The safety of graphene in human health: what science says about it

The safety of graphene in human health:

what science says about it

Part II. Are graphene materials safe for humans?

The family of graphene materials comprises a wide range of two-dimensional (2D) carbon nanostructures in the form of sheets that differ from each other by the particularities derived from the production method or by the innumerable functionalizations that can be performed after its obtaining. In 2022, Nature magazine, one of the most important scientific journals in the world, published a study in which 36 products from graphene suppliers from countries such as the United States, Norway, Italy, Canada, India, China, Malaysia and England were analyzed, concluding that graphenes represent a heterogeneous class of materials with variable characteristics and properties, whether mechanical, thermal, electrical, optical, biological, etc., which can be transferred to a large number of three-dimensional (3D) compounds to modify or create new products.

“Undoubtedly, graphene and nanotechnology in general continue to be controversial issues as they confront us with a world that is difficult to see and understand, but with simply amazing effects”

Are graphene materials safe?

Graphene materials promise to be an important tool within biomedical technologies. In principle, its benefits can be used for the design of diagnostic elements such as sensors and devices for images up to neural interfaces, gene therapy, drug delivery, tissue engineering, infection control, phototherapy for cancer treatment, bioelectronic and dental medicine, among other. But for them to be truly used in this type of technology, their interactions with the biological environment must first be understood or, failing that, ensure that their presence does not alter the natural environment of the cells. In this sense, numerous studies have been carried out with the different forms, presentations, and available concentrations of graphene whose findings have gradually paved the way for its safe use in biomedical technologies:

i) Graphene materials in their free form. In in vitro tests, exposure of human lung epithelial cells to graphene sheets at concentrations lower than 0.005 mg/ml did not cause significant changes in their morphology or adhesion,2,3 nor was cytotoxic activity identified in stem cells derived from adipose tissue. human, periodontal ligament and dental pulp exposed to 0.5 mg/ml of GO,4 even and understanding a possible dose-size dependent effect, other investigations report safe concentrations below 40 mg/ml or, that do not exceed 1, 5% w/v. 5-8

Finally, one of the most recent in vivo studies published by the University of Manchester, United Kingdom, on the pulmonary response of mice exposed to graphene oxide (GO) in the respiratory tract, did not identify significant damage or pulmonary fibrosis at 90-day follow-up. These results provide solid grounds for the safety of these nanostructures without underestimating basic safety measures, such as avoiding their inhalation.9 Likewise, scientists from the University of Trieste, Italy, analyzed the impact of graphene materials on the skin, reporting low toxicity on cells.10

“It is unlikely that graphene materials in their free form are used to be in contact with the biological environment, they are generally functionalized or immobilized in other materials to develop an application”

ii) Functionalized graphene materials. Functionalization is the term that refers to the chemical modification of a nanomaterial to give it a “function”, that is, to facilitate its incorporation with other compounds or to benefit its biocompatibility and better direct its use by anchoring functional groups, molecules, or nanoparticles. A study published in the journal Nature Communications on graphene bioapplications highlights the importance of its functionalization with amino groups to make it more compatible with human immune cells.11,12

“The most common functionalization of graphene is the anchoring of oxygenated groups on its surface, this material is known as graphene oxide”

iii) Immobilization in polymers. The use of graphene materials as nano-filling for plastics, resins, coatings, etc., is the most common way in which these nanostructures are used. For the biomedical sector, its immobilization in polymers has shown good biocompatibility and stimulation of cell proliferation; antimicrobial activity and improvement of the mechanical properties of polymers, being classified as excellent candidates for the manufacture of bone fixation devices, molecular scaffolds, orthopedic implants, or dental materials.13-15

Given the great potential of graphene materials in health sciences, but also due to the many questions about their safety, an international research team from the European Graphene Flagship project, led by EMPA (German acronym for the Federal Institute for Testing and Materials Research), conducted a study to assess the potential health effects of graphene materials immobilized within a polymer; the results showed that the graphene particles released from said polymeric compounds after abrasion induce insignificant effects.16

“It is reassuring to see that this study shows negligible effects, confirming the viability of graphene for mass applications. Andrea C. Ferrari, Graphene Flagship Science and Technology Officer.” 17,18

Energeia-Graphenemex, the pioneering Mexican company in Latin America in the research and development of applications with graphene materials, throughout its 10-year career has overcome numerous scientific and industrial challenges to reach the market with products for industrial use. In 2018, it began to explore the antimicrobial capabilities of its products with excellent results in vitro and in a relevant environment; currently, and in conjunction with other research centers, it is carrying out evaluations to explore the potential of its materials as nano-reinforcement of biopolymers.

Drafting: EF/DHS

References

  1. Cytotoxicity survey of commercial graphene materials from worldwide. npj 2D Materials and Applications (2022) 6:65
  2. Biocompatibility of Pristine Graphene Monolayers, Nanosheets and Thin Films. 2014, 1406.2497.
  3. Preliminary In Vitro Cytotoxicity, Mutagenicity and Antitumoral Activity Evaluation of Graphene Flake and Aqueous Graphene Paste. Life 2022, 12, 242
  4. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1
  5.  Graphene substrates promote adherence of human osteoblasts and mesenchymal stromal cells. Carbon. 2010; 48: 4323–9
  6. Multi-layer Graphene oxide in human keratinocytes: time-dependent cytotoxicity. Prolifer Gene Express Coat 2021; 11:1
  7. Cytotoxicity assessment of graphene-based nanomaterials on human dental follicle stem cells. Colloids Surf B Biointerfaces. 2015; 136:791
  8. Arabinoxylan/graphene-oxide/nHAp-NPs/PVA bionano composite scaffolds for fractured bone healing. 2021. J. Tissue Eng. Regen. Med. 15, 322.
  9. Size-Dependent Pulmonary Impact of Thin Graphene Oxide Sheets in Mice: Toward Safe-by-Design. Adv. Sci. 2020, 7, 1903200
  10. Differential cytotoxic effects of graphene and graphene oxide on skin keratinocytes. 2017. Sci Rep 7, 40572
  11. Amine-Modified Graphene: Thrombo-Protective Safer Alternative to Graphene Oxide for Biomedical Applications. ACS Nano 2012, 6, 2731
  12. Single-cell mass cytometry and transcriptome profiling reveal the impact of graphene on human immune cells. Nature Communications, 2017, 8: 1109,
  13. In-vitro cytotoxicity of zinc oxide, graphene oxide, and calcium carbonate nano particulates reinforced high-density polyethylene composite. J. Mater Res. Technol. 2022. 18: 921
  14. Graphene-Doped Polymethyl Methacrylate (PMMA) as a New Restorative Material in Implant-Prosthetics: In Vitro Analysis of Resistance to Mechanical FatigueJ. Clin. Med. 2023, 12, 1269
  15. High performance of polysulfone/ Graphene oxide- silver nanocomposites with excellent antibacterial capability for medical applications. Matter today commun. 2021. 27
  16. Hazard assessment of abraded thermoplastic composites reinforced with reduced graphene oxide. J. Hazard Mater. 2022. 435. 129053
  17. https://www.empa.ch/web/s604/graphene-dust
  18. https://www.graphene-info.com/researchers-asses-health-hazards-graphene-enhanced-composites

Graphene: The next revolution in biomedical applications

Graphene:

The next revolution in biomedical applications

Part I. Tissue Engineering

Advances in medicine have reached levels unimagined until recently. Among them, tissue engineering has an important participation. With it is possible to combine cells, biomaterials and biologically active molecules with the aim of repairing or replicating tissues or organs with a function similar to that of the original structure. In principle, biomaterials are used as molecular scaffolds to act as a three-dimensional (3D) support or guide for the anchoring and growth of the cells that will be in charge of forming the new tissue.

The first molecular scaffolds were designed with natural materials such as collagen, glycosaminoglycans (GAGs), chitosan, and alginates; then with artificial compounds such as polylactic acid (PLA), polyglycolic acid (PGA), poly(lactic-co-glycolic) acid (PLGA), polyurethanes (PUs), polytetrafluoroethylene (PTFE), polyethyleneterephthalate (PET); bioceramics such as hydroxyapatite (HA) and tricalcium phosphate; metals such as stainless steel, chrome-cobalt alloys (Co-Cr) or titanium alloys (Ti) and recently, new research is oriented towards the use of nanotechnology.

The relationship between nanotechnology and tissue engineering is due to the fact, that the extracellular matrix (ECM) that helps cells unite and communicate with each other, is made up of a network of nanometer-sized fibers made up of bioactive molecules. It is at this point where nanotechnology opens new possibilities for regenerative medicine, since it has been proven that the use of materials that act on the same nanometric scale as the ECM favors mimicking the physiological environment of the organism to stimulate cell growth and differentiation in a more natural environment.

Among the most studied nanomaterials in recent years are graphene materials, which consist of nanometric sheets of carbon atoms organized in two-dimensional (2D) hexagonal networks. Among the most interesting properties for tissue engineering are: its large surface area, mechanical resistance, thermal conductivity, biocompatibility and finally, an extraordinary ability to share its properties with other materials to improve their original characteristics.

For example, the use of graphene materials within the 3D architecture of certain biopolymers in tests carried out on heart, liver, bone, cartilage, and skin tissues has shown substantial improvements in their physicochemical, mechanical, electrical and biological properties, achieving excellent response. for stem cell adhesion and differentiation.

In 2022, the Andaltec technology center (Spain) reported the development of a material from polymers derived from graphene by 3D printing with great potential for the regeneration of muscle tissue. They demonstrated that in the presence of graphene derivatives, cells contract and expand without an external stimulus, therefore, it has great potential for use in regenerative medicine.

On the other hand, the Division of Postgraduate Studies and Research (DEPeI) on Odontology, UNAM and the National School of Higher Studies (ENES) León Unit, Mx., through a study published in J Oral Res 2021 supports the possibilities of graphene oxide (GO) in the design of biomaterials for dental use. The results of the research carried out with Graphenemex® GO samples, concluded that this nanomaterial in combination with polymethylmethacrylate (PMMA), in addition to improving its physical-mechanical properties, also demonstrated good compatibility and an interesting stimulation of cell proliferation when being evaluated on cultures with gingival-fibroblasts, dental-pulp-cells and human osteoblasts.

In 2020, researchers from the University of Malaga (Spain) published another study that identified GO as the ideal material for regenerative medicine. The study carried out on an animal model, showed high biocompatibility of different types of graphene oxide with dopaminergic cells, favoring their maturation and protecting them from the toxic conditions of Parkinson’s disease. These results postulate GO as an adequate scaffold to test new drugs or develop constructs for cell replacement therapy of Parkinson’s disease.

Despite the large amount of research on the interactions of graphene materials with biological media, there is still a long way to go to have these biomaterials available and in clinical operation. Energeia- Graphenemex, the pioneering Mexican company in Latin America in the research and development of applications with graphene materials, in collaboration with other companies and research centers, seeks to contribute with science to understand these interactions in a security framework, to lay solid foundations on the use of graphene nanotechnology in the biomedical sector for the benefit of society.

Drafting: EF/DHS

References

  1. Graphene and its derivatives: understanding the main chemical and medicinal chemistry roles for biomedical applications. J Nanostructure Chem, 2022, 12:693
  2. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1
  3. Graphene-Based Antimicrobial Biomedical Surfaces. ChemPhysChem 2021, 22, 250
  4. Functionalized Graphene Nanoparticles Induce Human Mesenchymal Stem Cells to Express Distinct Extracellular Matrix Proteins Mediating Osteogenesis. Int J Nanomed 2020:15 2501
  5. Graphene Oxide and Reduced Derivatives, as Powder or Film Scaffolds, Differentially Promote Dopaminergic Neuron Differentiation and Survival. Front. Neurosci., 21 December 2020. Sec. Neuropharmacology Volume 14
  6. International Journal of Nanomedicine 2019:14 5753
  7. Biocompatibility Considerations in the Design of Graphene Biomedical Materials. Adv. Mat. Interfaces 2019, 6, 1900229
  8. Graphene based scaffolds on bone tissue engineering. Bioengineered, 2018, 9:1, 38
  9. When stem cells meet graphene: Opportunities and challenges in regenerative medicine. Biomaterials, 2018, 155, 236
  10. Graphene-based materials for tissue engineering. Adv. Drug Deliv. Rev. 2016,105, 255

Chapter 92 e: Tissue Engineering, Anthony Atala. 2023 McGraw Hill.

Innovation in the plastics industry: how graphene masterbatches are changing the game

Innovation in the plastics industry:

how graphene masterbatches are changing the game

Graphene has extraordinary electrical, optical, thermal properties and high mechanical resistance. The properties of graphene are attributed to its structure in the form of two-dimensional (2D) sheets, formed by hexagonal bonded carbon atoms and a thickness of one carbon atom.

Today, graphene is the most promising nanotechnological additive in the plastics industry. The incorporation of graphene and its derivatives (graphene oxide, GO) in different polymer matrices (masterbatches), have great potential for a wide range of applications. The graphene masterbatch can act as a mechanical reinforcement or conductive additive for both thermoplastic and thermosetting materials. They can be used in the automotive, aerospace, electronics or packaging sectors.

Graphene-based polymeric compounds have shown significant improvements in properties such as elastic modulus, tensile strength, impact resistance, electrical conductivity, resistance to UV radiation, thermal stability, antimicrobial property, impermeability or barrier effect (it does not allow the diffusion of moisture or other molecules).

Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of applications at an industrial level, through its Graphenergy Masterbatch line, has developed and sells a wide range of masterbatches with graphene, based on various polymers, such as PP, HDPE, LDPE, PET and PA6.

Our Masterbatches are granular materials that act as multifunctional additives. The incorporation of graphene in different polymer matrices has shown important effects on the properties and processing conditions of plastics, among which are:

  • Increased resistance to tension, deformation and impact
  • Increased resistance to ultraviolet rays
  • Excellent dispersion
  • Improves processing conditions (thermal stability)
  • Acts as a nucleating agent (modification of the crystallization temperature of the polymer)

In this sense, it has been found that the incorporation of graphene and its derivatives, as well as the concentration, can modify the physicomechanical properties of the polymer to be processed. The addition of masterbatch to different polymers has improved the final characteristics of the material to a lesser or greater extent, for example:

  • Additivation of Polypropylene (PP) with polypropylene-graphene masterbatch (MB-PP/GO), increases tensile strength (8%) and rupture percentage (29%).
  • Additivation of Polyethylene (PE) with polyethylene-graphene masterbatch (MB-PE/GO), improves tensile strength (17%), flexural strength and rupture strength (66%).
  • Additivation of Polyethylene terephthalate (PET) with polyethylene terephthalate-graphene masterbatch (MB-PET/GO), improves resistance to humidity, increases tensile strength (72.2%) and improves impact resistance.
  • Additivation of Polycarbonate (PC) with polycarbonate-graphene masterbatch (MB-PC/GO), improves resistance to humidity and improves resistance to rupture (276%).

On the other hand, graphene masterbatches can also be incorporated into recycled polymers. Currently, the reuse and recycling of plastic materials are of vital importance in the transition path towards a circular economy. In this regard, the constant washing, pelletizing and reprocessing can cause the loss of physicomechanical properties of recycled plastics, therefore, by adding graphene, these properties can be restored or improved. In agricultural applications, mulch films with increased resistance to ultraviolet radiation can be produced.

References

  1. Fang, M., et al., Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites. Journal of Materials Chemistry. 19(38): p. 7098-7105.
  2. Kim, H., A.A. Abdala, and C.W. Macosko, Graphene/Polymer Nanocomposites. Macromolecules. 43(16): p. 6515-6530.
  3. Balandin, A.A., et al., Superior Thermal Conductivity of Sin gle-Layer Graphene. Nano Letters, 8(3): p. 902-907.
  4. Nabira Fatima, Umair Yaqub Qazi, Asim Mansha., Recent developments for antimicrobial applications of graphene-based polymeric composites: A review, https://doi.org/10.1016/j.jiec.2021.04.050

Graphene-reinforced lime paints: the revolution in the construction industry

Graphene-reinforced lime paints:

the revolution in the construction industry

Although the exact date on which lime was discovered by man is not known, there are records dating back more than 14,000 years regarding its use. In the case of Mexico, it has been used since pre-Hispanic times both for construction and for nixtamalization, in ancient Greece it was used to color numerous frescoes (2800 B.C.- 1000 A.D.), the Chinese wall was built after stabilizing the soil with lime (500 AD) and among many other historical data, lime became popular in Europe during the Middle Ages for its disinfectant, breathable and fire-retardant properties, being used mainly as a coating on the exterior of houses and barracks. Subsequently, its implementation in the cities extended until the beginning of 1900 and it was not until the middle of that same century that it reached rural areas, a period in which synthetic paints gained ground over lime thanks to their ease of application, wide range of colors and low cost.

However, at the end of the 1970s and due to the awareness of the dangers of some synthetic paints with respect to health and the environmental pollution caused by certain components (heavy metals and volatile organic compounds [VOC]), lime paints once again had a boom as they are safer products and have a smaller footprint on the environment.

Among the benefits of lime-based paints or coatings are that they are 100% natural, ecological and VOC-free products, which absorb CO2 during their hardening process, which means that their use contributes to air purification. They are also breathable materials, that is, they allow the structures to “breathe” and do not concentrate moisture. In addition, they are thermoregulators, this means that they do not allow drastic changes in temperature in the buildings and, on the contrary, they help the buildings to stay cool.

However, and despite their great advantages, one of the main drawbacks of lime-based paints is their high permeability and, therefore, poor resistance to humidity, which is in turn related to limited adherence that requires constant repair work. maintenance. On the other hand, and although antimicrobial or biocidal properties are attributed to lime, it is not convenient to ensure that all the products that contain it offer this protection, since they are materials susceptible to being attacked by microbial species such as Aspergillus spp., Cladosporium spp, Fusarium spp., Trichoderma spp., Actinobacteria and Bacteroidetes among other species responsible for its biodeterioration as well as some infections.

With the aim of contributing to a sustainable present and future, in 2022 the strategic alliance between the companies Energeia-Graphenemex® and Oxical®, after almost 2 years of research, launched a new coating made from modified high-purity lime with Graphene nanoparticles, under the Graphenecal® brand.

Graphenecal nanoengineering reaches the market to create a new generation of lime-based coatings that exceed the characteristics of water-based paints made from chemical resins. The nanometric network that generates the graphene nanoparticles in combination with the high-purity lime and other natural products used in its formulation, compacts and organizes its entire structure at the molecular level, offering greater durability to the coating and improving its characteristics, thanks to the perfect balance that exists between greater impermeability (>50-80%) with adequate breathability avoiding the accumulation of moisture on surfaces, coupled with the excellent benefits offered by its great antimicrobial capacity (>99.9%) that prevents the adhesion and formation of microbial biofilms not only to protect against the biodeterioration of structures but also as a tool in infection control, among other advantages such as excellent adhesion, covering power, resistance against the effects of weather, greater thermoregulation, CO2 capture and lower carbon footprint in comparison with other products, no need for chemical additives, biocide products or contaminants, placing Mexico at the vangard in the development of environmentally friendly products.

Greater Impermeability

After 4 days of application, Graphenecal is 50% more waterproof than lime-based paints without graphene. As of day 30, this property rises to 85% without affecting the breathability of the product.
Representative image of the impermeability of Graphenecal on two different substrates.

Antimicrobial Capacity

On the graphene-free lime paint, a microbial biofilm was formed on more than 90% of its surface. The Graphenecal coated area remained free of contamination during the test.

Protection against bacteria, viruses and fungi with graphene coatings

Protection against bacteria, viruses and fungi

with graphene coatings

In less than 20 years the world has faced a series of abnormal phenomena caused by highly infectious pathogens. The easy and rapid transmission of infections forces us to seek increasingly efficient strategies to strengthen health services, in addition to representing a radical change in our lifestyle, where extreme hygiene techniques are in first place of importance to avoid the spread and massive contagion inside and outside hospitals.

Viral diseases of greater impact.

  • 2002-2003. Severe acute respiratory syndrome (SARS-Cov).
  • 2012. Middle East Respiratory Syndrome (MERS-Cov).
  • 2014- 2016. Ebola.
  • 2019- 2022. SARS-Cov-2.

>6.5 million deaths.

Dangerous bacteria for human health:

  • Staphylococcus aureus.
  • Streptococcus pneumoniae.
  • Pseudomonas aeruginosa.
  • Haemophilus influenzae.
  • Helicobacter pylori.

Common fungi in the domestic environment:

  • Aspergillus spp.
  • Cladosporium spp.
  • Alternaria spp.
  • Acremonium spp.
  • Epiccocum spp.
  • Penicillium spp.
  • Stachybotrys spp.

Graphene as an adjuvant in infection control

In 2018, Energeia- Graphenemex® launched the antimicrobial Graphenergy line, made up of two specialized vinyl- and vinyl-acrylic-based coatings with graphene oxide, whose antimicrobial potential is 400 times higher than common products, helping to keep surfaces free of fungi and bacteria for a long time.

In vitro studies and in a relevant environment carried out by the Laboratory of Pathology, Biochemistry and Microbiology of the Faculty of Stomatology of the U.A.S.L.P., showed that surfaces protected with antimicrobial Graphenergy remain free of microorganisms for more than 6 months, without the need for additional chemicals. Figure 1.

Fig. 1. Results at 2, 4 and 6 months on the protection of antimicrobial Graphenergy compared to a control group (No Graphene Oxide).
Important: A clean surface is in the range of 1-10 CFU/cm2.

In 2022, the strategic alliance between the companies Energeia-Graphenemex® and Oxical® is preparing to launch a new 100% natural coating, without toxic compounds (VOCs), highly waterproof, breathable and highly antimicrobial, made from high-quality and purity lime modified with Graphene nanoparticles, under the ecological Graphenecal brand.

Its extraordinary antimicrobial capacity is not only a great aid in keeping spaces free of microorganisms, but also protects surfaces against biodeterioration, particularly those with high historical value. Figure 2.

Fig. 2. Graphene-free lime paint has a microbial biofilm on more than 90% of its surface. The area covered with organic Graphenecal remained free of contamination for more than 100 days of incubation. The antimicrobial effect of organic Graphenecal is highly effective, with a reduction of microorganisms of 7 Log10.

Is graphene nanotechnology safe?

Yes, Graphenergy and Graphenecal antimicrobial coatings are as safe as any conventional paint or coating. The graphene and graphene oxide nanoparticles contained in its formulations do not shed or release toxic substances into the environment.

“Not all microorganisms are dangerous, but it is better to keep them away”

How do graphene materials work?


  1. Physical barrier- High impermeability. Graphene materials are usually presented in millions of blocks composed of 1 to 10 nanometric sheets similar to a pack of cards, with multiple sinuous paths between each sheet that act as an external barrier that suppresses the entry of essential nutrients for microbial growth.

  2. Graphene and its derivatives can act as electron donors or acceptors, altering the respiratory chain of the microorganism or extracting its electrons. This imbalance in the form of a nano-circuit is so fast that it does not give the microorganism time to recover and, therefore, inactivates it before adhering to the surface.

  3. Structural damage. The edges of the nanomaterial sheets act like small knives that damage or break the cell membrane of the microorganism, altering its functioning and preventing its viability.

Do graphene materials have antiviral activity?

The antiviral effect of graphene materials seems not to be very different from that described against fungi and bacteria. The hypotheses are directed towards an interesting synergistic effect between impermeability, structural damage and electrostatic interactions due to the positive polarity of some viruses (SARS-Cov-2) and the negative polarity of graphene oxide, in addition to its great protein-anchoring capacity.

Energeia- Graphenemex®is the pioneer Mexican company in Latin America focused on the research and production of graphene materials for the development of applications at an industrial level. In addition to adding value to its products with the multifunctional properties of Graphene and its derivatives, the company also aims to create strategic alliances to support innovative developments with graphene nanotechnology.

References

  1. García-Contreras R, Guzmán Juárez H, López-Ramos D & Alvarez Gayosso C. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1-9. Doi:10.17126/joralres. 2021.019
  2. UM.D. Giulio, R. Zappacosta, S.D. Lodovico, E.D. Campli, G. Siani, A. Fontana, L. Cellini, Antimicrobial and antibiofilm eficacy of graphene oxide against chronic wound microorganisms. Antimicrob. Agents Chemother. 62(7), e00547-18 (2018). https://doi.org/10.1128/AAC.00547-18
  3. H.E. Karahan, C. Wiraja, C. Xu, J. Wei, Y. Wang, L. Wang, F. Liu, Y. Chen, Graphene materials in antimicrobial nanomedicine: current status and future perspectives. Adv. Healthc. Mater. 7(13), 1701406 (2018). https://doi.org/10.1002/ adhm.201701406
  4. Sydlik SA, Jhunjhunwala S, Webber MJ, Anderson DG, Langer R. In vivo compatibility of graphene oxide with differing oxidation states. ACS Nano. 2015. 9: 3866
  5. Yang K, Zhang S, Zhang G, Sun X, Lee ST, Liu Z. Graphene in mice: ultrahigh in vivo tumor uptake and efficient photothermal therapy. Nano Lett. 2010. 10: 3318.
  6. Bhattacharya K, Farcal LR, Fadeel B. Shifting identities of metal oxide nanoparticles: focus on inflammation. 2014. MRS Bull; 39: 970
  7. Huang PJ, Pautler R, Shanmugaraj J, Labbé G, Liu J. Inhibiting the VIM-2 metallo-β-lactamase by graphene oxide and carbon nanotubes. ACS Appl Mater Interfaces 2015; 7: 9898.
  8. Moghimi SM, Wibroe PP, Wu L, Farhangrazi ZS. Insidious pathogen-mimicking properties of nanoparticles in triggering the lectin pathway of the complement system. Eur J Nanomedicine. 2015; 7: 263.
  9. Bhattacharya K, Mukherjee SP., Gallud A., Burkert SC., Bistarelli S., Bellucci S., Bottini, M., Star A., Fadeel B. Biological interactions of carbon-based nanomaterials: From coronation to degradation. Nanomedicine: Nanotechnology, Biology, and Medicine. 2016. 12. 333

Graphene oxide: a promising alternative in nanotechnology

Graphene oxide:

a promising alternative in nanotechnology

Since graphene was isolated for the first time in 2004 by the Manchester group, this nanomaterial has proven to be the most revolutionary for the development of new applications at an industrial level.

Graphene has extraordinary electrical, optical, thermal properties and high mechanical resistance. The properties of graphene are attributed to its structure in the form of two-dimensional (2D) sheets, made up of hexagonally bonded carbon atoms and a thickness of one carbon atom.

Currently there are different methods of graphene production, these can be classified into two methods, according to their origin, the “bottom-up” method and the “top down” method. The “bottom-Up” method consists in the creation of graphene structures through building blocks (atoms, molecules), for example, by Chemical Vapor Deposition (CVD); and the “top down” method involves the production of graphene from the oxidation of graphite. Graphite is made up of sheets of graphene that are stacked on top of each other. The following diagram represents the process for obtaining graphene from the oxidation of graphite.

Schematic diagram of the process for obtaining GO, through the oxidation of graphite.

The graphite oxidation process begins with the addition of graphite in sulfuric acid (H2SO4), with constant mechanical stirring. Subsequently, potassium permanganate (KMnO4) is slowly added, producing a chemical reaction that allows the graphite (graphene sheets stacked on top of each other) to be chemically modified in its structure. When KMnO4 reacts with H2SO4, it forms manganese oxide VII (Mn2O7), which is a very selective oxidizing agent on double bond aromatic compounds, such as graphite. The oxidizing agent molecularly attacks the structure of each graphene sheet in the graphite, grafting oxygenated functional groups (with oxygen), such as epoxide groups (C-O-C) and hydroxyl groups (-OH), on each sheet, and carboxyl groups (-COOH, CO2H ) on the edges of each sheet, obtaining graphite oxide and graphene oxide (GO), see Figure 1.

Figure 1. Structure of graphene oxide

The incorporation of oxygenated functional groups allows a material such as graphite, which is highly hydrophobic (which repels water) and a good electrical conductor, to become graphite oxide and graphene oxide (GO), highly hydrophilic materials, that is, they mix and disperse easily with water (See Figure 2). GO is chemically similar to graphite oxide, but structurally differs in the arrangement and number of stacked sheets.

The GO can be defined as a single exfoliated graphene sheet or stack of few sheets (3-4) that is functionalized with different oxygenated groups. Among its main characteristics is that it is hydrophilic, insulating and hygroscopic (absorbs moisture). On the other hand, graphene oxide sheets possess a large surface area and exhibit high mechanical strength and flexibility.

Applications

Graphene oxide has attracted great interest in various fields of science and technology, due to its remarkable mechanical, chemical, and thermal properties, among others. So numerous investigations began, to take advantage of the properties of graphene oxide.

In 2011, the first investigations of the use of GO as a precursor in the large-scale production of graphene emerged, for use as filler/reinforcement material/in polymeric matrices, such as high-density polyethylene (HDPE) and low-density polyethylene (HDPE). density (LDPE).

By 2014, GO was considered feasible for use as a flame retardant agent. Research is still ongoing to functionalize it with different polymeric materials.

In 2017, the first reports of the manufacture of GO-based membranes began, since it is impermeable to gases and liquids, showing its ability to filter small particles, organic molecules and even its use for seawater desalination.

In 2018, Energeia-Graphenemex started research on graphene oxide as a new additive for the production of anticorrosive and antimicrobial coatings. By 2019, studies of graphene oxide in coatings with antibacterial behavior increased, associated with the fact that GO is capable of penetrating the cell membrane of bacteria, producing oxidative stress and inhibiting their reproduction.

In particular, the functionalization of GO allows it to be applicable in biological systems, development of biosensors for the identification of specific molecules, drug delivery systems, among others.

Energeia Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of industrial applications. It has extensive experience in the production of graphene oxide (GO) on a large scale, with different degrees of oxidation and high quality for use in different applications and industries. Currently, it uses graphene oxide in the production of concrete additives and anticorrosive and antimicrobial coatings that are marketed under the Graphenergy brand.

References

  1. M. Fang, K. Wang, H. Lu, Y. Yang y S. Nutt, «Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites,» Journal of Materials Chemistry, vol. 19, pp. 7098-7105, 2009.
  2. B. Dittrich, K.-a. Wartig, R. Mülhaupt y B. Schartel, «Flame-Retardancy Properties of Intumescent Ammonium Poly(Phosphate) and Mineral Filler Magnesium Hydroxide in Combination with Graphene,» Polymers, vol. 6, pp. 2875-2895, 2014.
  3. Y.-j. Wan, L.-x. Gong, L.-c. Tang, L.-b. Wu y J.-x. Jiang, «Mechanical properties of epoxy composites filled with silane-functionalized graphene oxide,» COMPOSITES PART A, vol. 64, pp. 79-89, 2014.
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Graphene and its impact on the packaging industry

Graphene

and its impact on the packaging industry

According to data from the World Bank, every year in Mexico 24 million tons of food are wasted. This means that 34% of the country’s production is not only NOT consumed, but also generates an average expense of 491 billion pesos.

This impact is not only economic, but it is a problem that extends to the social sphere, due to the well-known food crisis and to the environment, due to the high water requirements for food production processes that will not be used and whose decomposition will contribute considerable CO2 emissions that contribute to global warming.

According to the Food and Agriculture Organization of the United Nations, the loss and food waste exceeds 1,300 million tons per year.

Within this multifactorial problem, the container and packaging industry, also known as “packing”, is a crucial actor considering that there are unavoidable conditions such as temperature, humidity, lighting, oxygen and numerous handling practices throughout the entire supply chain. production of food, which affect its quality, shelf life and acceptability by consumers.

In the search for solutions to improve the quality of packing products and, consequently, their content, nanotechnology has been a great ally. For example, to avoid microbial contamination, nanoparticles of silver, titanium dioxide, copper oxide, carbon nanotubes or magnesium oxide are used; to improve the mechanical or barrier properties, it is common to use nanoparticles of silicate, clay, polyamide, iron or iron oxides, cellulose nanofibers and for other needs there are nanoparticles of tungsten, molybdenum, barium sulfate, barium titanate , chitosan, zeolites, activated carbon, etc.

Graphene nanoparticles are mainly made up of carbon, like graphite and diamond, but with multifunctional characteristics. This means that they do not have a single function, but rather, unlike other nanoparticles, Graphene, due to its extraordinary physical and chemical properties, can be used for different purposes, for example, to design lighter and more resistant products, with greater impermeability against liquids and gases, in addition to protecting against microbial contamination and against UV radiation, among other properties that substantially improve the performance of the compounds with which it is combined.

“Graphene has crossed the limits of laboratories to reach commercial applications to combat the main enemies of food”, these are some examples of what is being developed for the Packing industry:

Tetra Pak
The Swedish company Tetra Pak, leader in research and development in the packaging sector, through the European Graphene Flagship project, studies the use of Graphene for the manufacture of products with low environmental impact to reduce the carbon footprint, improve the performance of materials, add properties and optimize recyclability.

Applynano
The Spanish company Applynano uses nanomaterials, including graphene oxide, to promote the durability and recyclability of plastics, as well as to improve antimicrobial, thermal, and electrical properties, among others.

Plastic Technology Center (Andaltec)
The Technological Center of Plastic (Andaltec) within the European project Grafood, had the initiative to use derivatives of Graphene for the development of active packaging to increase the shelf life of food and reduce food waste.

Energeia – Graphenemex®
The Mexican company Energeia – Graphenemex®, through the polymer division Graphenergy Advanced Graphenic Solutions, promotes the use of Graphene and its derivatives as nano-reinforcement of plastic for different industries. Among the benefits it offers for the packing industry are mechanical resistance and resistance to degradation by UV radiation, greater barrier effect and interesting antimicrobial properties, highly promising for prolonging the life of products and their contents. Likewise, in addition to adding value to its developments with the multifunctional properties of Graphene and its derivatives, the company also aims to support other innovation projects with graphene nanotechnology, while seeking to collaborate with the circular economy to improve the quality of new and recycled plastic materials, to reduce the consumption of single-use products.

Polymeric nanocomposites with graphene: the future of the industry

Polymeric nanocomposites with graphene:

the future of the industry

Mexico City – Thanks to the extraordinary properties, innumerable investigations and business promises around Graphene in the world, in 2021 its market was valued at 127.12 million dollars, forecasting an annual growth rate of more than 70% in the period from 2022 to 2027. However, 18 years after its isolation and despite the enormous competition from companies to develop applications with this nanomaterial, there are still relatively few products available on the market that contain it and take advantage of its benefits. This is mainly due to the investment and complexity for the transformation of graphite into graphene or in any of its variants (graphene oxide and reduced graphene oxide), the difficulty of producing it on an industrial scale to have it available as the fundamental raw material in the transformation of new compounds, as well as the need for scientific-industrial knowledge for the creation of efficient and economically viable applications.

The Mexican company Energeia Fusion S.A. de C.V., has focused on solving the most representative obstacles that Graphene has faced to reach the market, working hard on the creation and standardization of its own methods and processes that today allow it to optimize resources for product development. quality in a short time.

Polymeric nanocomposites with graphene oxide

The polymer division of the Graphenergy Advanced Graphenic Solutions line is part of a new line of highly effective nanotechnological additives for the plastics industry that, in addition to the added value represented by the multifunctional properties that graphene provides to polymers (mechanical strength, impermeability, resistance to UV radiation and/or antimicrobial activity), it also adds value for the circular economy, since it allows the use, reuse and recycling of plastic products, reducing the exploitation of natural resources and reducing the generation of waste, resulting in significant social, economic and environmental impacts.

What is the science of Graphene for reinforcing materials?

  1. Las fuertes interacciones entre la región interfacial de la matriz polimérica y las partículas nanométricas del grafeno son decisivas para mejorar las propiedades de los materiales,
  2. La correcta integración del grafeno con los materiales poliméricos mejora la organización en su estructura, haciendola más densa y compacta y por lo tanto mejora las propiedades mecánicas.
  3. Mejora las propiedades de barrera contra líquidos y gases, aumenta el tiempo de vida útil del producto y permite tener diversas propiedades en un solo material, como: conductividad, resistencia a la radiación ultravioleta, impermeabilidad, flexibilidad, ligereza, actividad antimicrobiana, etc.

“Las propiedades del Grafeno son tan numerosas como las variables asociadas, por eso es difícil definir una fórmula estándar que satisfaga todas sus expectativas. El reto está en encontrar el equilibrio entre sus propiedades”.

A continuación, se describen algunos de los innumerables efectos y potenciales usos de los materiales grafénicos sobre distintas matrices poliméricas:

Mechanical strength

Graphene materials cause changes in the viscoelastic behavior of polymers, showing greater resistance to elongation, an interesting property for the design of products that are more resistant to deformation, such as sealing products, cushioning, transport or tires, footwear, sports, etc. In addition to increasing the elastic modulus, it also improves the impact resistance of polymers in the range of 20 to 200%, with weight reductions of up to 35%, this property is of interest for the manufacture of lighter products with equal or greater resistance than conventional plastics, opening the possibility of reducing or substituting the use of metal parts for plastic parts for the automotive, construction, and security industries, among others.

Resistance to degradation

On the other hand, this nanomaterial has also shown other interesting contributions, for example, in accelerated weathering tests carried out on plastics reinforced with graphene and/or derivatives, it has been identified that the use of low concentrations can increase its resistance to extreme conditions up to 7 times. of humidity, temperature and ultraviolet radiation. Furthermore, if we consider that when plastic is exposed to UV radiation, it emits greenhouse gases (methane and ethylene). Therefore, by increasing the resistance to degradation, we could also favor the reduction of these emissions, without affecting the ability of PET to be reused or recycled, but, on the contrary, using graphene offers it more opportunities to be recycled.

Fire resistance

Another recognized property of graphene is that it is an excellent thermal conductor. In tests carried out on different polymers, those modified with graphene oxide, in addition to improving their mechanical properties, also improved flame retardancy. Being the polypropylene the most benefited when identifying a self-extinguishing behavior. This contribution is attractive for its application in electrical cable and wire coatings or plastic materials in general that require thermal resistance.

These are just some of the multiple properties that graphene and its derivatives can offer the plastics industry and all those who benefit from it and that, despite efforts to reduce the circulation of plastic due to environmental impacts, the advantages offered by graphene can be well focused to make the use, reuse and recycling of plastic more efficient.

Some of the plastic products with graphene that have been commercialized are described below:

  1. Energeia Fusion-Graphenemex through its polymer division develops Masterbatches with graphene oxide for the production of personal protection equipment such as face shields and non-woven fabrics for face masks. Likewise, it has developed modified polymers for hydraulic concrete and asphalt concrete, in addition to the Graphenergy line of coatings for anticorrosive and antimicrobial protection (Mexico),
  2. Directa Plus designed a face mask with graphene for the fight against the pandemic caused by SARS-COV2 (United Kingdom),
  3. The international wheel producer Vittoria developed the bicycle wheels called Qurano (Italy),
  4. Progress, with its Progress Atom LTD model, provides better performance in terms of wear resistance, greater grip, greater impermeability, more efficient heat dissipation and greater lateral rigidity, with less weight (Spain),
  5. Dassi Bikes built the world’s first bicycle made from graphene (UK),
  6. FiiO Electronics launched headphones with a graphene-enhanced diaphragm driver (China),
  7. NanoCase created smartphone cases for better heat dissipation (China),
  8. Catlike uses graphene to produce cycling helmets (Spain).

References

Graphene oxide as an additive in concrete: innovation in construction

Graphene oxide as an additive in concrete:

innovation in construction

Mexico City – 9 years after being established, Energeia Fusion S.A. de C.V., the most important Mexican company in Latin America and promoter of the renowned Graphenemex® brand, launches the Graphenergy construction line, a new generation of nanotechnological additives for concrete with graphene oxide, which promises to strengthen the infrastructure and construction industry .

El Grafeno, también conocido como “el material del futuro”, finalmente traspasó la barrera de los laboratorios de investigación y se ha convertido en una realidad como potencial solución de innumerables necesidades sociales, ambientales e industriales. Este maravilloso nanomaterial consiste láminas atómicas de carbono extraídas del grafito y, gracias a sus interesantes propiedades mecánicas, eléctricas, térmicas, ópticas, etc., durante los últimos años se han invertido millones de dólares alrededor del mundo para tenerlo disponible en distintas aplicaciones, dentro de las cuales, la industria de la infraestructura y construcción ha logrado ser una de las más favorecidas.

Graphene career in the construction industry

2004 – Isolation of Graphene.

2010 – Recognition of the scientists Konstantin Novoselov and Andre Geim with the Nobel Prize in Physics for the isolation of Graphene.

2013 – Energeia Graphenemex is established, the first company in Latin America specialized in the production of graphene materials and development of applications.

2018 – Graphenemex® launches Nanocreto® on the market, the first additive for concrete with graphene oxide in the world (Mexico).

2019 – Graphenenano launches Smart additives, additives with graphene for concrete (Spain).

2019 – GrapheneCA presents its line of OG concrete admix products for the industry

concrete (USA).

2021- Scientists from the University of Manchester develop the concrete admixture Concretene (England).

2022 – Energeia – Graphenemex® launches the Graphenergy Construction line, a

improved version of its concrete admixture (Mexico).

Graphenergy construction is a water-based admixture compatible with other admixtures, designed to improve the quality of concrete or concrete, with the aim of reinforcing the pre-existing characteristics of concrete, such as mechanical resistance, but also to add value by providing non-existent properties in the original design, such as waterproofing, thermal insulation and antimicrobial protection.

How does Graphenergy construction work?

1. High impermeability and anti-corrosiveness

Graphenergy construction within the cementitious matrix forms molecularly more ordered and closed architectures that reduce the porosity of the structure and therefore create hydrophobic surfaces that, at a microstructural level, also hinder the passage of liquids and gases, hindering the passage of the agents that cause structural deterioration, especially in aggressive environments such as coastal or highly polluted environments.

Structure closure at the molecular level has also been demonstrated by electrical diffusivity measurements; These results support the protection of the metal structure of the concrete, increasing the useful life of the structure.

2. Improved mechanical properties

The more compact and organized architecture at the molecular level that Graphenergy Construction Graphene Oxide achieves within the concrete, allows microcrack limitation centers to form and therefore the structure becomes stronger when subjected to compression or tension loads, while favoring its flexibility.

3. Thermal insulation

The thermal insulation offered by Graphenergy construction is due to the ability of graphene oxide to dissipate heat with great efficiency and even to withstand intense electrical currents without heating up.

4. Antimicrobial protection

Graphenic additives offer different fronts of chemical and physical attacks of combined interaction, highly resistant to the formation of microbial biofilms, this means that microorganisms do not find a suitable environment to grow and release their by-products (eg. sulfuric acid) and, therefore, is not generated or, failing that, delays the appearance of microbiologically induced corrosion of concrete (MIC). This protection is extremely important, for example, for water systems since, inside the pipes, MIC is capable of dissolving up to 25 mm of concrete per year.

References

1. Basquiroto de Souza F., Proposed mechanism for the enhanced microstructure of graphene oxide–Portland cement composites. JOBE. 2022, 54, 104604

2. Dimov D., Ultrahigh Performance Nanoengineered Graphene Concrete Composites for Multifunctional Applications. Adv. Funct. Mother. 2018, 28, 1705183

3. Shamsaei E., Graphene-based nanosheets for stronger and more durable concrete: A review. Constr Build Mater. 2018, 183, 642

4. Krishnamurthy A., Superiority of Graphene over Polymer Coatings for Prevention of Microbially Induced Corrosion. 2015. Scientific Reports, 5:13858

5. https://blog.ferrovial.com/es/2022/04/graphene-sustainability-construction/

6. https://www.graphenano.com/graphene-arrives-in-construction-to-increase-the-resistance-of-concrete/

7. https://www.manchester.ac.uk/

8. https://www.cdt.cl/desarrollan-concrete-with-nanoparticles-of-graphene-to-repel-water-and-cracks/