Biogenic Sulfur-Based Chalcogenide Nanocrystals: Methods of Fabrication, Mechanistic Aspects, and Bio-Applications.

Bio-nanotechnology has emerged as an efficient and competitive methodology for the production of added-value nanomaterials (NMs). This review article gathers knowledge gleaned from the literature regarding the biosynthesis of sulfur-based chalcogenide nanoparticles (S-NPs), such as CdS, ZnS and PbS NPs, using various biological resources, namely bacteria, fungi including yeast, algae, plant extracts, single biomolecules, and viruses. In addition, this work sheds light onto the hypothetical mechanistic aspects, and discusses the impact of varying the experimental parameters, such as the employed bio-entity, time, pH, and biomass concentration, on the obtained S-NPs and, consequently, on their properties. Furthermore, various bio-applications of these NMs are described. Finally, key elements regarding the whole process are summed up and some hints are provided to overcome encountered bottlenecks towards the improved and scalable production of biogenic S-NPs.

Photochemical Synthesis of Gold and Silver Nanoparticles-A Review.

Nanomaterials have supported important technological advances due to their unique properties and their applicability in various fields, such as biomedicine, catalysis, environment, energy, and electronics. This has triggered a tremendous increase in their demand. In turn, materials scientists have sought facile methods to produce nanomaterials of desired features, i.e., morphology, composition, colloidal stability, and surface chemistry, as these determine the targeted application. The advent of photoprocesses has enabled the easy, fast, scalable, and cost- and energy-effective production of metallic nanoparticles of controlled properties without the use of harmful reagents or sophisticated equipment. Herein, we overview the synthesis of gold and silver nanoparticles via photochemical routes. We extensively discuss the effect of varying the experimental parameters, such as the pH, exposure time, and source of irradiation, the use or not of reductants and surfactants, reagents' nature and concentration, on the outcomes of these noble nanoparticles, namely, their size, shape, and colloidal stability. The hypothetical mechanisms that govern these green processes are discussed whenever available. Finally, we mention their applications and insights for future developments.

Green Synthesis of Selenium and Tellurium Nanoparticles: Current Trends, Biological Properties and Biomedical Applications.

The synthesis and assembly of nanoparticles using green technology has been an excellent option in nanotechnology because they are easy to implement, cost-efficient, eco-friendly, risk-free, and amenable to scaling up. They also do not require sophisticated equipment nor well-trained professionals. Bionanotechnology involves various biological systems as suitable nanofactories, including biomolecules, bacteria, fungi, yeasts, and plants. Biologically inspired nanomaterial fabrication approaches have shown great potential to interconnect microbial or plant extract biotechnology and nanotechnology. The present article extensively reviews the eco-friendly production of metalloid nanoparticles, namely made of selenium (SeNPs) and tellurium (TeNPs), using various microorganisms, such as bacteria and fungi, and plants' extracts. It also discusses the methodologies followed by materials scientists and highlights the impact of the experimental sets on the outcomes and shed light on the underlying mechanisms. Moreover, it features the unique properties displayed by these biogenic nanoparticles for a large range of emerging applications in medicine, agriculture, bioengineering, and bioremediation.

Sugar-Mediated Green Synthesis of Silver Selenide Semiconductor Nanocrystals under Ultrasound Irradiation.

Silver selenide (Ag2Se) is a promising nanomaterial due to its outstanding optoelectronic properties and countless bio-applications. To the best of our knowledge, we report, for the first time, a simple and easy method for the ultrasound-assisted synthesis of Ag2Se nanoparticles (NPs) by mixing aqueous solutions of silver nitrate (AgNO3) and selenous acid (H2SeO3) that act as Ag and Se sources, respectively, in the presence of dissolved fructose and starch that act as reducing and stabilizing agents, respectively. The concentrations of mono- and polysaccharides were screened to determine their effect on the size, shape and colloidal stability of the as-synthesized Ag2Se NPs which, in turn, impact the optical properties of these NPs. The morphology of the as-synthesized Ag2Se NPs was characterized by transmission electron microscopy (TEM) and both α- and ß-phases of Ag2Se were determined by X-ray diffraction (XRD). The optical properties of Ag2Se were studied using UV-Vis spectroscopy and its elemental composition was determined non-destructively using scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). The biological activity of the Ag2Se NPs was assessed using cytotoxic and bactericidal approaches. Our findings pave the way to the cost-effective, fast and scalable production of valuable Ag2Se NPs that may be utilized in numerous fields.

In Vivo Biosynthesis of Inorganic Nanomaterials Using Eukaryotes-A Review.

Bionanotechnology, the use of biological resources to produce novel, valuable nanomaterials, has witnessed tremendous developments over the past two decades. This eco-friendly and sustainable approach enables the synthesis of numerous, diverse types of useful nanomaterials for many medical, commercial, and scientific applications. Countless reviews describing the biosynthesis of nanomaterials have been published. However, to the best of our knowledge, no review has been exclusively focused on the in vivo biosynthesis of inorganic nanomaterials. Therefore, the present review is dedicated to filling this gap by describing the many different facets of the in vivo biosynthesis of nanoparticles (NPs) using living eukaryotic cells and organisms-more specifically, live plants and living biomass of several species of microalgae, yeast, fungus, mammalian cells, and animals. It also highlights the strengths and weaknesses of the synthesis methodologies and the NP characteristics, bio-applications, and proposed synthesis mechanisms. This comprehensive review also brings attention to enabling a better understanding between the living organisms themselves and the synthesis conditions that allow their exploitation as nanobiotechnological production platforms as these might serve as a robust resource to boost and expand the bio-production and use of desirable, functional inorganic nanomaterials.

Special Issue: Biogenic Nanomaterials: Versatility and Applications.

Greener processes have emerged as serious and competitive routes to produce various nanomaterials [...].

A Mechanistic View of the Light-Induced Synthesis of Silver Nanoparticles Using Extracellular Polymeric Substances of Chlamydomonas reinhardtii.

In the current study, extracellular polymeric substances (EPS) of Chlamydomonas reinhardtii and photon energy biosynthetically converted Ag+ to silver nanoparticles (AgNPs). The reaction mechanism began with the non-photon-dependent adsorption of Ag+ to EPS biomolecules. An electron from the EPS biomolecules was then donated to reduce Ag+ to Ag0, while a simultaneous release of H+ acidified the reaction mixture. The acidification of the media and production rate of AgNPs increased with increasing light intensity, indicating the light-dependent nature of the AgNP synthesis process. In addition, the extent of Ag+ disappearance from the aqueous phase and the AgNP production rate were both dependent on the quantity of EPS in the reaction mixture, indicating Ag+ adsorption to EPS as an important step in AgNP production. Following the reaction, stabilization of the NPs took place as a function of EPS concentration. The shifts in the intensities and positions of the functional groups, detected by Fourier-transform infrared spectroscopy (FTIR), indicated the potential functional groups in the EPS that reduced Ag+, capped Ag0, and produced stable AgNPs. Based on these findings, a hypothetic three-step, EPS-mediated biosynthesis mechanism, which includes a light-independent adsorption of Ag+, a light-dependent reduction of Ag+ to Ag0, and an EPS concentration-dependent stabilization of Ag0 to AgNPs, has been proposed.

Individual and Combined Effects of Extracellular Polymeric Substances and Whole Cell Components of Chlamydomonas reinhardtii on Silver Nanoparticle Synthesis and Stability.

The fresh water microalga Chlamydomonas reinhardtii bioreduced Ag⁺ to silver nanoparticles (AgNPs) via three biosynthetic routes in a process that could be a more sustainable alternative to conventionally produced AgNPs. The AgNPs were synthesized in either the presence of whole cell cultures, an exopolysaccharide (EPS)-containing cell culture supernatant, or living cells that had been separated from the EPS-containing supernatant and then washed before being suspended again in fresh media. While AgNPs were produced by all three methods, the washed cultures had no supernatant-derived EPS and produced only unstable AgNPs, thus the supernatant-EPS was shown to be necessary to cap and stabilize the biogenic AgNPs. TEM images showed stable AgNPs were mostly spherical and showed a bimodal size distribution about the size ranges of 3.0 ± 1.3 nm and 19.2 ± 5.0 nm for whole cultures and 3.5 ± 0.6 nm and 17.4 ± 2.6 nm for EPS only. Moreover, selected area electron diffraction pattern of these AgNPs confirmed their polycrystalline nature. FTIR of the as-produced AgNPs identified polysaccharides, polyphenols and proteins were responsible for the observed differences in the AgNP stability, size and shape. Additionally, Raman spectroscopy indicated carboxylate and amine groups were bound to the AgNP surface.

Evaluating microwave-synthesized silver nanoparticles from silver nitrate with life cycle assessment techniques.

Silver Nanoparticles (AgNPs) are well known for applications in electronics and as antimicrobial agents because of their unique optical, electrical, cytotoxic and thermal properties. These nanoparticles can be synthesized via a wide variety of techniques; however, they require the use of hazardous solvents which have very high environmental impacts. Nanoscience researchers have attempted novel synthesis routes that reduce resource requirements and use benign chemicals, while maintaining control over their unique properties. The present study evaluates the potential environmental impacts of one such benign method using Life Cycle Assessment (LCA) techniques which are used to assess the environmental impacts of a product's life through all the stages from raw material extraction to disposal/ recycling. This research evaluates AgNPs which were synthesized using glucose as the reducing agent and food grade corn starch as the stabilizing agent in a microwave-assisted reaction system. GaBi 6.0 software was used to carry out the Life Cycle Impact Assessment on a declared unit of 1 kg of 3.0 ±â€¯1.2 nm diameter AgNPs. The results indicate that the impacts are predominantly on acidification (AP), human health particulate air (HHAP) and human toxicity non-cancer (HTNCP) potentials. These impacts are mainly from the production of silver metal and electricity used. The starch and glucose used to produce AgNPs of 3.0 ±â€¯1.2 nm is shown to have negligible environmental impacts and is therefore considered to be environmentally benign.

High conversion synthesis of <10 nm starch-stabilized silver nanoparticles using microwave technology.

A microwave reaction to convert 99 ± 1% of Ag+ to silver nanoparticles (AgNPs) of size <10 nm within 4.5 min with a specific production rate and energy input of 5.75 mg AgNP L-1 min-1 and 5.45 W mL-1 reaction volume was developed. The glucose reduced and food grade starch stabilized particles remained colloidally stable with less than a 4% change in the surface plasmon resonance band at 425-430 nm at t > 300 days. TEM determined the size of AgNPs, while TEM-EDS and XRD verified elemental composition. The conversion was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and thermal gravimetric analysis (TGA). Additionally, the required silver to starch input mass ratio, 1.0:1.3, to produce colloidally stabilized AgNPs is significantly reduced compared to previous studies. The antibacterial activity of freshly prepared AgNPs and AgNPs aged >300 days was demonstrated against E. coli as determined by agar diffusion assays. This result, corroborated by spectrophotometric and TEM measurements, indicates long-term colloidal stability of the product. Thus, this study sustainably produced antibacterial AgNPs from minimal inputs. In the broader context, the current work has quantified a sustainable platform technology to produce sphere-like inorganic nanoparticles with antimicrobial properties.

Biosynthetic Conversion of Ag⁺ to highly Stable Ag° Nanoparticles by Wild Type and Cell Wall Deficient Strains of Chlamydomonas reinhardtii.

In the current study, two different strains of the green, freshwater microalga Chlamydomonas reinhardtii bioreduced Ag⁺ to silver nanoparticles (AgNPs), which have applications in biosensors, biomaterials, and therapeutic and diagnostic tools. The bioreduction takes place in cell cultures of C. reinhardtii at ambient temperature and atmospheric pressure, thus eliminating the need for specialized equipment, harmful reducing agents or the generation of toxic byproducts. In addition to the visual changes in the cell culture, the production of AgNPs was confirmed by the characteristic surface plasmon resonance (SPR) band in the range of 415⁻425 nm using UV-Vis spectrophotometry and further evolution of the SPR peaks were studied by comparing the peak intensity at maximum absorbance over time. X-ray diffraction (XRD) determined that the NPs were Ag°. Micrographs from transmission electron microscopy (TEM) revealed that 97 ± 2% AgNPs were <10 nm in diameter. Ag⁺ to AgNP conversion was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The AgNPs were stable over time in the cell culture media, acetone, NaCl and reagent alcohol solutions. This was verified by a negligible change in the features of the SPR band after t > 300 days of storage at 4 °C.

Biosynthesis of Inorganic Nanoparticles: A Fresh Look at the Control of Shape, Size and Composition.

Several methodologies have been devised for the design of nanomaterials. The "Holy Grail" for materials scientists is the cost-effective, eco-friendly synthesis of nanomaterials with controlled sizes, shapes and compositions, as these features confer to the as-produced nanocrystals unique properties making them appropriate candidates for valuable bio-applications. The present review summarizes published data regarding the production of nanomaterials with special features via sustainable methodologies based on the utilization of natural bioresources. The richness of the latter, the diversity of the routes adopted and the tuned experimental parameters have led to the fabrication of nanomaterials belonging to different chemical families with appropriate compositions and displaying interesting sizes and shapes. It is expected that these outstanding findings will encourage researchers and attract newcomers to continue and extend the exploration of possibilities offered by nature and the design of innovative and safer methodologies towards the synthesis of unique nanomaterials, possessing desired features and exhibiting valuable properties that can be exploited in a profusion of fields.

DBT desulfurization by decorating Rhodococcus erythropolis IGTS8 using magnetic Fe3O4 nanoparticles in a bioreactor.

Today, crude oil is an important source of energy and environmental contamination due to the continued use of petroleum products is a matter or urgent concern. In this work, two technological platforms, namely, the use of a robust desulfurizing bacteria and the use of nanotechnology to decorate the surface of the bacteria with nanoparticles (NP), were combined to enhance biodesulfurization (BDS). BDS is an ecologically friendly method for desulfurizing petroleum products while avoiding damage to the hydrocarbons due to the high temperatures normally associated with physical desulfurization methods. First, a bacterium known to be a good organism for desulfurization (Rhodococcus erythropolis IGTS8) was employed in cell culture to remove a recalcitrant sulfur molecule from a common sulfur-containing compound found in crude petroleum products (dibenzothiophene). 2-Hydroxybiphenyl (2-HBP) produced as a consequence of the BDS of dibenzothiophene was determined using Gibbs' assay. The synthesized NP were characterized by field emission scanning electron microscope, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, and vibrating sample magnetometer. The field emission scanning electron microscope and transmission electron microscopy images showed the size of the NP is 7-8 nm. The decorated cells had a long lag phase, but the growth continued until 148 h (at OD600 = 3.408) while the noncoated bacteria grow until 96 h before entering the stationary phase at OD600 = 2.547. Gibbs' assay results showed that production of 2-HBP by decorated cells was 0.210 mM at t = 148 h, while 2-HBP production by nondecorated cells was 0.182 mM at t = 96 h. Finally, the experiments were repeated in a fermenter.

Noble metal, oxide and chalcogenide-based nanomaterials from scalable phototrophic culture systems.

Phototrophic cell or tissue cultures can produce nanostructured noble metals, oxides and chalcogenides at ambient temperatures and pressures in an aqueous environment and without the need for potentially toxic solvents or the generation of dangerous waste products. These "green" synthesized nanobiomaterials can be used to fabricate biosensors and bio-reporting tools, theranostic vehicles, medical imaging agents, as well as tissue engineering scaffolds and biomaterials. While successful at the lab and experimental scales, significant barriers still inhibit the development of higher capacity processes. While scalability issues in traditional algal bioprocess engineering are well known, such as the controlled delivery of photons and gas-exchange, the large-scale algal synthesis of nanomaterials introduces additional parameters to be understood, i.e., nanoparticle (NP) formation kinetics and mechanisms, biological transport of metal cations and the effect of environmental conditions on the final form of the NPs. Only after a clear understanding of the kinetics and mechanisms can the strain selection, photobioreactor type, medium pH and ionic strength, mean light intensity and other relevant parameters be specified for an optimal bioprocess. To this end, this mini-review will examine the current best practices and understanding of these phenomena to establish a path forward for this technology.

Environmental life cycle optimization of essential terpene oils produced by the macroalga Ochtodes secundiramea.

The macroalga Ochtodes secundiramea is a well-known producer of essential terpene oils with promising biological activities and similar applications to those of microalgal biocompounds in the pharmaceutical, food or cosmetics sectors. This study assesses the environmental impacts associated with the production of five essential terpene oils (myrcene, 10Z-bromomyrcene, 10E-bromo-3-chloromyrcene, apakaochtodene B and acyclic C10H14Br2) by O. secundiramea cultivated in a closed airlift photobioreactor with artificial illumination. The results of the life cycle assessment (LCA) allowed analyzing the effect of implementing a semi-continuous operation on several stages of the life cycle of the products, which may lead to impact reductions from 1% up to 25%. Regarding the most problematic aspects of the process, the cultivation in the photobioreactor (S4) was identified as the main stage responsible for the environmental burdens, with contributions ranging between 60% and 80% of the total impacts for a semi-continuous production maintained during one year of operation. The electricity supply is the key activity affecting eight of the ten assessed categories and involves between 50% and 60% of the impact of the process. S4 is the main cause of the high energy requirements, with 86% of the total electricity consumption. Additionally, several scenarios aiming at improving the environmental profile of the system were evaluated. The application of LCA finally led to the proposal of two optimized scenarios with improvements between 8% and 40% with respect to the baseline case study.

Dimensionless equations to describe microalgal growth in a planar cultivation system.

OBJECTIVES: To develop dimensionless equations to describe microalgal growth in planar photobioreactor or raceway pond systems that are generalized to all phototrophic species and reactor length scales. RESULTS: Expressions for biomass growth and mean light intensity within a nutrient replete, well-mixed, phototrophic cell culture in a planar cultivation system were developed in terms of dimensionless variables for biomass, time and light intensity, plus two new dimensionless parameters. The first dimensionless parameter represents a species-specific physiological characteristic based on maximum growth rate and cell maintenance, while the second represents the light input. Optimal biomass productivities and photosynthetic conversion efficiencies are easily determined from the dimensionless expressions and system-specific performances can be easily determined by back substituting with the relevant cell culture and photobioreactor parameters. CONCLUSION: The dimensionless expressions are useful for understanding and determining the relevant bioprocess parameters in a generalized form applicable to all strains and reactor length scales.

Biogenic nanomaterials from photosynthetic microorganisms.

The use of algal cell cultures represents a sustainable and environmentally friendly platform for the biogenic production of nanobiomaterials and biocatalysts. For example, advances in the production of biogeneic nanomaterials from algal cell cultures, such as crystalline ß-chitin nanofibrils and gold and silver nanoparticles, could enable the 'green' production of biomaterials such as tissue-engineering scaffolds or drug carriers, supercapacitors and optoelectric materials. The in vivo functionalization, as well as newly demonstrated methods of production and modification, of biogenic diatom biosilica have led to the development of organic-inorganic hybrid catalytic systems as well as new biomaterials for drug delivery, biosensors and heavy-metal adsorbents.

Induction of canthaxanthin production in a Dactylococcus microalga isolated from the Algerian Sahara.

Secondary carotenoids are high-valued anti-oxidants which can be produced by some algae when exposed to an environmental stress (e.g. nutrient deprivation, high light intensities). To this end, we characterized the stress-induced carotenoid production of a new microalgal strain, Dactylococcus dissociatus MT1, which was isolated from the Sahara Desert of Algeria. Nitrate starvation, oxidative stress and varying light intensities were applied to determine the effect of illumination on carotenogenesis. Canthaxanthin was the main secondary carotenoid and light intensity had an important influence on the rate of its accumulation. The addition of NaCl also enhanced canthaxanthin production while nitrate depletion had more of an effect on lipid production. However, these two stresses in combination synergistically increased the production of both. Our results represent a step toward the development of strains suitable for secondary carotenoid production at the industrial scale.

Sustainable production of biologically active molecules of marine based origin.

The marine environment offers both economic and scientific potential which are relatively untapped from a biotechnological point of view. These environments whilst harsh are ironically fragile and dependent on a harmonious life form balance. Exploitation of natural resources by exhaustive wild harvesting has obvious negative environmental consequences. From a European industry perspective marine organisms are a largely underutilised resource. This is not due to lack of interest but due to a lack of choice the industry faces for cost competitive, sustainable and environmentally conscientious product alternatives. Knowledge of the biotechnological potential of marine organisms together with the development of sustainable systems for their cultivation, processing and utilisation are essential. In 2010, the European Commission recognised this need and funded a collaborative RTD/SME project under the Framework 7-Knowledge Based Bio-Economy (KBBE) Theme 2 Programme 'Sustainable culture of marine microorganisms, algae and/or invertebrates for high value added products'. The scope of that project entitled 'Sustainable Production of Biologically Active Molecules of Marine Based Origin' (BAMMBO) is outlined. Although the Union is a global leader in many technologies, it faces increasing competition from traditional rivals and emerging economies alike and must therefore improve its innovation performance. For this reason innovation is placed at the heart of a European Horizon 2020 Strategy wherein the challenge is to connect economic performance to eco performance. This article provides a synopsis of the research activities of the BAMMBO project as they fit within the wider scope of sustainable environmentally conscientious marine resource exploitation for high-value biomolecules.

Metabolic insertion of nanostructured TiO2 into the patterned biosilica of the diatom Pinnularia sp. by a two-stage bioreactor cultivation process.

Diatoms are single-celled algae that make silica shells or frustules with intricate nanoscale features imbedded within periodic two-dimensional pore arrays. A two-stage photobioreactor cultivation process was used to metabolically insert titanium into the patterned biosilica of the diatom Pinnularia sp. In Stage I, diatom cells were grown up on dissolved silicon until silicon starvation was achieved. In Stage II, soluble titanium and silicon were continuously fed to the silicon-starved cell suspension (approximately 4 x 10(5) cells/mL) for 10 h. The feeding rate of titanium (0.85-7.3 micromol Ti L(-1) h(-1)) was designed to circumvent the precipitation of titanate in the liquid medium, and feeding rate of silicon (48 micromol Si L(-1) h(-1)) was designed to sustain one cell division. The addition of titanium to the culture had no detrimental effects on cell growth and preserved the frustule morphology. Cofeeding of Ti and Si was required for complete intracellular uptake of Ti. The maximum bulk composition of titanium in the frustule biosilica was 2.3 g of Ti/100 g of SiO(2). Intact biosilica frustules were isolated by treatment of diatom cells with SDS/EDTA and then analyzed by TEM and STEM-EDS. Titanium was preferentially deposited as a nanophase lining the base of each frustule pore, with estimated local TiO(2) content of nearly 80 wt %. Thermal annealing in air at 720 degrees C converted the biogenic titanate to anatase TiO(2) with an average crystal size of 32 nm. This is the first reported study of using a living organism to controllably fabricate semiconductor TiO(2) nanostructures by a bottom-up self-assembly process.