Systemic metabolic depletion of gut microbiome undermines responsiveness to melanoma immunotherapy.

Immunotherapy has proven to be a boon for patients battling metastatic melanoma, significantly improving their clinical condition and overall quality of life. A compelling link between the composition of the gut microbiome and the efficacy of immunotherapy has been established in both animal models and human patients. However, the precise biological mechanisms by which gut microbes influence treatment outcomes remain poorly understood. Using a robust dataset of 680 fecal metagenomes from melanoma patients, a detailed catalog of metagenome-assembled genomes (MAGs) was constructed to explore the compositional and functional properties of the gut microbiome. Our study uncovered significant findings that deepen the understanding of the intricate relationship between gut microbes and the efficacy of melanoma immunotherapy. In particular, we discovered the specific metagenomic profile of patients with favorable treatment outcomes, characterized by a prevalence of MAGs with increased overall metabolic potential and proficiency in polysaccharide utilization, along with those responsible for cobalamin and amino acid production. Furthermore, our investigation of the biosynthetic pathways of short-chain fatty acids, known for their immunomodulatory role, revealed a differential abundance of these pathways among the specific MAGs. Among others, the cobalamin-dependent Wood-Ljungdahl pathway of acetate synthesis was directly associated with responsiveness to melanoma immunotherapy.

Engineering of graphene-based composites with hexagonal boron nitride and PEDOT:PSS for sensing applications.

A unique nanomaterial has been developed for sweat analysis, including glucose level monitoring. Simple resusable low-cost sensors from composite materials based on graphene, hexagonal boron nitride, and conductive PEDOT:PSS (poly(3,4-ethylenedioxythiophene)polystyrene sulfonate) polymer have been developed and fabricated via 2D printing on flexible substrates. The sensors were tested as biosensors using different water-based solutions. A strong increase in the current response (several orders of magnitude) was observed for aqua vapors or glucose solution vapors. This property is associated with the sorption capacity of graphene synthesized in a volume of plasma jets and thus having many active centers on the surface. The structure and properties of graphene synthesized in a plasma are different from those of graphene created by other methods. As a result, the current response for a wearable sensor is 3-5 orders of magnitude higher for the reference blood glucose concentration range of 4-14 mM. It has been found that the most promising sensor with the highest response was fabricated based on the graphene:PEDOT:PSS composite. The graphene:h-BN:PEDOT:PSS (h-BN is hexagonal boron nitride) sensors demonstrated a longer response and the highest response after the functionalization of the sensors with a glucose oxidase enzyme. The reusable wearable graphene:PEDOT:PSS glucose sensors on a paper substrate demonstrated a current response of 10-10 to 10-5 A for an operating voltage of 0.5 V and glucose range of 4-10 mM.

Graphene-based multifunctional humidity sensors with an ultrahigh current response.

Prospective composites, based on graphene (G) and hexagonal boron nitride (h-BN) nanoparticles, synthesized using a plasma jet and conducting polymer PEDOT:PSS, were used to create and study a set of sensors in the current study. The composites used were G:PEDOT:PSS (GPP) and G:h-BN:PEDOT:PSS (GBNPP). The PEDOT:PSS content in the composites was 10-3 wt%, and the ratio of G : h-BN was 1 : 1 in GBNPP. The development of these new highly conductive graphene-based composites makes it possible to create an active sensor layer with an ultra-low thickness of several nanometers. The ultra-high sensitivity of the current response, S, was ((2.0-3.3) × 106)% for GPP and GBNPP (2-3 printing layers) for a humidity range of 20-80%. The sensor response in the form of current pulses associated with human breathing has a range of ∼2-3 orders of magnitude. Two different processes are assumed to determine the form of the current pulse: the first is a fast process with a rise time of less than 1-4 seconds; the second is a relatively slow process with a front time of several tens of seconds. When touching with a finger (useful, for instance, for a flexible touchpad), a current response was observed as pulses of ∼2-3 orders of magnitude. We hypothesize that skin sweat is likely to play a critical role in the sensory response. Thus, this work presents an effective approach to creating a highly sensitive humidity sensor based on composite 2D materials. Moreover, the ultra-high sensitivity of the studied sensors is accompanied by their low cost and ease of manufacturing by 2D-printing.

Thin V2O5 films synthesized by plasma-enhanced atomic layer deposition for memristive applications.

In the present study, the V2O5 films synthesized by plasma-enhanced atomic layer deposition on p-Si and fluorinated graphene on Si (or FG/Si) substrates were analyzed for memristive applications. A number of samples were grown with V2O5 films with an average thickness of 1.0-10.0 nm, as determined by ellipsometric measurements. The study of surface morphology by atomic force microscopy showed that an island growth occurs in the initial stages of the film growth. The Raman spectra of the synthesized V2O5 films with an average thickness of more than 2.0 nm on the SiO2/Si substrates exhibit six distinct modes typical of the orthorhombic V2O5 phase. A large hysteresis was found in the C-V characteristics of the V2O5 films with a thickness of 1.0-4.2 nm. In general, the built-in charge in the V2O5 layers with an average thickness of 1.0-4.0 nm is positive and has a value of about ∼(2-8) × 1011 cm-2 at the 1 MHz frequency. Increasing the V2O5 film thickness leads to the accumulation of negative built-in charge up to -(1.7 to 2.3) × 1011 cm-2 at the 1 MHz frequency. The temperature dependence of the conductivity exhibits different electrically active states in V2O5/Si and V2O5/FG/Si structures. Thus, the FG layer can modify these states. V2O5 layers with an average film thickness of 1.0-3.6 nm demonstrate the memristive switching with an ON/OFF ratio of ∼1-4 orders of magnitude. At film thicknesses above 5.0 nm, the memristive switching practically vanishes. V2O5 films with an average thickness of 3.6 nm were found to be particularly stable and promising for memristive switching applications.

Results and lessons learned from the sbv IMPROVER metagenomics diagnostics for inflammatory bowel disease challenge.

A growing body of evidence links gut microbiota changes with inflammatory bowel disease (IBD), raising the potential benefit of exploiting metagenomics data for non-invasive IBD diagnostics. The sbv IMPROVER metagenomics diagnosis for inflammatory bowel disease challenge investigated computational metagenomics methods for discriminating IBD and nonIBD subjects. Participants in this challenge were given independent training and test metagenomics data from IBD and nonIBD subjects, which could be wither either raw read data (sub-challenge 1, SC1) or processed Taxonomy- and Function-based profiles (sub-challenge 2, SC2). A total of 81 anonymized submissions were received between September 2019 and March 2020. Most participants' predictions performed better than random predictions in classifying IBD versus nonIBD, Ulcerative Colitis (UC) versus nonIBD, and Crohn's Disease (CD) versus nonIBD. However, discrimination between UC and CD remains challenging, with the classification quality similar to the set of random predictions. We analyzed the class prediction accuracy, the metagenomics features by the teams, and computational methods used. These results will be openly shared with the scientific community to help advance IBD research and illustrate the application of a range of computational methodologies for effective metagenomic classification.

Consistent Stool Metagenomic Biomarkers Associated with the Response To Melanoma Immunotherapy.

The human gut microbiome plays an important role in both health and disease. Recent studies have demonstrated a strong influence of the gut microbiome composition on the efficacy of cancer immunotherapy. However, available studies have not yet succeeded in finding reliable and consistent metagenomic markers that are associated with the response to immunotherapy. Therefore, the reanalysis of the published data may improve our understanding of the association between the composition of the gut microbiome and the treatment response. In this study, we focused on melanoma-related metagenomic data, which are more abundant than are data from other tumor types. We analyzed the metagenomes of 680 stool samples from 7 studies that were published earlier. The taxonomic and functional biomarkers were selected after comparing the metagenomes of patients showing different treatment responses. The list of selected biomarkers was also validated on additional metagenomic data sets that were dedicated to the influence of fecal microbiota transplantation on the response to melanoma immunotherapy. According to our analysis, the resulting cross-study taxonomic biomarkers included three bacterial species: Faecalibacterium prausnitzii, Bifidobacterium adolescentis, and Eubacterium rectale. 101 groups of genes were identified to be functional biomarkers, including those potentially involved in the production of immune-stimulating molecules and metabolites. Moreover, we ranked the microbial species by the number of genes encoding functionally relevant biomarkers that they contained. Thus, we put together a list of potentially the most beneficial bacteria for immunotherapy success. F. prausnitzii, E. rectale, and three species of bifidobacteria stood out as the most beneficial species, even though some useful functions were also present in other bacterial species. IMPORTANCE In this study, we put together a list of potentially the most beneficial bacteria that were associated with a responsiveness to melanoma immunotherapy. Another important result of this study is the list of functional biomarkers of responsiveness to immunotherapy, which are dispersed among different bacterial species. This result possibly explains the existing irregularities between studies regarding the bacterial species that are beneficial to melanoma immunotherapy. Overall, these findings can be utilized to issue recommendations for gut microbiome correction in cancer immunotherapy, and the resulting list of biomarkers might serve as a good stepping stone for the development of a diagnostic test that is aimed at predicting patients' responses to melanoma immunotherapy.

Engineering of graphene flakes in the process of synthesis in DC plasma jets.

During the pyrolysis of hydrocarbons in helium plasma jets in a plasma-chemical reactor, graphene flakes of a different structure and resistance were obtained. The presence of hydrogen in these structures was established by physicochemical methods, and its content depends on the pressure in the plasma-chemical reactor and the composition of a plasma-forming system. In addition to hydrogen, a relatively low concentration of oxygen atoms is present in the graphene flakes. Hydrogen is involved in the graphene nucleation, whereas oxygen is absorbed on graphene flakes from the air at low temperatures. It was found that a pressure increase in the reactor (up to 710 Torr) leads to the formation of flakes with a low resistivity (0.12-0.20 kOhm sq-1) and low defect density. In the case of synthesis at a low pressure (350-500 Torr), the resistance of graphene flakes is increased by three orders of magnitude (100-400 kOhm sq-1) with a more complicated defect structure and built-in hydrogen. Moreover, hydrogen is difficult to remove from these flakes, and annealing at relatively high temperatures (up to 300 °C) leads to a weak decrease in the resistance due to flake deformation. Additionally, the functionalization of the graphene flakes synthesized at a low pressure with fluorine atoms is suppressed due to their structural features. In general, the selection of growth parameters (gas pressure in a camera, flow rate and content of impurity atoms) allows one to control the defects in graphene, and its structure and conductivity.

Intestinal microbiome changes in an infant with right atrial isomerism and recurrent necrotizing enterocolitis: A case report and review of literature.

BACKGROUND: Necrotizing enterocolitis (NEC) is a multifactorial disease that predominantly affects premature neonates. Intestinal dysbiosis plays a critical role in NEC pathogenesis in premature neonates. The main risk factor for NEC in term infants is mesenteric hypoperfusion associated with ductal-dependent congenital heart disease (CHD) that eventually leads to intestinal ischemia. The incidence of NEC in neonates with critical CHD is 6.8%-13%. However, the role of the intestinal microbiome in NEC pathogenesis in infants with ductal-dependent CHD remains unclear. CASE SUMMARY: A male term neonate with right atrial isomerism underwent modified Blalock-Taussig shunt placement on the 14th day of life and had persistent mesenteric hypoperfusion after surgery. The patient had episodes of NEC stage IIA on the 1st and 28th days after cardiac surgery. Fecal microbial composition was analyzed before and after cardiac surgery by sequencing region V4 of the 16S rRNA gene. Before surgery, species belonging to genera Veillonella and Clostridia and class Gammaproteobacteria were detected, Bifidobacteriaceae showed a low abundance. The first NEC episode was associated with postoperative hemodynamic instability, intestinal ischemia-reperfusion injury during cardiopulmonary bypass, and a high abundance of Clostridium paraputrificum (Clostridium sensu stricto I) (56.1%). Antibacterial therapy after the first NEC episode resulted in increased abundance of Gammaproteobacteria, decreased abundance of Firmicutes, and low alpha diversity. These changes in the microbial composition promoted the growth of Clostridium sensu stricto I (72.0%) before the second NEC episode. CONCLUSION: A high abundance of Clostridium sensu stricto I and mesenteric hypoperfusion may have contributed to NEC in the present case.

Benefits of Printed Graphene with Variable Resistance for Flexible and Ecological 5G Band Antennas.

The possibility of creating antennas of the 5G standard (5.2-5.9 GHz) with specified electrodynamic characteristics by printing layers of variable thickness using a graphene suspension has been substantiated experimentally and by computer simulation. A graphene suspension for screen printing on photographic paper and other flexible substrates was prepared by means of exfoliation from graphite. The relation between the graphene layer thickness and its sheet resistance was studied with the aim of determining the required thickness of the antenna conductive layer. To create a two-sided dipole, a technology has been developed for the double-sided deposition of graphene layers on photographic paper. The electrodynamic characteristics of graphene and copper antennas of identical design are compared. The antenna design corresponds to the operating frequency of 2.4 GHz. It was found that the use of graphene as a conductive layer made it possible to suppress the fundamental (first) harmonic (2.45 GHz) and to observe radiation at the second harmonic (5.75 GHz). This effect is assumed to observe in the case when the thickness of graphene is lower than that of the skin depth. The result indicates the possibility of changing the antenna electrodynamic characteristics by adjusting the graphene layer thickness.

Graphene: Hexagonal Boron Nitride Composite Films with Low-Resistance for Flexible Electronics.

The structure and electric properties of hexagonal boron nitride (h-BN):graphene composite with additives of the conductive polymer PEDOT:PSS and ethylene glycol were examined. The graphene and h-BN flakes synthesized in plasma with nanometer sizes were used for experiments. It was found that the addition of more than 10-3 mass% of PEDOT:PSS to the graphene suspension or h-BN:graphene composite in combination with ethylene glycol leads to a strong decrease (4-5 orders of magnitude, in our case) in the resistance of the films created from these suspensions. This is caused by an increase in the conductivity of PEDOT:PSS due to the interaction with ethylene glycol and synergetic effect on the composite properties of h-BN:graphene films. The addition of PEDOT:PSS to the h-BN:graphene composite leads to the correction of the bonds between nanoparticles and a weak change in the resistance under the tensile strain caused by the sample bending. A more pronounced flexibility of the composite films with tree components is demonstrated. The self-organization effects for graphene flakes and polar h-BN flakes lead to the formation of micrometer sized plates in drops and uniform-in-size nanoparticles in inks. The ratio of the components in the composite was found for the observed strong hysteresis and a negative differential resistance. Generally, PEDOT:PSS and ethylene glycol composite films are promising for their application as electrodes or active elements for logic and signal processing.

Memristive FG-PVA Structures Fabricated with the Use of High Energy Xe Ion Irradiation.

A new approach based on the irradiation by heavy high energy ions (Xe ions with 26 and 167 MeV) was used for the creation of graphene quantum dots in the fluorinated matrix and the formation of the memristors in double-layer structures consisting of fluorinated graphene (FG) on polyvinyl alcohol (PVA). As a result, memristive switchings with an ON/OFF current relation ~2-4 orders of magnitude were observed in 2D printed crossbar structures with the active layer consisting of dielectric FG films on PVA after ion irradiation. All used ion energies and fluences (3 × 1010 and 3 × 1011 cm-2) led to the appearance of memristive switchings. Pockets with 103 pulses through each sample were passed for testing, and any changes in the ON/OFF current ratio were not observed. Pulse measurements allowed us to determine the time of crossbar structures opening of about 30-40 ns for the opening voltage of 2.5 V. Thus, the graphene quantum dots created in the fluorinated matrix by the high energy ions are a perspective approach for the development of flexible memristors and signal processing.

Resistive switching on individual V2O5 nanoparticles encapsulated in fluorinated graphene films.

Memristors currently attract much attention as basic building blocks for future neuromorphic electronics. Due to their unusual electronic, optical, magnetic, electrochemical, and structural properties, transition metal oxides offer much potential in the development of memristors. Recent trends in the design and fabrication of electronic devices have led to miniaturization of their working elements, with nanometer-sized structures enjoying increasing demand. In the present study, we investigated resistive switching on individual vanadium oxide (V2O5) crystal-hydrate nanoparticles, 2 to 10 nm in size, encapsulated in fluorinated graphene (FG). Measurements using a conductive atomic force microscope (c-AFM) probe showed that the core-shell V2O5/FG nanoparticles make it possible to achieve bipolar resistive switching, reproducible during 104 switching cycles, with the ON/OFF current ratio reaching 103-105. The switching voltage of the structures depends on the thickness of the FG shells of the composite particles and equals ∼2-4 V. It is shown that the encapsulation of V2O5 particles in fluorinated graphene ensures a high stability of the resistive switching effect and, simultaneously, prevents the escape of water from the crystalline vanadium oxide hydrates. A qualitative model is proposed to describe the bipolar resistive switching effect in examined structures. Results reported in the present article will prove useful in creating bipolar nanoswitches.

Separation of Donor and Recipient Microbial Diversity Allows Determination of Taxonomic and Functional Features of Gut Microbiota Restructuring following Fecal Transplantation.

Fecal microbiota transplantation (FMT) is currently used in medicine to treat recurrent clostridial colitis and other intestinal diseases. However, neither the therapeutic mechanism of FMT nor the mechanism that allows the donor bacteria to colonize the intestine of the recipient has yet been clearly described. From a biological point of view, FMT can be considered a useful model for studying the ecology of host-associated microbial communities. FMT experiments can shed light on the relationship features between the host and its gut microbiota. This creates the need for experimentation with approaches to metagenomic data analysis which may be useful for the interpretation of observed biological phenomena. Here, the recipient intestine colonization analysis tool (RECAST) novel computational approach is presented, which is based on the metagenomic read sorting process per their origin in the recipient's post-FMT stool metagenome. Using the RECAST algorithm, taxonomic/functional annotation, and machine learning approaches, the metagenomes from three FMT studies, including healthy volunteers, patients with clostridial colitis, and patients with metabolic syndrome, were analyzed. Using our computational pipeline, the donor-derived and recipient-derived microbes which formed the recipient post-FMT stool metagenomes (successful microbes) were identified. Their presence is well explained by a higher relative abundance in donor/pre-FMT recipient metagenomes or other metagenomes from the human population. In addition, successful microbes are enriched with gene groups potentially related to antibiotic resistance, including antimicrobial peptides. Interestingly, the observed reorganization features are universal and independent of the disease. IMPORTANCE We assumed that the enrichment of successful gut microbes by lantibiotic/antibiotic resistance genes can be related to gut microbiota colonization resistance by third-party microbe phenomena and resistance to bacterium-derived or host-derived antimicrobial substances. According to this assumption, competition between the donor-derived and recipient-derived microbes as well as host immunity may play a key role in the FMT-related colonization and redistribution of recipient gut microbiota structure.

Hi-C Metagenomics in the ICU: Exploring Clinically Relevant Features of Gut Microbiome in Chronically Critically Ill Patients.

Gut microbiome in critically ill patients shows profound dysbiosis. The most vulnerable is the subgroup of chronically critically ill (CCI) patients - those suffering from long-term dependence on support systems in intensive care units. It is important to investigate their microbiome as a potential reservoir of opportunistic taxa causing co-infections and a morbidity factor. We explored dynamics of microbiome composition in the CCI patients by combining "shotgun" metagenomics with chromosome conformation capture (Hi-C). Stool samples were collected at 2 time points from 2 patients with severe brain injury with different outcomes within a 1-2-week interval. The metagenome-assembled genomes (MAGs) were reconstructed based on the Hi-C data using a novel hicSPAdes method (along with the bin3c method for comparison), as well as independently of the Hi-C using MetaBAT2. The resistomes of the samples were derived using a novel assembly graph-based approach. Links of bacteria to antibiotic resistance genes, plasmids and viruses were analyzed using Hi-C-based networks. The gut community structure was enriched in opportunistic microorganisms. The binning using hicSPAdes was superior to the conventional WGS-based binning as well as to the bin3c in terms of the number, completeness and contamination of the reconstructed MAGs. Using Klebsiella pneumoniae as an example, we showed how chromosome conformation capture can aid comparative genomic analysis of clinically important pathogens. Diverse associations of resistome with antimicrobial therapy from the level of assembly graphs to gene content were discovered. Analysis of Hi-C networks suggested multiple "host-plasmid" and "host-phage" links. Hi-C metagenomics is a promising technique for investigating clinical microbiome samples. It provides a community composition profile with increased details on bacterial gene content and mobile genetic elements compared to conventional metagenomics. The ability of Hi-C binning to encompass the MAG's plasmid content facilitates metagenomic evaluation of virulence and drug resistance dynamics in clinically relevant opportunistic pathogens. These findings will help to identify the targets for developing cost-effective and rapid tests for assessing microbiome-related health risks.

Graphene Flakes for Electronic Applications: DC Plasma Jet-Assisted Synthesis.

The possibility of graphene synthesis (the bottom-up approach) in plasma and the effective control of the morphology and electrical properties of graphene-based layers were demonstrated. Graphene flakes were grown in a plasma jet generated by a direct current plasma torch with helium and argon as the plasma-forming gases. In the case of argon plasma, the synthesized graphene flakes were relatively thick (2-6 nm) and non-conductive. In helium plasma, for the first time, graphene with a predominance of monolayer flakes and high conductivity was grown in a significant amount using an industrial plasma torch. One-dimensional (1D) flow modeling shows that the helium plasma is a less charged environment providing the formation of thinner graphene flakes with low defect density. These flakes might be used for a water-based suspension of the graphene with PEDOT:PSS (poly(3,4-ethylenedioxythiophene): polystyrene sulfonate) composite to create the structures employing the 2D printing technologies. Good structural quality, low layer resistance, and good mechanical strength combined with the ability to obtain a large amount of the graphene powder, and to control the parameters of the synthesized particles make this material promising for various applications and, above all, for sensors and other devices for flexible electronics and the Internet of things ecosystem.

Electron transfer in oriented donor-acceptor dyads, intralayer charge migration, and formation of interlayer charge separated states in multi-layered Langmuir-Schäfer films.

Photoinduced intra- and interlayer electron transfer (ET) of doubly bridged donor-acceptor molecule, porphyrin-fullerene dyad (PF), was studied in single- and multi-layered Langmuir-Schäfer (LS) films and in LS films, where PF and an efficient electron donating polymer polyhexyltiophene (PHT) formed a bilayer PHT/PF and multi-layered PHT/PF structures. The ET through layers were investigated by a method, which measures the photovoltaic (PV) response proportional to the number of charge-separated (CS) states and to the CS distance between the electrons and holes formed in pulsed photo-excitation. Primary conclusions were, that ET starts as formations of CS dyads (P+F-) in single-layers, continues as long-range intra-layer charge migrations following interlayer CS between two adjacent monolayers. Quantitative conclusions were, that the interlayer ET efficiency is 100% in the bi-layered PF structure (2PF), where two CS dyads in adjacent layers forms CS complexes (P+F/PF-) and that the probability to form longer or higher order of CS complexes follows an expression of a convergent geometric series, with a converting factor of 2/3. In the PHT/PF bilayer structure the ET efficiency was one order of magnitude higher, than that for the 2PF structure due to the ET from the CS dyads to ground state electron donor PHT, with an acceptor density, much higher than that of (P+F-).

Staged Interventional and Surgical Treatment of Patient with Chronic Pancreatitis Complicated by Pancreaticopleural Fistula with Lung Abscesses.

BACKGROUND Pancreaticopleural fistula is a rare complication of chronic pancreatitis. Its formation is associated with local disruption of the pancreatic duct or pseudocyst communicating with the ductal system. Rarely, other intrathoracic complications may develop such as mediastinitis, pericarditis, hemothorax, and pleural empyema. The combination of pancreaticopleural fistula with lung abscesses is extremely rare. CASE REPORT A 37-year-old male patient, a long-term alcohol abuser, was admitted with complaints on left thoracic and upper abdominal pain, fever with a body temperature of 39.1°C, and a severe cough with purulent sputum. Left-sided pneumonia with pleural effusion was diagnosed. Thoracentesis and then a pleural drainage were performed. However, the symptoms persisted. Pleural effusion amylase was very high - more than 60 000 IU/L. Computed tomography and magnetic resonance imaging revealed cystic changes in the pancreatic head, pseudocyst in the pancreatic body, dilation of the Wirsung duct, and pancreaticopleural fistula with several left lung abscesses. Step by step, the patient underwent drainage of lung abscesses, external drainage of the pancreatic pseudocyst, and external-internal stenting of the pancreatic duct under ultrasound guidance. After fistula resolution, the patient was readmitted and successfully underwent the Bern variant of the Beger procedure. Six months later, he had no complaints and returned to work. In a follow-up examination, there was no fistula, no ductal hypertension, and only small pulmonary residual changes. CONCLUSIONS A very rare case of chronic pancreatitis complicated by pancreaticopleural fistula with lung abscesses is presented. The clinical outcome was good due to the staged character of treatment and participation of a multidisciplinary specialist team.

Fluorinated graphene nanoparticles with 1-3 nm electrically active graphene quantum dots.

A new approach to creating a new and locally nanostructured graphene-based material is reported. We studied the electric and structural properties of partially fluorinated graphene (FG) films obtained from an FG-suspension and nanostructured by high-energy Xe ions. Local shock heating in ion tracks is suggested to be the main force driving the changes. It was found that ion irradiation leads to the formation of locally thermally expanded FG and its cracking into nanoparticles with small (∼1.5-3 nm) graphene quantum dots (GQD), embedded in them. The bandgap of GQD was estimated as 1 -1.5 eV. A further developed approach was applied to correct the functional properties of printed FG-based crossbar memristors. Dielectric FG films with small quantum dots may offer prospects in graphene-based electronics due to their stability and promising properties.

Flexibility of Fluorinated Graphene-Based Materials.

The resistivity of different films and structures containing fluorinated graphene (FG) flakes and chemical vapor deposition (CVD)-grown graphene of various fluorination degrees under tensile and compressive strains due to bending deformations was studied. Graphene and multilayer graphene films grown by means of the chemical vapor deposition (CVD) method were transferred onto the flexible substrate by laminating and were subjected to fluorination. They demonstrated a weak fluorination degree (F/C lower 20%). Compressive strains led to a strong (one-two orders of magnitude) decrease in the resistivity in both cases, which was most likely connected with the formation of additional conductive paths through fluorinated graphene. Tensile strain up to 3% caused by the bending of both types of CVD-grown FG led to a constant value of the resistivity or to an irreversible increase in the resistivity under repeated strain cycles. FG films created from the suspension of the fluorinated graphene with a fluorination degree of 20-25%, after the exclusion of design details of the used structures, demonstrated a stable resistivity at least up to 2-3% of tensile and compressive strain. The scale of resistance changes R/R0 was found to be in the range of 14-28% with a different sign at the 10% tensile strain (bending radius 1 mm). In the case of the structures with the FG thin film printed on polyvinyl alcohol, a stable bipolar resistive switching was observed up to 6.5% of the tensile strain (bending radius was 2 mm). A further increase in strain (6.5-8%) leads to a decrease in ON/OFF current ratio from 5 down to 2 orders of magnitude. The current ratio decrease is connected with an increase under the tensile strain in distances between conductive agents (graphene islands and traps at the interface with polyvinyl alcohol) and thickness of fluorinated barriers within the active layer. The excellent performance of the crossbar memristor structures under tensile strain shows that the FG films and structures created from suspension are especially promising for flexible electronics.

Resistive switching effects in fluorinated graphene films with graphene quantum dots enhanced by polyvinyl alcohol.

Two-layer films of partially fluorinated graphene (PFG) with graphene quantum dots and polyvinyl alcohol (PVA) were prepared by means of 2D printing technology. A stable resistive switching effect with the ON/OFF current ratio amounting from one to 4-5 orders of magnitude is found. The decrease in the PVA thickness leads to a change of the unipolar threshold switchings to the bipolar resistive switchings. The crossbar Ag/PFG/PVA/Ag structures retain their performance up to 6.5% deformation. The switching phenomenon is observed for a period about a year. The traps with characteristic activation energies ∼0.05 eV are suggested to be responsible for resistive switching. The time of charge-carrier emission from the localized states was found to be ∼5 µs. A quality model to describe the resistive switching effect in two-layer films implying the conduction over quantum dots proceeding with the participation of active traps at the PFG/PVA interface is proposed. The structures with the design demonstrated threshold resistive switching have their high potential for development of selector devices integrated to sensor or memristors circuits, for information storage and data processing, for flexible and wearable electronics. The structures with lower PVA thickness and the bipolar threshold switching are perspective for non-volatile memory cells for printed and flexible electronics.