A comprehensive review of biosurfactant production and its uses in the pharmaceutical industry.

Biosurfactants are naturally occurring, surface-active chemicals generated by microorganisms and have attracted interest recently because of their numerous industrial uses. Compared to their chemical equivalents, they exhibit qualities that include lower toxic levels, increased biodegradable properties, and unique physiochemical properties. Due to these traits, biosurfactants have become attractive substitutes for synthetic surfactants in the pharmaceutical industry. In-depth research has been done in the last few decades, demonstrating their vast use in various industries. This review article includes a thorough description of the various types of biosurfactants and their production processes. The production process discussed here is from oil-contaminated waste, agro-industrial waste, dairy, and sugar industry waste, and also how biosurfactants can be produced from animal fat. Various purification methods such as ultrafiltration, liquid-liquid extraction, acid precipitation, foam fraction, and adsorption are required to acquire a purified product, which is necessary in the pharmaceutical industry, are also discussed here. Alternative ways for large-scale production of biosurfactants using different statistical experimental designs such as CCD, ANN, and RSM are described here. Several uses of biosurfactants, including drug delivery systems, antibacterial and antifungal agents, wound healing, and cancer therapy, are discussed. Additionally, in this review, the future challenges and aspects of biosurfactant utilization in the pharmaceutical industry and how to overcome them are also discussed.

Challenges in Liquid-Phase Exfoliation, Processing, and Assembly of Pristine Graphene.

Recent developments in the exfoliation, dispersion, and processing of pristine graphene (i.e., non-oxidized graphene) are described. General metrics are outlined that can be used to assess the quality and processability of various "graphene" products, as well as metrics that determine the potential for industrial scale-up. The pristine graphene production process is categorized from a chemical engineering point of view with three key steps: i) pretreatment, ii) exfoliation, and iii) separation. How pristine graphene colloidal stability is distinct from the exfoliation step and is dependent upon graphene interactions with solvents and dispersants are extensively reviewed. Finally, the challenges and opportunities of using pristine graphene as nanofillers in polymer composites, as well as as building blocks for macrostructure assemblies are summarized in the context of large-scale production.

Tailored Crumpling and Unfolding of Spray-Dried Pristine Graphene and Graphene Oxide Sheets.

For the first time, pristine graphene can be controllably crumpled and unfolded. The mechanism for graphene is radically different than that observed for graphene oxide; a multifaced crumpled, dimpled particle morphology is seen for pristine graphene in contrast to the wrinkled, compressed surface of graphene oxide particles, showing that surface chemistry dictates nanosheet interactions during the crumpling process. The process demonstrated here utilizes a spray-drying technique to produce droplets of aqueous graphene dispersions and induce crumpling through rapid droplet evaporation. For the first time, the gradual dimensional transition of 2D graphene nanosheets to a 3D crumpled morphology in droplets is directly observed; this is imaged by a novel sample collection device inside the spray dryer itself. The degree of folding can be tailored by altering the capillary forces on the dispersed sheets during evaporation. It is also shown that the morphology of redispersed crumpled graphene powder can be controlled by solvent selection. This process is scalable, with the ability to rapidly process graphene dispersions into powders suitable for a variety of engineering applications.

Rheology and morphology of pristine graphene/polyacrylamide gels.

Enhancement of toughness in nanomaterial-based hydrogels is a critical metric for many of their engineering applications. Pristine graphene-polyacrylamide (PAM) hydrogels are synthesized via in situ polymerization of acrylamide monomer in PAM-stabilized graphene dispersion. In-situ polymerization leads to the uniform dispersion of the graphene sheets in the hydrogel. The graphene sheets interact with the elastic chains of the hydrogel through physisorption and permit gelation in the absence of any chemical cross-linker. This study represents the first report of pristine graphene as a physical cross-linker in a hydrogel. The properties of the graphene-polymer hydrogel are characterized by rheological measurements and compressive tests, revealing an increase in the storage modulus and toughness of the hydrogels compared to the chemically cross-linked PAM analogues. The physically cross-linked graphene hydrogels also exhibit self-healing properties. These hydrogels prove to be efficient precursors for graphene-PAM aerogels with enhanced electrical conductivity and thermal stability.

Ultralow percolation threshold in aerogel and cryogel templated composites.

We demonstrate a novel concept for preparing percolating composites with ultralow filler content by utilizing nanofiller-loaded aerogel and cryogels as a conductive template. This concept is investigated for several porous systems, including resorcinol-formaldehyde (RF), silica, and polyacrylamide (PAM) gels, and both graphene and carbon nanotubes are utilized as nanofiller. In each case, a stable, aqueous nanofiller dispersion is mixed with a sol-gel precursor and polymerized to form a hydrogel, which can then be converted to an aerogel by critical point drying or cryogel by freeze-drying. Epoxy resin is infused into the pores of the gels by capillary action without disrupting the monolithic structure. We show that conductive graphene/epoxy composites are formed with a very low graphene loading; a percolation threshold as low as 0.012 vol % is obtained for graphene-RF cryogel/epoxy composite. This is the lowest reported threshold of any graphene-based nanocomposites. Similar values are achieved in other aerogel and nanofiller systems, which demonstrates the versatility of this method.

Mobility of polyaromatic hydrocarbons (PAHs) in soil in the presence of carbon nanotubes.

Being a potential risk to the environment, a fate study of carbon nanotube (CNT) in the environment is urgently needed. A study of CNT impacts on the bioavailability of other conventional contaminants in a terrestrial system is particularly rare. This study explored PAH leaching behaviors in the presence of CNTs with column leaching tests. Four PAHs (Naphthalene, fluorene, phenanthrene, and pyrene), three CNTs (f-SWNTs, MWNTs, f-MWNTs), and a sandy loam soil were involved in this study. We found that at a concentration of 5mg/g, CNTs could significantly retain PAHs in soil. Such a strong PAH retention was caused by low mobilities of CNTs and their strong PAH sorption capacities. This study illustrated that the properties of both sorbents (e.g. available surface area and micropore volume) and sorbates (e.g. hydrophobicity and molecular volume) influenced the mobility of PAHs in soil.

Dispersions of non-covalently functionalized graphene with minimal stabilizer.

We demonstrate that functionalized pyrene derivatives effectively stabilize single- and few-layer graphene flakes in aqueous dispersions. The graphene/stabilizer yield obtained by this method is exceptionally high relative to conventional nanomaterial stabilizers such as surfactants or polymers. The mechanism of stabilization by pyrene derivatives is investigated by studying the effects of various parameters on dispersed graphene concentration and stability; these parameters include stabilizer concentration, initial graphite concentration, solution pH, and type and number of functional groups and counterions. The effectiveness of the pyrene derivatives is pH-tunable, as measured by zeta potential, and is also a function of the number of functional groups, the electronegativity of the functional group, the counterion, the relative polarity between stabilizer and solvent, and the distance from the functional group to the basal plane. Even if the dispersion is destabilized by extreme pH or lyophilization, the graphene does not aggregate because the stabilizer remains adsorbed on the surface. These dispersions also show promise for applications in graphene/polymer nanocomposites (examined in this paper), organic solar cells, conductive films, and inkjet-printed electronic devices.

Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO2) to earthworms (Eisenia fetida).

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.

Localized in situ polymerization on graphene surfaces for stabilized graphene dispersions.

We demonstrate a novel in situ polymerization technique to develop localized polymer coatings on the surface of dispersed pristine graphene sheets. Graphene sheets show great promise as strong, conductive fillers in polymer nanocomposites; however, difficulties in dispersion quality and interfacial strength between filler and matrix have been a persistent problem for graphene-based nanocomposites, particularly for pristine graphene. With this in mind, a physisorbed polymer layer is used to stabilize graphene sheets in solution. To create this protective layer, we formed an organic microenvironment around dispersed graphene sheets in surfactant solutions, and created a nylon 6, 10 or nylon 6, 6 coating via interfacial polymerization. Technique lies at the intersection of emulsion and admicellar polymerization; a similar technique was originally developed to protect luminescent properties of carbon nanotubes in solution. These coated graphene dispersions are aggregation-resistant and may be reversibly redispersed in water even after freeze-drying. The coated graphene holds promise for a number of applications, including multifunctional graphene-polymer nanocomposites.