bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Development of a Digital Data Management Platform for Battery Material and Processing Data
Authors: Oehm Jonas , Nebel Vincent , Beran Lisa , Perovic Milena , Gottschalk Laura , Haghipour Amir , Königer Veit , Gümbel Philip , Mutz Marcel , Kwade Arno , Presser Volker , Knoblauch Volker , Kraus Tobias
Published: August 2024

Research on battery materials and systems is broader than ever and a large amount of data is being generated. The data collected is often challenging to correlate or compare because they are not compiled in a structured way since no generally uniform data structure exists yet in the battery field. Besides, manufacturing steps and analysis parameters vary enormously from laboratory scale to industrial scale, from research institutions to consortia.

Within the "DigiBatMat project" we have created a digital platform for battery material data and processing data that combines collected material data and knowledge within a defined structure based on taxonomies and ontologies. The structure of the digital platform was developed to cover the Battery LabFactory Braunschweig (BLB) pilot-scale production line for lithium-ion cells while being compatible with other battery production processes, for example at the laboratory bench scale. The platform’s underlying data structure is divided into an “electrode production” and “cell production” taxonomy, providing input modules for the most typical battery material and cell characterization methods. This approach offers a commercially available platform with a defined structure, which still allows flexibility for individual electrode and cell productions through option based input. Due to this structure, we aim to go beyond simple data storage by implementing functionalities that allow users to work with and analyze the data within the digital platform. Beside the functionalities we have implemented so far, which are shown here, we also aim to develop further functionalities that enable the identification of new correlations that are otherwise difficult or even impossible to obtain.

A consistent data set is necessary to build up and validate such a digital platform. Hence, we specifically generated “reference” data and tested their management and analysis with the platform. We focus on three key use cases of collecting process data and characterizing electrodes and cells properties along the production process. In one of these key use cases we compare state-of-the-art cathodes with Ni-rich active materials, namely NMC811 and NCA. Data are collected from cells with such cathodes with varying loadings and electrode densities. Characterization of the electrodes includes, among other things, microscope data analysis of the microstructure and electrochemical characterization such as electrochemical impedance spectroscopy and rate capability. By showing how raw data can be imported into the database, processed and analyzed, we aim to demonstrate the possibilities and advantages of our digital platform.
Single Atom Catalyst Anchored on Nitrogen-Doped Porous Carbon As an Effective Sulfur Host for Lithium-Sulfur Batteries
Authors: Lin Xueyan , Baranwal Rishav Kumar , Wang Bin , Fan Zhaoyang
Published: August 2024

Lithium-sulfur batteries (LSBs) are considered highly promising for next-generation energy storage due to their high theoretical specific capacity and energy density. However, challenges such as the insulating nature of sulfur cathodes, the detrimental shuttle effect of lithium polysulfides (LiPSs), and sluggish conversion kinetics of LiPSs during charge/discharge cycles impede their commercial viability. In this study, we employed a facile ‘dissolution-carbonization’ approach to synthesize nitrogen-coordinated monometallic atomic catalysts anchored on mesoporous carbon to promote surface-mediated reactions of LiPSs. The hierarchical porous carbon support physically confines the sulfur species, while the introduction of single atoms efficiently captures polysulfide intermediates and facilitates their redox conversion kinetics with a lower activation energy barrier. The synergistic effect of the single atom and nitrogen-rich porous carbon (NC) significantly enhances reaction kinetics and sulfur species utilization. Consequently, LSBs incorporating single-atom catalysts (SACs) demonstrate remarkable performance metrics, including high-capacity retention (824.2 mAh g−1), superior Coulombic efficiency (>98.5%), low-capacity decay rate (0.042% per cycle) after 500 cycles at 1 C, and excellent rate capability (776 mA h g–1 at 3 C). This work presents an effective strategy that combines the functions of a nanoporous material host and SACs for lithium-sulfur batteries.
Cross-Sectional Preparation of Complex Energy Devices and Their Characterization By Advanced Microscopic Methods
Authors: Ogolla Charles Otieno , Hepp Marco , Butz Benjamin , Stepien Dominik , Bresser Dominic
Published: August 2024

Energy devices such as batteries, fuel cells, and solar cells are composed of multiple functional components with varying material properties. Achieving a fundamental understanding of structure-property relationships and systematically enhancing performance, while also investigating device degradation and failure mechanisms, requires high-quality cross-sections of entire devices or substantial regions. Given that many devices contain different classes of materials, including liquid and/or air-sensitive components, working under cryogenic or inert conditions is necessary to maintain their original state. To facilitate cross-sectional characterization of these devices from the macroscopic down to the atomic level, we use a range of preparation tools. A self-designed cryo-cutter allows us to efficiently produce cross-sections of entire devices, such as pouch cells, in a single step, enabling optical microscopy (OM) observation at the centimeter scale while preserving their pristine state. For finer scales, cryo-ultramicrotomy and focused ion beam (FIB) techniques are regularly employed. These methods can prepare high-quality thin samples under 50 nm for investigations using OM, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) at atomic resolution. In this presentation, we demonstrate the scale-bridging capabilities of these preparation techniques applied to various devices and their components in conjunction with advanced electron microscopic and spectroscopic methods. Examples include devices such as batteries (Fig. 1) and complex proton exchange membrane (PEM) fuel cells, as well as battery components (Fig. 2). The techniques used are ideal for assessing the integrity of entire devices and the interfaces of individual layers and components, including their morphology, contact, composition, and chemical bonding states.

Acknowledgement: Part of this work was performed at the Micro-and Nanoanalytics Facility (MNaF) of the University of Siegen.

Figure 1
Synthesis and Characterization of a Biocompatible, and Flexible Solid-Electrolyte for Zn-MnO2 Batteries
Authors: Khan Usman Ali , Madan Deepa
Published: August 2024

The new generation of flexible wearable electronics is becoming one of the most in-demand wearable tech in most parts of the world, be it for regular use or for medical reasons, which gives rise to the need for the development of safe and flexible rechargeable batteries. Some of the most basic requirements for such batteries constitute the ease of use, flexibility, mechanical strength, and environmental friendliness. This can be achieved by carefully designing the electrolyte for the battery such that it fulfills the mentioned properties without compromising the electrochemical performance of the battery. This study sheds light on the development of a safe, flexible, and environmentally friendly solid electrolyte film based on a biopolymer. The electrolyte film derived from Chitosan, which is a biocompatible biopolymer, offers various advantages over the conventional liquid electrolytes. When soaked in an alkaline liquid, KOH, this Chitosan-film can be used as an efficient electrolyte for Zn-MnO2 battery chemistry. According to optical imaging, the incorporation of freeze drying for the preparation of the solid electrolyte films provided a lamellar structure with a microporous morphology. Higher concentrations of Chitosan enabled the film to absorb and retain increased amount of KOH because of the hydrogen bonds present between the Chitosan molecules and KOH, which helped in enhancing the ionic conductivity (IC) of the freeze-dried electrolyte, i.e., 300-600 mS/cm, at a thickness of 150-170µm. Additionally, the obtained electrolyte demonstrated exceptional mechanical strength and flexibility which also makes it a promising solid electrolyte for Zinc metal batteries, as it has a potential to impede the progression of Zn dendrites during cycling, thereby improving the stability and lifespan of the battery.
(Invited) Electrochemical Tuning of Thermoelectric Performance of Carbon Nanotubes
Authors: Yanagi Kazuhiro
Published: August 2024

One-dimensional materials have potential for high performance thermoelectric energy conversion. To experimentally understand how one-dimensional electronic structures can enhance thermoelectric performance, we have investigated the thermoelectric properties of single walled carbon nanotubes (SWCNTs) such as the relationships among electronic structures, the location of Fermi-level, Seebeck coefficients, and Power factor by combining thermoelectric measurements and electrolyte gating techniques. Through the studies, we have revealed unique properties such as violation of thermoelectric trade-off, isotropic Seebeck coefficient, and gigantic power factor [1]. However, in addition to that, it is important to understand how the carrier density also affects the thermal conductivity of the carbon nanotube thin films for correct evaluation of ZT value. Therefore, we have developed a measurement system which can evaluate thermal conductivity by tuning the location of Fermi-level through electrochemical gating techniques. Time-domain thermoreflectance (TDTR) measurement is one of methods which can evaluate the thin film thermal conductivity. In conventional TDTR system, Al is used as metal transducer, but Al is electrochemical reactive, and thus it is very difficult to combine the TDTR measurements with electrochemical techniques. To solve this problem, we developed a TDTR system using Au as a metal transducer [2]. By using Au as a metal transducer, we can evaluate both the electrical and thermal properties at the same time. By using system, we can evaluate thermal properties of thin films during electrolyte gating, and have evaluated how the change of charrier density affects the thermal conductivity of carbon nanotube thin films [3]. By preparing the aligned single-walled carbon nanotube thin film, we evaluated the ZT value in the perpendicular direction to the nanotube axis as a function of carrier density. The ZT value in this direction can be maximized to be 0.1 by tuning the Femi-level around 1st van hove singularity [4].

References:

[1] Yanagi, JSAP Rev. 230424, (2023) [2] Ueji et al., Jpn. J. Appl. Phys. 58, 128006 (2019), Yuan et al., ACS Nano 15, 15902-15909 (2021) [3] Ueji et al., Appl. Phys. Lett. 117, 133104 (2020), Ueji et al., ACS Applied Nano Materials 5, 6100 (2022), [4] Ueji et al., in preparation.
Exploring the Photoluminescence Characteristics of Nitrogen-Doped Carbon Dots
Authors: Svrcek Vladimir , Dsouza Slavia Deeksha , Buerkle Marius , Maguire PAUL , Mariotti Davide
Published: August 2024

Carbon dots, or C-Dots, are graphitic particles below 10 nm that exhibit room temperature photoluminescence (PL). The specific PL mechanism of C-Dots varies with synthesis paths and remains unresolved. This study utilizes direct current microplasmas for reliable and reproducible synthesis, exploring precursor outcomes and the discharge current's impact on surface chemistry and optical properties. The nitrogen-doped C-Dots (N-CQDs) synthesized display crystalline structures with a graphitic core, nitrogen doping, and a functionalized surface. Luminescence, originating from both core and surface states, can be finely controlled by adjusting synthesis conditions. N-CQDs, with a high photoluminescence quantum yield, hold promise for next-gen solar cell applications. The N-CQDs exhibit intriguing quantum-confined optical properties dependent on the level of nitrogen incorporation. Notably, the band energy structure of the N-CQDs is clarified, and they are integrated into a photovoltaic device as the photoactive layer, achieving an extraordinary open-circuit voltage of 1.8 V corroborating well with energy gat of CQDs and PL properties [1, 2]. We specifically highlight the use of nitrogen-doped C-Dots as an active absorbing layer in solar cells and discuss how doping can engineer their electrical, optical, and chemical properties. Nitrogen doping mainly occurs in the graphitic core as a substituted type of doping (63–67 atomic%), with enough to create emissive states without impacting the core structure. The optical and chemical properties remain stable even with re-dispersion, suggesting easy applicability for cellular imaging or optoelectronics [3]. Highly stable nitrogen-doped graphite quantum dots, prepared by atmospheric pressure microplasma, without post-synthesis treatments, yields stable, water-dispersible, and non-toxic quantum dots with a high PL quantum yield of approximately 70%.

References:

Carolan, C. Rocks, D. B. Padmanaban, P. Maguire, V. Svrcek and D. Mariotti Sustain. Energy Fuels 1, 1611–9 (2017).

D. Dsouzaa, M. Buerkle, P. Brunet, Ch.Maddi, D. B. Padmanaban, A. Morelli, A. F. Payam, P. Maguire, D. Mariotti and V. Svrcek, Carbon, 183, 1-11 (2021).

D. Dsouzaa, M. Buerkle, B. Alessi, P. Brunet, A. Morelli, A. F. Payam, P. Maguire, D. Mariotti and V. Svrcek, Nanotechnology 34, 505601 (2023).
(Invited) Carbon in Electrochemical Energy Storage
Authors: Xiao Jie
Published: August 2024

Carbon materials play a pivotal role in the realm of electrochemical energy storage. Their significance stems from the diverse applications they find based on surface chemistries and morphologies. In batteries, various carbons serve as electrochemical active materials, hosting structures and additives. For instance, fluorinated carbon emerges as an excellent cathode material for primary batteries. Fine-tuning the C/F ratio on cabron surfaces allows customization of the power/energy ratio, catering to specific applications. Graphene, with its ability to self-assemble into hierarchical structures, has proven to be an ideal oxygen electrode. Porous nanocarbon structures are commonly employed to host sulfur, although addressing challenges at the electrode level is imprative for further processing. Carbon additives become essential components in cathode or anode materials for Li-ion batteries. Establishing a continuous electronic conductive network using a minimal amount of carbon in electrodes is a constant pursuit, aiming to reduce parasitic weight at the cell level. This talk wil ldelve into the fundamental roles that carbon play in various systems, such as Li/CFx, Li/O2, Li-S and advanced Li-ion batteries to underscore the crucial role of carbon in advancing battery technologies.
Particle Shape Resilient Framework for Long-Lasting Li-Ion Batteries
Authors: Park Kyu-Young , Lim Jong-Heon
Published: August 2024

The lattice structural dynamics of active materials within Li-ion batteries, contingent upon their state of charge (SoC), introduce challenges associated with volume expansion or contraction in a both particle and electrode levels1-2. This phenomenon induces mechanical fractures and alters electrode thickness, particularly problematic for high-Ni cathodes characterized by pronounced c-lattice changes during cycling, leading to substantial mechanochemical degradation and hindrance to long-term cycle retention3-4. This study proposes a resilient framework employing multi-wall carbon nanotubes to decorate the surface of active particles, imparting recoverable characteristics to high-Ni cathode materials. This surface framework, endowed with the capacity to absorb mechanical energy, effectively preserves the original secondary particle shape throughout multiple charge cycles, mitigating the serve propagation of cracking. Additionally, the control of particle shape alterations results in a noteworthy reduction of over 50% in electrode thickness changes. The consequential impact of this elastic framework particle engineering is exemplified by outstanding performance, even in a carbon-additive-free electrode with a density of 20 mg/cm². The battery exhibits superior cycle life, retaining 85% of its initial capacity after 500 cycles in a pouch cell. This advancement establishes a universal paradigm for the systematic design of Li-ion batteries with markedly extended cycle life, presenting a transformative prospect for robust and enduring energy storage

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Graphene Supported Silicon Nanocomposites As Anode for Lithium-Ion Batteries
Authors: Jang Dawoon , Kim Jung-Hyun , Park Sungjin
Published: August 2024

This work indicates Silicon/Grphene (Si/G) nanocomposites anode on the performance in lithium-ion batteries (LIBs).

The self-assembled graphene aerogel and silicon (Si/G) anode materials with some surface defects have been successfully prpared by hydrothermal synthesis using chemically modified graphene oxide and commercial Si nanopowder (about 50 nm) as precursor. The morphologies and textural properties of as-obtained Si/G were investigated by scanning electron microscopy, X-ray photoelectron spectroscopy, and other sturucture techniques. The surface defects and electrical conductivities of Si/G can be controlled by adjusting the amount of Si nanopowder. The results indicate that Si/G with Si amount of half exhibits excellent stability and reversible capacity and superior rate capability with excellent cycling stability. It is demonstrated that the 3D porous network with increased defect density, as well as the considerable electrical conductivity, results in the excellent electrochemical performance of the as-made Si/G anodes in LIBs.
Guiding the Choice of Carbon Nanotubes Conductive Additives for Silicon Anode Electrode through Microstructure Scale Analysis
Authors: Usseglio-Viretta Francois L. E. , Kim Jae Ho , Preimesberger Juliane Irine , Neale Nathan R. , Weddle Peter J , Verma Ankit , Colclasure Andrew M.
Published: August 2024

Silicon anode electrodes exhibit a large microstructure design space as several carbon additives are considered to improve its conductivity and thus electrochemical performance. Investigating each combination experimentally is time-consuming. In this work, microstructure scale modeling is used to discriminate between different carbon additives to accelerate electrode development [1]. Baseline spherical C45, single wall carbon nano tube (SWCNT, cf. Fig. 1), carbon nano rods (CNR), and mixed SWCNT-CNR are considered and their respective impact on connectivity, effective conductivity, specific surface area, pore size distributions, and effective diffusivity are calculated to provide design recommendations. To do so, microstructures are numerically generated using the NREL open-source Microstructure Analysis Toolbox (MATBOX) available to the battery community* [2].

Additionally, the model is used to correlate material utilization and silicon particle size, in agreement with experimental data, to further guide the selection of silicon material.

Lastly, the model is used to investigate the porosity specific surface area relationship in the low porosity range, for which the analytical expression 3ε/r (with ε the particle volume fraction and r the particle radius) is no longer valid due to the packing density limit, and revealed a non-monotonic correlation. Such result is very relevant for silicon anode development as one major hindrance to this chemistry is its limited calendar life due to SEI growth, for which the specific surface area is a key parameter.

*Nanotube generation new feature will be released after article [1] publication.

[1] F. L. E. Usseglio-Viretta, J. H. Kim, J. Preimesberger, N. Neale, P. Weddle, A. Verma, A. M. Colclasure, Guiding the Choice of Carbon Nanotubes Conductive Additives for Silicon Anode Electrode Through Microstructure Scale Analysis, in preparation

[2] F. L. E. Usseglio-Viretta, P. Patel, E. Bernhardt, A. Mistry, P. P. Mukherjee, J. Allen, S. J. Cooper, J. Laurencin, K. Smith, MATBOX: An Open-source Microstructure Analysis Toolbox for microstructure generation, segmentation, characterization, visualization, correlation, and meshing, SoftwareX, 17 (2022) 100915.

Figure 1
Near Infrared Nanosensors Enable Optical Imaging of Oxytocin with Selectivity over Vasopressin in Acute Mouse Brain Slices
Authors: Mun Jaewan , Navarro Nicole , Jeong Sanghwa , Landry Markita P
Published: August 2024

Oxytocin plays a critical role in regulating social behaviors, yet our understanding of its function in both neurological health and disease remains incomplete. Real-time oxytocin imaging probes with spatiotemporal resolution relevant to its endogenous signaling are required to fully elucidate oxytocin’s role in the brain. Herein, we describe a near-infrared oxytocin nanosensor (nIROXT), a synthetic probe capable of imaging oxytocin in the brain without interference from its structural analogue, vasopressin. nIROXT leverages the inherent tissue-transparent fluorescence of single-walled carbon nanotubes (SWCNT) and the molecular recognition capacity of an oxytocin receptor peptide fragment (OXTp) to selectively and reversibly image oxytocin. We employ these nanosensors to monitor electrically stimulated oxytocin release in brain tissue, revealing oxytocin release sites with a median size of 3 µm in the paraventricular nucleus (PVN) of C57BL/6 mice, which putatively represents the spatial diffusion of oxytocin from its point of release. These data demonstrate that covalent SWCNT constructs, such as nIROXT, are powerful optical tools that can be leveraged to measure neuropeptide release in brain tissue.
High-Throughput Evolution of Near-Infrared Oxytocin Nanosensors
Authors: Adams Jaquesta , Navarro Nicole , Komatsu Natsumi , Leem Esther , Sun Xiaoqi , Landry Markita P
Published: August 2024

Neuropeptide oxytocin is known for its crucial regulatory role in various social behaviors, yet our understanding of its function in the brain remains incomplete. There is a demonstrable need for an imaging probe with the requisite specificity and resolution to image endogenous oxytocin signaling. Here, we leverage an evolution-based molecular recognition platform called Systematic Evolution of Ligands by Exponential Enrichment on Carbon Nanotubes (SELEC).1

With an initial library of over 1010 DNA sequences, we conducted six iterative rounds of competitive DNA-SWNCT binding in the presence and absence of oxytocin, respectively termed experimental and control SELEC, followed by adsorbed DNA isolation and enzymatic amplification to prepare the aptamer library for the subsequent round. Deep sequencing analysis and oxytocin sensitivity screening of the most enriched constructs per round revealed that oxytocin incubation enhanced the appearance of highly responsive DNA-SWCNT; only top nanosensors from SELEC experimental rounds 5 and 6 demonstrated a normalized ΔF/F0 greater than 60% in response to 100 µM oxytocin. Furthermore, the most oxytocin-sensitive aptamer was identified as E6#4, the 4th most-enriched sequence from the 6th experimental round. We briefly discuss how machine learning approaches can mine sequencing data from our SELEC experimental rounds to identify top-performing oxytocin nanosensors.

Lastly, we characterize the top nanosensor candidates for sensitivity, selectivity, and reversibility, prior to demonstrating their use to image endogenous oxytocin release in acute brain slices. Our results indicate SELEC can serve as a general approach to evolving molecular recognition and developing imaging probes for complex targets such as oxytocin.

1. Jeong, S.; Yang, D.; Beyene, A. G.; Travis, J.; Bonis-O’donnell, D.; Gest, A. M. M.; Navarro, N.; Sun, X.; Landry, M. P. High-Throughput Evolution of near-Infrared Serotonin Nanosensors; 2019; Vol. 5, pp 3771–3789.

Figure 1
(Nanocarbons Division Award, 2nd Place) Assessment of Biomolecule-Carbon Nanotube Interactions in Machine Perception Nanosensor Arrays
Authors: Wollowitz Jaina Sarris , Goerzen Dana , Kim Mijin , Heller Daniel A.
Published: August 2024

Arrays of chemically modified and DNA-wrapped carbon nanotube-based nanosensors are powerful new tools for biomarker-independent diagnostics. When exposed to patient biofluids, an individual nanosensor can simultaneously interact with many different biological molecules, enabling the detection of collective molecular changes, constituting a “spectral fingerprint”, rather than measuring individual biomarkers. Biomolecule-nanosensor interactions result in quantitative changes in sensor emission that are employed by machine learning models as features to differentiate between sample categories, such as healthy versus disease. To determine the underlying molecular interactions responsible for changes in sensor emission, we conducted single-analyte titrations of biomolecules at physiologically relevant concentrations. Each sensor exhibited optical responses to multiple biological molecules, illustrating the ability of the nanosensors to concurrently interact with many biomolecules to detect subtle molecular shifts occurring in different disease states.
(Invited) Understanding Environmental Effects on Carbon Nanotube Fluorescence for Biomedicine
Authors: Kim Mijin , Jena Prakrit , Cupo Christian , Fagan Jeffrey , Heller Daniel A.
Published: August 2024

Semiconducting single-walled carbon nanotubes (SWCNTs) transduce subtle changes in the microenvironment via modulation of their near-infrared fluorescence with potential applications in sensing and imaging. Controlled liquid filling in an endohedral volume of SWCNTs modifies the optical properties of SWCNTs. However, the effects of endohedral solvent dielectric on the nanotube fluorescence and their structure property relationship for biomedical applications are largely unexplored. In this talk, we discuss the environmental effects on SWCNT fluorescence to improve the spectral response of SWCNT-based imaging and sensing agents. We analyze a large dataset of hyperspectral single-tube images of diverse SWCNT structures with controlled endohedral filling. We investigate the correlations between SWCNT structure and molecular descriptors of filled molecules to explain spectral homogeneity at a single tube level as well as at an ensemble.
Multiplex Bioimaging with Near-Infrared Fluorescent Graphene Quantum Dots
Authors: Valimukhametova Alina , Fannon Olivia , Topkiran Ugur , Dorsky Abby , Sottile Olivia , Gonzalez-Rodriguez Roberto , Coffer Jeffery , Naumov Anton V.
Published: August 2024

Due to high tissue penetration depth and low autofluorescence backgrounds, near-infrared (NIR) fluorescence imaging has recently become an advantageous diagnostic technique used in a variety of fields. However, most of the NIR fluorophores do not have therapeutic delivery capabilities, exhibit low photostabilities, and raise toxicity concerns. To address these issues, we developed and tested five types of biocompatible graphene quantum dots (GQDs) exhibiting spectrally separated fluorescence in the NIR range of 928 – 1053 nm with NIR excitation. Their optical properties in the NIR are attributed to either rare-earth metal dopants (Ho-NGQDs, Yb-NGQDs, Nd-NGQDs) or defect-states (NGQDs, RGQDs) as verified by Hartree-Fock calculations. Moderate up to 1.34 % quantum yields of these GQDs are well-compensated by their remarkable >4-hour photostability. At the biocompatible concentrations of up to 0.5 – 2 mg/mL GQDs successfully internalize into HEK-293 cells and enable in vitro imaging in the visible and NIR. Tested all together in HEK-293 cells five GQD types enable simultaneous multiplex imaging in the NIR-I and NIR-II shown for the first time in this work for GQD platforms. Substantial photostability, spectrally-separated NIR emission, and high biocompatibility of five GQD types developed here suggest their promising potential in multianalyte testing and multiwavelength bioimaging of combination therapies.
(Invited) Near-Infrared Optical Probes for the Detection of Electrolytes
Authors: Budhathoki-Uprety Januka , Dewey Hannah
Published: August 2024

Electrolytes play crucial roles in biological functions including but not limited to activating nerve impulses and regulating muscle, heart, and kidney functions. The imbalance of electrolytes in the body can lead to cardiovascular, neurological, ocular, and muscular dysfunctions. Thus, monitoring of electrolytes levels is important for disease diagnosis and monitoring therapies. Photoluminescent single-walled carbon nanotubes (SWCNTs) exhibit outstanding potential in developing molecular probes for optical detection systems. Surface coatings on carbon nanotubes could facilitate effective molecular interactions enabling targeted nanoscale probes. Here, we report development of carbon nanotube-based optical sensors to detect target electrolytes in biological systems. Photoluminescent SWCNTs were encapsulated within synthetic polymers that present electrolyte recognition motifs along the polymer chains. The resulting polymer-SWCNT complexes allowed optical detection of electrolytes at nanomolar range.
(Invited) Non-Invasive Injectable Nanotube-Hydrogel Formulations for Local Analyte Detection
Authors: Williams Ryan M. , Cohen Zachary , Gaikwad Pooja Vinod , Ryan Amelia K. , Israel Atara R , Roach Arantxa , Rahman Syeda , Alpert David , Weisel Adam C , Nicoll Steven B
Published: August 2024

Rapid, minimally-invasive in situ detection of analytes in vivo remains a goal to study inflammatory signaling molecules, disease biomarkers, and pharmacology of therapeutics. To achieve this, we are using the near-infrared fluorescent properties of single-walled carbon nanotubes (SWCNT) to design sensors for use in live mice. SWCNT fluorescence is responsive to the local environment, in the tissue-transparent window, and does not photobleach, allowing for long-term signal monitoring. In this work, we are exploring several formulations of SWCNT embedded within hydrogels which gel in situ. We have investigated the kinetics of penetration of several classes of analytes—proteins, small molecules, and ions—through the hydrogel and their interaction with SWCNT sensors in vitro. Then, we explored the long-term stability of these nanotube-hydrogel formulations in live mice prior to detection of the chemotherapeutic doxorubicin. In ongoing work, we are exploring disease biomarker-specific sensing and monitoring of inflammatory cytokines in mouse models of disease using this nanotube-hydrogel system. We anticipate long-term applications of this work may include minimally-invasive and rapid clinical diagnostic development.
Diagnostic QR Codes
Authors: Piletsky Stanislav , Heller Daniel A.
Published: August 2024

This work describes the development of a revolutionary new class of universal perception-based sensor capable of diagnosing a wide range of diseases, and compatible with low-cost mass production. This sensor takes the form of an array of fluorescent, environmentally sensitive single walled carbon nanotubes (SWCNTs), resembling a conventional two dimensional QR code. Each group of pixels of the QR code is formed from carbon nanotubes with different surface functionalisation and different environmental sensitivity. Addition of an analyte such as serum causes each pixel to change its fluorescence, generating a unique spectral ‘fingerprint’ characteristic for each disease. A machine-learning approach is then trained to identify the disease based on their corresponding fingerprint.

The basic principle of this technology has been previously described by the Heller Lab for the detection of ovarian cancer, but exclusively in a microplate-based format which requires extensive liquid handling. Translating this technology into a microarray format offers a number of significant advantages, including easier handling, lower production cost, less training required for operation, simpler read-out system that can be based on mobile phone devices and the ability to simultaneously screen for multiple diseases. In this way, this technology advances beyond the current state of the art of SWCNT-based sensors. In a microarray format, hundreds of nanotube assemblies can be analysed simultaneously.

By creating an array of sufficient complexity, we hope to remove the need to tailor an array for a specific disease that act as a universal platform for diagnosis of a range of different diseases. This format also significantly lowers the number of necessary sample handling steps, reducing the potential for user error and the amount of training necessary to employ the sensor.

Figure 1
High-Throughput Evolution Based Near-Infrared Nanosensors with 3D Printed Spheroids for Prostate Cancer Cell Diagnosis and Therapy
Authors: Lee Dakyeon , Jeong Sanghwa
Published: August 2024

Prostate cancer is the second most common cancer in men worldwide, with a mortality rate of 400,000 per year. IHC is used for diagnosis from prostate biopsy, though the precision and accuracy of the current biomarkers such as prostate specific antigen (PSA), prostate specific membrane antigen (PSMA), and alpha-methylacyl-CoA racemase (AMACR) used in IHC test remain controversial. The early detection of presence and progression of prostate cancer and recurrence are still not accurately validated by current biomarkers for prostate cancer. Therefore, many are looking for alternative specific and sensitive prostate cancer biomarkers to improve outcomes. In this study, we generated ssDNA-single walled carbon nanotubes (SWCNT) from a 1018 ssDNA library and evolved ssDNA-SWCNTs that specifically bind to the surface of prostate cancer cells by Cell-SELEX (systematic evolution of ligand by exponential enrichment) method using 3D prostate cancer cell spheroids for positive selection and fibroblasts for negative selection. ssDNA functionalities incorporated into carbon nanotubes enable the specific recognition of molecular target include biomarker proteins, small molecules, and a variety of surface proteins which are unknow as biomarkers. We use the 3D prostate cancer spheroids to more in vivo-like microenvionment that are relatively similar structures to native tissues in terms of cell-cell/cell-ECM interactions resulting in cell migration, cell proliferation, ad stem cell differentiation. It is important as screening tools to find probes that can specifically target prostate cancer cells in in vivo environment. Through sequencing and clustering of the evolved library, we verified that the selected sequence could be detected on the 3D printed spheroid from day 1 using near-infrared (nIR) imaging of SWCNTs. Additionally, we observed an increase in nIR intensity of the target on day 4 indicating the potential for diagnosing different cancer stages. Furthermore, we established that loading drugs onto ssDNA-SWCNTs resulted in cell cytotoxicity. This advanced approach holds promise for enhancing the early detection and treatment of prostate cancer, addressing a critical need in the field.
Endocytosis Pathways of Graphene Quantum Dots
Authors: Topkiran Ugur C. , Valimukhametova Alina , Vashani Diya , Paul Himish , Dorsky Abby , Sottile Olivia , Panda Mudit , Naumov Anton V.
Published: August 2024

Graphene quantum dots (GQDs) have emerged as a forerunner of carbon nanbiootechnology due to their multifunctional delivery and imaging capabilities as they exhibit fluorescence in the visible and near-infrared, high biocompatibility, and water solubility. These properties put GQDs forward as a compelling drug delivery platform that has already been utilized in a variety of applications including the delivery of chemotherapeutics, antibiotics as well as siRNA and CRISPR-based gene therapy. However, cellular entry pathways of this nanomaterial still remain largely undefined. In a number of studies describing GQD cellular internalization different and, often, conflicting results have been presented due to surveying only few endocytosis inhibitors and disregarding their potential off-target pathways. Understanding the cell internalization routes of GQDs is crucial while delivering drugs in different types of cell lines. Herein, we performed a holistic approach to cell uptake studies on GQDs of different charges by the comparative study of their preferred endocytosis paths in non-cancerous (HEK-293) and cancerous (HeLa) cell lines. The concentration and cell viability of GQDs were determined by MTT assays, while their endocytosis paths were investigated through confocal fluorescence microscopy on cells treated for up to 24 hours. The potential for GQD interactions with the cell membrane was also examined via zeta (ζ) potential measurements. Our findings provide insights into the internalization mechanisms of the GQDs into cell membranes of healthy and cancer cells. The optimization of these mechanisms can serve for the enhancement of a variety of novel GQD applications in biomedicine including therapeutic delivery, disease detection through sensing as well as diagnostic imaging.
(Invited) The “Duckweed Dip”: DNA-Wrapped Carbon Nanotubes for Transient Gene Expression
Authors: Ignatova Tetyana , Josephs Eric
Published: August 2024

This study reports on usage of functionalized carbon nanotubes as a transgene delivery cargo into higher plants. We show that aquatic Spirodela polyrhiza (Duckweed) plant, when incubated in a solution containing carbon nanotubes wrapped with a plasmid containing the gene for reporter protein β-glucuronidase (GUS), can directly uptake the DNA-CNTs with high efficiency. The mechanism of the DNA-CNT delivery, directly from growth media, and plasmid release is discussed. We show that transgenes encoded within the plasmids are expressed by the plants. This method allows to avoid using large doses of nanomaterials or direct infiltration of agrobacterium into plant tissue. We expect this new approach for transgene delivery will allow for more efficient plant engineering and can serve as a useful tool in synthetic biology.

ACKNOWLEDGMENT

The work was supported by the National Institutes of Health/National Institute of General Medical Sciences [1R35GM133483] and Department of Defense [Contract #W911QY2220006]. This work was performed in part at the Joint School of Nanoscience and Nanoengineering, a member of the Southeastern Nanotechnology Infrastructure Corridor (SENIC) and National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation [ECCS-1542174].
Near-Infrared Fluorescent Carbon Nanotube Sensors for the Plant Hormone Family Gibberellins
Authors: Boonyaves Kulaporn , Ang Mervin Chun-Yi , Park Minkyung , Cui Jianqiao , Khong Duc Thinh , Singh Gajendra Pratap , Koman Volodymyr B. , Gong Xun , Porter Thomas K. , Chua Nam-Hai , Urano Daisuke , Strano Michael S.
Published: August 2024

Gibberellins (GAs) are a class of phytohormones, important for plant growth, and very difficult to distinguish because of their similarity in chemical structures. Herein, we develop the first nanosensors for GAs by designing and engineering polymer-wrapped single-walled carbon nanotubes (SWNTs) with unique corona phases that selectively bind to bioactive GAs, GA3 and GA4, triggering near-infrared (NIR) fluorescence intensity changes. Using a new coupled Raman/NIR fluorimeter that enables self-referencing of nanosensor NIR fluorescence with its Raman G-band, we demonstrated detection of cellular GA in Arabidopsis, lettuce, and basil roots. The nanosensors reported increased endogenous GA levels in transgenic Arabidopsis mutants that overexpress GA and in emerging lateral roots. Our approach allows rapid spatiotemporal detection of GA across species. The reversible sensor captured the decreasing GA levels in salt-treated lettuce roots, which correlated remarkably with fresh weight changes. This work demonstrates the potential for nanosensors to solve longstanding problems in plant biotechnology.
Development of Biocompatible and Water-Soluble Reduced Graphene Oxide Using Non-Toxic Reducing Agents for Biomedical Applications
Authors: Sundeep Dola , K Varadharaj Eswaramoorthy
Published: August 2024

Graphene's appeal in various applications stems from its unique properties like remarkable electrical conductivity, impressive mechanical strength, expansive surface area, minimal thermal expansion, and a high aspect ratio. However, its insolubility in water poses challenges for its use in the biomedical sector. This research focuses on developing a method to produce water-soluble and biocompatible graphene suitable for biomedical uses. The study successfully created a stable solution of graphene oxide (GO) in water using a non-ionic Pluronic copolymer. This GO-tripolymer solution maintained its solubility in phosphate buffered saline (PBS) and displayed similar UV absorption characteristics to standard GO. Given the toxicity concerns with traditional reducing agents like hydrazine, this study opted for safer alternatives. Non-toxic substances such as ascorbic acid, galactose, and bovine serum albumin were employed to reduce GO, resulting in a reduced GO (RGO) -tripolymer solution that also showed excellent solubility in PBS. The final phase of the study involved assessing the cytotoxicity of these RGO-tripolymers. The results indicated that these novel RGO-tripolymers exhibit low levels of cytotoxicity, making them potentially suitable for biomedical applications.

Keywords: Graphene Oxide (GO), Biocompatibility, Non-Toxic Reducing Agents, Water Solubility and Biomedical Applications
Enhanced PMMA Denture Bases Using Functionalized MWCNT Fused g-C3N4 Nanocomposites
Authors: Jhansi Ragala , Sajjan MC Suresh , Raju Venkata Rama
Published: August 2024

This study presents the development and analysis of a new metal-free nanocomposite that incorporates functionalized multi-walled carbon nanotubes (f-MWCNTs) with graphitic carbon nitride (g-C3N4) for reinforcing polymethyl methacrylate (PMMA) denture bases. The f-MWCNTs were integrated with g-C3N4 nanoparticles, and their structural and morphological features were examined using various techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier-transform infrared spectroscopy (FT-IR), and Raman spectroscopy. A mechanical blending process was employed to synthesize the nanocomposite by mixing 2 wt% of the f-MWCNT/g-C3N4 with PMMA polymer powder, followed by heat curing to form the composite material. Specimens for mechanical testing were crafted to measure flexural strength, impact resistance, compressive performance, and hardness. The findings revealed that the f-MWCNT/g-C3N4-reinforced PMMA composites outperformed standard PMMA in mechanical robustness. Surface examination of the tested samples through SEM showed distinctive dimpling and roughness, indicating a toughened fracture surface in comparison to pure PMMA and g-C3N4 samples. The study concludes that this innovative f-MWCNT/g-C3N4 composite is a promising reinforcement for PMMA denture bases, enhancing both their mechanical and physical attributes.

Keywords: PMMA, functionalization, MWCNTs, Graphitic Carbide Nitride, Mechanical Properties and Denture Base
MoS2 Modified Aluminum Electrode for Detection of Calcium Oxalate through Electrochemical Oxidation
Authors: Sundeep Dola , K Varadharaj Eswaramoorthy
Published: August 2024

The disposal of electronic waste (E-waste), encompassing discarded items such as computers, televisions, fridges, cellphones, and associated cabling, presents a significant challenge to both societal welfare and environmental health. Addressing e-waste management is critical to achieving several of the Sustainable Development Goals (SDGs). This study introduces a novel approach to repurposing aluminum from discarded electrical cables for the creation of high-efficiency electrodes that can detect oxalic acid in human urine samples. The process involves stripping 2mm thick cables to yield 7cm long aluminum rods. These rods are then coated with MoS2 nanoparticles via a hydrothermal synthesis technique. X-ray diffraction (XRD) analysis confirms the presence of MoS2 in the 1T phase, while Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy provide insights into the vibrational modes and chemical composition. Field emission scanning electron microscopy (FESEM) imaging depicts the MoS2 as having a flower-like nanostructure composed of interwoven nanosheets. The resulting nanocomposite sensor demonstrates an enhanced electrical current response, along with notable selectivity and stability, likely due to the combined effects of the MoS2 materials. The sensor’s amperometric signal is directly correlated with the oxalate ion concentration within a range of 10 to 300 μM and exhibits a detection threshold as low as 2 μM. This sensor technique was evaluated alongside a standard colorimetric assay for measuring oxalic acid levels in urine specimens. Findings indicated a strong correlation (R=0.954) between oxalic acid concentrations assessed using the biosensor and those obtained through the colorimetric approach.

Keywords: E-waste, Aluminum Electrodes, MoS2 Nanoparticles, Oxalic Acid Detection, and Electrochemical Sensing,

Figure 1
(Invited) Advance in Single-Wall Carbon Nanotubes Filling
Authors: Forel Salome , Midiladji Bakary Yamaldi , Marichy Catherine , Li Han , Wenseleers Wim , Flavel Benjamin S , Cambre Sofie , Desroches Cerdric
Published: August 2024

Single-wall carbon nanotubes (SWCNTs) are renowned for their outstanding charge carrier mobility, optical, thermal, and mechanical properties. Combining these characteristics with their nanometer-scale diameter renders them highly promising for developing (opto)-electronic devices, where the challenge lies in achieving miniaturization without compromising performance. In addition to their intrinsic characteristics, SWCNTs feature a hollow core that can be filled with various molecules1, resulting in unique one-dimensional hybrids that integrate the properties of the nanotube with those of the encapsulated molecule. This study emphasizes recent advancements, particularly the extensive chirality-sorting2 of these hybrids and a novel methodology utilizing vapor phase infiltration and tailored synthesis strategies to create new fillers. These approaches aim to enhance control over the filling process for finer tuning of the SWCNT doping level or their photosensitization/reactivity capabilities under visible light.

References

[1] S. Cambré et al. Small, 2021 17, 2102585

[2] S. Forel et al. Nanoscale, 2022, 14, 8385
(Invited) Sulfur Addition Reaction Onto Carbon Nanotubes
Authors: Pimonov Vladimir , Sprocq Simon , Haddad Elie , Rochefort Alain , Martel Richard
Published: August 2024

The surface chemistry of carbon nanotubes is of interest for material’s processing and modification of their electronic and optical properties. Here, we present a new sulfur addition reaction to single-wall and multi-wall carbon nanotubes. Depending on the reaction conditions, we find strong evidence of addition reaction, which produces covalent bonding between sulfur atoms and the nanotube surfaces. Raman, TEM, and photoemission results are consistent with the formation of covalent S-C bonds on the sidewalls. DFT calculations also support a formation of sulfur-carbon bonding and predict electronic and vibrational states that are in good agreement with the experimental results. Based on a comparison between theory and experiments, we propose a stable episulfide (GS) grafting, which consists of of a sulfur atom bridging two carbon atoms repeated over the nanotube surface.