Synthesis of Raspberry-like Nanoparticles via Surface Grafting of Positively Charged Polyelectrolyte Brushes: Colloidal Stability and Surface Properties.

A method to synthesize stable, raspberry-like nanoparticles (NPs), using surface grafting of poly(glycidyl methacrylate) (PGMA) brushes on a polystyrene (PS) core with varying grafting densities, is reported. A two-step functionalization reaction of PGMA epoxide groups comprising an amination step first using ethylene diamine and then followed by a quaternization using glycidyltrimethylammonium chloride generates permanently and positively charged polyelectrolyte brushes, which result in both steric and electrostatic stabilization. The dispersion stability of the brush-bearing NPs is dramatically improved compared to that of the pristine PS core in salt solutions at ambient (25 °C) and elevated temperatures (60 °C). Additionally, the grafted polyelectrolyte chains undergo a reversible swelling in the presence of different ionic strength (IS) salts, which modulate the surface properties, including roughness, stiffness, and adhesion. An atomic force microscope under both dry and wet conditions was used to image conformational changes of the polyelectrolyte chains during the swelling and deswelling transitions as well as to probe the nanomechanical properties by analyzing the corresponding force-sample separation curves. The quaternized polyelectrolyte brushes undergo a conformational transition from a collapsed state to a swelled state in the osmotic brush (OB) regime triggered by the osmotic gradient of mobile ions to the interior of the polymer chain. At IS ∼ 1 M, the brushes contract and the globules reform (salted brush state) as evidenced by an increase in the surface roughness and a reduction in the adhesion of the brushes. Beyond IS ∼ 1 M, quartz crystal microbalance with dissipation monitoring measurements show that salt uptake continues to take place predominantly on the exterior surface of the brush since salt adsorption is not accompanied by a size increase as measured by dynamic light scattering. The study adds new insights into our understanding of the behavior of NPs bearing salt-responsive polyelectrolyte brushes with adaptive swelling thresholds that can ultimately modulate surface properties.

Graphene Nanobeacons with High-Affinity Pockets for Combined, Selective, and Effective Decontamination and Reagentless Detection of Heavy Metals.

Access to clean water for drinking, sanitation, and irrigation is a major sustainable development goal of the United Nations. Thus, technologies for cleaning water and quality-monitoring must become widely accessible and of low-cost, while being effective, selective, sustainable, and eco-friendly. To meet this challenge, hetero-bifunctional nanographene fluorescent beacons with high-affinity pockets for heavy metals are developed, offering top-rated and selective adsorption for cadmium and lead, reaching 870 and 450 mg g-1 , respectively. The heterobifunctional and multidentate pockets also operate as selective gates for fluorescence signal regulation with sub-nanomolar sensitivity (0.1 and 0.2 nm for Pb2+ and Cd2+ , respectively), due to binding affinities as low as those of antigen-antibody interactions. Importantly, the acid-proof nanographenes can be fully regenerated and reused. Their broad visible-light absorption offers an additional mode for water-quality monitoring based on ultra-low cost and user-friendly reagentless paper detection with the naked-eye at a limit of detection of 1 and 10 ppb for Pb2+ and Cd2+ ions, respectively. This work shows that photoactive nanomaterials, densely-functionalized with strong, yet selective ligands for targeted contaminants, can successfully combine features such as excellent adsorption, reusability, and sensing capabilities, in a way to extend the material's applicability, its life-cycle, and value-for-money.

Green Synthesis and Characterization of Silver Nanoparticles with High Antibacterial Activity Using Cell Extracts of Cyanobacterium Pseudanabaena/Limnothrix sp.

In this work, we demonstrated the ability of the cyanobacterium Pseudanabaena/Limnothrix sp. to produce ultra-small silver nanoparticlesin the forms of metallic silver (Ag0) and silver oxides (AgxOy) via a facile green synthetic process. The biological compounds in the cyanobacterial cellular extract acted both as reducing agents for silver ions and functional stabilizing agents for the silver nanoparticles. Furthermore, the antibacterical activity of the as-synthesized nanoparticles against Gram-negative Escherichia coli and Gram-positive Corynebacterium glutamicum bacterial cells was evaluated. The experimental results revealed a remarkable bactericidal activity of the nanoparticles that was both time-dependent and dose-dependent. In addition to their excellent bactericidal properties, the developed nanoparticles can be used as nanosupports in various environmental, biological, and medical applications.

A Four-enzyme Nanoassembly Consisting of Hydrolases and Oxidoreductases for Multi-step Cascade Reactions.

Cascade reactions catalyzed by multi-enzymatic systems have attracted enormous scientific interest over the last decade. They are an emerging technology that significantly expands the applicability of biocatalysts in several biotechnological processes, such as the synthesis of high value-added products. Immobilization of enzymes on a solid carrier is a commonly used strategy to improve the stability and reuse of multiple enzyme systems. Magnetic nanoparticles have been applied as promising nanocarriers for either the immobilization of one enzyme or the co-immobilization of multiple enzymes. In this chapter, we describe the preparation of magnetic iron oxide nanoparticles γ-Fe2O3 modified with 3-(aminopropyl)-triethoxysilane (APTES), for the simultaneous covalent co-immobilization of oxidoreductases and hydrolytic enzymes, such as cellulase, ß-glucosidase (bgl), glucose oxidase (GOx), and horseradish peroxidase (HRP). Several spectroscopic techniques that are used to characterize the structure and the catalytic performance of such systems are also described.

Graphene Oxide-Cytochrome c Multilayered Structures for Biocatalytic Applications: Decrypting the Role of Surfactant in Langmuir-Schaefer Layer Deposition.

Graphene, a two-dimensional single-layer carbon allotrope, has attracted tremendous scientific interest due to its outstanding physicochemical properties. Its monatomic thickness, high specific surface area, and chemical stability render it an ideal building block for the development of well-ordered layered nanostructures with tailored properties. Herein, biohybrid graphene-based layer-by-layer structures are prepared by means of conventional and surfactant-assisted Langmuir-Schaefer layer deposition techniques, whereby cytochrome c molecules are accommodated within ordered layers of graphene oxide. The biocatalytic activity of the as-developed nanobio-architectures toward the enzymatic oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt and decolorization of pinacyanol chloride is tested. The results show that the multilayer structures exhibit high biocatalytic activity and stability in the absence of surfactant molecules during the deposition of the monolayers.

Bimetallic gold-platinum nanoparticles as a drug delivery system coated with a new drug to target glioblastoma.

A drug delivery nanosystem of noble bimetallic nanoparticles (NPs) which consists of Au NPs capped with Pt NPs (Au@Pt NPs) is constructed and functionalised with a quinazoline based small molecule (Au@Pt@Q NPs), acting as a theranostic agent against glioblastoma. Two different hydrothermal synthetic procedures for bimetallic Au@Pt NPs are presented and the resulting nanostructures are fully characterised by means of spectroscopic and microscopic methods. The imaging and targeting capacity of the new drug delivery system is assessed through fluorescent optical microscopy and cytotoxicity evaluations. The constructed Au@Pt NPs consist a monodispersed colloidal solution of 25 nm with photoluminescent, fluorescent and X-Ray absorption properties that confirm their diagnostic potential. Haemolysis testing demonstrated that Au@Pt NPs are biocompatible and fluorescent microscopy confirmed their entering the cells. Cytological evaluation of the NPs through MTT assay showed that they do not inhibit the proliferation of control cell line HEK293, whereas they are toxic in U87MG, U251 and D54 glioblastoma cell lines; rendering them selective targeting agents for treating glioblastoma.

Hydrothermal Unzipping of Multiwalled Carbon Nanotubes and Cutting of Graphene by Potassium Superoxide.

The dual use of potassium superoxide (KO2) to unzip multiwalled carbon nanotubes (MWCNTs) and cut graphene under hydrothermal conditions is described in this work. The KO2-assisted hydrothermal treatment was proven to be a high-yield method for forming graphene nanoribbons and dots or sub-micro-sized graphene nanosheets. Starting with functionalized MWCNTs, the method produces water-dispersible graphene nanoribbons with characteristic photoluminescence depending on their width. Using pristine graphene, the hydrothermal treatment with KO2 produces nanosized graphene sheets and graphene quantum dots with diameters of less than 10 nm. The latter showed a bright white photoluminescence. The effective hydrothermal unzipping of MWNTs and the cutting of large graphene nanosheets is a valuable top-down approach for the preparation of graphene nanoribbons and small nanographenes. Both products with limited dimensions have interesting applications in nanoelectronics and bionanotechnology.

Synthesis, characterization and evaluation of aqueous Zn-based quantum dots for bioapplications.

Semiconducting nanoparticles called quantum dots (Qds) present unique optoelectronic properties based on their extremely small size, composition, and spherical shape, which make them suitable for use as diagnostic and theranostic agents in biological samples. The main scope of the fabrication of Qds is real-time diagnosis, therapy, drug delivery, and in vitro and in vivo tracking, presenting strong resistance to photobleaching. In this work, quantum dots such as ZnO, ZnSe, ZnS, and doped ZnS : Mn and ZnS : Cd were developed via a simple sol-gel synthesis in an aqueous solution. Morphological, structural, and optical characterizations were investigated. Moreover, an in vitro biological evaluation of Qds was performed. The results indicate that the photoluminescence is enhanced after doping ZnS Qds with Mn2+ and Cd2+. Qds have been synthesized for use as fluorescent agents for real-time monitoring in bio-applications.

Development of a Multi-Enzymatic Biocatalytic System through Immobilization on High Quality Few-Layer bio-Graphene.

In this work, we report the green production of few-layer bio-Graphene (bG) through liquid exfoliation of graphite in the presence of bovine serum albumin. Microscopic characterization evaluated the quality of the produced nanomaterial, showing the presence of 3-4-layer graphene. Moreover, spectroscopic techniques also confirmed the quality of the resulted bG, as well as the presence of bovine serum albumin on the graphene sheets. Next, for the first time, bG was used as support for the simultaneous covalent co-immobilization of three enzymes, namely ß-glucosidase, glucose oxidase, and horseradish peroxidase. The three enzymes were efficiently co-immobilized on bG, demonstrating high immobilization yields and activity recoveries (up to 98.5 and 90%, respectively). Co-immobilization on bG led to an increase of apparent KM values and a decrease of apparent Vmax values, while the stability of the nanobiocatalysts prevailed compared to the free forms of the enzymes. Co-immobilized enzymes exhibited high reusability, preserving a significant part of their activity (up to 72%) after four successive catalytic cycles at 30 °C. Finally, the tri-enzymatic nanobiocatalytic system was applied in three-step cascade reactions, involving, as the first step, the hydrolysis of p-Nitrophenyl-ß-D-Glucopyranoside and cellobiose.

Structure/Properties Relationship of Anionically Synthesized Diblock Copolymers "Grafted to" Chemically Modified Graphene.

A novel approach to obtaining nanocomposite materials using anionic sequential polymerization and post-synthetic esterification reactions with chemically modified graphene sheets (CMGs) is reported. The anionically synthesized diblock copolymer precursors of the PS-b-PI-OH type were grafted to the chemically modified -COOH groups of the CMGs, giving rise to the final composite materials, namely polystyrene-b-poly(isoprene)-g-CMGs, which exhibited enhanced physicochemical properties. The successful synthesis was determined through multiple molecular characterization techniques together with thermogravimetric analysis for the verification of increased thermal stability, and the structure/properties relationship was justified through transmission electron microscopy. Furthermore, the arrangement of CMGs utilizing lamellar and cylindrical morphologies was studied in order to determine the effect of the loaded CMGs in the adopted topologies.

Germanane Monolayer Films as Antibacterial Coatings.

Germanane (GeH), a graphane analogue, has attracted significant interest because of its optoelectronic properties; however, the environmental and biological effects of GeH have scarcely been investigated so far. Here we report a facile approach based on the Langmuir-Schaefer deposition to produce homogeneous and dense GeH monolayer films on various substrates. In view of possible applications and to extend the use of GeH to unexplored fields, we investigated its antibacterial activity for the first time and found that this promising 2D structure exhibits remarkable antibacterial activity against both Gram-negative and Gram-positive bacterial strains.

Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions.

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.

Green Synthesized Magnetic Nanoparticles as Effective Nanosupport for the Immobilization of Lipase: Application for the Synthesis of Lipophenols.

In this work, hybrid zinc oxide-iron oxide (ZnOFe) magnetic nanoparticles were synthesized employing Olea europaea leaf aqueous extract as a reducing/chelating and capping medium. The resulting magnetic nanoparticles were characterized by basic spectroscopic and microscopic techniques, namely, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fourier-transform infrared (FTIR) and atomic force microscopy (AFM), exhibiting a spherical shape, average size of 15-17 nm, and a functionalized surface. Lipase from Thermomyces lanuginosus (TLL) was efficiently immobilized on the surface of ZnOFe nanoparticles through physical absorption. The activity of immobilized lipase was found to directly depend on the enzyme to support the mass ratio, and also demonstrated improved pH and temperature activity range compared to free lipase. Furthermore, the novel magnetic nanobiocatalyst (ZnOFe-TLL) was applied to the preparation of hydroxytyrosyl fatty acid esters, including derivatives with omega-3 fatty acids, in non-aqueous media. Conversion yields up to 90% were observed in non-polar solvents, including hydrophobic ionic liquids. Different factors affecting the biocatalyst performance were studied. ZnOFe-TLL was reutilized for eight subsequent cycles, exhibiting 90% remaining esterification activity (720 h of total operation at 50 °C). The green synthesized magnetic nanoparticles, reported here for the first time, are excellent candidates as nanosupports for the immobilization of enzymes with industrial interest, giving rise to nanobiocatalysts with elevated features.

Synthesis of 2D Germanane (GeH): a New, Fast, and Facile Approach.

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a ß-CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (Eg ) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.

Nanocarbon from Rocket Fuel Waste: The Case of Furfuryl Alcohol-Fuming Nitric Acid Hypergolic Pair.

In hypergolics two substances ignite spontaneously upon contact without external aid. Although the concept mostly applies to rocket fuels and propellants, it is only recently that hypergolics has been recognized from our group as a radically new methodology towards carbon materials synthesis. Comparatively to other preparative methods, hypergolics allows the rapid and spontaneous formation of carbon at ambient conditions in an exothermic manner (e.g., the method releases both carbon and energy at room temperature and atmospheric pressure). In an effort to further build upon the idea of hypergolic synthesis, herein we exploit a classic liquid rocket bipropellant composed of furfuryl alcohol and fuming nitric acid to prepare carbon nanosheets by simply mixing the two reagents at ambient conditions. Furfuryl alcohol served as the carbon source while fuming nitric acid as a strong oxidizer. On ignition the temperature is raised high enough to induce carbonization in a sort of in-situ pyrolytic process. Simultaneously, the released energy was directly converted into useful work, such as heating a liquid to boiling or placing Crookes radiometer into motion. Apart from its value as a new synthesis approach in materials science, carbon from rocket fuel additionally provides a practical way in processing rocket fuel waste or disposed rocket fuels.

Rapid Carbon Formation from Spontaneous Reaction of Ferrocene and Liquid Bromine at Ambient Conditions.

Herein, we present an interesting route to carbon derived from ferrocene without pyrolysis. Specifically, the direct contact of the metallocene with liquid bromine at ambient conditions released rapidly and spontaneously carbon soot, the latter containing dense spheres, nanosheets, and hollow spheres. The derived carbon carried surface C-Br bonds that permitted postfunctionalization of the solid through nucleophilic substitution. For instance, treatment with diglycolamine led to covalent attachment of the amine onto the carbon surface, thus conferring aqueous dispersability to t he solid. The dispersed solid exhibited visible photoluminescence under UV irradiation as a result of surface passivation by the amine. Hence, the present method not only allowed a rapid and spontaneous carbon formation at ambient conditions, but also surface engineering of the particles to impart new properties (e.g., photoluminescence).

Hypergolics in Carbon Nanomaterials Synthesis: New Paradigms and Perspectives.

Recently we have highlighted the importance of hypergolic reactions in carbon materials synthesis. In an effort to expand this topic with additional new paradigms, herein we present novel preparations of carbon nanomaterials, such-like carbon nanosheets and fullerols (hydroxylated fullerenes), through spontaneous ignition of coffee-sodium peroxide (Na2O2) and C60-Na2O2 hypergolic mixtures, respectively. In these cases, coffee and fullerenes played the role of the combustible fuel, whereas sodium peroxide the role of the strong oxidizer (e.g., source of highly concentrated H2O2). The involved reactions are both thermodynamically and kinetically favoured, thus allowing rapid product formation at ambient conditions. In addition, we provide tips on how to exploit the released energy of such highly exothermic reactions in the generation of useful work.

Functional Carbon Materials Derived through Hypergolic Reactions at Ambient Conditions.

Carbon formation from organic precursors is an energy-consuming process that often requires the heating of a precursor in an oven at elevated temperature. In this paper, we present a conceptually different synthesis pathway for functional carbon materials based on hypergolic mixtures, i.e., mixtures that spontaneously ignite at ambient conditions once its ingredients contact each other. The reactions involved in such mixtures are highly exothermic, giving-off sizeable amounts of energy; hence, no any external heat source is required for carbonization, thus making the whole process more energy-liberating than energy-consuming. The hypergolic mixtures described here contain a combustible organic solid, such as nitrile rubber or a hydrazide derivative, and fuming nitric acid (100% HNO3) as a strong oxidizer. In the case of the nitrile rubber, carbon nanosheets are obtained, whereas in the case of the hydrazide derivative, photoluminescent carbon dots are formed. We also demonstrate that the energy released from these hypergolic reactions can serve as a heat source for the thermal conversion of certain triazine-based precursors into graphitic carbon nitride. Finally, certain aspects of the derived functional carbons in waste removal are also discussed.

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the "neat" BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures.

Use of functionalized carbon nanotubes for the development of robust nanobiocatalysts.

This chapter deals with the use of functionalized carbon nanotubes (fCNTs) as supports for the development of nanobiocatalytic systems through the immobilization of enzymes. The surface characteristics, properties and production of carbon nanotubes are described, while an analysis in their biological applications is also presented. The results presenting within the text are giving insights to the effect of carbon nanotubes on the catalytic and structural characteristics of different proteins, such as cytochrome c from equine heart (cyt c) and laccase from Trametes versicolor (TvL), either when they are used as additives in the reaction medium or as supports for protein immobilization. A variety of biochemical and spectroscopic techniques is applied to investigate the interactions between the protein biomolecules and carbon nanotubes. The results showed that the presence of fCNTs enables cyt c to maintain both its secondary structure and heme microenvironment. Non-covalent and covalent immobilization approaches are also described, while the immobilized biocatalysts are characterized with respect to their catalytic and structural characteristics. Immobilized TvL was found to exhibit higher catalytic activity when non-specific binding was used as immobilization procedure (up to 0.85Uµg-1), compared to covalent immobilization (up to 0.7Uµg-1), while the increase of the alkyl chain of the functionalized CNTs also seems to affect the catalytic efficiency of the immobilized enzymes. The nanobiocatalytic systems that are presented here demonstrated exceptional stability (up to 31% of their initial activity is maintained after 24h incubation at 60°C) and reusability (up to 58% remaining activity after 8 successive catalytic cycles) compared to the native enzymes, leading to robust biocatalytic systems appropriate for various applications of biotechnological and industrial interest.