Occurrence, behavior and effects of nanoparticles in the environment.

2.3. Ionic Liquids (ILs) 5374 2.4. Complexation Reactions on Oxidized CNTs 5375 2.5. Halogenation 5376 2.6. Cycloaddition Reactions 5377 2.7. Radical Additions 5379 2.8. Nucleophilic Additions 5381 2.9. Electrophilic Additions 5381 2.10. Electrochemical Modifications 5381 2.11. Plasma-Activation 5381 2.12. Mechanochemical Functionalizations 5382 3. Noncovalent Interactions 5382 3.1. Polynuclear Aromatic Compounds 5382 3.2. Interactions with Other Substances 5384 3.3. Interactions with Biomolecules 5385 4. Endohedral Filling 5386 4.1. Encapsulation of Fullerenes 5386 4.2. Encapsulation of Organic Substances 5387 4.3. Encapsulation of Inorganic Substances 5387 5. Decoration of CNTs with Metal Nanoparticles 5388 5.1. Covalent Linkage 5388 5.2. Direct Formation on Defect Sites 5388 5.3. Electroless Deposition 5388 5.4. Electrodeposition 5389 5.5. Chemical Decoration 5390 5.6. Deposition of Nanoparticles onto CNTs 5391 5.7. π-π Stacking and Electrostatic Interactions 5391 6. Concluding Remarks 5392 7. Acknowledgments 5392 8. References 5392

Current progress on the chemical modification of carbon nanotubes.

The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies.

https://www.tandfonline.com/doi/pdf/10.1080/13102818.2015.1008192

An overview of technologies for immobilization of enzymes and surface analysis techniques for immobilized enzymes

The ex vivo application of enzymes in various processes, especially via enzyme immobilization techniques, has been extensively studied in recent years in order to enhance the recyclability of enzymes, to minimize enzyme contamination in the product, and to explore novel horizons for enzymes in biomedical applications. Possessing remarkable amenability in structural design of the frameworks as well as almost unparalelled surface tunability, Metal–Organic Frameworks (MOFs) have been gaining popularity as candidates for enzyme immobilization platforms. Many MOF–enzyme composites have achieved unprecedented results, far outperforming free enzymes in many aspects. This review summarizes recent developments of MOF–enzyme composites with special emphasis on preparative techniques and the synergistic effects of enzymes and MOFs. The applications of MOF–enzyme composites, primarily in transferation, catalysis and sensing, are presented as well. The enhancement of enzymatic activity of the composites over free enzymes in biologically incompatible conditions is emphasized in many cases.

Enzyme–MOF (metal–organic framework) composites

Biochar application to soils is being considered as a means to sequester carbon (C) while concurrently improving soil functions. The main focus of this report is providing a critical scientific review of the current state of knowledge regarding the effects of biochar application to soils on soil properties and functions. Wider issues, including atmospheric emissions and occupational health and safety associated to biochar production and handling, are put into context. The aim of this review is to provide a sound scientific basis for policy development, to identify gaps in current knowledge, and to recommend further research relating to biochar application to soils. See Table 1 for an overview of the key findings from this report. Biochar research is in its relative infancy and as such substantially more data are required before robust predictions can be made regarding the effects of biochar application to soils, across a range of soil, climatic and land management factors. Definition In this report, biochar is defined as: “charcoal (biomass that has been pyrolysed in a zero or low oxygen environment) for which, owing to its inherent properties, scientific consensus exists that application to soil at a specific site is expected to sustainably sequester carbon and concurrently improve soil functions (under current and future management), while avoiding shortand long-term detrimental effects to the wider environment as well as human and animal health." Biochar as a material is defined as: "charcoal for application to soils". It should be noted that the term 'biochar' is generally associated with other co-produced end products of pyrolysis such as 'syngas'. However, these are not usually applied to soil and as such are only discussed in brief in the report. Biochar properties Biochar is an organic material produced via the pyrolysis of C-based feedstocks (biomass) and is best described as a ‘soil conditioner’. Despite many different materials having been proposed as biomass feedstock for biochar (including wood, crop residues and manures), the suitability of each feedstock for such an application is dependent on a number of chemical, physical, environmental, as well as economic and logistical factors. Evidence suggests that components of the carbon in biochar are highly recalcitrant in soils, with reported residence times for wood biochar being in the range of 100s to 1,000s of years, i.e. approximately 101,000 times longer than residence times of most soil organic matter. Therefore, biochar addition to soil can provide a potential sink for C. It is important to note, however, that there is a paucity of data concerning biochar produced from feedstocks other than wood, but the information that is available is discussed in the report. Owing to the current interest in climate change mitigation, and the irreversibility of biochar application to soil, an effective evaluation of biochar stability in the environment and its effects on soil processes and functioning is paramount. The current state of knowledge concerning these factors is discussed throughout this report.

Biochar Application to Soils - A Critical Scientific Review of Effects on Soil Properties, Processes and Functions

We report a simple method that uses proteins to solubilize single-walled carbon nanotubes (SWNTs) in water. Characterization by a variety of complementary techniques including UV−Vis spectroscopy, Raman spectroscopy, and atomic force microscopy confirmed the dispersion at the individual nanotube level. A variety of proteins differing in size and structure were used to generate individual nanotube solutions by this noncovalent functionalization procedure. Protein-mediated solubilization of nanotubes in water may be important for biomedical applications. This method of solubilization may also find use in approaches for controlling the assembly of nanostructures, and the wide variety of functional groups present on the adsorbed proteins may be used as orthogonal reactive handles for the functionalization of carbon nanotubes.

Protein-assisted solubilization of single-walled carbon nanotubes.

We report the activity, stability, and reusability of enzyme-carbon nanotube conjugates in aqueous solutions. A variety of enzymes were covalently attached to oxidized multi-walled carbon nanotubes (MWNTs). These conjugates were soluble in aqueous buffer, retained a high fraction of their native activity, and were stable at higher temperatures relative to their solution phase counterparts. Furthermore, the high surface area of MWNTs afforded high enzyme loadings, yet the intrinsic high length of the MWNT led to facile filtration. These water-soluble carbon nanotube-enzyme conjugates represent novel preparations that possess the virtues of both soluble and immobilized enzymes, thus providing a unique combination of useful attributes such as low mass transfer resistance, high activity and stability, and reusability.

Water‐soluble carbon nanotube‐enzyme conjugates as functional biocatalytic formulations

Proteins have been conjugated to carbon nanotubes for applications in biosensing, biorecognition, delivery, and functional composites. Despite the growing interest in these carbon nanotube-protein hybrids, very little is known about how carbon nanotubes affect the structure and function of bound proteins. Here we provide an overview of our recent efforts to gain a more fundamental understanding of how proteins interact with carbon nanotubes. We also discuss recent results from our laboratories which suggest several new opportunities for protein-carbon nanotube conjugates to address problems in materials science and biotechnology.

Edward Sellitto

Papers

Protein-assisted solubilization of single-walled carbon nanotubes.

Water‐soluble carbon nanotube‐enzyme conjugates as functional biocatalytic formulations

Protein-Carbon Nanotube Conjugates