First virtual Bilateral Conference on Functional Materials (BiC-FM)

Polymer composites, comprising single-atomic-layer graphenic inclusions. Preparation, structure and properties

Ayrat M. Dimiev

Laboratory for Advanced Carbon Nanomaterials,

Kazan Federal University, Kazan, Russian Federation

dimiev.labs@gmail.com

Doping with conductive inclusions is the most straightforward approach to alter conductivity of dielectric materials. Carbon nanostructures have several advantages as inclusions for their high aspect ratio. However, it is very difficult to uniformly disperse 2D graphenic materials in the polymer matrix. In a series of studies, we have developed the homogeneous liquid phase transfer method, allowing uniform distribution and nearly fully exfoliated condition of GO in the matrix.

Viscosity of the uncured liquid resin increases by 390 % after introducing 0.4 % GO, and by 4700 % after its subsequent in-situ reduction. The latter is explained by the reorganization of the original liquid crystalline structure of the GO-Epoxy formulations with GO reduction. At the filling fractions >0.1 %, the single-atomic-layer RGO flakes are assembled into the clusters, where they alternate with a thin resin layer. This structure is also responsible for very unusual dielectric behavior of the cured solid composites. From one side, the real part of the complex permittivity reaches relatively high values at extremely low filling fractions: 14 at 0.1 %, and 60 at 0.4 % RGO content. At the same time, the permittivity dispersion is accompanied with the well-pronounced symmetrical loss peaks on the imaginary part functions, which is typical for low permittivity materials. Such dielectric behavior is difficult to interpret in the frames of any single existing model. The relaxation time and activation energy, calculated from the temperature dependence experiments, suggest that the RGO clusters, but not individual RGO flakes, serve as conductive inclusions. The extremely long relaxation times are due to the charge transfer between the individual RGO flakes within the clusters. The striking difference between the newly prepared composites and control samples, comprising multi-layer RGO particles, exemplifies the unique structure of our materials.

Acknowledgement.This work was supported by the Russian Science Foundation, grant 16-13-10291.

Ayrat Dimiev, received his PhD degree in physical chemistry from Kazan State University, Russian Federation. In 2008 he joined the group of Prof. James Tour at Rice University, USA, where he started his works with carbon nanomaterials. In 2013, he accepted a personal invitation to join AZ Electronic Materials (presently EMD Performance Materials Corp., USA, a business of Merck KGaA, Darmstadt, Germany) to help in developing their newly started carbon program. In 2016 Dr. Dimiev returned to his Alma Mater in Kazan as research professor and head of the Laboratory for Advanced Carbon Nanomaterials. Ayrat Dimiev is the first and/or corresponding authors of the well-known publications in the field of graphene oxide.

H₂O molecule in nano-space

M.Belyanchikov¹, M.Savinov², Z.Bedran¹, V.Abalmasov³, E.Zhukova¹, V.Thomas⁴, A.Dudka⁵, A.Zhugayevych⁶, R.K.Kremer⁷, P.Lunkenheimer⁸, M.Dressel^1,9, B.Gorshunov¹

1- Moscow Institute of Physics and Technology (National Research University), Dolgoprudny, Moscow Region, Russia

2- Institute of Physics, Czech Academy of Sciences, Praha 8, Czech Republic

3- Institute of Automation and Electrometry SB RAS, Novosibirsk, Russia

4- Institute of Geology and Mineralogy, RAS, Novosibirsk, Russia

5- Shubnikov Institute of Crystallography, RAS, Moscow, Russia

6- Skolkovo Institute of Science and Technology, Moscow, Russia

7- Max-Planck-Institut für Festkörperforschung, Stuttgart, Germany

8- Experimental Physics V, University of Augsburg, Augsburg, Germany

9- 1. Physikalisches Institut, Universität Stuttgart, Stuttgart, Germany

bpgorshunov@gmail.com

The ever-increasing requirements for the characteristics of electronic devices dictate the need for a transition to nanoscales in the production of electronic components. However, the smaller these components are, the harder they are to manufacture. A way to avoid such problems is to manipulate charge/spin states of separate ions or molecules placed in certain frameworks, natural or artificial. Corresponding activities are presently very intensive and include, e.g., studies of single molecular magnets as candidates for quantum computing [1], using extraordinary properties of graphene for building field-effect transistors [2], terahertz detectors [3] or spintronic devices [4], using molecular nanoflakes as gas sensors [5], making use of carbon-based architectures with 0D (fullerenes [6]) or 1D (nanotubes [7]) spaces, empty or filled with ions or molecules. In this talk, we consider the properties of separate water molecules located within sub-nanosized spaces. Recently, we introduced [8] to the community a family of water-containing beryl crystals that allow for the studies of single-particle and collective states of polar (dipole moment 1.85 Debye) H₂O molecules that reside in ≈5 Å diameter voids within crystal lattice. Separated by a distance of 5-10 Å, these molecules only weakly interact with crystal lattice, do not experience H-bonding and strongly interact via electric dipole-dipole coupling thus representing a kind of “new state of water” [9]. Studies of such network not only are of fundamental importance [10,11], they also contribute to deeper understanding of natural phenomena and may even find practical applications in ferroelectric electronics, artificial quantum systems, and biocompatible nanoelectronics.

References:

[1] E.Coronado, Nat Rev Mater 5, 87 (2020)

[2] K.V.Voronin et al. Journal of Physics: Conf. Series 1461 (2020)

[3] D.A.Bandurin et al. Nat Commun 9, 5392 (2018)

[4] W.Han et al. Nature Nanotech 9, 794 (2014)

[5] F.S.Fedorov et al. J Mater Chem A 8,7214 (2020)

[6] L. Spree et al. Dalt. Trans 48, 2861 (2019)

[7] A.P.Tsapenko et al. Carbon 130

[8] B.P.Gorshunov et al. J. Physical Chemistry Letters 4, 2015 (2013)

[9] E.S.Zhukova et al. EPJ Web of Conferences 195, 06018 (2018)

[10] B.Gorshunov et al. Nat Commun 7, 12842 (2016)

[11] M.Belyanchikov et al. Nat Commun 11, 3927 (2020)

Surface characteristics control the attachment and functionality of (chimeric) avidin

Shao D.¹, Tapio K.¹, Auer S.², Toppari J.J.¹, Hytönen V.², Ahlskog M.¹

1 – Nanoscience Center and Department of Physics, University of Jyväskylä, Finland

2 – BioMediTech, University of Tampere, Tampere, Finland

ahlskog@jyu.fi

The physical adsorption (physisorption) of proteins to surfaces is an important but uncompletely understood factor in many biological processes, and of increasing significance in bionanotechnology as well [1]. Avidin is a most important protein due to the strong avidin-biotin binding which has numerous applications [2]. We have undertaken thorough experimentation on the physisorption of avidin, to chemically different flat surfaces, Si and graphite, and also to the curved version of the latter, on multiwalled carbon nanotubes (MWNT) of different diameter.

The difference between the behavior of avidin on Si and graphite is drastic, in that on Si avidin deposits as single globular tetrameric units, while on graphite it forms irregular networks of two layers thick filaments. On MWNTs avidin also deposits as one dimensional formations, or stripes, but as opposed to the irregular network appearance on graphite, the cylindrical nanometer sized curvature orders the stripes in a perpendicular and quasiperiodical arrangement to the MWNT axis. We also demonstrated the preserved functionality of the deposited avidin with respect to biotin binding.

Acknowledgement.This work was supported by the Academy of Finland, grant SA-263523.

References

[1] Kastantin, M.; Langdon, B. B.; Schwartz, D. K. Advances in Colloid and Interface

Science 207, 240 (2014).

[2] Laitinen, O. H.; Nordlund, H. R.; Hytönen, V. P.; Kulomaa, M. S. Trends in Biotechnology 25, 269–277 (2007).

Flash Oral

Prussian-blue lipid nanoparticles for effective siRNA delivery to liver

Abakumova T.O.¹, Prikazchikova T.A.¹, Komkova M.A², Karyakin A.A.², Zatsepin T.S.^1,2

1-Skolkovo Institute of Science and Technology, Moscow, Russia

2-Lomonosov Moscow State University

t.abakumova@skoltech.ru

Reactive oxygen species (ROS) play an essential role in liver cell damage and the progression of diseases. Therefore, the development of therapeutic strategy that will combine antioxidant and anti-inflammatory activity is an urgent task. For this purpose, we synthesized lipid nanoparticles loaded with Prussian blue nanoparticles (PBNP) and small interfering RNA (siRNA) that will neutralize ROS and effectively deliver siRNA to the hepatocytes. First, we synthesized PBNP with an average diameter 53±10 nm. These nanoparticles demonstrated high catalytic activity (k_cat 550–560 s^-1) and low cytotoxicity values (AML12, RAW264.7 cell lines). Encapsulation of PBNP and siRNA into lipid nanoparticles led to increase of average diameter up to 90±10 nm and almost no affect catalytic activity (k_cat 540 s^-1). We also demonstrated that obtained nanoparticles could successfully accumulate in cells (AML12) and neutralize ROS (DCFDA assay, HyPer probe). Taken together, we developed novel hybrid PBNP-lipid nanoparticles that could effectively deliver siRNA to the cells, neutralize ROS and potentially reduce inflammation and the toxicity of lipid particles.

Acknowledgement.This work was supported by the Russian Science Foundation, grant 20-74-00116 (synthesis of Prussian blue-lipid nanoparticles) and by the grant of President МК-1128.2020.4 (ROS measurement in vitro).

Fabrication of magnetic graphene oxide and its developmental toxicity to Artemia Salina Cyst and its three larval stage

Che Azurahanim Che Abdullah^1,2, Emmellie Laura Albert ^1,2 and Nurul Anis Athirah Ab Aziz³

¹Materials Synthesis and Characterization Laboratory, Institute of Advance Technology, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.

²Department of Physics, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.

³Department of Physics, Faculty of Science, University Teknologi Malaysia, 80990 0 Skudai, Johor, Malaysia

azurahanim@upm.edu.my

Current research focusing on the fabrication of magnetic graphene oxide (GO-IO) using graphene oxide (GO) and Iron (III) oxide (IO) via simple emulsion method. GO specialty such as big surface to volume ratio combined with IO superparamagnetic properties produce interesting nanocomposite material for removing pollutant from water [1]. After decontamination, the GO-IO residues can be collected and removed from the water using a magnetic field. Initially, the nanocomposites crystallinity, chemical interaction, structure, surface morphology and magnetic behavior were investigated using X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and Vibrating Sample Magnetization correspondingly. Afterward, the potential effects of GO-IO on marine ecosystems were explored using Artemia salina cysts and larvae (instar I, II and III) as experimental models, hatchability, and mortality were selected as endpoints to define the toxic responses. GO-IO attached onto the gills and body surface, resulting in irreversible damages. The combined results so far indicate that GO-IO have the potential to affect aquatic organisms when released into the marine ecosystems.

Acknowledgement.This work was partially supported by Fundamental Research Grant Scheme, Ministry of Higher Education, Malaysia (FRGS 5524949).

References:

[1] Sharma, M., Kalita, P., Senapati, K. K., & Garg, A. (2018). Study on Magnetic Materials for Removal of Water Pollutants. Emerging Pollutants-Some Strategies for the Quality Preservation of Our Environment, 61–78.

Toxicity evaluation of Herbs based Carbon Dots using Artemia Salina Cyst and its three larval stage

Che Azurahanim Che Abdullah^1,2, Emmellie Laura Albert ^1,2 and Muhd Afiq Aizzat Abd Kadir³

¹Materials Synthesis and Characterization Laboratory, Institute of Advance Technology, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.

²Department of Physics, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.

³Department of Physics, Faculty of Science, University Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

emmellielaura@gmail.com

Current research focusing on the fabrication of green synthesis of carbon materials, carbon dots. Nanosized materials may generate harmful physiological effects or potential health risks due to their unique physical and chemical properties. Herein, the toxicity of carbon dots (CDs) from commercial herbs was confirmed through a systematic study. The potential effects of various types of carbon dots on marine ecosystems were explored using Artemia salina cysts and larvae (instar I, II and III) as experimental models, hatchability, and mortality were selected as endpoints to define the toxic responses. Carbon dots expected to attach onto the gills and body surface, resulting in irreversible damages. The combined results so far indicate that there is lower potential to affect aquatic organisms when released into the marine ecosystems.

References:

[1] Xiao, Y. Y., Liu, L., Chen, Y., Zeng, Y. L., Liu, M. Z., & Jin, L. (2016). Developmental toxicity of carbon quantum dots to the embryos/larvae of rare minnow (Gobiocypris rarus). BioMed Research International, 2016.

Investigation of structural and optical properties of three-dimensional InGaPAs islands

Andryushkin V.V.¹, Gladyshev A.G.^1,2, Dragunova A.S.^3,5, Babichev A.V.^1,2, Nadtochiy A.M.^3,5, Kolodeznyi E.S.¹, Nevedomskii V.N.⁴,Novikov I.I.^1,2, Karachinsky L.Ya.^1,2, Kryzhanovskaya N.V.⁵ and Egorov A.Yu.¹

1 – ITMO University, St. Petersburg, Russia

2 – Connector Optics LLC, St. Petersburg, Russia

3 – Saint Petersburg National Research Academic University of the Russian Academy of Sciences, St. Petersburg, Russia

4 – Ioffe Institute, St. Petersburg, Russia

5 – National Research University Higher School of Economics, St. Petersburg, Russia

vvandriushkin@itmo.ru

At present, the creation of single photons sources and micro-emitter arrays has great interest. The best candidates for the role of active region for such emitters are quantum dots (QDs). However, in contrast to typical laser applications where QDs arrays must have a high density, the opposite requirement is imposed on QD arrays in the above applications – low QDs density (less than 1 * 10¹⁰ cm^-2) [1]. In this work, we propose a new method to obtain the three-dimensional quantum-sized objects (QD) arrays with reduced surface density formed by elastic transformation of the InGaP layer grown on the GaAs surface.

During the epi-growth QDs were formed by replacement of phosphorus in the InGaP epitaxial layer by As, upon exposure of InGaP layer in the As flow at temperatures of 520–535 °C. Using this procedure, a several heterostructures were grown on GaAs (100) substrates by molecular beam epitaxy (MBE). The influence of the InGaP layer thickness, growth temperature, and exposure time in the As flow on optical and structural properties of the formed QDs was studied.

Photoluminescence spectra were measured in the temperature range 77 – 300 K at different optical pump power densities. It was found that when P is replaced with As in a thin InGaP layer, three-dimensional islands are formed with estimated density of 1.3∙10¹⁰ cm^{-2 and} demonstrated the photoluminescence in the spectral range ~1 µm at 300 K. Obtained results are very promising for possible use of proposed QDs in single photon sources and micro-emitter arrays.

Acknowledgement.This work was supported by the Ministry of Science and Higher Education of the Russian Federation, research project no. 0791-2020-0002. The research was carried out within the framework of the National Research University Higher School of Economics Program of Basic Research in 2020.

References:

[1] P.Michler, Single semiconductor quantum dots, Berlin: Springer, 231 (2009)

Electrodynamic properties of low-dimensional water

Artemov V.G.

Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, Moscow, Russia

v.artemov@skoltech.ru

Interfacial (low-dimensional) water is ubiquitous in nature. It is a media where catalytic reactions, ion exchange, and phase transformations take place. Although these processes are key to understanding the most challenging questions of physical chemistry, our knowledge of the low-dimensional water is quite limited.

We discuss the electrodynamic properties of interfacial water confined in nano-pores of various sizes, ranging from 5 nm to 5 µm in diameter [1], and compare them with those for bulk water [2]. We show that the short-order nanoscale molecular dynamics in water governs the electrodynamic properties of interfacial and confined water. Using the infrared spectroscopy, we find that short-living ions, with concentrations of 2 %, coexist in water with long-living pH-active ions [3]. We assume that short-living ionic species govern the electrodynamics of low-dimensional water, resulting, for example in anomalous high DC conductivity, five orders of magnitude higher than that of the bulk water [2].

Our results shed light on the physical and chemical properties of both interfacial and bulk water, as well as pave the way to the development of new type of highly-efficient proton conductors for applications in electrochemical energy systems, membrane separations devices and nano-fluidics.

Acknowledgement.Author would like to thank Henni Ouerdane, Alexander Ryzhov, Alexei Kiselev, Ece Uykur, Martin Dressel, and Keith Stevenson for their close collaboration and fruitful discussions on related topics.

References:

[1] V. G. Artemov, E. Uykur, P. O. Kapralov, A. Kiselev, K. Stevenson, H. Ouerdane, M. Dressel, J. Phys. Chem. Lett., 11, 3623–3628 (2020)

[2] V. G. Artemov, Phys. Chem. Chem. Phys., 21, 8067 (2019)

[3] V. G. Artemov, E. Uykur, S. Roh, A. Pronin, H. Ouerdane, and M. Dressel, Scientific Reports, 10, 11320 (2020)

Terahertz-infrared excitations in the Ba_0.2Pb_0.8Al_1.2Fe_10.8O₁₉ single crystal

Asmaa Ahmed¹, Anatoly S. Prokhorov ^1,2, Vladimir Anzin ^1,2, Denis Vinnik³, Alexander Bush⁴, Boris Gorshunov¹, Liudmila Alyabyeva¹

1-Laboratory of Terahertz Spectroscopy, Center for Photonics and 2D Materials, Moscow Institute of Physics and Technology (State University), 9 Institutskiy per., Dolgoprudny, Russia

2-Prokhorov General Physics Institute of the Russian Academy of Sciences, 38 Vavilov Str, Moscow, Russia

3-South Ural State University, 76 Lenin prospect, Chelyabinsk, Russia

4-Research Institute of Solid State Electronics Materials, MIREA − Russian Technological University (RTU MIREA), 78 Vernadsky prospect, Moscow, Russia

a.gamal@phystech.edu

The single-crystalline M-type hexaferrite with double-cation substitution Ba_0.2Pb_0.8Al_1.2Fe_10.8O₁₉ [1] was investigated using methods of terahertz and infrared spectroscopy. The spectra of reflectivity R(ν), transmissivity T(ν) and complex dielectric permittivity *(ν) = '(ν) + i"(ν) were studied over a wide range of frequencies, 8-8000 cm^-1 (0.24-240 THz), at temperatures 4-300 K. To interpret the absorption bands discovered in the terahertz region, at 8-80 cm^-1, a model of the electronic transitions within the fine-structured ground state of four-fold coordinated Fe²⁺ is developed [2]. It is shown that the trigonal distortions of the crystal field lead to lowering of the symmetry of 4f₁ and 4e tetrahedral site-positions of Fe²⁺ and, as a result, to further splitting of the ground state spin-orbital sub-levels. It is electro-dipole transitions between the corresponding sub-levels that are considered to be at the origin of the observed absorption bands [3]. Absorption resonances at 80-1000 cm^-1 are assigned to lattice vibrations (phonons) basing on the factor group analysis. The study paves the way for the development of low-cost materials with high dielectric permittivity (about 30) at terahertz frequencies that are promising for the manufacture of electronic devices with enhanced characteristics.

Acknowledgement.The terahertz study was supported by the Russian Science Foundation, grant 19-72-00055, infrared temperature investigation is supported by Russian foundation for Basic Research, grant 20-32-90034.

References:

[1] R. C. Pullar, Progress in Materials Science, vol. 57, no. 7, pp. 1191–1334, 2012.

[2] L. N. Alyabyeva et al., New Journal of Physics, vol. 21, no. 6, p. 063016, 2019.

[3] J. P. Mahoney, C. C. Lin, W. H. Brumage, and F. Dorman, The Journal of Chemical Physics, vol. 53, no. 11, pp. 4286–4290, 1970.