[Paper: Reaching Biocompatibility with Nanoclays: Eliminating the Cytotoxicity of Ir(III) Complexes. Malte C. Grüner, Kassio P. S. Zanoni, Camila F. Borgognoni, Cristiane C. Melo, Valtencir Zucolotto, and Andrea S. S. de Camargo. ACS Applied Materials & Interfaces201810 (32), 26830-26834. DOI: 10.1021/acsami.8b10842.]
Nanoclays to overcome toxicity
Working in laboratories of the São Carlos Institute of Physics (IFSC – USP), a scientific team developed a strategy that eliminates the cytotoxicity (ability to destroy cells) of a group of compounds with very interesting photophysical properties for health applications . The study made viable the use of these substances, once toxic, in the study of living organisms and in the diagnosis and treatment of diseases. In addition to eliminating cytotoxicity, the strategy modifies some properties of compounds by adding new functions that can be harnessed for intracellular oxygen sensing and to improve the efficiency of luminescent devices such as OLEDs.
The work was reported in an article recently published in the journal ACS Applied Materials and Interfaces (impact factor 8,097).
It all started in an informal conversation between three postdoctoral fellows linked to IFSC-USP laboratories: Malte C. Grüner and Kassio P. S. Zanoni, both linked to the Laboratory of Functional Materials Spectroscopy (LEMAF), and Camila F. Borgognoni of the Group of Nanomedicine and Nanotoxicology (Gnano). Zanoni had worked with iridium (III) complexes during his doctorate, and wanted to take advantage of some properties of these compounds to use them as photodynamic therapy agents. Such therapy refers to a set of treatments for diseased tissues, such as those affected by cancer, in which an external radiation source is used for the activation at the appropriate time of a compound inserted into the body, which is responsible to destroy the cells that need to be eliminated.
The post-doc Zanoni’s desire, however, came up against the high cytotoxicity of iridium (III) complexes. The postdoc Grüner then had the innovative idea of trying to use laponites (materials he had studied in his doctorate) to inhibit the cytotoxicity of the compounds. From this idea, Grüner and Zanoni carried out the preparation and characterization of the materials in LEMAF, coordinated by Prof. Andrea S. S. de Camargo. At GNano, coordinated by Prof. Valtencir Zucolotto, the post-doc Borgognoni and the student Cristiane Melo were in charge to investigate the interactions of the nanoparticles with the cells.
Strategy and applications
One of the main properties of iridium (III) complexes is their intense luminescence (emission of light not resulting from heat) in a wide range of colors. This feature may be useful for illuminating cells within living organisms in bioimaging techniques, used for both research and for diagnosis and treatment of diseases.
In turn, laponites, which are synthetic nanoclays fully compatible with living tissues, have often been proposed in the scientific literature as nanoplataforms for transporting drugs and other compounds within living organisms. The laponites are about 25 nm in length and only 1 nm in height.
In the work of the IFSC-USP team, a new material was developed as a result of the adsorption of iridium (III) complex molecules on the surface of laponite nanodiscs.
The researchers found in the laboratory (in vitro) the ability of the new material to be absorbed by cells, its luminescence within cells and its low citotoxicity. For this, they used liver cells and observed their interaction with the new nanomaterial, comparing it with the interaction with the pure iridium (III) complex. The results were highly favorable to iridium (III) laponite nanodiscs, which proved to be harmless to the cells, besides presenting good penetration and high luminescence – characteristics that make them very suitable for application in bioimaging techniques.
“In this work, it was demonstrated for the first time that the adsorption of iridium (III) complexes (in general, highly toxic) on the surface of laponite nanodisks is capable to completely extinguish the cytotoxicity of these compounds “, summarizes the post-doc Kassio Zanoni , who in 2017 was the winner of B-MRS Young Researcher Award. “This makes it highly feasible to use previously toxic compounds in cell media without impairing the integrity of the medium and therefore has the potential to expand the research of new biocompatible materials for use in cell mapping, theranostics and photodynamic therapy”, he adds.
According to the authors, the new nanomaterial could act as a photodynamic therapy drug, since, when irradiated with certain types of radiation, it produces a molecule (the singlet oxygen) that acts in the destruction of cancer cells. In this way, the nanomaterial also becomes promising in the field of theranostics, which proposes the combination, on the same platform, of the diagnosis of diseases by bioimaging with its cure through photodynamic therapies.
In addition, the nanomaterial can be used as a sensor to accurately determine the amount of oxygen distributed inside a cell. “As demonstrated in our work, the emission intensity of this nanomaterial is a variable as a function of the concentration of oxygen”, justifies Zanoni.
Finally, the nanomaterial, in the form of a thin nanometric film, could also be applied to organic light-emitting diodes (OLEDs) – devices that are already used, for example, in cellular screens. “This is because the iridium (III) complex adsorbed on laponite aggregates photophysical, photochemical and electrochemical properties that are strategic for the development of more efficient devices”, explains Zanoni.
This research was carried out with funding from The São Paulo Research Foundation (FAPESP).
The scene repeated itself daily while the event lasted: around 8.30 a.m. and 2 p.m., under the strong João Pessoa sun, lines of hundreds of participants entered the convention center and settled at the refrigerated plenary room. There, scientists with outstanding careers, attested by their H indexes of values ranging from 40 and 73, coming from England, France, Germany, Italy, Portugal and United States, shared their knowledge about matters on which they are, without a shadow of a doubt, qualified specialists.
In the event’s final plenary lecture, Robert Chang, professor at the first department of materials science in the world, at Northwestern University, resumed two subjects that had been explained by Professor Arana Varela in the memorial lecture, and which permeated almost every plenary. The first one is the essential role that materials field and, in particular, nanotechnology play in meeting, in a sustainable way, the needs and demands of humanity in healthcare, food, transportation, security and communication. The second subject is the need for collaboration to face this challenge of the 21st century.
In this context Chang, who was president of the American Materials Research Society (MRS) and founded in 1991 the International Union of Materials Research Societies (IUMRS), called upon the young Brazilians [see video below] to be part of a global network released in 2012, which promotes the interaction of young researchers in the field around these global challenges through a biennial conference and virtual platforms.
However, Chang said, the scientific collaboration among physicists, chemists, engineers, mathematicians, biologists and other researchers to develop the necessary technologies is insufficient. It is also necessary, he added, to rely on the collective, global effort from governments, companies, communities, families and individuals to deploy these technologies on peoples’ daily lives. “That requires education”, he said. For the last 20 years, the scientist has conducted the Materials World Modules Programme, which developed interactive educational material about Materials and Nanotechnology for middle and high-school students.
Portuguese professor Luís Carlos, from the University of Aveiro, brought to XIII SBPMat Meeting many examples about the applications of nanotechnology in the healthcare field that are making a difference, or may make a difference in the short-term.
Being an expert in luminescent materials, which emit light not derived from heat, the scientist showed in his plenary lecture that these materials are already of great use in medical diagnosis. Luminescent organic complexes, for example, are marketed as contrast agents for magnetic resonance imaging, and as markers for fluoroimmunoassays (used in pre- and neonatal screening and detection of proteins, viruses, antibodies, drug residues etc.).
Besides, Luís Carlos said, luminescent nanoparticles (quantum dots and nanocrystals with lanthanide ions) emerge in diagnostic techniques and also in treatments, such as the hyperthermia process. This consists in the exposition of biological tissues, usually cancerous cells, at temperatures above 45°C, causing their deaths, with minimum collateral lesions to surrounding normal tissues. With proper temperature monitoring and control, the technique can soon become popular.
For the last few years, there have been efforts to develop nanothermometers that measure intracellular temperature to service this and other applications, not only regarding Nanomedicine, but also in fields such as Microelectronics, Photonics and Microfluidics. A successful example, presented by Luís Carlos at the plenary, is the development of a nanometric platform composed by nanorods, which work as thermometers, with gold nanoparticles on its surface, which function as heaters. This is a platform that, in contrast to its small size, can bring great benefits to the improvement of the technique of hyperthermia and the study of the processes of heat transfer at the nanoscale.
LEDs and other gallium nitride devices: savings of 25% in the global electricity consumption
When the Nobel Prize in Physics was announced for three Japanese scientists whose works were essential for the development of LED white light bulbs, those who had participated in XIII SBPMat Meeting certainly remembered the plenary lecture by Sir Colin Humphreys from University of Cambridge. The material chosen by the laureates when they decided to face the challenge of creating the blue LED that would allow the white light emitting LED was gallium nitride, which was also the object of Sir Colin’s lecture.
Professor Humphreys is an expert in this material. He created and directs a research center in Cambridge devoted to gallium nitride, and he also founded two spinoff companies to commercially exploit the technology developed by his research group and manufacture LEDs grown on relatively large silicon wafers, of about 15 cm, for low cost lighting. In 2012, the spinoffs were purchased by Plessey, a manufacturer of products based on semiconductor materials with over 50 years in the market. Now these LEDs are produced by Plessey in the United Kingdom.
The gallium nitride LED bulb currently offers one of the longest shelf lives in the market – 100,000 hours of use, equivalent to 69 years without switching the bulb, against 1,000 hours of life of the incandescent light bulb and 10,000 of the fluorescent. These LEDs also provide high energetic efficiency, ranging from 100 to 200 lumens (amount of light emitted in a second) per watt of power consumed.
At the plenary lecture, Sir Colin showed that the widespread use of LEDs in lighting would result in savings of about 15% in the total electricity consumed on the planet, and thus in a substantial decrease in emissions of carbon dioxide. In fact, lighting is one of the few segments where devices with high-energy efficiency are not yet universal.
More energy can be saved, Professor Humphreys said, by replacing silicon by gallium nitride in various electronic devices. In total, Humphreys concluded, up to 25% of all electricity used in the world today could be saved, reason why, added to the other applications of gallium nitride in the healthcare field, it was enough for the British scientist to state that this manmade material is one of the most important in the world.
Organic semiconductors: OLEDs and solar cells in the spotlight
Just like it happens with LEDs, the OLEDs, which are manufactured with organic materials justifying the “O” in the acronym, directly convert electricity into light and are, therefore, devices with high potential efficiency, which has been improved every year. Having each one particular advantages, LEDs and OLEDs already compete in certain markets, such as the one of displays and, in a more incipient manner in the case of organics, in the lighting market.
Along with organic solar cells, OLEDs were the focus of Karl Leo’s plenary lecture. He is a professor at the German TU Dresden and at the Saudi Arabian KAUST universities, and wrote over 550 papers with 23,000 references and 50 patent families. He is also founder of 8 spinoff companies, such as Heliatek and Novaled, which manufacture organic solar cells and OLEDs, respectively.
Professor Leo showed an important quantity of results achieved by his research groups, regarding the improvement of organic semiconductor devices. Along with his collaborators, Karl Leo has developed an extensive work about doping organic semiconductors in the transport layers of OLEDs and solar cells to increase significantly their electrical conductivity. This work resulted, for example, in obtaining white light-emitting OLEDs with energetic efficiency greater than those of fluorescent tubes.
Karl Leo was not the only internationally renowned scientist in João Pessoa in the field of organic semiconductors. On Wednesday afternoon, a roundtable organized by Symposium D gathered four of these specialists: Alberto Salleo (Stanford University), Franky So (University of Florida), Heinz von Seggern (TU Darmstadt) and Jenny Nelson (Imperial College London). Moderated by a prominent Brazilian scientist of the field, Roberto Mendonça Faria, professor at the São Carlos Institute of Physics at University of São Paulo and SBPMat president, the session gathered dozens of participants of the meeting, of various ages, that actively participated at the debate.
The discussion was around the challenges of organic electronics, from basic research to mass production (or individual production, as pointed out by a young man of the public drawing attention to the 3D printing techniques). Various subjects of the scientific, industrial and social fields were addressed bythe panelists based on the audience’s questions. “Fortunately, there are challenges for Materials Science. Unfortunately, there are challenges for mass production,” Professor Faria summed up, resuming, somehow, one of the first lines of the round table, in which Professor Jenny Nelson lamented that the scientific community celebrated a lot more the development of a device that works than the understanding of why a particular device did not work.
Alberto Salleo, creator of a group in Stanford that studies the relation between structure and properties on polymeric semiconductors to better understand the charge generation and transport, also delivered a plenary lecture at the event. In the lecture, Salleo cast doubt on the universality of a widespread assumption that links a high degree of crystallinity (or order) in the microstructure of these polymers to a higher charge mobility, or better performance of the devices. The scientist showed that the disorder is good for organic solar cells and cited examples of almost amorphous semiconducting polymers having similar performance to others much ordered.
Professor Salleo presented a model developed by his group to show how the charge transport in organic semiconductors works, since they are materials with heterogeneous microstructures, where disordered and ordered aggregates coexist with each other and with long polymer chains. In order to have high charge mobility, Salleo revealed, the important thing is for the aggregates to connect among themselves, which happens through the polymeric “spaghetti”.
Order, but without periodicity
The quasicrystals are far from the disorder, but also outside the traditional crystalline order. These materials were the general theme of the plenary of French researcher Jean-Marie Dubois, from Institut Jean Lamour, whose experience in this field was recognized by the scientific community through the creation of the “Jean-Marie Dubois International Award”, given every three years to research works related to quasicrystals.
First, Dubois presented an introduction to quasicrystals, materials in which the atoms are grouped into unit cells in patterns which are ordered (which may be determined by algorithms) but not periodic (never repeat themselves). Beautiful scientific and artistic images intermixed in Dubois’ presentation allowed the audience to view this aperiodic order.
The lecturer also paid homage to Dan Shechtman, who discovered quasicrystals in 1982 and, after many fights and resistance in the scientific community, eventually won the Nobel Prize in Chemistry in 2011 and generated a big shift in the vision of ordered condensed matter. Today, quasicrystalline materials are synthesized and used in various products, such as auto parts and pans, to improve their thermal conductivity, adhesion, friction, corrosion resistance etc. It is noteworthy that Dubois is among the pioneers in filing patents targeting applications of quasicrystals.
The quasicrystalline order can be observed in various types of materials. In the lecture at the XIII SBPMat Meeting, Dubois addressed, in particular, metal alloys formed by three elements (A, B and C), in which A – B and B – C form chemical bonds, while B and C repel themselves. Named by Dubois “push-pull alloys”, these materials can form very complex intermetallic compounds, with up to hundreds of atoms per unit cell. Among these, only a few can further increase their complexity to form a quasicrystalline order, which results in unique properties and open up possibilities for new applications.
In another plenary lecture of the XIII SBPMat Meeting, supporters of computer simulation as a complement to the experimental work in the investigation of material properties, and those interested in using it, were able to hear from Professor Roberto Dovesi (Università di Torino) that this dual approach is worthwhile.
Dovesi is one of the creators of CRYSTAL, a computational tool that allows the characterization of crystalline solids from the point of view of quantum mechanics, through ab initio calculations. The first version of the program was developed from 1976 onwards and released in 1988, making CRYSTAL the first periodic code distributed publicly to the scientific community. Now in its seventh version, the program allows the study of elastic, piezoelectric, photoelastic and dielectric properties, polarizability and hyperpolarizability tensors, IR and RAMAN spectrum, structure of electronic and phononic bands, among other properties.
The Italian chemist highlighted the affordable price and high working speed of today’s computers that are suitable to run such programs. As an example, he cited a machien recently acquired by his research group for computer simulation, which, costing around 6,500 euros, is able to do long calculations in a few hours with its 64 cores. Supercomputers are not necessary, Dovesi said, and are less robust. As for software, Dovesi remarked that today the field of materials has powerful, robust, easy-to-use programs at affordable prices (a basic license of the latest version of CRYSTAL, for example, costs 600 euros.
Brazilian Materials Research Society (SBPMat) newsletter
News update from Brazil for the Materials community
English edition. Year 1, issue 9.
Final arrangements for our meeting in João Pessoa!
– Read the message of the chairs of the event, which this year accepted 2,141 papers and has nearly 2,000 registrations from 28 countries so far. In the message, professors Ieda Garcia and Severino de Lima show the highlights of the program of this year’s meeting! Here.
– After lunch and before the afternoon plenary lectures, you can attend technical lectures of the meeting´s sponsors in João Pessoa: Shimadzu/Tescan will discourse about SEM with ion beam and TOF SIMS detector, and FEI will address DualBeam TEM. Learn more.
– Why is João Pessoa called “the sun door“? Learn more about the city, one of the oldest in Brazil, and its natural and cultural features. And get ready to dive into green waters at 28 °C! Read about João Pessoa.
– What to pack? Track the weather, whose temperatures should be between 20 °C and 30 °C. But pay attention, the meeting organization warns that, at the Convention Center, the air conditioner will make the room fresh … Link to weather in João Pessoa.
– Detailed schedule. Search for times and locations of symposia presentations: here.
– Some options of accommodation, car rental, transfers from the airports of the region, transportation from hotels to convention center, and tours: see on the home page of the site of the event.
– And what about the conference party? This year, it will be held on Wednesday evening at Espaço Caixa Econômica Federal in Cabo Branco. Tickets may be purchased in the information desk as of Monday 1 p.m..
Interviews with our plenary speakers
We interviewed Robert Chang, professor of the first department of Materials Science in the world at Northwestern University. Besides having a remarkable career as a researcher (his H index is 56), “Bob” has dedicated the past 20 years guiding the development of the Materials World Modules program, which develops educational, interactive and playful material (for example, card games) on Materials and Nanotechnology for pre-college students and their teachers. In his plenary lecture at the XIII SBPMat Meeting, Professor Chang will try to mobilize citizens of the world to solve global problems together. See our interview with the scientist.
We also spoke with Professor Colin Humphreys, a professor at the University of Cambridge. Among other honors, the scientist was knighted by the Queen of England for his services to science. Besides being the author of over 600 publications, the professor developed materials for the industry that currently fly in aircraft engines and created low cost LEDs based on gallium nitride, material on which he specialized. In João Pessoa, he will show, among other issues, how gallium nitride could reduce electricity consumption by 25% in the world. See our interview with Colin Humphreys.
We interviewed the German physicist Karl Leo, specialist in organic semiconductors. Beyond being the author of more than 550 papers with more than 23,000 citations and 50 families of patents, the scientist has already participated of the creation of 8 spin-off companies. In his lecture at the XIII SBPMat Meeting, Karl Leo will speak on highly efficient organic devices, as OLEDs and solar cells. See our interview with Karl Leo.
We also spoke with the Portuguese physicist Antonio Luis Ferreira Martins Dias Carlos, of the University of Aveiro, who will perform a lecture in our meeting in João Pessoa on luminescence applied to nanomedicine. In the interview, the professor shared with us his most prominent works in the field of Materials. He also told us about some challenges in the area of luminescence for medical applications, both in medical imaging and intra-cellular temperature mapping, and cited examples of applications of luminescent materials that have already been used in the diagnosis and treatment of various diseases. See our interview with Luis Dias Carlos.
We interviewed the French scientist Jean-Marie Dubois (Institut Jean-Lamour), specialist in quasicrystals (ordered, but aperiodic structures on solid materials) and pioneer in patenting applications for them. He told us a little about his main contributions to the field of Materials and gave a teaser on the theme of his plenary lecture in the XIII SBPMat Meeting: he will talk about quasicrystal structures, found in metallic alloys, polymers, oxides and artificial nanostructures, and their unprecedented properties. In the picture, Jean-Marie Dubois (on the left) and Dan Shechtman, who received a Nobel Prize in 2011 for the quasicrystals, using equal ties, both decorated with the Penrose tiling, an example of aperiodicity. Read our interview with Jean-Marie Dubois here.
We also interviewed the Italian chemist Roberto Dovesi (Universita’ degli Studi di Torino), one of the creators of CRYSTAL, a computational tool for ab initio quantum calculations used in the study of several solid materials properties. The CRYSTAL code is currently used in over 350 laboratories around the world. In his plenary lecture in the XIII SBPMat Meeting, Dovesi will attempt to demonstrate that today quantum simulations may be very useful tools to complement experiments. See our interview with Roberto Dovesi.
We have interviewed Professor Alberto Salleo, from Stanford University, who is going to give a plenary lecture on organic electronic devices in the XIII SBPMat Meeting. Young, yet holding a career that stands out internationally, Salleo told us about the work conducted by his group, which has been developing a deeper understanding on the role provided by the defects in charge transport in organic semiconductors. He also shared with us his main papers, published in Nature Materials. Finally, Salleo discussed the next challenges and applications on organic electronics, and anticipated what he is going to address in the plenary lecture, which promises to be very informative while mild enough for a wider audience. Read our interview with Alberto Salleo.
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