Multi-layer graphene as a selective detector for future lung cancer biosensing platforms

This is the final version. Available from the Royal Society of Chemistry via the DOI in this record.Highly selective, fast detection of specific lung-cancer biomarkers (CMs) in exhaled human breath is vital to the development of enhanced sensing devices. Today, e-nose is a promising approach for the diagnosis of lung cancer. Nevertheless, considerable challenges to early-stage disease diagnostics still remain: e.g. decrease in sensor sensitivities in the presence of water vapor, sensor drift leading to the inability to calibrate exactly, relatively short sensor lifetimes, and difficulty discriminating between multiple diseases. However, there is a wide scope for breath diagnostics techniques, and all advanced electrodes applicable to e-nose devices will benefit them. Here, we present the promising sensing capabilities of bare multi-layer graphene (MLG) as a proof of concept for advanced e-nose devices and demonstrate its utility for biomolecule discrimination of the most common lung CMs (ethanol, isopropanol, and acetone). We report on a comparative study involving exposure of the three CM solutions on flat MLG (f-MLG) and patterned MLG (p-MLG) electrodes, where the electrical conductivity of p-MLG is significantly increased while applying acetone. Based on sensitivity tests, we demonstrate the ability to monitor the electrical response of graphene electrodes employing graphene of various wettabilities. Specifically, the f-MLG electrode displays almost 2 times higher sheet resistance (30 Ω sq−1) compared to the hydrophilic p-MLG (12 Ω sq−1). We show significant sensitivity to selected specific molecules of pristine f-MLG and p-MLG while applying CM solutions with a 1.4 × 105 ppm concentration. Finally, we show the selectivity of f-MLG and p-MLG-based sensors when exposed to 2.0 × 105 ppm solutions containing different CM combinations. Both sensors were selective in particular to acetone, since the presence of acetone leads to a sheet resistance increase. We demonstrate that an advanced e-nose approach integrated with MLG electrodes has significant potential as a design concept for utilization of molecular detection at variable concentrations such as in early-stage disease diagnosis. This early-stage approach will provide convenient and reusable complex monitoring of CMs compared to typical contact sensors which require target analysis and are limited by disposable measuring. Moreover, further integration of the Internet of Things will introduce advanced e-nose devices as a biotechnological innovation for disease resilience with the potential for commercialization.Engineering and Physical Sciences Research Council (EPSRC)Engineering and Physical Sciences Research Council (EPSRC

Tuning silicon-rich nitride microring resonances with graphene capacitors for high-performance computing applications

This is the final version. Available from the Optical Society of America via the DOI in this record.We demonstrate the potential of a graphene capacitor structure on silicon-richnitride micro-ring resonators for multitasking operations within high performance computing.Capacitor structures formed by two graphene sheets separated by a 10 nm insulating siliconnitride layer are considered. Hybrid integrated photonic structures are then designed to exploitthe electro-absorptive operation of the graphene capacitor to tuneably control the transmissionand attenuation of different wavelengths of light. By tuning the capacitor length, a shift in theresonant wavelength is produced giving rise to a broadband multilevel photonic volatile memory.The advantages of using silicon-rich nitride as the waveguiding material in place of the moreconventional silicon nitride (Si3N4) are shown, with a doubling of the device’s operationalbandwidth from 31.2 to 62.41 GHz achieved while also allowing a smaller device footprint.A systematic evaluation of the device’s performance and energy consumption is presented.A difference in the extinction ratio between the ON and OFF states of 16.5 dB and energyconsumptions of<0.3 pJ/bit are obtained. Finally, it has been demonstrated that increasing thepermittivity of the insulator layer in the capacitor structure, the energy consumption per bit canbe reduced even further. Overall, the resonance tuning enabled by the novel graphene capacitormakes it a key component for future multilevel photonic memories and optical routing in highperformance computing.Engineering and Physical Sciences Research Council (EPSRC

Photoluminescence from NV− centres in 5 nm detonation nanodiamonds: Identification and high sensitivity to magnetic field

This is the final version. Available from the publisher via the DOI in this record.The content of nitrogen-vacancy (NV−) colour centres in the nanodiamonds (DNDs) produced during the detonation of nitrogen-containing explosives was found to be 1.1 ± 0.3 ppm. This value is impressive for nanodiamonds of size < 10 nm with intentionally created NV− centres. The concentration was estimated from the electron paramagnetic resonance as determined from the integrated intensity of the g = 4.27 line. This line is related with “forbidden” ∆ms = 2 transitions between the Zeeman levels of a NV− centre’s ground triplet state. Confocal fluorescence microscopy enables detection of the red photoluminescence (PL) of the NV− colour centres in nanoscale DND aggregates formed from the 5-nm nanoparticles. Subwavelength emitters consisting of NV− with sizes a few times smaller than the diffraction-limited spot are clearly distinguished. We have further observed an abrupt drop in the PL intensity when mixing and anti-crossing of the ground and excited states spin levels in NV− occurs under an applied external magnetic field. This effect is a unique quantum feature of NV− centres, which cannot be observed for other visible domain light-emitting colour centres in a diamond lattice.Engineering and Physical Sciences Research Council (EPSRC

2D WS2 liquid crystals: tunable functionality enabling diverse applications

This is the final version. Available on open access from Royal Society of Chemistry via the DOI in this recordThe first observation of liquid crystalline dispersions of liquid phase-exfoliated tungsten disulfide flakes is reported in a range of organic solvents. The liquid crystals demonstrate significant birefringence as observed in the linear and circular dichroism measurements respectively. In particular, linear dichroism is observed throughout the visible range while broad-band circular dichroism can be observed in the range from 500-800 nm. Under an applied magnetic field of ±1.5 T the circular dichroism can be switched ON/OFF, while the wavelength range for switching can be tuned from large to narrow range by the proper selection of the host solvent. In combination with photoluminescence capabilities of WS2, this opens a pathway to a wide variety of applications, such as deposition of highly uniform films over large areas for photovoltaic and terahertz devices.Engineering and Physical Sciences Research Council (EPSRC)Royal Societ

Dynamic in-situ sensing of fluid-dispersed 2D materials integrated on microfluidic Si chip

This is the author accepted manuscript. The final version is available from Nature Publishing Group via the DOI in this record.The supplementary videos associated with this article are located in ORE at: https://doi.org/10.24378/exe.1643In this work, we propose a novel approach for wafer-scale integration of 2D materials on CMOS photonics chip utilising methods of synthetic chemistry and microfluidics technology. We have successfully demonstrated that this approach can be used for integration of any fluid-dispersed 2D nano-objects on silicon-on-insulator photonics platform. We demonstrate for the first time that the design of an optofluidic waveguide system can be optimised to enable simultaneous in-situ Raman spectroscopy monitoring of 2D dispersed flakes during the device operation. Moreover, for the first time, we have successfully demonstrated the possibility of label-free 2D flake detection via selective enhancement of the Stokes Raman signal at specific wavelengths. We discovered an ultra-high signal sensitivity to the xyz alignment of 2D flakes within the optofluidic waveguide, which in turn enables precise in-situ alignment detection for the first practicable realisation of 3D photonic microstructure shaping based on 2D-fluid composites and CMOS photonics platform while also representing a useful technological tool for the control of liquid phase deposition of 2D materials.We acknowledge financial support from: The Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom via the EPSRC Centre for Doctoral Training in Electromagnetic Metamaterials (Grant No. EP/L015331/1) and also via Grant Nos. EP/N035569/1, EP/G036101/1, EP/M002438/1, and EP/M001024/1, Science Foundation Ireland Grant No. 12/IA/1300, the Ministry of Education and Science of the Russian Federation (Grant No. 14.B25.31.0002) and the Royal Society International Exchange Grant 2015/R3. The microfluidic structures were fabricated at Tyndall National Institute under the Science Foundation Ireland NAP368 and NAP94 programs

Ultra-sensitive label-free in-situ detection of dynamically driven self-assembly of 2D nanoplatelets on SOI chip

Fluid dispersed two-dimensional (2D) composite materials with dynamically tunable functional properties have recently emerged as a novel highly promising class of optoelectronic materials, opening up new routes not only for the emerging field of metamaterials but also to chip-scale multifunctional metadevices. However, in-situ monitoring and detection of the dynamic ordering of 2D nanoparticles on chip and during the device operation is still a huge challenge. Here we introduce a novel approach for on-chip, in-situ Raman characterisation of 2D-fluid composite materials incorporated into Si photonics chip. In this work the Raman signal for 2D nanoplatelets is selectively enhanced by Fabry-Perot resonator design of CMOS photonic-compatible microfluidic channels. This has then been extended to demonstrate the first in-situ Raman detection of the dynamics of individual 2D nanoplatelets, within a microfluidic channel. Our work paves the way for the first practicable realisation of 3D photonic microstructure shaping based on 2D-fluid composites and CMOS photonics platform.We acknowledge financial support from: the Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom via the EPSRC Centre for Doctoral Training in Electromagnetic Metamaterials (Grant No. EP/L015331/1) and also via Grants No. EP/G036101/1, EP/M002438/1, and EP/M001024/1, Science Foundation Ireland Grant No. 12/IA/1300, the Ministry of Education and Science of the Russian Federation (Grant No. 14.B25.31.0002) and the Royal Society International Exchange Grant 2015/R3. The microfluidic structures were fabricated at Tyndall National Institute under the Science Foundation Ireland NAP368 and NAP94 programmes

Mechanochemical synthesis of carbon-stabilized Cu/C, Co/C and Ni/C nanocomposites with prolonged resistance to oxidation

This is the final version. Available on open access from Nature Research via the DOI in this recordData availability: The authors declare that all relevant data are included in the paper and in Supplementary Information files.Metal-carbon nanocomposites possess attractive physical-chemical properties compared to their macroscopic counterparts. They are important and unique nanosystems with applications including in the future development of nanomaterial enabled sensors, polymer fillers for electromagnetic radiation shields, and catalysts for various chemical reactions. However, synthesis of these nanocomposites typically employs toxic solvents and hazardous precursors, leading to environmental and health concerns. Together with the complexity of the synthetic processes involved, it is clear that a new synthesis route is required. Herein, Cu/C, Ni/C and Co/C nanocomposites were synthesized using a two-step method including mechanochemical treatment of polyethylene glycol and acetates of copper, nickel and cobalt, followed by pyrolysis of the mixtures in an argon flow at 700 °C. Morphological and structural analysis of the synthesized nanocomposites show their core-shell nature with average crystallite sizes of 50 (Cu/C), 18 (Co/C) and 20 nm (Ni/C) respectively. The carbon shell originates from disordered sp2 carbon (5.2–17.2 wt.%) with a low graphitization degree. The stability and prolonged resistance of composites to oxidation in air arise from the complete embedding of the metal core into the carbon shell together with the presence of surface oxide layer of metal nanoparticles. This approach demonstrates an environmentally friendly method of mechanochemistry for controllable synthesis of metal-carbon nanocomposites.Engineering and Physical Sciences Research Council (EPSRC)International Visegrad Fun

Transmission Properties of FeCl₃-Intercalated Graphene and WS₂ Thin Films for Terahertz Time-Domain Spectroscopy Applications

This is the final version. Available on open access from Springer via the DOI in this recordTime-resolved terahertz spectroscopy has become a common method both for fundamental and applied studies focused on improving the quality of human life. However, the issue of finding materials applicable in these systems is still relevant. One of the appropriate solutions is 2D materials. Here, we demonstrate the transmission properties of unique graphene-based structures with iron trichloride FeCl3 dopant on glass, sapphire and Kapton polyimide film substrates that previously were not investigated in the framework of the above-described problems in near infrared and THz ranges. We also show properties of a thin tungsten disulfide WS2 film fabricated from liquid crystal solutions transferred to a polyimide and polyethylene terephthalate substrates. The introduction of impurities, the selection of structural dimensions and the use of an appropriate substrate for modified 2D layered materials allow to control the transmission of samples for both the terahertz and infrared ranges, which can be used for creation of effective modulators and components for THz spectroscopy systems.Engineering and Physical Sciences Research Council (EPSRC)Government of the Russian Federatio

Spatial tracking of individual fluid dispersed particles via Raman spectroscopy

This is the final version. Available on open access from Nature Research via the DOI in this recordWe demonstrate a method for the spatial tracking of individual particles, dispersed in a fluid host, via Raman spectroscopy. The effect of moving a particle upon the intensity of different bands within its Raman spectrum is first established computationally through a scattering matrix method. By comparing an experimental spectrum to the computational analysis, we show that the position of the particle can be obtained. We apply this method to the specific cases of molybdenum disulfide and graphene oxide particles, dispersed in a nematic liquid crystal, and contained within a microfluidic channel. By considering the ratio and difference between the intensities of the two Raman bands of molybdenum disulfide and graphene oxide, we demonstrate that an accurate position can be obtained in two dimensions.Engineering and Physical Sciences Research Council (EPSRC)Federal Target Program of the Ministry of Science and Higher Education of the Russian Federatio

Pathway-Specific Polygenic Risk Scores as Predictors of Amyloid-beta Deposition and Cognitive Function in a Sample at Increased Risk for Alzheimer's Disease

Polygenic risk scores (PRSs) have been used to combine the effects of variants with small effects identified by genome-wide association studies. We explore the potential for using pathway-specific PRSs as predictors of early changes in Alzheimer’s disease (AD)-related biomarkers and cognitive function. Participants were from the Wisconsin Registry for Alzheimer’s Prevention, a longitudinal study of adults who were cognitively asymptomatic at enrollment and enriched for a parental history of AD. Using genes associated with AD in the International Genomics of Alzheimer’s Project’s meta-analysis, we identified clusters of genes that grouped into pathways involved in amyloid-β (Aβ) deposition and neurodegeneration: Aβ clearance, cholesterol metabolism, and immune response. Weighted pathway-specific and overall PRSs were developed and compared to APOE alone. Mixed models were used to assess whether each PRS was associated with cognition in 1,200 individuals, cerebral Aβ deposition measured using amyloid ligand (Pittsburgh compound B) positron emission imaging in 168 individuals, and cerebrospinal fluid Aβ deposition, neurodegeneration, and tau pathology in 111 individuals, with replication performed in an independent sample. We found that PRSs including APOE appeared to be driven by the inclusion of APOE, suggesting that the pathway-specific PRSs used here were not more predictive than an overall PRS or APOE alone. However, pathway-specific PRSs could prove to be useful as more knowledge is gained on the genetic variants involved in specific biological pathways of AD