bluuebunny/crossref_metadata_2025 huggingface dataset:
The Influence of Calendering Process on the Graphite Anode
Authors: Zhu Wendi , Seo Minja , Liu Xin , Lim Soo Yoen , Rashti Ali , Jazowski Claudia , Oh Hyukkeun
Published: August 2024

Calendering, or pressing, is the final property-defining process for battery electrode manufacturing to maximize the volumetric capacity of the cell through the compaction of an electrode between two large calender rollers12. On one hand, it can reduce the porosity of battery materials thus increase the conductivity of the materials. On the other hand, it can control the thickness of the electrodes, making sure it is uniform and proper thickness to guarantee the minimal variation in the cell thickness, reaching even stack pressure for module assembly and impacting the thermal management [3]. The calendering process significantly influence the performance of lithium-ion battery (LIB).

Graphite anode coating on Cu foil was chosen as our baseline coating for this calendering process investigation. The slurry was mixed in a planetary and dispersive mixer and then coated using reverse comma coating method by a scale-up coater with drying zones of 70 °C. Then the coating was calendered by a calendering machine at various conditions.

Calendering, though seemingly a simply process, is influenced by several different parameters significantly. In this study, we systematically investigated the calendering process by carrying-out a Design-of-experiment (DOE). The following calendering parameters were investigated: the parameters of calendering machine gap size, calendering pressure, and the speed of the coating web. The calendered graphite coating was then measured for the morphology by scanning electron microscopy (SEM), the pore size change by BET surface area measurement, and Direct current internal resistance (DCIR) by building half cells and cycling and Electrochemical Impedance Spectroscopy (EIS) at 50% State-of-Charge (SOC).

The result showed that pressure is the most critical parameter for calendering and the internal resistance and ionic conductivity changes in response to the calendering parameters. The half-cell with calendering at the pressure of 37 MPa, gap size targeted for 30% porosity, the BET surface area around 0.75 m2/g showed highest cell capacity and lowest internal resistance.
Exploring Sodium Gadolinium Silicate as a Solid Electrolyte for Next-Generation Sodium Batteries
Authors: Sivakumaran Abinaya , Samson Alfred Junio , Bristi Afshana Afroj , Surendran Vishnu , Butler Shantel , Reid Samuel , Thangadurai Venkataraman
Published: August 2024

Sodium-ion batteries (SIBs) represent a promising alternative to commercially prevalent Lithium-ion batteries (LIBs), primarily attributed to the economic feasibility and widespread availability of sodium resources. Solid-State Sodium Batteries (SSSBs) have garnered significant attention owing to their capacity to mitigate safety risks associated with organic liquid electrolytes by utilizing solid electrolytes. Additionally, they offer higher energy density and wide operational temperature for next-generation, cost-effective battery technology.[
1
] Sodium rare-earth silicates are emerging as a solid electrolyte with enhanced ionic conductivity of 10-3 S cm-1 at room temperature (RT), alongside notable mechanical stability and a wide electrochemical window, attributed to their three-dimensional framework structure.[
2
] In this study, sodium gadolinium silicates were synthesized through a conventional solid-state method followed by high-temperature sintering. The highest ionic conductivity of 7.25 x 10-4 S cm-1 at room temperature was achieved through sintering at 1075 °C. Galvanostatic cycling experiments were conducted to assess the compatibility of Na metal with the silicate solid electrolyte, achieving a critical current density (CCD) of 0.4 mA cm-2 and long-term stability for 6000 h at 0.1 mA cm-2. Charge-discharge studies employed a battery configuration comprising Na metal anode, silicate solid electrolyte, and Na3V2(PO4)3 cathode, demonstrating excellent capacity retention of 98% after 100 charge-discharge cycles at 0.1 C.[
3
] These findings highlight the potential of sodium gadolinium silicate as a promising solid electrolyte for next-generation sodium batteries, characterized by its high ion conductivity and stable interface compatibility.

References

[1] C. Zhou, S. Bag and V. Thangadurai, ACS Energy Lett., 2018, 3, 2181–2198.

[2] A. Sivakumaran, A. J. Samson and V. Thangadurai, Energy Technol., 2023, 2201323.

[3] A. Sivakumaran, A. J. Samson, A. A. Bristi, V. Surendran, S. Butler, S. Reid and V. Thangadurai, J. Mater. Chem. A, 2023, 11, 15792–15801.
In-Situ Ionothermal Synthesis of Nanoporous Carbon/Oxide Composites: A New Key to Functional Separators for Stable Lithium-Sulfur Batteries
Authors: Tao Runming , Tan Susheng , Sun Xiao-Guang , Lyu Xiang , Yang Jun , Xie Di , Du Zhijia , Pupek Krzysztof , Dai Sheng , Li Jianlin
Published: August 2024

Lithium–sulfur batteries (LSBs) are promising high-energy energy storage systems. However, conventional polypropylene-based separator cannot avoid polysulfides shuttling and thus dramatically impedes the practical LSBs. Herein, a novel in-situ ionothermal synthesis strategy that concurrently applies ionic liquid as the solvent, template and high-yield carbon source is proposed for facile preparation of nanoporous carbon/oxides composites. Theoretical and experimental studies suggests that the composites exhibit features of high polarity, Ti3+ doping, oxygen vacancy, heteroatom doping, abundant defects and high electronic conductivity for fast trapping and conversion of polysulfides in LSBs. As functional materials towards separator modification, the assembled high-loading LSBs deliver enhanced performance due to the suppression of shuttle effects. Furthermore, the proposed strategy exhibits excellent versatility and good practicality.
Carbon-Interconnected Sodium Vanadium Phosphate Microparticles: Material Characterizations and Na+-Storage Performances
Authors: Chang Sheng-Ming , Hung Tai-Feng
Published: August 2024

Sodium vanadium phosphate (Na3V2(PO4)3) with continuous carbon-coating (NVP/C) has been regarded as one of the most promising cathode materials for sodium-ion batteries (SIBs) owing to the three-dimensional sodium superionic conductor (NASICON) structure for fast sodium-ion migrations, high theoretical energy density (ca. 400 Wh/kg), and good thermal stability (450°C). In this study, carbon-interconnected NVP/C microparticles (C@NVP/C MPs) were successfully synthesized by employing ascorbic acid and sodium-containing polymer as dual carbon sources, followed by calcination at 750°C in an argon atmosphere. The resulting C@NVP/C MPs not only exhibited great crystallinity, high purity, and size of 5-10 μm but also possessed carbon amounts of 9.9 wt. %, as confirmed through the X-ray diffractometer, scanning electron microscope, and thermogravimetric analyzer, respectively. The cyclic voltammogram revealed that the potential difference between oxidation and reduction peaks of C@NVP/C (174 mV at 0.1 mV/sec and 382 mV at 1.0 mV/sec) was less than that of the NVP/C nanoparticles (197 mV at 0.1 mV/sec and 391 mV at 1.0 mV/sec) that were synthesized without adding the sodium-containing polymer. Moreover, the same reversible capacity was delivered from C@NVP/C, i.e., 75 mAh/g at 0.1 C. Those improved electrochemical performances could be attributed to the well-interconnection between NVP/C and carbon originating from the pyrolysis of sodium-containing polymer, creating additional electronic transportation pathways. Accordingly, the C@NVP/C MPs synthesized in the present study are reasonably anticipated to be promising cathode materials for SIBs.
(Invited) Towards Understanding the Competition of Electron and Energy Transfer in “Molecular” Nanographenes on the Example of Hexa-Peri-Hexabenzocoronene
Authors: Guldi Dirk Michael
Published: August 2024

Bottom-up strategies have allowed the synthesis of “molecular” nanographenes with full control over size, shape and functionality. In recent years, the progress on wet chemical approaches, oxidative cyclodehydrogenation amongst all, has been the foundation to the synthesis of an impressive number of soluble and well-defined molecular nanographenes. The level of control over nanographene syntheses has allowed a fine-tuning of the photophysical and electrochemical properties and, in turn, has a compelling potential in the field of material science. In this regard, understanding and harnessing the competition between electron transfer and energy transfer in nanographenic systems is of utmost importance. However, a comprehensive structure-property relationship remains still an open aspect. In the present review we describe a large variety of hexa-peri-hexabenzocoronene (HBC)-based nanographenes obtained through wet chemical strategies and linked – either covalently or non-covalently – to porphyrins, rylenes, fullerenes, etc. Particular attention was placed on the optical, electrochemical and excited-state properties.
Insights into the Synaptic Properties of Dopamine Release Revealed by Single Walled Carbon Nanotube Biosensors
Authors: Bulumulla Chandima , Beyene Abraham G.
Published: August 2024

It is thought that there are two distinct modes of chemical neurotransmission, referred to as fast (synaptic) transmission and slow (volume) transmission. Fast transmission, mediated by ligand-gated ionotropic receptors, operate with millisecond temporal and nanometer spatial precision in excitatory and inhibitory synapses, primarily mediated by glutamate and GABA, respectively. In contrast, slow transmission relies on activation of G-protein coupled receptors (GPCRs) and is mediated by several classes of neuromodulators, including dopamine. Neuromodulators are thought to operate at temporal scales that range from hundreds of milliseconds to minutes, with a spatial specificity that is insufficiently understood but generally described as “diffuse”. In this work, we provide new evidence that shows the spatial precision of dopamine transmission is highly reminiscent of the spatial properties of signaling mediated by the fast acting neurotransmitters.

To gain this insight, we used an optical assay named “DopaFilm” that is based on oligonucleotide functionalized single walled carbon nanotube dopamine sensors (nanosensors). Primary dopaminergic neurons were grown on top of glass coverslips functionalized with nanosensors, which enabled visualization of dopamine exocytosis events in single release sites under a continuous 785nm excitation laser. In axonal arbors, DopaFilm can report evoked and spontaneous dopamine release events with high signal to noise ratios of up to 50. Recording on DopaFilm revealed dopamine release is fast, calcium-dependent, and reliant on similar presynaptic protein machinery employed by fast neurotransmitters. These findings challenge the notion that dopamine is a slow transmitter; however it doesn’t preclude the possibility of imprecise spatial signaling, consistent with volume transmission theory. More recent data from our lab now challenges the spatial characteristics of volume transmission model as currently understood in the literature. In this talk, I will discuss new insights gained on dopamine signaling including clear examples of precise spatial arrangements of dopamine release sites, and ultrastructural, biochemical and spatial transcriptomic data that shows that neuromodulatory action can be highly spatially precise in nature.
Single Molecule Imaging of Sp3 Functionalized Ultrashort Carbon Nanotubes for Deep Brain Tissue Investigation
Authors: Nandi Somen , Estaun-Panzano Juan , Lambert Benjamin Paul , Calaresu Ivo , Groc Laurent , Bezard Erwan , Cognet Laurent
Published: August 2024

Near-infrared (NIR) fluorescence microscopy has attracted significant attention for in vivo deep tissue imaging due to the combination of low light scattering and absorption by the tissues, resulting in good light penetration depth, especially in the NIR-II window (~1000–1350 nm). In this context, NIR photoluminescence (PL) (λem ~ 900–1400 nm) of single-walled carbon nanotubes overlapping with the so-called “tissue transparency window” laid the foundation for their use in bioimaging and sensing applications. Interestingly, although ultrashort carbon nanotubes (usCNTs) had long been sought for their advantages of mimicking bio-molecular dimensions, it is only when sp3 defects introduced bright fluorescent usCNTs could be generated [1]. In this work, we demonstrate the efficient preparation of bright fluorescent usCNTs specifically designed for biological applications, and we show how to create bright usCNTs wrapped by a biocompatible encapsulating agent (phospholipid-polyethylene glycol, PL-PEG). More precisely, we adapted a synthesis route where the sp3 functionalization is followed by chemical cutting [2]. We will present their full characterization and demonstrate their performance for deep tissue imaging in neuroscience. More precisely, our results performed on live brain tissue allow us to analyze their length specific behaviors in different compartments of mouse brains in comparison to the long sp3 functionalized CNTs [3].

References

[1] N. Danne, M. Kim, A. G. Godin, H. Kwon, Z. Gao, X. Wu, N. F. Hartmann, S. K. Doorn, B. Lounis, Y. Wang, L. Cognet, ACS Nano, 2018, 12, 6059−6065.

[2] Y. Li, X. Wu, M. Kim, J. Fortner, H. Qu, Y. Wang,Chem. Mater
., 2019, 31, 4536-4544.

[3] Nandi et al, in preparation.
(Nanocarbons Division Poster Award, Third Place) Development of an Optical Probe for the Detection of Steroid Hormones
Authors: Dewey Hannah , Thompson Jacob , Fisher Matthew , Budhathoki-Uprety Januka
Published: August 2024

Hormones play major roles in several biological processes. Steroid hormones are crucial for reproductive maturation in women. Abnormal steroid hormones (e.g., estrogen) levels have several pathological conditions, including ovarian failure, bone loss, or increased risk for breast cancer. Thus, accurate and precise detection of steroid hormone levels is crucial for timely health interventions. The current gold standard for steroid hormone detection is immunoassays. Optical measurement technologies are promising alternatives to traditional immunoassays. Optical tools could provide a novel platform for direct, sensitive, and specific measurements of target analytes. Due to their non-photobleaching near-infrared fluorescence, high optical sensitivity, high stability, and sizes within the nanoscale, photoluminescent single-walled carbon nanotubes have great potential for a rapid, sensitive, and specific detection. Here, we investigate an optical biosensor fabricated with SWCNT for hormone detection in biofluids.
Impact of Surfactant to DNA Exchange on Carbon Nanotube Emission for Biosensing Applications
Authors: Keblish Erin Elizabeth , Kim Mijin , Goerzen Dana , Heller Daniel A.
Published: August 2024

Synthesis methods of single walled carbon nanotubes (SWCNTs) result in mixtures of different chiralites. Chirality affects SWCNT diameter as well electronic and optical properties. For use in optical sensors, mono-chirality SWCNTs offer better signal compared to chirality mixtures. A common chirality separation method is aqueous two-phase extraction, where solutions of surfactants are used to partition SWCNTs based on chirality. The process results in a mono-chiral solution of SWCNTs wrapped in surfactant, however for sensing applications SWCNTs need to be exchanged from this surfactant wrapping to single stranded DNA wrapping. Concerns have been raised about residual surfactant remaining on the SWCNT surface after the exchange process and the effect this would have on the sensing capabilities of the SWCNT. To investigate this, we compared the emission spectra of covalently modified SWCNTs sonicated directly in DNA to that of SWCNTs exchanged from surfactant into DNA. We observed that emission from exchanged SWCNTs was red shifted compared to direct DNA sonicated SWCNTs, however exchanged SWCNTs had similar environmental responsivity to direct DNA sonicated SWCNTs.
Development of a Plasma-Based Nanosensor Platform for Triage of Neurological Tumors
Authors: Goerzen Dana , Kim Mijin , Schroff Chanel , Galbraith Kristyn , Wollowitz Jaina Sarris , Snuderl Matija , Heller Daniel A.
Published: August 2024

Neurological tumors have diverse etiologies and treatments. Presently, diagnostic technologies such as MRI or CT scans are limited by poor resolution, and thus imprecise identification of tumor classes. As a result, diagnostic methods rely on highly invasive intracranial biopsies for conclusive tumor identification. Development of non-invasive methods to accurately identify tumor class may lead to earlier and more accurate diagnoses, enabling prompt and targeted treatment strategies. To address this unmet clinical need, we report the development a molecular-recognition-based nanosensor array that can accurately identify a molecular fingerprint of glioma and meningioma from plasma. We developed this capability using sensor arrays of chemically modified carbon nanotubes that can transduce subtle differences in the physicochemical properties of molecules in biofluids via sensitive molecular binding interactions. Using high-throughput near-infrared fluorescence spectroscopy, we screened 23 chemically modified (6,5) carbon nanotubes sensors in 324 patient plasma samples. We trained machine learning models to classify sensor responses as coming from either glioma or meningioma tumors. The best performing models were able to achieve a positive predictive value of 0.75. Sensor feature analysis revealed a set of spectral features positively associated with class differentiation. This work has the potential to aid clinical care by facilitating the early triage of different types of tumors to provide better treatment options for patients.
Spectral Fingerprinting Coupled Machine Learning: An Optimized Tool for Cellular Phenotype Identification
Authors: Nadeem Aceer , Lyons Sarah , Kindopp Aidan , Roxbury Daniel
Published: August 2024

Spectral fingerprinting has emerged as a powerful tool for unraveling intricate interactions between the intracellular environment and nanomaterials. This study leverages spectral fingerprinting to deepen our comprehension of the interplay between macrophages and nanotubes, utilizing their Near Infrared fluorescence to discern cellular characteristics. This study employs Raman microscopy to showcase significant differences in defect ratio and intracellular processing of nanotubes, among macrophage phenotypes. The near infrared features of DNA-SWCNTs serve as distinctive markers for identifying different macrophage phenotypes. Here we use a support vector machine learning model to accurately identify M1 and M2 macrophages, achieving an impressive accuracy of 95%. The implications of this research extend to the development of nanomaterial-based platforms for cellular identification, holding promise for potential applications in real time in-vivo cell differentiation monitoring.

This study underlines the pivotal role of nanotubes in delineating the diverse micro-environments of distinct macrophage phenotypes for clinical research. It emphasizes the potential of short DNA sequences and machine learning in characterizing and classifying cell phenotypes, offering valuable insights into the intersection of nanotechnology and biomedical research.

This innovative approach holds great promise in advancing our understanding of dynamic cellular processes, disease states, disease progression, and response to stimuli in-vivo. The platform’s sensitivity to minute changes in the Near Infrared spectrum positions it as a valuable tool for researchers and clinicians. It facilitates the real time monitoring of cellular behavior within living systems, offering insights that extend to both fundamental research and clinical applications. The implications of this research pave the way for future developments in nanotechnology and biomedicine, bridging the gap between spectral analysis and cellular dynamics for enhanced diagnostic and therapeutic interventions.

Figure 1
The Effect of Carbon Nanotube Enantiomers in Macrophages
Authors: Quiroz Reyes Carlos Jose , Liu Te-I , Raabe Marco , Nguyen Ai-Phuong , Canales Chavez Ricardo Ernesto , Lin Ching-Wei
Published: August 2024

The inherent asymmetry within our bodies enables remarkable selectivity to chiral molecules. This selectivity is crucial because one stereoisomer may induce undesired effects, remain inactive, or, in the worst case, exhibit toxicity. Even though the knowledge of the interactions of stereoisomer, including enantiomer, with biological systems has been accumulated to a certain extent, our understanding of the body's response to single-wall carbon nanotube (SWCNT) enantiomers is very limited. In this study, we aimed to provide evidence of how macrophages respond to (6,5) enantiomers, finding the importance of their helicity at the nanometer scale. To achieve this, we first separated the left-handed (M) and right-handed (P) enantiomers of (6,5) using aqueous two-phase extraction (ATPE) and conducted a surfactant displacement procedure to coat them with single-stranded DNA. Following the separation and displacement processes, we quantified reactive oxygen species (ROS) as a crucial criterion for assessing the potential influence of the (6,5) enantiomers on macrophages. Considering ROS's role as a signaling molecule at a physiological level, quantifying ROS allows us to determine which enantiomer is more related to oxidative stress and, subsequently, nanotoxicity. To corroborate our findings, we conducted parallel assessments of cells, focusing on metabolic activity, cellular uptake, and proliferation. However, the complexity of the SWCNTs including the coating and aggregation states makes the observed cellular behaviors difficult to explain, even though the SWCNTs have been purified to the enantiomer level. In this regard, we probed the fluorescence signal to evaluate the aggregation states of SWCNTs, hoping to extract the sole enantiomer effects within biological environments. Our results improve the overall comprehension of the relation between SWCNT enantiomeric properties and macrophage responses, emphasizing the distinction between the left and right forms of SWCNTs and providing valuable insights for future biomedical applications of SWCNTs.
(Invited) Optimising CNT-FET Biosensor Design: Tuning Biomolecule Interfaces for Aptamer-Biomarker Sensing and Beta-Lactamase Detection
Authors: Palma Matteo
Published: August 2024

We will present different strategies to control the assembly of single walled carbon nanotube (SWCNT)-biomolecule interfaces towards the fabrication of bioelectronic devices, with a focus on the real-time biosensors with engineered aptamer and protein interfacing. In particular, we will report on the fabrication of nanoscale biosensing devices designed to present biorecognition moieties (aptamers and proteins) in defined orientations; this allowed us to control the local electrostatic surface presented within the Debye length, and thus modulate the conductance gating effect upon binding incoming targets, from biomarkers associated to stress and (neuro) trauma, to classes of enzyme relevant to antimicrobial resistance (beta-lactamases).

Our efforts focused in particular on using beta-lactamase binding protein (BLIP2) as receptor due to its potential as a biosensor for the most common antibiotic degrading enzymes, the beta-lactamases (BLs). Attaching BLIP2 at single designed residues positions directly to SCNTs using genetically encoded phenyl azide photochemistry, our devices were able to successfully detect the two different BLs, TEM-1 and KPC-2. The changes in conductance closely matched the predicted electrostatic profile sampled by the CNTs on BL binding.

These studies highlight the key role transducer-biomolecule interfaces play in biosensing devices, and the need to control and tune by design the electrostatic gating, for more effective and optimal CNT-FET biosensor construction.
(Invited) Single-Walled Carbon Nanotube Functionalization Strategies for Monitoring Enzymatic Activity and Inhibition
Authors: Bisker Gili
Published: August 2024

Semiconducting single-walled carbon nanotubes (SWCNTs) fluoresce in the near-infrared range, which overlaps with the transparency window of biological samples, and they do not photobleach or blink. Moreover, they benefit from biocompatibility and the large surface area available for functionalization. Using tailored surface functionalization, SWCNTs can be rendered optical nanosensors, such that surface binding events or changes in the local proximity of the nanotubes translate to a modulation of the emitted fluorescence. This approach was successfully used to demonstrate the detection of small molecules, volatiles, bacteria, microRNA, proteins, metals, self-assembly processes, and active processes in vivo. We will discuss different strategies for monitoring enzymatic activity and inhibition using SWCNT-based sensors, including the incorporation of the enzyme’s target bond within a synthetic molecular complex used for suspending the SWCNTs, or by the detection of the product of the enzyme hydrolytic activity. We will also highlight recent applications of these techniques in clinically relevant samples. These findings not only showcase the potential of near-infrared fluorescent SWCNT in tracking enzymatic activity but also underscore their promising role in advancing biomedical research and applications.
(Invited) Developing Optical Nanosensors for Biomedical Applications
Authors: Yaari Zvi
Published: August 2024

Novel biomedical application technologies have been rapidly improved in the past few decades. Despite recent technological progress, significant challenges persist toward more accessible, precise, inexpensive, rapid, automated, and patient-facing methods. Optical spectroscopic and imaging technologies have multiple advantages to current practices, such as versatility, fast and robust signal, and noninvasive and nondestructive probing techniques that can be easily integrated into current medical devices such as catheters, endoscopes, or biopsy needle channels. Single-walled carbon nanotubes (SWCNTs) have been developed as near-infrared (NIR) fluorescent nanosensors and demonstrated in vitro and in vivo with great interest for using them in biological and clinical applications and the methods designed to probe them. The advantages of SWCNT include resistance to photobleaching and high sensitivity towards biological environments.

Gynecologic cancers are challenging to diagnose. Patient prognosis and quality of life are affected substantially by this problem. In this talk, I will present recent work on developing new technologies to improve gynecological cancer detection and grant new research tools for understanding fundamental mechanisms in cancer development using liquid biopsy and in vitro and in vivo sensor approaches. With artificial intelligence algorithms, we harness SWCNTs' unique optical properties and sensitivity to develop intelligent optical sensors. We developed platforms to detect multiple gynecological cancer biomarkers as implantable devices in patient biofluids and the uterine cavity. Applying machine learning algorithms to analyze the optical response of the sensors enabled the precise detection of multiplexed biomarkers. In addition, when implanted in human uteri, the sensors detected the biomarkers and successfully differentiated between benign and malignant cases. These technologies will significantly improve diagnostics and cancer research, leading to robust, point-of-care technologies for early-stage diagnosis.

References

[1] Yaari, Z. et al., Science Advances, 2021.

[2] Yaari, Z. et al., Nano Letters, 2020.
(Invited) Chiral Graphene Quantum Dot Enhanced Drug Loading into Exosomes
Authors: Wang Yichun
Published: August 2024

As nanoscale extracellular vesicles secreted by cells, exosomes have enormous potential as safe and effective vehicles to deliver drugs into lesion locations. Despite promising advances with exosome=based drug delivery systems, there are still challenges to drug loading into exosomes, which hinder the clinical applications of exosomes. Herein, we report an exogenous drug-agnostic chiral graphene quantum dots (GQDs) exosome-loading platform, based on chirality matching with the exosomal lipid bilayer. Both hydrophobic and hydrophilic chemical and biological drugs can be functionalized or adsorbed onto GQDs by π–π stacking and van der Waals interactions. By tuning the ligands and GQD size to optimize its chirality, we demonstrate drug loading efficiency of 66.3% and 64.1% for doxorubicin and siRNA, which is significantly higher than other reported sEV loading techniques. These drug/siRNA loaded exosomes can be applied to cancer treatment and immunotheraoy, which showed significant higher efficacy due to the efficient encapsulation of drugs or genetic materials.As nanoscale extracellular vesicles secreted by cells, exosomes have enormous potential as safe and effective vehicles to deliver drugs into lesion locations. Despite promising advances with exosome=based drug delivery systems, there are still challenges to drug loading into exosomes, which hinder the clinical applications of exosomes. Herein, we report an exogenous drug-agnostic chiral graphene quantum dots (GQDs) exosome-loading platform, based on chirality matching with the exosomal lipid bilayer. Both hydrophobic and hydrophilic chemical and biological drugs can be functionalized or adsorbed onto GQDs by π–π stacking and van der Waals interactions. By tuning the ligands and GQD size to optimize its chirality, we demonstrate drug loading efficiency of 66.3% and 64.1% for doxorubicin and siRNA, which is significantly higher than other reported sEV loading techniques. These drug/siRNA loaded exosomes can be applied to cancer treatment and immunotheraoy, which showed significant higher efficacy due to the efficient encapsulation of drugs or genetic materials.
Developing Cytometries for Carbon Nanotube Fluorophores
Authors: Liu Te-I , Wang Jhih-Shan Jason , Nguyen Ai-Phoung , Raabe Marco , Lin Ching-Wei
Published: August 2024

Semiconducting single-wall carbon nanotubes (SWCNTs) have been demonstrated to be promising in vivo diagnostic probes due to their unique fluorescent properties in the short-wave infrared (SWIR), which ranges from 900 to 1,700 nm. The development of in vivo diagnostic modalities using SWCNT-based fluorescent probes will require fundamental studies of these probes in the cellular level, where many advanced bioanalytical tools need to be utilized for understanding their efficacies, side effects and many other metabolic and pathologic issues. Therefore, expanding the standard fluorescent-based analytical instruments from the visible to the SWIR range is necessary. In this work, we introduce SWIR-based flow and image cytometries for the cellular studies using racemic (6,5). We treated ssDNA-coated (6,5) with pre-incubated RAW macrophages and collected these treated cells for cytometric measurements. The absolute mass of the (6,5) in the cells was deduced and the detection limits of both systems were found to be in the level of femtograms of (6,5) per cell within a reasonable time of measurements. We will also conduct multi-channel measurements by combining the SWIR and visible channels for correlating SWCNT dose and cellular responses. We hope our study will fulfil this missing SWIR bioanalytical tool for SWCNT applications in the physiological systems.
(Invited) Microwires Based on Carbon Nanotubes for Medicine and Biology
Authors: Alvarez Noe T , Ruhunage Chethani , Dhawan Vaishnavi , Cui Xinyan Tracy
Published: August 2024

Flexible and biocompatible microwires are generally employed for biomedical implants in medicine, more specifically in neuroscience. These microwires used as electrodes need to be chemically inert and electrically conducting in order to record and stimulate the electrical activity of neurons in the nervous system. The electrodes available today are made of metals and silicon that lack the required flexibility resulting in a mechanical mismatch between soft tissues and rigid metals which induces faster biofouling and inconsistent performance for long-term implants. Biofouling triggered by inflammatory responses dramatically affects the performance of neural electrodes, resulting in decreased signal sensitivity and consistency over time. Thus, long-term clinical applications require electrically conducting flexible electrode materials with reduced dimensions and antibiofouling properties. These characteristics reduce the degree of inflammatory reactions and increase the lifetime of implanted neural electrodes. Carbon nanotubes (CNTs) are well known for their flexibility, electrical conductivity, and chemical inertness. This talk will report the fabrication of CNT fibers and subsequent coating using a biocompatible flexible polymer hydrogenated nitrile butadiene rubber (HNBR). Unlike the gold standard parylene-C coating that requires processing under vacuum, dissolved elastomer HNBR polymer can deposit uniform coating in solutions. Polymer dip-coating has been employed for uniform and continuous coating of meters-long CNT fibers of multiple diameters (26 to 66 mm) to evaluate the robustness of the approach. The polymer was able to provide uniform thickness and pinhole-free coating along the CNT fiber. Furthermore, the polymer has been shown to be biocompatible when tested with in vitro elusions and culturing neurons. The covalent functionalization of CNT microwire cross-section interfacing with the neurons using hydrophilic, anti-biofouling phosphorylcholine molecules displays reduced impedance and increased hydrophilicity. These CNT microwire assemblies are promising for the development of low-impedance neural electrodes with higher hydrophilicity and protein-fouling resistance to inhibit inflammatory responses.
Engineered Carbon Nanocatalysts for Homocysteine Catabolism
Authors: Chen Alan , Miyauchi Rei , Krishna Vijay
Published: August 2024

Cystathionine-β-synthase (CBS) deficiency or homocystinuria (HCU) is a rare inherited disorder with main clinical features of osteoporosis, dislocation of the optic lenses, learning difficulties and thromboembolism. CBS is a key enzyme in methionine catabolism pathway. CBS deficiency impairs the conversion of homocysteine (Hcy) to cystathionine, which leads to extracellular buildup of Hcy in toxic concentrations. Patients with CBS deficiency have elevated plasma Hcy and methionine.

Currently, there is no FDA approved drug for CBS deficiency. Clinical treatment options are low-protein diet and betaine for severely affected patients, and vitamin supplementation for mildly affected adults. Artificial protein-based enzymes for Hcy treatment are in clinical trials. However, protein-based artificial enzymes can be immunogenic, prone to intracellular modifications, and the treatment may not be viable after few months.

We propose a novel nanotechnology-based approach for the treatment of CBS deficiency. Carbon nanomaterials with multiple unsaturated carbons provide an excellent scaffold for engineering enzyme mimicking catalysts. We have designed carbon nanomaterial based catalytic artificial enzymes (CAEs) by surface engineering to mimic metabolic enzymes that catabolize Hcy under physiological conditions. Using a combination of paper chromatography and H1-NMR, our lab has shown that CAE can breakdown homocysteine and produce hydrogen sulfide similar to CGL enzyme. The degree of surface functionalization as well as surface curvature has profound effect on specificity and catalysis. We have shown that CAE can enter cells and lower homocysteine levels in cellular models. In preliminary studies, CAE was able to lower serum homocysteine levels in a murine model. Further studies will involve safety assessments of CAE as a treatment for HCU.
Graphene in Medicine: Revolutionizing Healthcare through Advanced Nanomaterials
Authors: Umadevi Kovuri , Ali Mohd Imran , Indira K
Published: August 2024

Nanomaterials, particularly carbon-based structures like graphene nanostructures, have revolutionized science and technology, offering groundbreaking advancements in bioengineering and medicine. These developments have enhanced our ability to detect, diagnose, and treat diseases, leading to significant innovations in therapy methods. The evolving field of graphene synthesis, with its less complex and more effective strategies, has captured the scientific community's interest. This review seeks to delve into the latest progress in the creation and application of graphene-based nanomaterials, especially their role in biomedical applications, with a primary focus on drug delivery systems. Graphene has emerged as a versatile material in the medical field. Its application as a sensor in monitoring vital parameters such as blood pressure and blood sugar levels, as well as nitric oxide levels in oxygen, has been noteworthy. In dentistry, graphene, combined with specific peptides, can identify individual bacterial strains, aiding in accurate disease diagnosis. Its role as an immunosensor is also significant, enabling the detection of trace amounts of substances like growth hormones. In the battle against cancer, graphene has shown promising results. It is actively being researched for broader medical applications including cancer therapy, diagnostic tools for diseases, tissue engineering, implants, DNA sequencing, biomarker identification, genetic material transfer, and in the combined fields of biomedical imaging and neuroscience. This review underscores the potential of graphene in medical science. As research continues, it is anticipated that graphene-based technologies will significantly contribute to personalized therapies, enhancing healthcare quality. The conclusion of this review emphasizes the need for ongoing research to explore and refine graphene-derived smart therapeutics. Such advancements will not only improve patient care but also drive us towards the zenith of human welfare, showcasing the transformative impact of nanotechnology in healthcare.

Keywords: Graphene, Biomedical Applications, Drug Delivery Systems, Diagnostic Innovations and Personalized Therapeutics
Aqueous Two-Phase Extraction of Single-Chirality Carbon Nanotubes with Functionalized ssDNA for Biomarker-Specific Antibody Conjugation
Authors: Williams Ryan M. , Ryan Amelia K. , Parveen Sadiyah , Israel Atara R , Cohen Zachary , Gaikwad Pooja Vinod
Published: August 2024

Multiplexed detection of biomarkers for cancer and chronic inflammatory diseases is necessary to improve diagnostic sensitivity and specificity. Our prior studies and that of others has used near-infrared fluorescent single-walled carbon nanotubes (SWCNT) as sensor transducers because of their sensitivity to the local environment, photostability, and emission in the tissue-transparent window. That work engineered the SWCNT surface through non-covalent interactions with short ssDNA oligonucleotides containing a functional group to which a biomarker-specific antibody was conjugated. Further, previous work by other groups has demonstrated the ability to obtain single SWCNT chiralities using the aqueous two-phase extraction (ATPE) technique with non-functionalized ssDNA sequences. Here, we have incorporated primary amine-functionalized ssDNA sequences into the ATPE separation technique to obtain individual SWCNT chiralities with functionalized ssDNA. To those primary amine-functionalized ssDNA-SWCNT complexes, we conjugated antibodies against two inflammatory cytokines. We investigated the sensitivity and specificity of these individual SWCNT chirality sensors specific to two biomarkers together in buffer and serum, finding that each chirality responds specifically only to its cognate biomarker and not the other. This is the first demonstration of single-chirality, molecularly-specific multiplexed SWCNT sensors. It forms the basis of ongoing work to obtain additional chiral species with other functional groups, as well as to develop multiplexed cytokine sensors for in vivo diagnostics.
Liquid Crystals and Macroscopically Aligned Fibers from Boron-Nitride Nanotubes
Authors: Marti Angel A. , Martínez-Jimenez Cecilia , Ginestra Cedric , Pasquali Matteo
Published: August 2024

Boron Nitride Nanotubes (BNNTs) are cylindrical structures with a morphology similar to a rolled hexagonal boron nitride sheet, reminiscent of carbon nanotubes (CNTs). BNNTs have some properties in common with CNTs, such as high strength and heat conduction, but also some different ones, such as electric insulation and thermal stability. These properties are mainly seen at the nanoscale level, but they can also be used at a larger scale by controlling how the BNNTs are aligned in the material. To uncover the incredible properties of BNNTs we have studied their dispersion, functionalization, alignment, and materials made from these building blocks. We found that BNNTs can be dispersed in chlorosulfonic acid, forming liquid crystals at high concentrations. The order in the liquid crystals can be imparted to the materials (e.g. fibers) by extrusion and coagulation. This allowed the formation of aligned fibers with neat BNNTs. These materials can be of great importance for applications in extreme environments where, thermal stability, heat conductivity, and high tensile strength are of importance.
In Situ Investigation of Defect Site Formation in Carbon Nanotubes
Authors: Lambert Benjamin Paul , Martín Muñoz Blanca , Cognet Laurent
Published: August 2024

Semiconducting single-walled carbon nanotubes (SWCNTs) exhibit a photostable excitonic fluorescence in the short wave near-infrared (SWIR). Recently, the covalent functionalization of nanotubes opened new avenues to manipulate their excitonic fluorescence [1]. These “organic color centers (OCCs)” act as localized potential wells on the nanotube surface, trapping locally otherwise diffusing excitons. This effectively results in an increase in the SWCNT emission, the trapped excitons avoiding possible quenching sites along the nanotube surface (structural defects, nanotube ends) [2]. This new radiative pathway results in a shifting of the SWCNT emission towards longer wavelengths and allows SWCNT excitation on their first-order excitonic transition (ca. SWIR) [3]. Altogether, these properties make OCC-functionalized SWCNTs particularly attractive for various applications ranging from biological imaging to quantum information. Yet, the functionalization reaction of SWCNTs with OCC is still poorly understood, stochastic and, as a result, poorly controlled. To gain knowledge and control over these reactions, we developed a two-color imaging platform to image simultaneously both the SWCNT and OCC emissions in situ during the functionalization reaction [4]. We will present how this platform allows to monitor the kinetics of the functionalization reaction and further discuss our findings which provide insights on the interactions existing between OCCs and the SWCNT surface.

[1] A. H. Brozena et al., Nat. Rev. Chem., vol. 3, no. 6, pp. 375–392, 2019

[2] N. Danné et al., ACS Nano, vol. 12, no. 6, pp. 6059–6065, 2018

[3] A. K. Mandal et al., Sci. Rep., vol. 10, no. 1, pp. 1–9, 2020

[4] B.P. Lambert et al., in preparation
Programmable DNA Quantum Defects in Carbon Nanotubes
Authors: Kim Mijin , Wu Xiaojian , Wang Lucy , Veetil Abhindev Kizhakke , Wang YuHuang
Published: August 2024

Atomic defect centers in solid-state systems hold immense potential for many quantum technologies. However, achieving precise, high-quality defects in dense arrays remains a formidable challenge. In this talk, we present a photochemical creation of programmable, defect color center arrays in semiconducting carbon nanotubes The precision defect chemistry is achieved via the strategic substitution of thymine with halogenated uracil in DNA strands that helically wrap around the nanotube and subsequent photochemical triggering of the covalent functionalization. Diverging from guanine-induced sp2 defects, our method introduces sp3 defects with deep exciton traps, producing a bright photoluminescence band with a pronounced energy shift in carbon nanotubes. Defect placements can be systematically controlled by either spacer DNAs or DNA sequences with multiple halogenated nucleobases. By intertwining advanced molecular chemistry with quantum material sciences, our approach marks a key step in expanding the chemical toolbox to craft quantum defects for quantum information science, imaging, and sensing.
(Invited) Assembly of Carbon Nanotubes Heterostructures Down to Single-Particle Control
Authors: Palma Matteo
Published: August 2024

We will present different chemical strategies for the in-solution assembly of single walled carbon nanotube (SWCNT)-based heterostructures, down to single-particle control and resolution. In particular, we interfaced SWCNTs to inorganic semiconducting nanoparticles and nanocrystals, perovskites, as well as metal nanoparticles and nanowires. We developed various approaches towards this end, from the selective and differential functionalisation of CNTs terminal ends with distinct individual nanomoieties , to the use of nanotubes as templates for the growth of nanomaterials on their sidewall or in their cavity. Solution-processed optoelectronic devices were fabricated employing the aforementioned nanohybrids, displaying various sensitivity to a broad range of illumination wavelengths.
(Invited) Correlation Measurements for Carbon Nanotubes with Quantum Defects
Authors: Krupke Ralph
Published: August 2024

Single-photon sources are one of the essential building blocks for the development of photonic quantum technology. In terms of potential practical application, an on-demand electrically driven quantum-light emitter on a chip is notably crucial for integrating photonic integrated circuits. Here, we propose functionalized single-walled carbon nanotube field-effect transistors as a promising solid-state quantum-light source by demonstrating photon antibunching behavior via electrical excitation. The sp3 quantum defects were formed on the surface of (7, 5) carbon nanotubes by 3,5-dichlorophenyl functionalization, and individual carbon nanotubes were wired to graphene electrode pairs. Filtered electroluminescent defect-state emission at 77 K was coupled into a Hanbury Brown and Twiss experiment setup, and single-photon emission was observed by performing second-order correlation function measurements. We discuss the dependence of the intensity correlation measurement on excitation power and emission wavelength highlighting the challenges of performing such measurements while simultaneously analyzing acquired data. Our results indicate a route toward room-temperature electrically-triggered single-photon emission.
(Invited) High Temperature Exciton Properties in Aggregated Single-Walled Carbon Nanotubes
Authors: Miyauchi Yuhei
Published: August 2024

Individual single-walled carbon nanotubes (SWCNTs) at high temperatures have been reported to generate narrow-band thermal radiation in the near-infrared region due to thermally robust excitonic effects [1,2]. This phenomenon potentially offers a new opportunity for utilizing exciton properties in thermal engineering such as thermophotovoltaic energy harvesting requiring excellent wavelength selective near-infrared thermal emitter. However, for its realistic applications in macroscale, it is necessary to make the distinct exciton effect available under high temperature conditions in macroscopic assemblies of SWCNTs. As a first step toward this goal, we have recently determined broadband complex refractive index spectra of single-chirality SWCNT membranes in which SWCNTs are aligned two-dimensionally in a plane [3] and reported their birefringent properties [4]. In the presentation, we will discuss the change in the optical spectra of SWCNT assemblies with increasing temperature, as well as how the aggregation states affect the exciton properties. [1] T. Nishihara, A. Takakura, Y. Miyauchi, and K. Itami, Nat. Commun. 9, 3144 (2018). [2] S. Konabe, T. Nishihara, and Y. Miyauchi, Opt. Lett. 46, 3021 (2021). [3] T. Nishihara, A. Takakura, M. Shimasaki, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Nanophotonics 11, 1011 (2022). [4] H. Wu, T. Nishihara, A. Takakura, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Carbon, in press.