these materials, particularly through redox-enzymes, micro-organisms and cells, to contribute toward the design of biocompatible and biodegradable functionalized carbon nanostructures, in order to use these materials safely and with minimum impact on the environment.

Towards long-term colloidal stability of silica-based nanocarriers for hydrophobic molecules: beyond the Stöber method.

The highly uniform micro- and mesoporous SiO(2) nanoparticles (40-70 nm) are hierarchically functionalized with antagonistic groups: hydrophobic (phenyl) on the internal pores and hydrophilic (methyl-phosphonate) on the external surface. Considering the large hydrophobic internal coating and the long-term colloidal stability, these systems are suitable nanocarriers by using the host-guest approach.

Structural and proactive safety aspects of oxidation debris from multiwalled carbon nanotubes.

The removal of oxidation debris from the oxidized carbon nanotube surface with a NaOH treatment is a key step for an effective functionalization and quality improvement of the carbon nanotube samples. In this work, we show via infrared spectroscopy and ultrahigh resolution and accuracy mass spectrometry that oxidation debris obtained from HNO(3)-treated multiwalled carbon nanotubes is a complex mixture of highly condensed aromatic oxygenated carbonaceous fragments. We have also evaluated their cytotoxicity by using BALB/c 3T3 mouse fibroblasts and HaCaT human keratinocytes as models. By knowing the negative aspects of dissolved organic carbon (DOC) to the water quality, we have demonstrated the removal of these carbon nanotube residues from the NaOH solution (wastewater) by using aluminium sulphate, which is a standard coagulant agent used in conventional drinking water purification and wastewater treatment plants. Our results contribute to elucidate the structural and proactive safety aspects of oxidation debris from oxidized carbon nanotubes towards a greener nanotechnology.

Surface chemistry in the process of coating mesoporous SiO2 onto carbon nanotubes driven by the formation of Si-O-C bonds.

The deposition of mesoporous silica (SiO(2)) on carbon nanotubes (CNTs) has opened up a wide range of assembling possibilities by exploiting the sidewall of CNTs and organosilane chemistry. The resulting systems may be suitable for applications in catalysis, energy conversion, environmental chemistry, and nanomedicine. However, to promote the condensation of silicon monomers on the nanotube without producing segregated particles, (OR)(4-x)SiO(x)(x-) units must undergo nucleophilic substitution by groups localized on the CNT sidewall during the transesterification reaction. In order to achieve this preferential attachment, we have deposited silica on oxidized carbon nanotubes (single-walled and multiwalled) in a sol-gel process that also involved the use of a soft template (cetyltrimethylammonium bromide, CTAB). In contrast to the simple approach normally used to describe the attachment of inorganic compounds on CNTs, SiO(2) nucleation on the tube is a result of nucleophilic attack mainly by hydroxyl radicals, localized in a very complex surface chemical environment, where various oxygenated groups are covalently bonded to the sidewall and carboxylated carbonaceous fragments (CCFs) are adsorbed on the tubes. Si-O-C covalent bond formation in the SiO(2)-CNT hybrids was observed even after removal of the CCFs with sodium hydroxide. By adding CTAB, and increasing the temperature, time, and initial amount of the catalyst (NH(4)OH) in the synthesis, the SiO(2) coating morphology could be changed from one of nanoparticles to mesoporous shells. Concomitantly, pore ordering was achieved by increasing the amount of CTAB. Furthermore, preferential attachment on the sidewall results mostly in CNTs with uncapped ends, having sites (carboxylic acids) that can be used for further localized reactions.